CN1156721A - 制备腈类的方法 - Google Patents

制备腈类的方法 Download PDF

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CN1156721A
CN1156721A CN96114461A CN96114461A CN1156721A CN 1156721 A CN1156721 A CN 1156721A CN 96114461 A CN96114461 A CN 96114461A CN 96114461 A CN96114461 A CN 96114461A CN 1156721 A CN1156721 A CN 1156721A
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amine
dehydrated
dehydration
oxazole
sulphur trioxide
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W·伯拉斯
H·帕林
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D Sm IP Assets Limited
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    • 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
    • C07D213/84—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
    • 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
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyridine Compounds (AREA)

Abstract

一种由酰胺脱水得到腈类的方法，包括在一种三氧化硫和一种胺的加合物作为脱水试剂存在下在一种碱性反应混合物中进行脱水。脱水试剂的胺尤其是一种叔胺，如一种脂肪族胺如一种三烷基胺或者一种含氮杂芳族化合物如吡啶或一种吡啶衍生物。例如，由此脂肪族的、芳香族的和杂芳族酰胺被脱水得到相应的腈类，例如，5-氨基甲酰基-4-甲基噁唑得到一种在吡哆素合成中有用的中间体5-氰基-4-甲基噁唑。

Description

制备腈类的方法
本发明涉及一种由相应的酰胺脱水制备腈类的新方法。
在过去的几年中已有数种由相应的酰胺脱水制备腈类的方法为人所知。例如，这些已知方法之一包括在五氧化二磷存在下进行脱水[T.Rinderspacher和B.Prijs，Helv.Chim.Acta，43，1522-1530(1960)]。然而，这一方法的缺点是由于在这一反应中非常容易发生碳化而造成产物的收率低。
本发明的目的是提供一种通过脱水由酰胺制备腈类的方法，根据本方法可在短的反应时间和温和的反应条件下以高收率得到腈。
根据本发明的方法包括在一种三氧化硫和一种胺的加合物存在下在一种碱性反应介质中进行脱水。这种加合物的胺尤其是一种叔胺。
脂肪族胺和含氮杂芳族化合物是形成这该三氧化硫-胺加合物的合适的胺类。
在本发明范围内的脂肪族胺中尤其可使用带含有1-20个碳原子的直链或支链烷基残基的三烷基胺。甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、正己基和正辛基是这样的烷基残基的例子。在这样的三烷基胺中，烷基残基可以是相同的或不同的。这些三烷基胺-以及同时优选的三烷基胺-的例子分别是三乙胺和二异丙基乙胺。
含氮杂芳族化合物尤其是含至少一个环上氮原子的杂环类。吡啶及吡啶的衍生物如甲基吡啶和喹啉是这样的例子。此类含氮杂芳族化合物也可被键合于聚合物载体上。在这些化合物中最优选的是吡啶。键合于一种聚合物载体上的吡啶的一个实例是聚(4-乙烯基吡啶)，它与三氧化硫的加合物有商品供应(Fluka Chemie AG，CH-9471 Buchs，Switzerland)。
在本发明的方法中使用三氧化硫-胺加合物作为脱水试剂由于具有可简单地从三氧化硫和胺的离析物中生产以及与三氧化硫单独使用时三氧化硫的腐蚀性相比较易操作的优点而有利。这些加合物部分是已知的而且在某些情况下有商品供应。它们可通过把三氧化硫导入如二氯甲烷这样的稀释剂所稀释的胺中而容易地产生。
对于脱水反应，酰胺与脱水试剂可顺利地在室温或在约120℃以内，优选在约50℃到约100℃，特别是在约70℃到约90℃的高温下反应。
脱水是在碱性反应介质中进行的。可使用与形成脱水试剂的胺相同的胺作反应介质。已经发现用三氧化硫-三乙胺加合物在三乙胺中进行脱水特别有利。如果需要，可用胺和一种有机溶剂的混合物作为反应介质，脂肪族或环状醚类如叔丁基甲基醚或分别如四氢呋喃或二噁烷、脂肪族腈类如乙腈、或者芳烃如甲苯是尤其合适的有机溶剂，但优选不使用任何有机溶剂。
当一种固体的酰胺反应时，那么该酰胺可顺利地被悬浮在这一碱性反应介质中。
酰胺与脱水试剂的合适的摩尔比为约1∶1到约1∶10，优选约1∶1到约1∶4，特别是约1∶1到约1∶2.5 。
为了得到粗产物，反应完成后可按照有机化学中使用的适当方法进行处理。例如，对于胺的分离，它可与氯化氢转化成盐酸盐，其中氯化氢可用稀盐酸(如25％的盐酸)，可用浓盐酸或甚至气体状态的氯化氢。粗产物也可通过蒸馏而分离。
本发明的方法使得腈类可在温和的反应条件以高收率从酰胺制得。它不仅适合于脂肪族酰胺的脱水，而且也适合于芳香族以及杂芳族酰胺的脱水。
例如，直链或支链的烷基酰胺如己酰胺可用作脂肪族酰胺。
2-萘甲酰胺、苯甲酰胺和取代的苯甲酰胺类，如4-氯苯甲酰胺或3，5-二氟苯甲酰胺例如可用作芳香酰胺。
烟酰胺例如可用作杂芳族酰胺。
本方法特别适合于制备5-氰基-4-低级烷基噁唑类如5-氰基-4-甲基噁唑，它是在吡哆素(维生素B6)的合成中有用的中间体。
下面的实施例更详细地说明本发明的方法，但并不表明任何限制。
                   实施例1
5-氰基-4-甲基噁唑的制备
a)脱水试剂：三乙胺-三氧化硫
200毫摩尔的5-氨基甲酰基-4-甲基噁唑与500毫摩尔的三乙胺-三氧化硫于200毫升三乙胺中的悬浮液在89℃搅拌6小时。
为了处理，反应混合物在冰浴中冷却至0℃后用150毫升甲基叔丁基醚处理。为了中和，滴加浓盐酸至pH值达到7。将产生的沉淀物过滤并用100毫升的甲基叔丁基醚洗涤。分离滤液各相并用每次50毫升甲基叔丁基醚萃取水相两次。有机相合并后以饱和碳酸氢钠溶液和饱和氯化钠溶液各洗涤一次，无水硫酸钠干燥并过滤。最后，滤液于40℃和500毫巴在旋转蒸发器上浓缩。产量：理论的93％，由气相色谱确定。
b)脱水试剂：二异丙基乙胺-三氧化硫
200毫摩尔的5-氨基甲酰基-4-甲基噁唑与500毫摩尔的二异丙基乙胺-三氧化硫于200毫升三乙胺中的悬浮液在89℃搅拌6小时。如a)所述进行处理。产量：理论的92％。
c)脱水试剂：吡啶-三氧化硫
200毫摩尔的5-氨基甲酰基-4-甲基噁唑与500毫摩尔的吡啶-三氧化硫于200毫升三乙胺中的悬浮液在89℃搅拌6小时。如a)所述进行处理。产量：理论的45％。
                   实施例2
                  己腈的制备
50毫摩尔的正己酰胺与125毫摩尔的三乙胺-三氧化硫于75毫升三乙胺中的悬浮液在89℃搅拌6小时。如实施例1a)所述进行处理。产量：理论的86％。
                    实施例3
                4-氯苄腈的制备
50毫摩尔的4-氯苯甲酰胺与125毫摩尔的三乙胺-三氧化硫于75毫升三乙胺中的悬浮液在89℃搅拌6小时。如实施例1a)所述进行处理。产量：理论的92％。
                    实施例4
               3，5-二氟苄腈的制备
10毫摩尔的3，5-二氟苯甲酰胺与25毫摩尔的三乙胺-三氧化硫于30毫升三乙胺中的悬浮液在89℃搅拌1小时。如实施例1a)所述进行处理。产量：理论的85.7％。
                    实施例5
                 萘-2-腈的制备
10毫摩尔的萘甲酰胺与25毫摩尔的三乙胺-三氧化硫于30毫升三乙胺中的悬浮液在89℃搅拌2小时。如实施例1a)所述进行处理。产量：理论的91％。
                    实施例6
               3-氰基吡啶的制备
10毫摩尔的烟酰胺与25毫摩尔的三乙胺-三氧化硫于30毫升三乙胺中的悬浮液在89℃搅拌2小时。如实施例1a)所述进行处理。产量：理论的95％。
                     实施例7
           5-乙氧基-4-甲基噁唑-2-腈的制备
10毫摩尔的5-乙氧基-4-甲基噁唑-2-甲酰胺与25毫摩尔的三乙胺-三氧化硫于30毫升三乙胺中的悬浮液在89℃搅拌6小时。如实施例1a)所述进行处理。产量：理论的76％。

Claims (11)

1.一种酰胺脱水制备腈类的方法，该方法包括在一种三氧化硫和一种胺的加合物作为脱水试剂存在下在碱性反应介质中进行脱水。
2.根据权利要求1的一种方法，其中脱水试剂的胺是一种叔胺。
3.根据权利要求2的一种方法，其中胺是一种脂肪族胺或一种含氮杂芳族化合物。
4.根据权利要求3的一种方法，其中脂肪族胺是一种其中每一个烷基残基包含1-20个碳原子的三烷基胺。
5.根据权利要求3的一种方法，其中杂芳族化合物是吡啶或一种吡啶衍生物。
6.根据权利要求1-5中任一项的一种方法，其中脱水在室温到约120℃，优选在约50℃到约100℃，特别是在约70℃到约90℃的温度下进行。
7.根据权利要求1-6中任一项的一种方法，其中酰胺与脱水试剂的摩尔比是1∶1到1∶10，优选1∶1到1∶4，特别是1∶1到1∶2.5。
8.根据权利要求1-7中任一项的一种方法，其中脂肪族酰胺被脱水。
9.根据权利要求1-7中任一项的一种方法，其中芳族酰胺被脱水。
10.根据权利要求1-7中任一项的一种方法，其中杂芳族酰胺被脱水。
11.根据权利要求10的一种方法，其中5-氨基甲酰基-4-甲基噁唑脱水得到5-氰基-4-甲基噁唑。
CN96114461A 1995-11-21 1996-11-13 制备腈类的方法 Expired - Fee Related CN1071311C (zh)

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CN102285902A (zh) * 2010-06-17 2011-12-21 刘�文 对(邻)氰基氯苄生产塔氯化工艺方法

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US5965764A (en) * 1997-08-06 1999-10-12 Toray Industries, Inc. Process for producing a nitrile
US20040028823A1 (en) * 2002-08-08 2004-02-12 Wilfried Dutt Multi-layer coating process to achieve a highly saturated color appearance on a vehicle
GB2462617A (en) 2008-08-13 2010-02-17 Hexcel Composites Ltd Curing agents and means of production using kaolin clay

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US2783264A (en) * 1955-03-21 1957-02-26 American Cyanamid Co Preparation of nitriles from amides
SU891650A1 (ru) * 1978-09-11 1981-12-23 Горьковский Политехнический Институт Им. А.А.Жданова Способ получени нитрилов карбоновых кислот
US4908452A (en) * 1987-12-21 1990-03-13 Merck & Co., Inc. Process for preparing nitriles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102285902A (zh) * 2010-06-17 2011-12-21 刘�文 对(邻)氰基氯苄生产塔氯化工艺方法

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DK0775691T3 (da) 2000-05-08
JP3964485B2 (ja) 2007-08-22
ATE189209T1 (de) 2000-02-15
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ES2143126T3 (es) 2000-05-01

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