TW201607934A - Novel bis(hydroxyphenyl)benzoxazole compound - Google Patents

Novel bis(hydroxyphenyl)benzoxazole compound Download PDF

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TW201607934A
TW201607934A TW103141934A TW103141934A TW201607934A TW 201607934 A TW201607934 A TW 201607934A TW 103141934 A TW103141934 A TW 103141934A TW 103141934 A TW103141934 A TW 103141934A TW 201607934 A TW201607934 A TW 201607934A
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西原匡彦
芦田一仁
水野卓巳
伊藤貴敏
三原正稔
岩井利之
中井猛夫
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本州化學工業股份有限公司
地方獨立行政法人大阪市立工業研究所
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic

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Abstract

Provided is a novel bis(hydroxyphenyl)benzoxazole compound useful as resin raw material of epoxy resin or polybenzoxazole resin, or an intermediate or raw material of medicine, agromedicine, dye and electronic material. The solution is providing a bis(hydroxyphenyl)benzoxazole compound represented by the following formula (1) wherein, R1 represents an alkyl group having a carbon number of 1~8, an alkoxyl group having a carbon number of 1~8, a phenyl group or a halogen atom, R2 represents a hydrogen atom, an alkyl group having a carbon number of 1~8, an alkoxyl group having a carbon number of 1~8, a phenyl group or a halogen atom, A represents a cycloalkylidene group having a carbon number of 5~10, n represents 0 or an integer of 1~4.

Description

新穎之雙(羥苯基)苯并 唑化合物Novel bis(hydroxyphenyl)benzoxazole compounds

本發明係關於新穎之雙(羥苯基)苯并唑化合物。更詳細而言，係關於作為環氧樹脂等之樹脂原料，或醫藥、農藥、染料以及電子材料或該等的中間體或原料時為有用之雙(羥苯基)苯并唑化合物。 The present invention relates to novel bis(hydroxyphenyl)benzo An azole compound. More specifically, it is useful as a resin raw material such as an epoxy resin, or a bis(hydroxyphenyl) benzo which is useful as a pharmaceutical, a pesticide, a dye, and an electronic material or an intermediate or a raw material thereof. An azole compound.

雙(羥苯基)苯并唑化合物類作為環氧樹脂等之樹脂原料來使用時，因其拉伸強度、抗彎強度、衝擊強度、耐熱性、電氣特性優異而作為原料受期待。 Bis(hydroxyphenyl)benzo When the azole compound is used as a resin raw material such as an epoxy resin, it is expected to be used as a raw material because of its excellent tensile strength, bending strength, impact strength, heat resistance, and electrical properties.

此種雙(羥苯基)苯并唑類，已知有2,2’-二(4-羥苯基)-6,6’-雙苯并唑、或具有2,2-六氟亞丙基之2,2-雙[2-(4-羥苯基)-5-苯并唑基]六氟丙烷等(專利文獻1、專利文獻2)。 Bis(hydroxyphenyl)benzophenone Azole, known as 2,2'-bis(4-hydroxyphenyl)-6,6'-dibenzo Azole or 2,2-bis[2-(4-hydroxyphenyl)-5-benzo with 2,2-hexafluoropropylene Zozolyl] hexafluoropropane or the like (Patent Document 1 and Patent Document 2).

在此，2,2’-二(4-羥苯基)-6,6’-雙苯并唑係具高熔點，又於溶劑的溶解性低，故於工業上實施時有作業性或操作性之問題，又，具有2,2-六氟亞丙基之2,2-雙[2-(4-羥苯基)-5-苯并唑基]六氟丙烷係耐熱性不足。 Here, 2,2'-bis(4-hydroxyphenyl)-6,6'-dibenzo The azole has a high melting point and low solubility in a solvent, so it has problems in workability or workability in industrial implementation, and 2,2-bis [2- having 2,2-hexafluoropropylene. (4-hydroxyphenyl)-5-benzo The azolyl]hexafluoropropane is insufficient in heat resistance.

因此，作業性或操作性良好，且耐熱性優異之具有新 穎的化學結構之雙(羥苯基)苯并唑化合物的開發被強烈需求。 Therefore, bis(hydroxyphenyl)benzoate having a novel chemical structure which is excellent in workability or workability and excellent in heat resistance The development of azole compounds is strongly demanded.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]美國專利第5270432號公報 [Patent Document 1] US Patent No. 5270432

[專利文獻2]日本特開2007-262204號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-262204

本發明之課題在於提供作為環氧樹脂或聚苯并唑樹脂等之樹脂原料，或作為醫藥、農藥、染料以及電子材料或該等的中間體或原料為有用的新穎之雙(羥苯基)苯并唑化合物。 The object of the present invention is to provide epoxy resin or polybenzoate a resin raw material such as an azole resin, or a novel bis(hydroxyphenyl) benzo which is useful as a medicine, a pesticide, a dye, and an electronic material or an intermediate or raw material thereof An azole compound.

本發明人們對如上述之雙(羥苯基)苯并唑化合物的問題點進行深入探討，結果，發現藉由將亞環烷基作為雙(羥苯基)苯并唑化合物的中心骨架，可獲得溶劑溶解性或耐熱性的平衡性優異之新穎之雙(羥苯基)苯并唑化合物，而完成本發明。 The present inventors have bis(hydroxyphenyl)benzophenone as described above The problem of the azole compound was further investigated, and as a result, it was found that by using a cycloalkylene group as a bis(hydroxyphenyl) benzo A novel bis(hydroxyphenyl)benzoate with excellent solvent solubility or heat resistance in the center skeleton of the azole compound The azole compound is used to complete the present invention.

根據本發明，提供下述通式(1)所示之雙(羥苯基)苯并唑化合物。 According to the present invention, there is provided a bis(hydroxyphenyl)benzene represented by the following formula (1) An azole compound.

通式(1) (式中，R1係表示碳原子數1至8的烷基、碳原子數1至8的烷氧基、苯基或鹵原子，R2係表示氫原子、碳原子數1至8的烷基、碳原子數1至8的烷氧基、苯基或鹵原子，A係表示碳原子數5至10的亞環烷基，n係表示0或1至4的整數。) General formula (1) (wherein R 1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and R 2 represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; a group, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, A means a cycloalkylene group having 5 to 10 carbon atoms, and n means 0 or an integer of 1 to 4.

本發明的雙(羥苯基)苯并唑化合物係於中心骨架具有亞環烷基骨架，由於此種中心骨架具有脂環結構，熔點較低且溶劑溶解性亦佳。 Bis(hydroxyphenyl)benzoxyl of the invention The azole compound has a cycloalkylene skeleton in the central skeleton, and since the central skeleton has an alicyclic structure, the melting point is low and the solvent solubility is also good.

又，以本發明的雙(羥苯基)苯并唑化合物作為原料之樹脂，相較於以2,2-雙[2-(4-羥苯基)-5-苯并唑基]六氟丙烷作為原料之樹脂，可期待耐熱性更優異。 Further, the bis(hydroxyphenyl)benzoate of the present invention The azole compound as a raw material resin compared to 2,2-bis[2-(4-hydroxyphenyl)-5-benzo A resin which is a raw material of azolyl]hexafluoropropane is expected to have more excellent heat resistance.

以下，詳細地說明本發明的雙(羥苯基)苯并唑化合物。 Hereinafter, the bis(hydroxyphenyl)benzoate of the present invention will be described in detail. An azole compound.

於本發明之上述通式(1)所示之雙(羥苯基)苯并唑化合物中，式中，R1、R2所示之碳原子數1至8的烷基係直鏈狀、支鏈狀或環狀的烷基，較佳為碳原子數1至4的烷基或碳原子數5至8的環烷基，更佳為碳原子數1至4的 直鏈狀或支鏈狀的烷基。 The bis(hydroxyphenyl)benzobenzene represented by the above formula (1) of the present invention In the azole compound, an alkyl group having 1 to 8 carbon atoms represented by R 1 and R 2 is a linear, branched or cyclic alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. The group or a cycloalkyl group having 5 to 8 carbon atoms is more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

該烷基具體而言可列舉，例如甲基、乙基、異丙基、第三丁基、異丁基、環己基、環戊基等。 Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, and a cyclopentyl group.

該烷基中，在不妨礙本發明之效果的範圍內，可經鹵原子、烷氧基、苯基等取代，但較佳為無取代者。 The alkyl group may be substituted by a halogen atom, an alkoxy group, a phenyl group or the like within a range not inhibiting the effects of the present invention, but is preferably an unsubstituted one.

又，式中，碳原子數1至8的烷氧基係直鏈狀、支鏈狀或環狀的烷氧基，較佳為碳原子數1至4的烷氧基或碳原子數5至8的環烷氧基，更佳為碳原子數1至4的直鏈狀或支鏈狀的烷氧基。該烷氧基具體而言可列舉，例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、環戊氧基、環己氧基等。該烷氧基中，在不妨礙本發明之效果的範圍內，可經鹵原子、烷氧基、苯基等取代，但較佳為無取代者。 Further, in the formula, the alkoxy group having 1 to 8 carbon atoms is a linear, branched or cyclic alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or 5 to 5 carbon atoms. The cycloalkyloxy group of 8 is more preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The alkoxy group may be substituted by a halogen atom, an alkoxy group, a phenyl group or the like within a range not inhibiting the effects of the present invention, but is preferably an unsubstituted one.

式中，R1、R2所示之苯基，較佳為無取代基之苯基。然而，苯基中，在不妨礙本發明之效果的範圍內，可經甲基等烷基、甲氧基等烷氧基、鹵原子等取代。 In the formula, the phenyl group represented by R 1 and R 2 is preferably a phenyl group having no substituent. However, the phenyl group may be substituted with an alkoxy group such as an alkyl group such as a methyl group or a methoxy group, a halogen atom or the like, within a range not inhibiting the effects of the present invention.

式中，R1、R2所示之鹵原子，具體而言可列舉氟原子、氯原子、溴原子、碘原子。 In the formula, the halogen atom represented by R 1 and R 2 may specifically be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

於上述取代基R1、R2中，較佳的R1係烷基或苯基，更佳的R1係烷基，較佳的R2係烷基、苯基或氫原子，更佳的R2係氫原子。 Preferred among the above substituents R 1 and R 2 are a R 1 -alkyl group or a phenyl group, more preferably an R 1 -based alkyl group, preferably an R 2 -based alkyl group, a phenyl group or a hydrogen atom, more preferably R 2 is a hydrogen atom.

又，羥苯基的取代基R1之取代數n係表示0或1至4的整數，較佳為0、1或2，更佳為0或1，特佳為0。R1的取代位置係相對於羥基，較佳為鄰位或對位，羥基的取 代位置，相對於與苯并唑骨架之鍵結位置為對位時，R1的取代位置相對於羥基，較佳為鄰位。 Further, the substitution number n of the substituent R 1 of the hydroxyphenyl group means 0 or an integer of 1 to 4, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The substitution position of R 1 is relative to the hydroxyl group, preferably ortho or para, and the position of substitution of the hydroxyl group relative to the benzoic acid When the bonding position of the azole skeleton is in the para position, the substitution position of R 1 is preferably ortho to the hydroxyl group.

羥苯基的羥基之取代位置，相對於與苯并唑骨架鍵結的位置，較佳為對位、間位，特佳為對位。 The position of the hydroxy group of the hydroxyphenyl group relative to the benzoate The position of the azole skeleton linkage is preferably a para position, a meta position, and particularly preferably a para position.

上述通式(1)中，式中，A係表示碳原子數5至10的亞環烷基。 In the above formula (1), in the formula, A represents a cycloalkylene group having 5 to 10 carbon atoms.

該亞環烷基具體而言可列舉，例如環戊-1,1-二基、環己-1,1-二基、環庚-1,1-二基、3,3,5-三甲基環己-1,1-二基等。 Specific examples of the cycloalkylene group include, for example, cyclopenta-1,1-diyl, cyclohex-1,1-diyl, cyclohepta-1,1-diyl, 3,3,5-trimethyl. Base ring-1,1-diyl and the like.

以耐熱性的觀點來看，更佳為3,3,5-三甲基環己-1,1-二基。 From the viewpoint of heat resistance, 3,3,5-trimethylcyclohexan-1,1-diyl is more preferable.

進一步，此種環烷骨架中，可以烷基取代，較佳為甲基，較佳的取代數為1至3。 Further, in the cycloalkane skeleton, an alkyl group may be substituted, preferably a methyl group, and a preferred number of substitutions is from 1 to 3.

如此之本發明的雙(羥苯基)苯并唑化合物具體而言可列舉，例如1,1-雙[2-(4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷、 Such a bis(hydroxyphenyl)benzophenone of the present invention Specific examples of the azole compound include, for example, 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Azyl]-3,3,5-trimethylcyclohexane,

1,1-雙[2-(3,5-二第三丁基-4-羥苯基)-5苯并唑基]-3,3,5-三甲基環己烷、 1,1-bis[2-(3,5-di-t-butyl-4-hydroxyphenyl)-5-benzoate Azyl]-3,3,5-trimethylcyclohexane,

1-雙[2-(3-第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷、1,1-雙[2-(4-羥苯基)-5-苯并唑基]環己烷、1,1-雙[2-(3-第三丁基-4-羥苯基)-5-苯并唑基]環己烷、1,1-雙[2-(4-羥苯基)-5-苯并唑基]環戊烷、1,1-雙[2-(4-羥苯基)-5-苯并唑基]環庚烷、1,1-雙[2-(3-甲基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷、1,1-雙[2-(4-羥苯基)-7-甲基-5-苯并唑基]-3,3,5-三甲基環己烷、1,1-雙[2-(3-甲基-4-羥苯基)-5-苯并唑基]環己烷、1,1-雙[2-(3-甲基-4-羥苯基)-5-苯并唑基]環戊烷、1,1-雙[2-(3-苯基-4-羥苯基)-5-苯并唑基]環己烷等。 1-bis[2-(3-tert-butyl-4-hydroxyphenyl)-5-benzo Azyl]-3,3,5-trimethylcyclohexane, 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Azolyl]cyclohexane, 1,1-bis[2-(3-tert-butyl-4-hydroxyphenyl)-5-benzo Oxyl]cyclohexane, 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Azolyl]cyclopentane, 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Azolyl]cycloheptane, 1,1-bis[2-(3-methyl-4-hydroxyphenyl)-5-benzo Azyl]-3,3,5-trimethylcyclohexane, 1,1-bis[2-(4-hydroxyphenyl)-7-methyl-5-benzo Azyl]-3,3,5-trimethylcyclohexane, 1,1-bis[2-(3-methyl-4-hydroxyphenyl)-5-benzo Oxyl]cyclohexane, 1,1-bis[2-(3-methyl-4-hydroxyphenyl)-5-benzo Azolyl]cyclopentane, 1,1-bis[2-(3-phenyl-4-hydroxyphenyl)-5-benzo Zozolyl] cyclohexane and the like.

如上述之本發明的雙(羥苯基)苯并唑化合物，其製造方法並不受任何限制。例如可列舉下列的方法。 Bis(hydroxyphenyl)benzophenone of the present invention as described above The azole compound is not limited in any way. For example, the following methods can be mentioned.

(方法1) (method 1)

可列舉出，將對應目標的雙(羥苯基)苯并唑化合物之下述通式(3)的雙胺基苯酚(bisaminophenol)類與羥基苯 甲酸類作為原料，於有機溶劑中，在加溫下進行縮合反應之方法(日本特開2007-262204號公報)。對於該製造方法，描述例如將雙胺基苯酚類中之1,1-雙(3-胺基-4-羥苯基)-3,3,5-三甲基環己烷、羥基苯甲酸類中之4-羥基苯甲酸苯酯作為原料之情形。其反應式係例如下述式所示。 It can be exemplified that the corresponding target bis(hydroxyphenyl)benzophenone A method in which a bisaminophenol of the following formula (3) and a hydroxybenzoic acid of the azole compound are used as a raw material, and a condensation reaction is carried out under heating in an organic solvent (JP-A-2007-262204) ). For the production method, for example, 1,1-bis(3-amino-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, hydroxybenzoic acid in the bisaminophenols will be described. The case of phenyl 4-hydroxybenzoate as a raw material. The reaction formula is, for example, the following formula.

上述反應所使用之羥基苯甲酸類，例如可列舉下述通式(2)所示之羥基苯甲酸苯酯類。 The hydroxybenzoic acid to be used in the above reaction may, for example, be a phenyl hydroxybenzoate represented by the following formula (2).

(式中，R1及n係與通式(1)者相同。) (wherein R 1 and n are the same as those of the formula (1).)

又，於上述反應時，雙胺基苯酚類與羥基苯甲酸苯酯類的原料之莫耳比，一般而言，相對於雙胺基苯酚類1莫耳，羥基苯甲酸苯酯類一般為2至5莫耳的範圍，較佳為2至3莫耳的範圍。所使用之反應溶劑較佳，例如可列舉N-甲基-2-吡咯啶酮等N-烷基醯胺溶劑、聯苯 等芳香族烴類或此等的混合溶劑。溶劑的使用量，一般而言，相對於雙胺基苯酚類1重量份為1至20重量份的範圍。又，反應溫度為150至250℃的範圍，反應壓力為常壓、減壓、加壓之任一者均可，但為了容易將副產物水或苯酚類除去，亦可進行減壓。 Further, in the above reaction, the molar ratio of the raw materials of the bisaminophenols to the phenyl hydroxybenzoates is generally 2, based on the dimethylaminophenols, the phenyl hydroxybenzoates are generally 2 A range of up to 5 moles, preferably in the range of 2 to 3 moles. The reaction solvent to be used is preferably, for example, an N-alkyl guanamine solvent such as N-methyl-2-pyrrolidone or a biphenyl. An aromatic hydrocarbon or a mixed solvent of these. The amount of the solvent to be used is, in general, in the range of 1 to 20 parts by weight based on 1 part by weight of the bisaminophenol. Further, the reaction temperature is in the range of 150 to 250 ° C, and the reaction pressure may be any of normal pressure, reduced pressure, and pressurization. However, in order to easily remove by-product water or phenol, the pressure may be reduced.

反應係將例如原料、反應溶劑同時加入反應容器，以惰性氣體取代，之後，升溫至150℃至180℃左右的反應溫度並攪拌，一邊使系統內減壓餾除副產物水或苯酚類一邊使之反應。之後，進一步將系統內升溫至200至250℃左右而完成脫水閉環反應。反應結束後，使用一般所知的精製方法，可由所得到的反應生成物得到目標物的粗製物乃至精製物。 In the reaction system, for example, a raw material and a reaction solvent are simultaneously added to a reaction vessel, and are replaced with an inert gas. Thereafter, the temperature is raised to a reaction temperature of about 150 ° C to 180 ° C and stirred, and the by-product water or phenol is distilled off under reduced pressure in the system. The reaction. Thereafter, the temperature in the system is further raised to about 200 to 250 ° C to complete the dehydration ring closure reaction. After completion of the reaction, a crude product or a purified product of the target product can be obtained from the obtained reaction product by a generally known purification method.

藉由例如將所得到的反應液冷卻、或加水，使析出或濾出再沉澱的固體或結晶，再以水、甲醇洗淨，乾燥之，而可得到目標物。 For example, the obtained reaction liquid is cooled or water is added to precipitate or filter out the reprecipitated solid or crystal, and then washed with water and methanol, and dried to obtain a target product.

上述方法中，雙胺基苯酚類係下述通式(3)所示。 In the above method, the bisaminophenol is represented by the following formula (3).

(式中，R2、A係與通式(1)者相同) (wherein R 2 and A are the same as those of the formula (1))

因此，此種雙胺基苯酚類，係對應本發明的雙(羥苯基) 苯并唑化合物，具體而言例如可列舉1,1-雙(3-胺基-4-羥苯基)環己烷、1,1-雙(3-胺基-5-甲基-4-羥苯基)環己烷、1,1-雙(3-胺基-4-羥苯基)-3,3,5-三甲基環己烷、1,1-雙(3-胺基-4-羥苯基)環戊烷、1,1-雙(3-胺基-4-羥苯基)環庚烷等。 Therefore, such bisaminophenols correspond to the bis(hydroxyphenyl)benzophenone of the present invention. Specific examples of the azole compound include 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane and 1,1-bis(3-amino-5-methyl-4-hydroxybenzene). Cyclohexane, 1,1-bis(3-amino-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-amino-4- Hydroxyphenyl)cyclopentane, 1,1-bis(3-amino-4-hydroxyphenyl)cycloheptane, and the like.

此種雙胺基苯酚類係例如反應式(2)所示般，可藉由將對應之雙酚化合物於硝酸的存在下予以硝基化，並使所得到的雙(硝基苯酚)化合物之硝基於例如鈀碳或鎳等氫化催化劑存在下進行與氫氣之反應等一般所知的還原反應(日本特開2003-12611公報、日本特開2003-81925公報等)而得到。 Such a bisaminophenol is, for example, represented by the reaction formula (2), and can be nitrated by the corresponding bisphenol compound in the presence of nitric acid, and the obtained bis(nitrophenol) compound can be obtained. The nitro group is obtained by a known reduction reaction such as a reaction with hydrogen gas in the presence of a hydrogenation catalyst such as palladium carbon or nickel (JP-A-2003-12611, JP-A-2003-81925, etc.).

(式中，R2、A係與通式(1)者相同) (wherein R 2 and A are the same as those of the formula (1))

(方法2) (Method 2)

得到本發明的雙(羥苯基)苯并唑化合物之其他的方法，可列舉將對應目標的雙(羥苯基)苯并唑化合物之下述通式(4)所示之雙硝基苯酚類與下述通式(5)所示之甲基苯酚類作為原料，於有機溶劑中，較佳於催化劑的存在下且加溫下進行脫水縮合反應之方法。 Obtaining the bis(hydroxyphenyl)benzoate of the present invention Other methods of the azole compound include bis(hydroxyphenyl)benzoxes corresponding to the target The azole compound has a bisnitrophenol represented by the following formula (4) and a methylphenol represented by the following formula (5) as a raw material, and is preferably used in an organic solvent in the presence of a catalyst. A method of performing a dehydration condensation reaction at a temperature.

描述將例如雙(硝基苯酚)類中之1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷、甲基苯酚類中之2,6-二第三丁基對甲基苯酚作為原料之情形。其反應係例如下 述反應式(3)所示。 Described, for example, 2 of 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and methylphenol in bis(nitrophenol) The case of 6-di-t-butyl-p-methylphenol as a raw material. Its reaction system is for example The reaction formula (3) is shown.

上述方法中，雙硝基苯酚類係下述通式(4)所示。 In the above method, the bisnitrophenol is represented by the following formula (4).

(式中，R2、A係與通式(1)者相同) (wherein R 2 and A are the same as those of the formula (1))

因此，如此之雙硝基苯酚類，對應本發明的雙(羥苯基)苯并唑化合物，具體而言可列舉1,1-雙(3-硝基-4-羥苯基)環己烷、1,1-雙(3-硝基-5-甲基-4-羥苯基)環己烷、1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷、1,1-雙(3-硝基-4-羥苯基)環戊烷、1,1-雙(3-硝基-4-羥苯基)環庚烷等。 Therefore, such bisnitrophenols correspond to the bis(hydroxyphenyl)benzophenone of the present invention. The azole compound specifically includes 1,1-bis(3-nitro-4-hydroxyphenyl)cyclohexane and 1,1-bis(3-nitro-5-methyl-4-hydroxyphenyl). Cyclohexane, 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-nitro-4-hydroxyl) Phenyl)cyclopentane, 1,1-bis(3-nitro-4-hydroxyphenyl)cycloheptane, and the like.

此種雙硝基苯酚類，例如可藉由將對應前述通式(4)所示之雙硝基苯酚類之下述通式(6)所示之雙酚類，於例如實質上無其他酸存在之條件下，以50至80% 的硝酸在5℃以下的溫度進行硝基化等公知的方法進行硝基化而得到。 For example, the bisphenol represented by the following formula (6) corresponding to the bisnitrophenol represented by the above formula (4) can be, for example, substantially free of other acids. 50 to 80% under the conditions of existence The nitric acid is obtained by nitration by a known method such as nitration at a temperature of 5 ° C or lower.

(式中，R2、A係與通式(2)者相同) (wherein R 2 and A are the same as those of the formula (2))

上述方法中之原料甲基苯酚類係下述通式(5)所示。 The starting material methylphenol in the above method is represented by the following formula (5).

(式中，R1、n係與通式(1)者相同) (wherein R 1 and n are the same as those of the formula (1))

因此，此種甲基苯酚類，對應本發明的雙(羥苯基)苯并唑化合物，具體而言例如可列舉2,6-二第三丁基-4-甲基苯酚、2,4-二甲基-6-第三丁基苯酚、2-第三丁基-4-甲基苯酚、2,4,6-三甲基苯酚、2-甲氧基-4-甲基苯酚等。 Therefore, such methylphenols correspond to the bis(hydroxyphenyl)benzophenone of the present invention. Specific examples of the azole compound include 2,6-di-t-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, and 2-tert-butyl-4-. Methyl phenol, 2,4,6-trimethyl phenol, 2-methoxy-4-methyl phenol, and the like.

上述反應之時，雙硝基苯酚類與甲基苯酚類的原料之莫耳比，一般而言，相對於雙硝基苯酚1莫耳，甲基苯酚類一般為2至10莫耳的範圍，較佳為3至5莫耳的範圍。 At the time of the above reaction, the molar ratio of the raw materials of the dinitrophenols to the methylphenols is generally in the range of 2 to 10 moles per mole of the nitrophenol. It is preferably in the range of 3 to 5 moles.

催化劑係不使用亦可，但為了收率的提升，以使用為佳。使用催化劑時，催化劑較佳為鐵(鐵粉)、硫黃或硫化鈉、或是該等之混合物，催化劑的量係相對於原料的雙硝基苯酚類1莫耳，一般為0.01至3莫耳的範圍，為鐵時，較佳為0.1至0.3莫耳的範圍，為硫黃時，較佳為1.5至2.5莫耳的範圍，更佳為2莫耳。 The catalyst system may not be used, but it is preferably used for the purpose of improving the yield. When the catalyst is used, the catalyst is preferably iron (iron powder), sulfur or sodium sulfide, or a mixture thereof, and the amount of the catalyst is 1 to 3 moles per nitronitrophenol of the starting material, generally 0.01 to 3 moles. The range of the ear, when it is iron, is preferably in the range of 0.1 to 0.3 mol, and in the case of sulfur, it is preferably in the range of 1.5 to 2.5 mol, more preferably 2 mol.

反應溶劑係以使用較佳，例如可列舉鄰二氯甲苯等鹵化芳香族化合物、聯苯等芳香族烴溶劑；2,6-二甲基萘、2,6-二異丁基萘等烷基萘類；N-甲基-2-吡咯啶酮等醯胺溶劑；四乙二醇二甲醚、二乙二醇二丁醚等聚烷二醇醚類或該等的混合物。溶劑的使用量係相對於雙硝基苯酚類1重量份，較佳為1至50重量份的範圍，更佳為10至40重量份的範圍。 The reaction solvent is preferably used, and examples thereof include a halogenated aromatic compound such as o-dichlorotoluene and an aromatic hydrocarbon solvent such as biphenyl; and an alkyl group such as 2,6-dimethylnaphthalene or 2,6-diisobutylnaphthalene. Naphthalenes; guanamine solvents such as N-methyl-2-pyrrolidone; polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether; or mixtures thereof. The solvent is used in an amount of preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 1 part by weight of the bisnitrophenol.

反應溫度較佳為160至200℃的範圍，更佳為170至190℃的範圍。反應壓力為常壓、減壓、加壓之任一者均可，反應溶劑在常壓下之沸點較反應溫度低之情況等，為了提高溫度，可加壓來調整。 The reaction temperature is preferably in the range of 160 to 200 ° C, more preferably in the range of 170 to 190 ° C. The reaction pressure may be any of normal pressure, reduced pressure, and pressure. The boiling point of the reaction solvent at normal pressure is lower than the reaction temperature. In order to increase the temperature, it may be adjusted by pressurization.

反應係例如於反應容器中加入既定量的雙硝基苯酚類、甲基苯酚類、催化劑及反應溶劑，於氮氣流下一邊攪拌一邊升溫至既定的反應溫度，並於維持該溫度下進行反應。 In the reaction system, for example, a predetermined amount of bisnitrophenols, methylphenols, a catalyst, and a reaction solvent are added to the reaction vessel, and the mixture is heated to a predetermined reaction temperature while stirring under a nitrogen stream, and the reaction is carried out while maintaining the temperature.

反應結束後，由所得到的反應混合物，依照一般的方法，適當使用催化劑分離、低沸點成分之餾去分離、結晶過濾等一般所知的方法，藉此可得到目標物之雙(羥苯基) 苯并唑類的粗製品，另視需要，再次以結晶過濾、管柱分離等方法來精製，即可得到高純度品。 After completion of the reaction, a generally known method such as catalyst separation, distillation of low-boiling components, and crystallization filtration can be suitably used from the obtained reaction mixture in accordance with a general method, whereby a bisphenol (hydroxyphenyl group) can be obtained. Benzo The crude product of the azole is purified by a method such as crystal filtration or column separation, as needed, to obtain a high-purity product.

例如，將反應液直接冷卻或添加貧溶劑，析出結晶時將該結晶濾出，即可得粗製或高純度之目標物。或者，反應結束後，於減壓下濃縮反應溶劑等，將所得殘渣藉由進行管柱層析等精製，即可得高純度品。 For example, the reaction liquid is directly cooled or a poor solvent is added, and when the crystal is precipitated, the crystal is filtered off to obtain a target of crude or high purity. Alternatively, after completion of the reaction, the reaction solvent or the like is concentrated under reduced pressure, and the obtained residue is purified by column chromatography or the like to obtain a high-purity product.

(方法3) (Method 3)

得到本發明的雙(羥苯基)苯并唑化合物之另一個方法，可列舉，得到上述通式(1)中，n為1以上，且取代基R1之至少一個為第三丁基等三級烷基、或/及取代基R2為第三丁基等三級烷基之作為中間體的雙(羥苯基)苯并唑化合物，從所得到的中間體之經三級烷基取代之雙(羥苯基)苯并唑，於酸催化劑的存在且加溫下，藉由脫丁基等一般所知的方法(日本特開平2-169530號公報、日本特開平8-143494號公報等)，脫去第三丁基等三級烷基，取代成氫原子而得到目標的雙(羥苯基)苯并唑之方法。 Obtaining the bis(hydroxyphenyl)benzoate of the present invention In another method of the azole compound, in the above formula (1), n is 1 or more, and at least one of the substituents R 1 is a tertiary alkyl group such as a third butyl group, or/and a substituent R 2 Bis(hydroxyphenyl)benzoate as an intermediate of a tertiary alkyl group such as a third butyl group An azole compound, a bis(hydroxyphenyl) benzoate substituted with a tertiary alkyl group from the obtained intermediate The azole is removed in the presence of an acid catalyst, and the third butyl group is removed by a generally known method such as debutylation (Japanese Patent Laid-Open No. Hei. 2-169930, JP-A No. 8-143494, etc.). A tertiary alkyl group, substituted with a hydrogen atom to give the desired bis(hydroxyphenyl)benzoate The method of azole.

描述例如將雙(硝基苯酚)類中之1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷、甲基苯酚類中之2,6-二第三丁基對甲基苯酚作為原料，從依照上述方法2的反應所得到的作為中間體之1,1-雙[2-(3,5-二第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷，將第三丁基脫去而得到目標的1,1-雙[2-(4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷之情形。 For example, 2 of 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and methylphenol in bis(nitrophenol) 1,2-di-tert-butyl-p-methylphenol as a raw material, 1,1-bis[2-(3,5-di-tert-butyl-4-) as an intermediate obtained by the reaction according to the above method 2 Hydroxyphenyl)-5-benzo Azolyl]-3,3,5-trimethylcyclohexane, the third butyl group is removed to give the target 1,1-bis[2-(4-hydroxyphenyl)-5-benzo The case of azolyl]-3,3,5-trimethylcyclohexane.

其反應係例如下述反應式(4)所示。 The reaction is shown, for example, in the following reaction formula (4).

於上述脫丁基化反應之時，作為酸催化劑，較佳為對甲苯磺酸、對甲苯磺酸酐等高沸點的酸，催化劑的量相對於雙(羥苯基)苯并唑化合物，較佳為1至50莫耳%的範圍，更佳為10至30莫耳%的範圍。反應時，一般所使用之溶劑，較佳之溶劑可列舉苯酚、間甲苯酚等苯酚類。溶劑之量係無特別限制，但一般相對於雙(羥苯基)苯并唑化合物1重量份，較佳為10至500重量份左右。反應溫度一般為200至250℃左右的範圍。 In the above debutylation reaction, as the acid catalyst, a high boiling point acid such as p-toluenesulfonic acid or p-toluenesulfonic anhydride is preferred, and the amount of the catalyst is relative to bis(hydroxyphenyl)benzoate. The azole compound preferably has a range of from 1 to 50 mol%, more preferably from 10 to 30 mol%. In the case of the reaction, a solvent which is generally used is preferably a phenol such as phenol or m-cresol. The amount of the solvent is not particularly limited, but is generally relative to bis(hydroxyphenyl)benzoate. The azole compound is preferably used in an amount of from 10 to 500 parts by weight, based on 1 part by weight. The reaction temperature is usually in the range of about 200 to 250 °C.

反應係例如於反應容器中加入既定量的第三丁基取代一雙(羥苯基)苯并唑化合物、催化劑及反應溶劑，於氮環境下一邊攪拌一邊升溫至既定的反應溫度，並於維持該溫度下進行反應。 The reaction system is, for example, adding a predetermined amount of a third butyl-substituted bis(hydroxyphenyl)benzene to the reaction vessel. The azole compound, the catalyst, and the reaction solvent are heated to a predetermined reaction temperature while stirring under a nitrogen atmosphere, and the reaction is carried out while maintaining the temperature.

反應結束後，由反應混合物得到目標物，可使用結晶、濃縮等一般所知的精製方法。藉由例如於反應液添加溶劑或水、或是濃縮、或是其組合來結晶化，將析出的目標物之結晶濾出。於反應液實施上述操作之前，可藉由加入與水分離之溶劑後水洗之，除去水溶性的雜質。又，藉由鹼性水溶液之中和處理或水洗等，由反應液除去催化 劑，或以濃縮進行低沸點物等之除去處理後，亦可藉由管柱層析進行精製。 After completion of the reaction, the target product is obtained from the reaction mixture, and a generally known purification method such as crystallization or concentration can be used. The crystal of the precipitated target is filtered off by, for example, adding a solvent or water to the reaction liquid, or concentrating or a combination thereof to crystallize. Before the reaction liquid is subjected to the above operation, water-soluble impurities can be removed by adding a solvent separated from water and then washing with water. Further, the catalyst is removed from the reaction solution by an alkaline aqueous solution neutralization treatment or water washing or the like. The agent may be purified by column chromatography after the removal of the low-boiling substance or the like by concentration.

(實施例) (Example)

(製造例) (Manufacturing example)

1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷的合成 Synthesis of 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane

將1,1-雙(4-羥苯基)-3,3,5-三甲基環己烷9.32g(0.030mol)、二氯甲烷50ml、與攪拌用磁石加入於100ml的三口燒瓶後，冷卻之，一邊維持反應溫度在0至5℃一邊以3小時滴下70%的硝酸6.10g(0.067mol)。進一步，一邊維持該溫度一邊反應3小時。反應結束後，過濾反應液，於濾出的結晶中依序注入1%的碳酸氫鈉水溶液、蒸餾水充分洗浄。乾燥後，得到純度99.9%(高效液相層析法)的1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷6.0g。 After adding 9.32 g (0.030 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 50 ml of dichloromethane, and adding a magnet for stirring to a 100 ml three-necked flask, After cooling, 6.10 g (0.067 mol) of 70% nitric acid was dropped over 3 hours while maintaining the reaction temperature at 0 to 5 °C. Further, the reaction was carried out for 3 hours while maintaining the temperature. After completion of the reaction, the reaction solution was filtered, and the filtered crystals were sequentially washed with a 1% aqueous sodium hydrogencarbonate solution and distilled water. After drying, 6.0 g of 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane having a purity of 99.9% (high performance liquid chromatography) was obtained.

(實施例1) (Example 1)

1,1-雙[2-(3,5-二第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷的合成 1,1-bis[2-(3,5-di-t-butyl-4-hydroxyphenyl)-5-benzo Synthesis of azolyl]-3,3,5-trimethylcyclohexane

將1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷600.5mg(1.50mmol)、2,6-二第三丁基對甲基苯酚1322.3mg(6.00mmol)、硫黃粉末96.2mg(3.00mmol)、與鐵粉16.8mg(0.30mmol)、與鄰二氯苯8m1加入100ml的試驗管後，於常溫下，將試驗管內用氬取代。 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane 600.5 mg (1.50 mmol), 2,6-di-t-butyl-p-methyl 132.3 mg (6.00 mmol) of phenol, 96.2 mg (3.00 mmol) of sulfur powder, 16.8 mg (0.30 mmol) of iron powder, and 8 ml of o-dichlorobenzene were added to a test tube of 100 ml, and the test tube was used at room temperature. Argon substitution.

之後，一邊攪拌一邊升溫至180℃，於該溫度一邊使之迴流一邊進行反應48小時。反應結束後，於減壓下餾去低沸點物，將濃縮殘渣以矽膠管柱層析精製，得到1,1-雙 [2-(3,5-二第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷571.5mg。相對於1,1-雙(3-硝基-4-羥苯基)-3,3,5-三甲基環己烷之收率為50%。 Thereafter, the temperature was raised to 180 ° C while stirring, and the reaction was carried out for 48 hours while refluxing at this temperature. After completion of the reaction, the low-boiling substance was distilled off under reduced pressure, and the concentrated residue was purified by silica gel column chromatography to give 1,1-bis[2-(3,5-di-tert-butyl-4-hydroxyphenyl). )-5-Benzene Azolyl]-3,3,5-trimethylcyclohexane 571.5 mg. The yield based on 1,1-bis(3-nitro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was 50%.

分子量(HRMS/MALDI-TOF)：769.4964(M+H)+ Molecular weight (HRMS/MALDI-TOF): 769.4964 (M+H) +

1H NMR鑑定結果(300MHz、溶劑：CDCl3、內部標準：四甲基矽烷) 1 H NMR identification results (300 MHz, solvent: CDCl 3 , internal standard: tetramethyl decane)

(實施例2) (Example 2)

1,1-雙[2-(4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷的合成 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Synthesis of azolyl]-3,3,5-trimethylcyclohexane

將實施例1所合成之1,1-雙[2-(3,5-二第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷154.2mg(0.20mmol)、苯酚2.91g、與對甲苯磺酸酐8.4mg(4.9×10-2mmol)加入於10ml的耐壓用試驗管並密封，以微波反應裝置一邊攪拌一邊升溫至210℃，以該溫度進行反應4小時。 The 1,1-bis[2-(3,5-di-t-butyl-4-hydroxyphenyl)-5-benzoate synthesized in Example 1 154.2 mg (0.20 mmol) of azolyl]-3,3,5-trimethylcyclohexane, 2.91 g of phenol, and 8.4 mg (4.9×10 -2 mmol) of p-toluenesulfonic anhydride were added to 10 ml of pressure resistance test. The tube was sealed and heated to 210 ° C while stirring in a microwave reactor, and the reaction was carried out at this temperature for 4 hours.

進一步升溫至230℃後，進行反應3小時，然後升溫至250℃，並進行反應5小時。 After further raising the temperature to 230 ° C, the reaction was carried out for 3 hours, and then the temperature was raised to 250 ° C, and the reaction was carried out for 5 hours.

反應後冷卻至室溫，將所得到的反應結束後液體加入 水中，進一步加入鹼性水溶液而中和至pH6左右，除去水層。將所得到的油層以矽膠管柱層析精製，得到1,1-雙[2-(4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷42.0mg。相對於1,1-雙[2-(3,5-二第三丁基-4-羥苯基)-5-苯并唑基]-3,3,5-三甲基環己烷，收率為39%。 After the reaction, the mixture was cooled to room temperature, and after the completion of the reaction, the liquid was added to water, and an aqueous alkaline solution was further added thereto to neutralize to about pH 6, to remove the aqueous layer. The obtained oil layer was purified by silica gel column chromatography to obtain 1,1-bis[2-(4-hydroxyphenyl)-5-benzo Azolyl]-3,3,5-trimethylcyclohexane 42.0 mg. Relative to 1,1-bis[2-(3,5-di-t-butyl-4-hydroxyphenyl)-5-benzo Azolyl]-3,3,5-trimethylcyclohexane, yield 39%.

熔點344℃(示差掃描量熱法) Melting point 344 ° C (differential scanning calorimetry)

分子量(HRMS/MALDI-TOF)：545.2461(M+H)+ Molecular weight (HRMS/MALDI-TOF): 545.2461 (M+H) +

1H NMR鑑定結果(300MHz、溶劑：THF-d8、內部標準：四甲基矽烷) 1 H NMR identification results (300 MHz, solvent: THF-d 8 , internal standard: tetramethyl decane)

(比較例) (Comparative example)

將以實施例相同的方法所合成之2,2’-二(4-羥苯基)-5,5’-苯并唑(比較例的化合物)與實施例2所得到的化合物分別在室溫下溶解於甲醇、甲苯、甲基異丁基酮(MIBK)，製作飽和溶液。取出飽和溶液的上澄液，以高效液相層析來測定濃度。個別的測定結果如下述表中所示。此外，比較例化合物之熔點為410℃(示差掃描量熱法)。 2,2'-bis(4-hydroxyphenyl)-5,5'-benzoic acid synthesized in the same manner as in the examples The azole (compound of the comparative example) and the compound obtained in Example 2 were each dissolved in methanol, toluene, and methyl isobutyl ketone (MIBK) at room temperature to prepare a saturated solution. The supernatant of the saturated solution was taken out and the concentration was measured by high performance liquid chromatography. The individual measurement results are shown in the table below. Further, the melting point of the comparative compound was 410 ° C (differential scanning calorimetry).

由上述的結果清楚地暸解，本發明的苯并唑化合物於甲醇、甲苯、MIBK各溶劑之溶解性，相較於比較例的化合物為非常的優異。 It is clear from the above results that the benzoyl of the present invention The solubility of the azole compound in each of methanol, toluene, and MIBK was extremely excellent compared to the compound of the comparative example.

Claims (1)

一種下述通式(1)所示之雙(羥苯基)苯并唑化合物； 式中，R1係表示碳原子數1至8的烷基、碳原子數1至8的烷氧基、苯基或鹵原子，R2係表示氫原子、碳原子數1至8的烷基、碳原子數1至8的烷氧基、苯基或鹵原子，A係表示碳原子數5至10的亞環烷基，n係表示0或1至4的整數。 a bis(hydroxyphenyl)benzobenzene represented by the following formula (1) Azole compound In the formula, R 1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and R 2 represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. An alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, A being a cycloalkylene group having 5 to 10 carbon atoms, and n being an integer of 0 or 1 to 4.
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