TWI691485B - Method for manufacturing diamine compound and its intermediate - Google Patents
Method for manufacturing diamine compound and its intermediate Download PDFInfo
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- TWI691485B TWI691485B TW105107205A TW105107205A TWI691485B TW I691485 B TWI691485 B TW I691485B TW 105107205 A TW105107205 A TW 105107205A TW 105107205 A TW105107205 A TW 105107205A TW I691485 B TWI691485 B TW I691485B
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- BCIGXGFGWJXDCK-UHFFFAOYSA-N CC(C)(C)OC(N(CC(CC1)CCN1c(cc1)ccc1[N+]([O-])=O)c(cc1)ccc1[N+]([O-])=O)=O Chemical compound CC(C)(C)OC(N(CC(CC1)CCN1c(cc1)ccc1[N+]([O-])=O)c(cc1)ccc1[N+]([O-])=O)=O BCIGXGFGWJXDCK-UHFFFAOYSA-N 0.000 description 1
- JZJSVUPFMWVQFS-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1NCC(CC1)CCN1c(cc1)ccc1[N+]([O-])=O)=O Chemical compound [O-][N+](c(cc1)ccc1NCC(CC1)CCN1c(cc1)ccc1[N+]([O-])=O)=O JZJSVUPFMWVQFS-UHFFFAOYSA-N 0.000 description 1
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
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- C09K19/56—Aligning agents
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Abstract
本發明提供一種可作為用以製造液晶配向膜之聚醯亞胺系聚合物之原料等而有用之二胺化合物及其中間體之新穎製造方法。 The present invention provides a novel method for producing a diamine compound and its intermediate useful as a raw material for a polyimide-based polymer used for manufacturing liquid crystal alignment films.
將對-氟硝基苯(D)與4-(胺基甲基)哌啶(E)於自二甲基乙醯胺、1,3-二甲基-2-咪唑啶酮、二甲基亞碸及N-甲基吡咯啶酮所成之群選出之溶劑中反應而獲得以式(C)表示之化合物。該化合物之胺基藉由第三丁氧羰基化而獲得以式(B)表示之化合物。進而,將該化合物還原獲得以式(A)表示之化合物。 Combine p-fluoronitrobenzene (D) and 4-(aminomethyl)piperidine (E) in dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl The compound represented by the formula (C) is obtained by reacting a solvent selected from the group consisting of sulfonamide and N-methylpyrrolidone. The amine group of this compound is obtained by the third butoxycarbonylation to obtain the compound represented by the formula (B). Furthermore, this compound is reduced to obtain a compound represented by formula (A).
Description
本發明有關可作為用以製造液晶配向膜之聚醯亞胺系聚合物之原料等而有用之二胺化合物及其中間體之新穎製造方法。 The present invention relates to a novel manufacturing method of diamine compounds and intermediates which are useful as raw materials for polyimide-based polymers used for manufacturing liquid crystal alignment films.
現在,於液晶顯示元件中所用之液晶配向膜中,多數情況係使用聚醯亞胺膜,聚醯亞胺膜之液晶配向膜係藉由如下方法製作:將聚醯亞胺前驅物之聚醯胺酸溶液或於溶劑中有可溶性之聚醯亞胺溶液塗佈於基板上並燒成,對所得膜進行摩擦處理等之配向處理之方法(參考專利文獻1、2)。 At present, in the liquid crystal alignment film used in the liquid crystal display element, the polyimide film is mostly used. The liquid crystal alignment film of the polyimide film is produced by the following method: the polyimide precursor polyimide A method of applying an amino acid solution or a polyimide solution soluble in a solvent on a substrate and firing it, and performing an alignment treatment such as a rubbing treatment on the resulting film (refer to Patent Documents 1 and 2).
此聚醯胺酸或聚醯亞胺一般係藉由四羧酸二酐等之四羧酸衍生物與二胺之縮聚合反應而製造。 This polyamic acid or polyimide is generally produced by polycondensation of tetracarboxylic acid derivatives such as tetracarboxylic dianhydride and diamine.
該聚醯胺酸或聚醯亞胺等之原料的二胺對於由其所得之液晶配向膜之特性亦即液晶顯示元件之特性的影響至為重要,過去以來已使用且提案各種二胺化合物。 The diamine of the raw material such as polyamic acid or polyimide has an important influence on the characteristics of the liquid crystal alignment film obtained therefrom, that is, the characteristics of the liquid crystal display element, and various diamine compounds have been used and proposed in the past.
專利文獻1:日本特開平7-120769號公報 Patent Literature 1: Japanese Patent Laid-Open No. 7-120769
專利文獻2:日本特開平9-146100號公報 Patent Document 2: Japanese Patent Laid-Open No. 9-146100
作為即使以摩擦法或光配向法進行配向處理,亦可獲得電壓保持率高、液晶之配向性優異、因直流電壓而累積之殘留電荷少的液晶配向膜之聚醯胺酸或聚醯亞胺的原料之二胺化合物,本發明人等發現以下述式(A)表示之二胺。 Polyamide acid or polyimide can be obtained as a liquid crystal alignment film with high voltage retention, excellent liquid crystal alignment, and low residual charge accumulated due to DC voltage even if the alignment process is performed by the rubbing method or the optical alignment method The raw material of the diamine compound, the present inventors discovered the diamine represented by the following formula (A).
作為上述二胺化合物之製造方法,本發明人等探討將對-氟硝基苯與4-(胺基甲基)哌啶反應,製造二硝基化合物,供於第三丁氧羰基化後進行還原之方法並實施。 As a method for producing the above-mentioned diamine compound, the present inventors have investigated the reaction of p-fluoronitrobenzene with 4-(aminomethyl)piperidine to produce a dinitro compound for the third butoxycarbonylation. The method of reduction and implementation.
然而,若觀察實施該製造方法,則生成各前步驟所得之上述二胺之中間體,而成為必須將其單離之情況,因此產率降低。且對-氟硝基苯與4-(胺基甲基)哌 啶反應時,在該反應之一般條件的碳酸鉀存在下使用DMF(N,N-二甲基甲醯胺)等之通常溶劑作為溶劑時,氟原子與源自DMF之二甲胺基進行取代反應,而副生對-硝基-N,N-二甲基苯胺,進而有產率降低之問題。 However, if the production method is observed and implemented, the intermediate of the diamine obtained in each previous step is generated, and it is necessary to separate it, so the yield is reduced. P-fluoronitrobenzene and 4-(aminomethyl)piper In the pyridine reaction, when a common solvent such as DMF (N,N-dimethylformamide) is used as a solvent in the presence of potassium carbonate under the general conditions of the reaction, the fluorine atom is substituted with the dimethylamino group derived from DMF The reaction, while the by-product p-nitro-N,N-dimethylaniline, has the problem of reduced yield.
本發明之目的在於提供可解決上述問題,並且反應速度快、容積效率高、副產物少、為高純度且無單離中間體之必要而以高產率製造以上述式(A)表示之二胺化合物及其中間體之方法。 The purpose of the present invention is to provide a diamine represented by the above formula (A) that can solve the above problems, has a fast reaction rate, high volumetric efficiency, few by-products, is of high purity, and does not require an isolated intermediate, and is produced in high yield Methods of compounds and their intermediates.
本發明人等鑑於上述狀況積極檢討之結果,發現可達成上述目的之製造以上述式(A)表示之二胺化合物及其中間體之方法,因而完成本發明。 The inventors of the present invention have found a method for producing the diamine compound represented by the above formula (A) and its intermediates in view of the results of the positive review of the above situation, and have completed the present invention.
亦即,本發明係以下述為要旨。 That is, the present invention is based on the following.
1.一種4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶(C)之製造方法,係將對-氟硝基苯與4-(胺基甲基)哌啶於自二甲基乙醯胺、1,3-二甲基-2-咪唑啶酮、二甲基亞碸及N-甲基吡咯啶酮所成之群選出之至少一種溶劑中反應:
2.如上述1之製造方法,其係在鹼存在下反應。 2. The production method as described in 1 above, which reacts in the presence of a base.
3.如上述1或2之製造方法,其中相對於4-(胺基甲基)哌啶1莫耳,與2~10莫耳之對-氟硝基苯反應。 3. The manufacturing method according to 1 or 2 above, wherein 1 mol of 4-(aminomethyl)piperidine is reacted with 2-10 mol of p-fluoronitrobenzene.
4.如上述1~3中任一項之製造方法,其中前述溶劑為N-甲基吡咯啶酮。 4. The production method according to any one of 1 to 3 above, wherein the solvent is N-methylpyrrolidone.
5.一種4-(N-對-硝基苯基-N-第三丁氧羰基胺基)甲基-N-(對-硝基苯基)哌啶(B)之製造方法,係使如上述1~3中任一項所得之4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶(C)進行第三丁氧羰基化:
6.如上述5之製造方法,其中前述第三丁氧羰基化係在鹼存在下進行。 6. The production method according to the above 5, wherein the third butoxycarbonylation is carried out in the presence of a base.
7.如上述5或6之製造方法,其中前述第三丁氧羰基化劑之使用量係相對於以式(C)表示之化合物1莫耳為1~5莫耳。 7. The production method according to 5 or 6 above, wherein the amount of the third butoxycarbonylating agent used is 1 to 5 moles relative to 1 mole of the compound represented by formula (C).
8.如上述5~7中任一項之製造方法,其中前述第三丁氧羰基化係在四氫呋喃之溶劑中進行。 8. The production method according to any one of 5 to 7 above, wherein the third butoxycarbonylation is performed in a solvent of tetrahydrofuran.
9.一種4-(N-對-胺基苯基-N-第三丁氧羰基胺基)甲基-N-(對-胺基苯基)哌啶(A)之製造方法,係使如上述5~8中任一項所得之4-(N-對-硝基苯基-N-第
三丁氧羰基胺基)甲基-N-(對-硝基苯基)哌啶(B)還原:
10.如上述9之製造方法,其中藉由在觸媒存在下之氫化反應而還原。 10. The production method according to 9 above, wherein the reduction is carried out by hydrogenation in the presence of a catalyst.
11.如上述9或10之製造方法,其中在活性碳擔載觸媒之存在下還原。 11. The production method according to 9 or 10 above, wherein the reduction is carried out in the presence of an activated carbon-supported catalyst.
依據本發明,提供反應速度快、容積效率高、副產物少、為高純度且無單離中間體之必要而以高產率製造作為聚醯亞胺前驅物或聚醯亞胺之製造原料有用之以上述式(A)表示之二胺化合物及其中間體之方法。 According to the present invention, it is provided that the reaction rate is fast, the volumetric efficiency is high, the amount of by-products is low, the purity is high, and there is no need to isolate the intermediate, and the high-yield production is useful as a raw material for the production of a polyimide precursor or polyimide. The method of the diamine compound and its intermediate represented by the above formula (A).
以下詳細說明本發明。 The present invention will be described in detail below.
本發明藉由使對-氟硝基苯(D)與4-(胺基甲基)哌啶(E)反應,而獲得4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶(C)。 In the present invention, by reacting p-fluoronitrobenzene (D) with 4-(aminomethyl)piperidine (E), 4-(p-nitrophenylaminomethyl)-N-( P-nitrophenyl)piperidine (C).
上述反應中,4-(胺基甲基)哌啶(E)與對-氟硝基苯(D)之使用比例,對於前者1莫耳,後者較好為2~10莫耳,基於抑制中間體殘存或過量反應物生成之觀點,更好為2.0~2.2莫耳。 In the above reaction, the ratio of 4-(aminomethyl)piperidine (E) to p-fluoronitrobenzene (D) is 1 mole for the former and 2 to 10 mole for the latter, based on the suppression of the intermediate The viewpoint of residual body or excessive reactant formation is more preferably 2.0 to 2.2 moles.
上述反應中,作為起始原料使用之對-氟硝基苯及4-(胺基甲基)哌啶可作為市售品獲得。又,本發明中,對-氟硝基苯之苯環亦可具有單個或複數個甲基等之取代基。 In the above reaction, p-fluoronitrobenzene and 4-(aminomethyl)piperidine used as starting materials are commercially available. In addition, in the present invention, the benzene ring of p-fluoronitrobenzene may have a single or plural substituents such as a methyl group.
反應形式可為旋轉式(批式)、流通式之任一者,但基於操作性之觀點,較好為批式。 The reaction format may be either a rotary type (batch type) or a flow type, but from the viewpoint of operability, a batch type is preferred.
反應較好在鹼存在下進行。作為鹼可使用例如氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物,碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽,碳酸氫鈉、碳酸氫鉀等之鹼金屬碳酸氫鹽,磷酸鉀;1,8-二氮雜雙環[5,4,0]-7-十一碳烯等之有機鹼等。 The reaction is preferably carried out in the presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, and potassium phosphate can be used; Organic bases such as 1,8-diazabicyclo[5,4,0]-7-undecene etc.
其中,較好為碳酸鈉、碳酸鉀等之鹼金屬碳酸鹽。尤其,若使用微粉末碳酸鉀,則反應性提高故較佳。作為市售之微粉末碳酸鉀,舉例為FG-F20(旭玻璃公司商品名)等。 Among them, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred. In particular, if fine powder potassium carbonate is used, the reactivity is improved, so it is preferable. Examples of commercially available fine powder potassium carbonate include FG-F20 (trade name of Asahi Glass Co., Ltd.).
鹼的使用量相對於4-(胺基甲基)哌啶(E)為1~4當量,較好使用1.0~1.5當量。 The use amount of the base is 1 to 4 equivalents relative to 4-(aminomethyl)piperidine (E), preferably 1.0 to 1.5 equivalents.
作為反應溶劑,使用自二甲基乙醯胺(DMAc)、1,3-二甲基-2-咪唑啶酮(DMI)、二甲基亞碸(DMSO)及N-甲基吡咯啶酮(NMP)所成之群選出之至少一種溶劑。其中,特佳為N-甲基吡咯啶酮。 As the reaction solvent, dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), and N-methylpyrrolidone ( NMP) at least one solvent selected from the group. Among them, N-methylpyrrolidone is particularly preferred.
使用該等溶劑時,於反應結束後,反應溶液可直接於下一Boc步驟中使用,於製造上亦有利。 When using these solvents, the reaction solution can be used directly in the next Boc step after the reaction is completed, which is also advantageous in manufacturing.
溶劑之使用量並未特別限定,相對於以式(C)表示之化合物1質量份,較好使用1~10質量倍之溶劑。更好為3~5質量倍,又更好為3.1~3.3質量倍。 The amount of the solvent used is not particularly limited, and it is preferably 1 to 10 times the mass of the solvent relative to 1 part by mass of the compound represented by formula (C). It is better to be 3 to 5 times the quality, and better to be 3.1 to 3.3 times the quality.
反應溫度為例如-10~200℃,較好為40~100℃。反應時間為批式處理時,為0.5~20小時,較好為1~15小時。 The reaction temperature is, for example, -10 to 200°C, preferably 40 to 100°C. When the reaction time is batch processing, it is 0.5 to 20 hours, preferably 1 to 15 hours.
本發明中,上述所得之含有上述反應所得之4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶(C)之反應溶液藉由第三丁氧羰基化,而獲得4-(N-對-硝基苯基-N-第三丁氧羰基胺基)甲基-N-(對-硝基苯基)哌啶(B)。本發明中,不單離4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶,而可直接將含其之反應溶液使用於下一步驟,就反應效率之提高或產率之提高等方面有利。 In the present invention, the reaction solution containing 4-(p-nitrophenylaminomethyl)-N-(p-nitrophenyl)piperidine (C) obtained by the above reaction is Oxycarbonylation to obtain 4-(N-p-nitrophenyl-N-third-butoxycarbonylamino)methyl-N-(p-nitrophenyl)piperidine (B). In the present invention, 4-(p-nitrophenylaminomethyl)-N-(p-nitrophenyl)piperidine is not isolated, but the reaction solution containing it can be used directly in the next step. The improvement of reaction efficiency or the improvement of yield is advantageous.
上述反應中,對於化合物(C)1莫耳,使用二碳酸二-第三丁酯(Boc2O)等之第三丁氧羰基化劑較好為1~5莫耳,較好為1.3~2.5莫耳,藉由該使用量,可控制二碳酸二第三丁酯(亦稱為Boc基)之導入數。 In the above reaction, for 1 mole of compound (C), the use of a third butoxycarbonylating agent such as di-tert-butyl dicarbonate (Boc 2 O) is preferably 1 to 5 moles, preferably 1.3 to 2.5 moles, the amount of introduction can be controlled by the amount of di-tert-butyl dicarbonate (also known as Boc group).
作為第三丁氧羰基化劑舉例為N-第三丁氧羰基咪唑、碳酸第三丁酯苯酯、肼基甲酸第三丁酯、氯甲酸第三丁酯、二碳酸二-第三丁酯等,特佳為二碳酸二第三丁酯。 Examples of the third butoxycarbonyl carbonylating agent include N-third butoxycarbonyl imidazole, third butyl carbonate phenyl ester, third butyl carbazate, third butyl chloroformate, and di-third butyl dicarbonate. Etc., particularly preferred is di-tert-butyl dicarbonate.
上述反應中鹼的存在並非必要,但使用鹼時,可使用例如氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸氫鈉、碳酸氫鉀、磷酸鉀、碳酸鈉、碳酸鉀、碳酸鋰、碳酸銫等之無機鹼;三甲胺、三乙胺、三丙胺、三異丙胺、三丁胺、二異丙基乙胺、吡啶、N,N-二甲基-4-胺基吡啶、咪唑、喹啉、三甲基吡啶等之胺類;氫化鈉、氫化鉀、第三丁氧化鈉、第三丁氧化鉀等之鹼;等。其中,較好為N,N-二甲基-4-胺基吡啶(DMAP)。 The presence of a base in the above reaction is not necessary, but when a base is used, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid Inorganic bases such as cesium; trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, N,N-dimethyl-4-aminopyridine, imidazole, quin Amines such as porphyrin and trimethylpyridine; bases such as sodium hydride, potassium hydride, sodium tributoxide, and potassium tributoxide; etc. Among them, N,N-dimethyl-4-aminopyridine (DMAP) is preferred.
鹼之使用量相對於以上述式(C)表示之化合物,較好為0.01~5.0當量,更好為0.01~0.10當量。 The use amount of the base is preferably 0.01 to 5.0 equivalents, more preferably 0.01 to 0.10 equivalents, relative to the compound represented by the above formula (C).
4-(對-硝基苯基胺基甲基)-N-(對-硝基苯基)哌啶與第三丁氧羰基化劑反應時之溶劑,若為不與各原料反應之溶劑則可使用。 4-(p-nitrophenylaminomethyl)-N-(p-nitrophenyl) piperidine is the solvent when reacting with the third butoxycarbonylating agent, if it is a solvent that does not react with each raw material be usable.
可使用例如,非質子性極性有機溶劑(二甲基甲醯胺(DMF)、DMSO、DMAc、NMP等);醚類(二***(Et2O)、二異丙醚(i-Pr2O)、第三丁基甲基醚 (TBME)、環戊基甲基醚(CPME)、四氫呋喃(THF)、二噁烷等);脂肪族烴類(戊烷、己烷、庚烷、石油醚等);芳香族烴類(苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯、四氫萘等);鹵系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等);低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等);腈類(乙腈、丙腈、丁腈等);等。該等溶劑可考慮引起反應容易性等而適當選擇。又,可單獨使用1種或混合2種以上使用。根據需要亦可使用適當脫水劑或乾燥劑將溶劑乾燥,作為非水溶劑使用。 For example, aprotic polar organic solvents (dimethylformamide (DMF), DMSO, DMAc, NMP, etc.); ethers (diethyl ether (Et 2 O), diisopropyl ether (i-Pr 2 O ), tert-butyl methyl ether (TBME), cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.) ; Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogenated hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, Dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); etc. These solvents can be appropriately selected in consideration of the ease of reaction and the like. In addition, one type may be used alone or two or more types may be used in combination. If necessary, an appropriate dehydrating agent or desiccant can be used to dry the solvent and used as a non-aqueous solvent.
作為溶劑較好為醚類,特佳為THF。使用THF時,於反應結束後添加水進行分液,可以含於THF中之狀態獲得目的物之式(B)表示之化合物。 The solvent is preferably an ether, and particularly preferably THF. In the case of using THF, water is added to complete liquid separation after the completion of the reaction, and the compound represented by formula (B) can be obtained in the state of being contained in THF.
THF與水通常混合合而為均一溶液,但本發明之製造方法中,縮合步驟中副生之氟化鉀因溶解於水相而使水相之鹽濃度增高,由於目的物的式(B)表示之化合物於水中為難溶性,故兩者可良好地分液。此時之THF與水之比例,相對於THF1質量份,較好水為0.1~0.5質量份,更好為0.3~0.4質量份。 THF and water are usually mixed to form a uniform solution. However, in the production method of the present invention, the by-produced potassium fluoride in the condensation step is dissolved in the water phase to increase the salt concentration of the water phase. Due to the target formula (B) The compound indicated is insoluble in water, so the two can be separated well. The ratio of THF to water at this time is preferably 0.1 to 0.5 parts by mass, more preferably 0.3 to 0.4 parts by mass relative to 1 part by mass of THF.
溶劑之使用量並未特別限定,但對於式(C)之二硝基化合物1質量份,較好使用0.1~100質量倍之溶劑。更好為0.5~30質量倍,進而更好為1~10質量倍。 The amount of the solvent used is not particularly limited, but for 1 part by mass of the dinitro compound of formula (C), it is preferred to use a solvent of 0.1 to 100 times by mass. It is more preferably 0.5 to 30 times the mass, and further preferably 1 to 10 times the mass.
反應溫度並未特別限定,可為自-100℃至所使用溶劑之沸點之範圍,較好為-50~150℃之範圍。 The reaction temperature is not particularly limited, but may range from -100°C to the boiling point of the solvent used, preferably -50 to 150°C.
反應時間通常為0.05~200小時,較好為0.5~100小時。 The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
反應結束後,如上述藉由添加水進行分液,獲得包含以式(B)表示之化合物之THF溶液。 After the reaction is completed, liquid separation is performed by adding water as described above to obtain a THF solution containing the compound represented by formula (B).
其次,本發明中,藉由使上述所得之4-(N-對-硝基苯基-N-第三丁氧羰基胺基)甲基-N-(對-硝基苯基)哌啶(B)還原,獲得4-(N-對-胺基苯基-N-第三丁氧羰基胺基)甲基-N-(對-胺基苯基)哌啶(A)。 Next, in the present invention, by using 4-(N-p-nitrophenyl-N-third butoxycarbonylamino)methyl-N-(p-nitrophenyl)piperidine ( B) Reduction to obtain 4-(N-p-aminophenyl-N-third-butoxycarbonylamino)methyl-N-(p-aminophenyl)piperidine (A).
本發明中,不單離式(B)之硝基化合物,而可將含其之溶液直接供於下一步驟之還原反應,此時基於反應效率之提高或產率之提高等方面而言較佳。 In the present invention, the nitro compound of formula (B) is not isolated, but the solution containing it can be directly supplied to the reduction reaction in the next step. In this case, it is preferred based on the improvement of reaction efficiency or the increase of yield. .
作為還原方法,舉例為在觸媒存在下之氫化反應、於質子共存下進行之還原反應、將甲酸作為氫源之還原、將聯胺作為氫源之還原反應等,亦可組合複數之該等還原反應。考慮式(B)之二硝基化合物之構造與反應性時,作為還原方法較好在觸媒存在下之氫化反應。 Examples of the reduction method include a hydrogenation reaction in the presence of a catalyst, a reduction reaction carried out in the presence of protons, a reduction using formic acid as a hydrogen source, and a reduction reaction using a hydrazine as a hydrogen source. Reduction reaction. When considering the structure and reactivity of the dinitro compound of formula (B), the hydrogenation reaction in the presence of a catalyst is preferred as the reduction method.
氫化反應中使用之觸媒較好為可作為市售品獲得之活性碳擔持金屬,舉例為例如鈀-活性碳、鉑-活性碳、釕-活性碳等。又,亦可使用氫氧化鈀、氧化鉑、阮尼鎳等,未必為活性碳擔持型之金屬觸媒。一般廣泛使用 之鈀-活性碳由於可獲得反應後不產生廢棄物,不易引起副反應等之良好結果故較佳。 The catalyst used in the hydrogenation reaction is preferably an activated carbon support metal available as a commercially available product, and examples thereof include palladium-activated carbon, platinum-activated carbon, ruthenium-activated carbon, and the like. In addition, palladium hydroxide, platinum oxide, Raney nickel, etc., which are not necessarily activated carbon supported metal catalysts, may also be used. Generally widely used The palladium-activated carbon is preferable because it does not produce waste after the reaction, and is not likely to cause good results such as side reactions.
觸媒之使用量並未特別限制,但基於反應性之方面,對於上述式(B)表示之化合物1莫耳,較好為0.0001~0.1莫耳,更好為0.001~0.01莫耳。 The amount of catalyst used is not particularly limited, but based on the reactivity, the compound represented by the above formula (B) is 1 mole, preferably 0.0001 to 0.1 mole, more preferably 0.001 to 0.01 mole.
為了更有效進行氫化反應,有時進而在活性碳共存下實施反應。此時,使用之活性碳之量並未特別限定,但對於式(B)之二硝基化合物之100質量%,較好為1~20質量%,更好為5~10質量%。 In order to perform the hydrogenation reaction more efficiently, the reaction may be further carried out in the presence of activated carbon. At this time, the amount of activated carbon used is not particularly limited, but for 100% by mass of the dinitro compound of formula (B), it is preferably 1-20% by mass, more preferably 5-10% by mass.
為了進一步促進反應,亦有時在加壓氫下實施反應。該情況,為了避免苯核還原,而在至多20大氣壓之加壓範圍內進行。較好在至多10大氣壓之範圍實施反應。 In order to further promote the reaction, the reaction is sometimes carried out under pressurized hydrogen. In this case, in order to avoid the reduction of the benzene nucleus, it is carried out within a pressure range of at most 20 atmospheres. The reaction is preferably carried out in the range of up to 10 atmospheres.
溶劑若為不與各原料反應之溶劑,則可無限制地使用。 If the solvent is a solvent that does not react with each raw material, it can be used without limitation.
可使用例如,非質子性極性有機溶劑(DMF、DMSO、DMAc、NMP等);醚類(Et2O、i-Pr2O、TBME、CPME、THF、二噁烷等);脂肪族烴類(戊烷、己烷、庚烷、石油醚等);芳香族烴類(苯、甲苯、二甲苯、均三甲苯、氯苯、二氯苯、硝基苯、四氫萘等);鹵系烴類(氯仿、二氯甲烷、四氯化碳、二氯乙烷等);低級脂肪酸酯類(乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯等);腈類(乙腈、丙腈、丁腈等);等。其中較好為THF、二噁烷、乙酸乙酯。 For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (Pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.); halogen Hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, Propionitrile, butyronitrile, etc.); etc. Among them, THF, dioxane and ethyl acetate are preferred.
該等溶劑可考慮引起反應之容易性等而適當選擇。又,可單獨使用1種或混合2種以上使用。根據需要亦可使用適當脫水劑或乾燥劑將溶劑乾燥,作為非水溶劑使用。 These solvents can be appropriately selected in consideration of the ease of causing the reaction and the like. In addition, one type may be used alone or two or more types may be used in combination. If necessary, an appropriate dehydrating agent or desiccant can be used to dry the solvent and used as a non-aqueous solvent.
溶劑之使用量(反應濃度)並未特別限制,但對於式(B)之二硝基化合物1質量份,為0.1~100質量倍。較好為0.5~30質量倍,又更好為1~10質量倍。 The use amount (reaction concentration) of the solvent is not particularly limited, but for 1 part by mass of the dinitro compound of formula (B), it is 0.1 to 100 times by mass. It is preferably 0.5 to 30 times the mass, and more preferably 1 to 10 times the mass.
反應溫度並未特別限定,可為自-100℃至所使用溶劑之沸點之範圍,較好為-50~150℃之範圍。反應時間通常為0.05~350小時,較好為0.5~100小時。 The reaction temperature is not particularly limited, but may range from -100°C to the boiling point of the solvent used, preferably -50 to 150°C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
以下藉由實施例更具體說明本發明,但本發明並非解釋為由該等實施例所限定者。又實施例中採用之分析裝置及分析條件如下述。 Hereinafter, the present invention will be described more specifically by examples, but the present invention is not to be construed as limited by these examples. The analysis devices and analysis conditions used in the examples are as follows.
裝置:Varian NMR system 400NB(400MHz)(Varian公司製)及JMTC-500/54/SS(500MHz)(JEOL公司製) Device: Varian NMR system 400NB (400MHz) (manufactured by Varian) and JMTC-500/54/SS (500MHz) (manufactured by JEOL)
測定溶劑:CDCl3(氘化氯仿)、DMSO-d6(氘化二甲基亞碸) Measurement solvent: CDCl 3 (deuterated chloroform), DMSO-d 6 (deuterated dimethyl sulfoxide)
基準物質:TMS(四甲基矽烷)(δ:0.0ppm,1H)及CDCl3(δ:77.0ppm,13C) Reference materials: TMS (tetramethylsilane) (δ: 0.0 ppm, 1 H) and CDCl 3 (δ: 77.0 ppm, 13 C)
裝置:LC-20AD(島津製作所公司製) Device: LC-20AD (manufactured by Shimadzu Corporation)
管柱:X Bridge BEHC18 5μm,4.6×250mm管柱(Waters) Column: X Bridge BEHC18 5μm, 4.6×250mm column (Waters)
檢測器:SPD-M20A(島津製作所製)(檢測波長:254nm) Detector: SPD-M20A (made by Shimadzu Corporation) (detection wavelength: 254nm)
溶離液:MeOH/0.2%AcOH、0.8%Et3N aq.=70/30[vol/vol] Dissolution solution: MeOH/0.2%AcOH, 0.8%Et 3 N aq.=70/30[vol/vol]
<4-(N-對-胺基苯基-N-第三丁氧羰基胺基)甲基-N-(對-胺基苯基)哌啶之合成> <Synthesis of 4-(N-p-aminophenyl-N-third-butoxycarbonylamino)methyl-N-(p-aminophenyl)piperidine>
於1L(升)之四頸燒瓶中饋入4-(胺基甲基)哌啶(15.0g,131.4mmol)、碳酸鉀(21.8g,157.7mmol)及N-甲基吡咯啶酮(40.5g),於翼攪拌下升溫至75℃。隨 後,以2小時滴加對-氟硝基苯(38.9g,275.9mmol)及N-甲基吡咯啶酮(7.5g),於75℃攪拌6小時。以HPLC確認反應結束後,直接使用反應液進行下一步驟。 In a 1 L (liter) four-necked flask was fed 4-(aminomethyl)piperidine (15.0 g, 131.4 mmol), potassium carbonate (21.8 g, 157.7 mmol) and N-methylpyrrolidone (40.5 g ), and warmed to 75°C with wing stirring. Follow After that, p-fluoronitrobenzene (38.9 g, 275.9 mmol) and N-methylpyrrolidone (7.5 g) were added dropwise over 2 hours, and stirred at 75°C for 6 hours. After confirming the completion of the reaction by HPLC, the reaction solution was directly used for the next step.
於前步驟之反應液中饋入四氫呋喃(270.0g)及DMAP(N,N-二甲基-4-胺基吡啶)(0.80g,6.57mmol),以30分鐘滴加Boc2O(二碳酸二第三丁酯)(57.3g,262.5mmol)後,攪拌1小時。以HPLC確認反應結束後,添加四氫呋喃(15.0g)及水(90.0g)並攪拌1小時。其次,進行分液去除水層,直接使用THF溶液進行下一步驟。 The reaction solution of the previous step was fed with tetrahydrofuran (270.0g) and DMAP (N,N-dimethyl-4-aminopyridine) (0.80g, 6.57mmol), and Boc 2 O (dicarbonate) was added dropwise over 30 minutes After di-tert-butyl ester) (57.3 g, 262.5 mmol), it was stirred for 1 hour. After confirming the completion of the reaction by HPLC, tetrahydrofuran (15.0 g) and water (90.0 g) were added and stirred for 1 hour. Next, the liquid layer was removed by liquid separation, and the THF solution was directly used for the next step.
於前述THF溶液中饋入5質量%Pd/C(50質量%含水型)(3.0g)及活性碳(白鷺WP-H(6.0g))。隨後,進行氫置換,升溫至50℃後,攪拌5小時。以HPLC確認反應結束後,藉由膜過濾器進行過濾,去除Pd/C等。隨後,將內容量濃縮至210.0g。其次,滴加2-丙醇(420.0g),冷卻至5℃,進而攪拌1小時。減壓過濾所析出之結晶,以2-丙醇(27.0g)洗淨後,乾燥,作為粉末結晶獲得4-(N-對-胺基苯基-N-第三丁氧羰基胺基)甲基-N-(對-胺基苯基)哌啶(產量44.3g,產率85.0%)。 5 mass% Pd/C (50 mass% aqueous type) (3.0 g) and activated carbon (Egret WP-H (6.0 g)) were fed into the aforementioned THF solution. Subsequently, hydrogen substitution was performed, the temperature was raised to 50°C, and the mixture was stirred for 5 hours. After confirming the completion of the reaction by HPLC, filtration was performed with a membrane filter to remove Pd/C and the like. Subsequently, the content amount was concentrated to 210.0 g. Next, 2-propanol (420.0 g) was added dropwise, cooled to 5°C, and further stirred for 1 hour. The precipitated crystals were filtered under reduced pressure, washed with 2-propanol (27.0g), and dried to obtain 4-(N-p-aminophenyl-N-third-butoxycarbonylamino)methyl as a powder crystal. -N-(p-aminophenyl)piperidine (yield 44.3 g, yield 85.0%).
1H-NMR(DMSO-d6):δ=6.83(d,2H,J=8.0),6.65(d,2H J=8.4),6.50(d,2H, J=8.4),6.45(d,2H,J=8.4),5.05(br,2H),4.54(br,2H),3.41(d,2H,J=6.8),3.29(d,2H,J=12.4),2.36(t,2H,J=10.8),1.64(d,2H,J=11.6),1.42-1.19(br,12H). 1 H-NMR(DMSO-d 6 ): δ =6.83(d,2H,J=8.0),6.65(d,2H J=8.4),6.50(d,2H,J=8.4),6.45(d,2H ,J=8.4),5.05(br,2H),4.54(br,2H),3.41(d,2H,J=6.8),3.29(d,2H,J=12.4),2.36(t,2H,J= 10.8), 1.64 (d, 2H, J=11.6), 1.42-1.19 (br, 12H).
本發明所得之4-(N-對-胺基苯基-N-第三丁氧羰基胺基)甲基-N-(對-胺基苯基)哌啶係作為可用於液晶配向膜等之聚醯亞胺前驅物或聚醯亞胺之原料材料為有用。 The 4-(N-p-aminophenyl-N-third-butoxycarbonylamino)methyl-N-(p-aminophenyl) piperidine obtained in the present invention can be used as a liquid crystal alignment film, etc. Polyimide precursors or raw materials of polyimide are useful.
又,2015年3月9日提出申請之日本特願2015-045862號說明書、申請專利範圍及摘要之全部內容引用於本文,係作為本發明說明書之揭示而併入者。 In addition, the entire contents of Japanese Patent Application No. 2015-045862, patent application scope, and abstract filed on March 9, 2015 are incorporated herein by reference, and are incorporated as disclosure of the specification of the present invention.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012155311A (en) * | 2011-01-05 | 2012-08-16 | Jnc Corp | Liquid crystal aligning agent for forming photo-aligning liquid crystal alignment layer, liquid crystal alignment layer and liquid crystal display element using the same |
JP2013152421A (en) * | 2011-12-26 | 2013-08-08 | Jsr Corp | Liquid crystal-aligning agent, liquid crystal alignment layer, liquid crystal display element, polymer and compound |
TW201609864A (en) * | 2014-05-30 | 2016-03-16 | Nissan Chemical Ind Ltd | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
TW201627354A (en) * | 2014-10-03 | 2016-08-01 | Nissan Chemical Ind Ltd | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same |
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WO2015122413A1 (en) * | 2014-02-13 | 2015-08-20 | 日産化学工業株式会社 | Novel liquid crystal orientation agent, diamine, and polyimide precursor |
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JP2012155311A (en) * | 2011-01-05 | 2012-08-16 | Jnc Corp | Liquid crystal aligning agent for forming photo-aligning liquid crystal alignment layer, liquid crystal alignment layer and liquid crystal display element using the same |
JP2013152421A (en) * | 2011-12-26 | 2013-08-08 | Jsr Corp | Liquid crystal-aligning agent, liquid crystal alignment layer, liquid crystal display element, polymer and compound |
TW201609864A (en) * | 2014-05-30 | 2016-03-16 | Nissan Chemical Ind Ltd | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
TW201627354A (en) * | 2014-10-03 | 2016-08-01 | Nissan Chemical Ind Ltd | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same |
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TW201708192A (en) | 2017-03-01 |
KR102592383B1 (en) | 2023-10-20 |
KR20170127495A (en) | 2017-11-21 |
CN107406385A (en) | 2017-11-28 |
JP6669159B2 (en) | 2020-03-18 |
WO2016143748A1 (en) | 2016-09-15 |
CN107406385B (en) | 2021-01-26 |
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