JPS6248665B2 - - Google Patents
Info
- Publication number
- JPS6248665B2 JPS6248665B2 JP54154426A JP15442679A JPS6248665B2 JP S6248665 B2 JPS6248665 B2 JP S6248665B2 JP 54154426 A JP54154426 A JP 54154426A JP 15442679 A JP15442679 A JP 15442679A JP S6248665 B2 JPS6248665 B2 JP S6248665B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- benzene
- dichloropropionitrile
- catalyst
- chlorohydrocinnamitrile
- 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
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 17
- RJJDLPQZNANQDQ-UHFFFAOYSA-N 2,3-dichloropropanenitrile Chemical compound ClCC(Cl)C#N RJJDLPQZNANQDQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- ZUPBNBYEVVGQKK-UHFFFAOYSA-N 2-chloro-3-phenylpropanenitrile Chemical compound N#CC(Cl)CC1=CC=CC=C1 ZUPBNBYEVVGQKK-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- FMHXHMLHGIPODY-UHFFFAOYSA-N 2,2-dichloropropanenitrile Chemical compound CC(Cl)(Cl)C#N FMHXHMLHGIPODY-UHFFFAOYSA-N 0.000 description 1
- JNAYPRPPXRWGQO-UHFFFAOYSA-N 2-chloropropanenitrile Chemical compound CC(Cl)C#N JNAYPRPPXRWGQO-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000007192 Meerwein reaction reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- -1 α-chloro-β-(3 Chemical class 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
本発明は、α―クロルヒドロシンナムニトリル
の製造法に関するものであり、更に詳しくはベン
ゼンと２，３―ジクロルプロピオニトリルとを触
媒の存在下で反応させるα―クロルヒドロシンナ
ムニトリルの新規な製造法に関するものである。
α―クロルヒドロシンナムニトリルは、例えば
鉱酸と加熱加水分解し、ついでアンモニアでアミ
ノ化すると容易にフエニルアラニンに誘導するこ
とができるから、フエニルアラニン合成の中間体
として極めて有用な化合物である。
α―クロルヒドロシンナムニトリルを製造する
従来の方法としては、アニリンから誘導されるベ
ンゼンジアゾニウム塩とアクリロニトリルを塩化
第二銅の存在下で反応させる、いわゆるメールヴ
アイン（Meerwein）反応による方法がある。し
かしながら、この方法は操作が煩雑であり、また
高価な原料を使用すること等から、工業的製造法
として必ずしも満足できるものではない。
α―クロルヒドロシンナムニトリルの核置換誘
導体、例えば、α―クロル―β―（３，４―ジオ
キシフエニル）―プロピオニトリル類をカテコー
ル類および２，３―ジクロルプロピオニトリルか
らフリーデル・クラフツ反応を利用して製造する
方法は公知である（特公昭46−15609，特公昭46
−15612）。２，３―ジクロルプロピオニトリルは
分子内に電子吸引基を多く含むため反応性に乏し
いが、ジメトキシ基のような電子供与基により活
性化された芳香環を持つ化合物との反応について
は、AlCl3などを触媒として進行する。しかし、
ベンゼンのように、反応性を増す置換基を持たな
い化合物との反応については全く知られていな
い。このときはこのような場合には反応が起こり
にくいことを示唆する。事実ベンゼンと２，３―
ジクロルプロピオニトリルからのα―クロルヒド
ロシンナムニトリルへの反応は、フリーデル・ク
ラフツ反応の触媒としては典型的で、かつ、通常
最も触媒活性が高いとされているAlBr3やAlCl3
を用いたのでは、ほとんど進行しない。
本発明者らは、２，３―ジクロルプロピオニト
リルとベンゼンの反応について鋭意研究した結
果、意外にもフリーデル・クラフツ触媒としては
比較的活性が低いとされている五塩化アンチモン
等を触媒として用いると、この反応が効果的に進
行することを見出して本発明を完成した。
従つて、本発明はベンゼンと２，３―ジクロル
プロピオニトリルとを、触媒成分として五塩化ア
ンチモン、五塩化モリブデン、塩化第二鉄または
これらの混合物を含む触媒の存在下で反応させる
ことを特徴とするα―クロルヒドロシンナムニト
リルの製造法を提供するものである。
本発明の方法で原料として使用するベンゼンと
２，３―ジクロルプロピオニトリルは、ともに工
業的に容易に入手できるものである。２，３―ジ
クロルプロピオニトリルは、例えば、アクリロニ
トリルに塩素を付加することにより容易に得られ
る。
本発明の方法でのベンゼンおよび２，３―ジク
ロルプロピオニトリルの使用量については格別の
限定はないが、後述する理由により、また原料の
価格等を考慮に入れると、２，３―ジクロルプロ
ピオニトリルに対して、ベンゼンを化学量論から
要求される量よりも過剰に使用するのが有利であ
る。過剰のベンゼンは反応溶媒としても役立つ。
本発明の方法で触媒の使用量は２，３―ジクロ
ルプロピオニトリル１モルに対して約0.1モルな
いし約３モル、好ましくは約0.5モルから約２モ
ルである。
本発明の方法では更に助触媒としてルイス酸や
塩酸，硫酸，リン酸，臭化水素酸等のブロンステ
ツド酸もしくはその水溶液またはシリカゲル等を
添加することにより更に収率よく反応を進行させ
ることができる。この場合、助触媒の使用量は触
媒１重量部に対して約0.5重量部以下が望まし
く、好ましくは約0.005ないし約0.5重量部であ
る。水溶液で用いる場合は、触媒１重量部に対し
て約0.005ないし約0.05重量部の範囲が好まし
く、この場合、水溶液中のブロンステツド酸の含
有量は約５重量％以上であることが望ましい。
反応温度は、低温では反応が進行し難く、高温
では原料や生成物が分解する傾向があるので、好
ましくは約40゜ないし約150℃、より好ましくは
約60℃ないし約110℃である。
反応時間は、反応温度，触媒の種類，その量等
により変りうるが、通常約30分ないし約50時間程
度である。
反応終了後、生成したα―クロルヒドロシンナ
ムニトリルの単離は、有機化学における通常の方
法を用いて行うことができる。例えば、反応混合
液を氷水にあけ、ジエチルエーテル，クロロホル
ム等の有機溶媒で抽出し、有機相を水、炭酸水素
ナトリウム水溶液および再度水で順次洗浄後乾燥
し、溶媒を留去し、ついで減圧蒸留することによ
り、α―クロルヒドロシンナムニトリルを単離す
ることができる。反応の際に大過剰量のベンゼン
を用いたときは過剰のベンゼンを抽出用の有機溶
媒とすることができる。
本発明によれば、容易に得られる原料を用いて
簡単な操作により、α―クロルヒドロシンナムニ
トリルを製造することができる。また、本発明に
よれば、カテコール類と２，３―ジクロルプロピ
オニトリルとの反応の場合のように、後者の過剰
量を用いて反応を行う必要がなく、逆にベンゼン
の過剰量を用いることができ、これが反応溶媒と
しても働くので反応が円滑に進行し、反応終了後
の生成物の処理もより容易となる。過剰のベンゼ
ンは生成物抽出の際の抽出剤として利用すること
もできる。
以下実施例により本発明を更に詳しく説明する
が、本発明はこれらの実施例に限定されるもので
ない。
実施例 １
２，３―ジクロルプロピオニトリル12.4ｇ
（0.1モル）とベンゼン100ml（1.13モル）の混合
物に五塩化アンチモン29.9ｇ（0.1モル）を加
え、撹拌しながら80℃で４時間半反応させた。反
応後、反応液を冷却し、100mlの氷水にあけて、
ジエチルエーテル200mlで３回抽出した。ジエチ
ルエーテル層を合わせ、水および炭酸水素ナトリ
ウム水溶液（２重量％）で洗浄して、無水硫酸マ
グネシウム上で一夜間乾燥させた。この溶液の一
部を分取し、内部標準としてジフエニルエーテル
を加えてガスクロマトグラフにより分析した。分
析条件は下記の通りである。
カラム：Silicone DC550（ガスクロ工業株式会
社製）
Celite545（同 上）
（各60〜80メツシユ）
３mmφ×２ｍ
注入温度：200℃
カラム温度：180℃
検出器温度：200℃
溶液中にはα―クロルヒドロシンナムニトリル
4.16ｇ（収率25.1％）が含まれていた。
次にこの溶液からジエチルエーテルおよびベン
ゼンを留去した後、減圧蒸留を行い、131〜133
℃／７〜８mmHgの留分として3.35ｇ（収率20.2
％）のα―クロルヒドロシンナムニトリルを単離
した。その融点および元素分析結果は下記の通り
であつた。
The present invention relates to a method for producing α-chlorohydrocinnamitrile, and more specifically to a method for producing α-chlorohydrocinnamitrile by reacting benzene and 2,3-dichloropropionitrile in the presence of a catalyst. It concerns a new manufacturing method. α-Chlorhydrocinnamnitrile is an extremely useful compound as an intermediate for the synthesis of phenylalanine because it can be easily derived into phenylalanine by, for example, heating and hydrolyzing it with a mineral acid and then aminating it with ammonia. be. A conventional method for producing α-chlorohydrocinnamitrile is the so-called Meerwein reaction, in which a benzenediazonium salt derived from aniline and acrylonitrile are reacted in the presence of cupric chloride. . However, this method is not necessarily satisfactory as an industrial production method because it requires complicated operations and uses expensive raw materials. Nucleically substituted derivatives of α-chlorohydrocinnamnitrile, such as α-chloro-β-(3,4-dioxyphenyl)-propionitriles, are prepared from catechols and 2,3-dichloropropionitrile by Friedel-Crafts. Manufacturing methods using reactions are well known (Japanese Patent Publication No. 46-15609, Japanese Patent Publication No. 46-15609)
−15612). 2,3-Dichloropropionitrile has poor reactivity because it contains many electron-withdrawing groups in its molecule, but when it comes to reactions with compounds that have aromatic rings activated by electron-donating groups such as dimethoxy groups, Proceeds using AlCl 3 etc. as a catalyst. but,
Nothing is known about reactions with compounds that do not have substituents that increase reactivity, such as benzene. This suggests that reactions are unlikely to occur in such cases. In fact, benzene and 2,3-
The reaction from dichloropropionitrile to α-chlorohydrocinnumnitrile is performed using AlBr 3 and AlCl 3 , which are typical catalysts for Friedel-Crafts reactions and are usually considered to have the highest catalytic activity.
If you use , almost no progress will be made. As a result of intensive research on the reaction between 2,3-dichloropropionitrile and benzene, the present inventors unexpectedly found that antimony pentachloride, which is said to have relatively low activity as a Friedel-Crafts catalyst, was used as a catalyst. The present invention was completed based on the discovery that this reaction proceeds effectively when used as a compound. Accordingly, the present invention provides for reacting benzene and 2,3-dichloropropionitrile in the presence of a catalyst containing antimony pentachloride, molybdenum pentachloride, ferric chloride or mixtures thereof as catalyst components. The present invention provides a method for producing α-chlorohydrocinnamnitrile characterized by its characteristics. Both benzene and 2,3-dichloropropionitrile used as raw materials in the method of the present invention are easily available industrially. 2,3-dichloropropionitrile can be easily obtained, for example, by adding chlorine to acrylonitrile. There is no particular limitation on the amount of benzene and 2,3-dichloropropionitrile used in the method of the present invention, but for the reasons described below and taking into account the price of raw materials, etc. It is advantageous to use benzene, based on chloropropionitrile, in excess of the amount required by stoichiometry. Excess benzene also serves as a reaction solvent. The amount of catalyst used in the process of the present invention is from about 0.1 mol to about 3 mol, preferably from about 0.5 mol to about 2 mol, per mol of 2,3-dichloropropionitrile. In the method of the present invention, the reaction can be carried out in even better yield by adding a Lewis acid, a Bronsted acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid, an aqueous solution thereof, or silica gel as a cocatalyst. In this case, the amount of co-catalyst used is preferably about 0.5 parts by weight or less, preferably about 0.005 to about 0.5 parts by weight, per 1 part by weight of the catalyst. When used in an aqueous solution, it is preferably in the range of about 0.005 to about 0.05 part by weight per part by weight of catalyst, and in this case, the content of Bronsted acid in the aqueous solution is preferably about 5% by weight or more. The reaction temperature is preferably about 40°C to about 150°C, more preferably about 60°C to about 110°C, since the reaction is difficult to proceed at low temperatures and the raw materials and products tend to decompose at high temperatures. The reaction time may vary depending on the reaction temperature, the type of catalyst, its amount, etc., but is usually about 30 minutes to about 50 hours. After completion of the reaction, the produced α-chlorohydrocinnamnitrile can be isolated using conventional methods in organic chemistry. For example, the reaction mixture is poured into ice water, extracted with an organic solvent such as diethyl ether or chloroform, the organic phase is washed successively with water, an aqueous sodium bicarbonate solution, and water again, and then dried, the solvent is distilled off, and then distilled under reduced pressure. By doing so, α-chlorohydrocinnamnitrile can be isolated. When a large excess amount of benzene is used during the reaction, the excess benzene can be used as an organic solvent for extraction. According to the present invention, α-chlorohydrocinnamitrile can be produced by simple operations using easily obtained raw materials. Furthermore, according to the present invention, unlike in the case of the reaction between catechols and 2,3-dichloropropionitrile, it is not necessary to conduct the reaction using an excess amount of the latter. Since this can be used as a reaction solvent, the reaction proceeds smoothly and the treatment of the product after the reaction is completed becomes easier. Excess benzene can also be used as an extractant during product extraction. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example 1 2,3-dichloropropionitrile 12.4g
29.9 g (0.1 mol) of antimony pentachloride was added to a mixture of (0.1 mol) and 100 ml (1.13 mol) of benzene, and the mixture was reacted with stirring at 80°C for 4.5 hours. After the reaction, cool the reaction solution and pour into 100ml of ice water.
Extracted three times with 200 ml of diethyl ether. The diethyl ether layers were combined, washed with water and aqueous sodium bicarbonate (2% by weight), and dried over anhydrous magnesium sulfate overnight. A portion of this solution was taken and analyzed by gas chromatography to which diphenyl ether was added as an internal standard. The analysis conditions are as follows. Column: Silicone DC550 (manufactured by Gascro Industries Co., Ltd.) Celite545 (same as above) (60 to 80 meshes each) 3 mmφ x 2 m Injection temperature: 200°C Column temperature: 180°C Detector temperature: 200°C α-chlorohydro in the solution cinnamitrile
It contained 4.16g (yield 25.1%). Next, diethyl ether and benzene were distilled off from this solution, and then vacuum distillation was performed.
3.35g (yield 20.2
%) of α-chlorohydrocinnamitrile was isolated. The melting point and elemental analysis results were as follows.
【表】
実施例 ２〜５
触媒および反応条件を第１表のようにしたほか
は、実施例１と同様にして反応および生成物の抽
出を行つた。得られたジエチルエーテル層につい
て、実施例１と同様にしてガスクロマトグラフイ
により分析した。結果を第１表に示す。[Table] Examples 2 to 5 The reaction and product extraction were carried out in the same manner as in Example 1, except that the catalyst and reaction conditions were as shown in Table 1. The obtained diethyl ether layer was analyzed by gas chromatography in the same manner as in Example 1. The results are shown in Table 1.
【表】
実施例 ６〜９
２，３―ジクロルプロピオニトリル12.4ｇ
（0.1モル）とベンゼン70ml（0.79モル）の混合物
に五塩化アンチモン29.9ｇ（0.1モル）と第２表
記載の添加物（助触媒）とを加え、撹拌しながら
80℃で反応させた。次いで反応混合物を実施例１
に準じて処理，分析した。結果を第２表に示す。[Table] Examples 6 to 9 2,3-dichloropropionitrile 12.4g
(0.1 mol) and benzene 70 ml (0.79 mol), add 29.9 g (0.1 mol) of antimony pentachloride and the additive (cocatalyst) listed in Table 2, and while stirring.
The reaction was carried out at 80°C. The reaction mixture was then prepared in Example 1.
Processed and analyzed in accordance with . The results are shown in Table 2.
【表】【table】
【表】
比較例１および２
触媒としてAlCl3またはAlBr3を用いた以外は
実施例１に準じて反応，処理および分析を行つ
た。結果を第３表に示す。[Table] Comparative Examples 1 and 2 The reaction, treatment, and analysis were carried out according to Example 1 except that AlCl 3 or AlBr 3 was used as a catalyst. The results are shown in Table 3.
Claims (1)
ルとを、触媒成分として五塩化アンチモン、五塩
化モリブデン、塩化第二鉄またはこれらの混合物
を含む触媒の存在下で反応させることを特徴とす
るα―クロルヒドロシンナムニトリルの製造法。 ２ ２，３―ジクロルプロピオニトリルに対して
ベンゼンを化学量論量以上用いる、特許請求の範
囲第１項記載の製造法。 ３ ベンゼンと２，３―ジクロルプロピオニトリ
ルとを、触媒成分として五塩化アンチモン、五塩
化モリブデン、塩化第二鉄またはこれらの混合物
を含む触媒及び助触媒としてのブロンステツド酸
もしくはその水溶液またはシリカゲルの存在下で
反応させることを特徴とするα―クロルヒドロシ
ンナムニトリルの製造法。[Claims] 1. Reacting benzene and 2,3-dichloropropionitrile in the presence of a catalyst containing antimony pentachloride, molybdenum pentachloride, ferric chloride, or a mixture thereof as a catalyst component. A method for producing α-chlorohydrocinnamitrile, characterized by: 2. The manufacturing method according to claim 1, wherein benzene is used in a stoichiometric or more amount relative to 2,3-dichloropropionitrile. 3. Benzene and 2,3-dichloropropionitrile are combined with a catalyst containing antimony pentachloride, molybdenum pentachloride, ferric chloride or a mixture thereof as a catalyst component, and Bronsted acid or its aqueous solution or silica gel as a co-catalyst. A method for producing α-chlorohydrocinnamitrile, which comprises reacting in the presence of α-chlorohydrocinnamitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15442679A JPS5679661A (en) | 1979-11-30 | 1979-11-30 | Preparation of alpha-chlorohydrocinnamnitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15442679A JPS5679661A (en) | 1979-11-30 | 1979-11-30 | Preparation of alpha-chlorohydrocinnamnitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5679661A JPS5679661A (en) | 1981-06-30 |
| JPS6248665B2 true JPS6248665B2 (en) | 1987-10-15 |
Family
ID=15583906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15442679A Granted JPS5679661A (en) | 1979-11-30 | 1979-11-30 | Preparation of alpha-chlorohydrocinnamnitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5679661A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02144858A (en) * | 1988-11-25 | 1990-06-04 | Yuasa Battery Co Ltd | Sodium-sulfur battery |
-
1979
- 1979-11-30 JP JP15442679A patent/JPS5679661A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02144858A (en) * | 1988-11-25 | 1990-06-04 | Yuasa Battery Co Ltd | Sodium-sulfur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5679661A (en) | 1981-06-30 |
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