JPH0341067A - Production of 2-(4-hydroxyphenyl)-2-(4'-maleimidephenyl) propane - Google Patents
Production of 2-(4-hydroxyphenyl)-2-(4'-maleimidephenyl) propaneInfo
- Publication number
- JPH0341067A JPH0341067A JP17419089A JP17419089A JPH0341067A JP H0341067 A JPH0341067 A JP H0341067A JP 17419089 A JP17419089 A JP 17419089A JP 17419089 A JP17419089 A JP 17419089A JP H0341067 A JPH0341067 A JP H0341067A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- propane
- hydroxyphenyl
- water
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title abstract description 36
- 239000001294 propane Substances 0.000 title abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- MFOZEMMOSBIWMZ-UHFFFAOYSA-N 1-[4-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(N2C(C=CC2=O)=O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 MFOZEMMOSBIWMZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- -1 etc. Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- NFGPNZVXBBBZNF-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(N)C=C1 NFGPNZVXBBBZNF-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- CUZZFWJPTIJWJL-UHFFFAOYSA-N 1-(2-propylphenyl)pyrrole-2,5-dione Chemical compound CCCC1=CC=CC=C1N1C(=O)C=CC1=O CUZZFWJPTIJWJL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- CJDZTJNITSFKRE-UHFFFAOYSA-N phosphorus dioxide Chemical compound O=[P]=O CJDZTJNITSFKRE-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリマー原料として有用なマレイミド化合物の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a maleimide compound useful as a polymer raw material.
従来２−（４−ヒドロキシフェニル）−２−（４°−マ
レイミドフェニル）プロパンの合成は、２−（４−ヒド
ロキシフェニル）−２−（４°−アミノフェニル）プロ
パン（以下、アミン化合物と称す）と無水マレイン酸か
ら得られるマレイミド酸を無水酢酸で代表される脂肪酸
無水物あるいは二酸化リン、五酸化リン、ピロメリット
酸、トリポリリン酸などのリンの酸化物および縮合リン
酸などの脱水剤を用いて閉環させ、目的物を得る方法が
提案されている（特開昭５５−１４９２５３） 。Conventionally, 2-(4-hydroxyphenyl)-2-(4°-maleimidophenyl)propane was synthesized using 2-(4-hydroxyphenyl)-2-(4°-aminophenyl)propane (hereinafter referred to as an amine compound). ) and maleimic acid obtained from maleic anhydride using a fatty acid anhydride represented by acetic anhydride or a dehydrating agent such as phosphorus oxides such as phosphorus dioxide, phosphorus pentoxide, pyromellitic acid, and tripolyphosphoric acid, and condensed phosphoric acid. A method has been proposed in which the desired product is obtained by ring-closing the compound (Japanese Patent Laid-Open No. 149253/1983).
なかでも、脱水剤として特に好ましいのは、取扱いが容
易で、かつ脱水閉環反応後の後処理の簡易な点で無水酢
酸、五酸化リンなどが有効であると指摘されているが、
無水酢酸を用いて脱水閉環する場合、収率よくマレイミ
ドを得るために、はコバルト塩などの高価な触媒を併用
しなければならず、さらに、原料アミン化合物が水酸基
を有しているためにアセチル化物を生成するためか、あ
るいは水酸基が無水マレイン酸の二重結合への付加反応
を起すためか、副生成物が生成され目的とするマレイミ
ドの純度が悪く収率が低下する。Among them, it has been pointed out that acetic anhydride, phosphorus pentoxide, etc. are particularly preferred as dehydrating agents because they are easy to handle and easy to perform post-treatment after the dehydration ring-closing reaction.
When dehydrating and ring-closing using acetic anhydride, it is necessary to use an expensive catalyst such as a cobalt salt in order to obtain maleimide in a good yield.Furthermore, since the raw material amine compound has a hydroxyl group, acetyl Perhaps due to the formation of a compound or because the hydroxyl group causes an addition reaction to the double bond of maleic anhydride, by-products are produced, resulting in poor purity of the desired maleimide and a decrease in yield.
また五酸化リンを用いて脱水閉環する方法でシよやはり
水酸基がエステル化されるか、あるいはこれら化合物自
体が重合するためか、副生成物が生成し、目的とするマ
レイミドの純度が悪く収率は低下する。In addition, in the dehydration ring closure method using phosphorus pentoxide, by-products are generated, probably because the hydroxyl group is esterified or because these compounds themselves are polymerized, resulting in poor purity of the target maleimide and poor yield. decreases.
いずれの方法においても、イミド化終了後の反応液から
生成したマレイミドを分離回収するためには、反応液を
大量の水中へ注入して析出する結晶を濾別し、この結晶
を更に多量の水で洗浄しなければならず、場合によって
は＠薄な炭酸ナトリウム水溶液や苛性ソーダ水溶液で洗
浄しなければならず、工業的に極めて不利な方法である
。In either method, in order to separate and recover the maleimide produced from the reaction solution after imidization, the reaction solution is poured into a large amount of water, the precipitated crystals are filtered out, and the crystals are poured into an even larger amount of water. In some cases, it is necessary to wash with a dilute sodium carbonate aqueous solution or a caustic soda aqueous solution, which is an extremely disadvantageous method from an industrial perspective.
本発明は２ｏ（４−ヒドロキシフェニル）−２−（４゜
−マレイミドフェニル）プロパンを製造するにあたって
、上記のような欠点を有しない工業的に有利な方法を提
供するものである。The present invention provides an industrially advantageous method for producing 2o(4-hydroxyphenyl)-2-(4°-maleimidophenyl)propane, which does not have the above-mentioned drawbacks.
（ｔ！ｌ１題を解決するための手段〕
本発明者らは本発明の目的を達成ずべく鋭意検討した結
果、高収率、高純度で黄色結晶の２−（４−ヒドロキシ
フェニル）−２−（４’−マレイミドフェニル）プロパ
ンを製造する方法を見出し本発明に至った。(Means for solving the problem t!l1) As a result of intensive studies aimed at achieving the object of the present invention, the present inventors have found that 2-(4-hydroxyphenyl)-2, which is a yellow crystal in high yield and high purity, -(4'-Maleimidophenyl)propane was discovered and the present invention was achieved.
すなわち、本発明は２−（４−ヒドロキシフェニ／Ｌｚ
）−２−（４’−アミノフェニル）プロパンと？Ｍ水マ
レイン酸を水と共沸可能な有機溶剤中、酸触媒および非
プロトン性極性溶媒の共存下で脱水閉環させることを特
徴とする２−（４−ヒドロキシフェニル）−２−（４”
−マレイミドフェニル）プロパンの製造方法である。That is, the present invention provides 2-(4-hydroxyphenylene/Lz
)-2-(4'-aminophenyl)propane? 2-(4-hydroxyphenyl)-2-(4''), which is characterized by dehydrating and ring-closing M-water maleic acid in an organic solvent capable of azeotroping with water in the coexistence of an acid catalyst and an aprotic polar solvent.
- Maleimidophenyl)propane.
以下本発明の具体的なＭ様を説明する。Hereinafter, a specific example of Mr. M of the present invention will be explained.
本発明の方法で使用される原料は、２−（４−ヒドロキ
シフェニル）−２−（４°−アミノフェニル）プロパン
と無水マレイン酸であり、無水マレイン酸の使用量は２
−（４−ヒドロキシフェニル）−２−＜４“−アミノフ
ェニル）プロパン１モルに対して１．０〜１．５モルで
あり、好ましくは１．０５〜１．３モル用いるのが良い
、無水マレイン酸に対しアミン化合物を過剰に使用した
場合には、過剰量の該アミン化合物が生成した２−（４
−ヒドロキシフェニル〉２−（４°−マレイミドフェニ
ル）プロパンに付加し、副生成物を生成することがある
ため好ましくない。The raw materials used in the method of the present invention are 2-(4-hydroxyphenyl)-2-(4°-aminophenyl)propane and maleic anhydride, and the amount of maleic anhydride used is 2-(4-hydroxyphenyl)-2-(4°-aminophenyl)propane.
-(4-hydroxyphenyl)-2-<4"-aminophenyl)propane in an amount of 1.0 to 1.5 mol, preferably 1.05 to 1.3 mol, anhydrous When the amine compound is used in excess of maleic acid, an excess amount of the amine compound is generated.
-Hydroxyphenyl> It is not preferable because it may add to 2-(4°-maleimidophenyl)propane and produce by-products.
本発明に用いられる酸触媒は硫酸、リン酸等の鉱酸、リ
ンタングステン酸、リンモリブデン酸等のへチロポリ酸
、ｐ−トルエンスルホン酸、メタンスルホン酸等の有機
スルホン酸、トリクロル酢酸、トリフルオル酢酸等のハ
ロゲン化カルボン酸等が使用され、特に硫酸、ｐ−）ル
エンスルホン酸が好適である。Acid catalysts used in the present invention include mineral acids such as sulfuric acid and phosphoric acid, hetyropolyacids such as phosphotungstic acid and phosphomolybdic acid, organic sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, trichloroacetic acid and trifluoroacetic acid. Halogenated carboxylic acids such as sulfuric acid and p-)luenesulfonic acid are particularly preferred.
これらの酸触媒は種類によっても異なるが、通常無水マ
レイン酸、アミン化合物との合計重量当りＯｏ、５〜５
重量％の量で使用することが好ましい。Although these acid catalysts vary depending on the type, they usually have Oo of 5 to 5 per total weight of maleic anhydride and amine compound.
Preferably, it is used in an amount of % by weight.
触媒量が０．５重量％よりも少ない場合所望の触媒効果
が達成されず、また５重量％より多く用いたとしても一
定以上の効果は得られず経済的に不利となるばかりか、
残存量触媒の除去が困難となる。If the catalyst amount is less than 0.5% by weight, the desired catalytic effect will not be achieved, and even if it is used in an amount greater than 5% by weight, the effect above a certain level will not be obtained, which will not only be economically disadvantageous.
It becomes difficult to remove the remaining amount of catalyst.
本発明で用いる有Ｒｉｇ剤としては脱水閉環反応で生成
する水を共沸除去できる溶剤が良く、ベンゼン、トルエ
ン、キシレン、メシチレン、クロルベンゼン等が挙られ
る。使用量は反応を円滑に行う上から無水マレイン酸に
対して３〜１０倍量（重量比）用いるのが良い。The Rig agent used in the present invention is preferably a solvent capable of azeotropically removing water produced in the dehydration ring-closing reaction, such as benzene, toluene, xylene, mesitylene, chlorobenzene, and the like. The amount used is preferably 3 to 10 times that of maleic anhydride (weight ratio) for smooth reaction.
また本発明の方法において用いる非プロトン性極性溶媒
としては、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジ
メチルホルムアミド、Ｎ−メチル−２−ピロリドン、
１．３−ジメチル−２−イミダゾリジノン、Ｎ、Ｎ−ジ
エチルアセドアごド等が挙げられ、使用量は使用する有
機溶剤の重量に対して１０〜４０重量％で、好ましくは
２０〜３０重量％用いるのが良い。Further, the aprotic polar solvent used in the method of the present invention includes N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone,
Examples include 1,3-dimethyl-2-imidazolidinone, N,N-diethylacedoago, etc., and the amount used is 10 to 40% by weight, preferably 20 to 30% by weight based on the weight of the organic solvent used. It is better to use weight %.
本発明の方法における反応は、無水マレイン酸と有機溶
剤の混合液に、アミン化合物を加えて１５０℃以下、好
ましくは２０〜１００°Ｃで１０分以上、好ましくは０
．５〜１時間攪拌してマレアミド酸を生成させ、ついで
得られた反応液に非プロトン性極性溶媒と酸触媒を加え
８０°Ｃ以上、好ましくは１００℃〜１８０℃の温度範
囲で加熱し、０．５〜２０時間、好ましくは４〜８時間
撹拌し、反応生成水を共沸分離することによって行なう
か、あるいは無水マレイン酸と有機溶剤および酸触媒の
混合液を８０〜１８０°Ｃの温度範囲で加熱し、予めア
ミン化合物を非プロトン性極性溶媒に）客層させた溶液
を滴下しながら反応させ、生成する水を共沸分離するこ
とによって行なっても良い。The reaction in the method of the present invention is carried out by adding an amine compound to a mixed solution of maleic anhydride and an organic solvent, and heating the mixture at 150°C or lower, preferably 20 to 100°C, for 10 minutes or more, preferably at 0.
．． Stir for 5 to 1 hour to generate maleamic acid, then add an aprotic polar solvent and an acid catalyst to the resulting reaction solution and heat at 80°C or higher, preferably in the temperature range of 100°C to 180°C. It is carried out by stirring for 5 to 20 hours, preferably 4 to 8 hours, and azeotropically separating the water produced by the reaction, or by heating the mixture of maleic anhydride, organic solvent and acid catalyst at a temperature range of 80 to 180 °C. Alternatively, the reaction may be carried out by heating the reaction solution while dropping a solution containing the amine compound in an aprotic polar solvent in advance, and azeotropically separating the water produced.
このような条件で反応を行なった後、６０〜８０’Ｃに
冷却し、直ちに減圧濃縮して溶剤を留去し、その抜水あ
るいは適当な溶剤、例えばメタノール、エタノール、イ
ソプロピルアルコールと水の混合溶媒を加えることによ
り２−（４−ヒドロキシフェニル）−２−（４“−マレ
イミドフェニル）プロパンを単離することが出来る。After the reaction is carried out under these conditions, it is cooled to 60-80'C, immediately concentrated under reduced pressure to remove the solvent, and the water is removed or mixed with a suitable solvent such as methanol, ethanol, isopropyl alcohol and water. By adding a solvent, 2-(4-hydroxyphenyl)-2-(4"-maleimidophenyl)propane can be isolated.
本発明の方法は、従来の製造法に比べ、反応操作が簡単
でかつ高純度、高収率で２−（４−ヒドロキシフェニル
）−２−（４’−マレイミドフェニル）プロパンを容易
に得ることが出来る工業的に有利な製造方法である。The method of the present invention has simpler reaction operations than conventional production methods, and can easily obtain 2-(4-hydroxyphenyl)-2-(4'-maleimidophenyl)propane with high purity and high yield. This is an industrially advantageous manufacturing method that allows for
以下実施例により本発明の方法を更に詳しく説明する。The method of the present invention will be explained in more detail with reference to Examples below.
実施例１
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応容器に無水マレイン酸６０ｇ （０，
６１モル）、トルエン４８０ｇ及び９５％ＨｚＳＯ４２
，６ｇを装入し攪拌下で還流温度まで加熱し、予めＮ、
Ｎ−ジメチルアセトアミド１６０ｇに２−（４−ヒドロ
キシフェニル）−２−（４’−アミノフェニル）プロパ
ン１１４ｇ （０，５モル）を？容器したｔ容器を滴下
ロートにより４〜５時間で滴下し、同温度で５時間反応
を行なった０反応により生成する水は共沸除去する０反
応終了後、反応液を８０〜９０°Ｃに冷却し、直ちに溶
剤を減圧下で留去し、続いて得られた有機層にイソプロ
ピルアルコール１００＋ｆ！を装入し、さらに水を３０
０ｄを装入して０．５〜１時間攪拌し結晶を析出させた
後、濾過乾燥して黄色結晶の２−（４−ヒドロキシフェ
ニル）−２−（４’−マレイミドフェニル）プロパンを
１４７ｇ （収率９６％）得た。得られた生成物の融点
は１６８〜１７１’Ｃ１ＧＰＣによる純度分析結果は９
９％であった。Example 1 60 g of maleic anhydride (0,
61 mol), 480 g toluene and 95% HzSO42
, 6g was charged and heated to reflux temperature under stirring, and N,
114 g (0.5 mol) of 2-(4-hydroxyphenyl)-2-(4'-aminophenyl) propane to 160 g of N-dimethylacetamide? The water produced by the reaction was azeotropically removed. After the reaction was completed, the reaction solution was heated to 80 to 90°C. After cooling, the solvent was immediately distilled off under reduced pressure, and then 100+f! of isopropyl alcohol was added to the resulting organic layer. and then add 30 ml of water.
0d and stirred for 0.5 to 1 hour to precipitate crystals, filtered and dried to obtain 147 g of 2-(4-hydroxyphenyl)-2-(4'-maleimidophenyl)propane as yellow crystals ( Yield: 96%). The melting point of the obtained product is 168-171'C1 Purity analysis result by GPC is 9
It was 9%.
また、元素分析値及びマススペクトル分析の結果は次の
通りであった。In addition, the results of elemental analysis and mass spectrum analysis were as follows.
元素分析値
計算値（％） ７４．３ ５．５ ４．６分析値（
％） ？４．１ ５゜６６ ４．５Ｍ５（Ｅｌ）
： ３０７”◆１）実施例２
撹拌器、温度計およびディーンスクーク共沸蒸留トラソ
ブを装着した反応容器に無水マレイン酸６０ｇ （０，
６１モル）、クロルベンゼン４８０ｇおよび９５％１１
□５ｏ４２．６ｇを装入し撹拌下で還流温度まで加熱し
、予めＮ、Ｎ−ジメチルアセトアミド１６０ｇに２−（
４−ヒドロキシフェニル）−２−（４’−アミノフェニ
ル）プロパン１１４ｇ （０，５モル）をｉ容器した？
８液を滴下ロートにより４〜５時間で滴下し、同温度で
４時間反応をｊ〒なった。反応により生成する水は共沸
除去する。反応終了後、反応液を８０〜９０゛Ｃに４却
し、直ちに溶剤を減圧下で留去し、続いて得られた有機
層にイソプロピルアルコール１００Ｉｄを装入し、さら
に水を３００ｍＡを装入して０．５〜１時間撹拌し、結
晶を析出させた後、濾過乾燥して黄色結晶の２−（４−
ヒドロキシフェニル）−２−（４°〜マレイミドフエニ
ル）プロパン１４９ｇ（収率９７％）を得た。得られた
生成物の融点は１６８〜１７１’Ｃ，ＧＰＣによる純度
分析結果は９９％であった。Elemental analysis value calculation value (%) 74.3 5.5 4.6 Analysis value (
%)? 4.1 5゜66 4.5M5(El)
: 307"◆1) Example 2 60 g of maleic anhydride (0,
61 mol), 480 g of chlorobenzene and 95% 11
□42.6 g of 5o was charged, heated to reflux temperature under stirring, and 2-(
114g (0.5 mol) of 4-hydroxyphenyl)-2-(4'-aminophenyl)propane was put in i container?
8 liquid was added dropwise through a dropping funnel over 4 to 5 hours, and the reaction was continued at the same temperature for 4 hours. Water produced by the reaction is removed azeotropically. After the reaction was completed, the reaction solution was cooled to 80 to 90°C, the solvent was immediately distilled off under reduced pressure, and then 100 Id of isopropyl alcohol was charged to the obtained organic layer, and 300 mA of water was charged. After stirring for 0.5 to 1 hour to precipitate crystals, the yellow crystals of 2-(4-
149 g (yield 97%) of hydroxyphenyl)-2-(4°~maleimidophenyl)propane were obtained. The melting point of the obtained product was 168-171'C, and the purity analysis result by GPC was 99%.
実施例３
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応容器に無水マレイン酸６０ｇ （０，
６１モル）、トルエン４８０ｇおよびメタンスルホン酸
２．６ｇを装入し、攪拌下で還流温度まで加熱し、予め
Ｎ−メチル−２−ピロリドン１６０ｇに２−（４−ヒド
ロキシフェニル）−２−（４’−アミノフェニル）プロ
パン１１４ｇ （０，５モル）を溶解した溶液を滴下ロ
ートにより４時間で滴下し、同温度で５時間反応を行な
った６反応により生成する水は共沸除去する。反応終了
後反応液を８０〜９０゛Ｃに冷却し、直ちに溶剤を減圧
下で留去し、続いて得られた有機層にイソプロピルアル
コール１００ｍ１：を装入し、さらに水を３００ｍ１を
装入して０．５〜１時間撹拌し、結晶を析出させた後、
濾過乾燥して黄色結晶の２−（４−ヒドロキシフェニル
）−２−（４’−マレイミドフェニル）プロパンを１４
７ｇ（収率９６％）得た。得られた生成物の融点は１６
７〜１７１″Ｃ１ＧＰＣによる純度分析結果は９８．５
％であった。Example 3 60 g of maleic anhydride (0,
61 mol), 480 g of toluene and 2.6 g of methanesulfonic acid were charged and heated to reflux temperature under stirring. A solution containing 114 g (0.5 mol) of '-aminophenyl)propane was added dropwise through a dropping funnel over a period of 4 hours, and the reaction was carried out at the same temperature for 5 hours. Water produced by the 6 reactions was azeotropically removed. After the reaction was completed, the reaction solution was cooled to 80 to 90°C, the solvent was immediately distilled off under reduced pressure, and then 100 ml of isopropyl alcohol was charged to the obtained organic layer, followed by 300 ml of water. After stirring for 0.5 to 1 hour to precipitate crystals,
Filter and dry to obtain 14 yellow crystals of 2-(4-hydroxyphenyl)-2-(4'-maleimidophenyl)propane.
7 g (yield 96%) was obtained. The melting point of the product obtained is 16
Purity analysis result by 7~171″C1GPC is 98.5
%Met.
実施例４
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応容器に無水マレイン酸３０ｇ （０，
３モル）、トルエン２４０ ｇを装入し、攪拌下で２−
（４−ヒドロキシフェニル）−２−（４°−アミノフェ
ニル）プロパン５７ｇ （０，２５モル）を加え反応を
１時間行なった６次いで、Ｐ−）ルエンスルホン酸１．
３ｇおよびＮ、Ｎ−ジメチルアセトアミド８０ｇを加え
還流温度まで加熱し、１０時間反応を行なった６反応に
より生成する水は共沸除去する。Example 4 30 g of maleic anhydride (0,
3 moles) and 240 g of toluene were charged, and 2-
57 g (0.25 mol) of (4-hydroxyphenyl)-2-(4°-aminophenyl)propane were added and the reaction was carried out for 1 hour.6 Then, 1.
3 g and 80 g of N,N-dimethylacetamide were added, heated to reflux temperature, and reacted for 10 hours. The water produced by the 6 reactions was azeotropically removed.
反応終了後、反応液を８０〜９０’Ｃに冷却し、直ちに
減圧下で留去し、続いて得られた有機層にメタノール１
０（ｌｄを装入し、さらに水を３００ｄ装入して０．５
〜１時間攪拌し結晶を析出させた後、濾過乾燥して黄色
結晶の２−（４−ヒドロキシフェニル）−２−（４’−
マレイミドフェニル）プロパン７４ｇを（収率９６．３
％）得た。得られた生成物の融点は１６８〜１７１’Ｃ
１ＧＰＣによる純度分析結果は９９％であった。After the reaction was completed, the reaction solution was cooled to 80-90'C and immediately distilled off under reduced pressure.
0(1d, then 300d of water, 0.5
After stirring for ~1 hour to precipitate crystals, filtration and drying yielded yellow crystals of 2-(4-hydroxyphenyl)-2-(4'-
74 g of (maleimidophenyl)propane (yield: 96.3
%)Obtained. The melting point of the product obtained is 168-171'C
The purity analysis result by 1GPC was 99%.
実施例５
撹拌器、温度計およびディーンスターク共沸草留トラッ
プを装着した反応容器に無水マレイン酸３０ｇ （０，
３モル）、キシレン２４０ｇを装入し、潰拌下で２−（
４−ヒドロキシフェニル）−２−（４”−アミノフェニ
ル）プロパン５７ｇ （０，２５モル）を加え、反応を
１時間行なった０次いで、Ｐ−）ルエンスルホン＃１．
３ｇおよびＮ、Ｎ−ジメチルホルムアミド４０ｇを加え
還流温度まで加熱し、１２時間反応を行なった０反応に
より生成する水は共沸除去する。Example 5 30 g of maleic anhydride (0,
3 mol), 240 g of xylene was charged, and 2-(
57 g (0.25 mol) of 4-hydroxyphenyl)-2-(4''-aminophenyl)propane were added and the reaction was carried out for 1 hour. Then P-)luenesulfone #1.
3 g and 40 g of N,N-dimethylformamide were added, heated to reflux temperature, and reacted for 12 hours. Water produced by the reaction was azeotropically removed.
反応終了後、反応液を８０〜９０°Ｃに冷却し、直ちに
減圧下で留去し、続いて得られた有機層にメタノールｆ
ｏｏｄを装入し、さらに水を３０ｈ＋ｆ装入して０．５
〜１時間攪拌し結晶を析出させた後、濾過乾燥して黄色
結晶の２−（４−ヒドロキシフェニル）２−（４’−マ
レイミドフェニル）プロパンｔ−７３，３ｇ（収率９５
．５％）得た。得られた生成物の融点は１６８〜１７１
°ｃ、 ｃｐｃによる純度分析結果は９９％であった
。After the reaction was completed, the reaction solution was cooled to 80-90°C and immediately distilled off under reduced pressure.
Charge ood and further charge 30h+f of water to 0.5
After stirring for ~1 hour to precipitate crystals, filtration and drying yielded yellow crystals of 2-(4-hydroxyphenyl)2-(4'-maleimidophenyl)propane t-73.3g (yield: 95%).
．． 5%) was obtained. The melting point of the product obtained is 168-171
The purity analysis result by °C and CPC was 99%.
Claims (1)
ミノフェニル）プロパンと無水マレイン酸を水と共沸可
能な有機溶剤中、酸触媒および非プロトン性極性溶媒の
共存下で脱水閉環させることを特徴とする２−（４−ヒ
ドロキシフェニル）−２−（４′−マレイミドフェニル
）プロパンの製造方法。1) Dehydration and ring closure of 2-(4-hydroxyphenyl), 2-(4'-aminophenyl)propane and maleic anhydride in an organic solvent capable of azeotroping with water in the coexistence of an acid catalyst and an aprotic polar solvent. A method for producing 2-(4-hydroxyphenyl)-2-(4'-maleimidophenyl)propane.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419089A JPH0341067A (en) | 1989-07-07 | 1989-07-07 | Production of 2-(4-hydroxyphenyl)-2-(4'-maleimidephenyl) propane |
| EP19900305668 EP0400898A3 (en) | 1989-05-30 | 1990-05-24 | Heat resistant epoxy resin composition |
| KR1019900007778A KR900018261A (en) | 1989-05-30 | 1990-05-29 | Heat Resistant Epoxy Resin Composition |
| CA002017695A CA2017695A1 (en) | 1989-05-30 | 1990-05-29 | Heat-resistant epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17419089A JPH0341067A (en) | 1989-07-07 | 1989-07-07 | Production of 2-(4-hydroxyphenyl)-2-(4'-maleimidephenyl) propane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0341067A true JPH0341067A (en) | 1991-02-21 |
Family
ID=15974298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17419089A Pending JPH0341067A (en) | 1989-05-30 | 1989-07-07 | Production of 2-(4-hydroxyphenyl)-2-(4'-maleimidephenyl) propane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0341067A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6438904B1 (en) | 1999-12-17 | 2002-08-27 | Mitsubishi Heavy Industries, Ltd. | Root wrapping type aseismic reinforcement construction and method for base of column member |
| WO2005110984A1 (en) * | 2004-05-17 | 2005-11-24 | Daicel Chemical Industries, Ltd. | Process for producing cyclic n-hydroxyimide compound |
-
1989
- 1989-07-07 JP JP17419089A patent/JPH0341067A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6438904B1 (en) | 1999-12-17 | 2002-08-27 | Mitsubishi Heavy Industries, Ltd. | Root wrapping type aseismic reinforcement construction and method for base of column member |
| WO2005110984A1 (en) * | 2004-05-17 | 2005-11-24 | Daicel Chemical Industries, Ltd. | Process for producing cyclic n-hydroxyimide compound |
| JPWO2005110984A1 (en) * | 2004-05-17 | 2008-03-21 | ダイセル化学工業株式会社 | Method for producing N-hydroxy cyclic imide compound |
| US7582774B2 (en) | 2004-05-17 | 2009-09-01 | Daicel Chemical Industries, Ltd. | Process for producing cyclic N-hydroxy imide compounds |
| JP4690314B2 (en) * | 2004-05-17 | 2011-06-01 | ダイセル化学工業株式会社 | Method for producing N-hydroxy cyclic imide compound |
| US8217182B2 (en) | 2004-05-17 | 2012-07-10 | Daicel Chemical Industries, Ltd. | Process for producing cyclic N-hydroxy imide compounds |
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