CN1159802A - 季铵化氨基乙腈的制备 - Google Patents

季铵化氨基乙腈的制备 Download PDF

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CN1159802A
CN1159802A CN95195357A CN95195357A CN1159802A CN 1159802 A CN1159802 A CN 1159802A CN 95195357 A CN95195357 A CN 95195357A CN 95195357 A CN95195357 A CN 95195357A CN 1159802 A CN1159802 A CN 1159802A
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amine
methyl
quaternized
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CN1054849C (zh
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U·安尼恩
H-P·瑟尔曼-艾吉伯特
R·威德尔
R·穆勒
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton

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Abstract

下式所示的季铵化氨基乙腈的制备方法(见式I)该方法包括，将下式所示的胺Ⅱ与下式所示的单醛Ⅲa或二醛Ⅲb和氢氰酸或碱金属氰化物在水基介质中的反应以及随后进行的用下式所示的烷基化试剂Ⅳ的季铵化反应，其中胺Ⅱ与醛Ⅲ和氢氰酸或碱金属氰化物的反应和季铵化反应是在不需分离出中间产物下在水基介质中连续进行的。

Description

季铵化氨基乙腈的制备
本发明涉及通式I所示的季铵化氨基乙腈的一种改进制备方法其中R1和R2可以相同或不同，各自为含1-30个碳原子的脂肪族、环
脂族或芳脂族基团，R1和R2也可以和与它们相连的氮原子一
起构成可另外含有其它杂原子、可被苯并稠合的以及可带有烷
基侧基的饱和或不饱和的五元或六元杂环，以及R2也可以为
H，R3为C1-C4烷基或苄基，R4为H、含有一个或多个不相邻氧原子的C1-C20烷基，或下式
所示的基团
Figure A9519535700042
其中R5为一化学键或C1-C6亚烷基桥，和
XΘ为抗衡离子，该方法包括，将通式II所示的胺
Figure A9519535700043
其中R1和R2如前定义与通式IIIa所示的单醛或通式IIIb所示的二醛
R6-CHO    (IIIa)    OHC-R5-CHO    (IIIb)
其中R5如前定义和R6为H或C1-C20烷基和氢氰酸或碱金属氰化物在水基介质中进行反应，并随后用通式IV所示的烷基化试剂进行季铵化
R3-x        (IV)
其中R3如前定义和X为离去基团。
美国专利US-A 5 236 616(1)和US-A 5 281 361(2)公开了含有如下式所示结构单元的阳离子腈阳离子腈化合物，例如(CH3)3N-CH2CNClΘ，在此作为强吸湿性亦即对水敏感的物质，可很快从空气中吸收水分，易水解生成相应的酰胺。因此阳离子腈化合物一般都在无水有机溶剂例如无水乙腈(见专利(1)的实施例1(i))中制备。
本发明的一个目的在于提供阳离子腈化合物的一种制备方法或其配方，由此得到的产物对水不具有敏感性。
我们发现此目的可通过前面所述的方法而达到，其中胺II与醛III和氢氰酸或碱金属氰化物的反应和季铵化反应是在不需分离出中间产物、在水基介质中连续进行的。
由此得到的前述季铵化氨基乙腈I的水溶液，在一般条件下具有很好的稳定性，也就是不易发生水解反应。根据本发明而得到的季铵化氨基乙腈I的水溶液在温度至高40℃下贮存时，即使是几个星期后一般也没有发现水解产物的生成。
未季铵化的氨基乙腈I前体，在本发明的方法中未进行分离和纯化，有关它们的制备可参看德国专利DE-A 25 03 582(3)、DE-A 25 55 769(4)和DE-A 26 20 445(5)。
R1和R2基团各自优选为C1-C18烷基，特别优选是C2-C10烷基；更优选C3-C10环烷基，尤其是C5-C7环烷基；或特别优选C7-C20的芳脂基，尤其是C7-C12的苯基烷基。
R1和R2形成的杂环是那些除了氨基乙腈结构中的氮原子外，不含有或还含有一个或两个氮或氧杂原子的杂环。这种杂环优选不含有或含有一个或两个稠合的苯环结构。如果带有烷基侧基，烷基优选C1-C4烷基，特别是甲基或乙基。
在本发明方法中，依照R1和R2的特殊含义，以下列伯胺  或仲胺作为起始化合物，可以获得良好的结果：
甲胺、乙胺、正丙胺、异丙胺、正丁胺、异丁胺、仲丁胺、叔丁胺、戊胺、戊-2-胺、戊-3-胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、2，2，6-三甲基正戊胺、2-乙基戊胺、3-乙基戊胺、2，3-二甲基正丁胺、2，2-二甲基正丁胺、2-甲基戊胺、3-甲基戊胺、2，2，4-三甲基戊胺、2-甲基庚胺、3-甲基庚胺、4-甲基庚胺、2-乙基己胺、3-乙基己胺、2，2-二甲基己胺、2，3-二甲基己胺、2，4-二甲基己胺、2，5-二甲基己胺、3，3-二甲基己胺、3，4-二甲基己胺、2-甲基-3-乙基戊胺、3-甲基-3-乙基戊胺、2，2，3-三甲基戊胺、2，2，4-三甲基戊胺、2，3，3-三甲基戊胺、2，3，4-三甲基戊胺、2，2，3，3-四甲基丁胺；
二甲胺、二乙胺、二正丙胺、二异丙胺、二正丁胺、二异丁胺、二仲丁胺、二叔丁胺、二戊胺、二戊-2-胺、二戊-3-胺、二正己胺、二正庚胺、二正辛胺、二正壬胺、二正癸胺、二(2，2，6-三甲基正戊基)胺、二(2-乙基戊基)胺、二(3-乙基戊基)胺、二(2，3-二甲基正丁基)胺、二(2，2-二甲基正丁基)胺、二(2-甲基戊基)胺、二(3-甲基戊基)胺、二(2，2，4-三甲基戊基)胺、二(2-甲基庚基)胺、二(3-甲基庚基)胺、二(4-甲基庚基)胺、二(2-乙基己基)胺、二(3-乙基己基)胺、二(2，2-二甲基己基)胺、二(2，3-二甲基己基)胺、二(2，4-二甲基己基)胺、二(2，5-二甲基己基)胺、二(3，3-二甲基己基)胺、二(3，4-二甲基己基)胺、二(2-甲基-3-乙基戊基)胺、二(3-甲基-3-乙基戊基)胺、二(2，2，3-三甲基戊基)胺、二(2，2，4-三甲基戊基)胺、二(2，3，3-三甲基戊基)胺、二(2，3，4-三甲基戊基)胺，二(2，2，3，3-四甲基丁基)胺；
含有上述两种、但不同的基团的相应脂肪胺，例如甲基乙基胺；
环己胺、环戊胺、环庚胺、苄胺、苯基乙基胺；
二环己胺、二环戊胺、二环庚胺、二苄胺、二苯基乙基胺；
吡咯烷、Δ2-吡咯啉、Δ3-吡咯啉、吡咯、吡唑、吡唑啉、吡唑烷、咪唑烷、六亚甲基亚胺、3-咪唑啉、哌啶、哌嗪、二氢吲哚、吲哚、异二氢吲哚、异吲哚、吲唑、苯并咪唑、1，2，3，4-四氢异喹啉、咔唑、吩噁嗪、4-甲基咪唑、2-甲基吲哚、3-甲基吲哚、2-甲基哌嗪、3-甲基吡咯、2-甲基吡咯、2-乙基哌啶、2-甲基吡咯烷。
作为引入R3的烷基化试剂IV，其适宜的化合物优选硫酸二甲酯、硫酸二乙酯、甲基卤或乙基卤、碳酸二甲酯、碳酸二乙酯、甲苯磺酸甲酯、甲苯磺酸乙酯、甲磺酸甲酯、甲磺酸乙酯或苄基卤。在本发明中卤是指氯、溴或碘。相应的，优选的离去基团X或抗衡离子XΘ为CH3OSO3、C2H5OSO3、Cl、Br、I、CH3OCO2、C2H5OCO2、对甲苯磺酰和CH3SO3。相应的，优选的R3为甲基、乙基或苄基。
由醛类组分III衍生的R4基团优选为氢，相应地起始化合物IIIa则为甲醛。但化合物IIIa也可以是C2-C21的链烷醛，特别是C2-C7链烷醛，例如乙醛、丙醛或丁醛。如果选用二醛IIIb，如乙二醛、丙二醛、丁二醛、戊二醛、3-氧杂戊二醛或己二醛，在适当的化学计量比下一般得到两个氨基乙腈结构。
从专利(3)-(5)中可知道胺II与醛III和氢氰酸或碱金属氰化物在水溶液介质中生成未季铵化氨基乙腈I的反应。该反应一般在0-80℃温度下、优选20-65℃、最好为30-55℃以及大气压下进行。一般在4-6小时后反应进行完全。
随后的用烷基化试剂IV进行的季铵化反应一般也在同样的温度和压力范围内进行。
由胺II的反应和季铵化来制备产物I，该过程在本发明中是一“单容器反应”，在纯水中或水和与之相溶的有机溶剂如醇(如甲醇、乙醇或异丙醇)的混合溶剂中进行反应较为有利。在混合溶剂中，有机溶剂可占至混合溶剂总量的30％(重量)，优选可至多15％(重量)，最好为可至多5％(重量)。
实施例N-甲基哌啶鎓乙腈甲氧硫酸盐的制备
在一搅拌的容器中先加入341g(4mol)哌啶。在40℃下，在2小时内同时计量加入400g(4mol)30％(重量)浓度的甲醛水溶液和108g(4mol)氢氰酸。在40℃下继续搅拌1小时后，在此温度下快速加入504g(4mol)硫酸二甲酯并继续在40℃下搅拌反应2小时。所得的溶液中不再能够检测到硫酸二甲酯的存在。

Claims (4)

1.通式I所示的季铵化氨基乙腈的制备方法
Figure A9519535700021
其中R1和R2可以是相同或不同的，各自为含1-30个碳原子的脂肪族、
环脂族或芳脂族基团，R1和R2也可以和与它们相连的氮原子
一起构成可另外含有其它杂原子、可被苯并稠合的以及可含有
烷基侧基的饱和或不饱和的五元或六元杂环，以及R2也可以
为H，R3为C1-C4烷基或苄基，R4为H、含有一个或多个不相邻氧原子的C1-C20烷基，或下式
所示的基团
Figure A9519535700022
其中R5为一化学键或C1-C6亚烷基桥，和
XΘ为抗衡离子，该方法包括，将通式II所示的胺
其中R1和R2如前定义与通式IIIa所示的单醛或通式IIIb所示的二醛
R6-CHO    (IIIa)    OHC-R5-CHO    (IIIb)
其中R5如前定义和R6为H或C1-C20烷基和氢氰酸或碱金属氰化物在水基介质中进行反应，并随后用通式IV所示的烷基化试剂进行季铵化
R3-x        (IV)
其中R3如前定义和X为离去基团，其中胺II与醛III和氢氰酸与碱金属氰化物的反应和季铵化反应是在不需分离出中间产物、在水基介质中连续进行的。
2.权利要求1的季铵化氨基乙腈I的制备方法，其中R4为H。
3.权利要求1或2的季铵化氨基乙腈I的制备方法，其中使用的烷基化试剂IV为硫酸二甲酯、硫酸二乙酯、甲基卤或乙基卤、碳酸二甲酯、碳酸二乙酯、甲苯磺酸甲酯、甲苯磺酸乙酯、甲磺酸甲酯、甲磺酸乙酯或苄基卤。
4.权利要求1-3中任一项的季铵化氨基乙腈I的制备方法，其中胺II的反应和季铵化反应是在纯水中或水与可占至总溶剂量30％(重量)的与水相溶的有机溶剂组成的混合溶剂中进行的。
CN95195357A 1994-09-02 1995-08-17 季铵化氨基乙腈的制备 Expired - Fee Related CN1054849C (zh)

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