KR20060090424A - METHOD OF PREPARING beta;-HYDROXYBUTYRONITRILE DERIVATIVES FROM RACEMIC EPOXIDES WITH AQUOUS HYDROGEN CYNIDE - Google Patents
METHOD OF PREPARING beta;-HYDROXYBUTYRONITRILE DERIVATIVES FROM RACEMIC EPOXIDES WITH AQUOUS HYDROGEN CYNIDE Download PDFInfo
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- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/12—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
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Abstract
본 발명은 라세믹 β-히드록시부티로나이트릴(β-hydroxybutyronitrile) 화합물을 합성하는 것에 관한 것으로 pH8~10의 시안화수소 수용액상에 하기 [반응식1]에서 일반식 1로 표시되는 에폭시드(epoxide)를 투입한 후 고리열림(ring-opening)반응시킴으로써 β-히드록시부티로나이트릴 화합물을 높은 수율로 제조하는 방법에 관한 것이다. 좀 더 상세하게는 시안화염과 무기산 중 특히 시안화칼륨(KCN)과 황산(H2SO4)을 혼합하여 황산칼륨(K2SO4)과 pH8~10의 시안화수소 용액을 제조하고, 이로부터 황산칼륨을 제거한 후, pH8~10의 시안화수소 수용액상에서 반응물인 프로필렌옥시드 또는 에피클로로히드린 등을 적가하여 라세믹 3-히드록시부티로나이트릴과 라세믹 4-클로로-3-히드록시부티로나이트릴 등을 제조하는 방법에 관한 것이다.The present invention relates to the synthesis of a racemic β-hydroxybutyronitrile (β-hydroxybutyronitrile) compound in an aqueous solution of pH 8-10 hydrogen cyanide (epoxide) represented by the general formula (1) The present invention relates to a method for producing β-hydroxybutyronitrile compound in high yield by ring-opening reaction after the addition of In more detail, potassium cyanide (KCN) and sulfuric acid (H 2 SO 4 ) are mixed with a cyanide salt and an inorganic acid to prepare potassium sulfate (K 2 SO 4 ) and a hydrogen cyanide solution having a pH of 8 to 10. After removing potassium, propylene oxide or epichlorohydrin, which is a reactant, is added dropwise in an aqueous hydrogen cyanide solution having a pH of 8 to 10 and racemic 3-hydroxybutyronitrile and racemic 4-chloro-3-hydroxybutyro It relates to a method for producing nitrile and the like.
상기의 제조방법은 반응성이 좋고 공정이 용이하며, 저렴한 비용으로 높은 수율의 β-히드록시부티로나이트릴 화합물을 합성할 수 있으므로 상업적으로 매우 유용하다.The above production method is very commercially useful because it has good reactivity, easy to process, and can synthesize high yield β-hydroxybutyronitrile compound at low cost.
3-히드록시부티로나이트릴, 4-클로로-3-히드록시부티로나이트릴, 에폭시드, 고리열림(ring-opening), 시안화수소3-hydroxybutyronitrile, 4-chloro-3-hydroxybutyronitrile, epoxide, ring-opening, hydrogen cyanide
Description
본 발명은 β-히드록시부티로나이트릴 유도체의 제조 방법에 관한 것으로, 더욱 상세하게는 에폭시드를 원료물질로 하여 pH8~10의 시안화수소가 존재하는 수용액상에서 3-히드록시부티로나이트릴 또는 4-클로로-3-히드록시부티로나이트릴 등을 높은 수율로 제조하는 방법에 관한 것이다. The present invention relates to a method for preparing β-hydroxybutyronitrile derivatives, and more particularly, 3-hydroxybutyronitrile or in an aqueous solution in which hydrogen cyanide at pH 8-10 is present using epoxide as a raw material. A method for producing 4-chloro-3-hydroxybutyronitrile and the like in high yield.
[반응식1][Scheme 1]
본 발명에 의해 제조되는 상기 일반식 2로 표시되는 β-히드록시부티로나이트릴 유도체들은 키랄 중간체 제조에 널리 쓰이고 있다. 본 발명에서 제조하고자 하는 3-히드록시부티로나이트릴 또는 4-클로로-3-히드록시부티로나이트릴과 같은 시아노히드린(cyanohydrin)들은 의약품, 농약 등의 제조에 중요 중간체로 쓰인다. 특히 카르니틴(carnitine), 4-아미노-3-히드록시부틸산과 4-클로로-3-히드록시부티레이트 제조에 적합하다.Β-hydroxybutyronitrile derivatives represented by the general formula (2) prepared by the present invention are widely used for the preparation of chiral intermediates. Cyanohydrins such as 3-hydroxybutyronitrile or 4-chloro-3-hydroxybutyronitrile to be prepared in the present invention are used as important intermediates in the manufacture of medicines, pesticides and the like. It is particularly suitable for the production of carnitine, 4-amino-3-hydroxybutyl acid and 4-chloro-3-hydroxybutyrate.
현재까지 보고에 따르면 β-히드록시부티로나이트릴은 효소적 방법과 화학적 방법으로 제조가 가능하다.Reported to date, β-hydroxybutyronitrile can be prepared by enzymatic and chemical methods.
효소적 방법에 의한 제조는 Nakamura 등(Biochemical and Biophysical Research communications, 1991, 180: 124-130)에 의해 보고된 바 있다. 이들은 재조합 균주를 이용하여 생산한 효소(halohydrin hydrogen-halide-lyase)를 촉매로하고 수용액상에서 프로필렌옥시드(propylene oxide)를 시안화칼륨(potassium cyanide)과 반응하여 3-히드록시부티로나이트릴을 제조하였다. 또한 프로필렌옥시드 대신 에피클로로히드린를 반응물로 하여 4-클로로-3-히드록시부티로나이트릴을 제조하였다. 그러나 상기의 제조방법은 반응농도가 매우 낮을 뿐만아니라 각각의 반응수율도 36.2%와 67.1 % 로 낮아서 실제 생산공정에 적용하기 어려운 단점이 있다.Preparation by enzymatic methods has been reported by Nakamura et al. (Biochemical and Biophysical Research communications, 1991, 180: 124-130). They catalyze the enzymes produced using recombinant strains (halohydrin hydrogen-halide-lyase) and react propylene oxide with potassium cyanide in aqueous solution to produce 3-hydroxybutyronitrile. It was. In addition, 4-chloro-3-hydroxybutyronitrile was prepared using epichlorohydrin as a reactant instead of propylene oxide. However, the above production method has a disadvantage that the reaction concentration is not only very low, but also the yield of each reaction is low as 36.2% and 67.1%, so it is difficult to apply to the actual production process.
화학적 제조방법은 다음과 같다.Chemical preparation method is as follows.
Braun (Journal of American Chemical Society, 1930, 52: 3167-3176)은 수산화나트륨 용액과 에피클로로히드린과 무수 시안화수소 용액(anhydrous hydrogen cinide)을 90시간동안 75~80℃ 에서 반응하여 2-히드록시-3-클로로부티로나이트릴(4-클로로-3-히드록시부티로나이트릴)(수율65%)을 제조하였다. 그러나 상기의 제조 방법에서 사용되는 무수 시안화수소는 취급하기가 힘들고 반응시간이 매우 길어 산업적으로 이용하기에는 어렵다.Braun (Journal of American Chemical Society, 1930, 52: 3167-3176) reacts 2-hydroxy by reacting sodium hydroxide solution, epichlorohydrin and anhydrous hydrogen cinide at 75 ~ 80 ℃ for 90 hours. 3-Chlorobutyronitrile (4-chloro-3-hydroxybutyronitrile) (yield 65%) was prepared. However, the anhydrous hydrogen cyanide used in the above production method is difficult to handle and the reaction time is very long, it is difficult to use industrially.
미국특허 4,413,142에서는 3-클로로-2-히드록시-1-토실 프로파놀(3-chloro-2-hydroxy-1-tosyl praopanol)을 메탄올상에서 시안화칼륨과 40 시간동안 상온반응하여 4-클로로-3-히드록시부티로나이트릴을 제조하였다. 이 때 반응 수율은 60 % 로 낮았다.In US Pat. No. 4,413,142, 3-chloro-2-hydroxy-1-tosyl prapanol is reacted with potassium cyanide in methanol for 40 hours at room temperature to give 4-chloro-3-. Hydroxybutyronitrile was prepared. At this time, the reaction yield was as low as 60%.
일본공개특허 평3-310671은 에피클로로히드린을 반응물로하여 4-클로로-3-히드록시부티로나이트릴을 제조하는 방법을 공지하고 있다. 반응물인 에피클로로히드린에 시안화칼륨 용액과 65 % 황산용액을 동시에 적가하여 pH를 8-10으로 조절하여 반응한 후 아세트산 에틸(ethyl acetate)로 추출하고 감압증류하여 무색의 액체인 4-클로로-3-히드록시부티로나이트릴을 합성하였다. 하지만 이 제조 방법에서 시안화칼륨 용액과 황산을 동시에 투입하여 반응액의 pH를 8-10으로 조절하는 것은 쉬운일이 아니며, 산과 염기를 동시에 투입할 때 발생되는 중화열을 조절하기 어려운 단점이 있다. Japanese Patent Laid-Open No. 3-310671 discloses a method for producing 4-chloro-3-hydroxybutyronitrile using epichlorohydrin as a reactant. Potassium cyanide solution and 65% sulfuric acid solution were added dropwise to the reaction product epichlorohydrin at the same time to adjust the pH to 8-10, followed by extraction with ethyl acetate and distillation under reduced pressure to give 4-chloro- as a colorless liquid. 3-hydroxybutyronitrile was synthesized. However, in this preparation method, it is not easy to adjust the pH of the reaction solution to 8-10 by simultaneously adding potassium cyanide solution and sulfuric acid, and it is difficult to control the heat of neutralization generated when acid and base are simultaneously added.
Kasai 등(Journal of molecular catalysis B:Enzymatic, 1998, 4:237-252)은 에폭시드가 시안화칼륨이 포함된 염기성 상태에 있게 되면 쉽게 알릴 알코올(allyl alcohol)로 전환되므로 이를 방지하기 위해서는 pH를 8-10 정도로 유지해야 한다고 보고하였다.Kasai et al. (Journal of molecular catalysis B: Enzymatic, 1998, 4: 237-252) easily convert epoxides to allyl alcohol when they are in a basic state containing potassium cyanide. Reported that it should be kept at around 10.
조성욱 등(한국특허출원 10-2003-0023968)은 시안화염 수용액과 산을 혼합한 pH7~8범위의 용액에 에피클로로히드린을 적가하여 용액중의 시안화염과 반응시켜 4-클로로-3-히드록시부티로니트릴(수율 89%)을 제조하였다.Cho, Sung-Wook et al. (Korean Patent Application No. 10-2003-0023968) added epichlorohydrin to a solution in the pH range of 7-8 with a mixture of cyanide salt solution and acid, and reacted with cyanide salt in solution to react with 4-chloro-3-hydride. Oxybutyronitrile (89% yield) was prepared.
한편, 본 발명자들은 한국특허출원10-2004-004887호에서 시안화칼륨과 황산을 먼저 혼합하여 반응액의 pH를 8-10으로 유지한 후 프로필렌옥시드 및 에피클로로히드린을 각각 적가하여 3-히드록시부티로나이트릴(반응수율 83.6%)과 4-클로로-3-히드록시부티로나이트릴(반응수율 97.8%)을 각각 제조하였다. Meanwhile, the present inventors first mixed potassium cyanide and sulfuric acid in Korean Patent Application No. 10-2004-004887 to maintain the pH of the reaction solution at 8-10, and then added dropwise propylene oxide and epichlorohydrin, respectively, to 3-hydrate. Oxybutyronitrile (reaction yield 83.6%) and 4-chloro-3-hydroxybutyronitrile (reaction yield 97.8%) were prepared, respectively.
이에 본 발명자들은 황산과 시안화칼륨을 사용하여 제조한 수용액 상에서 고리열림(ring-opening)반응하는 방법을 기초로하여 에폭시드로부터 β-히드록시부티로나이트릴을 합성하되, 경제적으로 우수하고, 공정이 개선되어 반응 수율이 높은 제조 방법을 개발하고자 하였다.Accordingly, the present inventors synthesized β-hydroxybutyronitrile from an epoxide based on a ring-opening reaction in an aqueous solution prepared using sulfuric acid and potassium cyanide, and economically superior, This improvement has been made to develop a manufacturing method having a high reaction yield.
조성욱 등과 본 발명자들이 고안한 발명에서, 반응물 투입전 시안화염과 산을 먼저 섞은 뒤 반응하는 경우 무기산과 시안화염이 반응하여 무기산염(예:황산염K2SO4)이 생성되는데 이 염들은 반응중 수용액상에 남아있으면서 점도의 증가와 고체물질의 형성 등에 의한 고리화반응에 영향을 주게 된다. 이에 본 발명자들은 얼음조에서 시안화칼륨을 녹인 수용액에 황산을 천천히 적가하여 pH가 8~10이 되는지 확인 한 후, 생성된 황산칼륨을 제거하고 시안화수소 수용액을 제조하였다. 20~25℃를 유지하면서 pH8~10의 시안화수소 수용액에 에폭시화합물을 적가하면서 반응하여 보다 높은 수율의 β-히드록시부티로나이트릴을 제조하였다. 본 발명에 의한 제조방법은 비료 등의 원료로 사용되는 황산칼륨 또는 황산나트륨과 염화칼륨 등이 부산물로 얻어지므로 경제적으로 우수하고 실제 대량생산에서 매우 유리 한 공정이 될 것으로 판단된다. In the invention devised by Sung-Wook et al. And the present inventors, when a cyanide salt and an acid are mixed before reacting with a reactant, an inorganic acid (eg, sulfate K 2 SO 4 ) is formed by reacting an inorganic acid and a cyanide salt. While remaining in the aqueous phase, it affects the cyclization reaction by increasing the viscosity and the formation of a solid material. Thus, the present inventors slowly added dropwise sulfuric acid to an aqueous solution of potassium cyanide in an ice bath to check whether the pH is 8 to 10, and then removes the produced potassium sulfate to prepare an aqueous hydrogen cyanide solution. Epoxy compound was added dropwise to an aqueous hydrogen cyanide solution having a pH of 8 to 10 while maintaining the temperature at 20 to 25 ° C. to prepare β-hydroxybutyronitrile of higher yield. Since the production method according to the present invention is obtained as a by-product of potassium sulfate or sodium sulfate and potassium chloride used as a raw material for fertilizers, it is considered to be economically excellent and very advantageous in mass production.
상기 목적을 달성하기 위한 본 발명의 제조방법은 시안화염 용액에 무기산용액을 투입하거나 또는 시안화산 수용액에 염화칼륨(KOH) 등을 첨가하여 일정한 pH(8~10)를 유지시킨 뒤, 프로필렌옥시드(1,2-에폭시프로판) 또는 에피클로로히드린을 수용액에 첨가하여 고리열림 반응시키는 것으로 이루어진다.
In the production method of the present invention for achieving the above object is to maintain a constant pH (8 ~ 10) by adding an inorganic acid solution to the cyanide salt solution or by adding potassium chloride (KOH) to the aqueous solution of cyanide, propylene oxide ( 1,2-epoxypropane) or epichlorohydrin is added to the aqueous solution for ring opening reaction.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다. 본 발명은 일반식 1로 표시되는 에폭시드(epoxide)를 pH 8~10의 시안화수소 수용액에 20~25℃의 온도조건으로 교반하여 일반식 2로 표시되는 β-히드록시부티로나이트릴 유도체를 높은 수율로 제조하는 방법을 그 특징으로 한다. Referring to the present invention in more detail as follows. The present invention is a β-hydroxybutyronitrile derivative represented by the general formula (2) by stirring the epoxide (epoxide) represented by the general formula (1) in an aqueous hydrogen cyanide solution of pH 8 ~ 10 at a temperature condition of 20 ~ 25 ℃ It is characterized by a method of manufacturing in high yield.
본 발명에서 제조되는 β-히드록시부티로나이트릴은 3-히드록시부티로나이트릴 또는 4-클로로-3-히드록시부티로나이트릴 등이 있으나 이에 한정되는 것은 아니다. 또한 본 발명의 제조 방법은 광학활성 β-히드록시부티로나이트릴 유도체의 합성에도 가능하다.Β-hydroxybutyronitrile prepared in the present invention include, but is not limited to, 3-hydroxybutyronitrile or 4-chloro-3-hydroxybutyronitrile. The production method of the present invention is also possible for the synthesis of optically active β-hydroxybutyronitrile derivatives.
본 발명에 있어서, 반응에 사용되는 반응물들과 생성물들은 HP-FFAP(Agilent사, 30 mm X 0.53 m)가 장착된 기체크로마토그래피(도남인스트루먼트사, 모델 DS6200)를 이용하여 다음의 온도조건으로 분석하였다.In the present invention, the reactants and products used in the reaction were analyzed by gas chromatography (Donam Instruments, Model DS6200) equipped with HP-FFAP (Agilent, 30 mm X 0.53 m) under the following temperature conditions It was.
프로필렌옥시드는 35 ℃에서 10 분간 가열하고 분당 10 ℃씩 220 ℃까지 증가시킨 후 220 ℃에서 10 분간 유지하였고, 담체로는 헬륨기체를 사용하고 컬럼헤 드 압력을 2psi로 유지하면서 230 ℃에서 FID(flame ionizaion detector)를 사용하여 검출하였다. 이 때 3.19 분에 검출되었다. 3-히드록시부티로나이트릴은 60 ℃에서 5 분간 가열하고 분당 10 ℃씩 220 ℃까지 증가시킨 후 220 ℃에서 20 분간 유지하였으며 나머지는 상기화 같이 분석하여 19.05 분에서 확인하였다. Propylene oxide was heated at 35 ° C. for 10 minutes, increased to 10 ° C. per minute to 220 ° C., and maintained at 220 ° C. for 10 minutes. Helium gas was used as the carrier, and the column head pressure was maintained at 2 psi. detection using a flame ionizaion detector. It was detected at 3.19 minutes. 3-hydroxybutyronitrile was heated at 60 ° C. for 5 minutes, increased to 10 ° C. per minute to 220 ° C., and maintained at 220 ° C. for 20 minutes.
에피클로로히드린과 4-클로로-3-히드록시부티로나이트릴은 70 ℃에서 10 분간 가열하고 분당 20 ℃씩 220 ℃까지 증가시킨 후 220 ℃에서 10 분간 유지하였다. 담체(carrier gas)로는 헬륨 기체를 사용하였으며 컬럼 헤드 압력을 6psi로 유지하면서 230 ℃에서 FID(flame ionizaion detector)를 사용하여 분석하였다.이 때 에피클로로히드린은 4.07 분, 4-클로로-3-히드록시부티로나이트릴은 19.52분에서 각각 검출되었다.Epichlorohydrin and 4-chloro-3-hydroxybutyronitrile were heated at 70 ° C. for 10 minutes, increased to 220 ° C. at 20 ° C. per minute, and held at 220 ° C. for 10 minutes. Helium gas was used as a carrier gas and analyzed using a flame ionizaion detector (FID) at 230 ° C. while maintaining the column head pressure at 6 psi. Epichlorohydrin was 4.07 min, 4-chloro-3- Hydroxybutyronitrile was detected at 19.52 minutes respectively.
이상에서 설명한 바와 같이 본 발명은 다음의 실시예를 통하여 더욱 상세히 설명하지만 본 발명이 다음의 실시예에 의해 한정되는 것은 아니다.As described above, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
실시예 1. 시안화수소 수용액 제조Example 1 Preparation of Aqueous Hydrogen Cyanide Solution
물 58ml에 시안화칼륨(KCN) 24.9 g 을 녹인 후 얼음조에서 65 % 황산 용액 23 ml을 천천히 적가하여 반응액의 pH를 8 ~ 10으로 조절하였다. 이때 생기는 황산칼륨(K2SO4)을 거름종이로 여과하여 제거하고 pH8~10의 시안화수소 수용액을 회수하였다. After dissolving 24.9 g of potassium cyanide (KCN) in 58 ml of water, 23 ml of a 65% sulfuric acid solution was slowly added dropwise in an ice bath to adjust the pH of the reaction solution to 8-10. At this time, potassium sulfate (K 2 SO 4 ) was removed by filtration with a filter paper to recover a hydrogen cyanide aqueous solution of pH 8 ~ 10.
실시예 2. 4-클로로3-히드록시부티로나이트릴의 제조Example 2. Preparation of 4-chloro3-hydroxybutyronitrile
실시예 1에서 제조된 시안화수소 수용액 20ml에 에피클로로히드린 1.18 g을 20℃ 이하에서 적가하여 반응하였다. 이때 5시간 반응 후, 반응 전환율은 99%이었고, 생성수율은 99%이었다.1.18 g of epichlorohydrin was added dropwise at 20 ° C. or lower to 20 ml of hydrogen cyanide aqueous solution prepared in Example 1 to react. At this time, after the reaction for 5 hours, the reaction conversion was 99%, the production yield was 99%.
4-클로로-3-히드록시부티로나이트릴은 다음과 같이 분석되었다. 4-chloro-3-hydroxybutyronitrile was analyzed as follows.
1H-NMR(CDCl3) : 2.79(2H, m), 3.65(2H, d), 3.86(1H,s), 4.20(1H,m) ppm 1 H-NMR (CDCl 3 ): 2.79 (2H, m), 3.65 (2H, d), 3.86 (1H, s), 4.20 (1H, m) ppm
실시예 3. 3-히드록시부티로나이트릴 제조Example 3. Preparation of 3-hydroxybutyronitrile
실시예 1에서 제조된 시안화수소 수용액 20ml에 프로필렌옥시드 0.829 g을 20℃ 이하에서 적가하여 반응하였다. 이때 반응 9.5시간 후, 반응 전환율은 97% 이었고, 생성수율은 95% 이었다.To 20 ml of the hydrogen cyanide aqueous solution prepared in Example 1, 0.829 g of propylene oxide was added dropwise at 20 占 폚 or lower to react. At this time, after 9.5 hours, the reaction conversion was 97% and the yield was 95%.
3-히드록시부티로나이트릴은 다음과 같이 분석되었다. 3-hydroxybutyronitrile was analyzed as follows.
1H-NMR(CDCl3) : 1.32(3H, d), 2.51(2H, m), 3.52(1H,s), 4.14(1H,m) ppm 1 H-NMR (CDCl3): 1.32 (3H, d), 2.51 (2H, m), 3.52 (1H, s), 4.14 (1H, m) ppm
이상에서 살펴본 바와 같이, 본 발명의 라세믹 β-히드록시부티로나이트릴의 제조 방법은 반응수율이 높을 뿐만아니라 비료의 원료로 사용되는 황산칼륨 등이 부산물로 얻어지는 경제적으로 매우 우수한 제조공정이다. 또한 라세믹 화합물뿐아니라 키랄 화합물의 제조에도 적용이 가능하여 기존방법에 비해 산업상 매우 유용하다.
As described above, the manufacturing method of the racemic β-hydroxybutyronitrile of the present invention is not only high reaction yield, but also an economically excellent manufacturing process in which potassium sulfate or the like used as a raw material of fertilizer is obtained as a by-product. In addition, it can be applied to the preparation of chiral compounds as well as racemic compounds, which is very useful industrially compared to the existing methods.
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