JP2011006330A - Method for producing aromatic carboxylic acid dianhydride having ester group - Google Patents
Method for producing aromatic carboxylic acid dianhydride having ester group Download PDFInfo
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- aromatic carboxylic
- carboxylic acid
- acid dianhydride
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- anhydride
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- 125000004185 ester group Chemical group 0.000 title claims abstract description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 96
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 60
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 40
- -1 aromatic carboxylic acid diester Chemical class 0.000 description 31
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 28
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 23
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 18
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- OFFSPAZVIVZPHU-UHFFFAOYSA-N 1-benzofuran-2-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)=CC2=C1 OFFSPAZVIVZPHU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LAZJJTHRAFGBOK-UHFFFAOYSA-N 4,6,7-trichloro-1,3-dioxo-2-benzofuran-5-carbonyl chloride Chemical compound ClC1=C(Cl)C(C(=O)Cl)=C(Cl)C2=C1C(=O)OC2=O LAZJJTHRAFGBOK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- 108010000916 Fimbriae Proteins Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000006389 diacetylation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
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- Furan Compounds (AREA)
Abstract
Description
本発明は、無水トリメリット酸を酸クロリド化反応して得られる無水トリメリット酸クロリドを芳香族ジヒドロキシ化合物と反応させて、ポリイミド樹脂等の原料として有用な、エステル基を有する芳香族カルボン酸二無水物（以下、「ジエステル化合物」ともいう。）を効率よく製造する方法に関する。 In the present invention, trimellitic anhydride chloride obtained by subjecting trimellitic anhydride to acid chloride reaction is reacted with an aromatic dihydroxy compound to produce an aromatic carboxylic acid diester having an ester group that is useful as a raw material for polyimide resins and the like. The present invention relates to a method for efficiently producing an anhydride (hereinafter also referred to as “diester compound”).
従来、エステル基を有する芳香族カルボン酸二無水物の製造法としては、例えばｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造する方法が公知であり、一例として、ヒドロキノンを無水酢酸でジアセチル化したのちこれを無水トリメリット酸と２５０〜３００℃で反応しエステル交換して製造する方法が提案されている（非特許文献１、特許文献１）。 Conventionally, as a method for producing an aromatic carboxylic acid dianhydride having an ester group, for example, a method for producing p-phenylenebis (trimellitic acid monoester acid anhydride) is known. As an example, hydroquinone is used as acetic anhydride. There has been proposed a method of producing a product by diacetylation with a trimellitic acid, reacting it with trimellitic anhydride at 250 to 300 ° C. and transesterifying (Non-patent Document 1, Patent Document 1).
また、無水トリメリット酸および脂肪族ジオール類を２１０〜２３０℃で脱水エステル化して無水トリメリット酸エステル類を製造する方法も提案されている（特許文献２）。しかし熱的に安定でないジオール類をこのような高温にさらすのは得策ではなく、工業的に高純度のｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造する方法として採用するは難しい。 A method for producing trimellitic anhydride esters by dehydrating ester of trimellitic anhydride and aliphatic diols at 210 to 230 ° C. has also been proposed (Patent Document 2). However, it is not a good idea to expose diols that are not thermally stable to such a high temperature, and it is difficult to adopt as a method for industrially producing highly pure p-phenylenebis (trimellitic acid monoester anhydride). .
一方、無水トリメリット酸無水物およびジオール類を原料として脱塩酸してトリメリット酸エステル無水物を製造する方法が提案されている。例えば特許文献３では、無水トリメリット酸クロリドおよびビスフェノールＡを原料として２，２−ビス（トリメリットキシフェニル）プロパンを製造している。本法によれば、溶媒としてテトラヒドロフラン（以下、「ＴＨＦ」と略称することがある。）を用い、塩酸捕捉剤としてピリジンを添加して脱塩酸することで２，２−ビス（トリメリットキシフェニル）プロパンを合成し、反応後副生するピリジン塩酸塩を濾過して除去後、ＴＨＦを留去して得られた生成物を無水酢酸で再結晶して製造している。しかしこの方法で無水トリメリット酸クロリドとヒドロキノンとを反応させてｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造しても、製品中にピリジン塩酸塩が残存し、また無水酢酸で再結晶しても副生物は除去できず製品純度は上がらない。 On the other hand, a method for producing trimellitic ester anhydride by dehydrochlorination using trimellitic anhydride and diol as raw materials has been proposed. For example, in Patent Document 3, 2,2-bis (trimeritoxyphenyl) propane is produced using trimellitic anhydride chloride and bisphenol A as raw materials. According to this method, tetrahydrofuran (hereinafter sometimes abbreviated as “THF”) is used as a solvent, and pyridine is added as a hydrochloric acid scavenger to remove hydrochloric acid, thereby removing 2,2-bis (trimeritoxyphenyl). ) Propane is synthesized, and pyridine hydrochloride formed as a by-product after the reaction is removed by filtration, and the product obtained by distilling THF off is recrystallized with acetic anhydride. However, even if p-phenylenebis (trimellitic acid monoester anhydride) is produced by reacting trimellitic anhydride chloride with hydroquinone by this method, pyridine hydrochloride remains in the product and acetic anhydride is used. Recrystallization does not remove by-products and does not increase product purity.
また、特許文献４では無水トリメリット酸クロリドとヒドロキノンを原料としてｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造している。本法によれば、溶媒としてトルエンを用い、塩酸捕捉剤としてピリジンを使用し還流下で反応後、濾過して固形物を分離し、水洗したのち乾燥して粗製物を得ている。ついで無水酢酸で加熱処理した後、Ｎ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」と略称することがある。）で再結晶してｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造している。しかしながら、副生するピリジン塩酸塩を水洗により除去しているため、目的物の一部が加水分解する。加水分解物を元に戻すために無水酢酸による加熱処理が必要となり合理的な方法ではない。 In Patent Document 4, p-phenylenebis (trimellitic acid monoester acid anhydride) is produced using trimellitic anhydride chloride and hydroquinone as raw materials. According to this method, toluene is used as a solvent, and pyridine is used as a hydrochloric acid scavenger. After reaction under reflux, the solid is separated by filtration, washed with water, and dried to obtain a crude product. Next, after heat treatment with acetic anhydride, recrystallization from N, N-dimethylformamide (hereinafter sometimes abbreviated as “DMF”) produces p-phenylenebis (trimellitic acid monoester acid anhydride). is doing. However, since the by-product pyridine hydrochloride is removed by washing with water, a part of the target product is hydrolyzed. In order to restore the hydrolyzate, heat treatment with acetic anhydride is required, which is not a rational method.
また、アセトニトリルを溶媒として、ピリジンを添加し、３，５，６−トリクロロ−４−クロロホルミルフタル酸無水物をヒドロキノンと反応させて３，５，６−トリクロロ−４−クロロホルミルフタル酸無水物ヒドロキノンを製造する方法が提案されている（特許文献５）。本法は、−１８℃で反応し、生成物を濾過して分離し、クロロホルムで数回洗浄後乾燥のみで光通信用モノマーとしての３，５，６−トリクロロ−４−クロロホルミルフタル酸無水物ヒドロキノンを製造している。しかしながら、本法で無水トリメリット酸クロリドとヒドロキノンを反応させてｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造しても、製品中にピリジン塩酸塩が残存し、また基質が異なることで副生物の形態も異なり、副生物は除去できない。さらに洗浄に環境負荷の大きなクロロホルムを使用すること、反応温度が−１８℃であること等、実際的ではなく工業的に満足する製法ではない。 Also, acetonitrile is used as a solvent, pyridine is added, and 3,5,6-trichloro-4-chloroformylphthalic anhydride is reacted with hydroquinone to produce 3,5,6-trichloro-4-chloroformylphthalic anhydride. A method for producing hydroquinone has been proposed (Patent Document 5). This method reacts at −18 ° C., and the product is separated by filtration, washed several times with chloroform, and then dried only 3,5,6-trichloro-4-chloroformylphthalic anhydride as a monomer for optical communication The product hydroquinone is manufactured. However, even if p-phenylenebis (trimellitic acid monoester anhydride) is produced by reacting trimellitic anhydride chloride with hydroquinone in this method, pyridine hydrochloride remains in the product and the substrate is different. As a result, the form of the by-product is different, and the by-product cannot be removed. Furthermore, it is not practical and industrially satisfactory, such as using chloroform with a large environmental load for washing, and having a reaction temperature of −18 ° C.
また、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）等の酸二無水物は、空気中の水分によって容易に加水分解する場合がある。加水分解を抑制するため、または加水分解物を元に戻すために、無水酢酸で再結晶する方法および無水酢酸と酢酸等の混合液で再結晶する方法が提案されている（特許文献３、非特許文献２）。より合理的な方法ではあるが製造法は煩雑で、工業的な製法として満足できないものである。 In addition, acid dianhydrides such as p-phenylenebis (trimellitic acid monoester acid anhydride) may be easily hydrolyzed by moisture in the air. In order to suppress hydrolysis or restore the hydrolyzate, a method of recrystallization with acetic anhydride and a method of recrystallization with a mixed solution of acetic anhydride and acetic acid have been proposed (Patent Document 3, non-patent document 3). Patent Document 2). Although it is a more rational method, the production method is complicated and unsatisfactory as an industrial production method.
本発明の目的は、より経済的に効率よく、エステル基を有する芳香族カルボン酸二無水物（ジエステル化合物）を製造する方法を提供することにある。 The objective of this invention is providing the method of manufacturing aromatic carboxylic dianhydride (diester compound) which has an ester group more economically efficiently.
本発明者らは、無水トリメリット酸クロリドをヒドロキノンと反応させてｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を製造する方法において、これまでに多く提案されている製造法の煩雑な操作、すなわち副生するピリジン塩酸塩を水洗して除去する操作、および水洗のために生成する加水分解物の処理操作を必要としない簡便な方法を鋭意検討した。 In the method of producing p-phenylenebis (trimellitic acid monoester anhydride) by reacting trimellitic anhydride chloride with hydroquinone, the present inventors have complicated the production methods that have been proposed so far. The inventors have intensively studied a simple method that does not require an operation, that is, an operation of removing by-product pyridine hydrochloride by washing with water and a treatment of hydrolyzate produced for washing with water.
また、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）は加水分解しやすいため、これを防止するための精製法として合理的と考えられる無水酢酸による再結晶方法や無水酢酸と酢酸等の混合液による再結晶方法では高純度化できない原因を調査した。 Moreover, since p-phenylenebis (trimellitic acid monoester anhydride) is easily hydrolyzed, a recrystallization method using acetic anhydride considered to be rational as a purification method for preventing this, acetic anhydride and acetic acid, etc. The reason why high purity could not be achieved by the recrystallization method using a mixed solution was investigated.
その結果、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）は無水酢酸中で容易に加溶媒分解して、溶媒洗浄、再結晶等の精製法で除去できない不純物として、以下の式（１）で示される構造のアセトキシフェニルトリメリット酸エステル（以下、このような、本来トリメット酸とのエステル結合が形成されるべき水酸基に酢酸とのエステル結合が形成された構造を有する化合物を「モノエステル化合物」と総称する。）を生成することを見出した。 As a result, p-phenylenebis (trimellitic acid monoester anhydride) is easily solvolyzed in acetic anhydride and is represented by the following formula (1) as an impurity that cannot be removed by purification methods such as solvent washing and recrystallization. A compound having a structure in which an ester bond with acetic acid is formed on a hydroxyl group that should originally form an ester bond with trimetic acid is referred to as a “monoester”. It was found to produce "compound".
すなわち、従来合理的と考えられていた無水酢酸を主体とする溶媒を用いた再結晶方法では当該モノエステル化合物が生成するため、高純度化を実現することは本質的に不可能なのである。 That is, since the monoester compound is produced by a recrystallization method using a solvent mainly composed of acetic anhydride, which has been conventionally considered to be rational, it is essentially impossible to achieve high purity.
なお、この不純物はＬＣＭＳ分析結果に基づき同定した。
上記の不純物であるモノエステル化合物を生成させないためには、無水酢酸を主体とする溶媒を反応後使用してはならないのであり、そうすると、反応により得られた濾過物を水洗してピリジン塩酸塩を溶解させる操作を避ける必要がある。したがって、反応溶媒には、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）を溶解させにくく、かつピリジン塩酸塩を溶解しやすいものが求められることになる。
This impurity was identified based on the LCMS analysis result.
In order not to produce the above monoester compound which is an impurity, a solvent mainly composed of acetic anhydride must not be used after the reaction. Then, the filtrate obtained by the reaction is washed with water to obtain pyridine hydrochloride. It is necessary to avoid the operation of dissolving. Therefore, the reaction solvent is required to be one in which p-phenylenebis (trimellitic acid monoester acid anhydride) is hardly dissolved and pyridine hydrochloride is easily dissolved.
この観点で検討したところ、無水トリメリット酸クロリドをヒドロキノンと反応させる際の溶媒にアセトニトリルを使用することで、上記課題を解決することができ、特別な精製操作（水洗、無水酢酸を主体とする溶媒による加熱）をすることなく、高純度ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）が製造できることを見出し、特願２００８−１６１８２２として提案した。この提案によれば、反応で副生するピリジン塩酸塩を水洗で除去する必要はない。従って水洗により生成する加水分解物の処理操作を必要としない簡便な方法で目的物を製造できる。 From this point of view, by using acetonitrile as a solvent for reacting trimellitic anhydride chloride with hydroquinone, the above problems can be solved, and special purification operations (mainly water washing and acetic anhydride are mainly used). It was found that high-purity p-phenylenebis (trimellitic acid monoester anhydride) can be produced without heating with a solvent, and proposed as Japanese Patent Application No. 2008-161822. According to this proposal, it is not necessary to remove pyridine hydrochloride formed as a by-product in the reaction by washing with water. Therefore, the target product can be produced by a simple method that does not require a treatment operation of the hydrolyzate produced by washing with water.
ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）等のエステル基を有する芳香族カルボン酸二無水物（ジエステル化合物）はポリイミド樹脂等の原料として有用で広範囲な用途が期待されている。そこで、この先願の提案をジエステル化合物の工業的な製法として他のジエステル化合物の製造に応用できないかという観点で鋭意検討した。その結果、代表的なジエステル化合物の製造に対しても適用可能であることを見出すに至った。 Aromatic carboxylic dianhydrides (diester compounds) having an ester group such as p-phenylenebis (trimellitic acid monoester anhydride) are useful as raw materials for polyimide resins and are expected to be used in a wide range of applications. Therefore, the proposal of this prior application was intensively studied from the viewpoint of whether it can be applied to the production of other diester compounds as an industrial production method of diester compounds. As a result, it has been found that the present invention is applicable to the production of typical diester compounds.
以上の知見に基づき完成された本発明は、無水トリメリット酸クロリドを塩基の存在下、芳香族ジヒドロキシ化合物と反応させてエステル基を有する芳香族カルボン酸二無水物（ジエステル化合物）を製造する方法において、反応溶媒にアセトニトリルを使用することを特徴とするエステル基を有する芳香族カルボン酸二無水物（ジエステル化合物）の製造方法である。 The present invention completed based on the above knowledge is a method for producing an aromatic carboxylic dianhydride (diester compound) having an ester group by reacting trimellitic anhydride chloride with an aromatic dihydroxy compound in the presence of a base. In the method for producing an aromatic carboxylic dianhydride (diester compound) having an ester group, wherein acetonitrile is used as a reaction solvent.
上記の製造方法における好ましい態様は次のとおりである：
塩基がピリジンである。
無水トリメリット酸クロリドのアセトニトリル溶液中に芳香族ジヒドロキシ化合物のアセトニトリル溶液を滴下するときの系内の温度を５〜４０℃とし、滴下終了後の反応は、系内の温度を５〜４０℃に保持することで行われる。
A preferred embodiment in the above production method is as follows:
The base is pyridine.
The temperature in the system when the acetonitrile solution of the aromatic dihydroxy compound is dropped into the acetonitrile solution of trimellitic anhydride chloride is set to 5 to 40 ° C., and the reaction after the completion of the dropping is performed at 5 to 40 ° C. It is done by holding.
本発明の方法においては、水洗操作を行うことなく副生する塩酸塩は除去されるため、加水分解物を元に戻すための処理操作（例えば無水酢酸を主成分とする溶媒中での加熱操作）が必要とされない。このため、上記式（１）に示すモノエステル化合物と同様の構造を有して精製によっても製品から除去されにくいと推測されるモノエステル化合物が生成しない。 In the method of the present invention, the by-product hydrochloride is removed without performing a washing operation, so that a treatment operation for returning the hydrolyzate (for example, a heating operation in a solvent containing acetic anhydride as a main component) is performed. ) Is not required. For this reason, the monoester compound which has the same structure as the monoester compound represented by the above formula (1) and is not likely to be removed from the product even by purification is not generated.
よって本発明の方法を実施することにより、不純物の生成が抑制され、工業的に有利にジエステル化合物を製造することが実現される。
また、前述のようにジエステル化合物はポリイミド樹脂の原料、すなわちモノマーとして使用される。このジエステル化合物が関与する重合反応において、上記のモノエステル化合物は阻害因子となる可能性がある。したがって、本発明に係る製造方法により製造されたジエステル化合物からなる重合原料は、ポリイミド樹脂の重合原料として好適である。
Therefore, by carrying out the method of the present invention, it is possible to suppress the production of impurities and to produce a diester compound advantageously industrially.
Further, as described above, the diester compound is used as a raw material of the polyimide resin, that is, a monomer. In the polymerization reaction involving the diester compound, the monoester compound may be an inhibitor. Therefore, the polymerization raw material which consists of the diester compound manufactured by the manufacturing method which concerns on this invention is suitable as a polymerization raw material of a polyimide resin.
以下、本発明に係るエステル基を有する芳香族カルボン酸二無水物（ジエステル化合物）の製造方法について詳細に説明する。
本発明においては、無水トリメリット酸クロリドを芳香族ジヒドロキシ化合物と反応させてジエステル化合物を製造する方法において、反応溶媒としてアセトニトリルを使用する。
Hereinafter, the manufacturing method of the aromatic carboxylic dianhydride (diester compound) which has an ester group based on this invention is demonstrated in detail.
In the present invention, acetonitrile is used as a reaction solvent in a method for producing a diester compound by reacting trimellitic anhydride chloride with an aromatic dihydroxy compound.
アセトニトリルの使用量は、無水トリメリット酸クロリドおよび芳香族ジヒドロキシ化合物を溶解し得る量で有れば良い。無水トリメリット酸クロリドを溶解するのに使用するアセトニトリル量は、通常、無水トリメリット酸クロリド仕込み重量の１．０〜３．０倍、好ましくは１．５〜２．０倍である。また、芳香族ジヒドロキシ化合物を溶解するのに使用するアセトニトリル量は、通常、芳香族ジヒドロキシ化合物仕込み重量の７．０〜１２．０倍、好ましくは９．０〜１０．０倍である。 The amount of acetonitrile used may be an amount that can dissolve the trimellitic anhydride chloride and the aromatic dihydroxy compound. The amount of acetonitrile used to dissolve the trimellitic anhydride chloride is usually 1.0 to 3.0 times, preferably 1.5 to 2.0 times the weight of trimellitic anhydride chloride charged. Further, the amount of acetonitrile used for dissolving the aromatic dihydroxy compound is usually 7.0 to 12.0 times, preferably 9.0 to 10.0 times the charged amount of the aromatic dihydroxy compound.
これよりも少ないと反応で副生する塩酸塩が溶解しにくく製品品質を低下させ、多ければ経済的に不利である。塩酸捕捉剤として使用する塩基は従来公知の塩基であって塩酸塩がアセトニトリルに溶解するものであれば良く、ピリジンが特に好ましい。塩基は芳香族ジヒドロキシ化合物のアセトニトリル溶液中に混合すればよい。 If it is less than this, the hydrochloride produced as a by-product in the reaction is difficult to dissolve, and the product quality is lowered, and if it is more, it is economically disadvantageous. The base used as the hydrochloric acid scavenger is a conventionally known base as long as the hydrochloride is dissolved in acetonitrile, and pyridine is particularly preferable. The base may be mixed in an acetonitrile solution of an aromatic dihydroxy compound.
なお、無水トリメリット酸クロリドのジヒドロキシ化合物に対する比率は、モル比として、２．１〜２．４とすることが好ましい。
また、塩基の無水トリメリット酸クロリドに対する比率は、モル比として、１．０〜１．２とすることが好ましい。
In addition, it is preferable that the ratio with respect to the dihydroxy compound of trimellitic anhydride chloride shall be 2.1-2.4 as molar ratio.
Moreover, it is preferable that the ratio with respect to the trimellitic anhydride chloride of a base shall be 1.0-1.2 as molar ratio.
溶解した無水トリメリット酸クロリドのアセトニトリル溶液中に芳香族ジヒドロキシ化合物のアセトニトリル溶液を滴下することで反応を開始させる。このとき、ピリンなどの塩酸塩は滴下する溶液である芳香族ジヒドロキシ化合物側の溶液に含有させる。なお、上記の滴下方法とは反対に、芳香族ジヒドロキシ化合物のアセトニトリル溶液中に無水トリメリット酸クロリドのアセトニトリル溶液を滴下すると、上記の滴下方法で滴下した場合よりも副生成物が生成しやすい。したがって、上記の滴下方法で滴下することが好ましい。 The reaction is started by dropping an acetonitrile solution of an aromatic dihydroxy compound dropwise into a dissolved acetonitrile solution of trimellitic anhydride chloride. At this time, hydrochloride such as pilin is contained in the solution on the aromatic dihydroxy compound side which is a solution to be dropped. In contrast to the above dropping method, when an acetonitrile solution of trimellitic anhydride chloride is dropped into an acetonitrile solution of an aromatic dihydroxy compound, a by-product is more likely to be produced than when the dropping method is used. Therefore, it is preferable to drop by the above dropping method.
滴下時は系内の温度を０〜４０℃、好ましくは５〜２５℃にすることが好ましい。滴下時間に制約はなく、所定温度を保時できる滴下速度でよい。
滴下終了後は、系内の温度を１５〜４０℃、好ましくは２０〜３０℃で１〜１０時間反応させる。
At the time of dropping, the temperature in the system is preferably 0 to 40 ° C, preferably 5 to 25 ° C. There is no restriction | limiting in dripping time, The dripping speed | rate which can hold | maintain predetermined temperature may be sufficient.
After completion of the dropping, the temperature in the system is reacted at 15 to 40 ° C., preferably 20 to 30 ° C. for 1 to 10 hours.
反応終了後、生成したジエステル化合物の固形物を濾過して回収する。副生した塩酸塩、好ましい態様ではピリジン塩酸塩はアセトニトリルに溶解するため、反応液を濾過するのみでジエステル化合物から除去される。 After completion of the reaction, the produced diester compound solid is collected by filtration. By-product hydrochloride, in a preferred embodiment, pyridine hydrochloride, is dissolved in acetonitrile, and thus is removed from the diester compound simply by filtering the reaction solution.
この固形物を有機溶媒で洗浄することでより高純度のジエステル化合物が得られる。
また、この固形物を有機溶媒に加温して溶解する。有機溶媒としてはジエステル化合物を可溶媒分解させないものであれば特に制限されず、ＤＭＦもしくはＮ，Ｎ−ジメチルアセトアミドまたはそれらの任意の混合液を用いることが好ましい。使用する有機溶媒量はジエステル化合物の固形物の２．５〜５．０重量倍、好ましくは３．０〜４．０重量倍である。
By washing the solid with an organic solvent, a higher purity diester compound can be obtained.
The solid is dissolved by heating in an organic solvent. The organic solvent is not particularly limited as long as it does not decompose the diester compound in a solvent, and it is preferable to use DMF, N, N-dimethylacetamide, or any mixture thereof. The amount of the organic solvent to be used is 2.5 to 5.0 times by weight, preferably 3.0 to 4.0 times by weight of the solid substance of the diester compound.
ここで、一般的に、これらの有機溶媒は、工業レベルで入手可能なものの場合には、少量の水分を含有していることが多く、この水分によって少量の加水分解物が生成する可能性がある。しかしながら、少量の加水分解物であれば再結晶時に濾液に移って除去できるため製品品質には影響しない。むしろ、収率を高める観点のみから脱水品を使用すると、経済的に不利となる場合もある。したがって、工業レベルで入手される有機溶媒を使用しつつ、これらの有機溶媒中に脱水剤として無水酢酸を１質量％程度添加したものを使用することが好ましい。この程度であれば、上記式（１）に示される化合物と同様の構造を有するモノエステル化合物が副生成物として生成しても、純度に与える影響は軽微であり、収率と純度とを高いレベルで両立することが実現される。 Here, in general, these organic solvents often contain a small amount of water when available at an industrial level, and this water may generate a small amount of hydrolyzate. is there. However, since a small amount of hydrolyzate can be removed by moving to the filtrate during recrystallization, the product quality is not affected. Rather, if a dehydrated product is used only from the viewpoint of increasing the yield, it may be economically disadvantageous. Therefore, it is preferable to use what added about 1 mass% of acetic anhydride as a dehydrating agent in these organic solvents, using the organic solvent obtained on an industrial level. If it is this grade, even if the monoester compound which has the structure similar to the compound shown by said Formula (1) produces | generates as a by-product, the influence on purity is slight, and yield and purity are high. It is possible to achieve both levels.
有機溶媒によるジエステル化合物の溶解温度は６０〜１１０℃、好ましくは７０〜８５℃である。温度が高い場合には着色が懸念される。一方、温度が低いと溶解しにくくなるため、良好な精製効果を得ることが困難となる。 The dissolution temperature of the diester compound in the organic solvent is 60 to 110 ° C, preferably 70 to 85 ° C. If the temperature is high, coloring is a concern. On the other hand, since it becomes difficult to melt | dissolve when temperature is low, it becomes difficult to acquire a favorable purification effect.
有機溶媒にジエステル化合物を溶解させたら、その溶液を冷却してジエステル化合物を晶析させる。冷却する温度は−１０〜３０℃、好ましくは５〜２５℃である。温度が低すぎると結晶の移送が困難となりハンドリング上好ましくない。温度が高すぎると製品収率が低下して経済的に不利である。 When the diester compound is dissolved in the organic solvent, the solution is cooled to crystallize the diester compound. The cooling temperature is −10 to 30 ° C., preferably 5 to 25 ° C. If the temperature is too low, it is difficult to transfer crystals, which is not preferable for handling. If the temperature is too high, the product yield is lowered, which is economically disadvantageous.
析出した固形物を濾過してジエステル化合物を分離する。分離したジエステル化合物の固形物は有機溶媒で洗浄する。有機溶媒としては、脂肪族ケトン類、エーテル類、芳香族炭化水素類が使用される。例えば、脂肪族ケトン類としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等、エーテル類としては、テトラヒドロフラン、メチルイソブチルエーテル、メチルイソプロピルエーテル等、芳香族炭化水素類としてはベンゼン、トルエン、キシレン、エチルベンゼン等が挙げられる。 The precipitated solid is filtered to separate the diester compound. The separated diester compound solid is washed with an organic solvent. As the organic solvent, aliphatic ketones, ethers, and aromatic hydrocarbons are used. For example, as aliphatic ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., as ethers, tetrahydrofuran, methyl isobutyl ether, methyl isopropyl ether, etc., as aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, etc. Can be mentioned.
この洗浄したジエステル化合物を８０℃で２４時間程度減圧乾燥することで、高純度のジエステル化合物が製造される。 The washed diester compound is dried under reduced pressure at 80 ° C. for about 24 hours to produce a high-purity diester compound.
以下、実施例により本発明をさらに詳細に説明する。分析は、試料を無水メタノールに加温溶解し、下記条件の高速液体クロマトグラフィー(ＨＰＬＣ)で行った。尚、実施例において濃度は面積％を示し、収率はモル％を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The analysis was performed by high-performance liquid chromatography (HPLC) under the following conditions after dissolving the sample in anhydrous methanol with heating. In the examples, the concentration indicates area%, and the yield indicates mol%.
測定条件
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−８０Ａ（ジーエルサイエンス株式会社製）
長さ２５０ｍｍ、内径４．２ｍｍ
移動相：アセトニトリル／０．１％リン酸水、
（混合容積比１：１を２０分で１：０とするグラジェント）
検出器：ＵＶ（２５４ｎｍ）
Measurement conditions Column: Inertsil ODS-80A (manufactured by GL Sciences Inc.)
Length 250mm, inner diameter 4.2mm
Mobile phase: acetonitrile / 0.1% aqueous phosphoric acid,
(Gradient of mixing volume ratio 1: 1 to 1: 0 in 20 minutes)
Detector: UV (254 nm)
（参考例１）
還流冷却器、温度測定管および電磁攪拌機を備えた５００ｍｌのガラス製反応容器に、窒素雰囲気下、無水トリメリット酸１００ｇ（０．５２ｍｏｌ）、トルエン１８１ｇおよびＤＭＦ０．１５ｇを仕込んだ。内温を８０℃に昇温したのち、塩化チオニル６８．１ｇ（０．５７ｍｏｌ）を３０分かけて添加した。その後、この温度で９時間反応させた。反応後、残存する塩化チオニルおよび溶媒のトルエンをエバポレーターで留去し、無水トリメリット酸クロライドを１２５ｇ得た。
(Reference Example 1)
A 500 ml glass reaction vessel equipped with a reflux condenser, a temperature measuring tube and an electromagnetic stirrer was charged with 100 g (0.52 mol) of trimellitic anhydride, 181 g of toluene and 0.15 g of DMF under a nitrogen atmosphere. After raising the internal temperature to 80 ° C., 68.1 g (0.57 mol) of thionyl chloride was added over 30 minutes. Then, it was made to react at this temperature for 9 hours. After the reaction, the remaining thionyl chloride and the solvent toluene were distilled off with an evaporator to obtain 125 g of trimellitic anhydride chloride.
（実施例１）
参考例１で合成した無水トリメリット酸クロライド１９．４３ｇおよびアセトニトリル３５．０ｇを還流冷却器、温度測定管および電磁攪拌機を備えた２００ｍｌのガラス製反応容器に、窒素雰囲気下仕込み、溶解して内温を５℃に冷却した。ついで、２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン１５．５７g（４６．３１ｍｍｏｌ）をアセトニトリル５１．６５ｇに溶解し、ピリジン８．１９ｇを添加した溶液を滴下ロートにより内温を５℃に保ちながら１時間かけて滴下した。滴下後内温５℃〜２５℃で６時間攪拌した。生成物を濾別して、白色固体を得た。得られた白色固体をＨＰＬＣで分析した結果、純度は８９．１％、ピリジン７．４％であった。この白色固体を、無水酢酸０．１０ｇを含有するアセトニトリル９．３８ｇで洗浄した。洗浄した結晶を５ｍｍＨｇの減圧下、５０℃で２４時間乾燥し、純度９８．５％、ピリジン０％で白色の式（２）に示す１，３−ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸−［２，２，２−トリフルオロ−１−（１−トリフルオロメチル）エチリデン］ジ−４，１−フェニレンエステル１３．１１ｇを得た。２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン基準の収率は４０．７％であった。
Example 1
19.43 g of trimellitic anhydride chloride synthesized in Reference Example 1 and 35.0 g of acetonitrile were charged into a 200 ml glass reaction vessel equipped with a reflux condenser, a temperature measuring tube and a magnetic stirrer under a nitrogen atmosphere, dissolved, and dissolved. The temperature was cooled to 5 ° C. Next, 15.57 g (46.31 mmol) of 2,2-bis (4-hydroxyphenyl) hexafluoropropane was dissolved in 51.65 g of acetonitrile, and a solution containing 8.19 g of pyridine was added to the inner temperature at 5 ° C. with a dropping funnel. The solution was added dropwise over 1 hour while maintaining the temperature. After dropping, the mixture was stirred at an internal temperature of 5 ° C to 25 ° C for 6 hours. The product was filtered off to give a white solid. As a result of analyzing the obtained white solid by HPLC, the purity was 89.1% and pyridine 7.4%. This white solid was washed with 9.38 g of acetonitrile containing 0.10 g of acetic anhydride. The washed crystals were dried under reduced pressure of 5 mmHg at 50 ° C. for 24 hours, and the white 1,3-dihydro-1,3-dioxo-5-isoformate represented by the formula (2) having a purity of 98.5% and pyridine of 0% was obtained. 13.11 g of benzofurancarboxylic acid- [2,2,2-trifluoro-1- (1-trifluoromethyl) ethylidene] di-4,1-phenylene ester was obtained. The yield based on 2,2-bis (4-hydroxyphenyl) hexafluoropropane was 40.7%.
（実施例２）
参考例１で合成した無水トリメリット酸クロライド５．００ｇとアセトニトリル８．９２ｇを５０ｍｌのガラス製反応容器に、窒素雰囲気下仕込み、溶解して内温を５℃に冷却した。ついで、ビス（４−ヒドロキシフェニル）スルフィド２．５８ｇ（１１．８２ｍｍｏｌ）をアセトニトリル１３．２６ｇに溶解し、ピリジン２．０５ｇを添加した溶液を滴下ロートにより内温を５℃に保ちながら１時間かけて滴下した。滴下後内温５℃〜２５℃で５時間攪拌した。生成物を濾別してアセトニトリル２．３８ｇで洗浄し白色固体を得た。得られた白色固体をＨＰＬＣで分析した結果、純度は９１．３％、ピリジン１．１％であった。この白色固体を、無水酢酸０．２８ｇを含有するアセトン２８．２１ｇで洗浄した。洗浄した結晶を５ｍｍＨｇの減圧下、５０℃で２４時間乾燥し、純度９４．０％、ピリジン０％で白色の式（３）に示す１，３−ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸−チオジ−４，１−フェニレンエステル５．０７ｇを得た。ビス（４−ヒドロキシフェニル）スルフィド基準の収率は７１．２％であった。
(Example 2)
Trimellitic anhydride chloride (5.00 g) synthesized in Reference Example 1 and 8.92 g of acetonitrile were charged into a 50 ml glass reaction vessel under a nitrogen atmosphere, dissolved, and the internal temperature was cooled to 5 ° C. Next, 2.58 g (11.82 mmol) of bis (4-hydroxyphenyl) sulfide was dissolved in 13.26 g of acetonitrile, and a solution containing 2.05 g of pyridine was added over 1 hour while maintaining the internal temperature at 5 ° C. with a dropping funnel. And dripped. After the dropping, the mixture was stirred at an internal temperature of 5 ° C to 25 ° C for 5 hours. The product was filtered off and washed with 2.38 g of acetonitrile to give a white solid. As a result of analyzing the obtained white solid by HPLC, the purity was 91.3% and pyridine was 1.1%. This white solid was washed with 28.21 g of acetone containing 0.28 g of acetic anhydride. The washed crystals were dried under reduced pressure of 5 mmHg at 50 ° C. for 24 hours, and the white 1,3-dihydro-1,3-dioxo-5-isoformate represented by the formula (3) having a purity of 94.0% and pyridine of 0% was obtained. Benzofurancarboxylic acid-thiodi-4,1-phenylene ester (5.07 g) was obtained. The yield based on bis (4-hydroxyphenyl) sulfide was 71.2%.
（実施例３）
参考例１で合成した無水トリメリット酸クロライド１５．２９ｇとアセトニトリル２６．８２ｇを２００ｍｌのガラス製反応容器に、窒素雰囲気下仕込み、溶解して内温を５℃に冷却した。ついで、４，４’−ジヒドロキシジフェニルメタン７．２７ｇ（３６．３１ｍｍｏｌ）をアセトニトリル４０．０１ｇに溶解し、ピリジン６．２９ｇを添加した溶液を滴下ロートにより内温を５℃に保ちながら１時間かけて滴下した。滴下後内温５℃〜２５℃で６．５時間攪拌した。生成物を濾別して白色固体を得た。ＨＰＬＣで分析した結果、純度は７７．６％、ピリジン１６．３％であった。この白色固体を、５ｍｍＨｇの減圧下、常温で２４時間乾燥した後、無水酢酸０．４２ｇを含有するＤＭＦ４１．５９ｇから再結晶精製し、５ｍｍＨｇの減圧下、５０℃で２４時間乾燥し、純度９６．９％、ピリジン０％で白色の式（４）に示す１，３−ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸−メチレンジ−４，１−フェニレンエステル９．１４ｇを得た。４，４’−ジヒドロキシジフェニルメタン基準の収率は収率４４．５％であった。
(Example 3)
In a 200 ml glass reaction vessel, 15.29 g of trimellitic anhydride chloride synthesized in Reference Example 1 and 26.82 g of acetonitrile were charged in a nitrogen atmosphere, dissolved, and the internal temperature was cooled to 5 ° C. Subsequently, 7.27 g (36.31 mmol) of 4,4′-dihydroxydiphenylmethane was dissolved in 40.01 g of acetonitrile, and a solution in which 6.29 g of pyridine was added was added for 1 hour while maintaining the internal temperature at 5 ° C. with a dropping funnel. It was dripped. After dropping, the mixture was stirred at an internal temperature of 5 ° C to 25 ° C for 6.5 hours. The product was filtered off to give a white solid. As a result of analysis by HPLC, the purity was 77.6% and pyridine 16.3%. This white solid was dried at room temperature under a reduced pressure of 5 mmHg for 24 hours, and then recrystallized and purified from 41.59 g of DMF containing 0.42 g of acetic anhydride, and dried at 50 ° C. under a reduced pressure of 5 mmHg for 24 hours. 9.13 g of 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-methylenedi-4,1-phenylene ester represented by the formula (4), which was white with 9% and pyridine 0%, was obtained. The yield based on 4,4′-dihydroxydiphenylmethane was 44.5%.
（実施例４）
参考例１で合成した無水トリメリット酸クロライド２５．１４ｇとアセトニトリル４４．２３ｇを２００ｍｌのガラス製反応容器に、窒素雰囲気下仕込み、溶解して内温を５℃に冷却した。ついで、４，４’−ジヒドロキシジフェニルエーテル１１．９７ｇ（５９．２０ｍｍｏｌ）をアセトニトリル６６．３３ｇに溶解し、ピリジン１０．３３ｇを添加した溶液を滴下ロートにより内温を５℃に保ちながら１時間かけて滴下した。滴下後内温５℃〜２５℃で６時間攪拌した。生成物を濾別して、白色固体を得た。得られた白色固体をＨＰＬＣで分析した結果、純度は６９．７％、ピリジン１０．０％であった。この白色固体を、無水酢酸０．６４ｇを含有するＤＭＦ６４．４４ｇから再結晶精製し、５ｍｍＨｇの減圧下、５０℃で２４時間乾燥し、純度９７．２％、ピリジン０％で白色の式（５）に示す１，３−ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸−オキシジ−４，１−フェニレンエステル１３．３２ｇを得た。４，４’−ジヒドロキシジフェニルエーテル基準の収率は収率３９．９％であった。
Example 4
25.14 g of trimellitic anhydride chloride synthesized in Reference Example 1 and 44.23 g of acetonitrile were charged in a 200 ml glass reaction vessel under a nitrogen atmosphere, dissolved, and the internal temperature was cooled to 5 ° C. Next, 11.97 g (59.20 mmol) of 4,4′-dihydroxydiphenyl ether was dissolved in 66.33 g of acetonitrile, and a solution containing 10.33 g of pyridine was added over 1 hour while maintaining the internal temperature at 5 ° C. with a dropping funnel. It was dripped. After dropping, the mixture was stirred at an internal temperature of 5 ° C to 25 ° C for 6 hours. The product was filtered off to give a white solid. As a result of analyzing the obtained white solid by HPLC, the purity was 69.7% and pyridine 10.0%. This white solid was recrystallized and purified from 64.44 g of DMF containing 0.64 g of acetic anhydride and dried at 50 ° C. for 24 hours under a reduced pressure of 5 mmHg. The white formula (5% purity 97.2%, pyridine 0%) Of 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-oxydi-4,1-phenylene ester shown in FIG. The yield based on 4,4′-dihydroxydiphenyl ether was 39.9%.
（実施例５）
参考例１で合成した無水トリメリット酸クロライド５．０５ｇとアセトニトリル１５．０ｇを５０ｍｌのガラス製反応容器に、窒素雰囲気下仕込み、溶解して内温を５℃に冷却した。ついで、レゾルシノール１．１０ｇ（１０．０ｍｍｏｌ）をアセトニトリル１．１０ｇに溶解し、ピリジン１．９０ｇを添加した溶液を滴下ロートにより内温を５℃に保ちながら１時間かけて滴下した。滴下後内温５℃で１時間攪拌した。生成物を濾別してアセトニトリル２．０ｇで洗浄し白色固体を得た。ＨＰＬＣで分析した結果、純度は８５．９％、ピリジン１．５％であった。この白色固体を、無水酢酸０．０４ｇを含有するアセトン４．０ｇで洗浄した。洗浄した結晶を５ｍｍＨｇの減圧下、５０℃で２４時間乾燥し、純度９６．０％、ピリジン０％で白色の式（６）に示す１，３−ジヒドロ−１，３−ジオキソ−５−イソベンゾフランカルボン酸−１，３−フェニレンエステル２．０ｇを得た。レゾルシノール基準の収率は４１．９％であった。
(Example 5)
In a 50 ml glass reaction vessel, 5.05 g of trimellitic anhydride chloride synthesized in Reference Example 1 and 15.0 g of acetonitrile were charged in a nitrogen atmosphere and dissolved, and the internal temperature was cooled to 5 ° C. Then, 1.10 g (10.0 mmol) of resorcinol was dissolved in 1.10 g of acetonitrile, and a solution to which 1.90 g of pyridine was added was dropped over 1 hour while maintaining the internal temperature at 5 ° C. with a dropping funnel. After dropping, the mixture was stirred for 1 hour at an internal temperature of 5 ° C. The product was filtered off and washed with 2.0 g of acetonitrile to give a white solid. As a result of analysis by HPLC, the purity was 85.9% and pyridine 1.5%. This white solid was washed with 4.0 g of acetone containing 0.04 g of acetic anhydride. The washed crystals were dried under reduced pressure of 5 mmHg at 50 ° C. for 24 hours, and the white 1,3-dihydro-1,3-dioxo-5-isopropylene represented by the formula (6) having a purity of 96.0% and pyridine 0% was obtained. 2.0 g of benzofurancarboxylic acid-1,3-phenylene ester was obtained. The yield based on resorcinol was 41.9%.
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| CN103626728A (en) * | 2013-12-04 | 2014-03-12 | 山东凯盛新材料股份有限公司 | Preparation method for high purity TMAC |
| JP2017203005A (en) * | 2016-05-12 | 2017-11-16 | 田岡化学工業株式会社 | Manufacturing method of tetracarboxylic acid dianhydride having ester group |
| WO2020218134A1 (en) * | 2019-04-24 | 2020-10-29 | 本州化学工業株式会社 | Method for producing tetracarboxylic acid dianhydride |
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