JPS6213342B2 - - Google Patents
Info
- Publication number
- JPS6213342B2 JPS6213342B2 JP8891877A JP8891877A JPS6213342B2 JP S6213342 B2 JPS6213342 B2 JP S6213342B2 JP 8891877 A JP8891877 A JP 8891877A JP 8891877 A JP8891877 A JP 8891877A JP S6213342 B2 JPS6213342 B2 JP S6213342B2
- Authority
- JP
- Japan
- Prior art keywords
- phenoxybenzaldehyde
- bisulfite adduct
- dimethylformamide
- solvent
- anhydrous
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 8
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002609 medium Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 claims description 3
- -1 α-cyano-3-phenoxybenzyl Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- CKFBFQHBUCDOHL-UHFFFAOYSA-N phenoxy(phenyl)methanol Chemical compound C=1C=CC=CC=1C(O)OC1=CC=CC=C1 CKFBFQHBUCDOHL-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000007333 cyanation reaction Methods 0.000 description 12
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- PJWSWBRTZKODSD-UHFFFAOYSA-N acetic acid;benzene;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O.C1=CC=CC=C1 PJWSWBRTZKODSD-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007193 benzoin condensation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/53—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】
本発明の主題は、α−シアノ−３−フエノキシ
ベンジルアルコールの新製造法にある。DETAILED DESCRIPTION OF THE INVENTION The subject of the present invention is a new process for the production of α-cyano-3-phenoxybenzyl alcohol.
本発明の主題をなすこの方法は、次式
のｍ−フエノキシベンズアルデヒドの重亜硫酸塩
付加物を溶媒又は溶媒混合物の存在下にCN−イ
オン発生化合物と反応させることを特徴とする。 This method, which is the subject of the present invention, is based on the following formula: The bisulfite adduct of m-phenoxybenzaldehyde is reacted with a CN- ion generating compound in the presence of a solvent or solvent mixture.
CN−イオンを発生する化合物の中でも、特に
シアン化水素酸、シアン化アンモニア、シアン化
アルカリ及びシアン化アルカリ土金属をあげるこ
とができる。 Among the compounds generating CN- ions, mention may be made in particular of hydrocyanic acid, ammonia cyanide, alkali cyanides and alkaline earth metal cyanides.
シアン化を実施する有利な方法はシアン化アル
カリを用いることによりなる。 An advantageous method of carrying out the cyanidation is by using an alkali cyanide.
重亜硫酸塩付加物のシアン化は、水性媒質中で
実施することができる。 Cyanation of the bisulfite adduct can be carried out in an aqueous medium.
ｍ−フエノキシベンズアルデヒドの重亜硫酸塩
付加物のシアン化を行う溶媒混合物は、特に、一
方の水と、他方の中性双極性溶媒、例えばジメチ
ルホルムアミド、ジメトキシエタン、ジメチルス
ルホキシド又はアセトニトリルとからなる。 The solvent mixture carrying out the cyanation of the bisulfite adduct of m-phenoxybenzaldehyde consists in particular of water on the one hand and a neutral dipolar solvent on the other hand, such as dimethylformamide, dimethoxyethane, dimethylsulfoxide or acetonitrile. .
有利な実施態様によれば、シアン化は水とジメ
チルホルムアミドとの混合物中で行なわれる。 According to a preferred embodiment, the cyanation is carried out in a mixture of water and dimethylformamide.
本発明の方法を実施する特に好ましい実施態様
にあつては、水性媒質中でのシアン化は、酸性試
剤の存在下に行なわれる。 In a particularly preferred embodiment of carrying out the process of the invention, the cyanidation in an aqueous medium is carried out in the presence of an acidic agent.
この酸性試剤は硫酸又は塩酸のような強酸であ
つてもよいが、好ましくは弱酸性のカルボン酸が
用いられる。 This acidic agent may be a strong acid such as sulfuric acid or hydrochloric acid, but preferably a weakly acidic carboxylic acid is used.
しかして、重亜硫酸塩付加物の水性媒質中での
シアン化を実施する有利な実施態様は酢酸の存在
下で実施することよりなる。 A preferred embodiment of carrying out the cyanation of the bisulfite adduct in aqueous medium thus consists in carrying out the cyanation in the presence of acetic acid.
シアン化を実施する本発明の方法の好ましい実
施方法によれば、ｍ−フエノキシベンズアルデヒ
ドの重亜硫酸塩付加物の懸濁液がシアン化ナトリ
ウム水溶液中に導入される。 According to a preferred method of carrying out the process of the invention for carrying out the cyanation, a suspension of the bisulfite adduct of m-phenoxybenzaldehyde is introduced into an aqueous sodium cyanide solution.
また、シアン化を実施する本発明の方法の他の
好ましい実施方法によれば、シアン化ナトリウム
水溶液がｍ−フエノキシベンズアルデヒドの重亜
硫酸塩付加物の懸濁液に導入され、次いで酢酸が
添加される。 According to another preferred method of carrying out the process of the invention for carrying out the cyanidation, an aqueous sodium cyanide solution is introduced into the suspension of the bisulfite adduct of m-phenoxybenzaldehyde, and then acetic acid is added. be done.
また、ｍ−フエノキシベンズアルデヒドの重亜
硫酸塩付加物のシアン化は、無水媒質中で実施す
る非常にオリジナルな操作態様で行なうこともで
きる。 The cyanation of bisulfite adducts of m-phenoxybenzaldehyde can also be carried out in a very original operating mode, carried out in anhydrous medium.
そしてシアン化剤は好ましくは無水シアン化ア
ルカリである。 And the cyanating agent is preferably anhydrous alkali cyanide.
シアン化を実施するのに用いられる溶媒又は溶
媒混合物は、特に無水の中性双極性溶媒、例えば
ジメチルホルムアミド、ジメトキシエタン、ジメ
チルスルホキシド及びアセトニトリルから選ばれ
る。 The solvent or solvent mixture used to carry out the cyanation is chosen in particular from anhydrous, neutral dipolar solvents such as dimethylformamide, dimethoxyethane, dimethylsulfoxide and acetonitrile.
このシアン化を実施するのに好んで用いられる
溶媒は、無水ジメチルホルムアミドである。 The preferred solvent for carrying out this cyanation is anhydrous dimethylformamide.
無水媒質中でのシアン化は、好ましくは酸性試
剤の添加なしで行なわれる。しかし、酢酸のよう
な無水の弱酸性試剤も用いることができる。 Cyanation in anhydrous medium is preferably carried out without the addition of acidic agents. However, anhydrous weakly acidic reagents such as acetic acid can also be used.
無水媒質中でのシアン化法の有利な実施方法
は、ｍ−フエノキシベンズアルデヒドの重亜硫酸
塩付加物の無水のジメチルホルムアミド懸濁液に
無水シアン化アルカリを導入することからなる。 A preferred method of carrying out the cyanation process in an anhydrous medium consists in introducing anhydrous alkali cyanide into a suspension of the bisulfite adduct of m-phenoxybenzaldehyde in anhydrous dimethylformamide.
かくて、ｍ−フエノキシベンズアルデヒドの重
亜硫酸塩付加物がα−シアノ−３−フエノキシベ
ンジルアルコールの製造にとつて非常に有用な化
合物であることが証明される。 Thus, the bisulfite adduct of m-phenoxybenzaldehyde proves to be a very useful compound for the production of alpha-cyano-3-phenoxybenzyl alcohol.
この重亜硫酸塩付加物は、溶媒又は溶媒混合物
中で重亜硫酸アルカリとｍ−フエノキシベンズア
ルデヒドとを反応させることによつて製造するこ
とができる。 This bisulfite adduct can be prepared by reacting an alkali bisulfite with m-phenoxybenzaldehyde in a solvent or solvent mixture.
溶媒の混合物としては、水とエーテルとメタノ
ールとの混合物又は水とイソプロパノールとの混
合物を特に用いることができる。 As mixtures of solvents it is possible in particular to use mixtures of water, ether and methanol or mixtures of water and isopropanol.
ｍ−フエノキシベンズアルデヒドの重亜硫酸塩
付加物は、アルデヒド単独よりも、さらに安定で
あり且つ酢酸エチルのような有機溶媒で結晶化す
ることによつて精製できるという利点を有する。
このようにして得られた精製物は、98％程度の高
い純度のものであり、シアン化によりほとんど定
量的収率でα−シアノ−３−フエノキシベンジル
アルコールに変換することができる。 The bisulfite adduct of m-phenoxybenzaldehyde has the advantage that it is more stable than the aldehyde alone and can be purified by crystallization in an organic solvent such as ethyl acetate.
The purified product thus obtained has a high purity of about 98%, and can be converted to α-cyano-3-phenoxybenzyl alcohol in almost quantitative yield by cyanation.
α−シアノ−３−フエノキシベンジルアルコー
ルは、これが大きな殺虫活性のジハロゲノビニル
鎖含有シクロプロパンカルボン酸エステルを製造
するのに特に用いられるために、工業的見地から
非常に有用な化合物である。 α-Cyano-3-phenoxybenzyl alcohol is a very useful compound from an industrial point of view, since it is particularly used to prepare dihalogenovinyl chain-containing cyclopropane carboxylic esters of great insecticidal activity. .
下記の実施例は本発明を例示するが、これを制
限するものではない。 The following examples illustrate, but do not limit, the invention.
ｍ−フエノキシベンズアルデヒドの重亜硫酸塩付
加物の製造
200ｇのｍ−フエノキシベンズアルデヒドを800
c.c.のイソプロピルエーテルに溶解し、この溶液
に、200ｇのメタ重亜硫酸ナトリウムを800c.c.の水
に溶解してなる溶液を加え、次いで250c.c.のメタ
ノールを加え、３時間かきまぜ、生じた沈殿を真
空過により単離し、メタノールと水との混合物
（50：50）で次いでイソプロピルエーテルで洗浄
し、沈殿を乾燥し、295ｇのｍ−フエノキシベン
ズアルデヒドの重亜硫酸塩付加物（不安定水素量
95.5％）を得る。Production of bisulfite adduct of m-phenoxybenzaldehyde.
cc of isopropyl ether, and to this solution was added a solution of 200 g of sodium metabisulfite dissolved in 800 c.c. of water, then 250 c.c. of methanol was added, and the mixture was stirred for 3 hours. The precipitate was isolated by vacuum filtration, washed with a mixture of methanol and water (50:50) and then with isopropyl ether, the precipitate was dried, and 295 g of the bisulfite adduct of m-phenoxybenzaldehyde (labile hydrogen amount
95.5%).
この化合物は、４倍量の酢酸エチルより結晶化
して精製することができる（収率97.6％）。精製
された化合物の不安定水素量は少なくとも98％で
ある。 This compound can be purified by crystallization from 4 times the amount of ethyl acetate (yield 97.6%). The amount of labile hydrogen in the purified compound is at least 98%.
例 １
α−シアノ−３−フエノキシベンジルアルコー
ルの製造（水素媒質中）
40c.c.のジメチルホルムアミドに20ｇのｍ−フエ
ノキシベンズアルデヒドの重亜硫酸塩付加物を窒
素雰囲気下に約１分間で加え、生じた懸濁液を20
℃で15分かきまぜ、＋５℃に冷却し、5.4ｇのシア
ン化カリウムを20c.c.の水に溶解してなる溶液を＋
10℃を越えないようにして20分間で加え、＋５℃
で２時間かきまぜ、沈殿を別し、液に100c.c.
の水と100c.c.の酢酸エチルを加え、かきまぜ、水
性相をデカンテーシヨンにより分離し、100c.c.の
酢酸エチルで抽出し、各有機相を一緒にし、水洗
し、脱水し、減圧下に濃縮乾固し、その残留物を
エーテルに溶解し、エーテル溶液を水洗し、乾燥
し、濃縮し、14.46ｇのα−シアノ−３−フエノ
キシベンジルアルコールを得た。収率97％。Example 1 Preparation of α-cyano-3-phenoxybenzyl alcohol (in hydrogen medium) Add the bisulfite adduct of 20 g of m-phenoxybenzaldehyde to 40 c.c. of dimethylformamide under a nitrogen atmosphere for about 1 minute. and the resulting suspension at 20
Stir for 15 minutes at ℃, cool to +5℃, and prepare a solution of 5.4 g of potassium cyanide dissolved in 20 c.c. of water.
Add for 20 minutes without exceeding 10℃, and then heat to +5℃.
Stir for 2 hours, separate the precipitate, and add 100 c.c.
of water and 100 c.c. of ethyl acetate, stir, the aqueous phase is separated by decantation and extracted with 100 c.c. of ethyl acetate, the organic phases are combined, washed with water, dried and vacuumed. The residue was dissolved in ether, the ether solution was washed with water, dried and concentrated to obtain 14.46 g of α-cyano-3-phenoxybenzyl alcohol. Yield 97%.
例 ２
α−シアノ−３−フエノキシベンジルアルコー
ルの製造（水性媒質中）
3700Kgのｍ−フエノキシベンズアルデヒドの重
亜硫酸塩付加物（タイター98％）を7.4のジメ
チルホルムアミドに導入し、0.765Kgのシアン化
ナトリウムを3.8の水に溶解してなる溶液を５
℃でかきまぜ下に約10分間で加え、3.8の酢酸
を＋５℃で約30分にわたり加え、＋10℃でさらに
30分かきまぜ、この反応混合物を水と酢酸エチル
との混合物に注入し、かきまぜ、水性相をデカン
テーシヨンにより分離し、再び酢酸エチルで２回
抽出し、有機相を一緒にし、水洗し、脱水し、
0.37Kgの活性炭と0.37Kgの硫酸ナトリウムを加
え、かきまぜ、過し、減圧蒸留により濃縮乾固
し、2770Kgのα−シアノ−３−フエノキシベンジ
ルアルコール（約１％のジメチルホルムアミドを
含有）を得た。収率99.6％。Example 2 Preparation of α-cyano-3-phenoxybenzyl alcohol (in aqueous medium) 3700 Kg of bisulfite adduct of m-phenoxybenzaldehyde (titer 98%) is introduced into 7.4 of dimethylformamide and 0.765 Kg A solution made by dissolving 3.8 parts of sodium cyanide in 5 parts of water
℃ for about 10 minutes with stirring, 3.8% acetic acid was added at +5℃ for about 30 minutes, and further at +10℃.
Stir for 30 minutes, pour the reaction mixture into a mixture of water and ethyl acetate, stir, separate the aqueous phase by decantation and extract again twice with ethyl acetate, combine the organic phases, wash with water and dehydrate. death,
Add 0.37Kg of activated carbon and 0.37Kg of sodium sulfate, stir, filter, and concentrate to dryness by vacuum distillation to obtain 2770Kg of α-cyano-3-phenoxybenzyl alcohol (containing about 1% dimethylformamide). Obtained. Yield 99.6%.
得られた化合物は、下記の特性を有する。窒素
量6.3ｇ／100ｇ（理論6.20ｇ）、不安定水素量100
％。 The obtained compound has the following properties. Nitrogen amount 6.3g/100g (theoretical 6.20g), unstable hydrogen amount 100
%.
貯蔵のためにこの化合物に13.5c.c.の酢酸を加え
た。 13.5cc of acetic acid was added to this compound for storage.
例 ３
α−シアノ−３−フエノキシベンジルアルコー
ルの製造（無水媒質中）
20ｇの無水のｍ−フエノキシベンズアルデヒド
の重亜硫酸塩付加物を80c.c.の無水ジメチルホルム
アミドに導入し、不活性雰囲気下に０℃で3.3ｇ
の無水シアン化ナトリウムを加え、０℃で45分か
きまぜ、この反応混合物から試料を採取し、クロ
マトグラフ分析によりｍ−フエノキシベンズアル
デヒドの重亜硫酸塩付加物のα−シアノ−３−メ
トキシベンジルアルコールへの転化が完全である
ことを確かめ、反応混合物を水、氷、酢酸及びイ
ソプロピルの混合物に注入し、かきまぜ、有機相
をデカンテーシヨンによつて分離し、イソプロピ
ルエーテルで抽出し、有機相を水洗し、脱水し、
濃縮乾固し、13.8ｇのα−シアノ−３−フエノキ
シベンジルアルコールを得た。収率92.6％。Example 3 Preparation of α-cyano-3-phenoxybenzyl alcohol (in anhydrous medium) 20 g of the bisulfite adduct of anhydrous m-phenoxybenzaldehyde are introduced into 80 c.c. of anhydrous dimethylformamide and the 3.3g at 0℃ under active atmosphere
of anhydrous sodium cyanide was added, stirred for 45 minutes at 0°C, a sample was taken from the reaction mixture, and chromatographic analysis revealed that α-cyano-3-methoxybenzyl alcohol, a bisulfite adduct of m-phenoxybenzaldehyde, was added. To ensure that the conversion to Wash with water, dehydrate,
The mixture was concentrated to dryness to obtain 13.8 g of α-cyano-3-phenoxybenzyl alcohol. Yield 92.6%.
参考例
200mlの脱塩水に100ｇのｍ−フエノキシベンズ
アルデヒドの重亜硫酸塩付加物（94.8％純度）を
加え、次いで17ｇのシアン化ナトリウムを200ml
の水に溶解してなる溶液を20℃で加えた。この混
合物を窒素雰囲気下に20〜25℃で16時間かきま
ぜ、次いでイソプロピルエーテルで抽出した。有
機相を水洗し、乾燥し、蒸発させて70ｇの粗α−
シアノ−３−フエノキシベンジルアルコールを得
た。この生成物の純度は、アセチル化法で決定し
て71.5％であり、したがつて収率は出発物質を基
にして70.8％となつた。Reference example Add 100 g of bisulfite adduct of m-phenoxybenzaldehyde (94.8% purity) to 200 ml of demineralized water, then add 17 g of sodium cyanide to 200 ml.
A solution prepared by dissolving in water was added at 20°C. The mixture was stirred at 20-25° C. for 16 hours under nitrogen atmosphere and then extracted with isopropyl ether. The organic phase was washed with water, dried and evaporated to give 70 g of crude α-
Cyano-3-phenoxybenzyl alcohol was obtained. The purity of this product was 71.5% as determined by the acetylation method, giving a yield of 70.8% based on starting material.
シリカゲルでの薄層クロマトグラフイー及びベ
ンゼン−酢酸エチル−酢酸混合物（90−８−２）
による溶離によつて不純物を検出したが、７〜10
％のｍ−フエノキシベンズアルデヒド及び約４％
のベンゾイン縮合生成物などが含まれていた。 Thin layer chromatography on silica gel and benzene-ethyl acetate-acetic acid mixture (90-8-2)
Impurities were detected by elution with 7-10
% m-phenoxybenzaldehyde and about 4%
Contains benzoin condensation products.
このように、水のみの存在下ではα−シアノ−
３−フエノキシベンジルアルコールの全収率は約
70％程度である。 Thus, in the presence of water alone, α-cyano-
The total yield of 3-phenoxybenzyl alcohol is approximately
It is about 70%.
Claims (1)
付加物を少なくとも１種の中性双極性溶媒の存在
下にCN−イオン発生化合物と反応させることを
特徴とするα−シアノ−３−フエノキシベンジル
アルコールの製造法。 ２ CN−イオン発生化合物がシアン化アルカリ
であることを特徴とする特許請求の範囲第１項記
載の方法。 ３ 反応を水性媒質中で行なうことを特徴とする
特許請求の範囲第１又は２項記載の方法。 ４ 溶媒が水とジメチルホルムアミドとの混合物
であることを特徴とする特許請求の範囲第１〜３
項のいずれかに記載の方法。 ５ ｍ−フエノキシベンズアルデヒドの重亜硫酸
塩付加物の懸濁液をシアン化ナトリウム水溶液中
に導入することを特徴とする特許請求の範囲第１
〜４項のいずれかに記載の方法。 ６ 反応を無水媒質中で行なうことを特徴とする
特許請求の範囲第１又は２項記載の方法。 ７ 反応を行なう溶媒が無水のジメチルホルムア
ミドであることを特徴とする特許請求の範囲第
１，２又は６項記載の方法。 ８ ｍ−フエノキシベンズアルデヒドの重亜硫酸
塩付加物の無水ジメチルホルムアミド懸濁液に無
水シアン化アルカリを導入することを特徴とする
特許請求の範囲第１，２，６又は７項記載の方
法。 ９ 次式 のｍ−フエノキシベンズアルデヒドの重亜硫酸塩
付加物を少なくとも１種の中性双極性溶媒中で酸
性試剤の存在下にCN−イオン発生化合物と反応
させることを特徴とするα−シアノ−３−フエノ
キシベンジルアルコールの製造法。 １０ CN−イオン発生化合物がシアン化アルカ
リであることを特徴とする特許請求の範囲第９項
記載の方法。 １１ 反応を水性媒質中で行なうことを特徴とす
る特許請求の範囲第９又は１０項記載の方法。 １２ 溶媒が水とジメチルホルムアミドとの混合
物であることを特徴とする特許請求の範囲第９〜
１１項のいずれかに記載の方法。 １３ 反応を酢酸の存在下に行なうことを特徴と
する特許請求の範囲第９〜１２項のいずれかに記
載の方法。 １４ シアン化ナトリウム水溶液をｍ−フエノキ
シベンズアルデヒドの重亜硫酸塩付加物のジメチ
ルホルムアミド懸濁液に導入し、次いで酢酸を添
加することを特徴とする特許請求の範囲第９〜１
２項のいずれかに記載の方法。[Claims] Linear formula α-cyano-3-phenoxybenzyl, characterized in that the bisulfite adduct of m-phenoxybenzaldehyde is reacted with a CN- ion generating compound in the presence of at least one neutral dipolar solvent. Alcohol manufacturing method. 2. The method according to claim 1, wherein the CN- ion generating compound is an alkali cyanide. 3. The method according to claim 1 or 2, characterized in that the reaction is carried out in an aqueous medium. 4 Claims 1 to 3, characterized in that the solvent is a mixture of water and dimethylformamide
The method described in any of the paragraphs. Claim 1, characterized in that a suspension of a bisulfite adduct of 5 m-phenoxybenzaldehyde is introduced into an aqueous sodium cyanide solution.
4. The method according to any one of items 4 to 4. 6. The method according to claim 1 or 2, characterized in that the reaction is carried out in an anhydrous medium. 7. The method according to claim 1, 2 or 6, characterized in that the solvent in which the reaction is carried out is anhydrous dimethylformamide. 8. The method according to claim 1, 2, 6 or 7, characterized in that anhydrous alkali cyanide is introduced into the anhydrous dimethylformamide suspension of the bisulfite adduct of m-phenoxybenzaldehyde. 9th equation α-cyano-3-, characterized in that the bisulfite adduct of m-phenoxybenzaldehyde is reacted with a CN- ion generating compound in the presence of an acidic agent in at least one neutral dipolar solvent. Method for producing phenoxybenzyl alcohol. 10. The method according to claim 9, wherein the 10CN- ion generating compound is an alkali cyanide. 11. The method according to claim 9 or 10, characterized in that the reaction is carried out in an aqueous medium. 12 Claims 9 to 12, wherein the solvent is a mixture of water and dimethylformamide.
12. The method according to any one of Item 11. 13. The method according to any one of claims 9 to 12, characterized in that the reaction is carried out in the presence of acetic acid. 14. Claims 9 to 1, characterized in that an aqueous sodium cyanide solution is introduced into a dimethylformamide suspension of a bisulfite adduct of m-phenoxybenzaldehyde, and then acetic acid is added.
The method described in any of Section 2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7625938A FR2362829A1 (en) | 1976-08-27 | 1976-08-27 | BISULFIC COMBINATION OF METAPHENOXY BENZALDEHYDE, METHOD OF PREPARATION AND APPLICATION TO THE PREPARATION OF A-CYANO 3-PHENOXY BENZYL ALCOHOL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5328142A JPS5328142A (en) | 1978-03-16 |
| JPS6213342B2 true JPS6213342B2 (en) | 1987-03-25 |
Family
ID=9177185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8891877A Granted JPS5328142A (en) | 1976-08-27 | 1977-07-26 | Novel production method of alphaacyanoo33phenoxy benzyl alcohol |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5328142A (en) |
| BE (1) | BE858127A (en) |
| CA (1) | CA1088566A (en) |
| CH (1) | CH623808A5 (en) |
| DE (1) | DE2738643C2 (en) |
| DK (1) | DK158303C (en) |
| FR (1) | FR2362829A1 (en) |
| GB (1) | GB1567531A (en) |
| IE (1) | IE45374B1 (en) |
| IT (1) | IT1079949B (en) |
| NL (1) | NL7709435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0547946Y2 (en) * | 1987-02-20 | 1993-12-17 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA7911B (en) * | 1978-01-31 | 1980-01-30 | Roussel Uclaf | Optically-active substituted benzyl alcohol and process for preparing it |
| FR2458542A1 (en) * | 1979-06-12 | 1981-01-02 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF OPTICALLY ACTIVE ALCOHOL A-CYANES |
| DE2938112A1 (en) * | 1979-09-20 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING (ALPHA) -CYANO-PHENOXY-BENZYL ESTERS |
| JPS5970481A (en) * | 1982-10-14 | 1984-04-20 | Toyota Central Res & Dev Lab Inc | Spot welding method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515450B1 (en) * | 1971-06-29 | 1976-02-20 |
-
1976
- 1976-08-27 FR FR7625938A patent/FR2362829A1/en active Granted
-
1977
- 1977-07-26 JP JP8891877A patent/JPS5328142A/en active Granted
- 1977-08-03 GB GB3259877A patent/GB1567531A/en not_active Expired
- 1977-08-25 IT IT5078577A patent/IT1079949B/en active
- 1977-08-26 IE IE179077A patent/IE45374B1/en unknown
- 1977-08-26 CA CA285,527A patent/CA1088566A/en not_active Expired
- 1977-08-26 DK DK378877A patent/DK158303C/en not_active IP Right Cessation
- 1977-08-26 NL NL7709435A patent/NL7709435A/en not_active Application Discontinuation
- 1977-08-26 DE DE19772738643 patent/DE2738643C2/en not_active Expired
- 1977-08-26 BE BE180440A patent/BE858127A/en not_active IP Right Cessation
- 1977-08-26 CH CH1047077A patent/CH623808A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0547946Y2 (en) * | 1987-02-20 | 1993-12-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2738643C2 (en) | 1986-06-05 |
| JPS5328142A (en) | 1978-03-16 |
| CA1088566A (en) | 1980-10-28 |
| DK158303B (en) | 1990-04-30 |
| IE45374B1 (en) | 1982-08-11 |
| DK158303C (en) | 1990-10-01 |
| CH623808A5 (en) | 1981-06-30 |
| IE45374L (en) | 1978-02-27 |
| NL7709435A (en) | 1978-03-01 |
| FR2362829B1 (en) | 1979-03-02 |
| DE2738643A1 (en) | 1978-03-02 |
| DK378877A (en) | 1978-02-28 |
| IT1079949B (en) | 1985-05-13 |
| GB1567531A (en) | 1980-05-14 |
| BE858127A (en) | 1978-02-27 |
| FR2362829A1 (en) | 1978-03-24 |
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