CN110922285B - 一种金属催化一锅法制备芳基伯酰胺的方法 - Google Patents

一种金属催化一锅法制备芳基伯酰胺的方法 Download PDF

Info

Publication number
CN110922285B
CN110922285B CN201911239052.3A CN201911239052A CN110922285B CN 110922285 B CN110922285 B CN 110922285B CN 201911239052 A CN201911239052 A CN 201911239052A CN 110922285 B CN110922285 B CN 110922285B
Authority
CN
China
Prior art keywords
reaction
aryl
aryl bromide
primary amide
solution
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.)
Active
Application number
CN201911239052.3A
Other languages
English (en)
Other versions
CN110922285A (zh
Inventor
王晓炜
姚炼滨
朱景仰
傅小勇
陈民章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai SynTheAll Pharmaceutical Co Ltd
Original Assignee
Shanghai SynTheAll Pharmaceutical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai SynTheAll Pharmaceutical Co Ltd filed Critical Shanghai SynTheAll Pharmaceutical Co Ltd
Priority to CN201911239052.3A priority Critical patent/CN110922285B/zh
Publication of CN110922285A publication Critical patent/CN110922285A/zh
Application granted granted Critical
Publication of CN110922285B publication Critical patent/CN110922285B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/06—Formation or introduction of functional groups containing nitrogen of amide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

本发明公开一种金属催化一锅法合成芳基伯酰胺的方法，是以芳基溴代物为原料，在钯催化剂作用下与氰源反应，由氰基取代芳环上的溴得到氰基芳烃，不经后处理，直接将碱的水溶液加入到反应液中，经过水解反应得到芳基伯酰胺。本发明与已有技术相比，由芳基溴代物制备芳基伯酰胺的方法，合成路线短、反应步骤少、操作简单、条件温和、转化率高、且毒性小具有工业化生产的潜力。

Description

一种金属催化一锅法制备芳基伯酰胺的方法
技术领域
本发明涉及化学合成领域，特别是涉及一种芳基伯酰胺的金属催化一锅法的制备方法。
背景技术
芳基伯酰胺是一种重要的化工中间体，也是一种非常重要的合成砌块，应用于很多医药中间体的合成。而且，酰胺基团的引入还可以改变芳基化合物的一些物理或生物学性能。
常用的芳基酰胺制备方法是以芳基卤代物为原料，与一氧化碳(CO)气体在金属催化剂作用下发生插羰反应，然后与胺类亲核试剂进行取代，多用于二级或三级酰胺的合成(Organometallics 2008,27,5402–5422)。据相关文献报道(Chem.Eur.J.2010,16,9750–9753)，芳基卤代物可在金属钯与配体的作用下，与CO和氨气(NH3)反应，直接生成芳基伯酰胺。其中CO和NH3毒性大，易燃易爆，使该反应受到限制。进一步研究发现，六甲基二硅氮烷(Tetrahedron Lett.1998,39,2835-2838)，叔丁胺(Org.Lett.2005,7,3327-3329)，苄胺(J.Org.Chem.2010,75,1841-1847)等试剂，可用来替代氨气，制备芳基伯酰胺，但均需要后处理或简单脱保护操作才能得到目标产物。
氰基芳烃在强酸或强碱条件下水解，也可用于制备相应的芳基伯酰胺。传统制备氰基芳烃的方法(Rosenmund-von Braun reaction)一般采用芳基卤代物为原料，与化学计量的氰化亚铜在高温150-250℃下进行反应，后处理操作繁琐，且产生大量重金属废物。采用过渡金属催化氰基化，是更加有效可靠合成氰基芳烃的方法，其中底物可为芳基卤代物或芳基磺酸，氰化钠，氰化钾以及氰化锌为常用的氰源(Chem.Soc.Rev.2011,40,5049-5067)，钯，铜，镍，铑均可做过渡金属催化剂。因所采用的氰源多为剧毒品，使该反应应用受限。近来，Beller等人报道可用更安全的铁氰化钾作为氰源，与芳基卤代物在钯催化下进行氰基化反应(Chem.Commun.2004,1388-1389)。
如何将过渡金属催化氰基化与碱水解连投，一锅法制备芳基伯酰胺，仍无文献报道，因此，该研究是一项富有挑战的工作。
发明内容
本发明所要解决的技术问题在于，提供一种利用过渡金属催化一锅法合成芳基伯酰胺的方法，能够克服芳基卤代物直接制备芳基伯酰胺的现有路线步骤较为繁琐的缺陷，同时还具有操作简单，条件温和，转化率高，且毒性小，具有工业化生产的潜力等优点。
为了解决上述技术问题，本发明采用的技术方案为：
一种金属催化一锅法合成芳基伯酰胺的方法，是以芳基溴代物(如式1化合物所示)为原料，在钯催化剂作用下与氰源反应，由氰基取代芳环上的溴得到氰基芳烃(如式2化合物所示)，不经后处理，直接将碱的水溶液加入到反应液中，经过水解反应得到芳基伯酰胺(如式3化合物所示)，其合成反应路线如下：
Figure BDA0002305686330000021
其中，所述R为一个或多个，所述R选自氢、烷基、氨基、酰基、甲氧基或硝基；当所述R为多个时，多个R之间可以是相同或不同；
所述氰源为提供氰基以取代芳基溴代物上的溴的反应试剂。
具体的，所述Ar为芳香环。优选为单环或双环的芳香环。更优选为苯基、吡啶基、吡喃基、嘧啶基、吡咯基、呋喃基、噻吩基、噻唑基、咪唑基。R与Br可以在同一环上，也可以在不同环上；R与Br可以在同一环上的邻位、间位或对位。
具体的，所述芳基溴代物选自溴代苯化合物或溴代杂环化合物中的一种。
具体的，所述方法包括以下步骤：
(a)将芳基溴代物、钯催化剂、配体和氰源依次加入到反应器中，加入有机溶剂与水作为混合溶剂，反应温度为90-110℃，反应时间为14-24h；其中，所述芳基溴代物与所述氰源摩尔比为1:0.5，所述芳基溴代物与所述钯催化剂摩尔比为1:0.01，所述芳基溴代物与所述配体摩尔比为1:0.02；
(b)将碱与水混合，配制成碱水溶液，加入到步骤(a)获得的反应液中，反应温度控制在25-30℃，反应时间控制在18-24h；所述芳基溴代物与所述的碱摩尔比为1:1.2；
(c)将步骤(b)的反应液，经硅胶柱分离制得芳基酰胺。
具体的，所述氰源选自三水合亚铁氰酸钾。
具体的，所述钯催化剂选自醋酸钯，三(二亚苄基丙酮)二钯或烯丙基氯化钯二聚体中的至少一种。
具体的，所述的配体选自2-二环己基磷-2'4'6'-三异丙基联苯，4,5-双二苯基膦-9,9-二甲基氧杂蒽，N,P-双齿配体或N,N-双齿配体中的至少一种。
具体的，所述的碱选择氢氧化钾或氢氧化钠中的至少一种。
具体的，所述的有机溶剂选自甲苯，1,4-二氧六环，N,N-二甲基乙酰胺或四氢呋喃中的一种
具体的，所述有机溶剂的量为1-20mL。
本发明的有益效果是：本发明以芳基溴代物为原料，在钯催化剂作用下与氰源反应，反应完毕后，加入碱水溶液水解氰基，一步实现从芳基溴得到芳基伯酰胺的转化。本发明与已有技术相比，由芳基溴代物制备芳基伯酰胺的方法，合成路线短、反应步骤少、操作简单、条件温和、转化率高、且毒性小具有工业化生产的潜力。
具体实施方式
下面将对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.26g(8mmol,1.0eq.)2-溴吡啶、1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体0.86g，收率88.0％。
所得产品，经高效液相色谱法，液质联用色谱仪和核磁分析,。分析条件：安捷伦1260液相色谱仪和紫外检测器，Eclipse Plus C18(50×4.6mm，1.8μm)色谱柱，流动相：A:0.05％甲酸水溶液，B:0.05％甲酸乙腈溶液。40℃，1.5mL/min下平衡，检测波长220nm。核磁：Bruker 400MHz.
实施例2
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.26g(8mmol,1.0eq.)3-溴吡啶，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体0.75g，收率76.8％。分析条件同实施例1
实施例3
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.26g(8mmol,1.0eq.)4-溴吡啶，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体0.69g，收率70.1％。分析条件同实施例1
实施例4
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.38g(8mmol,1.0eq.)2-溴-6-甲基吡啶，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体1.00g，收率91.6％。分析条件同实施例1
实施例5
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.38g(8mmol,1.0eq.)2-溴-3-甲基吡啶，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体1.02g，收率93.6％。分析条件同实施例1
实施例6
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.3g(8mmol,1.0eq.)溴苯，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体0.74g，收率75.8％。分析条件同实施例1
实施例7
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.38g(8mmol,1.0eq.)对溴甲苯，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体0.93g，收率85.6％。分析条件同实施例1
实施例8
在40mL反应瓶中，依次加入29.3mg(0.08mmol,0.01eq.)烯丙基氯化钯二聚体，92.6mg(0.16mmol,0.02eq.)4,5-双二苯基膦-9,9-二甲基氧杂蒽,10.1mL 1,4-二恶烷,1.62g(8mmol,1.0eq.)邻溴硝基苯，1.69g(4mmol,0.5eq.)三水合亚铁氰酸钾和5.1mL水中，调整并控制反应液温度95-105℃，搅拌18小时；反应完毕后，加入氢氧化钠水溶液[0.38g(9.6mmol,1.2eq.)氢氧化钠溶解于5.1mL水中]，调整并控制反应液温度35-45℃，搅拌3小时，用6M盐酸水溶液调整pH到7-8，在50℃减压蒸馏浓缩，得黄绿色固体，经柱层析(200-300目硅胶)分离得到淡黄色固体1.05g，收率79.0％。分析条件同实施例1
综上所述，上述各实施例仅为本发明的较佳实施例而已，并不用以限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，皆应包含在本发明的保护范围内。

Claims (3)

1.一种金属催化一锅法合成芳基伯酰胺的方法，其特征在于，以芳基溴代物（1）为原料，在钯催化剂作用下与氰源反应，由氰基取代芳环上的溴得到氰基芳烃（2），不经后处理，直接将碱的水溶液加入到反应液中，经过水解反应得到芳基伯酰胺（3），其合成反应路线如下：
Figure 940258DEST_PATH_IMAGE001
，
其中，芳基溴代物（1）选自2-溴吡啶、3-溴吡啶、4-溴吡啶、2-溴-6-甲基吡啶、2-溴-3-甲基吡啶、溴苯、对溴甲苯、邻溴硝基苯中的一种；
所述氰源为提供氰基以取代芳基溴代物上的溴的反应试剂，所述氰源为三水合亚铁氰酸钾；
所述钯催化剂为烯丙基氯化钯二聚体；所述方法包括以下具体步骤：
(a) 将芳基溴代物、钯催化剂、配体和氰源依次加入到反应器中，加入1,4-二氧六环与水作为混合溶剂，反应温度为90-110℃，反应时间为14-24 h；其中，所述芳基溴代物与所述氰源摩尔比为1:0.5，所述芳基溴代物与所述钯催化剂摩尔比为1:0.01，所述芳基溴代物与所述配体摩尔比为1:0.02；
(b) 将碱与水混合，配制成碱水溶液，加入到步骤(a)获得的反应液中，反应温度控制在25-30°C，反应时间控制在18-24 h；所述芳基溴代物与所述的碱摩尔比为1:1.2；
(c) 将步骤(b)的反应液，经硅胶柱分离制得芳基酰胺；
所述步骤（a）中的配体为4,5-双二苯基膦-9,9-二甲基氧杂蒽。
2.如权利要求1所述的方法，其特征在于，所述的碱选择氢氧化钾或氢氧化钠中的至少一种。
3.如权利要求1所述的方法，其特征在于，所述1,4-二氧六环的量为1-20 mL。
CN201911239052.3A 2019-12-06 2019-12-06 一种金属催化一锅法制备芳基伯酰胺的方法 Active CN110922285B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911239052.3A CN110922285B (zh) 2019-12-06 2019-12-06 一种金属催化一锅法制备芳基伯酰胺的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911239052.3A CN110922285B (zh) 2019-12-06 2019-12-06 一种金属催化一锅法制备芳基伯酰胺的方法

Publications (2)

Publication Number Publication Date
CN110922285A CN110922285A (zh) 2020-03-27
CN110922285B true CN110922285B (zh) 2022-08-23

Family

ID=69858038

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911239052.3A Active CN110922285B (zh) 2019-12-06 2019-12-06 一种金属催化一锅法制备芳基伯酰胺的方法

Country Status (1)

Country Link
CN (1) CN110922285B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115894361A (zh) * 2022-12-28 2023-04-04 上海合全药业股份有限公司 一种钯催化合成1-乙酰基-6-氰基-四氢喹啉的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002231694B2 (en) * 2000-12-14 2007-02-15 Biotage Ab Organic reactions with CO generating materials
US6958243B2 (en) * 2000-12-14 2005-10-25 Biotage Ab Organic reactions with CO generating materials
WO2010072632A1 (en) * 2008-12-24 2010-07-01 Syngenta Limited Methods for the preparation of aryl amides
CN102432488A (zh) * 2011-11-10 2012-05-02 江南大学 制备苯基酰胺类化合物的方法
CN102875276B (zh) * 2012-10-24 2015-04-08 大连理工大学 一种由芳基溴代物制备氰基芳烃的方法

Also Published As

Publication number Publication date
CN110922285A (zh) 2020-03-27

Similar Documents

Publication Publication Date Title
Kobayashi The new world of organic reactions in water
Shakhmaev et al. Stereoselective synthesis of allylamines by iron-catalyzed cross-coupling of 3-chloroprop-2-en-1-amines with grignard reagents. Synthesis of naftifine
CN110922285B (zh) 一种金属催化一锅法制备芳基伯酰胺的方法
Henry et al. One-pot ortho-amination of aryl C–H bonds using consecutive iron and copper catalysis
Boldrini et al. Pd-catalyzed allylative dearomatisation using Grignard reagents
Punna et al. Stille cross-coupling of secondary and tertiary α-(trifluoromethyl)-benzyl chlorides with allylstannanes
Singh et al. Facile synthesis of quinolines and N-alkylation reactions catalyzed by ruthenium (II) pincer type complexes: Reaction mechanism and evidences for ruthenium hydride intermediate
CN115417781B (zh) 一种制备氯虫苯甲酰胺中间体k胺的方法
CN111484436B (zh) 一种在吲哚c3位引入异戊烯基的方法
CN104649945A (zh) 一种磺酰脲类、磺酰胺基甲酸酯类化合物的制备方法
CN108503501B (zh) 一种合成2-氟代-n-取代芳基甲酰胺类化合物的方法
Bansal et al. Chemodivergent coupling of azoarenes with benzyl alcohols via a borrowing hydrogen strategy using a well-defined nickel catalyst
CN113004248B (zh) 一种钴催化碳氢胺化反应合成咔唑类化合物的方法
Marais et al. The development of a Cu (I)/pyrazolylpyridineamine catalyst system for the hydroxylation of aryl halides
Kalita et al. A three-component synthesis of homoallylic amines catalyzed by CuI
Yoon et al. Cu-Catalyzed electrophilic amination of internal alkynes via hydroalumination
KR20140038466A (ko) 2-알케닐아민 화합물의 제조방법
Suzuki et al. Intramolecular Aminotrifluoromethanesulfinyloxylation of ω-Aminoalkenes by CF3SO2Na/Pd (OAc) 2/PhI (OAc) 2/tBuOCl/PivOH System
García‐Viada et al. Pd‐Catalyzed δ‐C (sp3)− H Thiolation of Amino Acid Derivatives
CA2551412A1 (en) Transition metal complexes of n-heterocyclic carbenes, method of preparation and use in transition metal catalyzed organic transformations
CA3059585A1 (en) Process for the preparation of deuterated ethanol from d2o
EP3066064B1 (en) Cyclopropanation
CN110317160B (zh) 一种通过c-h活化磺酰胺化2-苯基异靛红的新方法
Qu et al. Chelation controlled reductive amination of cyclic ketones to trans-4-methoxycyclohexylamines: 9-BBN reduction mediated with FeCl3
CN107935882B (zh) 一种高立体选择性制备反式芳香叔胺偶氮类化合物的方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant