WO2024130897A1 - 一种巴豆腈的制备方法 - Google Patents

一种巴豆腈的制备方法 Download PDF

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WO2024130897A1
WO2024130897A1 PCT/CN2023/087084 CN2023087084W WO2024130897A1 WO 2024130897 A1 WO2024130897 A1 WO 2024130897A1 CN 2023087084 W CN2023087084 W CN 2023087084W WO 2024130897 A1 WO2024130897 A1 WO 2024130897A1
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crotononitrile
add
reactor
preparing
reaction
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PCT/CN2023/087084
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French (fr)
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彭建
陆电云
漆伟君
孙彭
宋宏峰
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浦拉司科技(上海)有限责任公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/09Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/20Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/32Separation; Purification; Stabilisation; Use of additives
    • C07C253/34Separation; Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/01Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/07Mononitriles
    • C07C255/08Acrylonitrile; Methacrylonitrile

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  • the invention relates to a method for preparing crotononitrile, and belongs to the technical field of fine chemicals.
  • Crotonitrile also known as acryl cyanide. It is a colorless to light yellow liquid, soluble in ether and acetone; its chemical structure is Crotononitrile is an important pharmaceutical intermediate and is widely used in the field of organic synthesis.
  • the international market demand is large, but there are very few domestic manufacturers and the production process is backward.
  • the current commercial products are usually a mixture of cis and trans isomers, with the cis isomer accounting for about 20%.
  • the main synthesis methods of crotononitrile are as follows:
  • Method 2 Crotonaldehyde-iodine, ammonia method
  • method 1 uses potassium cyanide, a highly toxic substance, in the reaction, which is dangerous to operate and has a low yield;
  • method 2 uses iodine, which is expensive and requires special equipment for ammonia, which is costly, dangerous to operate and has a low yield;
  • method 3 is relatively simple, but 2-hydroxybutyronitrile causes serious environmental pollution;
  • method 4 reacts at 150°C for 48 hours, which has a high reaction temperature, a low yield, and uses a high-boiling point solvent, which makes post-processing difficult.
  • the purpose of the present invention is to provide a method for preparing crotononitrile, wherein the raw material crotonic acid is used to prepare single-configuration trans-crotononitrile with high yield, and then benzenesulfonyl chloride or pyridine is used for dehydration to prepare crude crotononitrile, and the final product is obtained by distillation using conventional vacuum equipment.
  • benzenesulfonyl chloride or pyridine is used for dehydration to prepare crude crotononitrile, and the final product is obtained by distillation using conventional vacuum equipment.
  • pyridine can be recovered by adding alkali to the aqueous phase, which saves production costs and is suitable for large-scale industrial production.
  • the use of a distillation tower for distillation is avoided, the operation is simple, and the production efficiency is significantly improved.
  • a method for preparing crotononitrile according to the present invention comprises the following steps:
  • step S1 the mass ratio of crotonic acid, DMF, thionyl chloride and ammonia water is 1:0.009-0.01:1.60-1.80:4.50-4.80.
  • reaction temperature is 0-10°C.
  • step S1 the filter cake is washed with ice water, and the filter cake drying temperature is at 60-70°C.
  • step S2 the mass ratio of crotonamide, pyridine and benzenesulfonyl chloride is 1:1.5-2.0:2.0-3.0.
  • step S2 the citric acid aqueous solution used for quenching is 10% citric acid aqueous solution.
  • the raw material crotonic acid used is cheap and the production cost is low.
  • Pyridine can be recovered after the aqueous phase is treated with alkali, which can reduce costs and solve environmental problems.
  • the crude crotononitrile obtained by using benzenesulfonyl chloride and pyridine does not require distillation in a distillation tower, but can be distilled using conventional pressure reduction equipment to obtain the finished product. The operation is simple and safe, saving production time.
  • R2 was stirred at 0-10°C for 20-30 min, and a part of the ammonia was removed by vacuum for 10-20 min, and the materials in the R2 reactor were centrifuged at 0-10°C.
  • the filter cake was washed with a small amount of ice water and dried at 60-70°C to obtain 80.0 g of white intermediate crotonamide, with a yield of 80.9%.
  • the oil temperature was heated to 60-90°C and the distillation temperature at the head of the distillation column was 35-45°C to obtain 52.0 g of crotononitrile with GC purity of 99.5% (trans-crotononitrile 99.2%, cis-crotononitrile 0.5%, total purity 99.7%) and molar yield of 82.4%.
  • R2 was stirred at 0-10°C for 20-30 min, and a part of ammonia was removed by vacuum for 10-20 min, and the materials in the R2 reactor were centrifuged at 0-10°C.
  • the filter cake was washed with a small amount of ice water and dried at 60-70°C to obtain 82 g of white intermediate crotonamide, with a yield of 83.0%.
  • the oil temperature was heated to 60-90°C and the distillation temperature at the head of the distillation column was 35-45°C to obtain 72.0g of crotononitrile with GC purity of 99.5% (trans-crotononitrile 99.1%, cis-crotononitrile 0.3%, total purity 99.4%) and molar yield of 91.3%.
  • R2 was stirred at 0-10°C for 20-30 min, and a part of ammonia was removed by vacuum for 10-20 min, and the materials in the R2 reactor were centrifuged at 0-10°C.
  • the filter cake was washed with a small amount of ice water and dried at 60-70°C to obtain 86 g of white intermediate crotonamide, with a yield of 87.0%.
  • the oil temperature was heated to 60-90°C and the distillation temperature at the head of the distillation column was 35-45°C to obtain 70.0g of crotononitrile with GC purity of 99.5% (trans-crotononitrile 99.0%, cis-crotononitrile 0.5%, total purity 99.5%) and molar yield of 88.8%.
  • R2 was stirred at 0-10°C for 20-30min, and a part of ammonia was removed by vacuum for 10-20min, and the materials in the R2 reactor were centrifuged at 0-10°C.
  • the filter cake was washed with a small amount of ice water and dried at 60-70°C to obtain 90g of white intermediate crotonamide, with a yield of 91.0%.
  • the oil temperature was heated to 60-90°C and the distillation temperature at the head of the distillation column was 35-45°C to obtain 68.0g of crotononitrile with GC purity of 99.5% (trans-crotononitrile 99.3%, cis-crotononitrile 0.3%, total purity 99.6%) and molar yield of 86.3%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种巴豆腈的制备方法,属于精细化工领域。以廉价易得的巴豆酸为起始原料,高收率制成单一构型反式巴豆腈,再采用苯磺酰氯和吡啶脱水制备得到粗品巴豆腈,利用常规减压设备蒸馏得到最终巴豆腈成品。本发明制备过程中水相加碱可回收呲啶,节约了生产成本,适合大规模工业生产,还避免了采用精馏塔蒸馏,操作简单,生产效率提高明显。

Description

一种巴豆腈的制备方法 技术领域
本发明涉及一种巴豆腈的制备方法,属于精细化工技术领域。
背景技术
巴豆腈 (Crotonitrile ) ,别名:丙烯基氰。无色至淡黄色液体,溶于乙醚、 丙酮;化学结构式为  。巴豆腈是一种重要的医药中间体,在有机合成领域中应用广泛。国际市场需求量大,而目前国内生产厂家极少,且生产工艺落后。目前市售产品中,通常为顺反异构体混合物,顺式异构体大约占比 20%。 目前巴豆腈的主要合成方法如下:
方法 1 :1-氯代丙烯-氰化钾法;
 方法 2 :巴豆醛-碘、氨气法; 
方法 3:2-羟基丁腈-对甲苯磺酰氯法;
  方法 4:巴豆醛肟法-DMF 法 ;                                              
上述方法中,方法 1 反应中使用剧毒物质氰化钾,操作危险,收率低;方法 2 碘价格昂贵,氨气需特殊设备,成本贵、操作危险、收率低;方法 3 较为简单, 但 2-羟基丁腈对环境污染较为严重;方法 4 在 150℃反应 48h ,反应温度高,收 率低,且用到高沸点溶剂,后处理困难。
鉴于目前市场上该产品多数为顺反异构体混合物,且现有合成方法中存在的 上述问题,因此就有必要开发低成本、高效率、低污染制备单一反式高纯度巴豆 腈的工艺方法。
发明内容
本发明的目的在于提供一种巴豆腈的制备方法,通过原料巴豆酸高收率制成 单一构型的反式巴豆腈,再采用苯磺酰氯或呲啶脱水制备得到粗品巴豆腈,利用 常规减压设备蒸馏得到最终成品,制备过程中水相加碱还可回收呲啶,节约了生 产成本,适合大规模工业生产。并且避免了使用精馏塔蒸馏,操作简单,生产效 率提高明显。
本发明所述一种巴豆腈的制备方法,包括以下步骤:
S1:将巴豆酸、二氯甲烷和催化量 DMF 混合,滴加氯化亚砜并搅拌反应, 反应结束,将反应物料滴加入氨水溶液中;反应结束,减压除去过量氨水;反应 体系离心,滤饼洗涤干燥得到巴豆酰胺;
S2:将巴豆酰胺加入二氯甲烷溶解,接着加入吡啶和苯磺酰氯反应;反应结束,加水淬灭,有机层柠檬酸水溶液洗,饱和碳酸氢钠水溶液洗,减压浓缩得到 巴豆腈成品。
进一步地,在上述技术方案中,步骤 S1 中,巴豆酸、DMF 、氯化亚砜与氨 水质量比为 1 :0.009-0.01:1.60- 1.80:4.50-4.80。
进一步地,在上述技术方案中,步骤 S1 和 S2 中,反应温度为 0- 10℃。
进一步地,在上述技术方案中,步骤 S1 中,滤饼采用冰水洗涤,滤饼干燥 温度在 60-70℃。
进一步地,在上述技术方案中,步骤 S2 中,巴豆酰胺、吡啶与苯磺酰氯质量比为 1 :1.5-2.0 :2.0-3.0。
进一步地,在上述技术方案中,步骤 S2 中,淬灭时为柠檬酸水溶液采用 10% 柠檬酸水溶液。
本发明有益效果:
A 、所采用的原料巴豆酸价格便宜,生产成本较低;B 、水相加碱处理后可 以回收呲啶,一方面降低成本,一方面可以解决环保问题;C 、采用苯磺酰氯和 吡啶得到的粗品巴豆腈不用精馏塔蒸馏,使用常规减压设备蒸馏即可得到成品, 操作简单安全,节约了生产时间。
具体实施方式
实施例  1
向 R1 反应釜中加入 200g DCM,搅拌时加入 100g 巴豆酸,加入 1.0g DMF, 并将 R1 反应釜内温调至 0- 10℃ ,并控制内温在 0- 10℃ ,缓慢滴加 165g 氯化亚砜,滴加完搅拌 2-3 小时。
向 R2 反应釜中加入 474g 25%氨水溶液,内温调至 0-5℃ 。在 0- 10℃下,将 R1 反应釜内物料缓慢滴加到 R2 反应釜中,并搅拌 1-2 小时。
R2 在 0- 10 ℃下搅拌20-30min,抽真空除去部分氨气 10-20 分钟,并在 0- 10 ℃ 下 R2 反应釜内物料离心。滤饼用少量冰水洗涤后在 60-70℃下干燥得到白色中间体巴豆酰胺 80.0g ,收率 80.9%。
向 R1 反应釜加入 400g DCM 搅拌分散,搅拌时加入 80.0g 巴豆酰胺。R1 反 应釜内温调整至 0- 10℃,加入 120g 吡啶,搅拌 20-30 分钟。滴加 160.0g 苯磺酰氯,搅拌 1-2 小时。
将 R1 反应釜内温调至 0- 10℃搅拌 1-2h.  然后内温调整至 25-35℃,搅拌 8- 16 小时。然后 R1 反应釜内温不超过35℃,往内缓慢加入 160g 工艺水。将 R1 反应 釜静止后,分出上层水相,下层有机相每次用 160g 10%柠檬酸水溶液洗涤 1-2 次,再用 160g 7% NaHCO3 水溶液洗涤,有机相常压外温蒸馏至 60-70℃浓缩掉 DCM ,浓缩残余继续水泵减压蒸馏,加热油温 60-90℃ ,蒸馏柱头馏出温度为 35-45℃得到巴豆腈 52.0 g,GC 纯度 99.5%(反式巴豆腈 99.2%,顺式巴豆腈 0.5%, 总纯度 99.7%) 摩尔收率 82.4%。
实施例  2
向 R1 反应釜中加入 300g DCM,搅拌时加入 100.0g 巴豆酸,加入 1.0g DMF, 并将 R1 反应釜内温调至 0- 10℃ ,并控制内温在 0- 10℃ ,缓慢滴加 166g 氯化亚砜,滴加完搅拌 2-3 小时。
向 R2 反应釜中加入 475g 25%氨水溶液,内温调至 0-5℃ 。在 0- 10℃下,将 R1 反应釜内物料缓慢滴加到 R2 反应釜中,并搅拌 1-2 小时。
R2 在 0- 10 ℃下搅拌20-30min,抽真空除去部分氨气 10-20 分钟,并在 0- 10 ℃ 下 R2 反应釜内物料离心。滤饼用少量冰水洗涤后在 60-70℃下干燥得到白色中 间体巴豆酰胺 82g ,收率 83.0%。
向 R1 反应釜加入 420g DCM 搅拌分散,搅拌时加入 80.0g 巴豆酰胺。R1 反 应釜内温调整至 0- 10℃,加入 160g 吡啶,搅拌 20-30 分钟。滴加 240.0g 苯磺酰氯,搅拌 1-2 小时。
将 R1 反应釜内温调至 0- 10℃搅拌 1-2h.  然后内温调整至 25-35℃,搅拌 8- 16 小时。然后 R1 反应釜内温不超过35℃,往内缓慢加入 160g 工艺水。将 R1 反应 釜静止后,分出上层水相,下层有机相每次用 160g 10%柠檬酸水溶液洗涤 1-2 次,再用 160g 7% NaHCO3 水溶液洗涤,有机相常压外温蒸馏至 60-70℃浓缩掉 DCM ,浓缩残余继续水泵减压蒸馏,加热油温 60-90℃ ,蒸馏柱头馏出温度为 35-45℃得到巴豆腈 72.0g,GC 纯度 99.5%(反式巴豆腈 99. 1%,顺式巴豆腈 0.3%,总纯度 99.4%) 摩尔收率 91.3%。
实施例  3
向 R1 反应釜中加入 400gDCM,搅拌时加入 100.0g 巴豆酸,加入 1.0gDMF, 并将 R1 反应釜内温调至 0- 10℃ ,并控制内温在 0- 10℃ ,缓慢滴加 176g 氯化亚砜,滴加完搅拌 2-3 小时。
向 R2 反应釜中加入 475g 25%氨水溶液,内温调至 0-5℃ 。在 0- 10℃下,将 R1 反应釜内物料缓慢滴加到 R2 反应釜中。并搅拌 1-2 小时。
R2 在 0- 10 ℃下搅拌20-30min,抽真空除去部分氨气 10-20 分钟,并在 0- 10 ℃ 下 R2 反应釜内物料离心。滤饼用少量冰水洗涤后在 60-70℃下干燥得到白色中 间体巴豆酰胺 86g,  收率 87.0%。
向 R1 反应釜加入 420g DCM 搅拌分散,搅拌时加入 80.0g 巴豆酰胺。R1 反 应釜内温调整至 0- 10℃,加入 160g 吡啶,搅拌 20-30 分钟。滴加 208.0g 苯磺酰氯,搅拌 1-2 小时。
将 R1 反应釜内温调至 0- 10℃搅拌 1-2h;然后内温调整至 25-35℃,搅拌 8- 16 小时。然后 R1 反应釜内温不超过35℃,往内缓慢加入 160g 工艺水。将 R1 反应 釜静止后,分出上层水相,下层有机相每次用 160g 10%柠檬酸水溶液洗涤 1-2 次,再用 160g 7% NaHCO3 水溶液洗涤,有机相常压外温蒸馏至 60-70℃浓缩掉 DCM ,浓缩残余继续水泵减压蒸馏,加热油温 60-90℃ ,蒸馏柱头馏出温度为 35-45℃得到巴豆腈 70.0g,GC 纯度 99.5%(反式巴豆腈 99.0%,顺式巴豆腈 0.5%, 总纯度 99.5%) 摩尔收率 88.8%。
实施例  4
向 R1 反应釜中加入 500g DCM,搅拌时加入 100.0g 巴豆酸,加入 1.0gDMF, 并将 R1 反应釜内温调至 0- 10℃ ,并控制内温在 0- 10℃ ,缓慢滴加 180g 氯化亚砜,滴加完搅拌 2-3 小时。
向 R2 反应釜中加入 480g 25%氨水溶液,内温调至 0-5℃ 。在 0- 10℃下,将 R1 反应釜内物料缓慢滴加到 R2 反应釜中,并搅拌 1-2 小时。
R2 在 0- 10 ℃下搅拌20-30min,抽真空除去部分氨气 10-20 分钟,并在 0- 10 ℃ 下 R2 反应釜内物料离心。滤饼用少量冰水洗涤后在 60-70℃下干燥得到白色中 间体巴豆酰胺 90g,  收率 91.0%。
向 R1 反应釜加入 450g DCM 搅拌分散,搅拌时加入 80.0g 巴豆酰胺。R1 反 应釜内温调整至 0- 10℃,加入 136g 吡啶,搅拌 20-30 分钟。滴加 200.0g 苯磺酰氯,搅拌 1-2 小时。
将 R1 反应釜内温调至 0- 10℃搅拌 1-2h;然后内温调整至 25-35℃,搅拌 8- 16 小时。然后 R1 反应釜内温不超过35℃,往内缓慢加入 160g 工艺水。将 R1 反应 釜静止后,分出上层水相,下层有机相每次用 160g 10%柠檬酸水溶液洗涤 1-2 次,再用 160g 7% NaHCO3 水溶液洗涤,有机相常压外温蒸馏至 60-70℃浓缩掉 DCM ,浓缩残余继续水泵减压蒸馏,加热油温 60-90℃ ,蒸馏柱头馏出温度为 35-45℃得到巴豆腈 68.0g,GC 纯度 99.5%(反式巴豆腈 99.3%,顺式巴豆腈 0.3%, 总纯度 99.6%) 摩尔收率 86.3%。
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员 应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说 明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进, 这些变化和改进均落入本发明保护的范围内。

Claims (6)

  1. 一种巴豆腈的制备方法,其特征在于,包括以下步骤:
    S1:将巴豆酸、二氯甲烷和催化量 DMF 混合,滴加氯化亚砜并搅拌反应, 反应结束,将反应物料滴加入氨水溶液中;反应结束,减压除去过量氨水;反应 体系离心,滤饼洗涤干燥得到巴豆酰胺;
    S2:将巴豆酰胺加入二氯甲烷溶解,接着加入吡啶和苯磺酰氯反应;反应结束,加水淬灭,有机层柠檬酸水溶液洗,饱和碳酸氢钠水溶液洗,减压浓缩得到 巴豆腈成品。
  2. 根据权利要求 1 所述巴豆腈的制备方法,其特征在于:步骤 S1 中,巴豆酸、 DMF 、氯化亚砜与氨水摩尔比为 1 :0.009-0.01:1.60- 1.80:4.50-4.80。
  3. 根据权利要求 1 所述巴豆腈的制备方法,其特征在于:步骤 S1 和 S2 中,反 应温度为 0- 10℃。
  4. 根据权利要求 1 所述巴豆腈的制备方法,其特征在于:步骤 S1 中,滤饼采用 冰水洗涤,滤饼干燥温度在 60-70℃。
  5. 根据权利要求 1 所述巴豆腈的制备方法,其特征在于:步骤 S2 中,巴豆酰胺、 吡啶与苯磺酰氯摩尔比为 1 :1.5-2.0 :2.0-3.0。
  6. 根据权利要求 1 所述巴豆腈的制备方法,其特征在于:步骤 S2 中,淬灭时为 柠檬酸水溶液采用 10%柠檬酸水溶液。
PCT/CN2023/087084 2022-12-21 2023-04-07 一种巴豆腈的制备方法 WO2024130897A1 (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1170116A (fr) * 1954-02-19 1959-01-09 Pfizer & Co C Procédé pour préparer des nitriles organiques
CN108727224A (zh) * 2017-04-20 2018-11-02 株式会社Lg化学 药物合成用中间体的制备方法
CN111094237A (zh) * 2017-09-09 2020-05-01 诺沃梅尔公司 酰胺化合物和腈化合物及其生产与使用方法
CN112041298A (zh) * 2018-04-26 2020-12-04 株式会社Api 芳香族腈化合物的制造方法
CN115784929A (zh) * 2022-12-21 2023-03-14 浦拉司科技(上海)有限责任公司 一种巴豆腈的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1170116A (fr) * 1954-02-19 1959-01-09 Pfizer & Co C Procédé pour préparer des nitriles organiques
CN108727224A (zh) * 2017-04-20 2018-11-02 株式会社Lg化学 药物合成用中间体的制备方法
CN111094237A (zh) * 2017-09-09 2020-05-01 诺沃梅尔公司 酰胺化合物和腈化合物及其生产与使用方法
CN112041298A (zh) * 2018-04-26 2020-12-04 株式会社Api 芳香族腈化合物的制造方法
CN115784929A (zh) * 2022-12-21 2023-03-14 浦拉司科技(上海)有限责任公司 一种巴豆腈的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
METTERNICH JAN B., ARTIUKHIN DENIS G., HOLLAND MAREIKE C., VON BREMEN-KÜHNE MAXIMILIAN, NEUGEBAUER JOHANNES, GILMOUR RYAN: "Photocatalytic E → Z Isomerization of Polarized Alkenes Inspired by the Visual Cycle: Mechanistic Dichotomy and Origin of Selectivity", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 82, no. 19, 6 October 2017 (2017-10-06), United States, pages 9955 - 9977, XP093187114, ISSN: 0022-3263, DOI: 10.1021/acs.joc.7b01281 *
OLSON KRISTA M., STARKS COURTNEY M., WILLIAMS RUSSELL B., O'NEIL-JOHNSON MARK, HUANG ZHONGPING, ELLIS MICHAEL, REILLY JOHN E., ELD: "Novel Pentadecenyl Tetrazole Enhances Susceptibility of Methicillin-Resistant Staphylococcus aureus Biofilms to Gentamicin", ANTIMICROBIAL AGENTS AND CHEMOTHERAPY, vol. 55, no. 8, 1 August 2011 (2011-08-01), US , pages 3691 - 3695, XP093187118, ISSN: 0066-4804, DOI: 10.1128/AAC.00302-11 *
REN YANRONG: "Synthesis of Crotonic Nitrile Using Microwave Heating", CHEMICAL REAGENTS, vol. 34, no. 9, 1 January 2012 (2012-01-01), pages 853 - 855, XP093187082, DOI: 10.13822/j.cnki.hxsj.2012.09.023 *

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