TW202104147A - Compound having fluorene skeleton and method for producing same - Google Patents

Abstract

A compound having a fluorene skeleton represented by formula (1), which is characterized in that a resin obtained by using this compound having a fluorene skeleton as a starting material is excellent in terms of various characteristics (such as optical characteristics, heat resistance and moldability). (In the formula, R1 represents a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an aromatic group having 1-12 carbon atoms; each of Ar1 and Ar2 independently represents an aromatic group which may have a substituent having 6-12 carbon atoms; L1 represents an alkylene group having 1-12 carbon atoms; m1 and n1 may be the same or different, and each represents an integer of 0-4; m2 and n2 may be the same or different, and each represents an integer of 0-3; and (m1 + m2) ≥ 1 is satisfied. Meanwhile, (m1 + n1) is an integer of 4 or less, and (m2 + n2) is an integer of 3 or less. Each of o1 and o2 independently represents an integer of 0-5.).

Description

具有茀骨架之化合物及其之製造方法Compound with 茀 frame and its manufacturing method

本發明係關於一種適宜作為形成熱塑性樹脂之單體，該熱塑性樹脂係構成由光學透鏡或光學膜所代表之光學構件者，且關於一種適宜作為熱塑性樹脂之原料之具有茀骨架之化合物及其之製造方法，該熱塑性樹脂係高折射率、低雙折射，及耐熱性與成形性之平衡優異者。The present invention relates to a monomer suitable for forming a thermoplastic resin that constitutes an optical member represented by an optical lens or an optical film, and to a compound having a phytoskeleton suitable as a raw material for a thermoplastic resin and its The manufacturing method is that the thermoplastic resin has a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability.

近年來，將由9,9-雙(4-(2-羥基乙氧基)苯基)茀(BPEF)所代表之具有茀骨架之醇作為原料之聚碳酸酯、聚酯、聚酯碳酸酯等之熱塑性樹脂材料，由於光學特性、耐熱性、成形性等優異，故作為光學透鏡或光學薄片等之光學構件而受到矚目。In recent years, polycarbonates, polyesters, polyester carbonates, etc. have been used as raw materials for alcohols with a stilbene skeleton represented by 9,9-bis(4-(2-hydroxyethoxy)phenyl) pyrene (BPEF) The thermoplastic resin material has excellent optical properties, heat resistance, moldability, etc., so it has attracted attention as an optical member such as an optical lens or an optical sheet.

例如，專利文獻1揭示將具有BPEF骨架之醇作為原料之聚碳酸酯樹脂。然而，雖記載使用該醇之聚碳酸酯樹脂之折射率為1.64，但近年來伴隨急速之技術革新，故要求前述特性之更加提升。因此，目標朝向更加之高折射率化，專利文獻2雖已開發出將9,9-雙[4-(2-羥基乙氧基)-3-苯基苯基]茀(BOPBPEF)作為原料之熱塑性樹脂，但該專利文獻記載之樹脂也係在折射率上仍尚有改善之餘地。又，專利文獻3雖記載將9,9-雙[6-(2-羥基乙氧基)-2-萘基]茀(BNEF)作為原料之高折射率樹脂，但由於折射率為高且雙折射也變高，故適用於光學透鏡等之透明材料時則會造成大問題。For example, Patent Document 1 discloses a polycarbonate resin using an alcohol having a BPEF skeleton as a raw material. However, although it is stated that the refractive index of the polycarbonate resin using the alcohol is 1.64, in recent years, with rapid technological innovation, further improvement of the aforementioned properties is required. Therefore, the goal is to increase the refractive index. Although Patent Document 2 has developed 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl] 茀 (BOPBPEF) as a raw material Thermoplastic resin, but the resin described in the patent document still has room for improvement in refractive index. In addition, although Patent Document 3 describes a high refractive index resin using 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl] 茀 (BNEF) as a raw material, the refractive index is high and double The refraction also becomes higher, so it will cause a big problem when it is applied to transparent materials such as optical lenses.

因此，在高折射率與低雙折射上具有取捨之關係，過往之聚碳酸酯或聚酯樹脂則係難以使兩特性併存。Therefore, there is a trade-off between high refractive index and low birefringence. In the past, polycarbonate or polyester resins had difficulty coexisting the two characteristics.

另一方面，作為9,9-雙(4-(2-羥基乙氧基)苯基)茀(BPEF)之製造方法，已知有使用硫酸與硫醇類作為觸媒，使9-茀酮與2-苯氧基乙醇進行脫水縮合之方法。又，作為9,9-雙[6-(2-羥基乙氧基)-2-萘基]茀(BNEF)之製造方法，已揭示有與BPEF同樣地使用硫酸與硫醇類作為觸媒而使茀酮與2-萘氧基乙醇進行脫水縮合之方法(專利文獻4)。並且，已揭示9,9-雙[4-(2-羥基乙氧基)-3-苯基苯基]茀(BOPBPEF)也係與BPEF或BNEF同樣地使用硫酸與硫醇類作為觸媒而使茀酮與2-(2-聯苯基氧基)乙醇進行脫水縮合之方法(專利文獻5)。又，作為9,9-雙[6-(2-羥基乙氧基)-2-萘基]茀(BNEF)之製造方法，已揭示取代硫酸而改用磷鎢酸與n-十二基硫醇作為酸觸媒，使9-茀酮與2-萘酚在甲苯及γ-丁內酯中，使其減壓並同時脫水縮合後，不進行純化而直接加成碳酸伸乙酯之方法(專利文獻6)。On the other hand, as a method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl) pyrene (BPEF), it is known to use sulfuric acid and mercaptans as catalysts to make 9-pyrone A method of dehydration and condensation with 2-phenoxyethanol. In addition, as a method for producing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl] 茀 (BNEF), it has been revealed that the same as BPEF, the use of sulfuric acid and mercaptans as catalysts A method of dehydrating and condensing ketone and 2-naphthoxyethanol (Patent Document 4). In addition, it has been revealed that 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]sulfuric acid (BOPBPEF) is also based on the same method as BPEF or BNEF using sulfuric acid and mercaptans as catalysts. A method of dehydrating and condensing ketone and 2-(2-biphenyloxy)ethanol (Patent Document 5). In addition, as a manufacturing method of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]sulfuric acid (BNEF), it has been disclosed to replace sulfuric acid with phosphotungstic acid and n-dodecylsulfur. Alcohol is used as an acid catalyst. After 9-Tunone and 2-Naphthol are decompressed in toluene and γ-butyrolactone and dehydrated and condensed at the same time, they are directly added to ethylene carbonate without purification ( Patent Document 6).

然而，上述任一之方法皆係使用大量硫酸，或係使用少量之稱為n-十二基硫醇之硫源作為酸觸媒，故必須要有反應後之中和・純化等繁雜之純化操作，且會導致大量之中和用排水。又，由於製品中混入源自觸媒之硫成分，故產生製品之著色或安定性降低，純度降低等之問題。並且，為了取得光學用樹脂材料等，高純度之製品，則有必要重複執行去除硫成分用之純化操作，故在工業上無法說係為有利之方法。 [先前技術文獻] [專利文獻]However, any of the above methods uses a large amount of sulfuric acid, or uses a small amount of sulfur source called n-dodecyl mercaptan as the acid catalyst, so complicated purification such as neutralization and purification after the reaction is necessary. Operation, and will result in a large amount of neutralization drainage. In addition, since the sulfur component derived from the catalyst is mixed into the product, problems such as reduced coloration or stability of the product, and reduced purity of the product occur. In addition, in order to obtain high-purity products such as optical resin materials, it is necessary to repeat the purification operation for removing sulfur components, so it cannot be said to be an advantageous method in the industry. [Prior Technical Literature] [Patent Literature]

[專利文獻1]國際公開第2007/142149號公報 [專利文獻2]日本特開2015-86265號公報 [專利文獻3]日本特開2017-171885號公報 [專利文獻4]日本特開2016-79405號公報 [專利文獻5]日本特開2009-256342號公報 [專利文獻6]日本特開2019-1780號公報[Patent Document 1] International Publication No. 2007/142149 [Patent Document 2] JP 2015-86265 A [Patent Document 3] JP 2017-171885 A [Patent Document 4] JP 2016-79405 A [Patent Document 5] JP 2009-256342 A [Patent Document 6] Japanese Patent Application Publication No. 2019-1780

[發明所欲解決之課題][The problem to be solved by the invention]

本發明中經分子設計之下述式(1)之化合物之製造方法係由2個步驟所構成，本案發明者即便使用上述專利文獻記載之方法，反應完全不會進行，或反應即便進行但反應速度為慢，故在工業上為不利者。又，由於所使用之觸媒量為多，故倘若不實施活性碳處理或與此酷似之金屬除去處理，則在下述式(1)所示之具有茀骨架之白色化合物中會混入源自經使用之鈀系觸媒之黑色粒子，從而導致該醇化合物之色相惡化。又，由於包括硫或溴之雜質為多，故會有該醇化合物之色相惡化，將該醇作為原料進行聚合時造成反應不良的情況。In the present invention, the molecularly designed method for producing the compound of the following formula (1) consists of two steps. Even if the inventor of the present case uses the method described in the above patent document, the reaction does not proceed at all, or the reaction proceeds but the reaction The speed is slow, so it is disadvantageous in industry. In addition, since the amount of catalyst used is large, if activated carbon treatment or metal removal treatment similar to this is not performed, the white compound having a 茀 skeleton represented by the following formula (1) will be mixed with The black particles of the palladium-based catalyst used lead to the deterioration of the hue of the alcohol compound. In addition, since there are many impurities including sulfur or bromine, the hue of the alcohol compound may deteriorate, which may cause poor reaction when the alcohol is used as a raw material for polymerization.

因此，本發明為了解決上述先前技術之問題點進行檢討之結果所達成者，其目的在於提供一種新穎之具有茀骨架之化合物及其之製造方法，該具有茀骨架之化合物係使用作為原料而得之樹脂之各種特性(光學特性、耐熱性、成形性等)為優異者。Therefore, the present invention is achieved as a result of the review in order to solve the above-mentioned problems of the prior art, and its purpose is to provide a novel compound with a stilbene skeleton and a method for producing the same. The compound with a stilbene skeleton is obtained by using as a raw material. The various properties of the resin (optical properties, heat resistance, moldability, etc.) are excellent.

又，本發明之目的在於提供一種新穎之具有茀骨架之化合物及其之製造方法，該具有茀骨架之化合物較佳係鈀含量等之特定金屬含量為少，其之原料，或使用該原料之樹脂之色相優異者。In addition, the object of the present invention is to provide a novel compound with a turbidity skeleton and a method for producing the same. The compound with a turbidity skeleton preferably has a low content of specific metals such as palladium. Those with excellent resin hue.

更進一步，本發明之目的在於提供一種新穎之具有茀骨架之化合物及其之製造方法，該具有茀骨架之化合物係為原料醇中之包括硫之雜質含量為少，較佳係鈀含量等之特定金屬含量或包括溴之雜質含量為少，該原料或使用該原料而得之樹脂之色相或各種特性(光學特性、耐熱性、成形性等)優異者。 [用以解決課題之手段]Furthermore, the object of the present invention is to provide a novel compound having a stilbene skeleton and a method for producing the same. The compound having a stilbene skeleton contains less impurities including sulfur in the raw material alcohol, preferably the content of palladium, etc. The content of the specific metal or the content of impurities including bromine is small, and the raw material or the resin obtained by using the raw material has excellent hue or various characteristics (optical properties, heat resistance, moldability, etc.). [Means to solve the problem]

本發明係為了解決上述先前技術之問題點進行檢討之結果所達成者，且係提供一種具有固定品質，且作為聚合物原料為優異之具有茀骨架之化合物及其之製造方法。具體而言，本發明係關於以下所示之具有茀骨架之化合物及其之製造方法。The present invention is achieved as a result of reviewing to solve the above-mentioned problems of the prior art, and provides a compound having a stilbene skeleton having a fixed quality and being excellent as a polymer raw material, and a manufacturing method thereof. Specifically, the present invention relates to a compound having a 茀 skeleton shown below and its production method.

[1]一種下述式(1)所示之具有茀骨架之化合物。

(式中，R¹ 表示氫原子、鹵素原子，或碳數1~12之可包含芳香族基之烴基，Ar¹ 及Ar² 係各自獨立表示碳數6~12之可具有取代基之芳香族基，L¹ 表示碳數1~12之伸烷基，m1及n1係相同或相異地表示0~4之整數，m2及n2係相同或相異地表示0~3之整數，m1+m2≧1。但，m1+n1為4以下之整數，m2+n2為3以下之整數。о1及о2係各自獨立表示0~5之整數。)[1] A compound represented by the following formula (1) having a sulphur skeleton.

(In the formula, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms that may contain an aromatic group, and Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 12 carbon atoms that may have a substituent Base, L ¹ represents an alkylene group with 1 to 12 carbon atoms, m1 and n1 represent the same or different integers from 0 to 4, m2 and n2 represent the same or different integers from 0 to 3, m1+m2≧1 .However, m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less. о1 and о2 each independently represent an integer from 0 to 5.)

[2]如前項1之具有茀骨架之化合物，其中前述式(1)所示之具有茀骨架之化合物中之硫元素之含量為200ppm以下。[2] The compound having a turbidity skeleton according to the preceding item 1, wherein the sulfur content in the compound with a turbidity skeleton represented by the aforementioned formula (1) is 200 ppm or less.

[3]如前項1或2之具有茀骨架之化合物，其中前述式(1)所示之具有茀骨架之化合物中之鈀元素之含量滿足下述式(2)。 0≦Pd≦50ppm　　　　(2)[3] The compound having a sulphur skeleton according to the preceding item 1 or 2, wherein the content of the palladium element in the compound having a sulphur skeleton represented by the aforementioned formula (1) satisfies the following formula (2). 0≦Pd≦50ppm　　　　(2)

[4]如前項1或2之具有茀骨架之化合物，其中使前述式(1)所示之化合物溶解於二甲基甲醯胺而成之5重量%溶液之APHA為500以下。[4] The compound having a citric acid skeleton according to item 1 or 2, wherein the APHA of a 5 wt% solution obtained by dissolving the compound represented by the aforementioned formula (1) in dimethylformamide is 500 or less.

[5]如前項1或2之具有茀骨架之化合物，其中前述式(1)所示之化合物中之溴元素之含量為150ppm以下。[5] The compound having a chlorophyll skeleton according to item 1 or 2, wherein the content of bromine element in the compound represented by the aforementioned formula (1) is 150 ppm or less.

[6]如前項1或2之具有茀骨架之化合物，其中前述式(1)為下述式(1a)~(1d)所示當中之1者。

(式中，R² ~R¹³ 係各自獨立表示氫原子、鹵素原子，或碳數1~12之可包含芳香族基之烴基。Ar¹ 、Ar² 、L¹ 及о1係與前述式(1)中相同)。[6] The compound having a sulphur skeleton according to the preceding item 1 or 2, wherein the aforementioned formula (1) is one of the following formulas (1a) to (1d).

(In the formula, R ² to R ¹³ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group with 1 to 12 carbon atoms that may contain an aromatic group. Ar ¹ , Ar ² , L ¹ and о1 are the same as the aforementioned formula (1 ) Is the same).

[7]前項6之具有茀骨架之化合物，其中前述式(1)為前述式(1b)。[7] The compound having a sulphur skeleton according to the preceding paragraph 6, wherein the aforementioned formula (1) is the aforementioned formula (1b).

[8]如前項1或2之具有茀骨架之化合物，其中前述式(1)中之Ar¹ 及Ar² 表示苯基或萘基。[8] The compound having a sulphur skeleton according to the preceding item 1 or 2, wherein Ar ¹ and Ar ² in the aforementioned formula (1) represent a phenyl group or a naphthyl group.

[9]如前項1或2之具有茀骨架之化合物，其中前述式(1)為下述式(1-b)所示之化合物。

[9] The compound having a sulphur skeleton according to item 1 or 2, wherein the aforementioned formula (1) is a compound represented by the following formula (1-b).

[10]如前項9之化合物，其中式(1-b)所示之化合物中之二苯基茀酮之含量為0.2%以下。[10] The compound of the preceding paragraph 9, wherein the content of diphenylquinone in the compound represented by the formula (1-b) is 0.2% or less.

[11]如前項9之化合物，其中其之結晶在示差掃描熱量分析下，在230~247℃具有吸熱峰。[11] The compound of 9 above, wherein its crystal has an endothermic peak at 230~247°C under differential scanning calorimetry analysis.

[12]如前項9之化合物，其中其之結晶在利用Cu-Kα線而得之粉末X線繞射圖型中之繞射角2θ為10.6±0.2°、10.8±0.2°、17.1±0.2°、17.6±0.2°及18.7±0.2°處具有波峰。[12] The compound of 9 above, wherein the diffraction angle 2θ of the crystal in the powder X-ray diffraction pattern obtained by using Cu-Kα line is 10.6±0.2°, 10.8±0.2°, 17.1±0.2° , 17.6±0.2° and 18.7±0.2° have crests.

[13]一種具有茀骨架之化合物之製造方法，其係前述式(1)所示之具有茀骨架之化合物之製造方法，其特徵為包含至少下述之步驟1及步驟2而成； 步驟1：使下述式(3)所示之茀酮類與下述式(4)或(5)所示之硼酸類在反應溶劑中，在鹼及鈀系觸媒之存在下進行反應的步驟 步驟2：使步驟1所製造之反應物(6)與下述式(7)所示之醇類在反應溶劑中，在酸觸媒之存在下，減壓下使其反應，反應後，不取出進行中和所而得之下述式(8)所示之反應物而直接在鹼之存在下與碳酸伸乙酯反應來製造目的物的步驟

(式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子。)

(式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子。l為0、1或2，l=2時，R¹⁴ 可為相同或亦可為相異。)

(式中，Ar¹ 及Ar² 係與式(1)中相同。)

(式中，p1及p2係相同或相異為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同。)

(式中，R¹ 、Ar¹ 及Ar² 係與式(1)中相同。p1及p2係與式(7)中相同。n1及n2為0~3之整數。)[13] A method for producing a compound having a stilbene skeleton, which is the method for producing a compound having a stilbene skeleton represented by the aforementioned formula (1), characterized by including at least the following steps 1 and 2; Step 1 : The step of reacting the ketones represented by the following formula (3) and the boric acids represented by the following formula (4) or (5) in the reaction solvent in the presence of a base and a palladium-based catalyst 2: The reactant (6) produced in step 1 and the alcohol represented by the following formula (7) are reacted in the reaction solvent in the presence of an acid catalyst under reduced pressure. After the reaction, it is not taken out The step of neutralizing the reactant represented by the following formula (8) and directly reacting with ethylene carbonate in the presence of a base to produce the target product

(In the formula, X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position and represents a halogen atom, and X ² is a substituent at the 5-position, 6-position, 7-position or 8-position and represents a halogen atom. )

(In the formula, Y represents an aromatic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1 or 2, and when l=2, R ¹⁴ may be the same or may be Is different.)

(In the formula, Ar ¹ and Ar ² are the same as in the formula (1).)

(In the formula, p1 and p2 are the same or different as an integer of 0-4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1).)

(In the formula, R ¹ , Ar ¹ and Ar ² are the same as in formula (1). p1 and p2 are the same as in formula (7). n1 and n2 are integers from 0 to 3.)

[13-1]如前項13之具有茀骨架之化合物之製造方法，其中式(3)所示之化合物為2,7-二溴茀酮。[13-1] The method for producing a compound having a stilbene skeleton according to the above item 13, wherein the compound represented by the formula (3) is 2,7-dibromopyrone.

[13-2]如前項13之具有茀骨架之化合物之製造方法，其中式(4)所示之化合物為苯基硼酸。[13-2] The method for producing a compound having a stilbene skeleton according to the above item 13, wherein the compound represented by formula (4) is phenylboronic acid.

[13-3]如前項13之具有茀骨架之化合物之製造方法，其中式(5)所示之化合物為苯基硼酸之酐。[13-3] The method for producing a compound having a sulphur skeleton according to the preceding item 13, wherein the compound represented by the formula (5) is an anhydride of phenylboronic acid.

[13-4]如前項13之具有茀骨架之化合物之製造方法，其中式(6)所示之化合物為2,7-二苯基茀酮。[13-4] The method for producing a compound having a stilbene skeleton according to the above item 13, wherein the compound represented by the formula (6) is 2,7-diphenyl quinone.

[13-5]如前項13之具有茀骨架之化合物之製造方法，其中式(7)所示之化合物為2-萘酚。[13-5] The method for producing a compound having a stilbene skeleton according to the above item 13, wherein the compound represented by the formula (7) is 2-naphthol.

[13-6]如前項13之具有茀骨架之化合物之製造方法，其中式(8)所示之化合物為9,9’-雙(6-羥基-2-萘基)-2,7-二苯基茀。[13-6] The method for producing a compound having a stilbene skeleton according to the preceding item 13, wherein the compound represented by formula (8) is 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-bis Phenylpyridine.

[13-7]如前項13之具有茀骨架之化合物之製造方法，其中步驟1所使用之鈀系觸媒為肆(三苯基膦)鈀，及/或，Pd/SiO₂ 所示之鈀系觸媒。[13-7] The method for producing a compound having a fluoride skeleton as in the preceding paragraph 13, wherein the palladium-based catalyst used in step 1 is palladium (triphenylphosphine) palladium, and/or palladium represented by _{Pd/SiO 2} Department of catalyst.

[13-8]如前項13之具有茀骨架之化合物之製造方法，其中步驟1所使用之鹼為碳酸鉀及/或碳酸鈉。[13-8] The method for producing a compound having a stilbene skeleton as described in the preceding item 13, wherein the base used in step 1 is potassium carbonate and/or sodium carbonate.

[13-9]如前項13之具有茀骨架之化合物之製造方法，其中使用甲苯與乙醇之混合溶劑作為步驟1所使用之反應溶劑。[13-9] The method for producing a compound having a chlorophyll skeleton as described in the preceding item 13, wherein a mixed solvent of toluene and ethanol is used as the reaction solvent used in step 1.

[13-10]前項13之具有茀骨架之化合物之製造方法，其中 步驟2所使用之酸觸媒係由磷酸或矽酸，與選自釩、鉬及鎢之至少一個元素之含氧酸離子所構成之雜多酸。[13-10] The method for producing a compound having a 茀skeleton in the preceding paragraph 13, wherein The acid catalyst used in step 2 is a heteropolyacid composed of phosphoric acid or silicic acid and an oxoacid ion of at least one element selected from vanadium, molybdenum and tungsten.

[13-11]如前項13之具有茀骨架之化合物之製造方法，其中在步驟2中一同併用酸觸媒與具有巰基之化合物。[13-11] The method for producing a compound having a sulphur skeleton as described in the preceding item 13, wherein in step 2, an acid catalyst and a compound having a mercapto group are used together.

[13-12]如前項13之具有茀骨架之化合物之製造方法，其中使用甲苯與γ-丁內酯之混合溶劑作為步驟2所使用之反應溶劑。[13-12] The method for producing a compound having a 茀skeleton as described in item 13 above, wherein a mixed solvent of toluene and γ-butyrolactone is used as the reaction solvent used in step 2.

[13-13]如前項13之具有茀骨架之化合物之製造方法，其中使用甲苯與碳酸伸乙酯之混合溶劑作為步驟2所使用之反應溶劑。[13-13] The method for producing a compound having a chlorophyll skeleton as described in the preceding item 13, wherein a mixed solvent of toluene and ethylene carbonate is used as the reaction solvent used in step 2.

[14]一種具有茀骨架之化合物之製造方法，其係前述式(1)所示之具有茀骨架之化合物之製造方法，其特徵為包含至少下述之步驟1~3而成； 步驟1：使下述式(13)所示之茀酮類與下述式(14)所示之醇類在反應溶劑中，在酸觸媒之存在下使其反應而取得下述式(15)所示之化合物的步驟 步驟2：使下述式(15)所示之化合物與碳酸伸乙酯在反應溶劑中，鹼之存在下進行反應而取得下述式(16)所示之化合物的步驟 步驟3：使下述式(16)所示之化合物與下述式(17)或(18)所示之硼酸類在反應溶劑中，在鹼及鈀系觸媒之存在下進行反應，而取得前述式(1)所示之化合物的步驟

(式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子。)

(式中，p1及p2係相同或相異為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同。)

(式中，X¹ 及X² 係與前述式(13)中相同。R¹ 、p1及p2係與式(14)中相同。n1及n2為0~3之整數。)

(式中，X¹ 及X² 係與前述式(13)中相同。R¹ 、L¹ 、m1、m2、n1、n2、o1及o2係與式(1)中相同。

(式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子。l為0、1或2，l=2時，R¹⁴ 可為相同或亦可為相異。)[14] A method for producing a compound having a stilbene skeleton, which is the method for producing a compound having a stilbene skeleton represented by the aforementioned formula (1), characterized by including at least the following steps 1 to 3; Step 1: The ketones represented by the following formula (13) and the alcohols represented by the following formula (14) are reacted in the reaction solvent in the presence of an acid catalyst to obtain the following formula (15) Step 2: The compound represented by the following formula (15) and ethylene carbonate are reacted in the reaction solvent in the presence of a base to obtain the compound represented by the following formula (16). Step 3 : The compound represented by the following formula (16) and the boric acid represented by the following formula (17) or (18) are reacted in the reaction solvent in the presence of a base and a palladium-based catalyst to obtain the aforementioned formula (1) The steps of the compound shown

(In the formula, X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position and represents a halogen atom, and X ² is a substituent at the 5-position, 6-position, 7-position or 8-position and represents a halogen atom. )

(In the formula, p1 and p2 are the same or different as an integer of 0-4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1).)

(In the formula, X ¹ and X ² are the same as in the aforementioned formula (13). R ¹ , p1 and p2 are the same as in the formula (14). n1 and n2 are integers from 0 to 3.)

(In the formula, X ¹ and X ² are the same as in the aforementioned formula (13). R ¹ , L ¹ , m1, m2, n1, n2, o1 and o2 are the same as in the formula (1).

(In the formula, Y represents an aromatic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1 or 2, and when l=2, R ¹⁴ may be the same or may be Is different.)

[14-1]如前項14之製造方法，其中不取出前述式(15)所示之化合物，而在一鍋(one pot)內進行前述步驟1與步驟2。[14-1] The manufacturing method of the preceding item 14, wherein the compound represented by the formula (15) is not taken out, and the aforementioned step 1 and step 2 are carried out in a one pot (one pot).

[14-2]如前項14之製造方法，其中不取出前述式(15)及(16)所示之化合物，而在一鍋內進行前述步驟1~3。[14-2] The manufacturing method of the preceding item 14, wherein the compounds represented by the formulas (15) and (16) are not taken out, and the aforementioned steps 1 to 3 are carried out in a pot.

[14-3]如前項14之具有茀骨架之化合物之製造方法，其中式(13)所示之化合物為2,7-二溴茀酮。[14-3] The method for producing a compound having a chlorophyll skeleton as described in the preceding item 14, wherein the compound represented by the formula (13) is 2,7-dibromocholonone.

[14-4]如前項14之具有茀骨架之化合物之製造方法，其中式(17)所示之化合物為苯基硼酸。[14-4] The method for producing a compound having a sulphur skeleton according to the preceding item 14, wherein the compound represented by the formula (17) is phenylboronic acid.

[14-5]如前項14之具有茀骨架之化合物之製造方法，其中式(18)所示之化合物為苯基硼酸之酐。[14-5] The method for producing a compound having a sulphur skeleton according to the preceding item 14, wherein the compound represented by the formula (18) is an anhydride of phenylboronic acid.

[14-6]前項14之具有茀骨架之化合物之製造方法，其中式(14)所示之化合物為2-萘酚。[14-6] The method for producing a compound having a stilbene skeleton according to the preceding paragraph 14, wherein the compound represented by formula (14) is 2-naphthol.

[14-7]如前項14之具有茀骨架之化合物之製造方法，其中式(15)所示之化合物為9,9’-雙(6-羥基-2-萘基)-2,7-二溴茀。[14-7] The method for producing a compound having a sulphur skeleton according to the preceding item 14, wherein the compound represented by formula (15) is 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-bis Bromine.

[14-8]如前項14之具有茀骨架之化合物之製造方法，其中步驟3所使用之鈀系觸媒為肆(三苯基膦)鈀，及/或，Pd/SiO₂ 所示之鈀系觸媒。[14-8] The method for producing a compound having a 茀 framework as described in item 14, wherein the palladium catalyst used in step 3 is palladium (triphenylphosphine) palladium, and/or palladium represented by _{Pd/SiO 2} Department of catalyst.

[14-9]如前項14之具有茀骨架之化合物之製造方法，其中步驟3所使用之鹼為碳酸鉀及/或碳酸鈉。[14-9] The method for producing a compound having a stilbene skeleton as described in item 14, wherein the base used in step 3 is potassium carbonate and/or sodium carbonate.

[14-10]如前項14之具有茀骨架之化合物之製造方法，其中使用甲苯與乙醇之混合溶劑作為步驟3所使用之反應溶劑。[14-10] The method for producing a compound having a 茀skeleton as described in item 14 above, wherein a mixed solvent of toluene and ethanol is used as the reaction solvent used in step 3.

[14-11]如前項14之具有茀骨架之化合物之製造方法，其中步驟1所使用之酸觸媒係由磷酸或矽酸，與選自釩、鉬及鎢之至少一種元素之含氧酸離子所構成之雜多酸。[14-11] The method for producing a compound having a fluoride skeleton as described in the preceding paragraph 14, wherein the acid catalyst used in step 1 is an oxyacid containing at least one element selected from the group consisting of phosphoric acid or silicic acid and vanadium, molybdenum and tungsten Heteropoly acid composed of ions.

[14-12]如前項14之具有茀骨架之化合物之製造方法，其中在步驟1中一同併用酸觸媒與具有巰基之化合物。[14-12] The method for producing a compound having a sulphur skeleton according to the above item 14, wherein in step 1, an acid catalyst and a compound having a mercapto group are used together.

[14-13]如前項14之具有茀骨架之化合物之製造方法，其中使用甲苯與碳酸伸乙酯之混合溶劑作為步驟1所使用之反應溶劑。[14-13] The method for producing a compound having a chlorophyll skeleton according to item 14 above, wherein a mixed solvent of toluene and ethylene carbonate is used as the reaction solvent used in step 1.

[15]一種前項1之具有茀骨架之化合物之使用方法，其作為熱塑性樹脂之原料。 [發明之效果][15] A method of using the compound having a 茀 skeleton of the preceding paragraph 1, which is used as a raw material for a thermoplastic resin. [Effects of Invention]

本發明之茀化合物不僅係在茀環之9位上被集合環芳烴環(arene ring)所取代，且(較佳係在2,7位之位置上也)具有二芳基，將該茀化合物作為原料之熱塑性樹脂不僅光學特性優異，並且各種特性(耐熱性、透明性、成形性等)亦為優異。又，本發明之茀化合物較佳係包括硫之雜質之含量為少，並且鈀等之特定金屬之含量或包括溴之雜質之含量為少，且色相亦優。又，將該茀化合物作為原料之熱塑性樹脂不僅光學特性優異，並且各種特性(耐熱性、透明性、色相、成形性等)亦為優異。更進一步，本發明係能效率良好地製造此種特性優異之具有茀骨架之化合物。The tea compound of the present invention is not only substituted by an arene ring at the 9 position of the tea ring, but also has a diaryl group (preferably at the positions 2,7). The tea compound The thermoplastic resin used as a raw material is not only excellent in optical properties, but also excellent in various properties (heat resistance, transparency, moldability, etc.). In addition, it is preferable that the stilbene compound of the present invention has a low content of impurities including sulfur, and a low content of specific metals such as palladium or impurities including bromine, and also has excellent hue. In addition, the thermoplastic resin using the stilbene compound as a raw material is not only excellent in optical properties, but also excellent in various properties (heat resistance, transparency, hue, moldability, etc.). Furthermore, the present invention is capable of efficiently producing compounds having such excellent properties and having a scaffold skeleton.

詳細進行說明本發明，但以下記載之構成要件之說明為本發明之實施態樣之代表例，而並非係受限於該等內容者。The present invention will be described in detail, but the description of the constituent elements described below is a representative example of the implementation of the present invention, and is not limited to those contents.

＜本發明之態樣I＞ [具有茀骨架之化合物] 本發明之態樣I之具有茀骨架之化合物為下述式(1)所示之具有茀骨架之化合物，即，在茀類之9位上取代或加成2個具有至少1個羥基之芳香族烴而成之化合物。<Aspect I of the Invention> [Compounds with 茀skeleton] The compound having a sulfur skeleton in aspect I of the present invention is a compound having a sulfur skeleton represented by the following formula (1), namely, substitution or addition of two aromatic compounds having at least one hydroxyl group at the 9 position of the sulfur Compounds made from group hydrocarbons.

(式中，R¹ 表示氫原子、鹵素原子，或碳數1~12之可包含芳香族基之烴基，Ar¹ 及Ar² 係各自獨立表示碳數6~12之可具有取代基之芳香族基，L¹ 表示碳數1~12之伸烷基，m1及n1係相同或相異地表示0~4之整數，m2及n2係相同或相異地表示0~3之整數，m1+m2≧1。但，m1+n1為4以下之整數，m2+n2為3以下之整數。о1及о2係各自獨立表示0~5之整數。)

(In the formula, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms that may contain an aromatic group, and Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 12 carbon atoms that may have a substituent Base, L ¹ represents an alkylene group with 1 to 12 carbon atoms, m1 and n1 represent the same or different integers from 0 to 4, m2 and n2 represent the same or different integers from 0 to 3, m1+m2≧1 .However, m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less. о1 and о2 each independently represent an integer from 0 to 5.)

上述式(1)中，作為萘環之具體例，以1,4-萘二基或2,6-萘二基為佳，以2,6-萘二基為較佳。In the above formula (1), as a specific example of the naphthalene ring, 1,4-naphthalenediyl or 2,6-naphthalenediyl is preferred, and 2,6-naphthalenediyl is preferred.

尚且，在茀環之9位上進行取代之2個萘環可互為相同或亦可為相異，但以相同之環之情況為較佳。尚且，在茀骨架之9位上進行取代之萘環之取代基並無特別限定。例如，在為萘環之情況，對應於在茀環之9位上進行取代之萘環的基可為1-萘基、2-萘基等。Furthermore, the two naphthalene rings substituted at the 9-position of the chrysene ring may be the same or different from each other, but the same ring is preferred. Furthermore, the substituent of the naphthalene ring substituted at the 9 position of the 茀 skeleton is not particularly limited. For example, in the case of a naphthalene ring, the group corresponding to the naphthalene ring substituted at the 9 position of the chrysene ring may be 1-naphthyl, 2-naphthyl, and the like.

上述式(1)中，R¹ 表示氫原子、鹵素原子，或碳原子數1~12之可包含芳香族基之烴基，以氫原子、甲基或苯基為佳。In the above formula (1), R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms that may contain an aromatic group, preferably a hydrogen atom, a methyl group, or a phenyl group.

上述式(1)中，作為R¹ 所示之烴基，可例示如烷基、環烷基、芳基、萘基、芳烷基等。作為烷基之具體例，以甲基、乙基、丙基、異丙基、丁基、t-丁基等之C_1-6 烷基、C_1-4 烷基、C_1-3 烷基為佳，以C_1-3 烷基為較佳，其中以甲基或乙基為更佳。In the above formula (1), ^{examples of the hydrocarbon group represented by R 1} include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, and an aralkyl group. As specific examples of alkyl groups, C _{1-6 alkyl, C 1-4} alkyl, C _1-3 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc. Preferably, C _1-3 alkyl is preferred, and methyl or ethyl is more preferred.

又，作為環烷基之具體例，以環戊基、環己基等之C_5-8 環烷基、C_5-6 環烷基等為佳，以C_5-6 環烷基為較佳。Further, as specific examples of the cycloalkyl group, C _{5-8 cycloalkyl, C 5-6} cycloalkyl, etc. such as cyclopentyl and cyclohexyl are preferred, and C _5-6 cycloalkyl is preferred.

又，作為芳基之具體例，以苯基、烷基苯基(單或二甲基苯基、甲苯基、2-甲基苯基、茬基等)等為佳，以苯基為較佳。In addition, as specific examples of aryl groups, phenyl, alkylphenyl (mono- or dimethylphenyl, tolyl, 2-methylphenyl, stubyl, etc.) are preferred, and phenyl is preferred. .

又，作為芳烷基之具體例，較佳可例示如苄基、苯乙基等之C_6-10 芳基-C_1-4 烷基等。Furthermore, as specific examples of the aralkyl group, a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group are preferably exemplified.

又，作為鹵素原子，以氟原子、氯原子、溴原子等為佳。In addition, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferable.

上述式(1)中，取代基R¹ 之取代數即n1及n2係可因應縮合烴之縮合環數等來適宜選擇，並無特別限定，以各自獨立為0以上為佳，較佳為1以上之整數。尚且，取代數n1及n2在萘環中可為相同或亦可為相異，通常多為相同之情況。The above-described formula (1), the substituents R ¹ i.e. the number n1 and n2 substituted line may be due to the condensation of several other ring condensed hydrocarbon is appropriately selected, not particularly limited to preferably each independently 0 or more, preferably 1 The above integer. Furthermore, the substitution numbers n1 and n2 may be the same or different in the naphthalene ring, and they are usually the same.

上述式(1)中，L¹ 表示2價連結基，以碳數1~12之伸烷基為佳，以伸乙基為較佳。通常L¹ 在相同之萘環中可為相同之伸烷基。又，L¹ 在相異之萘環中可互為相同或亦可為相異，通常也可為相同。In the above formula (1), L ¹ represents a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an ethylene group. Generally, L ¹ can be the same alkylene group in the same naphthalene ring. In addition, L ¹ may be the same or different from each other in the different naphthalene rings, and usually may be the same.

氧伸烷基(OL¹ )之數(加成莫耳數)即о1及о2係分別可從0~5之範圍來選擇，下限係以0以上為佳，上限係以4以下為佳，較佳3以下，更佳為2以下。特佳為0或1，最佳為1。尚且，о1及о2可為整數亦可為平均值，在相異之萘環中可為相同亦可為相異。又，m1係以1，m2係以0為佳。The number of oxyalkylene groups (OL ¹ ) (additional molar number), namely о1 and о2 can be selected from the range of 0 to 5, respectively. The lower limit is preferably 0 or more, and the upper limit is 4 or less. Preferably it is 3 or less, more preferably 2 or less. Especially preferably, it is 0 or 1, and most preferably is 1. Furthermore, о1 and о2 may be integers or average values, and may be the same or different in different naphthalene rings. In addition, it is preferable that m1 is 1, and m2 is 0.

上述式(1)中，Ar¹ 及Ar² 係各自獨立表示碳原子數6~10之芳香族基，以苯基或萘基為佳。基Ar¹ 及Ar² 係可互為相異亦可為相同，但通常為相同。又，Ar¹ 及Ar² 之各自之鍵結位置係以在茀骨架之1位與8位、2位與7位、3位與6位，或4位與5位為佳，以2位與7位、3位與6位或4位與5位為較佳，以2位與7位為更佳。In the above formula (1), Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 10 carbon atoms, preferably a phenyl group or a naphthyl group. The bases Ar ¹ and Ar ² may be different from each other or the same, but they are usually the same. In addition, ^{the bonding positions of Ar 1} and Ar ² are preferably at positions 1 and 8, positions 2 and 7, positions 3 and 6, or positions 4 and 5, and preferably positions 2 and 5. 7 bits, 3 bits and 6 bits or 4 bits and 5 bits are preferable, and 2 bits and 7 bits are more preferable.

以下例示前述式(1)所示之二醇成分之代表例，但作為本發明之前述式(1)所使用之原料，則並非係受到該等所限定者。The representative examples of the diol component represented by the aforementioned formula (1) are illustrated below, but the raw materials used as the aforementioned formula (1) of the present invention are not subject to these limitations.

作為二苯基茀類型，較佳可舉出如9,9-雙(6-羥基-2-萘基)-1,8-二苯基茀、9,9-雙(6-羥基-2-萘基)-2,7-二苯基茀、9,9-雙(6-羥基-2-萘基)-3,6-二苯基茀、9,9-雙(6-羥基-2-萘基)-4,5-二苯基茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-1,8-二苯基茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-3,6-二苯基茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-4,5-二苯基茀等。其中亦以下述式(1-a)~(1-b)所示之下述式(1-a)：9,9-雙(6-羥基-2-萘基)-2,7-二苯基茀、下述式(1-b)：9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀為較佳，尤其係以下述式(1-b)：9,9-雙(4-(2-羥基乙氧基)苯基)-2,7-二苯基茀為佳。As the type of diphenylpyridine, preferably, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-diphenylpyrene, 9,9-bis(6-hydroxy-2- Naphthyl)-2,7-diphenylpyridine, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-diphenylpyridine, 9,9-bis(6-hydroxy-2- Naphthyl)-4,5-diphenylpyridine, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-1,8-diphenylpyridine, 9,9-bis [6-(2-Hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]- 3,6-diphenylpyridine, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-4,5-diphenylpyridine, etc. Among them, the following formula (1-a) represented by the following formulas (1-a)~(1-b): 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenyl The following formula (1-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine is preferred, especially the following Formula (1-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylpyridine is preferred.

作為二萘基茀類型，較佳可舉出如9,9-雙(6-羥基-2-萘基)-1,8-二(1-萘基)茀、9,9-雙(6-羥基-2-萘基)-2,7-二(1-萘基)茀、9,9-雙(6-羥基-2-萘基)-3,6-二(1-萘基)茀、9,9-雙(6-羥基-2-萘基)-4,5-二(1-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-1,8-二(1-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二(1-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-3,6-二(1-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-4,5-二(1-萘基)茀、9,9-雙(6-羥基-2-萘基)-1,8-二(2-萘基)茀、9,9-雙(6-羥基-2-萘基)-2,7-二(2-萘基)茀、9,9-雙(6-羥基-2-萘基)-3,6-二(2-萘基)茀、9,9-雙(6-羥基-2-萘基)-4,5-二(2-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-1,8-二(2-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二(2-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-3,6-二(2-萘基)茀、9,9-雙[6-(2-羥基乙氧基)-2-萘基]-4,5-二(2-萘基)茀等。其中亦以下述式(2-a)~(2-b)所示之下述式(2-a)：9,9-雙(6-羥基-2-萘基)-2,7-二(2-萘基)茀、下述式(2-b)：9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二(2-萘基)茀為較佳，尤其係以下述式(2-b)：9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二(2-萘基)茀為佳。As the type of dinaphthyl pyrene, preferably, for example, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-bis(1-naphthyl) pyrene, 9,9-bis(6- Hydroxy-2-naphthyl)-2,7-bis(1-naphthyl)sulfuron, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-bis(1-naphthyl)sulfuron, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-bis(1-naphthyl)茀, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl ]-1,8-bis(1-naphthyl)sulphur, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-bis(1-naphthyl)sulphur , 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-3,6-bis(1-naphthyl)pyridium, 9,9-bis[6-(2-hydroxyethyl) (Oxy)-2-naphthyl)-4,5-bis(1-naphthyl)sulfuryl, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-bis(2-naphthyl)茀, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-bis(2-naphthyl) 茀, 9,9-bis(6-hydroxy-2-naphthyl)-3,6 -Bis(2-naphthyl)sulfurium, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-bis(2-naphthyl)sulfuron, 9,9-bis[6-(2- Hydroxyethoxy)-2-naphthyl]-1,8-bis(2-naphthyl)茀、9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2, 7-Bis(2-naphthyl)sulphur, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-3,6-bis(2-naphthyl)sulphur, 9,9 -Bis[6-(2-hydroxyethoxy)-2-naphthyl]-4,5-bis(2-naphthyl)stilbene and the like. Among them, the following formula (2-a) represented by the following formulas (2-a)~(2-b): 9,9-bis(6-hydroxy-2-naphthyl)-2,7-bis( 2-naphthyl)茀, the following formula (2-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-bis(2-naphthyl) Chrysanthemum is preferred, especially with the following formula (2-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-bis(2-naphthyl) Long is better.

本發明之具有茀骨架之化合物中，鈀元素之含量以滿足下述式(2)為佳。 0≦Pd≦50ppm　　　　　(2) 較佳係滿足下述式(2-1)。 0≦Pd≦25ppm　　　　　(2-1) 更佳係滿足下述式(2-2)。 0≦Pd≦10ppm　　　　　(2-2) 較更佳係滿足下述式(2-3)。 0≦Pd≦5ppm　　　　(2-3) 特佳係滿足下述式(2-4)。 0≦Pd≦3ppm　　　　(2-4) 最佳係滿足下述式(2-5)。 0≦Pd≦1ppm　　　　(2-5)The content of palladium element in the compound having a turbidity skeleton of the present invention satisfies the following formula (2). 0≦Pd≦50ppm　　　　　(2) It is preferable to satisfy the following formula (2-1). 0≦Pd≦25ppm　　　　　(2-1) More preferably, it satisfies the following formula (2-2). 0≦Pd≦10ppm　　　　　(2-2) More preferably, it satisfies the following formula (2-3). 0≦Pd≦5ppm　　　　(2-3) The particularly preferred system satisfies the following formula (2-4). 0≦Pd≦3ppm　　　　(2-4) The best system satisfies the following formula (2-5). 0≦Pd≦1ppm　　　　(2-5)

超過上述範圍之上限時，則有會對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件產生不良影響的情況。鈀元素之含量之下限可為0.01ppm以上、0.05ppm以上、或0.10ppm以上。When the upper limit of the above-mentioned range is exceeded, the hue of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical member using the same may be adversely affected. The lower limit of the content of palladium can be 0.01 ppm or more, 0.05 ppm or more, or 0.10 ppm or more.

本發明之具有茀骨架之化合物在溶解於二甲基甲醯胺而成之5重量%溶液之APHA係以500以下為佳，以200以下為較佳，以100以下為更佳。APHA大於500時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件產生不良影響的情況。The APHA of the 5 wt% solution of the compound having a 茀 skeleton of the present invention dissolved in dimethylformamide is preferably 500 or less, preferably 200 or less, and more preferably 100 or less. When APHA is greater than 500, it may have an adverse effect on the color of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical member using it.

本發明之具有茀骨架之化合物中，前述式(1-b)所示之化合物中之二苯基茀酮之含量係以0.2%以下為佳，以0.1%以下為較佳，以0.05%以下為較更佳。二苯基茀酮之含量大於0.2%時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響的情況。In the compound with a stilbene skeleton of the present invention, the content of diphenyl ketone in the compound represented by the aforementioned formula (1-b) is preferably 0.2% or less, preferably 0.1% or less, and 0.05% or less For better. When the content of diphenylphenone is greater than 0.2%, it may adversely affect the hue of the resin using the raw material alcohol represented by the aforementioned formula (1) or the optical component using it.

[聯萘化合物之結晶多形體] 本發明之前述式(1-b)所示之化合物之結晶係以在230~247℃之範圍具有利用示差掃描熱量分析所得之吸熱峰為佳。又，利用Cu-Kα線而得之粉末X線繞射圖型中之繞射角2θ係在10.6±0.2°、10.8±0.2°、17.1±0.2°、17.6±0.2°及18.7±0.2°處具有特徵性波峰。又，以繞射角2θ在10.8±0.2°處具有最大波峰為佳。本發明之前述式(1-b)所示之化合物之結晶係操作性優異，且色相、純度皆為良好之結晶。[Crystal polymorph of binaphthyl compound] The crystal of the compound represented by the aforementioned formula (1-b) of the present invention preferably has an endothermic peak obtained by differential scanning calorimetry in the range of 230 to 247°C. In addition, the diffraction angle 2θ in the powder X-ray diffraction pattern obtained by using Cu-Kα line is at 10.6±0.2°, 10.8±0.2°, 17.1±0.2°, 17.6±0.2° and 18.7±0.2° Has a characteristic wave crest. In addition, it is preferable that the diffraction angle 2θ has the largest peak at 10.8±0.2°. The crystal system of the compound represented by the aforementioned formula (1-b) of the present invention has excellent operability, and is a crystal with good hue and purity.

[具有茀骨架之化合物之製造方法] 本發明之態樣I之具有茀骨架之化合物之製造方法係包括大致分為2個步驟，且係可藉由：在鈀系觸媒以及鹼存在下，使下述式(3)所示之茀酮類與下述式(4)或(5)所示之硼酸類進行反應之第1步驟1，在酸觸媒之存在下(較佳係酸觸媒以及硫醇系化合物之存在下)，使反應系內部在減壓下使副生成之水排出至系統外並同時使步驟1所製造之反應物(6)與下述式(7)所示之醇類之化合物進行反應後，反應結束後直接進行中和且不取出生成物(8)，添加鹼性觸媒而與碳酸伸乙酯進行反應之第2步驟2來製造。[Manufacturing method of compound with 茀 frame] The method for producing a compound having a 茀 skeleton of aspect I of the present invention is roughly divided into two steps, and can be achieved by: in the presence of a palladium-based catalyst and a base, the following formula (3) The first step 1 of the reaction between the ketones and the boric acid represented by the following formula (4) or (5) is in the presence of an acid catalyst (preferably in the presence of an acid catalyst and a thiol-based compound) , The reaction system is allowed to discharge the by-produced water out of the system under reduced pressure, and at the same time, the reactant (6) produced in step 1 is reacted with the alcohol compound represented by the following formula (7), and then react After the completion, neutralization is performed without taking out the product (8), and a basic catalyst is added to produce the second step 2 of reacting with ethylene carbonate.

上述製造方法中，由於步驟1中下述式(4)或(5)所示之硼酸類之反應性為高且不會引起副反應，且步驟2中藉由併用硫醇系化合物，在與不併用其之情況相比，反應速度較快，且藉由將系統內部作成在減壓下，而能效率良好地將副生成之水排出，因此反應快且副生成物之生成受到抑制，且不取出反應物(8)，即能在相同反應釜進行製造，故所使用之溶劑量也變少，從而能以低成本且效率良好地製造本發明之具有茀骨架之化合物。In the above-mentioned production method, since the boronic acids represented by the following formula (4) or (5) in step 1 have high reactivity and do not cause side reactions, and in step 2, the thiol-based compound is used in combination with Compared with the case where it is not used in combination, the reaction speed is faster, and the by-product water can be discharged efficiently by making the system interior under reduced pressure, so the reaction is fast and the generation of by-products is suppressed, and The reactant (8) can be manufactured in the same reactor without taking out the reactant (8), so the amount of solvent used is also reduced, so that the compound having a stilbene skeleton of the present invention can be manufactured at low cost and efficiently.

步驟1：

(式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子。)

(式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子。l為0、1或2，l=2時，R¹⁴ 係可為相同或亦可為相異。)step 1:

(In the formula, X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position and represents a halogen atom, and X ² is a substituent at the 5-position, 6-position, 7-position or 8-position and represents a halogen atom. )

(In the formula, Y represents an aromatic group, and R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1 or 2, and when l=2, the R ¹⁴ system may be the same or the same Can be different.)

步驟2：

(式中，Ar¹ 及Ar² 係與式(1)中相同。)

(式中，p1及p2係相同或相異為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同。)

(式中，R¹ 、Ar¹ 及Ar² 係與式(1)中相同。p1及p2係與式(7)中相同。n1及n2為0~3之整數。)Step 2:

(In the formula, Ar ¹ and Ar ² are the same as in the formula (1).)

(In the formula, p1 and p2 are the same or different as an integer of 0-4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1).)

(In the formula, R ¹ , Ar ¹ and Ar ² are the same as in formula (1). p1 and p2 are the same as in formula (7). n1 and n2 are integers from 0 to 3.)

上述式(3)所示之化合物係對應前述式(1)中茀骨架之茀酮化合物，X¹ 為1位、2位、3位或4位之取代基，X² 為5位、6位、7位或8位之取代基，X¹ 及X² 皆表示鹵素原子。The compound represented by the above formula (3) corresponds to the ketone compound of the stilbene skeleton in the above formula (1), X ¹ is a substituent at position 1, 2, 3 or 4, and X ² is a substituent at position 5 and 6. , 7 or 8 substituents, X ¹ and X ^{2 both} represent a halogen atom.

以下例示上述式(3)所示之茀酮化合物之代表例，但作為本發明之前述式(1)所使用之原料，則並非係受到該等所限定者。The representative examples of the ketone compound represented by the above formula (3) are exemplified below, but the raw materials used in the above formula (1) of the present invention are not subject to these limitations.

作為具體例，較佳可舉出如1,8-二氟茀酮、2,7-二氟茀酮、3,6-二氟茀酮、4,5-二氟茀酮、1,8-二氯茀酮、2,7-二氯茀酮、3,6-二氯茀酮、4,5-二氯茀酮、1,8-二碘茀酮、2,7-二碘茀酮、3,6-二碘茀酮、4,5-二碘茀酮、1,8-二溴茀酮、2,7-二溴茀酮、3,6-二溴茀酮、4,5-二溴茀酮等。其中亦以1,8-二溴茀酮、2,7-二溴茀酮、3,6-二溴茀酮、4,5-二溴茀酮為佳，尤其係以2,7-二溴茀酮為佳。As specific examples, preferred examples include 1,8-difluorochodone, 2,7-difluorochodone, 3,6-difluorochodone, 4,5-difluorochodone, 1,8- Dichloropyrone, 2,7-dichloropyrone, 3,6-dichloropyrone, 4,5-dichloropyrone, 1,8-diiodopyrone, 2,7-diiodopyrone, 3,6-diiodopyrone, 4,5-diiodopyrone, 1,8-dibromopyrone, 2,7-dibromopyrone, 3,6-dibromopyrone, 4,5-di Bromopyrone and so on. Among them, 1,8-dibromopyrone, 2,7-dibromopyrone, 3,6-dibromopyrone, 4,5-dibromopyrone are preferred, especially 2,7-dibromopyrone Chloride is better.

該等係可單獨使用，或可混合2種以上，且可根據目的而任意地選擇。本發明中係以2,7-二溴茀酮為佳。These systems may be used alone, or two or more types may be mixed, and they may be arbitrarily selected according to the purpose. In the present invention, 2,7-dibromopyrone is preferred.

所使用之前述式(3)所示之茀酮類之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。尚且，茀酮類係可使用市售品，也可使用經合成者。例如，作為製造二溴茀酮類之方法，可舉出如非專利文獻(美國化學會期刊(Journal of American Chemical Society), 2017, Vol.139, 11073-11080)記載之方法，即使9-茀酮與溴在水中進行反應之方法等。The purity of the ketones represented by the aforementioned formula (3) used is not particularly limited, and is generally preferably 95% or more, preferably 99% or more. Furthermore, for the ketone series, commercially available products can be used, or synthetic ones can also be used. For example, as a method of producing dibromopyrones, there are methods described in non-patent literature (Journal of American Chemical Society (Journal of American Chemical Society), 2017, Vol.139, 11073-11080). The method of reacting ketone and bromine in water, etc.

上述式(4)或(5)所示之化合物之環Y係對應在前述式(1)中之基Ar¹ 及Ar² 。又，前述式(4)及(5)中，基R¹⁴ 之較佳態樣係與前述R¹ 之較佳態樣相同，l之較佳態樣係與前述n1及n2之較佳態樣相同。The ring Y of the compound represented by the above formula (4) or (5) corresponds to the groups Ar ¹ and Ar ² in the above formula (1). In addition, in the foregoing formulas (4) and (5), the preferred aspect of the ^{radical R 14 is the same as the preferred aspect of the foregoing R 1, and} the preferred aspect of l is the same as the foregoing preferred aspect of n1 and n2 the same.

所使用之硼酸類之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。尚且，硼酸類係可使用市售品，也可使用經合成者。作為製造硼酸類之方法，可舉出例如專利文獻(日本特開2002-47292號公報)記載之方法，即使苯基格林納試劑與溶解於非醚系芳香族溶劑中之硼酸酯類進行反應的方法等。The purity of the boronic acids used is not particularly limited, but it is usually more than 95%, preferably more than 99%. Moreover, commercially available products can be used for the boric acid series, and those synthesized can also be used. As a method of producing boronic acids, for example, the method described in the patent document (Japanese Patent Application Laid-Open No. 2002-47292), even if the phenyl Griener reagent reacts with boric acid esters dissolved in a non-ether-based aromatic solvent Methods, etc.

本發明所使用之硼酸係包括前述式(4)及(5)所示之烷基硼酸、烯基硼酸、芳基硼酸、雜芳基硼酸及其酐等，作為烷基硼酸，包括丁基硼酸、環己基硼酸、環戊基硼酸、2-乙基硼酸、4-乙基硼酸、己基硼酸、異丁基硼酸、異丙基硼酸、甲基硼酸、n-辛基硼酸、丙基硼酸、戊基硼酸、2-苯基乙基硼酸或該等之酐，作為烯基硼酸，包括1-環戊烯基硼酸、二茂鐵硼酸、1,1’-二茂鐵二硼酸或該等之酐，作為芳基硼酸，包括2-蒽硼酸、9-蒽硼酸、苄基硼酸、2-聯苯基硼酸、3-聯苯基硼酸、4-聯苯基硼酸、2,3-二甲基苯基硼酸、2,4-二甲基苯基硼酸、2,5-二甲基苯基硼酸、2,6-二甲基苯基硼酸、3,4-二甲基苯基硼酸、3,5-二甲基苯基硼酸、2-乙氧基苯基硼酸、3-乙氧基苯基硼酸、4-乙氧基苯基硼酸、6-甲氧基-2-萘硼酸、2-甲基苯基硼酸、3-甲基苯基硼酸、4-甲基苯基硼酸、1-萘硼酸、2-萘硼酸、9-菲硼酸、10-苯基-9-蒽硼酸、苯基硼酸、苯基乙烷硼酸、4-苯基(萘-1-基)硼酸、3-丙氧基苯基硼酸、3-異-丙氧基苯基硼酸、4-異-丙氧基苯基硼酸、4-丙基苯基硼酸、4-異-丙基苯基硼酸、10-(萘-1-基)-9-蒽硼酸、10-(萘-2-基)-9-蒽硼酸或該等之酐，作為雜芳基硼酸，包括苯並呋喃-2-硼酸、二苯並呋喃-4-硼酸、5-甲醯基-2-呋喃硼酸、5-甲醯基噻吩-2-硼酸、呋喃-2-硼酸、呋喃-3-硼酸、吡啶-3-硼酸、吡啶-4-硼酸、喹啉-2-硼酸、喹啉-3-硼酸、喹啉-4-硼酸、喹啉-5-硼酸、喹啉-6-硼酸、喹啉-8-硼酸、異-喹啉-4-硼酸、2-噻吩硼酸、3-噻吩硼酸、5-嘧啶硼酸或該等之酐。The boric acid used in the present invention includes the alkyl boronic acid, alkenyl boronic acid, aryl boronic acid, heteroaryl boronic acid and anhydride thereof represented by the aforementioned formulas (4) and (5), and the alkyl boronic acid includes butyl boronic acid , Cyclohexylboronic acid, cyclopentylboronic acid, 2-ethylboronic acid, 4-ethylboronic acid, hexylboronic acid, isobutylboronic acid, isopropylboronic acid, methylboronic acid, n-octylboronic acid, propylboronic acid, pentane Boronic acid, 2-phenylethyl boronic acid or their anhydrides, as alkenyl boronic acids, including 1-cyclopentenyl boronic acid, ferrocene boronic acid, 1,1'-ferrocene diboric acid or such anhydrides , As aryl boronic acid, including 2-anthracene boronic acid, 9-anthracene boronic acid, benzyl boronic acid, 2-biphenyl boronic acid, 3-biphenyl boronic acid, 4-biphenyl boronic acid, 2,3-dimethylbenzene Boric acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5 -Dimethylphenylboronic acid, 2-ethoxyphenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthaleneboronic acid, 2-methyl Phenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 1-naphthaleneboronic acid, 2-naphthaleneboronic acid, 9-phenanthreneboronic acid, 10-phenyl-9-anthraceneboronic acid, phenylboronic acid, benzene Ethane boronic acid, 4-phenyl (naphthalene-1-yl) boronic acid, 3-propoxy phenyl boronic acid, 3-iso-propoxy phenyl boronic acid, 4-iso-propoxy phenyl boronic acid, 4 -Propylphenylboronic acid, 4-iso-propylphenylboronic acid, 10-(naphthalene-1-yl)-9-anthraceneboronic acid, 10-(naphthalene-2-yl)-9-anthraceneboronic acid or the like Anhydrides, as heteroaryl boronic acids, include benzofuran-2-boronic acid, dibenzofuran-4-boronic acid, 5-methanyl-2-furanboronic acid, 5-methanylthiophene-2-boronic acid, furan- 2-boric acid, furan-3-boronic acid, pyridine-3-boronic acid, pyridine-4-boronic acid, quinoline-2-boric acid, quinoline-3-boronic acid, quinoline-4-boronic acid, quinoline-5-boronic acid, Quinoline-6-boronic acid, quinoline-8-boronic acid, iso-quinoline-4-boronic acid, 2-thiophene boronic acid, 3-thiophene boronic acid, 5-pyrimidine boronic acid or their anhydrides.

該等係可單獨使用，或也可混合2種以上，可根據目的而任意地選擇。本發明中係以苯基硼酸、2-萘硼酸或其酐為佳，特佳為苯基硼酸或其酐。These systems may be used alone, or two or more types may be mixed, and they may be arbitrarily selected according to the purpose. In the present invention, phenylboronic acid, 2-naphthaleneboronic acid or its anhydride are preferred, and phenylboronic acid or its anhydride is particularly preferred.

使用作為原料之前述式(4)所示之化合物之使用比率，在相對於前述式(3)所示之化合物(鹵化茀酮化合物)1莫耳而言，較佳可為2~5莫耳，更佳可為2.05~3.0莫耳，較更佳可為2.1~2.5莫耳程度。該硼酸類若未滿2莫耳時，前述式(6)所示之生成物之收率會有變低的情況。又，超過5莫耳時，反應速度雖會變快且收率變高，但該具有茀骨架之化合物之製造成本會有上升的情況。The use ratio of the compound represented by the aforementioned formula (4) as a raw material is preferably 2 to 5 mol relative to 1 mol of the compound represented by the aforementioned formula (3) (halogenated ketone compound) , More preferably 2.05~3.0 mol, more preferably 2.1~2.5 mol. If the boric acid is less than 2 mol, the yield of the product represented by the aforementioned formula (6) may be low. In addition, if it exceeds 5 mol, the reaction rate becomes faster and the yield becomes higher, but the production cost of the compound having a citron skeleton may increase.

又，前述式(5)所示之化合物之使用比率，在相對於前述式(3)所示之化合物(鹵化茀酮化合物)1莫耳而言，較佳可為0.7~5莫耳，更佳可為0.8~3莫耳，較更佳可為1~2莫耳程度。該硼酸類若未滿0.7莫耳時，前述式(6)所示之生成物之收率有變低的情況。又，超過5莫耳時，反應速度雖會變快且收率變高，但該具有茀骨架之化合物之製造成本會有上升的情況。In addition, the usage ratio of the compound represented by the aforementioned formula (5) is preferably 0.7-5 mol relative to 1 mol of the compound represented by the aforementioned formula (3) (halogenated ketone compound), and more Preferably, it is 0.8 to 3 mol, and even more preferably is 1 to 2 mol. If the boric acid is less than 0.7 mol, the yield of the product represented by the aforementioned formula (6) may be low. In addition, if it exceeds 5 mol, the reaction rate becomes faster and the yield becomes higher, but the production cost of the compound having a citron skeleton may increase.

步驟1之前述式(3)與前述式(4)及/或(5)所示之化合物之反應(脫鹵化反應)係可在反應溶劑中，鹼及觸媒之存在下進行。The reaction (dehalogenation reaction) of the aforementioned formula (3) and the compound represented by the aforementioned formula (4) and/or (5) in step 1 can be carried out in the presence of a base and a catalyst in the reaction solvent.

作為步驟1之反應中使用之鹼，可舉出例如，氫氧化鈉、氫氧化鉀等之氫氧化物、碳酸鈉(Na₂ CO₃ )、碳酸鉀(K₂ CO₃ )、碳酸銫(Cs₂ CO₃ )等之碳酸鹽、乙酸鈉、乙酸鉀等之乙酸鹽、磷酸鈉(Na₃ PO₄ )、磷酸鉀(K₃ PO₄ )等之磷酸鹽等之無機鹽、三乙基胺類、吡啶、嗎啉、喹啉、哌啶、苯胺類、四正丁基銨乙酸酯等之銨鹽等之有機鹽等。其中，較佳使用碳酸鹽，且以碳酸鉀及/或碳酸鈉為佳。此種鹼係可單獨使用，又，也可合併使用2種類以上。As the base used in the reaction of step 1, for example, hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ) and other carbonates, sodium acetate, potassium acetate and other acetates, sodium phosphate (Na ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ) and other phosphates and other inorganic salts, triethylamines Organic salts such as ammonium salts of pyridine, morpholine, quinoline, piperidine, anilines, tetra-n-butylammonium acetate, etc. Among them, carbonates are preferably used, and potassium carbonate and/or sodium carbonate are preferred. Such an alkali system may be used alone, or two or more types may be used in combination.

又，步驟1之反應中，上述鹼之使用量並無特別限定，相對於硼酸類1莫耳，以添加1~30當量為佳，較佳係添加1~10當量。In addition, in the reaction of step 1, the amount of the above-mentioned base used is not particularly limited. It is preferable to add 1 to 30 equivalents relative to 1 mole of boric acid, and preferably to add 1 to 10 equivalents.

作為步驟1之反應中使用之鈀系觸媒，以鈴木耦合中使用之鈀化合物為佳，可舉出例如，肆(三苯基膦)鈀、二氯化雙(三苯基膦)鈀、乙酸鈀、參(二苯亞基丙酮)二鈀、雙(二苯亞基丙酮)鈀、二氯化雙[4-(N, N-二甲基胺基)苯基]二-tert-丁基膦鈀、二氯化雙(二-tert-丁基異戊二烯基膦)鈀、二氯化雙(二-tert-巴豆基膦)鈀、Pd/SiO₂ 所示之鈀系觸媒等。其中，以肆(三苯基膦)鈀，及/或，Pd/SiO₂ 所示之鈀系觸媒為佳。此種鈀系觸媒係可單獨使用，又，也可合併使用2種以上。As the palladium-based catalyst used in the reaction of step 1, the palladium compound used in Suzuki coupling is preferred. For example, palladium (triphenylphosphine) palladium, bis(triphenylphosphine) palladium dichloride, Palladium acetate, ginseng (diphenylylidene acetone) two palladium, bis (diphenylylidene acetone) palladium, dichloride bis [4-(N, N-dimethylamino) phenyl] bis-tert-butyl Phosphine palladium, bis(di-tert-butylisoprenylphosphine) palladium dichloride, bis(di-tert-crotonylphosphine) palladium dichloride, palladium-based catalyst shown by _{Pd/SiO 2} Wait. Among them, palladium (triphenylphosphine) palladium and/or palladium-based catalysts represented by _{Pd/SiO 2 are preferred.} Such palladium-based catalysts may be used alone, or two or more of them may be used in combination.

步驟1之反應中，上述觸媒之使用量並無特別限定，相對於前述式(3)所示之茀酮化合物1莫耳，在鈀金屬原子換算下，以0.1~10毫莫耳為佳，較佳為0.5~5毫莫耳。鈀觸媒之使用量在鈀金屬原子換算下未滿0.1毫莫耳時，則有反應變得難以完結的情況。又，鈀觸媒之使用量在鈀金屬原子換算下超過10毫莫耳時，則有反應雖會完結，但變得難以將該具有茀骨架之化合物中之鈀元素含量作成在式(2)之範圍內，且不僅有令使用該醇原料所製造之熱塑性樹脂之色相惡化的可能性，也會有該具有茀骨架之化合物之製造成本上升的情況。In the reaction of step 1, the amount of the above catalyst used is not particularly limited. Relative to 1 mol of the ketone compound represented by the aforementioned formula (3), in terms of palladium metal atom, it is preferably 0.1 to 10 millimoles , Preferably 0.5 to 5 millimoles. When the amount of palladium catalyst used is less than 0.1 millimolar in terms of palladium metal atom, the reaction may become difficult to complete. In addition, when the amount of palladium catalyst used exceeds 10 millimoles in terms of palladium metal atom, the reaction may be completed, but it becomes difficult to formulate the palladium element content in the compound having a pyridium skeleton into the formula (2) Within the range, not only may the hue of the thermoplastic resin manufactured using the alcohol raw material deteriorate, but also the manufacturing cost of the compound having a citric skeleton may increase.

作為步驟1使用之反應溶劑，並未係特別受到限定者，可單獨使用例如甲苯、二甲苯等之芳香族烴系溶劑，及甲醇、乙醇、異丙基醇、n-丁醇等之醇類，或亦可併用。芳香族烴系溶劑由於為高沸點溶劑，故可將反應溫度設定為較高，又，藉由使用醇而與水之親和性為良好，且反應性變得良好，從而適宜使用。此種溶劑係可單獨使用，或也可合併使用2種以上。並且，也可使用如N,N-二甲基甲醯胺或N,N-二甲基乙醯胺等之非質子性溶劑、o-二氯苯等之鹵苯類。此種溶劑也係可單獨使用，又，亦可合併使用2種以上。本發明中，以甲苯與乙醇之混合溶劑為較佳。The reaction solvent used in step 1 is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene and xylene, and alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol can be used alone. , Or can also be used in combination. Since the aromatic hydrocarbon-based solvent is a high boiling point solvent, the reaction temperature can be set higher, and the affinity with water is good by using alcohol, and the reactivity becomes good, so it is suitable for use. Such solvent systems may be used alone or in combination of two or more kinds. In addition, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, and halogenated benzenes such as o-dichlorobenzene can also be used. Such solvents may be used alone, or two or more of them may be used in combination. In the present invention, a mixed solvent of toluene and ethanol is preferred.

前述反應溶劑(本發明之情況，甲苯與乙醇之混合溶劑)之使用量並無特別限定，相對於前述式(3)所示之茀酮類，甲苯係以0.1重量倍以上為佳，較佳為0.5~100重量倍，更佳為1~50重量倍。甲苯之使用量在未滿0.1重量倍之情況，有生成物析出而變得難以攪拌之可能性。又，甲苯之使用量若超過100重量倍之情況，則有不具有與使用量相符之效果，且容積效率也惡化，該具有茀骨架之化合物之製造成本上升的情況。又，乙醇之使用量也並無特別限定，相對於前述式(3)所示之茀酮類，以0.1~50重量倍為佳，較佳為1~20重量倍。乙醇之使用量在未滿0.1重量倍之情況，有反應速度慢，收率下降之可能性。又，在乙醇之使用量超過50重量倍之情況，則有與甲苯同樣地不具有使用量相符之效果，且容積效率也惡化，該具有茀骨架之化合物之製造成本上升的情況。The amount of the reaction solvent (the mixed solvent of toluene and ethanol in the present invention) is not particularly limited. Compared with the ketones represented by the aforementioned formula (3), the toluene is preferably 0.1 times by weight or more, preferably It is 0.5-100 weight times, more preferably 1-50 weight times. When the amount of toluene used is less than 0.1 times by weight, the product may precipitate and it may become difficult to stir. In addition, if the amount of toluene used exceeds 100 times by weight, it does not have the effect corresponding to the amount used, and the volumetric efficiency also deteriorates, which may increase the manufacturing cost of the compound having a phytoskeleton. In addition, the amount of ethanol used is not particularly limited, and it is preferably 0.1 to 50 times by weight, preferably 1 to 20 times by weight, relative to the ketones represented by the aforementioned formula (3). When the amount of ethanol used is less than 0.1 times by weight, the reaction speed may be slow and the yield may decrease. In addition, when the amount of ethanol used exceeds 50 weight times, the same as toluene does not have the effect of the amount used, and the volumetric efficiency also deteriorates, and the manufacturing cost of the compound having a phytoskeleton may increase.

反應溫度係根據所使用之原料、溶劑之種類而相異，以50~150℃為佳，較佳為60~130℃，更佳為70~120℃。反應係能以液體層析法等之分析手段來追蹤。The reaction temperature varies according to the types of raw materials and solvents used, and is preferably 50 to 150°C, preferably 60 to 130°C, and more preferably 70 to 120°C. The reaction system can be traced by analytical means such as liquid chromatography.

反應結束後之反應混合物中，通常除了包含已生成之前述式(6)所示之化合物以外，也包括未反應之茀酮類、未反應之硼酸類、鹼、觸媒、副反應生成物等。因此，可藉由慣用之方法，例如，過濾、濃縮、萃取、晶析、再結晶、再沉澱、活性碳處理或與其酷似之金屬除去處理、管柱層析法等之分離手段，或組合該等而成之分離手段來分離純化前述式(6)所示之化合物。例如，藉由慣用之方法(添加鹼水溶液而形成水溶性複合物之方法等)除去硼酸類，進行活性碳處理或與其酷似之金屬除去處理來除去鈀化合物後，藉由添加再結晶溶劑進行冷卻使其再結晶化，其次進行過濾分離來進行純化。After the reaction, the reaction mixture usually contains not only the compound represented by the aforementioned formula (6), but also unreacted ketones, unreacted boronic acids, alkalis, catalysts, side reaction products, etc. . Therefore, conventional methods such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatment, column chromatography and other separation means can be used, or a combination of these And other separation means to separate and purify the compound represented by the aforementioned formula (6). For example, after removing the boric acid by a conventional method (a method of adding an aqueous alkali solution to form a water-soluble complex, etc.), performing an activated carbon treatment or a metal removal treatment similar to it to remove the palladium compound, and then cooling by adding a recrystallization solvent It is recrystallized, and then filtered and separated for purification.

前述式(7)所示之醇類係對應前述式(6)所示之二芳基茀衍生物中在9位上經取代之含(多)羥基之芳烴環。即，前述式(7)中萘環係對應前述式(1)之萘環，R¹ 、n1及n2係對應前述式(1)之R¹ 、n1及n2。The alcohol represented by the aforementioned formula (7) corresponds to the (poly)hydroxyl-containing aromatic hydrocarbon ring substituted at the 9-position in the diaryl fluoride derivative represented by the aforementioned formula (6). That is, the formula (7) is a naphthalene ring system corresponding to the naphthalene ring of formula (1) of, R ^1, n1 and n2 lines corresponding to the formula R (1) of ^1, n1 and n2.

作為前述式(7)所示之化合物之具體例，可舉出如萘酚類(例如，萘酚(1-萘酚、2-萘酚)、具有烴基之萘酚(甲基萘酚、乙基萘酚、二甲基萘酚、丙基萘酚、丁基萘酚(C_1-4 烷基萘酚)等之烷基萘酚)、烷氧基萘酚(乙氧基萘酚等之C_1-4 烷氧基萘酚)、鹵萘酚(氯萘酚、溴萘酚))、對應該等萘酚類(或單羥基萘類)之多羥基萘(例如，1,3-二羥基萘、1,4-二羥基萘、2,3-二羥基萘、1,5-羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,6-二羥基萘、2,7-二羥基萘、1,2,4-三羥基萘、1,3,8-三羥基萘等之二或三羥基萘類)等。其中亦以1-萘酚、2-萘酚為佳，尤其係以2-萘酚為佳。Specific examples of the compound represented by the aforementioned formula (7) include naphthols (for example, naphthol (1-naphthol, 2-naphthol), naphthol having a hydrocarbon group (methyl naphthol, ethyl Alkyl naphthol, dimethyl naphthol, propyl naphthol, butyl naphthol (C _1-4 alkyl naphthol), alkoxy naphthol (ethoxy naphthol, etc.) C _1-4 alkoxy naphthol), halonaphthol (chloronaphthol, bromonaphthol)), corresponding to these naphthols (or monohydroxy naphthalenes) polyhydroxy naphthalenes (for example, 1,3-di Hydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4-trihydroxynaphthalene, 1,3,8-trihydroxynaphthalene, etc. (two or trihydroxynaphthalenes), etc. Among them, 1-naphthol and 2-naphthol are also preferred, and 2-naphthol is especially preferred.

該等醇類係可單獨使用，或可混合2種以上而與茀酮類進行反應，且可根據目的而任意地選擇。本發明中係以2-萘酚為佳。These alcohols may be used alone, or two or more of them may be mixed to react with the ketones, and they may be arbitrarily selected according to the purpose. In the present invention, 2-naphthol is preferred.

步驟2之反應中，上述式(7)所示之醇類之使用量並非係受到特別限定者，但從抑制副反應及經濟性之觀點，相對於茀酮類1莫耳，以2~20莫耳為佳，較佳為2.1~10莫耳，更佳為2.3~5莫耳。In the reaction of step 2, the amount of alcohol represented by the above formula (7) is not particularly limited, but from the viewpoint of suppression of side reactions and economic efficiency, it is 2-20 per mole of ketones. Molar is preferred, preferably 2.1-10 mol, more preferably 2.3-5 mol.

該等上述式(7)所示之醇類係可使用市售品，也可使用經合成者。例如，作為製造萘酚類之方法，可舉出如專利文獻(日本特開昭61-115039號公報)記載之方法，即將萘予以磺化之2-萘磺酸再以鹼進行中和而取得2-萘磺酸鈉後，鹼融解生成物而作成鹼鹽後，進行水解來製造2-萘酚之方法等。Commercial products may be used for the alcohols represented by the above-mentioned formula (7), or synthetic ones may be used. For example, as a method of producing naphthols, a method described in the patent document (Japanese Patent Application Laid-Open No. 61-115039), which is obtained by sulfonating 2-naphthalenesulfonic acid in which naphthalene is sulfonated, is neutralized with an alkali. After sodium 2-naphthalenesulfonate, the product is melted with an alkali to form an alkali salt, and then hydrolyzed to produce 2-naphthol.

使用作為原料之上述式(7)所示之醇類(例如，萘酚類等)之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。The purity of the alcohols represented by the above formula (7) (for example, naphthols, etc.) used as a raw material is not particularly limited, and is generally preferably 95% or more, preferably 99% or more.

步驟2之反應通常係可在酸觸媒之存在下進行。作為酸觸媒，可舉出例如，硫酸、硫羥酸(thiolic acid)、蒙脫石、雜多酸等，該等之中，由於源自酸觸媒之雜質之生成為少，且容易取得本發明之具有茀骨架之化合物，故以雜多酸為特佳。The reaction of step 2 can usually be carried out in the presence of an acid catalyst. As the acid catalyst, for example, sulfuric acid, thiolic acid, montmorillonite, heteropoly acid, etc., among them, the formation of impurities derived from the acid catalyst is small and easy to obtain As the compound with a citron skeleton of the present invention, heteropolyacid is particularly preferred.

本發明中較佳使用之雜多酸係指一般相異2種以上之無機含氧酸進行縮合而生成之化合物之總稱，藉由中心之含氧酸與在其周圍進行縮合之別種含氧酸之組合，而能成為各種之雜多酸。將形成中心之含氧酸之數量少之元素稱為雜元素，將形成在其周圍進行縮合之含氧酸之元素稱為多元素(polyelement)。多元素可為單一種類之元素，亦可為複數種類之元素。The heteropoly acid preferably used in the present invention refers to the general term of the compound formed by the condensation of two or more different inorganic oxyacids. The oxyacid in the center is condensed with other oxyacids around it. The combination can become a variety of heteropoly acids. The element with a small number of oxyacids forming the center is called heteroelement, and the element that forms oxyacids condensed around it is called polyelement. The multi-element may be a single type of element, or may be a plurality of types of elements.

構成雜多酸之含氧酸之雜元素並非係受到特別限定者，可舉出例如，銅、鈹、硼、鋁、碳、矽、鍺、錫、鈦、鋯、鈰、釷、氮、磷、砷、銻、釩、鈮、鉭、鉻、鉬、鎢、鈾、硒、碲、錳、碘、鐵、鈷、鎳、銠、鋨、銥、鉑。以磷(磷酸)或矽(矽酸)為佳。又，構成雜多酸之含氧酸之多元素並非係受到特別限定者，可舉出例如，釩、鉬、鎢、鈮、鉭。以選自釩、鉬及鎢之至少1種元素為佳。The hetero elements constituting the oxo acids of the heteropoly acid are not particularly limited, and examples include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, and phosphorus. , Arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, platinum. Phosphorus (phosphoric acid) or silicon (silicic acid) is preferred. In addition, the multiple elements constituting the oxo acid of the heteropoly acid are not particularly limited, and examples include vanadium, molybdenum, tungsten, niobium, and tantalum. At least one element selected from vanadium, molybdenum and tungsten is preferred.

作為構成雜多酸骨架之雜多酸陰離子，可使用各種之組成者。可舉出例如，XM₁₂ O₄₀ 、XM₁₂ O₄₂ 、XM₁₈ O₆₂ 、XM₆ O₂₄ 等。較佳之雜多酸陰離子之組成為XM₁₂ O₄₀ 。各式中，X為雜元素，M為多元素。作為具有該等組成之雜多酸，具體地可例示如磷鉬酸、磷鎢酸、矽鉬酸、矽鎢酸、磷釩鉬酸等。As the heteropoly acid anion constituting the heteropoly acid skeleton, various compositions can be used. For example, XM ₁₂ O ₄₀ , XM ₁₂ O ₄₂ , XM ₁₈ O ₆₂ , XM ₆ O ₂₄ and the like can be mentioned. The composition of the preferred heteropolyacid anion is XM ₁₂ O ₄₀ . In each formula, X is a miscellaneous element, and M is a multi-element. Specific examples of heteropolyacids having such compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

雜多酸可為遊離之雜多酸，亦可質子之一部分或全部被其他陽離子取代而使用作為雜多酸之鹽。因此，本發明所稱之雜多酸也係包括該等雜多酸之鹽。作為能取代質子之陽離子，可舉出例如，銨、鹼金屬、鹼土類金屬等。The heteropoly acid may be a free heteropoly acid, or part or all of the protons may be replaced by other cations and used as a salt of the heteropoly acid. Therefore, the heteropoly acid referred to in the present invention also includes the salt of the heteropoly acid. Examples of cations capable of substituting protons include ammonium, alkali metals, alkaline earth metals and the like.

雜多酸可為酐，也可為結晶水含有物，但以酐之反應較快且會抑制副生成物之生成而為佳。在結晶水含有物之情況，預先藉由實施減壓乾燥或與溶劑之共沸脫水等之脫水處理，而可取得與酐相同之效果。雜多酸係也可使用載持於活性碳、氧化鋁、二氧化矽-氧化鋁、矽藻土等之載體上之形態。The heteropoly acid may be an anhydride or a crystal water-containing substance, but it is preferable that the anhydride reacts quickly and inhibits the formation of by-products. In the case of crystal water content, dehydration treatment such as reduced pressure drying or azeotropic dehydration with a solvent can be performed in advance to achieve the same effect as an anhydride. The heteropoly acid can also be used in the form of a carrier supported on activated carbon, alumina, silica-alumina, diatomaceous earth, etc.

該等雜多酸係可單獨使用，也可組合2種以上使用。又，因應必要，在不損及本發明目的之範圍內，亦可併用雜多酸以外之其他觸媒。These heteropoly acids may be used alone or in combination of two or more kinds. In addition, if necessary, other catalysts other than heteropoly acid may be used in combination within the scope of not impairing the purpose of the present invention.

雜多酸之使用量並非係受到特別限定者，為了取得充足之反應速度，相對於茀酮，以0.0001重量倍以上為佳，較佳為0.001~30重量倍，更佳為0.01~5重量倍。The amount of heteropoly acid used is not particularly limited. In order to obtain a sufficient reaction rate, it is preferably 0.0001 weight times or more relative to the ketone, preferably 0.001 to 30 weight times, and more preferably 0.01 to 5 weight times. .

實施本發明之際，步驟2之反應中藉由一同併用上述雜多酸與具有巰基(以下有略稱為SH基之情況)之化合物，而可使反應速度提升且可抑制雜質之生成。作為本發明中可併用之硫醇化合物，可舉出例如，巰基羧酸、烷硫醇及該等之鹽。When carrying out the present invention, the above-mentioned heteropolyacid and a compound having a mercapto group (hereinafter abbreviated as SH group) are used together in the reaction of step 2, so that the reaction rate can be increased and the generation of impurities can be suppressed. As the thiol compound that can be used in combination in the present invention, for example, mercaptocarboxylic acid, alkanethiol, and salts of these can be mentioned.

作為巰基羧酸，可舉出如α-巰基丙酸、β-巰基丙酸、硫代乙酸、巰基乙酸、硫代草酸、巰基琥珀酸、巰基安息香酸等。又，作為烷硫醇，可舉出如甲硫醇、乙硫醇、1-丙硫醇、2-丙硫醇、1-丁硫醇、2-丁硫醇、1-戊硫醇、2-戊硫醇、1-己硫醇、1-庚硫醇、2-庚硫醇、1-辛硫醇、2-辛硫醇、1-壬硫醇、1-癸硫醇、1-十一硫醇、1-十二硫醇等之C_1-16 烷基硫醇等。此種具有SH基之化合物當中，由於能平價取得，故以β-巰基丙酸及1-十二硫醇為佳，以1-十二硫醇為特佳。Examples of mercaptocarboxylic acids include α-mercaptopropionic acid, β-mercaptopropionic acid, thioacetic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, and mercaptobenzoic acid. In addition, examples of the alkanethiol include methyl mercaptan, ethyl mercaptan, 1-propane mercaptan, 2-propane mercaptan, 1-butane mercaptan, 2-butane mercaptan, 1-pentyl mercaptan, 2 -Pentyl mercaptan, 1-hexyl mercaptan, 1-heptane mercaptan, 2-heptane mercaptan, 1-octyl mercaptan, 2-octyl mercaptan, 1-nonane mercaptan, 1-decane mercaptan, 1-decane _{C 1-16} alkyl mercaptan such as monothiol, 1-dodecanethiol, etc. Among such compounds with SH groups, β-mercaptopropionic acid and 1-dodecanethiol are preferred, and 1-dodecanethiol is particularly preferred, because they can be obtained cheaply.

此種具有SH基之化合物係可單獨使用，又，也可合併使用2種以上。Such SH group-containing compounds may be used alone, or two or more of them may be used in combination.

實施步驟2之反應之方法並非係受到特別限定者，通常係可藉由將前述式(6)與前述式(7)所示之化合物與雜多酸及/或硫醇化合物放入反應裝置中，在空氣中或氮、氬等之惰性氣體環境下，在甲苯或二甲苯等之芳香族烴類及乙酸乙酯或γ-丁內酯等之酯類之惰性溶劑存在下進行加熱攪拌來進行。此時，藉由在會將含觸媒之水或反應生成水等反應系統內之水分予以去除之脫水條件下進行反應，比起不脫水之情況，反應會更快地進行，且副生成物之生成受到抑制，而能以更高收率取得目的物。作為脫水之方法，並非係受到特別限定者，可舉出例如，利用添加脫水劑之脫水、利用減壓之脫水、利用在常壓或減壓下與溶劑之共沸之脫水等。The method for carrying out the reaction of step 2 is not particularly limited, and it can usually be done by putting the compound represented by the aforementioned formula (6) and the aforementioned formula (7) and the heteropolyacid and/or thiol compound into the reaction device , In the air or in an inert gas environment such as nitrogen, argon, etc., in the presence of an inert solvent such as aromatic hydrocarbons such as toluene or xylene and esters such as ethyl acetate or γ-butyrolactone for heating and stirring. . At this time, by performing the reaction under dehydration conditions that remove water in the reaction system such as catalyst-containing water or reaction product water, the reaction proceeds faster than if it is not dehydrated, and the by-products The production is suppressed, and the target can be obtained with a higher yield. The method of dehydration is not particularly limited. Examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, and dehydration by azeotrope with a solvent under normal pressure or reduced pressure.

作為步驟2使用之反應溶劑，並非係受到特別限定者，可舉出例如甲苯、二甲苯等之芳香族烴溶劑，氯苯、二氯苯等之鹵化芳香族烴溶劑，戊烷、己烷、庚烷等之脂肪族烴溶劑，二氯甲烷、1,2-二氯乙烷等之鹵化脂肪族烴溶劑，二乙基醚、二-iso-丙基醚、甲基-t-丁基醚、二苯基醚、四氫呋喃、二噁烷等之脂肪族及環狀醚溶劑，乙酸乙酯、乙酸丁酯、γ-丁內酯、碳酸伸乙酯等之酯溶劑，乙腈、丙腈、丁腈、苄腈等之腈溶劑，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1-甲基-2-吡咯啶酮等之醯胺溶劑等。以芳香族烴溶劑及酯溶劑為佳，較佳為甲苯、二甲苯、氯苯或二氯苯，與乙酸乙酯、乙酸丁酯、γ-丁內酯或碳酸伸乙酯之混合溶劑，更佳為甲苯與γ-丁內酯或碳酸伸乙酯之混合溶劑。該等反應溶劑係可單獨使用，又，也可合併使用2種以上。The reaction solvent used in step 2 is not particularly limited. Examples include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, pentane, hexane, etc. Aliphatic hydrocarbon solvents such as heptane, halogenated aliphatic hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-t-butyl ether , Diphenyl ether, tetrahydrofuran, dioxane and other aliphatic and cyclic ether solvents, ethyl acetate, butyl acetate, γ-butyrolactone, ethylene carbonate and other ester solvents, acetonitrile, propionitrile, butane Nitrile solvents such as nitrile and benzonitrile, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc. Aromatic hydrocarbon solvents and ester solvents are preferred, preferably toluene, xylene, chlorobenzene or dichlorobenzene, mixed solvents with ethyl acetate, butyl acetate, γ-butyrolactone or ethylene carbonate, and more It is preferably a mixed solvent of toluene and γ-butyrolactone or ethylene carbonate. These reaction solvents may be used alone, or two or more of them may be used in combination.

又，該使用量並非係受到特別限定者，從經濟性之觀點，相對於上述式(6)所示之二苯基茀酮，以0.1重量倍以上為佳，較佳為0.5~100重量倍，更佳為1~20重量倍。In addition, the amount used is not particularly limited. From the viewpoint of economy, it is preferably 0.1 weight times or more, preferably 0.5 to 100 weight times, relative to the diphenyl quinone represented by the above formula (6). , More preferably 1-20 weight times.

步驟2之反應溫度係根據所使用之原料、溶劑之種類而不同，以50~300℃為佳，較佳為80~250℃，更佳為100~180℃。反應係可利用液體層析法等之分析手段來追蹤。The reaction temperature of step 2 varies according to the types of raw materials and solvents used, and is preferably 50 to 300°C, preferably 80 to 250°C, and more preferably 100 to 180°C. The reaction system can be traced using analytical means such as liquid chromatography.

步驟2之反應時之內壓係以101.3kPa以下之壓力為佳，較佳為60.0kPa以下。由於使副生成之水在該內壓下從系統內排出並同時反應之方式而會令反應更有效率地進行，且生成之副生成物也會變少，故以該方式為佳。The internal pressure during the reaction in step 2 is preferably 101.3 kPa or less, preferably 60.0 kPa or less. Since the by-product water is discharged from the system under the internal pressure and reacted at the same time, the reaction will proceed more efficiently, and the generated by-products will also be reduced, so this method is preferred.

步驟2之反應後，因應必要可藉由過濾去除所使用之固體酸或也可進行中和。作為中和時所使用之鹼，可舉出例如，氫氧化鈉、氫氧化鉀、氫氧化鈣等之鹼金屬或鹼土類金屬之氫氧化物、碳酸鉀、碳酸鈣、碳酸鈉、碳酸鈉等之鹼金屬或鹼土類金屬之碳酸鹽(碳酸氫)鹽、胺類等。After the reaction in step 2, if necessary, the solid acid used can be removed by filtration or neutralization can also be carried out. As the alkali used in the neutralization, for example, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, sodium carbonate, sodium carbonate, etc. Carbonate (bicarbonate) salts of alkali metals or alkaline earth metals, amines, etc.

步驟2之反應中，中和後之反應液係可不去除因中和所生成之鹽，而使用於與碳酸伸乙酯之反應。因應必要也可藉由實施利用過濾來分離因中和所生成之鹽，添加水進行攪拌並靜置後使其分液並去除水層之操作(有稱為水洗步驟之情況)，而從反應系統內分離因中和所生成之鹽。該水洗步驟係因應必要也可重複實施。In the reaction of step 2, the neutralized reaction solution can be used for the reaction with ethylene carbonate without removing the salt produced by the neutralization. If necessary, the salt produced by the neutralization can be separated by filtration, and water is added, stirred and left to stand, then the liquid is separated and the water layer is removed (there is a case called a water washing step), and the reaction The salt produced by neutralization is separated in the system. The washing step can be repeated as necessary.

步驟2中，在步驟1所製造之反應物(6)與上述式(7)所示之醇類之反應後，可不取出上述式(8)所示之茀化合物，而使其與碳酸伸乙酯進行反應。藉由濃縮或晶析等之方法取出上述式(8)所示之茀化合物時，則變得有收率降低且成本提升之可能性。In step 2, after the reactant (6) produced in step 1 is reacted with the alcohol represented by the above formula (7), the stilbene compound represented by the above formula (8) can be mixed with ethylene carbonate. The ester reacts. When the stilbene compound represented by the above formula (8) is taken out by a method such as concentration or crystallization, there is a possibility that the yield will be reduced and the cost will be increased.

步驟2中，碳酸伸乙酯係相對於步驟1所使用之上述式(6)所示之二苯基茀酮1莫耳，通常使用2~10莫耳，較佳使用2~5莫耳。In step 2, ethylene carbonate is 1 mol of diphenyl ketone represented by the above formula (6) used in step 1, usually 2-10 mol, preferably 2-5 mol.

步驟2中，在實施上述式(8)所示之茀化合物與碳酸伸乙酯之反應之際，因應必要也可在鹼性化合物存在下進行反應。在鹼性化合物存在下進行反應之情況，步驟1所使用之固體酸係以在實施步驟2之前預先藉由過濾進行分離或進行中和為佳。In step 2, when the reaction of the stilbene compound represented by the above formula (8) and ethylene carbonate is carried out, the reaction may be carried out in the presence of a basic compound as necessary. When the reaction is carried out in the presence of a basic compound, the solid acid used in step 1 is preferably separated by filtration or neutralized before step 2 is carried out.

作為步驟2中能使用之鹼性化合物，可例示如碳酸鹽類、碳酸氫鹽類、氫氧化物類、有機鹼類等。作為碳酸鹽類，可舉出如碳酸鉀、碳酸鈉、碳酸銫、碳酸鋰等。作為碳酸氫鹽類，可舉出如碳酸氫鉀、碳酸氫鈉、碳酸氫鋰、碳酸氫銫等。作為氫氧化物類，可舉出如氫氧化鈉、氫氧化鉀、氫氧化鋰等。作為有機鹼類，可舉出如三乙基胺、二甲基胺基吡啶、三苯基膦、溴化四甲基銨、氯化四甲基銨等。Examples of basic compounds that can be used in step 2 include carbonates, bicarbonates, hydroxides, and organic bases. Examples of carbonates include potassium carbonate, sodium carbonate, cesium carbonate, and lithium carbonate. Examples of bicarbonates include potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, cesium bicarbonate, and the like. Examples of hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Examples of organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride.

上述之鹼性化合物之中，從操作性或安全性之觀點，較佳使用碳酸鉀、碳酸鈉。該等鹼性化合物係可單獨使用，又，也可合併使用2種以上。Among the above-mentioned basic compounds, potassium carbonate and sodium carbonate are preferably used from the viewpoint of operability and safety. These basic compounds may be used alone, or two or more of them may be used in combination.

在步驟2中使用鹼性化合物之情況，該使用量係相對於步驟1所使用之上述式(6)所示之二苯基茀酮1莫耳，通常為0.01~1.0莫耳，以0.03~0.5莫耳為佳。In the case of using a basic compound in step 2, the usage amount is relative to 1 mol of diphenylquinone represented by the above formula (6) used in step 1, usually 0.01~1.0 mol, with 0.03~ 0.5 mol is better.

步驟2之反應結束後，可對取得之反應混合物添加稀釋溶劑而使前述式(1)所示之化合物直接析出，也可在施加洗淨、濃縮、稀釋、活性碳處理等之後處理後，在未滿50℃下使前述式(1)所示之化合物析出。因應必要從已施加上述後處理之反應混合物中使前述式(1)所示之化合物析出之操作係因應必要可藉由將已與溶劑混合之反應混合物作成50℃以上且溶劑之沸點以下(較佳為70~110℃)，並使其冷卻至未滿50℃來實施。在50℃以上從反應混合物中使前述式(1)所示之化合物之結晶析出的情況，藉由實施將在50℃以上結晶變得不會析出之量之稀釋溶劑與反應混合物予以混合後，將取得之混合物作成 50℃以上且溶劑之沸點以下(較佳為70~110℃)，並使其冷卻至未滿50℃即可。作為稀釋溶劑，可舉出如例示作為上述反應所使用之溶劑者，或可舉出如甲醇、乙醇、丙醇、異丙醇、丁醇、tert-丁醇、異丁醇及戊醇等之醇溶劑，碳酸二甲酯、碳酸二乙酯等之碳酸溶劑，乙酸乙酯、乙酸丁酯、γ-丁內酯、安息香酸丁酯、安息香酸甲酯、乙酸苯酯等之酯溶劑，二乙基醚、二-isо-丙基醚、甲基-tert-丁基醚、二苯基醚、四氫呋喃等之醚溶劑、己烷、庚烷、辛烷、戊烷等之脂肪族烴溶劑等，以甲醇、乙醇或碳酸二甲酯為佳，以甲醇及乙醇為較佳。After the reaction of step 2 is completed, a dilution solvent can be added to the obtained reaction mixture to directly precipitate the compound represented by the aforementioned formula (1), or it can be treated after washing, concentration, dilution, activated carbon treatment, etc. The compound represented by the aforementioned formula (1) is precipitated at less than 50°C. If necessary, the operation of precipitating the compound represented by the formula (1) from the reaction mixture that has been subjected to the above-mentioned post-treatment can be performed by making the reaction mixture mixed with the solvent to be 50°C or higher and the boiling point of the solvent below (compared to Preferably 70-110°C), and cool to less than 50°C for implementation. When crystals of the compound represented by the formula (1) are precipitated from the reaction mixture at 50°C or higher, after mixing the reaction mixture with a diluent solvent in an amount that does not precipitate crystals at 50°C or higher, The obtained mixture is made to be above 50°C and below the boiling point of the solvent (preferably 70~110°C), and cool it to less than 50°C. As the diluent solvent, there can be exemplified solvents used in the above-mentioned reaction, or examples such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, isobutanol, and pentanol. Alcohol solvents, carbonic acid solvents such as dimethyl carbonate and diethyl carbonate, ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, butyl benzoate, methyl benzoate, phenyl acetate, etc. Ethyl ether, di-isо-propyl ether, methyl-tert-butyl ether, diphenyl ether, tetrahydrofuran and other ether solvents, hexane, heptane, octane, pentane and other aliphatic hydrocarbon solvents, etc. , Methanol, ethanol or dimethyl carbonate are preferred, and methanol and ethanol are preferred.

此種晶析操作係可進行一次，也可重複進行複數次。尤其，前述步驟2之反應中，由於若使用甲醇或乙醇等之醇，則能簡便且有效率地除去未反應之2-萘酚或副生成之乙二醇單(2-萘基)醚等之雜質，故即使僅以一次之晶析操作，也可取得滿足式(2)之前述式(1)所示之化合物。This crystallization operation system may be performed once or repeated multiple times. In particular, in the reaction of step 2 above, if alcohols such as methanol or ethanol are used, unreacted 2-naphthol or by-produced ethylene glycol mono(2-naphthyl) ether, etc. can be removed easily and efficiently. Therefore, even with only one crystallization operation, the compound represented by the aforementioned formula (1) satisfying the formula (2) can be obtained.

藉由過濾等來回收已析出之結晶。取得之結晶係可利用上述反應所使用之溶劑等來洗淨，或也可實施乾燥。藉此而得之前述式(1)所示之化合物之純化物之純度係以95%以上為佳。The precipitated crystals are recovered by filtration or the like. The obtained crystal system may be washed with the solvent used in the above-mentioned reaction, etc., or may be dried. The purity of the purified compound represented by the aforementioned formula (1) thus obtained is preferably 95% or more.

藉由本發明之製造方法所得之具有茀骨架之化合物之純度係可選自60~100%之廣泛範圍，以70%以上為佳，較佳為80%以上，更佳為90%以上。The purity of the compound having a stilbene skeleton obtained by the production method of the present invention can be selected from a wide range of 60-100%, preferably 70% or more, preferably 80% or more, and more preferably 90% or more.

[具有茀骨架之化合物之特徵及用途] 本發明之具有茀骨架之化合物由於較佳係組合二苯基茀骨架及二萘基茀骨架與芳烴環，故不僅折射率、耐熱性為高，且作成聚合物時可減低雙折射。至今為止為了提升折射率，使用在茀骨架之9位上取代有集合環芳烴環之茀化合物，該物之折射率、耐熱性雖高，但會導致雙折射降低。相對於此，本發明之具有茀骨架之化合物或許由於係具有二苯基茀骨架及二萘基茀骨架，故即使折射率為高，雙折射仍也會變小。並且，芳烴環上由於具有1個以上之羥基，且茀化合物全體具有複數之羥基，故反應性為高。因此，本發明之具有茀骨架之化合物係可利用作為各種樹脂之原料(單體)。可使用作為例如，熱塑性樹脂(例如，聚酯樹脂、聚碳酸酯樹脂、聚酯碳酸酯樹脂、聚胺基甲酸酯樹脂等)或熱硬化性樹脂(例如，環氧樹脂、酚樹脂、熱硬化性聚胺基甲酸酯樹脂、(甲基)丙烯酸酯((甲基)丙烯酸酯)等)之多元醇成分。使用本發明之具有茀骨架之化合物作為多元醇成分時，或許係由於茀骨架之9位被萘環取代，且在茀骨架具有二芳基，故取得之樹脂具備能以高層次使高折射率與低雙折射性併存之優點。[Characteristics and Uses of Compounds with Fu skeleton] Since the compound with a pyrene skeleton of the present invention preferably combines a diphenyl pyrene skeleton, a dinaphthyl pyrene skeleton and an aromatic hydrocarbon ring, not only the refractive index and heat resistance are high, but also the birefringence can be reduced when it is made into a polymer. So far, in order to increase the refractive index, a pyridine compound substituted with an assembling aromatic hydrocarbon ring at the 9-position of the pyridine skeleton has been used. Although the refractive index and heat resistance of this compound are high, it will reduce the birefringence. In contrast, the compound with a sulphur skeleton of the present invention may have a diphenyl sulphate skeleton and a dinaphthyl sulphate skeleton, so even if the refractive index is high, the birefringence will still be small. In addition, since the aromatic hydrocarbon ring has one or more hydroxyl groups, and the entire stilbene compound has plural hydroxyl groups, the reactivity is high. Therefore, the compound having a 茀 skeleton of the present invention can be used as a raw material (monomer) of various resins. It can be used as, for example, thermoplastic resins (for example, polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.) or thermosetting resins (for example, epoxy resins, phenol resins, thermal Curable polyurethane resin, (meth)acrylate ((meth)acrylate, etc.) polyol component. When using the compound with a 茀 framework of the present invention as a polyol component, perhaps because the 9 position of the 茀 framework is substituted by a naphthalene ring and there is a diaryl group in the 茀 framework, the obtained resin has the ability to achieve high refractive index at a high level. The advantages of coexisting with low birefringence.

又，本發明之具有茀骨架之化合物係能在泛用之溶劑中效率良好地調製衍生物。In addition, the compound having a stilbene skeleton of the present invention can efficiently prepare derivatives in a general-purpose solvent.

本發明之具有茀骨架之化合物之融點係可選自100~300℃之廣泛範圍，以120~280℃為佳，較佳為130~260℃，更佳為140~240℃，特佳為150~230℃。The melting point of the compound with a 茀 skeleton of the present invention can be selected from a wide range of 100 to 300°C, preferably 120 to 280°C, preferably 130 to 260°C, more preferably 140 to 240°C, particularly preferably 150~230℃.

＜本發明之態樣II＞ [具有茀骨架之化合物] 本發明之態樣II之具有茀骨架之化合物為前述＜本發明之態樣I＞所說明之前述式(1)所示之具有茀骨架之化合物。<Aspect II of the present invention> [Compounds with Fu skeleton] The compound having a quince skeleton in the aspect II of the present invention is the compound having a quince skeleton represented by the aforementioned formula (1) described in the aforementioned <the aspect I of the present invention>.

本發明之態樣II之具有茀骨架之化合物之硫元素含量為200ppm以下，以100ppm以下為佳，以50ppm以下為較佳，以30ppm以下為更佳。硫元素之含量大於200ppm時，會對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響。又，在使用前述式(1)所示之原料醇取得樹脂之際而出現反應不良。The sulfur element content of the compound having a sulfur skeleton in aspect II of the present invention is 200 ppm or less, preferably 100 ppm or less, preferably 50 ppm or less, and more preferably 30 ppm or less. When the content of sulfur element is greater than 200 ppm, it will adversely affect the color of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical component using it. In addition, when the raw material alcohol represented by the aforementioned formula (1) is used to obtain a resin, poor reaction occurs.

本發明之具有茀骨架之化合物之溴元素含量係以150ppm以下為佳，以50ppm以下為較佳，以20ppm以下為更佳。溴元素之含量大於150ppm時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響的情況。又，在使用前述式(1)所示之原料醇取得樹脂之際，有出現反應不良的情況。The bromine element content of the compound having a citron skeleton of the present invention is preferably 150 ppm or less, preferably 50 ppm or less, and more preferably 20 ppm or less. When the content of the bromine element is greater than 150 ppm, it may adversely affect the color of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical member using it. In addition, when the raw material alcohol represented by the aforementioned formula (1) is used to obtain a resin, poor reactions may occur.

本發明之具有茀骨架之化合物之鈀元素之含量係以滿足下述式(2)為佳。 0≦Pd≦50ppm　　　　　(2) 較佳係滿足下述式(2-1)。 0≦Pd≦25ppm　　　　　(2-1) 更佳係滿足下述式(2-2)。 0≦Pd≦10ppm　　　　　(2-2) 較更佳係滿足下述式(2-3)。 0≦Pd≦5ppm　　　　(2-3) 特佳係滿足下述式(2-4)。 0≦Pd≦3ppm　　　　(2-4)The content of the palladium element in the compound having a turbidity skeleton of the present invention is preferably to satisfy the following formula (2). 0≦Pd≦50ppm　　　　　(2) It is preferable to satisfy the following formula (2-1). 0≦Pd≦25ppm　　　　　(2-1) More preferably, it satisfies the following formula (2-2). 0≦Pd≦10ppm　　　　　(2-2) More preferably, it satisfies the following formula (2-3). 0≦Pd≦5ppm　　　　(2-3) The particularly preferred system satisfies the following formula (2-4). 0≦Pd≦3ppm　　　　(2-4)

超出上述範圍之上限時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響的情況。鈀元素之含量下限可為0.01ppm以上、0.05ppm以上，或0.10ppm以上。When the upper limit of the above-mentioned range is exceeded, the hue of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical member using the same may be adversely affected. The lower limit of the content of palladium can be 0.01 ppm or more, 0.05 ppm or more, or 0.10 ppm or more.

本發明之具有茀骨架之化合物溶解於二甲基甲醯胺而成之5重量%溶液之APHA係以500以下為佳，以200以下為較佳，以100以下為更佳。APHA大於500時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響的情況。The APHA of a 5 wt% solution of the compound having a 茀 skeleton of the present invention dissolved in dimethylformamide is preferably 500 or less, preferably 200 or less, and more preferably 100 or less. When APHA is greater than 500, it may have an adverse effect on the color of the resin using the raw alcohol represented by the aforementioned formula (1) or the optical member using it.

本發明之具有茀骨架之化合物中，前述式(1-b)所示之化合物中之二苯基茀酮之含量係以0.2%以下為佳，以0.1%以下為較佳，以0.05%以下為更佳。二苯基茀酮之含量大於0.2%時，則有對使用前述式(1)所示之原料醇之樹脂色相或使用其之光學構件造成不良影響的情況。In the compound with a stilbene skeleton of the present invention, the content of diphenyl ketone in the compound represented by the aforementioned formula (1-b) is preferably 0.2% or less, preferably 0.1% or less, and 0.05% or less For better. When the content of diphenylphenone is greater than 0.2%, it may adversely affect the hue of the resin using the raw material alcohol represented by the aforementioned formula (1) or the optical component using it.

[具有茀骨架之化合物之製造方法] 本發明之態樣II之具有茀骨架之化合物之製造方法係可藉由下述步驟1~3來製造。 步驟1：使下述式(13)所示之茀酮類與下述式(14)所示之醇類在反應溶劑中，在酸觸媒之存在下進行反應，而取得下述式(15)所示之化合物的步驟 步驟2：使下述式(15)所示之化合物與碳酸伸乙酯在反應溶劑中，鹼之存在下進行反應，而取得下述式(16)所示之化合物的步驟 步驟3：使下述式(16)所示之化合物與下述式(17)或(18)所示之硼酸類在反應溶劑中，在鹼及鈀系觸媒之存在下進行反應，而取得上述式(1)所示之化合物的步驟[Manufacturing method of compound with 茀 frame] The method for producing the compound having a stilbene skeleton of aspect II of the present invention can be produced by the following steps 1 to 3. Step 1: The ketones represented by the following formula (13) and the alcohols represented by the following formula (14) are reacted in a reaction solvent in the presence of an acid catalyst to obtain the following formula (15) ) Steps of the compound shown Step 2: A step of reacting a compound represented by the following formula (15) with ethylene carbonate in the presence of a base in a reaction solvent to obtain a compound represented by the following formula (16) Step 3: The compound represented by the following formula (16) and the boric acid represented by the following formula (17) or (18) are reacted in the reaction solvent in the presence of a base and a palladium-based catalyst to obtain The steps of the compound represented by the above formula (1)

(式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子。)

(In the formula, X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position and represents a halogen atom, and X ² is a substituent at the 5-position, 6-position, 7-position or 8-position and represents a halogen atom. )

(式中，p1及p2係相同或相異為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同。)

(In the formula, p1 and p2 are the same or different as an integer of 0-4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1).)

(式中，X¹ 及X² 係與前述式(13)中相同。R¹ 、p1及p2係與式(14)中相同。n1及n2為0~3之整數。)

(In the formula, X ¹ and X ² are the same as in the aforementioned formula (13). R ¹ , p1 and p2 are the same as in the formula (14). n1 and n2 are integers from 0 to 3.)

(式中，X¹ 及X² 係與前述式(13)中相同。R¹ 、L¹ 、m1、m2、n1、n2、o1及o2係與式(1)中相同。

(In the formula, X ¹ and X ² are the same as in the aforementioned formula (13). R ¹ , L ¹ , m1, m2, n1, n2, o1 and o2 are the same as in the formula (1).

(式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子。l為0、1或2，l=2時，R¹⁴ 係可為相同或亦可為相異。)

(In the formula, Y represents an aromatic group, and R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1 or 2, and when l=2, the R ¹⁴ system may be the same or the same Can be different.)

上述式(13)所示之化合物為對應前述式(1)中茀骨架之茀酮化合物，X¹ 為1位、2位、3位或4位之取代基，X² 為5位、6位、7位或8位之取代基，X¹ 及X² 皆表示鹵素原子。The compound represented by the above formula (13) is a ketone compound corresponding to the quinone skeleton in the above formula (1), X ¹ is a substituent at the 1, 2, 3 or 4 position, and X ² is the 5, 6 position , 7 or 8 substituents, X ¹ and X ^{2 both} represent a halogen atom.

以下例示上述式(13)所示之茀酮化合物之代表例，但作為本發明之前述式(1)所使用之原料，並非係受到該等所限定者。The following illustrates representative examples of the ketone compound represented by the above formula (13), but the raw material used in the above formula (1) of the present invention is not limited by these.

作為具體例，較佳可舉出如1,8-二氟茀酮、2,7-二氟茀酮、3,6-二氟茀酮、4,5-二氟茀酮、1,8-二氯茀酮、2,7-二氯茀酮、3,6-二氯茀酮、4,5-二氯茀酮、1,8-二碘茀酮、2,7-二碘茀酮、3,6-二碘茀酮、4,5-二碘茀酮、1,8-二溴茀酮、2,7-二溴茀酮、3,6-二溴茀酮、4,5-二溴茀酮等。其中亦以1,8-二溴茀酮、2,7-二溴茀酮、3,6-二溴茀酮、4,5-二溴茀酮為佳，尤其係以2,7-二溴茀酮為佳。As specific examples, preferred examples include 1,8-difluorochodone, 2,7-difluorochodone, 3,6-difluorochodone, 4,5-difluorochodone, 1,8- Dichloropyrone, 2,7-dichloropyrone, 3,6-dichloropyrone, 4,5-dichloropyrone, 1,8-diiodopyrone, 2,7-diiodopyrone, 3,6-diiodopyrone, 4,5-diiodopyrone, 1,8-dibromopyrone, 2,7-dibromopyrone, 3,6-dibromopyrone, 4,5-di Bromopyrone and so on. Among them, 1,8-dibromopyrone, 2,7-dibromopyrone, 3,6-dibromopyrone, 4,5-dibromopyrone are preferred, especially 2,7-dibromopyrone Chloride is better.

該等係可單獨使用，或也可混合2種以上，可因應目的而任意選擇。本發明中係以2,7-二溴茀酮為佳。These systems may be used alone, or two or more of them may be mixed, and they can be arbitrarily selected according to the purpose. In the present invention, 2,7-dibromopyrone is preferred.

使用之前述式(13)所示之茀酮類之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。尚且，茀酮類係可使用市售品，也可使用經合成者。例如，作為製造二溴茀酮類之方法，可舉出如非專利文獻(美國化學會期刊(Journal of American Chemical Society), 2017, Vol.139, 11073-11080)記載之方法，即使9-茀酮與溴在水中下反應之方法等。The purity of the ketones represented by the aforementioned formula (13) used is not particularly limited, and is generally preferably 95% or more, preferably 99% or more. Furthermore, for the ketone series, commercially available products can be used, or synthetic ones can also be used. For example, as a method of producing dibromopyrones, there are methods described in non-patent literature (Journal of American Chemical Society (Journal of American Chemical Society), 2017, Vol.139, 11073-11080). The method of reacting ketone and bromine in water, etc.

前述式(14)所示之醇類係對應前述式(13)所示之茀衍生物中在9位上取代之含(多)羥基之芳烴環。即，前述式(14)中萘環係對應前述式(1)之萘環，R¹ 、n1及n2係對應前述式(1)之R¹ 、n1及n2。The alcohol represented by the aforementioned formula (14) corresponds to the (poly)hydroxyl-containing aromatic hydrocarbon ring substituted at the 9-position in the fluoride derivative represented by the aforementioned formula (13). That is, the formula (14) in the naphthalene ring system corresponding to the naphthalene ring of formula (1) of, R ^1, n1 and n2 lines corresponding to the formula R (1) of ^1, n1 and n2.

作為前述式(14)所示之化合物之具體例，可舉出如萘酚類(例如，萘酚(1-萘酚、2-萘酚)、具有烴基之萘酚(甲基萘酚、乙基萘酚、二甲基萘酚、丙基萘酚、丁基萘酚(C_1-4 烷基萘酚)等之烷基萘酚)、烷氧基萘酚(乙氧基萘酚等之C_1-4 烷氧基萘酚)、鹵萘酚(氯萘酚、溴萘酚))、對應該等萘酚類(或單羥基萘類)之多羥基萘(例如，1,3-二羥基萘、1,4-二羥基萘、2,3-二羥基萘、1,5-羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,6-二羥基萘、2,7-二羥基萘、1,2,4-三羥基萘、1,3,8-三羥基萘等之二或三羥基萘類)等。其中亦以1-萘酚、2-萘酚為佳，尤其係以2-萘酚為佳。該等醇類係可單獨使用，或也可混合2種以上而與茀酮類反應，且可因應目的而任意地選擇。本發明係以2-萘酚為佳。Specific examples of the compound represented by the aforementioned formula (14) include naphthols (for example, naphthol (1-naphthol, 2-naphthol), naphthol having a hydrocarbon group (methyl naphthol, ethyl Alkyl naphthol, dimethyl naphthol, propyl naphthol, butyl naphthol (C _1-4 alkyl naphthol), alkoxy naphthol (ethoxy naphthol, etc.) C _1-4 alkoxy naphthol), halonaphthol (chloronaphthol, bromonaphthol)), corresponding to these naphthols (or monohydroxy naphthalenes) polyhydroxy naphthalenes (for example, 1,3-di Hydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4-trihydroxynaphthalene, 1,3,8-trihydroxynaphthalene, etc. (two or trihydroxynaphthalenes), etc. Among them, 1-naphthol and 2-naphthol are also preferred, and 2-naphthol is especially preferred. These alcohols may be used alone, or two or more of them may be mixed to react with the ketones, and they may be arbitrarily selected according to the purpose. The present invention is preferably 2-naphthol.

步驟1之反應中，上述式(14)所示之醇類之使用量並非係受到特別限定者，從抑制副反應及經濟性之觀點，相對於茀酮類1莫耳，以2~20莫耳為佳，較佳為2.1~10莫耳，更佳為2.3~5莫耳。In the reaction of step 1, the use amount of the alcohol represented by the above formula (14) is not particularly limited. From the viewpoint of suppression of side reactions and economic efficiency, it is 2-20 moles relative to 1 mole of ketones. The ear is better, preferably 2.1-10 mol, more preferably 2.3-5 mol.

該等上述式(14)所示之醇類係可使用市售品，也可使用經合成者。例如，作為製造萘酚類之方法，可舉出如專利文獻(日本特開昭61-115039號公報)記載之方法，即將萘予以磺化之2-萘磺酸再以鹼進行中和而取得2-萘磺酸鈉後，鹼融解生成物而作成鹼鹽後，進行水解來製造2-萘酚之方法等。The alcohols represented by the above formula (14) may be commercially available or synthesized. For example, as a method of producing naphthols, a method described in the patent document (Japanese Patent Application Laid-Open No. 61-115039), which is obtained by sulfonating 2-naphthalenesulfonic acid in which naphthalene is sulfonated, is neutralized with an alkali. After sodium 2-naphthalenesulfonate, the product is melted with an alkali to form an alkali salt, and then hydrolyzed to produce 2-naphthol.

使用作為原料之上述式(14)所示之醇類(例如，萘酚類等)之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。The purity of the alcohols represented by the above formula (14) (for example, naphthols, etc.) used as a raw material is not particularly limited, and is generally preferably 95% or more, preferably 99% or more.

步驟1之反應通常係可在酸觸媒之存在下進行。作為酸觸媒，可舉出例如，硫酸、硫羥酸、蒙脫石、雜多酸等，該等之中尤其係由於源自酸觸媒之雜質之生成為少，且容易取得本發明之具有茀骨架之化合物，故以雜多酸為特佳。The reaction of step 1 can usually be carried out in the presence of an acid catalyst. As acid catalysts, for example, sulfuric acid, thiol acid, montmorillonite, heteropolyacids, etc. are mentioned. Among them, the generation of impurities derived from acid catalysts is small, and it is easy to obtain the present invention. It is a compound with a citron skeleton, so heteropoly acid is particularly preferred.

本發明中較佳使用之雜多酸係指一般相異2種以上之無機含氧酸進行縮合而生成之化合物之總稱，藉由中心之含氧酸與在其周圍進行縮合之別種含氧酸之組合，而能成為各種之雜多酸。將形成中心之含氧酸之數量少之元素稱為雜元素，將形成在其周圍進行縮合之含氧酸之元素稱為多元素。多元素可為單一種類之元素，亦可為複數種類之元素。The heteropoly acid preferably used in the present invention refers to the general term of the compound formed by the condensation of two or more different inorganic oxyacids. The oxyacid in the center is condensed with other oxyacids around it. The combination can become a variety of heteropoly acids. The element with a small number of oxyacids forming the center is called heteroelement, and the element that forms oxyacids condensed around it is called polyelement. The multi-element may be a single type of element, or may be a plurality of types of elements.

構成雜多酸之含氧酸之雜元素並非係受到特別限定者，可舉出例如，銅、鈹、硼、鋁、碳、矽、鍺、錫、鈦、鋯、鈰、釷、氮、磷、砷、銻、釩、鈮、鉭、鉻、鉬、鎢、鈾、硒、碲、錳、碘、鐵、鈷、鎳、銠、鋨、銥、鉑。較佳為磷(磷酸)或矽(矽酸)。又，構成雜多酸之含氧酸之多元素並非係受到特別限定者，可舉出例如，釩、鉬、鎢、鈮、鉭。以選自釩、鉬及鎢之至少1種元素為佳。The hetero elements constituting the oxo acids of the heteropoly acid are not particularly limited, and examples include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, and phosphorus. , Arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, platinum. Preferably, it is phosphorous (phosphoric acid) or silicon (silicic acid). In addition, the multiple elements constituting the oxo acid of the heteropoly acid are not particularly limited, and examples include vanadium, molybdenum, tungsten, niobium, and tantalum. At least one element selected from vanadium, molybdenum and tungsten is preferred.

作為構成雜多酸骨架之雜多酸陰離子，可使用各種之組成者。可舉出例如，XM₁₂ O₄₀ 、XM₁₂ O₄₂ 、XM₁₈ O₆₂ 、XM₆ O₂₄ 等。較佳之雜多酸陰離子之組成為XM₁₂ O₄₀ 。各式中，X為雜元素，M為多元素。作為具有該等組成之雜多酸，具體地可例示如磷鉬酸、磷鎢酸、矽鉬酸、矽鎢酸、磷釩鉬酸等。As the heteropoly acid anion constituting the heteropoly acid skeleton, various compositions can be used. For example, XM ₁₂ O ₄₀ , XM ₁₂ O ₄₂ , XM ₁₈ O ₆₂ , XM ₆ O ₂₄ and the like can be mentioned. The composition of the preferred heteropolyacid anion is XM ₁₂ O ₄₀ . In each formula, X is a miscellaneous element, and M is a multi-element. Specific examples of heteropolyacids having such compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

雜多酸可為遊離之雜多酸，亦可質子之一部分或全部被其他陽離子取代而使用作為雜多酸之鹽。因此，本發明所稱之雜多酸也係包括該等雜多酸之鹽。作為能取代質子之陽離子，可舉出例如，銨、鹼金屬、鹼土類金屬等。The heteropoly acid may be a free heteropoly acid, or part or all of the protons may be replaced by other cations and used as a salt of the heteropoly acid. Therefore, the heteropoly acid referred to in the present invention also includes the salt of the heteropoly acid. Examples of cations capable of substituting protons include ammonium, alkali metals, alkaline earth metals and the like.

雜多酸可為酐，也可為結晶水含有物，但以酐之反應較快且會抑制副生成物之生成而為佳。在結晶水含有物之情況，預先藉由實施減壓乾燥或與溶劑之共沸脫水等之脫水處理，而可取得與酐相同之效果。雜多酸係也可使用載持於活性碳、氧化鋁、二氧化矽-氧化鋁、矽藻土等之載體上之形態。The heteropoly acid may be an anhydride or a crystal water-containing substance, but it is preferable that the anhydride reacts quickly and inhibits the formation of by-products. In the case of crystal water content, dehydration treatment such as reduced pressure drying or azeotropic dehydration with a solvent can be performed in advance to achieve the same effect as an anhydride. The heteropoly acid can also be used in the form of a carrier supported on activated carbon, alumina, silica-alumina, diatomaceous earth, etc.

該等雜多酸係可單獨使用，也可組合2種以上使用。又，因應必要，在不損及本發明目的之範圍內，亦可併用雜多酸以外之其他觸媒。These heteropoly acids may be used alone or in combination of two or more kinds. In addition, if necessary, other catalysts other than heteropoly acid may be used in combination within the scope of not impairing the purpose of the present invention.

雜多酸之使用量並非係受到特別限定者，為了取得充足之反應速度，相對於茀酮類，以0.0001重量倍以上為佳，較佳為0.001~30重量倍，更佳為0.01~5重量倍。The amount of heteropoly acid used is not particularly limited. In order to obtain a sufficient reaction rate, it is preferably 0.0001 weight times or more relative to ketones, preferably 0.001 to 30 weight times, and more preferably 0.01 to 5 weight times. Times.

實施本發明之際，步驟1之反應中藉由一同併用上述雜多酸與具有巰基(以下有略稱為SH基之情況)之化合物，而可使反應速度提升且可抑制雜質之生成。作為本發明中可併用之硫醇化合物，可舉出例如，巰基羧酸、烷硫醇及該等之鹽。When carrying out the present invention, the above-mentioned heteropolyacid and a compound having a mercapto group (hereinafter referred to as SH group) are used together in the reaction of step 1, so that the reaction rate can be increased and the generation of impurities can be suppressed. As the thiol compound that can be used in combination in the present invention, for example, mercaptocarboxylic acid, alkanethiol, and salts of these can be mentioned.

作為巰基羧酸，可舉出如α-巰基丙酸、β-巰基丙酸、硫代乙酸、巰基乙酸、硫代草酸、巰基琥珀酸、巰基安息香酸等。又，作為烷硫醇，可舉出如甲硫醇、乙硫醇、1-丙硫醇、2-丙硫醇、1-丁硫醇、2-丁硫醇、1-戊硫醇、2-戊硫醇、1-己硫醇、1-庚硫醇、2-庚硫醇、1-辛硫醇、2-辛硫醇、1-壬硫醇、1-癸硫醇、1-十一硫醇、1-十二硫醇等之C_1-16 烷基硫醇等。此種具有SH基之化合物當中，由於能平價取得，故以β-巰基丙酸及1-十二硫醇為佳，以1-十二硫醇為特佳。Examples of mercaptocarboxylic acids include α-mercaptopropionic acid, β-mercaptopropionic acid, thioacetic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, and mercaptobenzoic acid. In addition, examples of the alkanethiol include methyl mercaptan, ethyl mercaptan, 1-propane mercaptan, 2-propane mercaptan, 1-butane mercaptan, 2-butane mercaptan, 1-pentyl mercaptan, 2 -Pentyl mercaptan, 1-hexyl mercaptan, 1-heptane mercaptan, 2-heptane mercaptan, 1-octyl mercaptan, 2-octyl mercaptan, 1-nonane mercaptan, 1-decane mercaptan, 1-decane _{C 1-16} alkyl mercaptan such as monothiol, 1-dodecanethiol, etc. Among such compounds with SH groups, β-mercaptopropionic acid and 1-dodecanethiol are preferred, and 1-dodecanethiol is particularly preferred, because they can be obtained cheaply.

此種具有SH基之化合物係可單獨使用，又，也可合併使用2種以上。Such SH group-containing compounds may be used alone, or two or more of them may be used in combination.

實施步驟1之反應之方法並非係受到特別限定者，通常係可藉由將前述式(13)與前述式(14)所示之化合物與雜多酸及/或硫醇化合物放入反應裝置中，在空氣中或氮、氬等之惰性氣體環境下，在甲苯或二甲苯等之芳香族烴類及乙酸乙酯、γ-丁內酯、碳酸伸乙酯等之酯類之惰性溶劑存在下進行加熱攪拌來進行。此時，藉由在會將含觸媒之水或反應生成水等反應系統內之水分予以去除之脫水條件下進行反應，比起不脫水之情況，反應會更快地進行，且副生成物之生成受到抑制，而能以更高收率取得目的物。作為脫水之方法，並非係受到特別限定者，可舉出例如，利用添加脫水劑之脫水、利用減壓之脫水、利用在常壓或減壓下與溶劑之共沸之脫水等。The method for carrying out the reaction of step 1 is not particularly limited, and usually can be done by putting the compound represented by the aforementioned formula (13) and the aforementioned formula (14) and the heteropolyacid and/or thiol compound into the reaction device , In the air or in an inert gas environment such as nitrogen and argon, in the presence of inert solvents such as aromatic hydrocarbons such as toluene or xylene and esters such as ethyl acetate, γ-butyrolactone, and ethylene carbonate Perform heating and stirring. At this time, by performing the reaction under dehydration conditions that remove water in the reaction system such as catalyst-containing water or reaction product water, the reaction proceeds faster than if it is not dehydrated, and the by-products The production is suppressed, and the target can be obtained with a higher yield. The method of dehydration is not particularly limited. Examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, and dehydration by azeotrope with a solvent under normal pressure or reduced pressure.

作為步驟1使用之反應溶劑，並非係受到特別限定者，可舉出例如甲苯、二甲苯等之芳香族烴溶劑，氯苯、二氯苯等之鹵化芳香族烴溶劑，戊烷、己烷、庚烷等之脂肪族烴溶劑，二氯甲烷、1,2-二氯乙烷等之鹵化脂肪族烴溶劑、二乙基醚、二-iso-丙基醚、甲基-t-丁基醚、二苯基醚、四氫呋喃、二噁烷等之脂肪族及環狀醚溶劑，乙酸乙酯、乙酸丁酯、γ-丁內酯、碳酸伸乙酯等之酯溶劑，乙腈、丙腈、丁腈、苄腈等之腈溶劑，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1-甲基-2-吡咯啶酮等之醯胺溶劑等。以芳香族烴溶劑及酯溶劑為佳，較佳為甲苯、二甲苯、氯苯或二氯苯，與乙酸乙酯、乙酸丁酯、γ-丁內酯或碳酸伸乙酯之混合溶劑，更佳為甲苯與碳酸伸乙酯之混合溶劑。該等反應溶劑係可單獨使用，又，也可合併使用2種以上。The reaction solvent used in step 1 is not particularly limited. Examples include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, pentane, hexane, etc. Aliphatic hydrocarbon solvents such as heptane, halogenated aliphatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-t-butyl ether , Diphenyl ether, tetrahydrofuran, dioxane and other aliphatic and cyclic ether solvents, ethyl acetate, butyl acetate, γ-butyrolactone, ethylene carbonate and other ester solvents, acetonitrile, propionitrile, butane Nitrile solvents such as nitrile and benzonitrile, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc. Aromatic hydrocarbon solvents and ester solvents are preferred, preferably toluene, xylene, chlorobenzene or dichlorobenzene, mixed solvents with ethyl acetate, butyl acetate, γ-butyrolactone or ethylene carbonate, and more It is preferably a mixed solvent of toluene and ethylene carbonate. These reaction solvents may be used alone, or two or more of them may be used in combination.

又，其之使用量並非係受到特別限定者，從經濟性之觀點，相對於茀酮類，以0.1重量倍以上為佳，較佳為0.5~100重量倍，更佳為1~20重量倍。In addition, the amount used is not particularly limited. From the viewpoint of economy, it is preferably 0.1 times or more by weight, preferably 0.5 to 100 times by weight, and more preferably 1 to 20 times by weight relative to ketones. .

步驟1之反應溫度係根據所使用之原料、溶劑之種類而不同，以50~300℃為佳，較佳為80~250℃，更佳為100~180℃。反應係可利用液體層析法等之分析手段來追蹤。The reaction temperature of step 1 varies according to the types of raw materials and solvents used, and is preferably 50 to 300°C, preferably 80 to 250°C, and more preferably 100 to 180°C. The reaction system can be traced using analytical means such as liquid chromatography.

步驟1之反應時之內壓係以101.3kPa以下之壓力為佳，較佳為60.0kPa以下。由於使副生成之水在該內壓下從系統內排出並同時反應之方式而會令反應更有效率地進行，且生成之副生成物也會變少，故以該方式為佳。The internal pressure during the reaction in step 1 is preferably 101.3 kPa or less, preferably 60.0 kPa or less. Since the by-product water is discharged from the system under the internal pressure and reacted at the same time, the reaction will proceed more efficiently, and the generated by-products will also be reduced, so this method is preferred.

步驟1之反應後，因應必要可藉由過濾來去除所使用之固體酸或也可進行中和。作為中和時所使用之鹼，可舉出例如，氫氧化鈉、氫氧化鉀、氫氧化鈣等之鹼金屬或鹼土類金屬之氫氧化物、碳酸鉀、碳酸鈣、碳酸鈉、碳酸鈉等之鹼金屬或鹼土類金屬之碳酸鹽(碳酸氫)鹽、胺類等。又，也可藉由過濾、濃縮、抽出、晶析、再結晶、再沉澱、活性碳處理或其酷似之金屬之除去處理、管柱層析法等之分離手段，組合該等而成之分離手段來進行分離純化。After the reaction in step 1, if necessary, the solid acid used can be removed by filtration or can be neutralized. As the alkali used in the neutralization, for example, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, sodium carbonate, sodium carbonate, etc. Carbonate (bicarbonate) salts of alkali metals or alkaline earth metals, amines, etc. In addition, it can also be separated by combining separation means such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or removal treatment of metal similar to it, column chromatography, etc. Means to carry out separation and purification.

步驟1之反應中，中和後之反應液係可不去除因中和所生成之鹽，而使用於與碳酸伸乙酯之反應。因應必要也可藉由實施利用過濾來分離因中和所生成之鹽，添加水進行攪拌並靜置後使其分液並去除水層之操作(有稱為水洗步驟之情況)，而從反應系統內分離因中和所生成之鹽。該水洗步驟係因應必要也可重複實施。In the reaction of step 1, the neutralized reaction solution can be used for the reaction with ethylene carbonate without removing the salt produced by the neutralization. If necessary, the salt produced by the neutralization can be separated by filtration, and water is added, stirred and left to stand, then the liquid is separated and the water layer is removed (there is a case called a water washing step), and the reaction The salt produced by neutralization is separated in the system. The washing step can be repeated as necessary.

步驟1之反應後，可不取出上述式(15)所示之茀化合物而使其與碳酸伸乙酯進行反應。即，可在一鍋內進行步驟1與步驟2。藉由濃縮或晶析等之方法來取出上述式(15)所示之茀化合物時，則變得有收率降低且成本提升的可能性。After the reaction in step 1, it is possible to react with ethylene carbonate without taking out the stilbene compound represented by the above formula (15). That is, steps 1 and 2 can be performed in one pot. When the stilbene compound represented by the above formula (15) is taken out by methods such as concentration or crystallization, there is a possibility that the yield will decrease and the cost will increase.

步驟2中，碳酸伸乙酯係相對於茀酮類1莫耳，通常使用2~10莫耳，較佳使用2~8莫耳，更佳使用2~6莫耳。In step 2, ethylene carbonate is 1 mol relative to the ketones, usually 2-10 mols, preferably 2-8 mols, and more preferably 2-6 mols.

步驟2中，在實施上述式(15)所示之茀化合物與碳酸伸乙酯之反應之際，因應必要也可在鹼性化合物存在下進行反應。在鹼性化合物存在下進行反應之情況，步驟1所使用之固體酸係以在實施步驟2之前預先藉由過濾進行分離或進行中和為佳。In step 2, when the reaction between the stilbene compound represented by the above formula (15) and ethylene carbonate is carried out, the reaction may be carried out in the presence of a basic compound as necessary. When the reaction is carried out in the presence of a basic compound, the solid acid used in step 1 is preferably separated by filtration or neutralized before step 2 is carried out.

作為步驟2中能使用之鹼性化合物，可例示如碳酸鹽類、碳酸氫鹽類、氫氧化物類、有機鹼類等。作為碳酸鹽類，可舉出如碳酸鉀、碳酸鈉、碳酸銫、碳酸鋰等。作為碳酸氫鹽類，可舉出如碳酸氫鉀、碳酸氫鈉、碳酸氫鋰、碳酸氫銫等。作為氫氧化物類，可舉出如氫氧化鈉、氫氧化鉀、氫氧化鋰等。作為有機鹼類，可舉出如三乙基胺、二甲基胺基吡啶、三苯基膦、溴化四甲基銨、氯化四甲基銨等。上述鹼性化合物之中，從操作性或安全性之觀點，較佳使用碳酸鉀、碳酸鈉。該等鹼性化合物係可單獨使用，又，也可合併使用2種以上。Examples of basic compounds that can be used in step 2 include carbonates, bicarbonates, hydroxides, and organic bases. Examples of carbonates include potassium carbonate, sodium carbonate, cesium carbonate, and lithium carbonate. Examples of bicarbonates include potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, cesium bicarbonate, and the like. Examples of hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Examples of organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. Among the above-mentioned basic compounds, potassium carbonate and sodium carbonate are preferably used from the viewpoint of operability and safety. These basic compounds may be used alone, or two or more of them may be used in combination.

在步驟2中使用鹼性化合物之情況，其之使用量係相對於茀酮類1莫耳，通常為0.01~1.0莫耳，以0.03~0.5莫耳為佳。In the case of using a basic compound in step 2, the usage amount is relative to 1 mol of stiltones, usually 0.01 to 1.0 mol, preferably 0.03 to 0.5 mol.

步驟2之反應結束後，以實施對取得之反應混合物添加濃度3重量%以上之鹼水溶液，在50℃以上之溫度下進行加熱攪拌之步驟(以下，稱為鹼純化步驟)為佳。添加於反應混合物溶液之鹼水溶液之濃度係以3重量%以上為佳，以6重量%為較佳，以8重量%以上為更佳。藉由添加3重量%以上之濃度之鹼水溶液，並以50℃以上之溫度進行加熱攪拌，式(15)所示之化合物1莫耳與碳酸伸乙酯3莫耳以上進行反應而成之副生物會進行分解而成為式(16)所示之化合物。又，由於能從鹼水溶液中除去著色成分，故可取得高純度且著色少之式(16)所示之化合物。鹼水溶液之濃度低於3重量%時，因變得無法有效率地去除副生成物或著色成分，故不佳。鹼濃度若在3重量%以上，即並非係受到特別限定者，從鹼之溶解度或操作容易性之觀點，以50重量%以下為佳，較佳為30重量%以下，更佳為15重量%以下之濃度。After the reaction of step 2 is completed, it is preferable to implement a step of adding an alkali aqueous solution with a concentration of 3% by weight or more to the obtained reaction mixture and heating and stirring at a temperature of 50°C or more (hereinafter referred to as alkali purification step). The concentration of the aqueous alkali solution added to the reaction mixture solution is preferably 3% by weight or more, preferably 6% by weight, and more preferably 8% by weight or more. By adding an alkali aqueous solution with a concentration of 3% by weight or more, and heating and stirring at a temperature of 50°C or more, the compound represented by formula (15) 1 mol and 3 mol or more ethylene carbonate are reacted to form a sub The organism will decompose to become the compound represented by formula (16). In addition, since the coloring component can be removed from the alkaline aqueous solution, it is possible to obtain the compound represented by the formula (16) with high purity and little coloring. When the concentration of the alkaline aqueous solution is less than 3% by weight, it becomes impossible to efficiently remove by-products and coloring components, which is not preferable. If the alkali concentration is 3% by weight or more, it is not particularly limited. From the standpoint of alkali solubility or ease of handling, it is preferably 50% by weight or less, preferably 30% by weight or less, and more preferably 15% by weight. The following concentration.

加熱攪拌鹼水溶液之溫度係以50℃以上為佳，以60℃以上為較佳，以80℃以上為更佳。又，以在所使用之溶劑之沸點以下之溫度，較佳在130℃以下進行。溫度低於50℃時，由於無法去除副生成物或無法有效率地去除，故不佳。又，溫度高於130℃，由於雜質會增加且純度降低，或色相惡化，故不佳。又，攪拌時間並非特別限定，以0.5~10小時為佳，較佳為1~9小時，更佳為2~8小時。The temperature for heating and stirring the alkaline aqueous solution is preferably 50°C or higher, preferably 60°C or higher, and more preferably 80°C or higher. In addition, it is carried out at a temperature below the boiling point of the solvent used, preferably below 130°C. When the temperature is lower than 50°C, the by-products cannot be removed or cannot be removed efficiently, which is not preferable. In addition, if the temperature is higher than 130°C, impurities will increase and the purity will decrease, or the hue will deteriorate, which is not good. In addition, the stirring time is not particularly limited, but is preferably 0.5 to 10 hours, preferably 1 to 9 hours, and more preferably 2 to 8 hours.

本發明之鹼水溶液所使用之鹼並非係受到特別限定者，可舉出如氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化鈣、氫氧化鋇、碳酸鈉、碳酸鉀等。以氫氧化鈉、氫氧化鉀為佳。鹼之使用量並非係受到特別限制者，為了有效率地進行去除副生成物或去除著色成分，通常相對於式(16)所示之化合物1莫耳，以0.1~20莫耳為佳，以0.2~10莫耳為較佳，以0.3~5莫耳為更佳。鹼量少於0.1莫耳時，有無法有效率地去除副生物的情況。又有無法有效率地去除著色成分的情況，故不佳。鹼量多餘20莫耳時，有純度降低或色相惡化的情況，故不佳。The alkali used in the aqueous alkali solution of the present invention is not particularly limited, and examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, Barium hydroxide, sodium carbonate, potassium carbonate, etc. Sodium hydroxide and potassium hydroxide are preferred. The amount of alkali used is not particularly limited. In order to efficiently remove by-products or remove coloring components, it is usually 0.1-20 mol relative to 1 mol of the compound represented by formula (16). 0.2-10 mol is preferable, and 0.3-5 mol is more preferable. When the amount of alkali is less than 0.1 mol, by-products may not be removed efficiently. In addition, coloring components cannot be removed efficiently, which is not good. When the amount of alkali exceeds 20 mol, the purity may be lowered or the hue may deteriorate, so it is not good.

本發明中，鹼純化步驟係可對包含式(16)所示之化合物之反應混合物溶液添加鹼水溶液進行加熱攪拌，也可以有機溶劑稀釋反應混合物溶液後添加鹼水溶液進行加熱攪拌。通常，鹼純化步驟係以有機溶劑稀釋後才實施。稀釋之有機溶劑並非係受到特別限定者，可舉出如苯、甲苯、二甲苯、均三甲苯等之芳香族烴，戊烷、己烷、庚烷等之脂肪族烴，氯苯、二氯苯等之鹵化芳香族烴，二甲基甲醯胺、二甲亞碸等等。鹼純化操作後係可分液去除鹼水溶液。In the present invention, the alkali purification step can be performed by adding an aqueous alkali solution to the reaction mixture solution containing the compound represented by formula (16), or by diluting the reaction mixture solution with an organic solvent and adding an aqueous alkali solution for heating and stirring. Usually, the alkaline purification step is carried out after diluting with an organic solvent. The organic solvent to be diluted is not particularly limited. Examples include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, aliphatic hydrocarbons such as pentane, hexane, and heptane, chlorobenzene, and dichlorobenzene. Halogenated aromatic hydrocarbons such as benzene, dimethylformamide, dimethylsulfide, etc. After the alkali purification operation, the aqueous alkali solution can be removed by liquid separation.

步驟2之反應結束後，取得之反應混合物係可藉由洗淨、過濾、濃縮、抽出、晶析、再結晶、再沉澱、活性碳處理或與其酷似之金屬之除去處理、管柱層析法等之分離手段，或組合該等而成之分離手段來進行分離純化。因應必要從已施加上述後處理之反應混合物中使前述式(16)所示之化合物析出之操作係因應必要可藉由將已與溶劑混合之反應混合物作成50℃以上且溶劑之沸點以下(較佳為70~110℃)，並使其冷卻至未滿50℃來實施。在 50℃以上從反應混合物中使前述式(16)所示之化合物之結晶析出的情況，藉由實施將在50℃以上結晶變得不會析出之量之稀釋溶劑與反應混合物予以混合後，將取得之混合物作成50℃以上且溶劑之沸點以下(較佳為70~110℃)，並使其冷卻至未滿50℃即可。作為晶析溶劑，可舉出如例示作為上述反應所使用之溶劑者，或可舉出如甲醇、乙醇、丙醇、異丙醇、丁醇、tert-丁醇、異丁醇及戊醇等之醇溶劑，碳酸二甲酯、碳酸二乙酯等之碳酸溶劑，乙酸乙酯、乙酸丁酯、γ-丁內酯、安息香酸丁酯、安息香酸甲酯、乙酸苯酯等之酯溶劑，二乙基醚、二-isо-丙基醚、甲基-tert-丁基醚、二苯基醚、四氫呋喃等之醚溶劑，己烷、庚烷、辛烷、戊烷等之脂肪族烴溶劑等，以甲醇、乙醇、甲苯或碳酸二甲酯為佳。After the reaction of step 2 is completed, the obtained reaction mixture can be cleaned, filtered, concentrated, extracted, crystallized, recrystallized, reprecipitated, activated carbon treatment or removal treatment of similar metals, column chromatography Separation means such as other or a combination of these separation means for separation and purification. If necessary, the operation of precipitating the compound represented by the formula (16) from the reaction mixture that has been subjected to the above-mentioned post-treatment can be performed by making the reaction mixture mixed with the solvent to be 50°C or higher and the boiling point of the solvent below (compared to Preferably 70-110°C), and cool to less than 50°C for implementation. When crystals of the compound represented by the aforementioned formula (16) are precipitated from the reaction mixture at 50°C or higher, after mixing the reaction mixture with a diluent solvent in an amount that does not precipitate crystals at 50°C or higher, The obtained mixture is made to be above 50°C and below the boiling point of the solvent (preferably 70~110°C), and cool it to less than 50°C. Examples of the crystallization solvent include those exemplified as the solvent used in the above reaction, or include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, isobutanol, pentanol, etc. Alcohol solvents, carbonic acid solvents such as dimethyl carbonate and diethyl carbonate, ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, butyl benzoate, methyl benzoate, phenyl acetate, etc., Diethyl ether, di-isо-propyl ether, methyl-tert-butyl ether, diphenyl ether, tetrahydrofuran and other ether solvents, hexane, heptane, octane, pentane and other aliphatic hydrocarbon solvents Etc., preferably methanol, ethanol, toluene or dimethyl carbonate.

此種晶析操作係可僅進行一次，亦可重複進行複數次。尤其，若使用甲醇或乙醇等之醇，可簡便且效率良好地去除未反應之2-萘酚或副生成之乙二醇單(2-萘基)醚等之雜質。This crystallization operation system may be performed only once, or may be repeated multiple times. In particular, if alcohols such as methanol or ethanol are used, impurities such as unreacted 2-naphthol or by-produced ethylene glycol mono(2-naphthyl) ether can be easily and efficiently removed.

藉由過濾等來回收已析出之結晶。取得之結晶係可利用上述反應所使用之溶劑等來洗淨，或也可實施乾燥。藉此而得之前述式(16)所示之化合物之純化物之純度係以90%以上為佳，較佳為95%以上。步驟2之反應後，也可不取出上述式(16)所示之化合物，以一鍋來進行步驟3。並且，亦可以一鍋來進行全部步驟1~3。藉由以一鍋來進行，可提升收率或生產性。The precipitated crystals are recovered by filtration or the like. The obtained crystal system may be washed with the solvent used in the above-mentioned reaction, etc., or may be dried. The purity of the purified compound represented by the aforementioned formula (16) thus obtained is preferably 90% or more, preferably 95% or more. After the reaction in step 2, it is also possible to perform step 3 in one pot without taking out the compound represented by the above formula (16). In addition, all steps 1 to 3 can be performed in one pot. By doing it in one pot, the yield or productivity can be improved.

上述式(17)或(18)所示之化合物之環Y係對應前述式(1)中基Ar¹ 及Ar² 。又，前述式(17)及(18)中，基R¹⁴ 之較佳態樣係與前述R¹ 之較佳態樣相同，l之較佳態樣係與前述n1及n2之較佳態樣相同。The ring Y of the compound represented by the above formula (17) or (18) corresponds to the groups Ar ¹ and Ar ² in the above formula (1). In addition, in the foregoing formulas (17) and (18), the preferred aspect of the ^{base R 14 is the same as the preferred aspect of the foregoing R 1, and} the preferred aspect of l is the same as the foregoing preferred aspect of n1 and n2 the same.

使用之硼酸類之純度並無特別限定，通常係以95%以上為佳，較佳為99%以上。尚且，硼酸類係可使用市售品，也可使用經合成者。作為製造硼酸類之方法，可舉出例如專利文獻(日本特開2002-47292號公報)記載之方法，即，使苯基格林納試劑與溶解於非醚系芳香族溶劑之硼酸酯類進行反應之方法等。The purity of the boronic acids used is not particularly limited, but it is usually more than 95%, preferably more than 99%. Moreover, commercially available products can be used for the boric acid series, and those synthesized can also be used. As a method of producing boronic acids, for example, a method described in the patent document (Japanese Patent Application Laid-Open No. 2002-47292), that is, the phenyl Griener reagent is reacted with boric acid esters dissolved in a non-ether-based aromatic solvent. The method and so on.

本發明使用之硼酸係包括前述式(14)及(15)所示之烷基硼酸、烯基硼酸、芳基硼酸、雜芳基硼酸及其酐等，作為烷基硼酸，包括丁基硼酸、環己基硼酸、環戊基硼酸、2-乙基硼酸、4-乙基硼酸、己基硼酸、異丁基硼酸、異丙基硼酸、甲基硼酸、n-辛基硼酸、丙基硼酸、戊基硼酸、2-苯基乙基硼酸或該等之酐，作為烯基硼酸，包括1-環戊烯基硼酸、二茂鐵硼酸、1,1’-二茂鐵二硼酸或該等之酐，作為芳基硼酸，包括2-蒽硼酸、9-蒽硼酸、苄基硼酸、2-聯苯基硼酸、3-聯苯基硼酸、4-聯苯基硼酸、2,3-二甲基苯基硼酸、2,4-二甲基苯基硼酸、2,5-二甲基苯基硼酸、2,6-二甲基苯基硼酸、3,4-二甲基苯基硼酸、3,5-二甲基苯基硼酸、2-乙氧基苯基硼酸、3-乙氧基苯基硼酸、4-乙氧基苯基硼酸、6-甲氧基-2-萘硼酸、2-甲基苯基硼酸、3-甲基苯基硼酸、4-甲基苯基硼酸、1-萘硼酸、2-萘硼酸、9-菲硼酸、10-苯基-9-蒽硼酸、苯基硼酸、苯基乙烷硼酸、4-苯基(萘-1-基)硼酸、3-丙氧基苯基硼酸、3-異-丙氧基苯基硼酸、4-異-丙氧基苯基硼酸、4-丙基苯基硼酸、4-異-丙基苯基硼酸、10-(萘-1-基)-9-蒽硼酸、10-(萘-2-基)-9-蒽硼酸或該等之酐，作為雜芳基硼酸，包括苯並呋喃-2-硼酸、二苯並呋喃-4-硼酸、5-甲醯基-2-呋喃硼酸、5-甲醯基噻吩-2-硼酸、呋喃-2-硼酸、呋喃-3-硼酸、吡啶-3-硼酸、吡啶-4-硼酸、喹啉-2-硼酸、喹啉-3-硼酸、喹啉-4-硼酸、喹啉-5-硼酸、喹啉-6-硼酸、喹啉-8-硼酸、異-喹啉-4-硼酸、2-噻吩硼酸、3-噻吩硼酸、5-嘧啶硼酸或該等之酐。The boric acid used in the present invention includes alkyl boronic acid, alkenyl boronic acid, aryl boronic acid, heteroaryl boronic acid and anhydrides thereof represented by the aforementioned formulas (14) and (15). As alkyl boronic acid, including butyl boronic acid, Cyclohexyl boronic acid, cyclopentyl boronic acid, 2-ethyl boronic acid, 4-ethyl boronic acid, hexyl boronic acid, isobutyl boronic acid, isopropyl boronic acid, methyl boronic acid, n-octyl boronic acid, propyl boronic acid, pentyl Boric acid, 2-phenylethyl boronic acid or their anhydrides, as alkenyl boronic acids, include 1-cyclopentenyl boronic acid, ferrocene boronic acid, 1,1'-ferrocene diboric acid or these anhydrides, As aryl boronic acid, include 2-anthracene boronic acid, 9-anthracene boronic acid, benzyl boronic acid, 2-biphenyl boronic acid, 3-biphenyl boronic acid, 4-biphenyl boronic acid, 2,3-dimethyl phenyl boronic acid Boric acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5- Dimethylphenylboronic acid, 2-ethoxyphenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthaleneboronic acid, 2-methylbenzene Boric acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 1-naphthaleneboronic acid, 2-naphthaleneboronic acid, 9-phenanthreneboronic acid, 10-phenyl-9-anthraceneboronic acid, phenylboronic acid, phenyl Ethaneboronic acid, 4-phenyl(naphthalene-1-yl)boronic acid, 3-propoxyphenylboronic acid, 3-iso-propoxyphenylboronic acid, 4-iso-propoxyphenylboronic acid, 4- Propylphenylboronic acid, 4-iso-propylphenylboronic acid, 10-(naphthalene-1-yl)-9-anthraceneboronic acid, 10-(naphthalene-2-yl)-9-anthraceneboronic acid or their anhydrides , As heteroaryl boronic acid, including benzofuran-2-boronic acid, dibenzofuran-4-boronic acid, 5-methanyl-2-furan boronic acid, 5-methanylthiophene-2-boronic acid, furan-2 -Boric acid, furan-3-boronic acid, pyridine-3-boronic acid, pyridine-4-boronic acid, quinoline-2-boric acid, quinoline-3-boronic acid, quinoline-4-boronic acid, quinoline-5-boronic acid, quinoline Lin-6-boronic acid, quinoline-8-boronic acid, iso-quinoline-4-boronic acid, 2-thiophene boronic acid, 3-thiophene boronic acid, 5-pyrimidine boronic acid or their anhydrides.

該等係可單獨使用，或亦可混合2種以上，且可因應目的而任意地選擇。本發明中係以苯基硼酸、2-萘硼酸或其酐為佳，特佳為苯基硼酸或其酐。These systems may be used alone, or two or more types may be mixed, and they may be arbitrarily selected according to the purpose. In the present invention, phenylboronic acid, 2-naphthaleneboronic acid or its anhydride are preferred, and phenylboronic acid or its anhydride is particularly preferred.

使用作為原料之前述式(17)所示之化合物之使用比率係相對於前述式(16)所示之化合物1莫耳，較佳可為2~5莫耳，更佳可為2.05~3.0莫耳，較更佳可為2.1~2.5莫耳程度。該硼酸類未滿2莫耳時，則有前述式(1)所示之生成物之收率變低的情況，又，超過5莫耳時，雖然反應速度變快且收率變高，但會有該具有茀骨架之化合物之製造成本上升的情況。The use ratio of the compound represented by the aforementioned formula (17) used as a raw material is relative to 1 mole of the compound represented by the aforementioned formula (16), preferably 2 to 5 moles, more preferably 2.05 to 3.0 moles Ears, preferably 2.1~2.5 moles. When the boric acid is less than 2 mol, the yield of the product represented by the above formula (1) may be low, and when it exceeds 5 mol, the reaction rate becomes faster and the yield becomes higher. There may be cases where the manufacturing cost of the compound having a 茀 skeleton increases.

又，前述式(18)所示之化合物之使用比率係相對於前述式(16)所示之化合物1莫耳，較佳可為0.7~5莫耳，更佳可為0.8~3莫耳，較更佳可為1~2莫耳程度。該硼酸類未滿0.7莫耳時，則有前述式(1)所示之生成物之收率變低的情況。又，超過5莫耳時，雖然反應速度變快且收率變高，但有該具有茀骨架之化合物之製造成本上升的情況。In addition, the use ratio of the compound represented by the aforementioned formula (18) is relative to 1 mol of the compound represented by the aforementioned formula (16), preferably 0.7-5 mol, more preferably 0.8-3 mol, More preferably, it can be about 1 to 2 moles. When the boric acid is less than 0.7 mol, the yield of the product represented by the aforementioned formula (1) may become low. In addition, when it exceeds 5 mol, although the reaction rate becomes faster and the yield becomes higher, the production cost of the compound having a 茀 skeleton may increase.

步驟3之前述式(16)與前述式(17)及/或(18)所示之化合物之反應(脫鹵化反應)係可在反應溶劑中，在鹼及觸媒之存在下進行。The reaction (dehalogenation reaction) of the aforementioned formula (16) with the aforementioned formula (17) and/or (18) in step 3 can be carried out in the reaction solvent in the presence of a base and a catalyst.

作為步驟3之反應所使用之鹼，可舉出例如，氫氧化鈉、氫氧化鉀等之氫氧化物、碳酸鈉(Na₂ CO₃ )、碳酸鉀(K₂ CO₃ )、碳酸銫(Cs₂ CO₃ )等之碳酸鹽、乙酸鈉、乙酸鉀等之乙酸鹽、磷酸鈉(Na₃ PO₄ )、磷酸鉀(K₃ PO₄ )等之磷酸鹽等之無機鹽、三乙基胺類、吡啶、嗎啉、喹啉、哌啶、苯胺類、四n丁基銨乙酸酯等之銨鹽等之有機鹽等。其中，較佳使用碳酸鹽，以碳酸鉀及/或碳酸鈉為佳。此種鹼係可單獨使用，又，也可合併使用2種類以上。As the base used in the reaction of step 3, for example, hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ) and other carbonates, sodium acetate, potassium acetate and other acetates, sodium phosphate (Na ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ) and other phosphates and other inorganic salts, triethylamines Organic salts such as ammonium salts of pyridine, morpholine, quinoline, piperidine, anilines, tetra-n-butylammonium acetate, etc. Among them, carbonates are preferably used, and potassium carbonate and/or sodium carbonate are preferred. Such an alkali system may be used alone, or two or more types may be used in combination.

又，步驟3之反應中，上述鹼之使用量並非特別限定，相對於硼酸類1莫耳，以添加1~30當量為佳，較佳為添加1~10當量。In addition, in the reaction of step 3, the amount of the above-mentioned base used is not particularly limited, and it is preferable to add 1 to 30 equivalents relative to 1 mole of boric acid, and preferably to add 1 to 10 equivalents.

作為步驟3之反應所使用之鈀系觸媒，以鈴木耦合所使用之鈀化合物為佳，可舉出例如，肆(三苯基膦)鈀、二氯化雙(三苯基膦)鈀、乙酸鈀、參(二苯亞基丙酮)二鈀、雙(二苯亞基丙酮)鈀、二氯化雙[4-(N, N-二甲基胺基)苯基]二-tert-丁基膦鈀、二氯化雙(二-tert-丁基異戊二烯基膦)鈀、二氯化雙(二-tert-巴豆基膦)鈀、Pd/SiO₂ 所示之鈀系觸媒等。其中亦以肆(三苯基膦)鈀，及/或，Pd/SiO₂ 所示之鈀系觸媒為佳。此種鈀系觸媒係可單獨使用，又，也可合併使用2種以上。As the palladium-based catalyst used in the reaction of step 3, the palladium compound used in Suzuki coupling is preferred. For example, palladium (triphenylphosphine) palladium, bis(triphenylphosphine) palladium dichloride, Palladium acetate, ginseng (diphenylylidene acetone) two palladium, bis (diphenylylidene acetone) palladium, dichloride bis [4-(N, N-dimethylamino) phenyl] bis-tert-butyl Phosphine palladium, bis(di-tert-butylisoprenylphosphine) palladium dichloride, bis(di-tert-crotonylphosphine) palladium dichloride, palladium-based catalyst shown by _{Pd/SiO 2} Wait. Among them, palladium (triphenylphosphine) and/or palladium-based catalysts represented by _{Pd/SiO 2 are also preferred.} Such palladium-based catalysts may be used alone, or two or more of them may be used in combination.

步驟3之反應中，上述觸媒之使用量並無特別限定，相對於前述式(16)所示之化合物1莫耳，在鈀金屬原子換算下以0.1~10毫莫耳為佳，較佳為0.5~5毫莫耳。鈀觸媒之使用量在鈀金屬原子換算下未滿0.1毫莫耳之情況，有反應變得難以完結的情況。又，鈀觸媒之使用量在鈀金屬原子換算下超過10毫莫耳時，則有反應雖會完結，但變得難以將該具有茀骨架之化合物中之鈀元素含量作成在式(2)之範圍內，且不僅有令使用該醇原料所製造之熱塑性樹脂之色相惡化的可能性，也會有該具有茀骨架之化合物之製造成本上升的情況。In the reaction of step 3, the amount of the catalyst used is not particularly limited. Relative to 1 mol of the compound represented by the aforementioned formula (16), it is preferably 0.1-10 millimoles based on the conversion of palladium metal atoms, preferably It is 0.5 to 5 millimoles. When the amount of palladium catalyst used is less than 0.1 millimolar in terms of palladium metal atom, the reaction may become difficult to complete. In addition, when the amount of palladium catalyst used exceeds 10 millimoles in terms of palladium metal atom, the reaction may be completed, but it becomes difficult to formulate the palladium element content in the compound having a pyridium skeleton into the formula (2) Within the range, not only may the hue of the thermoplastic resin manufactured using the alcohol raw material deteriorate, but also the manufacturing cost of the compound having a citric skeleton may increase.

作為步驟3使用之反應溶劑，並未係特別受到限定者，可單獨使用例如甲苯、二甲苯等之芳香族烴系溶劑，及甲醇、乙醇、異丙基醇、n-丁醇等之醇類，或亦可併用。芳香族烴系溶劑由於為高沸點溶劑，故可將反應溫度設定為較高，又，藉由使用醇而與水之親和性為良好，且反應性變得良好，從而適宜使用。此種溶劑係可單獨使用，或也可合併使用2種以上。並且，也可使用如N,N-二甲基甲醯胺或N,N-二甲基乙醯胺等之非質子性溶劑、o-二氯苯等之鹵苯類。此種溶劑也係可單獨使用，又，亦可合併使用2種以上。本發明中，以甲苯與乙醇之混合溶劑為較佳。The reaction solvent used in step 3 is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene and xylene, and alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol can be used alone. , Or can also be used together. Since the aromatic hydrocarbon-based solvent is a high boiling point solvent, the reaction temperature can be set higher, and the affinity with water is good by using alcohol, and the reactivity becomes good, so it is suitable for use. Such solvent systems may be used alone or in combination of two or more kinds. In addition, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, and halogenated benzenes such as o-dichlorobenzene can also be used. Such solvents may be used alone, or two or more of them may be used in combination. In the present invention, a mixed solvent of toluene and ethanol is preferred.

前述反應溶劑(本發明之情況，甲苯與乙醇之混合溶劑)之使用量並無特別限定，相對於前述式(16)所示之化合物1莫耳，甲苯係以0.1重量倍以上為佳，較佳為0.5~100重量倍，更佳為1~50重量倍。甲苯之使用量在未滿0.1重量倍之情況，有生成物析出而變得難以攪拌之可能性。又，甲苯之使用量若超過100重量倍之情況，則有不具有與使用量相符之效果，且容積效率也惡化，該具有茀骨架之化合物之製造成本上升的情況。又，乙醇之使用量也並無特別限定，相對於前述式(16)所示之化合物1莫耳，以0.1~50重量倍為佳，較佳為1~20重量倍。乙醇之使用量在未滿0.1重量倍之情況，有反應速度慢，收率下降之可能性。又，在乙醇之使用量超過50重量倍之情況，則有與甲苯同樣地不具有使用量相符之效果，且容積效率也惡化，該具有茀骨架之化合物之製造成本上升的情況。The usage amount of the aforementioned reaction solvent (in the present invention, a mixed solvent of toluene and ethanol) is not particularly limited. Compared to 1 mole of the compound represented by the aforementioned formula (16), toluene is preferably 0.1 times by weight or more. It is preferably 0.5 to 100 times by weight, more preferably 1 to 50 times by weight. When the amount of toluene used is less than 0.1 times by weight, the product may precipitate and it may become difficult to stir. In addition, if the amount of toluene used exceeds 100 times by weight, it does not have the effect corresponding to the amount used, and the volumetric efficiency also deteriorates, which may increase the manufacturing cost of the compound having a phytoskeleton. In addition, the amount of ethanol used is not particularly limited, and it is preferably 0.1 to 50 times by weight, preferably 1 to 20 times by weight, relative to 1 mole of the compound represented by the aforementioned formula (16). When the amount of ethanol used is less than 0.1 times by weight, the reaction speed may be slow and the yield may decrease. In addition, when the amount of ethanol used exceeds 50 weight times, the same as toluene does not have the effect of the amount used, and the volumetric efficiency also deteriorates, and the manufacturing cost of the compound having a phytoskeleton may increase.

反應溫度係根據所使用之原料、溶劑之種類而相異，以50~150℃為佳，較佳為60~130℃，更佳為70~120℃。反應係能以液體層析法等之分析手段來追蹤。The reaction temperature varies according to the types of raw materials and solvents used, and is preferably 50 to 150°C, preferably 60 to 130°C, and more preferably 70 to 120°C. The reaction system can be traced by analytical means such as liquid chromatography.

反應結束後之反應混合物中，通常除了包含已生成之前述式(1)所示之化合物以外，也包括未反應之硼酸類、鹼、觸媒、副反應生成物等。因此，可藉由慣用之方法，例如，過濾、濃縮、抽出、晶析、再結晶、再沉澱、活性碳處理或其酷似之金屬除去處理、管柱層析法等之分離手段，或組合該等而成之分離手段進行分離純化。例如，以藉由慣用之方法(添加鹼水溶液而形成水溶性複合物之方法等)除去硼酸類，進行活性碳處理或其酷似之金屬除去處理來除去鈀化合物後，藉由添加再結晶溶劑進行冷卻使其再結晶化，其次進行過濾分離為佳。再結晶之方法係與前述步驟2記載之方法相同。The reaction mixture after the completion of the reaction usually contains not only the compound represented by the aforementioned formula (1) that has been produced, but also unreacted boric acids, alkalis, catalysts, side reaction products, etc. Therefore, it can be separated by conventional methods such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or its similar metal removal treatment, column chromatography, etc., or a combination of the separation methods Separation and purification are carried out by means of separation. For example, after removing the boric acid by a conventional method (a method of adding an aqueous alkali solution to form a water-soluble complex, etc.), performing an activated carbon treatment or a metal removal treatment similar to it to remove the palladium compound, then adding a recrystallization solvent It is better to cool to recrystallize, and then to filter and separate. The method of recrystallization is the same as the method described in step 2 above.

藉由本發明之製造方法而得之前述式(1)所示之化合物之純度係可選自60~100%之廣泛範圍，以70%以上為佳，較佳為80%以上，更佳為90%以上，較更佳為95%以上。The purity of the compound represented by the aforementioned formula (1) obtained by the manufacturing method of the present invention can be selected from a wide range of 60-100%, preferably 70% or more, preferably 80% or more, more preferably 90% % Or more, more preferably 95% or more.

[具有茀骨架之化合物之特徵及用途] 本發明之具有茀骨架之化合物由於較佳係組合二苯基茀骨架及二萘基茀骨架與芳烴環，故不僅折射率、耐熱性為高，且作成聚合物時可減低雙折射。至今為止為了提升折射率，使用在茀骨架之9位上取代有集合環芳烴環之茀化合物，該物之折射率、耐熱性雖高，但會導致雙折射降低。相對於此，本發明之具有茀骨架之化合物或許由於係具有二苯基茀骨架及二萘基茀骨架，故即使折射率為高，雙折射仍也會變小。並且，芳烴環上由於具有1個以上之羥基，且茀化合物全體具有複數之羥基，故反應性為高。因此，本發明之具有茀骨架之化合物係可利用作為各種樹脂之原料(單體)。可使用作為例如，熱塑性樹脂(例如，聚酯樹脂、聚碳酸酯樹脂、聚酯碳酸酯樹脂、聚胺基甲酸酯樹脂等)或熱硬化性樹脂(例如，環氧樹脂、酚樹脂、熱硬化性聚胺基甲酸酯樹脂、(甲基)丙烯酸酯((甲基)丙烯酸酯)等)之多元醇成分。使用本發明之具有茀骨架之化合物作為多元醇成分時，或許係由於茀骨架之9位被萘環取代，且在茀骨架具有二芳基，故取得之樹脂具備能以高層次使高折射率與低雙折射性併存之優點。[Characteristics and Uses of Compounds with Fu skeleton] Since the compound with a pyrene skeleton of the present invention preferably combines a diphenyl pyrene skeleton, a dinaphthyl pyrene skeleton and an aromatic hydrocarbon ring, not only the refractive index and heat resistance are high, but also the birefringence can be reduced when it is made into a polymer. So far, in order to increase the refractive index, a pyridine compound substituted with an assembling aromatic hydrocarbon ring at the 9-position of the pyridine skeleton has been used. Although the refractive index and heat resistance of this compound are high, it will reduce the birefringence. In contrast, the compound with a sulphur skeleton of the present invention may have a diphenyl sulphate skeleton and a dinaphthyl sulphate skeleton, so even if the refractive index is high, the birefringence will still be small. In addition, since the aromatic hydrocarbon ring has one or more hydroxyl groups, and the entire stilbene compound has plural hydroxyl groups, the reactivity is high. Therefore, the compound having a 茀 skeleton of the present invention can be used as a raw material (monomer) of various resins. It can be used as, for example, thermoplastic resins (for example, polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.) or thermosetting resins (for example, epoxy resins, phenol resins, thermal Curable polyurethane resin, (meth)acrylate ((meth)acrylate, etc.) polyol component. When using the compound with a 茀 framework of the present invention as a polyol component, perhaps because the 9 position of the 茀 framework is substituted by a naphthalene ring and there is a diaryl group in the 茀 framework, the obtained resin has the ability to achieve high refractive index at a high level. The advantages of coexisting with low birefringence.

又，本發明之具有茀骨架之化合物係可泛用之溶劑中效率良好地調製衍生物。In addition, the compound having a citron skeleton of the present invention is a solvent that can be used in general to prepare derivatives efficiently.

本發明之具有茀骨架之化合物之融點係可選自100~300℃之廣泛範圍，以120~280℃為佳，較佳為130~260℃，更佳為140~240℃。 [實施例]The melting point of the compound having a citron skeleton of the present invention can be selected from a wide range of 100 to 300°C, preferably 120 to 280°C, preferably 130 to 260°C, and more preferably 140 to 240°C. [Example]

以下，根據實施例更加詳細說明本發明，但本發明只要不超出該要旨，即並非係受到以下之實施例所限定者。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples as long as it does not exceed the gist.

＜本發明之態樣I＞ 實施例中，各種測量係如以下所示來進行。<Aspect I of the Invention> In the examples, various measurement systems were performed as shown below.

(1)高速液體層析(HPLC)測量 使用日立製高速液體層析L-2350，在下表1之測量條件下測量實施例取得之化合物。實施例中，在並未特別界定時，%為去除HPLC中之溶劑而經補正之面積百分率值。(1) High-speed liquid chromatography (HPLC) measurement Using Hitachi high-speed liquid chromatography L-2350, the compounds obtained in the examples were measured under the measurement conditions shown in Table 1 below. In the examples, when not specifically defined,% is the area percentage value corrected by removing the solvent in the HPLC.

(2)NMR測量 使用下述之裝置、溶劑來測量實施例取得之化合物、樹脂。 裝置：日本電子公司製 JNM-AL400(400MHz) 溶劑：CDCl₃ (2) NMR measurement The following equipment and solvent were used to measure the compounds and resins obtained in the examples. Device: JNM-AL400 (400MHz) manufactured by JEOL Ltd. Solvent: CDCl ₃

(3)ICP測量 使用下述之裝置來測量實施例取得之化合物。 使用機器：Agilent Technologies 裝置：Agilent 5100 ICP-OES(3) ICP measurement The following devices were used to measure the compounds obtained in the examples. Machine used: Agilent Technologies Device: Agilent 5100 ICP-OES

(4)玻璃轉移溫度(Tg)測量、示差掃描熱量測量(DSC) 使用下述之裝置、條件來測量實施例取得之化合物、樹脂。 裝置：TA Instruments製Discovery DSC25 條件：升溫速度20℃/min(4) Glass transition temperature (Tg) measurement, differential scanning calorimetry (DSC) The following equipment and conditions were used to measure the compounds and resins obtained in the examples. Device: Discovery DSC25 manufactured by TA Instruments Conditions: heating rate 20℃/min

(5)顆粒(pellet)b*值測量 使用下述之裝置來測量實施例取得之樹脂。 裝置：X-Rite公司製 積分球分光光度計CE-7000A(5) Particle (pellet) b* value measurement The following device was used to measure the resin obtained in the example. Device: Integrating sphere spectrophotometer CE-7000A manufactured by X-Rite

(6)折射率(nD)、阿貝數測量 使用下述之裝置、手法來測量實施例取得之樹脂。 裝置：ATAGO公司製 DR-M2阿貝折射計 手法：測量使聚合結束後取得之樹脂顆粒溶解於二氯甲烷，並澆鑄於玻璃培養皿上進行乾燥所作成之膜在25℃之折射率(波長：589nm)及阿貝數(從波長：486nm、589nm、656nm處之折射率使用下述式來算出)。 ν=(nD-1)/(nF-nC) 尚且，本發明中，意指 nD：波長589nm處之折射率， nC：波長656nm處之折射率， nF：波長486nm處之折射率。(6) Refractive index (nD), Abbe number measurement The following devices and methods were used to measure the resin obtained in the examples. Device: DR-M2 Abbe refractometer manufactured by ATAGO Method: Measure the refractive index (wavelength: 589nm) and Abbe number (from the wavelength: 486nm) of the film made by dissolving the resin particles obtained after polymerization in dichloromethane and casting on a glass petri dish for drying. The refractive index at 589nm and 656nm is calculated using the following formula). ν=(nD-1)/(nF-nC) Furthermore, in the present invention, it means nD: the refractive index at a wavelength of 589nm, nC: the refractive index at a wavelength of 656nm, nF: The refractive index at a wavelength of 486nm.

(7)粉末X線繞射測量 使用RIGAKU RINT TTR III，在下述測量條件下進行測量。 X線源：Cu-Kα、輸出：50kV-300mA(15kW) DS：1/2°、HS：10mm、SS：1/2°、RS：0.15°、 Step：0.01°、掃描速度：1.0°/min(7) Powder X-ray diffraction measurement Use RIGAKU RINT TTR III to perform measurement under the following measurement conditions. X-ray source: Cu-Kα, output: 50kV-300mA (15kW) DS: 1/2°, HS: 10mm, SS: 1/2°, RS: 0.15°, Step: 0.01°, scanning speed: 1.0°/min

[實施例I-1] ＜步驟1＞ 在裝設有攪拌機、冷卻器，以及溫度計之燒瓶中，使2,7-二溴茀酮(以下，有略稱為DBFN之情況)101.4g(0.30莫耳)、苯基硼酸76.8g(0.63毫莫耳)溶解於甲苯1L及乙醇200mL之混合溶劑，再添加肆(三苯基膦)鈀1.7g(1.45毫莫耳)、2M碳酸鉀水溶液347mL後，藉由在80℃下攪拌6小時來進行反應。使用HPLC來確認反應之進行狀況，確認到DBFN之殘留量為0.1%以下時結束反應。減壓濃縮取得之反應液並餾除甲苯及乙醇後，對殘渣添加1M氫氧化鈉水溶液並氯仿進行萃取。使用活性碳對氯仿層進行脫鈀觸媒處理來去除殘留於系統內之鈀觸媒後，濃縮氯仿，在黃色結晶析出之時間點停止濃縮並直接進行再結晶。過濾取出已析出之黃色固結晶，藉由在85℃下乾燥24小時，以收率81%取得目的物之2,7-二苯基茀酮(以下，有略稱為DPFN之情況)之黃色結晶80.5g。使用HPLC測量取得之黃色結晶之純度為99.8%。[Example I-1] <Step 1> In a flask equipped with a stirrer, a cooler, and a thermometer, 101.4 g (0.30 mol) of 2,7-dibromopyrone (hereinafter referred to as DBFN) and 76.8 g (0.63 Millimoles) was dissolved in a mixed solvent of 1L toluene and 200mL ethanol, and 1.7g (1.45 millimoles) of palladium (triphenylphosphine) and 347mL of 2M potassium carbonate aqueous solution were added, followed by stirring at 80°C for 6 hours To react. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DBFN was confirmed to be 0.1% or less. After concentrating the obtained reaction solution under reduced pressure and distilling off toluene and ethanol, a 1M aqueous sodium hydroxide solution was added to the residue, and chloroform was extracted. The chloroform layer was depalladium catalyst treated with activated carbon to remove the palladium catalyst remaining in the system, and the chloroform was concentrated. The concentration was stopped at the time when the yellow crystals precipitated and the recrystallization was carried out directly. The precipitated yellow solid crystals were filtered out, and dried at 85°C for 24 hours to obtain the target 2,7-diphenylquinone (hereinafter, referred to as DPFN in the case of DPFN) with a yield of 81%. Crystal 80.5g. The purity of the yellow crystal obtained by HPLC measurement was 99.8%.

＜步驟2＞ 對裝設有攪拌機、冷卻器、水分離器，以及溫度計之燒瓶添加步驟1製造之DPFN56.5g(0.17莫耳)、2-萘酚58.8g(0.41莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.8g(0.24毫莫耳)、n-十二硫醇1.8g(0.01莫耳)、甲苯53mL、γ-丁內酯13mL後，減壓至55kPa後，升溫至100℃，在同溫度下進行攪拌10小時。使用HPLC來確認反應之進行狀況，確認到DPFN之殘留量為0.3%以下時結束反應。<Step 2> To a flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 56.5g (0.17 mol) of DPFN manufactured in Step 1, 58.8g (0.41 mol) of 2-naphthol, 12 tungsten ( VI) Phosphoric acid n-hydrate (H ₃ [PW ₁₂ O ₄₀ ]・nH ₂ O) 0.8 g (0.24 mmol), n-dodecanethiol 1.8 g (0.01 mol), toluene 53 mL, γ-butyrolone After 13 mL of the ester, the pressure was reduced to 55 kPa, then the temperature was raised to 100°C, and stirring was performed at the same temperature for 10 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DPFN was confirmed to be 0.3% or less.

反應後，添加25重量%氫氧化鈉水溶液，並將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水(稱為水洗步驟)。水洗步驟結束後，添加碳酸鉀1.2g(8.87毫莫耳)、碳酸伸乙酯37.4g(0.42莫耳)，在110℃下攪拌15小時來進行反應。使用HPLC來確認反應之進行狀況，確認到下述(8-1)所示之9,9’-雙(6-羥基-2-萘基)-2,7-二苯基茀之殘留量為0.2%以下時結束反應。After the reaction, a 25% by weight aqueous sodium hydroxide solution was added, and 12 tungsten (VI) phosphoric acid n-hydrate (H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O) was neutralized, and then the system was distilled off at 120°C The water (called the washing step). After the water washing step, 1.2 g (8.87 mmol) of potassium carbonate and 37.4 g (0.42 mol) of ethylene carbonate were added, and the mixture was stirred at 110°C for 15 hours to perform the reaction. Using HPLC to confirm the progress of the reaction, it was confirmed that the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylpyridine shown in (8-1) below was The reaction ends when it is less than 0.2%.

反應結束後，對取得之反應液添加水及25重量%氫氧化鈉水溶液，在85℃下攪拌5小時後，分離水層。藉由使取得之反應液冷卻至20℃並直接使其晶析，而取得目的之9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀(以下，有略稱為BNDP之情況)之淡黃色固體。取得之BNDP經過活性碳處理及水洗後，減壓加熱乾燥一晚，以收率78%、純度98.8%取得淡黃色固體。藉由ICP測量殘留金屬量，Pd為1ppm以下。DPFN為0.2%，APHA為500。After the completion of the reaction, water and a 25% by weight aqueous sodium hydroxide solution were added to the obtained reaction liquid, and after stirring at 85°C for 5 hours, the water layer was separated. The obtained reaction liquid was cooled to 20°C and directly crystallized to obtain the objective 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di Phenyl sulfone (hereinafter, abbreviated as BNDP) is a pale yellow solid. After the obtained BNDP was treated with activated carbon and washed with water, it was heated and dried under reduced pressure overnight, and a light yellow solid was obtained with a yield of 78% and a purity of 98.8%. The residual metal content was measured by ICP, and the Pd was less than 1 ppm. DPFN is 0.2% and APHA is 500.

將藉此合成之9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀25.91質量份、9,9-雙[4-(2-羥基乙氧基)苯基]茀16.44質量份、二苯基碳酸酯16.23質量份、及碳酸氫鈉3.15×10^-3 質量份放入附攪拌機及餾除裝置之反應釜中，進行氮取代3次後，將夾套加熱至200℃而使原料熔融。完全溶解後，花費5分鐘減壓至20kPa並同時以60℃/hr之速度使夾套升溫至260℃，而進行酯交換反應。其後，將夾套保持在260℃，花費50分鐘減壓至0.13kPa，在260℃、0.13kPa以下之條件下，進行聚合反應直到抵達指定之力矩為止。反應結束後，將經生成之樹脂予以顆粒化並同時取出，而取得聚碳酸酯樹脂之顆粒。藉由¹ H NMR來分析取得之聚碳酸酯樹脂，確認到9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀成分係相對於全單體成分而被導入有50mol%。取得之聚碳酸酯樹脂之折射率為1.682，阿貝數為17.1，Tg為177℃，顆粒b*值為13.5。The 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylsulfonate 25.91 parts by mass, 9,9-bis[4-(2 -Hydroxyethoxy) phenyl] 茀 16.44 parts by mass, 16.23 parts by mass of diphenyl carbonate, and 3.15×10 ^-3 parts by mass of sodium bicarbonate are placed in a reactor with agitator and distillation device for nitrogen substitution After 3 times, the jacket was heated to 200°C to melt the raw materials. After the complete dissolution, the pressure was reduced to 20 kPa in 5 minutes and the temperature of the jacket was raised to 260°C at a rate of 60°C/hr to proceed the transesterification reaction. Thereafter, the jacket was maintained at 260°C, and the pressure was reduced to 0.13 kPa in 50 minutes, and the polymerization reaction was carried out under the conditions of 260°C and 0.13 kPa or less until the specified torque was reached. After the reaction is completed, the formed resin is pelletized and taken out at the same time to obtain pellets of polycarbonate resin. The ^{obtained polycarbonate resin was analyzed by 1} H NMR, and it was confirmed that 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine is relatively 50 mol% of all monomer components are introduced. The obtained polycarbonate resin has a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177°C, and a particle b* value of 13.5.

[實施例I-2] 除了將步驟1中之苯基硼酸變更成苯基硼酸之酐以外，其他係與實施例I-1同樣地操作而取得目的之茀化合物(收率78%、純度98.8%)。藉由ICP測量殘留金屬量，Pd為1ppm以下。[Example I-2] Except that the phenylboronic acid in step 1 was changed to an anhydride of phenylboronic acid, the other systems were performed in the same manner as in Example I-1 to obtain the desired sesame compound (yield 78%, purity 98.8%). The residual metal content was measured by ICP, and the Pd was less than 1 ppm.

[實施例I-3] 除了將步驟1中之鹼變更成碳酸鈉以外，其他係與實施例I-1同樣地操作而取得茀化合物(收率78%，純度98.8%)。藉由ICP測量殘留金屬量，Pd為1ppm以下。[Example I-3] Except that the base in step 1 was changed to sodium carbonate, the other systems were performed in the same manner as in Example I-1 to obtain a stilbene compound (yield 78%, purity 98.8%). The residual metal content was measured by ICP, and the Pd was less than 1 ppm.

[實施例I-4] 除了將步驟1中之鈀系觸媒變更成Pd/SiO₂ 所示之PL觸媒以外，其他係與實施例I-1同樣地操作而取得茀化合物(收率78%，純度98.9%)。藉由ICP測量殘留金屬量，Pd為1ppm以下。[Example I-4] Except that the palladium-based catalyst in step 1 was changed to _{the PL catalyst shown by Pd/SiO 2} , the other systems were performed in the same manner as in Example I-1 to obtain a tea compound (yield 78 %, purity 98.9%). The residual metal content was measured by ICP, and the Pd was less than 1 ppm.

[實施例I-5] 除了將步驟2中之酸觸媒變更成矽鎢酸之n水合物(H₄ [SiW₁₂ O₄₀ ]・nH₂ O)以外，其他係與實施例I-1同樣地操作而取得茀化合物(收率78%，純度98.8%)。藉由ICP測量殘留金屬量，Pd為1ppm以下。[Example I-5] Except that the acid catalyst in step 2 was changed to n-hydrate of silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ]·nH ₂ O), the other systems were the same as in Example I-1 Operate carefully to obtain the Fu compound (yield 78%, purity 98.8%). The residual metal content was measured by ICP, and the Pd was less than 1 ppm.

[實施例I-6] 對裝設有攪拌機、冷卻器、水分離器，以及溫度計之燒瓶添加實施例I-1之步驟1所製造之DPFN28.1g(0.08莫耳)、2-萘酚29.3g(0.20莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.4g(0.12毫莫耳)、n-十二硫醇1.8g(0.01莫耳)、甲苯30mL、碳酸伸乙酯7.8g(0.09莫耳)後，減壓至55kPa後，升溫至100℃，在同溫度下進行攪拌3小時。使用HPLC來確認反應之進行狀況，確認到DPFN之殘留量為0.0%時結束反應。[Example I-6] To a flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 28.1 g (0.08 mol) of DPFN manufactured in step 1 of Example I-1 and 29.3 were added to the flask. g (0.20 mol), 12 tungsten (VI) phosphoric acid n hydrate (H ₃ [PW ₁₂ O ₄₀ ]・nH ₂ O) 0.4 g (0.12 millimoles), n-dodecanethiol 1.8 g (0.01 mol) Ears), 30 mL of toluene, and 7.8 g (0.09 mol) of ethylene carbonate, the pressure was reduced to 55 kPa, the temperature was raised to 100°C, and stirring was carried out at the same temperature for 3 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DPFN was confirmed to be 0.0%.

反應後，添加25重量%氫氧化鈉水溶液而將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水(稱為水洗步驟)。水洗步驟結束後，添加碳酸鉀0.6g(4.41毫莫耳)、碳酸伸乙酯29.4g(0.33莫耳)、二甲基甲醯胺100mL，在110℃下攪拌4小時來進行反應。使用HPLC來確認反應之進行狀況，確認到9,9’-雙(6-羥基-2-萘基)-2,7-二苯基茀之殘留量為0.0%時結束反應。After the reaction, a 25% by weight aqueous sodium hydroxide solution was added _{to neutralize 12 tungsten (VI) phosphoric acid n-hydrate (H 3} [PW ₁₂ O ₄₀ ] · nH ₂ O), and then the system was distilled off at 120°C. Water (called the water washing step). After the water washing step, 0.6 g (4.41 mmol) of potassium carbonate, 29.4 g (0.33 mol) of ethylene carbonate, and 100 mL of dimethylformamide were added, and the mixture was stirred at 110°C for 4 hours to perform the reaction. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylsulfone was 0.0%.

反應結束後，對取得之反應液添加水及25重量%氫氧化鈉水溶液並在85℃下進行攪拌1.5小時後，分離水層。藉由使取得之反應液冷卻至20℃並直接使其晶析，而取得BNDP。取得之BNDP經過活性碳處理及水洗後，減壓加熱乾燥一晚，以收率78%、純度98.8%取得白色結晶。又，Pd為1ppm以下，DPFN為0.0%，APHA為80，利用DSC之吸熱峰：237℃。將DSC圖表展示於圖1，將粉末X線測量圖表展示於圖2，將粉末X線測量之主要波峰展示於表2。After the completion of the reaction, water and a 25% by weight aqueous sodium hydroxide solution were added to the obtained reaction liquid and stirred at 85°C for 1.5 hours, and then the water layer was separated. BNDP is obtained by cooling the obtained reaction liquid to 20°C and directly crystallizing it. After the obtained BNDP was treated with activated carbon and washed with water, it was heated and dried under reduced pressure overnight, and white crystals were obtained with a yield of 78% and a purity of 98.8%. In addition, Pd is 1 ppm or less, DPFN is 0.0%, APHA is 80, and the endothermic peak by DSC: 237°C. The DSC chart is shown in Figure 1, the powder X-ray measurement chart is shown in Figure 2, and the main peaks of the powder X-ray measurement are shown in Table 2.

[實施例I-7] 對裝設攪拌機、冷卻器、水分離器，以及溫度計之燒瓶添加步驟1所製造之DPFN28.1g(0.08莫耳)、2-萘酚29.3g(0.20莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.8g(0.23毫莫耳)、n-十二硫醇1.8g(0.01莫耳)、甲苯45mL、碳酸伸乙酯37.20g(0.42莫耳)後，減壓至55kPa後，升溫至100℃，在同溫度下進行攪拌9小時。使用HPLC來確認反應之進行狀況，確認到DPFN之殘留量為0.0%時結束反應。 反應後，添加25重量%氫氧化鈉水溶液而將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水(稱為水洗步驟)。水洗步驟結束後，添加碳酸鉀0.6g(4.41毫莫耳)、二甲基甲醯胺100mL，並在110℃下攪拌4小時進行反應。使用HPLC來確認反應之進行狀況，確認到9,9’-雙(6-羥基-2-萘基)-2,7-二苯基茀之殘留量為0.0%以下時結束反應。[Example I-7] To a flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 28.1 g (0.08 mol) of DPFN manufactured in step 1 and 29.3 g (0.20 mol) of 2-naphthol were added, 12 tungsten (VI) phosphoric acid n hydrate (H ₃ [PW ₁₂ O ₄₀ ]・nH ₂ O) 0.8 g (0.23 mmol), n-dodecane mercaptan 1.8 g (0.01 mol), toluene 45 mL, carbonic acid After 37.20 g (0.42 mol) of ethylene glycol, the pressure was reduced to 55 kPa, and the temperature was raised to 100° C., and stirring was performed at the same temperature for 9 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DPFN was confirmed to be 0.0%. After the reaction, a 25% by weight aqueous sodium hydroxide solution was added _{to neutralize 12 tungsten (VI) phosphoric acid n-hydrate (H 3} [PW ₁₂ O ₄₀ ] · nH ₂ O), and then the system was distilled off at 120°C. Water (called the water washing step). After the water washing step, 0.6 g (4.41 millimoles) of potassium carbonate and 100 mL of dimethylformamide were added, and the mixture was stirred at 110° C. for 4 hours to perform the reaction. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylsulfone was 0.0% or less.

反應結束後，對取得之反應液添加水及25重量%氫氧化鈉水溶液，並在85℃下攪拌1.5小時後，分離水層。藉由使取得之反應液冷卻至20℃並直接使其晶析，而取得BNDP。取得之BNDP經活性碳處理及水洗後，減壓加熱乾燥一晚，以收率78%、純度98.8%取得白色結晶。又，Pd為1ppm以下，DPFN為0.0%，APHA為90。After the completion of the reaction, water and a 25% by weight aqueous sodium hydroxide solution were added to the obtained reaction liquid, and after stirring at 85°C for 1.5 hours, the water layer was separated. BNDP is obtained by cooling the obtained reaction liquid to 20°C and directly crystallizing it. After the obtained BNDP was treated with activated carbon and washed with water, it was heated and dried under reduced pressure overnight, and white crystals were obtained with a yield of 78% and a purity of 98.8%. In addition, Pd is 1 ppm or less, DPFN is 0.0%, and APHA is 90.

[比較例I-1] 除了在步驟1中，將反應溶劑變更成甲苯以外，其他係與實施例I-1同樣地操作來進行茀酮化合物之合成，但反應並未進行而無法取得目的之茀酮化合物。[Comparative Example I-1] Except that in Step 1, the reaction solvent was changed to toluene, the other systems were performed in the same manner as in Example I-1 to synthesize the stellone compound, but the reaction did not proceed and the desired stellone compound could not be obtained.

[比較例I-2] 除了將步驟1中之肆(三苯基膦)鈀之使用量變更成0.56g(0.48毫莫耳)以外，其他係與實施例I-1同樣地操作來進行茀化合物之合成，反應雖會進行，但造成二苯基體與單苯基體係以95：5(重量比)進行混合，而無法以高純度取得目的之茀酮化合物。[Comparative Example I-2] Except that the amount of palladium (triphenylphosphine) used in step 1 was changed to 0.56 g (0.48 millimoles), the other operations were carried out in the same manner as in Example I-1 to synthesize the stilbene compound, although the reaction was good However, the diphenyl body and the monophenyl system were mixed at a ratio of 95:5 (weight ratio), and the desired quinone compound could not be obtained with high purity.

[比較例I-3] 除了在步驟2中將酸觸媒變更成硫酸及3-巰基丙酸以外，其他係與實施例I-1同樣地操作來進行茀化合物之合成，但反應並未進行而無法取得目的之茀化合物。[Comparative Example I-3] Except that the acid catalyst was changed to sulfuric acid and 3-mercaptopropionic acid in step 2, the other systems were performed in the same manner as in Example I-1 to synthesize the stilbene compound, but the reaction did not proceed and the desired stilbene compound could not be obtained .

[參考例I-1] 除了在步驟1及步驟2中，並未進行活性碳處理以外，其他係與實施例I-1同樣地操作而取得茀化合物(BNDP)之黃色固體(收率78%，純度98.1%)。藉由ICP測量殘留金屬量，Pd為70ppm。APHA超過500。[Reference example I-1] Except that the activated carbon treatment was not performed in Step 1 and Step 2, the other operations were performed in the same manner as in Example I-1 to obtain a yellow solid (yield 78%, purity 98.1%) of the stilbene compound (BNDP). The residual metal content was measured by ICP, and the Pd was 70 ppm. APHA exceeds 500.

除了在步驟2中使用上述方法所合成之9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀以外，其他係與實施例1同樣地操作而取得聚碳酸酯樹脂之顆粒。藉由1H NMR分析取得之聚碳酸酯樹脂，確認到9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀成分係相對於全單體成分而被導入有50莫耳%。取得之聚碳酸酯樹脂之折射率為1.682，阿貝數為17.1，Tg為177℃，顆粒b＊值為32.3。Except for the 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine synthesized by the above method in step 2, the others are the same as in Example 1. The same procedure is used to obtain pellets of polycarbonate resin. According to the polycarbonate resin obtained by 1H NMR analysis, it was confirmed that the 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine component is relatively The monomer component is introduced at 50 mol%. The obtained polycarbonate resin has a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177°C, and a particle b* value of 32.3.

[參考例I-2] 除了在步驟2中將反應壓力變更成101.3kPa(常壓)以外，其他係與實施例I-1同樣地操作來進行茀化合物之合成，但反應並未完結，導致DPFN殘留5重量%，而引起BNDP之純度下降。並且，與實施例I-1之步驟2同樣地使用該單體所得之聚碳酸酯樹脂之顆粒b＊值為105。[Reference example I-2] Except that the reaction pressure was changed to 101.3kPa (normal pressure) in step 2, the other systems were the same as in Example I-1 to synthesize the stilbene compound, but the reaction was not completed, resulting in the remaining 5 wt% of DPFN, and Cause the purity of BNDP to decrease. In addition, the polycarbonate resin pellet obtained by using this monomer had a b* value of 105 in the same manner as in Step 2 of Example I-1.

[參考例I-3] 除了在步驟2中將反應溶劑變更成甲苯以外，其他係與實施例I-1同樣地操作來進行茀化合物之合成，但反應並未完結，導致DPFN殘留10重量%，而引起目的之BNDP之純度下降。取得之黃色固體之收率為50%，純度為88.7%。與實施例I-1之步驟2同樣地使用該單體所得之聚碳酸酯樹脂之顆粒b＊值為200。[Reference example I-3] Except that the reaction solvent was changed to toluene in step 2, the other systems were operated in the same manner as in Example I-1 to synthesize the stilbene compound, but the reaction was not completed, resulting in the remaining 10% by weight of DPFN, which caused the target BNDP Decrease in purity. The yield of the yellow solid obtained was 50%, and the purity was 88.7%. The b* value of the polycarbonate resin pellet obtained by using the monomer in the same manner as in Step 2 of Example I-1 was 200.

＜本發明之態樣II＞ 實施例中，各種測量係如以下所示般地實施。 (1)高速液體層析(HPLC)測量 使用日立製高速液體層析L-2350，在表3之測量條件下進行測量。實施例中，在並未特別界定時，%為除去HPLC中之溶劑而經過補正之面積百分率值。<Aspect II of the present invention> In the examples, various measurement systems were implemented as shown below. (1) High-speed liquid chromatography (HPLC) measurement High-speed liquid chromatography L-2350 manufactured by Hitachi was used, and the measurement was performed under the measurement conditions in Table 3. In the examples, when not specifically defined,% is the area percentage value after removing the solvent in the HPLC and being corrected.

(2)ICP測量 使用下述之裝置來測量實施例取得之化合物。 使用機器：Agilent Technologies 裝置：Agilent 5100 ICP-OES(2) ICP measurement The following devices were used to measure the compounds obtained in the examples. Machine used: Agilent Technologies Device: Agilent 5100 ICP-OES

(3)燃燒離子層析法測量 使用三菱化學製自動試料燃燒裝置AQF-2100及賽默飛世爾製離子層析系統DIONEX AQUION，在下述測量條件下進行硫元素之含量(S量)及溴元素之含量(Br量)之測量。尚且，檢量線作成係使用WAKO製溴化物離子標準液(Br-1000)及硫酸離子標準液(SO4(2-)：1000)來進行。 測量溫度：900℃→1000℃ 吸收液：含有過氧化氫之超純水 管柱：AS-17/AG-17 流速：1ml/min 槽溫度：40℃、管柱溫度：35℃(3) Combustion ion chromatography measurement Using Mitsubishi Chemical's automatic sample combustion device AQF-2100 and Thermo Fisher's ion chromatography system DIONEX AQUION, the sulfur content (S content) and bromine content (Br content) were measured under the following measurement conditions. In addition, the calibration curve was created using WAKO's bromide ion standard solution (Br-1000) and sulfate ion standard solution (SO4(2-): 1000). Measuring temperature: 900℃→1000℃ Absorbent: ultrapure water containing hydrogen peroxide String: AS-17/AG-17 Flow rate: 1ml/min Tank temperature: 40℃, column temperature: 35℃

(4)APHA測量 將使測量試料0.5g溶解於二甲基甲醯胺10ml溶液放入φ25mm之試驗管中，使用日本電色製工業(股)製TZ6000進行測量。(4) APHA measurement A solution of 0.5 g of the measurement sample dissolved in 10 ml of dimethylformamide was placed in a φ25 mm test tube, and measurement was performed using TZ6000 manufactured by Nippon Denshoku Industries Co., Ltd.

[實施例II-1] ＜步驟1及步驟2＞ 對裝設有攪拌機、冷卻器，以及溫度計之燒瓶添加2,7-二溴茀酮(以下，有略稱為DBFN之情況)28.1g(0.08莫耳)、2-萘酚28.8g(0.20莫耳)、n-十二硫醇1.8g(0.01莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.4g(0.12毫莫耳)、甲苯30ml、碳酸伸乙酯7.7g後，減壓至50kPa後，升溫至100℃，在同溫度下攪拌5小時。使用HPLC來確認反應之進行狀況，確認到DBFN之殘留量為0.0%時結束反應。[Example II-1] <Step 1 and Step 2> To a flask equipped with a stirrer, a cooler, and a thermometer, 28.1 g of 2,7-dibromopyrone (hereinafter referred to as DBFN for abbreviation) was added to a flask equipped with a stirrer, a cooler, and a thermometer. 0.08 mol), 2-naphthol 28.8g (0.20 mol), n-dodecanethiol 1.8g (0.01 mol), 12 tungsten (VI) phosphoric acid n hydrate (H ₃ [PW ₁₂ O ₄₀ ]・After nH ₂ O) 0.4 g (0.12 mmol), 30 ml of toluene, and 7.7 g of ethylene carbonate, the pressure was reduced to 50 kPa, the temperature was raised to 100° C., and the mixture was stirred at the same temperature for 5 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DBFN was confirmed to be 0.0%.

反應後，添加25重量%氫氧化鈉水溶液而將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水。其後，添加碳酸鉀0.6g(4.16毫莫耳)、碳酸伸乙酯28.9g(0.33莫耳)、二甲基甲醯胺100mL，在110℃下攪拌5小時進行反應。使用HPLC來確認反應之進行狀況，確認到9,9’-雙(6-羥基-2-萘基)-2,7-二溴茀之殘留量為0.0%時結束反應。反應結束後，對取得之反應液添加水及25重量%氫氧化鈉水溶液，在85℃下攪拌1.5小時後，分離水層。濃縮取得之反應液，添加甲苯使其溶解後，進行溫水洗淨5次。其後，以甲醇進行再結晶2次，減壓加熱乾燥一晚，以收率77%、純度97.4%取得9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二溴茀(以下，有略稱為BNDB的情況)之白色結晶。After the reaction, a 25% by weight aqueous sodium hydroxide solution was added _{to neutralize 12 tungsten (VI) phosphoric acid n-hydrate (H 3} [PW ₁₂ O ₄₀ ] · nH ₂ O), and then the system was distilled off at 120°C. water. Then, 0.6 g (4.16 mmol) of potassium carbonate, 28.9 g (0.33 mol) of ethylene carbonate, and 100 mL of dimethylformamide were added, and the mixture was stirred at 110°C for 5 hours to perform the reaction. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-dibromosulfonium was confirmed to be 0.0%. After the completion of the reaction, water and a 25% by weight aqueous sodium hydroxide solution were added to the obtained reaction liquid, and after stirring at 85°C for 1.5 hours, the water layer was separated. After concentrating the obtained reaction liquid, adding toluene to dissolve it, and washing with warm water 5 times. After that, it was recrystallized twice with methanol, heated and dried under reduced pressure overnight to obtain 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl] with a yield of 77% and a purity of 97.4%. -2,7-Dibromopyridinium (hereinafter, abbreviated as BNDB) is a white crystal.

＜步驟3＞ 對裝設有攪拌機、冷卻器、水分離器，以及溫度計之燒瓶添加步驟1所製造之BNDB44.7g(0.06莫耳)、苯基硼酸17.2g(0.14莫耳)、肆(三苯基膦)鈀0.7g(0.64毫莫耳)、2M碳酸鉀水溶液78ml、甲苯292ml、乙醇96ml後，在80℃下攪拌3小時。使用HPLC來確認反應之進行狀況，確認到BNDB之殘留量為0.0%時結束反應。反應後，過濾回收經析出之BNDP後，使其溶解於四氫呋喃中並進行活性碳處理後，以甲苯進行再結晶，減壓加熱乾燥取得之結晶一晚，以收率74%、純度99.2%取得9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀(以下，有略稱為BNDP之情況)之白色結晶。又，APHA為60，S為20ppm，Br為8ppm，Pd為5ppm，二苯基茀酮(以下，有省略為DPFN之情況)在使用HPLC測量時為0.0%。<Step 3> Add 44.7g (0.06 mol) of BNDB manufactured in step 1, 17.2g (0.14 mol) of phenylboronic acid, and four (triphenylphosphine) to a flask equipped with a stirrer, a cooler, a water separator, and a thermometer. After 0.7 g (0.64 millimoles) of palladium, 78 ml of 2M potassium carbonate aqueous solution, 292 ml of toluene, and 96 ml of ethanol, the mixture was stirred at 80°C for 3 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of BNDB was confirmed to be 0.0%. After the reaction, the precipitated BNDP was recovered by filtration, dissolved in tetrahydrofuran and treated with activated carbon, then recrystallized with toluene, heated under reduced pressure and dried overnight. The crystal was obtained with a yield of 74% and a purity of 99.2%. White crystals of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine (hereinafter, abbreviated as BNDP). In addition, APHA is 60, S is 20 ppm, Br is 8 ppm, Pd is 5 ppm, and diphenylfluoroketone (hereinafter, sometimes abbreviated as DPFN) is 0.0% when measured by HPLC.

[實施例II-2] ＜步驟1~3＞ 對裝設有攪拌機、冷卻器，以及溫度計之燒瓶添加2,7-二溴茀酮(以下，有略稱為DBFN之情況)28.1g(0.08莫耳)、2-萘酚28.8g(0.20莫耳)、n-十二硫醇0.2g(0.83毫莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.4g(0.12毫莫耳)、甲苯30ml、碳酸伸乙酯7.7g後，減壓至50kPa後，升溫至100℃，在同溫度下攪拌3小時。使用HPLC來確認反應之進行狀況，確認到DBFN之殘留量為0.0%時結束反應。[Example II-2] <Steps 1 to 3> 2,7-Dibromopyrone (hereinafter referred to as DBFN) 28.1g (0.08) was added to a flask equipped with a stirrer, a cooler, and a thermometer Mol), 2-naphthol 28.8g (0.20 mol), n-dodecanethiol 0.2g (0.83 mol), 12 tungsten (VI) phosphoric acid n hydrate (H ₃ [PW ₁₂ O ₄₀ ]・After nH ₂ O) 0.4 g (0.12 mmol), 30 ml of toluene, and 7.7 g of ethylene carbonate, the pressure was reduced to 50 kPa, the temperature was raised to 100° C., and the mixture was stirred at the same temperature for 3 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DBFN was confirmed to be 0.0%.

反應後，添加25重量%氫氧化鈉水溶液而將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水。其後，添加碳酸鉀0.6g(4.16毫莫耳)、碳酸伸乙酯28.9g(0.33莫耳)、二甲基甲醯胺100mL，在110℃下攪拌4小時。使用HPLC來確認反應之進行狀況，確認到9,9’-雙(6-羥基-2-萘基)-2,7-二溴茀之殘留量為0.0%時結束反應。After the reaction, a 25% by weight aqueous sodium hydroxide solution was added _{to neutralize 12 tungsten (VI) phosphoric acid n-hydrate (H 3} [PW ₁₂ O ₄₀ ] · nH ₂ O), and then the system was distilled off at 120°C. water. Then, 0.6 g (4.16 mmol) of potassium carbonate, 28.9 g (0.33 mol) of ethylene carbonate, and 100 mL of dimethylformamide were added, and the mixture was stirred at 110°C for 4 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-dibromosulfonium was confirmed to be 0.0%.

反應後，添加苯基硼酸22.3g(0.18莫耳)、肆(三苯基膦)鈀0.5g(0.42毫莫耳)、2M碳酸鉀水溶液91ml、甲苯170ml、乙醇100ml後，在80℃下攪拌3小時。使用HPLC來確認反應之進行狀況，確認到BNDB之殘留量為0.0%時結束反應。反應後，過濾回收經析出之BNDP後，使其溶解於四氫呋喃並進行活性碳處理後，以甲苯進行再結晶，減壓加熱乾燥取得之結晶一晚，以收率75%、純度99.0%取得9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀(以下，有略稱為BNDP之情況)之白色結晶。又，APHA為80，S為8ppm，Br為15ppm，Pd為3ppm，DPFN使用HPLC測量時為0.0%。After the reaction, 22.3 g (0.18 mol) of phenylboronic acid, 0.5 g (0.42 mmol) of palladium (triphenylphosphine), 91 ml of 2M potassium carbonate aqueous solution, 170 ml of toluene, and 100 ml of ethanol were added, followed by stirring at 80°C 3 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of BNDB was confirmed to be 0.0%. After the reaction, the precipitated BNDP was recovered by filtration, dissolved in tetrahydrofuran and treated with activated carbon, then recrystallized with toluene, and heated under reduced pressure to dry the crystals obtained overnight. The yield was 75% and the purity was 99.0%. ,9-Bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridine (hereinafter, abbreviated as BNDP) is a white crystal. In addition, APHA is 80, S is 8 ppm, Br is 15 ppm, Pd is 3 ppm, and DPFN is 0.0% when measured by HPLC.

[比較例II-1] 除了在步驟3中將反應溶劑變更成甲苯以外，其他係與實施例II-1同樣地操作來進行茀酮化合物之合成，但反應並未進行而無法取得目的之茀酮化合物。[Comparative Example II-1] Except that the reaction solvent was changed to toluene in step 3, the other systems were performed in the same manner as in Example II-1 to synthesize the stellone compound, but the reaction did not proceed and the desired stellone compound could not be obtained.

[比較例II-2] 除了將步驟3中之肆(三苯基膦)鈀之使用量變更成0.56g(0.48毫莫耳)以外，其他係與實施例II-1同樣地操作來進行茀化合物之合成，反應雖會進行，但導致二苯基體與單苯基體以95：5(重量比)進行混合，而無法以高純度取得目的之茀酮化合物。[Comparative Example II-2] Except that the amount of palladium (triphenylphosphine) used in step 3 was changed to 0.56 g (0.48 millimoles), the others were operated in the same manner as in Example II-1 to synthesize the stilbene compound, although the reaction was good However, the diphenyl body and the monophenyl body were mixed at a ratio of 95:5 (weight ratio), and the desired quinone compound could not be obtained with high purity.

[比較例II-3] 除了在步驟1中將酸觸媒變更成硫酸及3-巰基丙酸以外，其他係與實施例II-1同樣地操作來進行茀化合物之合成，但反應並未進行而無法取得目的之茀化合物。[Comparative Example II-3] Except that the acid catalyst was changed to sulfuric acid and 3-mercaptopropionic acid in step 1, the other methods were performed in the same manner as in Example II-1 to synthesize the stilbene compound, but the reaction did not proceed and the desired stilbene compound could not be obtained .

[比較例II-4] 在裝設有攪拌機、冷卻器，以及溫度計之燒瓶中，使2,7-二溴茀酮(以下，有略稱為DBFN之情況)101.4g(0.30莫耳)、苯基硼酸76.8g(0.63毫莫耳)溶解於甲苯1L及乙醇200mL之混合溶劑中，再添加肆(三苯基膦)鈀1.7g(1.45毫莫耳)、2M碳酸鉀水溶液347mL後，藉由在80℃下攪拌6小時來進行反應。使用HPLC來確認反應之進行狀況，確認到DBFN之殘留量為0.1%以下時結束反應。減壓濃縮取得之反應液並餾除甲苯及乙醇後，對殘渣添加1M氫氧化鈉水溶液並以氯仿進行萃取。濃縮氯仿，在黃色結晶析出之時間點停止濃縮並直接進行再結晶。過濾取出經析出之黃色固結晶，藉由在85℃下乾燥24小時，以80.5g、收率81%取得目的物之2,7-二苯基茀酮(以下，有略稱為DPFN之情況)之黃色結晶。使用HPLC測量取得之黃色結晶之純度時為99.8%。[Comparative Example II-4] In a flask equipped with a stirrer, a cooler, and a thermometer, 101.4 g (0.30 mol) of 2,7-dibromopyrone (hereinafter referred to as DBFN) and 76.8 g (0.63 Millimoles) was dissolved in a mixed solvent of 1L toluene and 200mL ethanol, and 1.7g (1.45 millimoles) of palladium (triphenylphosphine) and 347mL of 2M potassium carbonate aqueous solution were added, followed by stirring at 80°C for 6 Hours to react. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DBFN was confirmed to be 0.1% or less. After concentrating the obtained reaction solution under reduced pressure and distilling off toluene and ethanol, 1M aqueous sodium hydroxide solution was added to the residue, and extraction was performed with chloroform. Concentrate the chloroform, stop the concentration at the time when the yellow crystals precipitate out, and proceed directly to recrystallization. The precipitated yellow solid crystals were filtered out, and dried at 85°C for 24 hours to obtain the target 2,7-diphenylquinone (hereinafter referred to as DPFN) with a yield of 80.5g and a yield of 81%. ) Of yellow crystals. The purity of the yellow crystal obtained by HPLC measurement was 99.8%.

對裝設有攪拌機、冷卻器、水分離器，以及溫度計之燒瓶添加上述取得之DPFN56.5g(0.17莫耳)、2-萘酚58.8g(0.41莫耳)、12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)0.8g(0.24毫莫耳)、n-十二硫醇3.6g(0.02莫耳)、甲苯53mL、γ-丁內酯13mL後，減壓至55kPa後，升溫至100℃，在同溫度下進行攪拌10小時。使用HPLC來確認反應之進行狀況，確認到DPFN之殘留量為0.3%以下時結束反應。Add 56.5g (0.17 mol) of DPFN obtained above, 58.8g (0.41 mol) of 2-naphthol, 12 tungsten (VI) phosphoric acid n hydrated to a flask equipped with a stirrer, a cooler, a water separator, and a thermometer. (H ₃ [PW ₁₂ O ₄₀ ]·nH ₂ O) 0.8g (0.24 millimoles), n-dodecanethiol 3.6g (0.02 mol), toluene 53mL, γ-butyrolactone 13mL, and then subtract After pressing to 55kPa, the temperature was raised to 100°C, and stirring was carried out at the same temperature for 10 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when the residual amount of DPFN was confirmed to be 0.3% or less.

反應後，添加25重量%氫氧化鈉水溶液而將12鎢(VI)磷酸n水合物(H₃ [PW₁₂ O₄₀ ]・nH₂ O)予以中和後，在120℃下餾除系統內之水(稱為水洗步驟)。水洗步驟結束後，添加碳酸鉀1.2g(8.87毫莫耳)、碳酸伸乙酯37.4g(0.42莫耳)，在110℃下攪拌15小時來進行反應。使用HPLC來確認反應之進行狀況，確認到9,9’-雙(6-羥基-2-萘基)-2,7-二苯基茀之殘留量為0.2重%以下時結束反應。After the reaction, a 25% by weight aqueous sodium hydroxide solution was added _{to neutralize 12 tungsten (VI) phosphoric acid n-hydrate (H 3} [PW ₁₂ O ₄₀ ] · nH ₂ O), and then the system was distilled off at 120°C. Water (called the water washing step). After the water washing step, 1.2 g (8.87 mmol) of potassium carbonate and 37.4 g (0.42 mol) of ethylene carbonate were added, and the mixture was stirred at 110°C for 15 hours to perform the reaction. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the residual amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylsulfone was 0.2% by weight or less.

反應結束後，對取得之反應液添加水及25重量%氫氧化鈉水溶液，在85℃下攪拌5小時後，分離水層。藉由使取得之反應液冷卻至20℃並直接使其晶析，而取得目的之BNDP之淡黃色固體。水洗取得之BNDP後，減壓加熱乾燥一晚，以收率78%、純度98.8%取得淡黃色固體。又，APHA為超過500，S為235ppm，Br為170ppm，Pd為70ppm，DPFN使用HPLC測量時為0.2%。 [產業上之可利用性]After the completion of the reaction, water and a 25% by weight aqueous sodium hydroxide solution were added to the obtained reaction liquid, and after stirring at 85°C for 5 hours, the water layer was separated. The obtained reaction liquid was cooled to 20°C and directly crystallized to obtain the objective BNDP light yellow solid. After washing the obtained BNDP with water, it was heated and dried under reduced pressure overnight to obtain a pale yellow solid with a yield of 78% and a purity of 98.8%. In addition, APHA is more than 500, S is 235 ppm, Br is 170 ppm, Pd is 70 ppm, and DPFN is 0.2% when measured by HPLC. [Industrial availability]

根據本發明之具有茀骨架之化合物及其之製造方法，由於能效率良好地製造具有高折射率、耐熱性、低雙折射等之優異特性之樹脂之原料(單體)，故可適宜使用於樹脂之原料(單體)，衍生物之反應成分等。According to the compound having a 茀 skeleton and its production method of the present invention, since the raw material (monomer) of a resin with excellent characteristics such as high refractive index, heat resistance, and low birefringence can be produced efficiently, it can be suitably used in Resin raw materials (monomers), reaction components of derivatives, etc.

因此，本發明之具有茀骨架之化合物或其衍生物，或將新穎之具有茀骨架之化合物作為原料(單體)之樹脂係可使用於例如，膜、透鏡、稜鏡、光碟、透明導電性基板、光學卡、光學片、光纖、光學膜、光學過濾器、硬塗覆膜等之光學構件，尤其係極度適宜使用於透鏡。Therefore, the compound or its derivative with a 茀 skeleton of the present invention, or a resin system using a novel compound with a 茀 skeleton as a raw material (monomer) can be used in, for example, films, lenses, scallops, optical discs, transparent conductivity Optical components such as substrates, optical cards, optical sheets, optical fibers, optical films, optical filters, hard coating films, etc., are especially suitable for use in lenses.

[圖1]展示實施例I-6取得之9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀之示差掃描熱量測量(DSC)曲線的圖。 [圖2]展示實施例I-6取得之9,9-雙[6-(2-羥基乙氧基)-2-萘基]-2,7-二苯基茀之粉末X線測量圖表的圖。[Figure 1] shows the differential scanning calorimetry (DSC) of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylpyridium obtained in Example I-6 ) Graph of the curve. [Figure 2] A graph showing the powder X-ray measurement of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenyl sulfonate obtained in Example I-6 Figure.

Claims (15)

一種下述式(1)所示之具有茀骨架之化合物；

式中，R¹ 表示氫原子、鹵素原子，或碳數1~12之可包含芳香族基之烴基，Ar¹ 及Ar² 係各自獨立表示碳數6~12之可具有取代基之芳香族基，L¹ 表示碳數1~12之伸烷基，m1及n1係相同或相異地表示0~4之整數，m2及n2係相同或相異地表示0~3之整數，m1+m2≧1；但，m1+n1為4以下之整數，m2+n2為3以下之整數；о1及о2係各自獨立表示0~5之整數。A compound having a citron skeleton represented by the following formula (1);

In the formula, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms that may contain an aromatic group, and Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 12 carbon atoms that may have a substituent , L ¹ represents an alkylene group with 1 to 12 carbon atoms, m1 and n1 represent the same or different integers from 0 to 4, m2 and n2 represent the same or different integers from 0 to 3, m1+m2≧1; However, m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less; о1 and о2 each independently represent an integer of 0-5. 如請求項1之具有茀骨架之化合物，其中前述式(1)所示之具有茀骨架之化合物中之硫元素之含量為200ppm以下。The compound having a turbidity skeleton according to claim 1, wherein the content of sulfur in the compound with a turbidity skeleton represented by the aforementioned formula (1) is 200 ppm or less. 如請求項1或2之具有茀骨架之化合物，其中前述式(1)所示之具有茀骨架之化合物中之鈀元素之含量為滿足下述式(2)； 0≦Pd≦50ppm　　　　(2)。According to claim 1 or 2, the compound having a turbidity skeleton, wherein the content of the palladium element in the compound with a turbidity skeleton represented by the aforementioned formula (1) satisfies the following formula (2); 0≦Pd≦50ppm　　　　 (2). 如請求項1或2之具有茀骨架之化合物，其中使前述式(1)所示之化合物溶解於二甲基甲醯胺而成之5重量%溶液之APHA為500以下。The compound having a 茀 skeleton according to claim 1 or 2, wherein the APHA of a 5 wt% solution obtained by dissolving the compound represented by the aforementioned formula (1) in dimethylformamide is 500 or less. 如請求項1或2之具有茀骨架之化合物，其中前述式(1)所示之化合物中之溴元素之含量為150ppm以下。According to claim 1 or 2, the compound having a chlorophyll skeleton, wherein the content of the bromine element in the compound represented by the aforementioned formula (1) is 150 ppm or less. 如請求項1或2之具有茀骨架之化合物，其中前述式(1)為下述式(1a)~(1d)所示當中之1者；

式中，R² ~R¹³ 係各自獨立氫原子、鹵素原子，或碳數1~12之可包含芳香族基之烴基；Ar¹ 、Ar² 、L¹ 及о1係與前述式(1)中相同。According to claim 1 or 2, the compound having a citron skeleton, wherein the aforementioned formula (1) is one of the following formulas (1a) to (1d);

In the formula, R ² to R ¹³ are independently hydrogen atoms, halogen atoms, or hydrocarbon groups with 1 to 12 carbon atoms that may contain aromatic groups; Ar ¹ , Ar ² , L ¹ and о1 are the same as those in the aforementioned formula (1) the same. 如請求項6之具有茀骨架之化合物，其中前述式(1)為前述式(1b)。The compound having a fluoride skeleton according to claim 6, wherein the aforementioned formula (1) is the aforementioned formula (1b). 如請求項1或2之具有茀骨架之化合物，其中前述式(1)中之Ar¹ 及Ar² 為苯基或萘基。According to claim 1 or 2, the compound having a sulfonium skeleton, wherein Ar ¹ and Ar ² in the aforementioned formula (1) are phenyl or naphthyl. 如請求項1或2之具有茀骨架之化合物，其中前述式(1)為下述式(1-b)所示之化合物；

。The compound having a citron skeleton according to claim 1 or 2, wherein the aforementioned formula (1) is a compound represented by the following formula (1-b);

. 如請求項9之化合物，其中式(1-b)所示之化合物中之二苯基茀酮之含量為0.2%以下。The compound of claim 9, wherein the content of diphenylquinone in the compound represented by formula (1-b) is 0.2% or less. 如請求項9之化合物，其中其之結晶在示差掃描熱量分析下，在230~247℃具有吸熱峰。Such as the compound of claim 9, wherein its crystal has an endothermic peak at 230~247°C under differential scanning calorimetry analysis. 如請求項9之化合物，其中其之結晶在利用Cu-Kα線而得之粉末X線繞射圖型中之繞射角2θ為10.6±0.2°、10.8±0.2°、17.1±0.2°、17.6±0.2°及18.7±0.2°處具有波峰。Such as the compound of claim 9, wherein the diffraction angle 2θ of its crystal in the powder X-ray diffraction pattern obtained by using Cu-Kα line is 10.6±0.2°, 10.8±0.2°, 17.1±0.2°, 17.6 There are crests at ±0.2° and 18.7±0.2°. 一種具有茀骨架之化合物之製造方法，其係前述式(1)所示之具有茀骨架之化合物之製造方法，其特徵為包含至少下述之步驟1及步驟2而成； 步驟1：使下述式(3)所示之茀酮類與下述式(4)或(5)所示之硼酸類在反應溶劑中，在鹼及鈀系觸媒之存在下進行反應的步驟； 步驟2：使步驟1所製造之反應物(6)與下述式(7)所示之醇類在反應溶劑中，在酸觸媒之存在下，減壓下使其反應，反應後，不取出進行中和所而得之下述式(8)所示之反應物而直接在鹼之存在下與碳酸伸乙酯反應來製造目的物的步驟；

式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子；

式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子；l為0、1或2，l=2時，R¹⁴ 可為相同亦可為相異；

式中，Ar¹ 及Ar² 係與式(1)中相同；

式中，p1及p2係相同或相異地為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同；

式中，R¹ 、Ar¹ 及Ar² 係與式(1)中相同；p1及p2係與式(7)中相同；n1及n2為0~3之整數。A method for producing a compound with a stilbene skeleton, which is the method for producing a compound with a stilbene skeleton represented by the aforementioned formula (1), characterized by including at least the following steps 1 and 2; Step 1: Make the following The step of reacting the ketones represented by the formula (3) and the boric acids represented by the following formula (4) or (5) in the reaction solvent in the presence of a base and a palladium-based catalyst; Step 2: The reactant (6) produced in step 1 and the alcohol represented by the following formula (7) are reacted in the reaction solvent in the presence of an acid catalyst under reduced pressure. After the reaction, it is not taken out. The step of directly reacting with the resulting reactant represented by the following formula (8) with ethylene carbonate in the presence of a base to produce the target product;

In the formula, X ¹ is a substituent at position 1, 2, 3 or 4 and represents a halogen atom, and X ² is a substituent at position 5, 6, 7 or 8 and represents a halogen atom;

In the formula, Y represents an aromatic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, a halogen atom; l is 0, 1 or 2, and when l=2, R ¹⁴ can be the same or phase different;

In the formula, Ar ¹ and Ar ² are the same as in formula (1);

In the formula, p1 and p2 are the same or differently an integer from 0 to 4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1);

In the formula, R ¹ , Ar ¹ and Ar ² are the same as in formula (1); p1 and p2 are the same as in formula (7); n1 and n2 are integers from 0 to 3. 一種具有茀骨架之化合物之製造方法，其係前述式(1)所示之具有茀骨架之化合物之製造方法，其特徵為包含至少下述之步驟1~3而成； 步驟1：使下述式(13)所示之茀酮類與下述式(14)所示之醇類在反應溶劑中，在酸觸媒之存在下使其反應而取得下述式(15)所示之化合物的步驟； 步驟2：使下述式(15)所示之化合物與碳酸伸乙酯在反應溶劑中，鹼之存在下進行反應而取得下述式(16)所示之化合物的步驟； 步驟3：使下述式(16)所示之化合物與下述式(17)或(18)所示之硼酸類在反應溶劑中，在鹼及鈀系觸媒之存在下進行反應，而取得前述式(1)所示之化合物的步驟；

式中，X¹ 為1位、2位、3位或4位之取代基，且表示鹵素原子，X² 為5位、6位、7位或8位之取代基，且表示鹵素原子；

式中，p1及p2係相同或相異為0~4之整數，R¹ 、n1及n2係與前述式(1)中相同；

式中，X¹ 及X² 係與前述式(13)中相同；R¹ 、p1及p2係與式(14)中相同；n1及n2為0~3之整數；

式中，X¹ 及X² 係與前述式(13)中相同；R¹ 、L¹ 、m1、m2、n1、n2、o1及o2係與式(1)中相同；

式中，Y表示芳香族基，R¹⁴ 表示氫原子、烷基、烯基、烷氧基、鹵素原子；l為0、1或2，l=2時，R¹⁴ 可為相同或亦可為相異。A method for producing a compound having a stilbene skeleton, which is the method for producing a compound having a stilbene skeleton represented by the aforementioned formula (1), characterized by including at least the following steps 1 to 3; Step 1: Make the following The ketones represented by the formula (13) and the alcohols represented by the following formula (14) are reacted in the reaction solvent in the presence of an acid catalyst to obtain the compound represented by the following formula (15) Step; Step 2: A step of reacting the compound represented by the following formula (15) with ethylene carbonate in the reaction solvent in the presence of a base to obtain the compound represented by the following formula (16); Step 3: The compound represented by the following formula (16) and the boric acid represented by the following formula (17) or (18) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst to obtain the aforementioned formula ( 1) The steps of the compound shown;

In the formula, X ¹ is a substituent at position 1, 2, 3 or 4 and represents a halogen atom, and X ² is a substituent at position 5, 6, 7 or 8 and represents a halogen atom;

In the formula, p1 and p2 are the same or different as an integer of 0-4, and R ¹ , n1 and n2 are the same as in the aforementioned formula (1);

In the formula, X ¹ and X ² are the same as in the aforementioned formula (13); R ¹ , p1 and p2 are the same as in the formula (14); n1 and n2 are integers from 0 to 3;

In the formula, X ¹ and X ² are the same as in the aforementioned formula (13); R ¹ , L ¹ , m1, m2, n1, n2, o1 and o2 are the same as in the formula (1);

In the formula, Y represents an aromatic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, a halogen atom; l is 0, 1 or 2, and when l=2, R ¹⁴ may be the same or may be Different. 一種如請求項1之具有茀骨架之化合物之使用方法，其係作為熱塑性樹脂之原料。A method for using a compound having a 茀 skeleton as in claim 1, which is used as a raw material for a thermoplastic resin.

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