JPH04149171A - Production of 3-mercaptopropionitrile - Google Patents
Production of 3-mercaptopropionitrileInfo
- Publication number
- JPH04149171A JPH04149171A JP26933390A JP26933390A JPH04149171A JP H04149171 A JPH04149171 A JP H04149171A JP 26933390 A JP26933390 A JP 26933390A JP 26933390 A JP26933390 A JP 26933390A JP H04149171 A JPH04149171 A JP H04149171A
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- mercaptopropionitrile
- sodium
- added
- 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.)
- Granted
Links
- FCTXEFOUDMXDPD-UHFFFAOYSA-N 3-sulfanylpropanenitrile Chemical compound SCCC#N FCTXEFOUDMXDPD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- NDVLTZFQVDXFAN-UHFFFAOYSA-N 3-(2-cyanoethylsulfanyl)propanenitrile Chemical compound N#CCCSCCC#N NDVLTZFQVDXFAN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000006227 byproduct Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 9
- 150000002825 nitriles Chemical class 0.000 description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 7
- 230000005070 ripening Effects 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003464 sulfur compounds Chemical class 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WRYBVNBPNIZGQQ-UHFFFAOYSA-N 2-sulfanylpropanenitrile Chemical compound CC(S)C#N WRYBVNBPNIZGQQ-UHFFFAOYSA-N 0.000 description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 3
- 239000003490 Thiodipropionic acid Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-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 class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 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 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアクリロニトリルと水硫化ナトリウムの反応に
より高収率で３−メルカプトプロピオニトリルを製造す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 3-mercaptopropionitrile in high yield by the reaction of acrylonitrile and sodium bisulfide.
３−メルカプトプロピオニトリルは医薬、農薬、樹脂、
香料をはじめとする多くの有機合成品の原料として、ま
た塩化ビニルの安定剤、エポキシ樹脂やアクリル酸エス
テルポリマーの架橋剤、プラスチックレンズモノマー等
の原料として使用される３−メルカプトプロピオン酸の
合成中間体として有用な化合物である。3-Mercaptopropionitrile is used in pharmaceuticals, agricultural chemicals, resins,
An intermediate in the synthesis of 3-mercaptopropionic acid, which is used as a raw material for many organic synthetic products including fragrances, as a stabilizer for vinyl chloride, as a crosslinking agent for epoxy resins and acrylic acid ester polymers, and as a raw material for plastic lens monomers. It is a compound that is useful for the body.
［従来の技術〕
３−メルカプトプロピオニトリルの製造法としては従来
から種々の方法が知られているが、合成繊維や合成樹脂
の原料として大量に生産され、安価なアクリロニトリル
にイオウ化合物を付加させる方法が一般的である。[Prior art] Various methods have been known for producing 3-mercaptopropionitrile, but one method involves adding a sulfur compound to acrylonitrile, which is produced in large quantities as a raw material for synthetic fibers and synthetic resins and is inexpensive. The method is common.
イオウ化合物としてはチオ酢酸（ＩＩｓＰ ２，６３０
．４５２）、チオ尿素ＣＪ、Ｏｒｇ、Ｃｈｅ１１． 、
２６．１４４３ （１９６１） ）、チオ硫酸塩（特開
昭５９−２９６５８）、硫化水素（ＵＳＰ２．７４８．
１５５）、チオキサントゲン酸塩（特開昭５９−７１５
７、特開昭５９−９８０５４）等が知られている。As a sulfur compound, thioacetic acid (IIsP 2,630
．． 452), Thiourea CJ, Org, Che11. ,
26.1443 (1961)), thiosulfate (JP 59-29658), hydrogen sulfide (USP 2.748.
155), thioxanthate (JP-A-59-715)
7, Japanese Unexamined Patent Publication No. 59-98054), etc. are known.
また、３−メルカプトプロピオニトリルを中間体とする
３−メルカプトプロピオン酸の製造法に関する特許にお
いては、イオウ化合物として水硫化ナトリウム（特開昭
５８−１９８４６０）、硫化ナトリウムと水酸化ナトリ
ウムの組合せ（特公昭６３−６５４５）の使用が示され
ている。In addition, in a patent relating to a method for producing 3-mercaptopropionic acid using 3-mercaptopropionitrile as an intermediate, the sulfur compound is sodium hydrogen sulfide (Japanese Patent Application Laid-open No. 198460), a combination of sodium sulfide and sodium hydroxide ( The use of Japanese Patent Publication No. 63-6545) is shown.
イオウ化合物としてチオ酢酸、チオ尿素は高価でアリ、
チオｇ酸塩、チオキサントゲン酸塩を含めこれらのイオ
ウ化合物をアクリロニトリルへ付加した後、中間体を加
水分解することが必要で製造工程が複雑となる。As sulfur compounds, thioacetic acid and thiourea are expensive and expensive.
After addition of these sulfur compounds, including thiogates and thioxanthates, to acrylonitrile, it is necessary to hydrolyze the intermediates, complicating the manufacturing process.
硫化水素、水硫化ナトリウム、硫化ナトリウムと水酸化
ナトリウムの組合せによる方法の製造工程は比較的単純
であるが、３，３“−チオジブロピオニトリルの副生が
避けられず、これが原因で３−メルカプトプロピオニト
リルの収率は６０〜８０％程度と不十分である。また、
硫化水素の場合はアクリロニトリルに対して硫化水素を
大過剰に使用し加圧下Ｓこ行うことが必要であり、硫化
水素の回収を含めると複雑なプロセスとなる。Although the production process using hydrogen sulfide, sodium bisulfide, and the combination of sodium sulfide and sodium hydroxide is relatively simple, the by-product of 3,3"-thiodibropionitrile is unavoidable, and this causes - The yield of mercaptopropionitrile is insufficient at about 60-80%.
In the case of hydrogen sulfide, it is necessary to use a large excess of hydrogen sulfide relative to acrylonitrile and carry out the S reaction under pressure, which results in a complicated process when hydrogen sulfide recovery is included.
水硫化ナトリウムの場合は、アクリロニトリルを水硫化
ナトリウムに加える速度及びモル比を制御する必要があ
り、硫化ナトリウムと水酸化ナトリウムの組合せでは付
加反応と同時にニトリルの加水分解が進行し、３−メル
カプトプロピオン酸のみならず、３，３゛−チオジプロ
ピオン酸が多量に副生ずるという問題がある。In the case of sodium bisulfide, it is necessary to control the rate and molar ratio of adding acrylonitrile to sodium bisulfide; in the combination of sodium sulfide and sodium hydroxide, hydrolysis of the nitrile proceeds at the same time as the addition reaction, and 3-mercaptopropion There is a problem in that not only acid but also 3,3'-thiodipropionic acid is produced in large quantities as a by-product.
本発明の目的は、これらの問題点を解決し３−メルカプ
トプロピオニトリルを高収率で得るための製造方法を提
供することである。An object of the present invention is to provide a production method for solving these problems and obtaining 3-mercaptopropionitrile in high yield.
（ｆ題を解決するための手段〕
本発明者等は、安価で取扱い易い水硫化ナトリウムとア
クリロニトリルの反応による３−メルカプトプロピオニ
トリルの製造方法を検討した結果、水硫化ナトリウム水
溶液にアクリロニトリルを加えると３−メルカプトプロ
ピオニトリルと同時に多量の３，３゛−チオジブロピオ
ニトリルの副生を確認したが６驚くべきことにアクリロ
ニトリルを加えた後の反応液を撹拌し続けると３，３”
−チオジブロビオニトリルが３−メルカプトプロピオニ
トリルに徐々に変換され高収率で３−メルカプトプロピ
オニトリルが得られることを見出した。また、３，３チ
オジブロビオニトリルは水に不溶でありアクリロニトリ
ルを加えた直後の反応液は２層に分離する。そこで、反
応液に相間移動触媒を添加すると３．３゛−チオジブロ
ビオニトリルから３−メルカプトプロピオニトリルへの
変換が短時間で完結することを見出し、本発明を完成す
るに至った。(Means for Solving Problem f) The present inventors investigated a method for producing 3-mercaptopropionitrile by reacting sodium bisulfide and acrylonitrile, which is inexpensive and easy to handle, and as a result, added acrylonitrile to an aqueous solution of sodium bisulfide. At the same time as 3-mercaptopropionitrile, a large amount of 3,3'-thiodibropionitrile was produced as a by-product.6 Surprisingly, however, when the reaction solution was continued to be stirred after acrylonitrile was added, 3,3''
It has been found that -thiodibrobionitrile is gradually converted to 3-mercaptopropionitrile and 3-mercaptopropionitrile can be obtained in high yield. Furthermore, 3,3 thiodibrobionitrile is insoluble in water, and the reaction solution immediately after adding acrylonitrile is separated into two layers. Therefore, the present inventors have discovered that when a phase transfer catalyst is added to the reaction solution, the conversion of 3.3'-thiodibrobionitrile to 3-mercaptopropionitrile can be completed in a short time, and the present invention has been completed.
すなわち、本発明は水硫化ナトリウム水溶液にアクリロ
ニトリルを加え３−メルカプトプロピオニトリルを製造
する方法において、アクリロニトリルを加えた後、相関
移動触媒存在下に撹拌塾成することにより副生した３、
３′−チオジプロピオニトリルを３−メルカプトプロピ
オニトリルに短時間で変換することを特徴とする３−メ
ルカプトプロピオニトリルの製造方法である。That is, the present invention relates to a method for producing 3-mercaptopropionitrile by adding acrylonitrile to an aqueous sodium bisulfide solution.
This is a method for producing 3-mercaptopropionitrile, which is characterized by converting 3'-thiodipropionitrile into 3-mercaptopropionitrile in a short time.
水砕化ナトリウムに対するアクリロニトリルのモル比は
０．５〜１で好適に実施されるが、０．８〜１の水硫化
ナトリウム少過剰で十分である。モル比が１より高いと
３，３”−チオジブロビオニトリルは軌成しても消失せ
ず残り、モル比が０．５より低いと反応後に多量の水硫
化ナトリウムが残り、中和時に硫化水素として損失する
ため不経済である。The molar ratio of acrylonitrile to granulated sodium is preferably 0.5 to 1, although a small excess of sodium hydrosulfide of 0.8 to 1 is sufficient. When the molar ratio is higher than 1, 3,3''-thiodibrobionitrile does not disappear and remains even after orbiting, and when the molar ratio is lower than 0.5, a large amount of sodium bisulfide remains after the reaction and sulfides during neutralization. It is uneconomical because it is lost as hydrogen.
水硫化ナトリウム水溶液濃度は５〜５０重量％が好まし
く、５％より低いと容積効率が悪く、５０％より高いと
反応液の粘度が高く撹拌に支障がある。The concentration of the sodium hydrosulfide aqueous solution is preferably 5 to 50% by weight; if it is lower than 5%, the volumetric efficiency will be poor, and if it is higher than 50%, the viscosity of the reaction liquid will be high and stirring will be hindered.
しかし、水硫化ナトリウム水溶液の濃度は本発明の効果
自体にはほとんど影響しない。However, the concentration of the sodium hydrosulfide aqueous solution has little effect on the effects of the present invention itself.
水硫化ナトリウム水溶液にアクリロニトリルを加える時
、及び熟成時の温度は０〜６０℃が好ましく、より好ま
しくは１０〜５０℃の範囲である。、０℃より低いと反
応液が固化する恐れがあり好ましくない。The temperature when adding acrylonitrile to the aqueous sodium hydrosulfide solution and during aging is preferably from 0 to 60°C, more preferably from 10 to 50°C. If the temperature is lower than 0°C, the reaction solution may solidify, which is not preferable.
温度が高いほどアクリロニトリルを加え終わった直後の
３，３゛−チオジブロビオニトリルの副生量は少なく、
軌成による３、３′−チオジプロビオニトリルの３−メ
ルカプトプロピオニトリルへの変換も速いが、６０’Ｃ
より高いとニトリルの加水分解による３−メルカプトプ
ロピオン酸、３．３゛−チオジプロピオン酸の副生が増
加し、３−メルカプトプロピオニトリルの収率が低下し
好ましくない。The higher the temperature, the smaller the amount of 3,3゛-thiodibrobionitrile produced immediately after adding acrylonitrile.
Conversion of 3,3'-thiodiprobionitrile to 3-mercaptopropionitrile by orbital orbital is also fast, but at 60'C
If it is higher, the by-products of 3-mercaptopropionic acid and 3.3'-thiodipropionic acid due to the hydrolysis of nitrile will increase, and the yield of 3-mercaptopropionitrile will decrease, which is not preferable.
水硫化ナトリウム水溶液にアクリロニトリルを加える速
度は反応熱の除去により反応温度を０〜６０℃に保つに
支障のない限り、出来るだけ速く加えるのが好ましく、
通常１時間以内で好適に実施される。アクリロニトリル
を加え終わった直後の３．３“−チオジプロピオニトリ
ルの副生量はアクリロニトリルを加える速度にほとんど
影響されないため、加える速度が遅いほど生産に要する
時間が延び好ましくない。また、この事実は反応液を熟
成することが３−メルカプトプロピオニトリルを高収率
で得るための必須要件であることを示している。It is preferable to add acrylonitrile to the sodium hydrosulfide aqueous solution as fast as possible, as long as it does not interfere with keeping the reaction temperature between 0 and 60°C by removing the reaction heat.
It is usually suitably carried out within one hour. The amount of 3.3"-thiodipropionitrile by-product immediately after the addition of acrylonitrile is almost unaffected by the rate of addition of acrylonitrile, so the slower the addition rate, the longer the time required for production, which is undesirable. This shows that aging the reaction solution is an essential requirement for obtaining 3-mercaptopropionitrile in high yield.
熟成時間はアクリロニトリルを加え絆わった直後の３，
３゛−チオジプロビオニトリルの副生量及び軌成温度に
より異なるが約１〜５時間を要し、反応液を高速液体ク
ロマトグラフィーで分析し３，３チオジプロピオニトリ
ルがほぼ完全に消失した時点を終点とする。 ３．３’
−チオジプロビオニトリルが消失後も熟成を続けるとニ
トリルの加水分解による３−メルカプトプロピオン酸等
の副生物が徐々に増加するため、熟成時間は］〜５時間
とするのが好ましい。The aging time is 3, immediately after adding acrylonitrile and bonding.
It took about 1 to 5 hours, depending on the amount of 3'-thiodiprobionitrile by-product and the orbital temperature, and the reaction solution was analyzed by high-performance liquid chromatography, and 3,3-thiodipropionitrile had almost completely disappeared. The end point is the point in time. 3.3'
If the ripening continues even after the -thiodiprobionitrile disappears, by-products such as 3-mercaptopropionic acid due to the hydrolysis of the nitrile will gradually increase, so the ripening time is preferably set to ~5 hours.
相間移動触媒としては、トリメチルベンジルアンモニウ
ム、テトラエチルアンモニウム、テトラブチルアンモニ
ウム等の水酸化物、塩化物で代表される第４級アンモニ
ウム塩が適当であり、これらによって熟成時間は無添加
のときの１／２以下に短縮される。Suitable phase transfer catalysts include quaternary ammonium salts represented by hydroxides and chlorides such as trimethylbenzylammonium, tetraethylammonium, and tetrabutylammonium, which reduce the aging time to 1/1 of that without additives. It is shortened to 2 or less.
相間移動触媒の添加量はアクリロニトリルに対して０．
０１〜５モル％の使用が好ましく、０，０１モル％より
少ないと十分な効果が発揮されず、５モル％より多いと
熟成温度によってはニトリルの加水分解が加速され好ま
しくない。相間移動触媒の添加は熟成に入る直前でも、
アクリロニトリルを加える前の水硫化ナトリウム水溶液
にあらかしめ添加しておいても良い。The amount of phase transfer catalyst added is 0.00% relative to acrylonitrile.
It is preferable to use an amount of 0.01 to 5 mol %, and if it is less than 0.01 mol %, a sufficient effect will not be exhibited, and if it is more than 5 mol %, the hydrolysis of the nitrile will be accelerated depending on the aging temperature, which is undesirable. The phase transfer catalyst can be added even just before ripening.
It may be added in advance to the aqueous sodium bisulfide solution before adding acrylonitrile.
熟成後、反応液中には３−メルカプトプロピオニトリル
がナトリウム塩として存在する。３−メルカプトプロピ
オニトリルの単離は一般的な方法で良く、まず酸を加え
て中和後、遊離する３−メルカプトプロピオニトリルを
有機溶媒で抽出し、抽出液を脱溶媒後、茅留することに
より行われる。中和に使用する酸としては塩酸、硫酸、
リン酸等の鉱酸が好適に使用される。After aging, 3-mercaptopropionitrile is present in the reaction solution as a sodium salt. 3-Mercaptopropionitrile can be isolated by a general method. First, add an acid to neutralize it, then extract the liberated 3-mercaptopropionitrile with an organic solvent, remove the solvent, and distill the extract. It is done by doing. Acids used for neutralization include hydrochloric acid, sulfuric acid,
Mineral acids such as phosphoric acid are preferably used.
［実施例〕
以下、実施例及び比較例により本発明の詳細な説明する
が、本発明はこれら実施例のみに限定されるものではな
い。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例１
７０％水硫化ナトリウム４０ ｇ （０，５モル）に水
４０ｇを加え熔解した後、４０〜４５℃に保ちながらア
クリロニトリル２６．５ ｇ （０，５モル）を３０分
間で滴下した。Example 1 40 g of water was added to 40 g (0.5 mol) of 70% sodium hydrosulfide and dissolved, and then 26.5 g (0.5 mol) of acrylonitrile was added dropwise over 30 minutes while maintaining the temperature at 40 to 45°C.
滴下直後の反応液組成を液体クロマトグラフィーで定量
し、表１に示す結果を得た。この時点では３．３゛−チ
オジプロビオニトリルが４５％副生じていた。The composition of the reaction solution immediately after the dropwise addition was determined by liquid chromatography, and the results shown in Table 1 were obtained. At this point, 45% of 3.3'-thiodiprobionitrile was produced as a by-product.
次に、トリメチルベンジルアンモニウムクロリド０．５
ｇを反応液に加え４０〜４５℃に保ったまま、さらに３
時間撹拌を続けた後、再び反応液組成を液体クロマトグ
ラフィーで定量し、表１に示す結果を得た。この熟成後
の３，３′−チオジブロピオニトリルは不検出であり、
３−メルカプトプロピオニトリルの反応収率は９５％に
達した。Next, trimethylbenzylammonium chloride 0.5
g was added to the reaction solution and kept at 40-45°C for an additional 3
After continuing stirring for a period of time, the composition of the reaction solution was again determined by liquid chromatography, and the results shown in Table 1 were obtained. After this ripening, 3,3'-thiodibropionitrile was not detected,
The reaction yield of 3-mercaptopropionitrile reached 95%.
３時間の熟成後３５％塩酸６０ｇを加え、クロロホルム
５０ｇで２回抽出した。有機層を合せ、溶媒を減圧で除
去し、残液を４５〜４８℃／ ３ Ｔｏｒｒで減圧蒸留
し、純度９９．８％の３−メルカプトプロピオニトリル
３９．９ｇ （収率９１％）を得た。After aging for 3 hours, 60 g of 35% hydrochloric acid was added, and the mixture was extracted twice with 50 g of chloroform. The organic layers were combined, the solvent was removed under reduced pressure, and the residual liquid was distilled under reduced pressure at 45-48°C/3 Torr to obtain 39.9 g of 3-mercaptopropionitrile with a purity of 99.8% (yield 91%). Ta.
実施例２
実施例１において水酸化トリメチルヘンシルアンモニウ
ムの４０％水溶液１．０ｇをあらかしめ水硫化ナトリウ
ム水溶液に添加し、同様にアクリロニトリルを加えた。Example 2 In Example 1, 1.0 g of a 40% aqueous solution of trimethylhensyl ammonium hydroxide was added to an aqueous sodium bisulfide solution, and acrylonitrile was added in the same manner.
続いて４０〜４５℃に保ち、さらに３時間撹拌熟成を続
けた。この時点で３，３°−チオジプロピオニトリルは
不検出であり、３−メルカプトプロピオニトリルの反応
収率は９４％に達した。Subsequently, the temperature was maintained at 40 to 45°C, and stirring and aging were continued for an additional 3 hours. At this point, 3,3°-thiodipropionitrile was not detected, and the reaction yield of 3-mercaptopropionitrile reached 94%.
結果を表１に示した。The results are shown in Table 1.
実施例３
７０％水硫化ナトリウム４０ ｇ （０，５モル）に水
４０ｇを加え熔解した後、４０〜４５℃に保ちアクリロ
ニトリル２４ｇ （０，４５モル）を６時間で滴下した
。滴下直後の反応液中には３，３゛−チオジブロビオニ
トリルが４２％副生じていた。トリメチルヘンシルアン
モニウムクロリド２ｇを添加し、同温度で２時間撹拌を
続けると３，３゛−チオジプロビオニトリルは不検出と
なり、３−メルカプトプロピオニトリルの反応収率は９
３％に達した。分析結果を表１に示した。Example 3 After adding 40 g (0.5 mol) of 70% sodium hydrosulfide to 40 g of water and melting the mixture, 24 g (0.45 mol) of acrylonitrile was added dropwise over 6 hours while maintaining the temperature at 40-45°C. Immediately after the dropwise addition, 42% of 3,3'-thiodibrobionitrile was produced as a by-product in the reaction solution. When 2 g of trimethylhensyl ammonium chloride was added and stirring was continued for 2 hours at the same temperature, 3,3゛-thiodiprobionitrile was not detected, and the reaction yield of 3-mercaptopropionitrile was 9.
It reached 3%. The analysis results are shown in Table 1.
実施例４
実施例１において反応温度５〜１０゛Ｃでアクリロニト
リルを滴下した。滴下直後の反応液中には３３゛−チオ
ジブロビオニトリルが７１％副生じ、アクリロニトリル
が６％残っていた。テトラエチルアンモニウムクロリド
１．０ｇを加え同温度で５時間撹拌を続けると３，３”
−チオジプロビオニトリル、アクリロニトリルは不検出
となり、３−メルカプトプロピオニトリルの反応収率は
９５％に達した。結果を表１に示した。Example 4 In Example 1, acrylonitrile was added dropwise at a reaction temperature of 5 to 10°C. Immediately after the dropwise addition, 71% of 33'-thiodibrobionitrile was produced as a by-product, and 6% of acrylonitrile remained. Add 1.0 g of tetraethylammonium chloride and continue stirring at the same temperature for 5 hours to obtain 3.3"
-thiodiprobionitrile and acrylonitrile were not detected, and the reaction yield of 3-mercaptopropionitrile reached 95%. The results are shown in Table 1.
実施例５
実施例１において反応温度５５〜６０℃でアクリロニト
リルを滴下した。滴下直後の反応液中には３３゛、チオ
ジブロビオニトリル２８％が副生じていた。Example 5 In Example 1, acrylonitrile was added dropwise at a reaction temperature of 55 to 60°C. Immediately after the dropwise addition, 33% of thiodibrobionitrile and 28% of thiodibrobionitrile were produced as by-products.
テトラエチルアンモニウムクロリドＩｇを加え同温度で
１時間撹拌熟成により３，３゛−チオジプロピオン酸は
不検出となり、３−メルカプトプロピオニトリルの反応
収率は９４％に達した。結果を表１に示した。After adding tetraethylammonium chloride Ig and aging with stirring at the same temperature for 1 hour, 3,3'-thiodipropionic acid was not detected and the reaction yield of 3-mercaptopropionitrile reached 94%. The results are shown in Table 1.
比較例１
実施例１においてトリメチルヘンシルアンモニウムクロ
リドを添加セす、４０〜４５℃で撹拌熟成を行った。３
．３゛−チオジブロビオニトリルが不検出となるまでに
６時間を要し、３−メルカプトプロピオニトリルの反応
収率は９４％であった。結果を表１に示した。Comparative Example 1 In Example 1, trimethylhensyl ammonium chloride was added, and the mixture was stirred and aged at 40 to 45°C. 3
．． It took 6 hours for 3'-thiodibrobionitrile to become undetectable, and the reaction yield of 3-mercaptopropionitrile was 94%. The results are shown in Table 1.
比較例２
実施例】において熟成時間を１０時間行った以外は同様
に反応した。熟成後の反応液中には３．３チオジプロビ
オニトリルは不検出であったが、ニトリルの加水分解物
による３−メルカプトプロピオン酸等の副生が１１％と
多く、３−メルカプトプロピオニトリルの収率が低下し
た。結果を表１に示す。Comparative Example 2 The reaction was carried out in the same manner as in Example except that the aging time was 10 hours. Although 3.3thiodiprobionitrile was not detected in the reaction solution after ripening, by-products such as 3-mercaptopropionic acid due to nitrile hydrolyzate were as high as 11%, and 3-mercaptopropionitrile yield decreased. The results are shown in Table 1.
比較例３
実施例１において反応温度７０〜７５℃でアクリロニト
リルを滴下した。滴下直後の反応液中には３３゛−チオ
ジブロビオニトリル１７％、３−メルカプトプロピオン
酸８％、３，３゛−チオジプロピオン酸３％が副生して
いた。テトラエチルアンモニウムクロリド１ｇを加え同
温度で１時間熟成により３□３′チオジブロビオニトリ
ルは不検出となったが、ニトリルの加水分解物が多く、
３−メルカプトプロピオニトリルの収率は７０％と低か
った。結果を表１にボした。Comparative Example 3 In Example 1, acrylonitrile was added dropwise at a reaction temperature of 70 to 75°C. Immediately after the dropwise addition, 17% of 33'-thiodibrobionitrile, 8% of 3-mercaptopropionic acid, and 3% of 3,3'-thiodipropionic acid were produced as by-products. After adding 1 g of tetraethylammonium chloride and aging at the same temperature for 1 hour, 3□3'thiodibrobionitrile was not detected, but there were many nitrile hydrolysates,
The yield of 3-mercaptopropionitrile was as low as 70%. The results are shown in Table 1.
比較例４
７０％水硫化ナトリウム５５ｇ、水酸化ナトリウム３８
５ｇを水］００ｇに溶解し、４０〜５０″ＣＴ７りｌＪ
ｔ：＋ニトリル２６．５ ｇを４０分間で滴下した。滴
下直後の反応液中には３，３゛−チオジブロビオニトリ
ル２８％、３−メルカプ１−プロピオン酸１５％、３，
３゛−チオジプロピオン酸８％が副生していた。滴下後
４５〜５０”Ｃで１時間撹拌すると３，３”−チオジブ
ロビオニトリルは２％まで減少しでぃたが、３−メルカ
プトプロピオン酸３７％、３．３”−チオジプロピオン
酸１４％とニトリルの加水分解物が多く、３−メルカプ
トプロピオニトリルの反応収率は４３％と低かった。結
果を表１に示した。Comparative example 4 70% sodium bisulfide 55g, sodium hydroxide 38g
Dissolve 5g in 00g of water, 40-50" CT7 lJ
t:+26.5 g of nitrile was added dropwise over 40 minutes. The reaction solution immediately after dropping contained 28% of 3,3'-thiodibrobionitrile, 15% of 3-mercap-1-propionic acid, 3,
8% of 3'-thiodipropionic acid was produced as a by-product. When stirred for 1 hour at 45-50"C after dropping, 3,3"-thiodibrobionitrile decreased to 2%, but 3-mercaptopropionic acid 37%, 3.3"-thiodipropionic acid 14 % and a large amount of nitrile hydrolyzate, and the reaction yield of 3-mercaptopropionitrile was as low as 43%.The results are shown in Table 1.
（以下余白）
〔発明の効果〕
水硫化ナトリウムとアクリロニトリルの反応による３−
メルカプトプロピオニトリルの製造において、３．３°
−チオジブロビオニトリルの副生を回避することは困難
と考えられていたが、本発明により相関移動触媒存在下
に熟成し副生じたチオジプロビオニトリルを目的物３−
メルカプトプロピオニトリルに短時間で変換することが
でき、高収率で３−メルカプトプロピオニトリルが製造
される。(Left below) [Effects of the invention] 3- by the reaction of sodium hydrosulfide and acrylonitrile
In the production of mercaptopropionitrile, 3.3°
It was thought that it would be difficult to avoid the by-product of thiodiprobionitrile, but according to the present invention, thiodiprobionitrile, which is a by-product after ripening in the presence of a phase transfer catalyst, can be converted to the target product 3-
It can be converted to mercaptopropionitrile in a short time, and 3-mercaptopropionitrile is produced in high yield.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
３−メルカプトプロピオニトリルを製造する方法におい
て、０〜６０℃で水硫化ナトリウムに対して０．５〜１
．０モル比のアクリロニトリルを加えた後、相間移動触
媒の存在下０〜６０℃で１〜５時間撹拌熟成することを
特徴とする３−メルカプトプロピオニトリルの製造法。 ２、相間移動触媒が第４級アンモニウム塩である請求項
１記載の製造法。 ３、相間移動触媒量がアクリロニトリルに対して０．０
１〜５モル％である請求項１記載の製造法。[Claims] 1. A method for producing 3-mercaptopropionitrile by adding acrylonitrile to an aqueous solution of sodium bisulfide at a temperature of 0 to 60°C with respect to sodium bisulfide of 0.5 to 1.
．． A method for producing 3-mercaptopropionitrile, which comprises adding 0 molar ratio of acrylonitrile and then aging with stirring at 0 to 60°C for 1 to 5 hours in the presence of a phase transfer catalyst. 2. The production method according to claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt. 3. Phase transfer catalyst amount is 0.0 relative to acrylonitrile
The manufacturing method according to claim 1, wherein the amount is 1 to 5 mol%.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269333A JP2854955B2 (en) | 1990-10-09 | 1990-10-09 | Method for producing 3-mercaptopropionitrile |
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