JPH0832668B2 - Suberonitrile manufacturing method - Google Patents
Suberonitrile manufacturing methodInfo
- Publication number
- JPH0832668B2 JPH0832668B2 JP62028190A JP2819087A JPH0832668B2 JP H0832668 B2 JPH0832668 B2 JP H0832668B2 JP 62028190 A JP62028190 A JP 62028190A JP 2819087 A JP2819087 A JP 2819087A JP H0832668 B2 JPH0832668 B2 JP H0832668B2
- Authority
- JP
- Japan
- Prior art keywords
- suberonitrile
- dichlorohexane
- yield
- mol
- reaction
- 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 - Lifetime
Links
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)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、1,6−ジクロルヘキサンと青化ソーダより
スベロニトリルを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing suberonitrile from 1,6-dichlorohexane and sodium cyanide.
スベロニトリルは農医薬品やジカルボン酸、ジアミン
などの製造用中間体として、有機化学および生物化学の
分野で有用である。Suberonitrile is useful in the fields of organic chemistry and biochemistry as an intermediate for the production of agricultural drugs, dicarboxylic acids, diamines and the like.
（従来の技術） スベロニトリルの製造方法は、ケミカルアブストラク
ト（vol.94 P.46803h）に酸化亜鉛の存在下、スベリン
酸とアンモニアを反応させる方法が記載されており、ま
た特開昭61−122258号には、1,6−ヘキサンジオールと
ヨウ化水素またはアルカリ金属のヨウ化物とを反応させ
て得られた1,6−ジヨードヘキサンを青化ソーダ、青化
カリおよび青酸などのシアノ化剤と反応させる方法が記
載されている。(Prior Art) As a method for producing suberonitrile, a method of reacting suberic acid with ammonia in the presence of zinc oxide in a chemical abstract (vol.94 P.46803h) is described, and JP-A-61-122258. In addition, 1,6-diiodohexane obtained by reacting 1,6-hexanediol with hydrogen iodide or an alkali metal iodide is used as a cyanating agent such as sodium cyanide, potassium cyanide and cyanic acid. A method of reacting is described.
スベリン酸を原料とする方法は、スベリン酸が高価で
あり、また反応温度が240〜300℃と高く、収率が低いた
め工業化が困難である。The method of using suberic acid as a raw material is difficult to industrialize because suberic acid is expensive, the reaction temperature is high at 240 to 300 ° C., and the yield is low.
1,6−ヘキサンジオールとヨウ素化合物を反応させ、
シアノ化する方法も、高価なヨウ素化合物が必要であ
る。また反応終了後、エーテル、クロロホルムなどの疎
水性有機溶剤で抽出し、更に水洗、乾燥および減圧蒸溜
の操作が必要で、精製工程が複雑である。Reacting 1,6-hexanediol with an iodine compound,
The method of cyanation also requires an expensive iodine compound. Further, after the reaction, extraction with a hydrophobic organic solvent such as ether or chloroform, washing with water, drying and distillation under reduced pressure are required, and the purification process is complicated.
（発明が解決しようとする問題点） 発明者等は1,6−ヘキサンジオールと塩酸より安価に
得られる1,6−ジクロルヘキサンを原料としてスベロニ
トリルを工業的に製造する方法を検討した。(Problems to be Solved by the Invention) The inventors studied a method for industrially producing suberonitrile using 1,6-dichlorohexane, which is cheaper than 1,6-hexanediol and hydrochloric acid, as a raw material.
1,6−ジクロルヘキサンは、非プロトン極性溶媒、例
えばジメチルホルムアミド中で青化ソーダ粉末と反応さ
せれば、容易にスベロニトリルが得られる。しかしなが
らこの方法は、青化ソーダ粉末に毒性があり、粉立ちが
著しいので工業的な取り扱いが厄介である。また反応液
より副生NaClを分離するためには、冷却後濾別する必要
があり、更に溶媒の留去、エーテル抽出、水洗、乾燥、
減圧蒸溜などの操作が必要で精製工程が複雑であり、多
くの費用と労力を要する。Suberonitrile can be easily obtained by reacting 1,6-dichlorohexane with sodium cyanide powder in an aprotic polar solvent such as dimethylformamide. However, this method is difficult to handle industrially because the soda powder is toxic and the powdering is remarkable. Further, in order to separate the by-product NaCl from the reaction solution, it is necessary to filter after cooling, further distilling off the solvent, ether extraction, washing with water, drying,
Since operations such as vacuum distillation are necessary and the purification process is complicated, much cost and labor are required.
（問題点を解決するための手段） 発明者等は1,6−ジクロルヘキサンを原料とするスベ
ロニトリルの製造方法に関して以上の如き問題点を解決
すべく鋭意検討し、原料の青化ソーダとしては市販さ
れており取り扱いの容易な青化ソーダの水溶液を用いる
こと、触媒として相間移動触媒を用い、油溶性の1,6
−ジクロルヘキサンやスベロニトリルと水溶性の青化ソ
ーダや副生するNaClを分離すること、この相間移動触
媒としては一般式が、 R4は炭素数３〜10のアルキル基を示し、これらは互いに
同一でも異なっていても良い）で表されるテトラアルキ
ルアンモニウムブロミドが有効であることを見出し本発
明に至った。(Means for Solving Problems) The inventors of the present invention have diligently studied to solve the above problems with respect to a method for producing suberonitrile using 1,6-dichlorohexane as a raw material, Use an aqueous solution of soda cyanide that is commercially available and easy to handle, and use a phase transfer catalyst as a catalyst.
-Separation of dichlorohexane or suberonitrile from water-soluble sodium cyanide or by-product NaCl, the general formula for this phase transfer catalyst is R 4 represents an alkyl group having 3 to 10 carbon atoms, and these may be the same or different from each other), and it was found that a tetraalkylammonium bromide represented by the formula is effective, and the present invention has been completed.
即ち本発明は、一般式が、 （R1〜R4は、炭素数３〜10のアルキル基を示し、これら
は互いに同一でも異なっていても良い）で表される相間
移動触媒の存在下、1,6−ジクロルヘキサンと青化ソー
ダ水溶液とを反応させることを特徴とするスベロニトリ
ルの製造方法である。That is, the present invention has the general formula (R 1 to R 4 represent an alkyl group having 3 to 10 carbon atoms, and these may be the same or different from each other), in the presence of a phase transfer catalyst represented by 1,6-dichlorohexane and blue. A method for producing suberonitrile, which comprises reacting with a sodium hydroxide aqueous solution.
本発明に使用する相間移動触媒としては、テトラプロ
ピルアンモニウムブロミド、テトラブチルアンモニウム
ブロミドなどがあるが、特にテトラブチルアンモニウム
ブロミドが好適である。Examples of the phase transfer catalyst used in the present invention include tetrapropylammonium bromide, tetrabutylammonium bromide and the like, and tetrabutylammonium bromide is particularly preferable.
青化ソーダ水溶液は、工業的に市販されている濃度30
〜35％の水溶液をそのまま使用することができ、また更
に必要に応じて濃度を下げて使用することもできる。Aqueous soda blue solution has an industrial concentration of 30
A ~ 35% aqueous solution can be used as it is, or the concentration can be lowered if necessary.
青化ソーダの使用量は1,6−ジクロルヘキサンに対す
る青化ソーダのモル比を理論量の2.0に対し2.1〜2.6程
度に若干過剰とすることが好ましい。このモル比が低過
ぎる場合は収率が低く、1,6−ジクロルヘキサンの損失
が大きくなる。またこのモル比が高い場合は排水中にCN
イオンが残留し、排水処理の費用が増加する。It is preferable that the amount of soda cyanide used is slightly excessive such that the molar ratio of soda soda to 1,6-dichlorohexane is 2.1 to 2.6 with respect to the theoretical amount of 2.0. If this molar ratio is too low, the yield will be low and the loss of 1,6-dichlorohexane will be large. If this molar ratio is high, the CN
Ions remain, increasing the cost of wastewater treatment.
テトラブチルアンモニウムブロミドの使用量は1,6−
ジクロルヘキサン１モル当たり1.5〜10g、好ましくは1.
5〜6gとする。テトラブチルアンモニウムブロミドの使
用量が少なすぎると収率が低く、多い場合は次の精製工
程の負荷が大きくなる。The amount of tetrabutylammonium bromide used is 1,6-
1.5 to 10 g per mol of dichlorohexane, preferably 1.
Set to 5-6g. If the amount of tetrabutylammonium bromide used is too small, the yield will be low, and if it is too large, the load of the next purification step will be large.
反応温度は80〜140℃、好ましくは90〜110℃とする。
反応温度が低いと反応が進行せず、高すぎる場合は収率
が低下する。The reaction temperature is 80 to 140 ° C, preferably 90 to 110 ° C.
If the reaction temperature is low, the reaction does not proceed, and if it is too high, the yield decreases.
反応圧力は特に制限が無いが、通常は常圧で行う。反
応時間は通常0.5〜8hr、好ましくは２〜4hrである。The reaction pressure is not particularly limited, but is usually atmospheric pressure. The reaction time is usually 0.5 to 8 hr, preferably 2 to 4 hr.
（効果） 本発明によるスベロニトリルの製造方法は、従来技術
に比較して次の特徴を有する。(Effect) The method for producing suberonitrile according to the present invention has the following features as compared with the conventional art.
（１）原料として工業的に安価に得られる1,6−ジクロ
ルヘキサンを使用し、高い収率が得られる。(1) 1,6-dichlorohexane, which is industrially inexpensively obtained, is used as a raw material, and a high yield is obtained.
（２）酸化亜鉛やヨウ素化合物、或いは青化ソーダ粉末
の如き個体粉末を使用しないので取り扱い操作が容易で
ある。(2) Since zinc oxide, iodine compound, or solid powder such as soda powder is not used, the handling operation is easy.
（３）相間移動触媒を用いるので、副生するNaClは食塩
水として排出されるから、濾過、抽出、水洗、乾燥など
の操作が不要で精製工程が非常に簡略化される。(3) Since the phase transfer catalyst is used, the by-produced NaCl is discharged as a saline solution, so that operations such as filtration, extraction, washing with water, and drying are unnecessary, and the purification process is greatly simplified.
以上による本発明の工業的意義が大きい。As described above, the present invention has great industrial significance.
（実施例） 実施例１ 1,6−ジクロルヘキサン155.0g（1.0モル）、34％青化
ソーダ水溶液576g（NaCN純分4.0モル）、テトラブチル
アンモニウムブロミド3.3g（0.01モル）を還流冷却器、
攪拌機、温度計の付いた反応器に仕込み激しく攪拌しな
がら110℃まで加熱した。引き続き110℃で２時間攪拌し
ながら反応させた。常温まで冷却し、水150gを加えて食
塩を溶解した後、分液漏斗に移し静置することにより上
層と下層に分液した。上層液をガスクロマトグラフィー
で分析したところ、スベロニトリル濃度91.2％、収量13
5.3g、収率90.7％であった。(Example) Example 1 A reflux condenser of 155.0 g (1.0 mol) of 1,6-dichlorohexane, 576 g of a 34% sodium hydroxide solution (NetCN 4.0 mol), and 3.3 g (0.01 mol) of tetrabutylammonium bromide. ,
A reactor equipped with a stirrer and a thermometer was charged and heated to 110 ° C. with vigorous stirring. The reaction was continued at 110 ° C. for 2 hours with stirring. After cooling to room temperature and adding 150 g of water to dissolve the salt, the mixture was transferred to a separatory funnel and allowed to stand to separate into upper and lower layers. When the upper layer liquid was analyzed by gas chromatography, the suberonitrile concentration was 91.2% and the yield was 13
The yield was 5.3 g and the yield was 90.7%.
実施例２ 1,6−ジクロルヘキサン155.0g（1.0モル）、50％テト
ラブチルアンモニウムブロミド水溶液13.3g（純分0.02
モル）を還流冷却器、攪拌機、温度計の付いた反応器に
仕込み激しく攪拌しながら110℃まで加熱した。その後3
4％青化ソーダ水溶液403.5g（NaCN純分2.8モル）を約90
分かけて滴下し、更に４時間攪拌しながら反応させた。
常温まで冷却した後、水80gを加えて食塩を溶解し、次
に分液漏斗に移し静置することにより上層と下層に分液
した。上層液の分析を行ったところ、スベロニトリル濃
度80.5％、収量152.0g、収率90.0％であった。Example 2 1,6-Dichlorohexane 155.0 g (1.0 mol), 50% tetrabutylammonium bromide aqueous solution 13.3 g (purity 0.02)
(Mol) was charged into a reactor equipped with a reflux condenser, a stirrer, and a thermometer, and heated to 110 ° C. with vigorous stirring. Then 3
About 90% of 403.5 g of 4% blue soda aqueous solution (NaCN net content 2.8 mol)
The solution was added dropwise over minutes, and the reaction was continued for 4 hours with stirring.
After cooling to room temperature, 80 g of water was added to dissolve the salt, and then the mixture was transferred to a separatory funnel and left to stand to separate into upper and lower layers. When the upper layer liquid was analyzed, the suberonitrile concentration was 80.5%, the yield was 152.0 g, and the yield was 90.0%.
比較例１ 1,6−ジクロルヘキサン155.0g（1.0モル）、34％青化
ソーダ456.4g（NaCN4モル）、テトラメチルアンモニウ
ムクロリド3.1g（0.0283モル）を、還流冷却器、攪拌
機、温度計の付いた反応器に仕込み激しく攪拌しながら
110℃まで加熱した。引き続き110℃で２時間攪拌しなが
ら反応させた。常温まで冷却し、水150gを加えて食塩を
溶解した後、分液漏斗に移し静置することにより上層と
下層に分液した。上層液をガスクロマトグラフィーで分
析したところ、1,6−ジクロルヘキサン反応率５％、ス
ベロニトリル収率0.4％であった。Comparative Example 1 1,6-Dichlorohexane 155.0 g (1.0 mol), 34% sodium cyanide 456.4 g (NaCN 4 mol), tetramethylammonium chloride 3.1 g (0.0283 mol) were mixed with a reflux condenser, a stirrer and a thermometer. Charge into the attached reactor while stirring vigorously
Heated to 110 ° C. The reaction was continued at 110 ° C. for 2 hours with stirring. After cooling to room temperature and adding 150 g of water to dissolve the salt, the mixture was transferred to a separatory funnel and allowed to stand to separate into upper and lower layers. When the upper layer liquid was analyzed by gas chromatography, the reaction rate of 1,6-dichlorohexane was 5% and the yield of suberonitrile was 0.4%.
比較例２ 比較例１において、テトラメチルアンモニウムクロリ
ドの代わりにベンジルトリメチルアンモニウムクロリド
3.7g（0.017モル）を用いた以外は全く同じ操作で合成
したところ、1,6−ジクロルヘキサン反応率4.7％、スベ
ロニトリル収率0.0％であった。Comparative Example 2 In Comparative Example 1, benzyltrimethylammonium chloride was used instead of tetramethylammonium chloride.
When the synthesis was carried out by the same procedure except that 3.7 g (0.017 mol) was used, the reaction rate of 1,6-dichlorohexane was 4.7%, and the yield of suberonitrile was 0.0%.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−122258（ＪＰ，Ａ) 特公 昭40−6330（ＪＰ，Ｂ１) 特公 昭38−19961（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-61-122258 (JP, A) JP-B-40-6330 (JP, B1) JP-B-38-19961 (JP, B1)
Claims (1)
互いに同一でも異なっていても良い）で表される相間移
動触媒の存在下、1,6−ジクロルヘキサンと青化ソーダ
水溶液とを反応させることを特徴とするスベロニトリル
の製造方法1. The general formula is (Wherein R 1 to R 4 represent an alkyl group having 3 to 10 carbon atoms, and these may be the same or different from each other) in the presence of a phase transfer catalyst, 1,6-dichlorohexane and bluing Suberonitrile production method characterized by reacting with soda solution
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028190A JPH0832668B2 (en) | 1987-02-12 | 1987-02-12 | Suberonitrile manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028190A JPH0832668B2 (en) | 1987-02-12 | 1987-02-12 | Suberonitrile manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63196547A JPS63196547A (en) | 1988-08-15 |
| JPH0832668B2 true JPH0832668B2 (en) | 1996-03-29 |
Family
ID=12241773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62028190A Expired - Lifetime JPH0832668B2 (en) | 1987-02-12 | 1987-02-12 | Suberonitrile manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0832668B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4571740B2 (en) * | 2000-10-27 | 2010-10-27 | 株式会社日本ファインケム | Method for producing 1,6-dicyanohexane |
-
1987
- 1987-02-12 JP JP62028190A patent/JPH0832668B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63196547A (en) | 1988-08-15 |
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