JPH0521103B2 - - Google Patents
Info
- Publication number
- JPH0521103B2 JPH0521103B2 JP59179384A JP17938484A JPH0521103B2 JP H0521103 B2 JPH0521103 B2 JP H0521103B2 JP 59179384 A JP59179384 A JP 59179384A JP 17938484 A JP17938484 A JP 17938484A JP H0521103 B2 JPH0521103 B2 JP H0521103B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- acetophenone
- glycinonitrile
- methylbenzylidene
- 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.)
- Expired - Fee Related
Links
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SCLCDBISIMXAPM-UHFFFAOYSA-N 2-(benzylideneamino)propanenitrile Chemical compound N#CC(C)N=CC1=CC=CC=C1 SCLCDBISIMXAPM-UHFFFAOYSA-N 0.000 claims description 13
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000004927 clay Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- -1 BF 3 etherate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YHFHMOBBPOUKRV-UHFFFAOYSA-N O=ClOCCOCl=O Chemical compound O=ClOCCOCl=O YHFHMOBBPOUKRV-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明は新規化合物α−メチルベンジリデンア
ミノアセトニトリルおよびその製造法に関するも
のである。
本発明のα−メチルベンジリデンアミノアセト
ニトリルはベンジルクロライド等の有機ハロゲン
化物、またはホルムアルデヒド等のアルデヒド類
と反応させる等により各種のα−アミノ酸を始め
とする種々の有機化合物の合成原料、中間体とな
り、工業的に有用な物質である。
ロ 従来の技術及び問題点
α−メチルベンジリデンアミノアセトニトリル
は原理的にはグリシノニトリルをアセトフエノン
から合成することが出来るが、原料であるグリシ
ノニトリルが安定性の低い物質であるためか、従
来その合成が試みられた例をみない。僅かに類似
の例として最近ケトンとしてベンゾフエノンを用
いたグリシノニトリルのシツフ塩基の合成例が報
告されているに過ぎない（Tetrahedron Letters
No.49、P.4625）。
ハ 問題点を解決するための手段
本発明者はグリシノニトリルとアセトフエノン
の反応を有利に行なわせることにより、高い収率
で新規化合物であるα−メチルベンジリデンアミ
ノアセトニトリルを得ることに成功した。
即ち、本発明によれば下記の式で示されるα−
メチルベンジリデンアミノアセトニトリル
が提供される。また更にその製造法としてグリシ
ノニトリルをアセトフエノンと酸触媒の存在下に
おいて反応させ、反応生成水を公知の共沸蒸留に
より除去することを特徴とする方法が提供され
る。
本発明の方法によればアセトフエノンをベンゼ
ン、トルエン等の水と共沸する溶媒を溶かし、こ
れに酸触媒を加え、グリシノニトリルを直接一度
に加えるか、または時間をかけて滴下する。反応
により生成した水は共沸成分として系外へ留去
し、反応を完結させる。
一般に芳香族ケトンとアミノの縮合反応は遅い
ので触媒を用いる。用いられる触媒としてプロト
ン酸、BF3・エーテラート、塩化亜鉛等が挙げら
れる。〔Comprehensive Organic Chemistry、
Vol.2、P.387（1979）〕
本反応の触媒について種々検討したところ上記
触媒の他に、活性アルミナ、シリカアルミナ、シ
リカマグネシア、シリカ、Ｈ型Ｙ−ゼオライト、
希上類交換Ｙ−ゼオライト、Ｈ型モリデナイト、
酸性白土、水素型酸性白土、金属交換酸性白土、
活性白土、酸性イオン交換樹脂等の固体酸触媒、
酢酸、プロピオン酸、メタンスルホン酸、ベンゼ
ンスルホン酸、パラトルエンスルホン酸等の有機
酸が有効であることを見出した。
本反応の原料の一つであるグリシノニトリルは
それ自体の安定性が低いので反応条件、触媒を選
ばないと、分解反応が併発し、シツフ塩基の収率
が上がらない。このため、上に挙げた触媒群の内
でとくにシツフ塩基の反応収率の高い触媒は次に
挙げるものに限られる。活性アルミナ、Ｈ型Ｙ−
ゼオライト、Ｈ型Ｘ−ゼオライト、希上類交換Ｙ
−ゼオライト、酸性白土、水素型酸性白土、金属
交換酸性白土、活性白土、パラトルエンスルホン
酸。
これらの内、固体触媒は反応の連続化が可能で
あり、後処理の容易さ、廃棄物が少ない等の利点
を有する。
有機酸触媒ではパラトルエンスルホン酸が特異
的に優れた効果を示した。
触媒の使用量は固体酸の場合、グリシノニトリ
ルの重量を１とすると、0.1〜２、好ましくは0.5
〜1.0である。
反応温度は、溶媒と水の共沸温度であるので、
溶媒の種類、反応の圧力により決まるが、通常20
〜150℃である。反応の圧力は通常は常圧である
が、反応温度を調節するために、減圧または加圧
してもかまわない。
反応時間は１〜30時間である。
用いるグリシノニトリルとアセトフエノンの比
率はいずれか一方を過剰に用いると反応速度の点
で有利である。安定性、回収の両面からアセトフ
エノンの過剰に用いる方が有利であり、その比率
は副生物の生成、回収の点から自ずと限度があ
り、１：101〜2.0（モル比）が適当である。
溶媒は、水と共沸し、かつ水の溶解度の小さい
溶媒で適当な共沸温度を有するものである。ベン
ゼン、トルエン、シクロヘキサン、エチレンジク
ロライト等が挙げられる。
水の除去は通常の方法がとられるが、共沸蒸気
を系外で冷却凝縮し、静置し、溶媒層のみ、系に
戻すことにより達成される。
反応生成物であるα−メチルベンジリデンアミ
ノアセトニトリルは反応終了液から溶媒を留去し
た後、減圧蒸留により未反応のアセトフエノン等
の共沸物質から単離することが出来る。
ニ 実施例
以下、実施例を挙げて説明する。
実施例 １
還流冷却器付の水分定量器をつけた1500mlのセ
パラブルフラスコにベンゼン800mlを入れ、アセ
トフエノン120.7ｇ（1.05モル）を溶解し、パラ
トルエンスルホン酸１・水和物0.25ｇを加え、
100℃のオイルバスで加温する。
攪拌還流下、90％グリシノニトリル水溶液54.5
ｇ（0.875モル）を20分間で滴下した。水分定量
器で水を分離しながら反応させた。６時間後、反
応液をガスクロマトグラフで分析したところ、α
−メチルベンジリデンアミノアセトニトリルが
131.5ｇ（0.831モル）生成していた。収率95％。
該反応液から、ベンゼンを減圧留去後、窒素雰
囲気減圧蒸留し、３mmHgにて133℃〜134℃の留
分を得た。淡黄色結晶。このものは下記の物性値
を得た。
融点 44〜46℃
元素分析値（CH10H10N2）
Ｃ％ Ｈ％ Ｎ％
実測値 73.88 6.34 17.47
計算値 75.92 6.37 17.711
H該磁気共鳴スペクトル（CDCl3溶媒中）
4.37ppm（2H）
2.30（3H）
7.25〜7.90（5H）
実施例 ２
エチレンジクロライド30mlにアセトフエノン
6.4ｇ（53.0ミリモル）、パラトルエンスルホン酸
１・水和物200mgを加え、還流下グリシノニトリ
ル2.0ｇ（35.3ミリモル）を加え、水分定量器で
水を除きながら反応させた。２時間後、反応液を
ガスクロマトグラフで分析したところ収率83.8％
でα−メチルベンジリデンアミノアセトニトリル
が生成していた。
実施例 ３
エチレンジクロライド30mlにアセトフエノン
3.2ｇ（26.5ミリモル）、グリシノニトリル1.0ｇ
（17.7ミリモル）を溶解し、これに触媒として酸
性白土（水沢化学製）1.0ｇを加え、還流下、水
分定量器で水を分離しながら反応させた。２時間
後反応液を分析したところ収率75.4％でα−メチ
ルベンジリデンアミノアセトニトリルが生成して
いた。
実施例 ４〜10
触媒を表１に示すものにかえた以外は実施例３
と同様に反応させた。結果を表１にまとめて示
す。
【表】DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a new compound α-methylbenzylidene aminoacetonitrile and a method for producing the same. The α-methylbenzylidene aminoacetonitrile of the present invention can be reacted with organic halides such as benzyl chloride or aldehydes such as formaldehyde to become raw materials and intermediates for the synthesis of various organic compounds including various α-amino acids. It is an industrially useful substance. B. Prior art and problems α-Methylbenzylideneaminoacetonitrile can be synthesized from glycinonitrile from acetophenone in principle, but it has not been possible to synthesize α-methylbenzylidene aminoacetonitrile from acetophenone. I have not seen any attempt at synthesis. As a slightly similar example, the synthesis of the Schiff base of glycinonitrile using benzophenone as the ketone has recently been reported (Tetrahedron Letters).
No.49, P.4625). C. Means for Solving the Problems The present inventors succeeded in obtaining α-methylbenzylidene aminoacetonitrile, a novel compound, in high yield by conducting the reaction between glycinonitrile and acetophenone advantageously. That is, according to the present invention, α-
Methylbenzylidene aminoacetonitrile is provided. Furthermore, a method for producing the same is provided, which comprises reacting glycinonitrile with acetophenone in the presence of an acid catalyst, and removing water produced by the reaction by known azeotropic distillation. According to the method of the present invention, acetophenone is dissolved in a solvent that is azeotropic with water, such as benzene or toluene, an acid catalyst is added thereto, and glycinonitrile is added directly at once or added dropwise over time. The water produced by the reaction is distilled out of the system as an azeotropic component to complete the reaction. Generally, the condensation reaction between aromatic ketones and amino is slow, so a catalyst is used. Examples of catalysts used include protonic acid, BF 3 etherate, and zinc chloride. [Comprehensive Organic Chemistry,
Vol. 2, P. 387 (1979)] Various catalysts for this reaction were investigated. In addition to the above catalysts, activated alumina, silica alumina, silica magnesia, silica, H-type Y-zeolite,
Rarely exchanged Y-zeolite, H-type molidenite,
Acid clay, hydrogen type acid clay, metal exchange acid clay,
Solid acid catalysts such as activated clay and acidic ion exchange resins,
It has been found that organic acids such as acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, and paratoluenesulfonic acid are effective. Glycinonitrile itself, which is one of the raw materials for this reaction, has low stability, so unless the reaction conditions and catalyst are selected, decomposition reactions will occur and the yield of Schiff's base will not increase. For this reason, among the above-mentioned catalyst groups, the catalysts that have a particularly high Schiff base reaction yield are limited to the following. Activated alumina, H type Y-
Zeolite, H type X-zeolite, rarefied exchange Y
-Zeolite, acid clay, hydrogen type acid clay, metal exchanged acid clay, activated clay, para-toluenesulfonic acid. Among these, solid catalysts have advantages such as continuous reaction, ease of post-treatment, and less waste. Among organic acid catalysts, para-toluenesulfonic acid showed a particularly excellent effect. In the case of a solid acid, the amount of catalyst used is 0.1 to 2, preferably 0.5 when the weight of glycinonitrile is 1.
~1.0. Since the reaction temperature is the azeotropic temperature of the solvent and water,
Depends on the type of solvent and reaction pressure, but usually 20
~150℃. The reaction pressure is usually normal pressure, but the pressure may be reduced or increased in order to control the reaction temperature. Reaction time is 1 to 30 hours. Regarding the ratio of glycinonitrile and acetophenone used, using an excess of either one is advantageous in terms of reaction rate. It is advantageous to use an excess of acetophenone in terms of both stability and recovery, but the ratio is naturally limited in terms of by-product production and recovery, and a suitable molar ratio is 1:101 to 2.0. The solvent is a solvent that is azeotropic with water and has a low solubility in water and has an appropriate azeotropic temperature. Examples include benzene, toluene, cyclohexane, and ethylene dichlorite. Water can be removed by conventional methods, such as cooling and condensing the azeotropic vapor outside the system, allowing it to stand, and returning only the solvent layer to the system. The reaction product α-methylbenzylideneaminoacetonitrile can be isolated from unreacted azeotropic substances such as acetophenone by distillation under reduced pressure after distilling off the solvent from the reaction-completed liquid. D. Examples The following will explain examples. Example 1 Put 800 ml of benzene into a 1500 ml separable flask equipped with a water meter equipped with a reflux condenser, dissolve 120.7 g (1.05 mol) of acetophenone, add 0.25 g of para-toluenesulfonic acid monohydrate,
Warm in an oil bath at 100℃. 90% glycinonitrile aqueous solution 54.5 under stirring and refluxing
g (0.875 mol) was added dropwise over 20 minutes. The reaction was carried out while separating water using a water meter. After 6 hours, the reaction solution was analyzed by gas chromatography, and it was found that α
-Methylbenzylidene aminoacetonitrile
131.5g (0.831 mol) was produced. Yield 95%. Benzene was distilled off under reduced pressure from the reaction solution, and then distilled under reduced pressure in a nitrogen atmosphere to obtain a fraction having a temperature of 133°C to 134°C at 3 mmHg. Pale yellow crystals. This product obtained the following physical property values. Melting point 44-46℃ Elemental analysis value (CH 10 H 10 N 2 ) C% H% N% Actual value 73.88 6.34 17.47 Calculated value 75.92 6.37 17.71 1H magnetic resonance spectrum (in CDCl 3 solvent) 4.37ppm (2H) 2.30 (3H) 7.25-7.90 (5H) Example 2 Acetophenone in 30ml of ethylene dichloride
6.4 g (53.0 mmol) and 200 mg of para-toluenesulfonic acid monohydrate were added thereto, and 2.0 g (35.3 mmol) of glycinonitrile was added under reflux, followed by reaction while removing water with a water meter. After 2 hours, the reaction solution was analyzed by gas chromatography and the yield was 83.8%.
α-methylbenzylideneaminoacetonitrile was produced. Example 3 Acetophenone in 30ml of ethylene dichloride
3.2g (26.5mmol), glycinonitrile 1.0g
(17.7 mmol) was dissolved, 1.0 g of acid clay (manufactured by Mizusawa Chemical) was added as a catalyst, and the mixture was reacted under reflux while separating water using a water meter. Analysis of the reaction solution after 2 hours revealed that α-methylbenzylideneaminoacetonitrile had been produced in a yield of 75.4%. Examples 4 to 10 Example 3 except that the catalyst was changed to one shown in Table 1.
reacted in the same way. The results are summarized in Table 1. 【table】
図１、図２はα−メチルベンジリデンアミノア
セトニトリルのマススペクトル、該磁気共鳴スペ
クトルである。
FIGS. 1 and 2 show the mass spectrum and magnetic resonance spectrum of α-methylbenzylidene aminoacetonitrile.
Claims (1)
アミノアセトニトリル。 ２ グリシノニトリルをアセトフエノンと酸触媒
の存在下において反応させ、反応生成水を公知の
共沸蒸留により除去することを特徴とするα−メ
チルベンジリデンアミノアセトニトリルの製造
法。[Claims] 1. α-Methylbenzylidene aminoacetonitrile represented by the following formula. 2. A method for producing α-methylbenzylidene aminoacetonitrile, which comprises reacting glycinonitrile with acetophenone in the presence of an acid catalyst and removing water produced by the reaction by known azeotropic distillation.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59179384A JPS6160639A (en) | 1984-08-30 | 1984-08-30 | Alpha-metylbenzylideneaminoacetonitrile and its preparation |
| DE19853531084 DE3531084A1 (en) | 1984-08-30 | 1985-08-30 | Process for the preparation of phenylalanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59179384A JPS6160639A (en) | 1984-08-30 | 1984-08-30 | Alpha-metylbenzylideneaminoacetonitrile and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6160639A JPS6160639A (en) | 1986-03-28 |
| JPH0521103B2 true JPH0521103B2 (en) | 1993-03-23 |
Family
ID=16064914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59179384A Granted JPS6160639A (en) | 1984-08-30 | 1984-08-30 | Alpha-metylbenzylideneaminoacetonitrile and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6160639A (en) |
-
1984
- 1984-08-30 JP JP59179384A patent/JPS6160639A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6160639A (en) | 1986-03-28 |
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