JPS5982369A - Preparation of 1-cyanoethyl-2-phenylimidazole trimellitate - Google Patents
Preparation of 1-cyanoethyl-2-phenylimidazole trimellitateInfo
- Publication number
- JPS5982369A JPS5982369A JP57192923A JP19292382A JPS5982369A JP S5982369 A JPS5982369 A JP S5982369A JP 57192923 A JP57192923 A JP 57192923A JP 19292382 A JP19292382 A JP 19292382A JP S5982369 A JPS5982369 A JP S5982369A
- Authority
- JP
- Japan
- Prior art keywords
- phenylimidazole
- cyanoethyl
- trimellitic acid
- acrylonitrile
- alcohol
- 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.)
- Granted
Links
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 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 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 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 abstract description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 15
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 239000011541 reaction mixture Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- -1 imidazole compound Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UAFNNYNGQVOTOM-UHFFFAOYSA-N 2-(2-phenyl-1h-imidazol-5-yl)propanenitrile Chemical compound N1C(C(C#N)C)=CN=C1C1=CC=CC=C1 UAFNNYNGQVOTOM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は１−シアノエチル−２−フェニルイミダゾール
トリメリット酸塩の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1-cyanoethyl-2-phenylimidazole trimellitate.
本発明方法によって得られる化合物は、エポキシ松脂の
硬化剤として既に広く使用されている。（特公昭４７−
５０２４０号公報参照）
この枇イミダゾール化合物の製法に関する従来技術とし
ては、無水トリメリット酸を水と加熱してトリメリット
酸に転換し、これをメタノール、イソプロピルアルコー
ルなどのアルコール溶媒中で１−シアノエチ／Ｉ／−２
−フェニルイミダゾールと反応させる方法が知られてい
る。The compounds obtained by the method of the present invention are already widely used as curing agents for epoxy pine resins. (Special Public Service 1977-
(See Publication No. 50240) As a conventional technique for producing this imidazole compound, trimellitic anhydride is heated with water to convert it to trimellitic acid, and this is converted to trimellitic acid in an alcohol solvent such as methanol or isopropyl alcohol. I/-2
- A method of reacting with phenylimidazole is known.
しかしながら、トリメリント酸と１−シアノエチル−２
−フェニルイミダゾールをアルコール溶媒中で反応させ
ると、１−シアノエチＡｌ−２−７エニルイミダゾール
の加水分解反応を完全に防ぐことができるけれども、ア
ルコール溶媒とトリメリット酸の副反応が相当に進行し
、収率の低下並びに品質の悪化を来たすなどの間ｉが存
在していた。However, trimellitic acid and 1-cyanoethyl-2
- When phenylimidazole is reacted in an alcohol solvent, the hydrolysis reaction of 1-cyanoethylAl-2-7 enylimidazole can be completely prevented, but the side reaction between the alcohol solvent and trimellitic acid proceeds considerably; i existed during the process, causing a decrease in yield and deterioration of quality.
このような事情に艦み本発明者等は、製品の収草を高め
且つ純度の向上を目指して試験研究をｆねた結果、２−
フェニルイミダゾールとアクリロニトリルを反応し、そ
の反応液に加水トリメリット酸と水を直かに加えて反応
させ、且つその反応液に低級アルコールを加えて結晶を
分離し、回収することによって量産に適する製法を確立
したものである。In view of these circumstances, the inventors of the present invention conducted research and experimentation with the aim of increasing the yield and purity of the product.
A manufacturing method suitable for mass production by reacting phenylimidazole and acrylonitrile, directly adding hydrated trimellitic acid and water to the reaction solution, and adding lower alcohol to the reaction solution to separate and collect crystals. was established.
本発明方法において注目すべきは、水溶媒中で１−シア
ノエチル−２−フェニルイミダゾールとトリメリット酸
を中和反応を行わせる際に、従来考えられていた１−シ
アノエチ／に−２−フェニルイミダゾールの加水分解反
応は全く起らず、且つ２−フェニルイミダゾールとアク
リロニトリルの反応工程において残存する２−フェニル
イミダゾールとトリメリット酸の反応によって生じた副
生よって目的物と選択的に単離しうることを見い出した
ことである。What should be noted in the method of the present invention is that when carrying out the neutralization reaction of 1-cyanoethyl-2-phenylimidazole and trimellitic acid in an aqueous solvent, 1-cyanoethyl-2-phenylimidazole, which was previously thought to be The hydrolysis reaction of 2-phenylimidazole and acrylonitrile does not occur at all, and the target product can be selectively isolated due to the by-product generated by the reaction of 2-phenylimidazole and trimellitic acid remaining in the reaction process of 2-phenylimidazole and acrylonitrile. This is what I discovered.
本発明方法によれば従来の製法に比べて、１−シアノエ
チル−２−フェニルイミダゾールの結晶化、分離および
乾燥の各工程を省熱化してその生産性を高揚し、全体と
しての溶解度損失を低減し、製品の収率を大幅に向上さ
せることができる。According to the method of the present invention, compared to conventional production methods, each step of crystallization, separation, and drying of 1-cyanoethyl-2-phenylimidazole saves heat, increases productivity, and reduces overall solubility loss. and can significantly improve product yield.
本発明を実施するに当り、２−フェニルイミダゾールと
アクリロニトリルを反応して１−シアノエｆ／Ｉ／−２
−フェニルイミダゾールを製造する工程はｍＷ媒下で加
熱し、１−シアノエチル−２−フェニルイミダゾールを
含む反応液とトリメリット酸を反応させる工程は、無水
トリメリット酸と過剰の水を加えて５０〜１００℃の温
度に加熱し、その反応混合物に低級アルコール、好まし
くはイソプロピルアルコールを水と同量程度加えて濾過
し、結晶を分離し回収すれば良い。In carrying out the present invention, 2-phenylimidazole and acrylonitrile are reacted to obtain 1-cyanoe f/I/-2
- The step of producing phenylimidazole is performed by heating under mW medium, and the step of reacting the reaction solution containing 1-cyanoethyl-2-phenylimidazole with trimellitic acid is performed by adding trimellitic anhydride and excess water. The reaction mixture may be heated to a temperature of 100° C., a lower alcohol, preferably isopropyl alcohol, added in an amount equal to that of water, and filtered to separate and collect crystals.
シ下本発明を実施例および参考例をもって具体的に説明
する。Below, the present invention will be specifically explained with reference to Examples and Reference Examples.
実施例
撹拌様を偵えた四ツ目フラスコに２−フェニルイミダゾ
ール７２ｇ（０，５モル）を入れ、８０℃の温度に加熱
してアクリロニトリル２９．２ｇ（０゜５５モル）を３
０分間に亘って涙下し、更に９０〜９５℃に昇温して１
０時間加熱をｂけた。Example 72g (0.5 mol) of 2-phenylimidazole was placed in a four-eye flask with stirring, heated to 80°C, and 29.2g (0°55 mol) of acrylonitrile was added to 3
The temperature was further increased to 90-95℃ for 1 minute.
Heating was continued for 0 hours.
次いでこの反応生成物に水３７５ｇと無水トリメリツ）
！９６ｇ（０−５モル）を加えて８０℃の温度で１０分
間加熱攪拌し、その後反応混合物にイソプロピルアルコ
ール１６３ｇを加え約８０℃に昇温して結晶を溶解し、
これを約１５℃まで冷却して結晶を析出させ、生じた結
晶を遠心分離様によって決別し、乾燥して１−シアンエ
チル−２−フェニルイミダゾールトリメリットｍｍ１６
８．９ｇを得た。Then, add 375 g of water and anhydrous trimelitz to this reaction product.
! 96 g (0-5 mol) was added and heated and stirred at a temperature of 80°C for 10 minutes, and then 163 g of isopropyl alcohol was added to the reaction mixture and the temperature was raised to about 80°C to dissolve the crystals.
This was cooled to about 15°C to precipitate crystals, separated by centrifugation, and dried to give 1-cyanethyl-2-phenylimidazole trimellit mm16.
8.9g was obtained.
本市を高速液体クロマトダラフイーで分析したところ、
純度は９９．６３％不純峻２−フェニルイミ〆ト
ダゾールトリメ）１ツト酸坂の含有ｉ： ０．２０％で
あり、ＪＲＩ２−フェニルイミダゾールに対する収率は
理Ｗｉ価の８３．０％に相当した。When Motoichi was analyzed using high performance liquid chromatography, it was found that
The purity was 99.63%, and the content of 2-phenylimidazole trimester was 0.20%, and the yield based on JRI 2-phenylimidazole was 83.0% of the physical value.
参考例１
ｈｊＡ’ ｉ＆＝＝を側１えた四ツ目フラスコに２−フ
ェニルイミダゾール１４４ｇ（１モル）を入れて８０℃
に力１■熱し、アクリロニトリ／Ｉ１５８．３ ｇ （
１，１モル）を３０分間に亘って滴下し、その後９０〜
９５℃に昇澹・シ、この温度で１０時間か拌を続け、そ
の反応生成物にイソプロピルアルコール２００ｇを加え
、７０℃前後に昇温して処理液を結晶を溶解させたのち
１５℃に冷却し、生じた結晶を遠心分離し乾燥して、１
−シアノエチル−２−フェニルイミダゾール１４３．８
ｇを得た。Reference Example 1 144 g (1 mol) of 2-phenylimidazole was placed in a four-eye flask with hjA'i&== on the side and heated to 80°C.
Heat for 1 hour and add 158.3 g of acrylonitrile/I (
1.1 mol) was added dropwise over 30 minutes, then 90~
Raise the temperature to 95°C, continue stirring at this temperature for 10 hours, add 200g of isopropyl alcohol to the reaction product, raise the temperature to around 70°C, dissolve the crystals in the treated liquid, and then cool it to 15°C. The resulting crystals were centrifuged and dried, and 1
-cyanoethyl-2-phenylimidazole 143.8
I got g.
本市の原料２−７エニルイミダゾールに対する収率は、
理給値の７３．０％に相当した。The yield for Motoichi's raw material 2-7 enylimidazole is:
This was equivalent to 73.0% of the salary value.
次いで攬、拌様を備えた四ツ目フラスコに１−シアノエ
チル−２−７エニルイミタｙ−に７８．８ ｇ （０，
４モル）と無水トリメリット酸７６．８ ｇ （０，４
モル）および水３５０ｇを入れて、これを１００℃の溶
度に１時間加熱した。その彼、反応混合物を釣１５℃ま
で冷却し、結晶を分離し、乾燥して斜度９９．６８％の
１−シアノエチに−２−フェニルイミダゾールトリメリ
ット酸塩１５９．２ｇを得た。Then, in a four-eye flask equipped with a stirrer, 78.8 g (0,
4 mol) and 76.8 g of trimellitic anhydride (0,4
mol) and 350 g of water were added and heated to a solubility of 100° C. for 1 hour. Thereafter, the reaction mixture was cooled to 15 DEG C., and the crystals were separated and dried to obtain 159.2 g of 1-cyanoethyl-2-phenylimidazole trimellitate with a slope of 99.68%.
本市の原料１−シアノエチルー２−７エニルイミダゾー
ルに対する収津は９７．８％であり、出発原料２−フェ
ニルイミダゾールに対する目的物の収率は７１．４％に
相当するものであった。The yield for Motoichi's raw material 1-cyanoethyl-2-7 enylimidazole was 97.8%, and the yield of the target product for the starting material 2-phenylimidazole was equivalent to 71.4%.
参考例２
実施例において水と無水トリメリット酸を加えし、生じ
た結晶を分離し乾燥したところ、その反応生成物１８７
．２ｇは１−シアノエチル−２−フェニルイミダゾール
トリメリット酸塩８７．３２％と２−フェニルイミダゾ
ールトリメリット酸塩１０．１８％を含有するものであ
った。Reference Example 2 In Example, when water and trimellitic anhydride were added and the resulting crystals were separated and dried, the reaction product 187
．． 2 g contained 87.32% of 1-cyanoethyl-2-phenylimidazole trimellitate and 10.18% of 2-phenylimidazole trimellitate.
手続補正書（自発）
昭和５８年 ３月／７日
特許庁長官 若杉和夫殿
１、事件の表示
昭和５７年特許願第１９２９２３号
２、発明の名称
１−シアノエチル−２−フェニルイミダゾールトリメリ
ット酸塩の製造法
３、補正をする者
事件との関係：特許出願人
（〒７６３ 置０８７７２−２−４１１１）４、補
正の対象
明細書の発明の詳ｊ■１な説明の開
５、補正の内容
（１）明細書第４頁下から４行目の「水３７５ｇ−」を
「水１７２ｇノに補正する。Procedural amendment (voluntary) March/7, 1980 Commissioner of the Japan Patent Office Mr. Kazuo Wakasugi1, Indication of the case Patent Application No. 192923 of 19822, Name of the invention 1-cyanoethyl-2-phenylimidazole trimellitic acid salt Manufacturing method 3. Person making the amendment Relationship with the case: Patent applicant (08772-2-4111) 4. Detailed description of the invention in the specification to be amended 5. Contents of the amendment (1) "Water 375g-" in the fourth line from the bottom of page 4 of the specification is corrected to "Water 172g-".
（２）明細書第５頁下から３行目の「処理液を結晶を」
（３）明細書箱６頁４行目から１６行目の「次いで攪拌
機を備えた・・・に相当するものであった。」の記載を
下記のとおり補正する。(2) "Crystallize the treatment liquid" on the third line from the bottom of page 5 of the specification.
(3) The statement "It was equipped with a stirrer..." in lines 4 to 16 on page 6 of the specification box is amended as follows.
記
１次いて攪拌機を備えた四ツ目フラスコに無水ｌ〜リメ
リット酸１６．ｈ （０，４モル）と水７２ｇ （
４モル）を入れて加タハ攪拌し、これを１時間１００°
Ｃの温度に保った。これにメタノール１６６ｇと１−シ
アンエチル−２−フェニルイミダゾール１８．８ｇ （
０，４モル）を加えて加熱攪拌し、１時間７０〜７５°
Ｃのを乾燥して１−シアンエチル−２−フェニルイミダ
ソールの１−リメリソト酸塩１４６．６ｇを得た。1. Next, in a four-eye flask equipped with a stirrer, add 1 liter of anhydride to 16. h (0.4 mol) and 72 g of water (
4 mol), stirred and heated at 100° for 1 hour.
The temperature was maintained at C. To this, 166 g of methanol and 18.8 g of 1-cyanoethyl-2-phenylimidazole (
0.4 mol), heated and stirred at 70-75° for 1 hour.
C was dried to obtain 146.6 g of 1-limerisotate of 1-cyanoethyl-2-phenylimidasole.
本市の原料１−シアンエチル−２−フェニルイミダゾー
ルｌ／に対する収率は９０．０％であり、出発原料２−
フェニルイミダゾールに対する目的物の収率は６５．７
％乙こ相当するものであった。」以上
６−The yield of Motoichi's raw material 1-cyanoethyl-2-phenylimidazole per liter was 90.0%, and the starting material 2-
The yield of the target product based on phenylimidazole is 65.7
It was equivalent to %. ” Above 6-
Claims (1)
せる第１過程と前記過程において生じる反応液に無水ト
リメリット酸と水を加えて反応させる第２過程および第
２過程における反応液に低級アルコールを加えて結晶を
分離し回収する第３過程からなることを特徴とする１−
シアンエチル−２ｆ、フェニルイミダゾールトリメリッ
ト酸塩の製造法。A first step in which 2-phenylimidazole and acrylonitrile are reacted, a second step in which trimellitic anhydride and water are added to the reaction solution produced in the above step, and a lower alcohol is added to the reaction solution in the second step to separate crystals. 1- characterized in that it consists of a third step of collecting
Method for producing cyanethyl-2f, phenylimidazole trimellitate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57192923A JPS6055073B2 (en) | 1982-11-01 | 1982-11-01 | Method for producing 1-cyanoethyl-2-phenylimidazole trimellistate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57192923A JPS6055073B2 (en) | 1982-11-01 | 1982-11-01 | Method for producing 1-cyanoethyl-2-phenylimidazole trimellistate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5982369A true JPS5982369A (en) | 1984-05-12 |
| JPS6055073B2 JPS6055073B2 (en) | 1985-12-03 |
Family
ID=16299226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57192923A Expired JPS6055073B2 (en) | 1982-11-01 | 1982-11-01 | Method for producing 1-cyanoethyl-2-phenylimidazole trimellistate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6055073B2 (en) |
-
1982
- 1982-11-01 JP JP57192923A patent/JPS6055073B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6055073B2 (en) | 1985-12-03 |
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