CN103298342B - 制备烯胺的方法 - Google Patents

制备烯胺的方法 Download PDF

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CN103298342B
CN103298342B CN201180058178.6A CN201180058178A CN103298342B CN 103298342 B CN103298342 B CN 103298342B CN 201180058178 A CN201180058178 A CN 201180058178A CN 103298342 B CN103298342 B CN 103298342B
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tetramethyleneimine
methylsulfany
reaction
enamine
butyraldehyde
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D.C.布兰德
T.W.托伊赞
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Corteva Agriscience LLC
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    • 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
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    • 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
    • C07D295/08—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 singly bound oxygen or sulfur atoms
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    • C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
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    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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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Abstract

在以下文件中公开的本发明涉及制备烯胺的方法的领域，

Description

制备烯胺的方法
相关申请的交叉引用
本申请要求2010年12月3日提交的美国临时申请61/419,300的优先权。该临时申请的全部内容通过参考并入本申请。
技术领域
本文件中公开的本发明涉及制备烯胺的方法的领域。
背景技术
烯胺是非常有用的分子。它们已经用于多种反应，例如，亲电取代和加成，氧化和还原，和环加成(J.Kang，Y.R.Cho，and J.H.Lee，Bull.KoreanChem Soc.Vol.13，No.2，1992)。
制备烯胺的早期方法包括醛和酮与仲胺(C.Mannich and H.Davidsen，Ber.，69，2106(1936)的缩合反应。Mannich和Davidsen发现，醛与仲胺的缩合反应可以在接近0℃的温度在碳酸钾(K2CO3)的存在下进行，但是，酮与仲胺的缩合反应需要氧化钙(CaO)和升高的温度。之后，Herr和Heyl发现，该类型的缩合反应可以通过在与苯的共沸蒸馏过程中移除水(H2O)改善(M.E.Herr and F.W.Heyl，J.Am.Chem.Soc.，74，3627(1952)；F.W.Heyl and M.E.Herr，J.Am.Chem.Soc.，75，1918(1953)；M.E.Herr and F.W.Heyl，J.Am.Chem.Soc.，75，5927(1953)；F.W.Heyl and M.E.Herr，J.Am.Chem.Soc.，77，488(1955))。因为这些公开，已经披露了多种变型方法。通常，这些变型方法基于使用脱水试剂例如K2CO3，CaO，对-甲苯磺酸(TsOH)，三氟化硼二乙基醚化物(BF3-OEt2)，乙酸(AcOH)，硫酸镁(MgSO4)，氢化钙(CaH2)，四氯化钛(TiCl4)，和分子筛(参见以上J.Kang)。其它变型方法涉及在缩合反应过程中将水化学转化成其它物质(参见以上J.Kang)。制备烯胺的众多方法的详细总结讨论于“ENAMINES，Synthesis，Structure，and Reactions,”2ndEdition，Edited by A.G.Cook，Chap.2，(1988)。制备烯胺的方法的具体实例可以见以下文献：
美国专利3,074,940，其公开了某些醛与水形成共沸混合物，这可用于移除在某些烯胺缩合反应过程中形成的反应水；
美国专利3,530,120，其公开了在惰性气氛中用某些胂分子进行某些烯胺缩合反应；
美国专利5,247,091，其公开了在含水介质中进行某些烯胺缩合反应；
S.Kaiser，S.P.Smidt，and A.Pfaltz，Angew.Int.Ed.2006，45，5194-5197-参见支持信息低10-11页；和
WO 2009/007460 A2，参见第13页，实施例1.a。
烯胺例如1-(3-硫代丁-1-烯基)吡咯烷是制备某些新杀虫剂的有用中间体(参见，例如，美国专利公开2005/0228027和2007/0203191)。制备这样的硫代烯胺的目前已知方法无法有效制备这样的烯胺，由于多种原因--在防止硫代烯胺的热降解方面存在问题，同时使用的碳酸钾是有效的干燥剂，但是在大于实验室规模生产的过程中过滤这样的干燥剂是存在问题的。因此，需要一种方法，其可以在不使用固体干燥剂的情况下、或使用促进这样烯胺热降解的温度条件下在这些类型的缩合反应过程中移除水。
具体实施方式
通常，本文件中公开的方法可以在方案1中说明。
通常，本发明是一种方法，包括：
(A)在包含溶剂、胺和羰基化合物的反应区域中使它们反应，生成烯胺和H2O
(1)其中所述胺具有下式
其中R4和R5各自独立地选自C1-C8烷基，C3-C8环烷基，C2-C8烷氧基烷基，C7-C12芳基烷基，C2-C8烷基氨基烷基，芳基，和杂芳基，或者R4和R5与N共同表示5-元或6-元饱和或不饱和环；和
(2)其中所述羰基化合物(即醛或酮)具有下式
(a)其中R1和R2各自独立地选自C1-C8烷基，C3-C8环烷基，C2-C8烷氧基烷基，C7-C12芳基烷基，C2-C8烷基氨基烷基，芳基，和杂芳基，它们各自独立地取代有一个或多个S-R6，其中R6各自独立地选自C1-C8烷基，C3-C8环烷基，C2-C8烷氧基烷基，C7-C12芳基烷基，C2-C8烷基氨基烷基，芳基，和杂芳基，和
(b)其中R3选自H，C1-C8烷基，C3-C8环烷基，C2-C8烷氧基烷基，C7-C12芳基烷基，C2-C8烷基氨基烷基，芳基，和杂芳基；
(3)其中在所述反应区域中的所述反应在蒸馏条件下进行，所述蒸馏条件包括
(a)压力为约100帕斯卡(Pa)至约120,000Pa，和
(b)温度低于约、但是优选为低于在所述反应过程中所述烯胺的热分解温度；和
(4)其中所述溶剂最初包括非极性高沸点液体，极性高沸点液体，然后进一步包括从所述胺和所述羰基化合物的制备所述烯胺的缩合反应生成的H2O；和
(B)从所述反应区域移除蒸气相，其中所述蒸气相包括H2O。
约等摩尔量的所述胺和所述羰基化合物可以用于所述方法，但是也可以使用过量的一种或另一种。胺与羰基化合物的摩尔比为约0.9至约1.2，但是，稍微摩尔过量的胺与羰基化合物的比率是优选的，例如，摩尔比大于1但小于约1.1。
反应在初始包括以下物质的溶剂存在下进行：
(1)非极性高沸点液体，例如，烃液体，最优选为芳族烃液体，例如，苯，甲苯，或二甲苯。目前，甲苯是优选的液体；
(2)极性高沸点液体，例如，乙腈，乙醇；然后
(3)进一步包括由所述胺和所述羰基化合物的制备所述烯胺的缩合反应生成的H2O。
在本发明的另一种实施方式中，所述反应在蒸馏条件下进行，所述蒸馏条件包括：压力为约1000Pa至约60,000Pa，温度为约10℃至约80℃。
在本发明的另一种实施方式中，所述反应在蒸馏条件下进行，所述蒸馏条件包括：压力为约2500Pa至约30,000Pa，温度为约20℃至约70℃。
在本发明的另一种实施方式中，所述反应在蒸馏条件下进行，所述蒸馏条件包括：压力为约5000Pa至约15,000Pa，温度为约25℃至约65℃。在本发明的另一种实施方式中，当制备1-(3-甲基硫基-丁-1-烯基)-吡咯烷时，在所述反应过程中低于约1-(3-甲基硫基-丁-1-烯基)-吡咯烷的热分解温度的温度是优选的。
在这样的方法中优选的是，H2O在共沸条件下除去。也优选的是，没有干燥剂用于除去H2O。
在本发明的另一种实施方式中，R1和R2独立地为C1-C8烷基，C3-C8环烷基，它们各自独立地取代有一个或多个S-R6，其中R6各自独立地选自C1-C8烷基。
在本发明的另一种实施方式中，R3是H。
在本发明的另一种实施方式中，其中R4和R5各自独立地选自C1-C8烷基和C3-C8环烷基。在本发明的另一种实施方式中，R4和R5与N共同表示5-元或6-元饱和或不饱和环。
在本发明的另一种实施方式中，所述胺是吡咯烷，所述羰基化合物是3-甲基硫基-丁醛。在本发明的另一种实施方式中，所述烯胺是1-(3-甲基硫基-丁-1-烯基)-吡咯烷。
实施例
实施例仅针对说明目的，不应该理解为限制该文件公开的本发明为仅是这些实施例中公开的这些实施方式。
对比例：制备1-(3-甲基硫代丁-1-烯基)吡咯烷。
装备有短程蒸馏头的三颈250mL圆底烧瓶连接于包含干冰丙酮冷凝器的接收器烧瓶。向该反应容器装入19.8g(0.28mol)吡咯烷，然后装入70mL甲苯。将混合物在冰水浴中冷却，直至内部反应罐温度为约3℃。然后将真空(约3300Pa)施用于系统，然后将作为在甲苯中17.5wt％溶液的94.4g(0.14mol)的3-甲基硫代丁醛经注射器历时一小时连续添加到反应混合物中。在添加醛溶液的过程中，内部反应温度从3℃升至18℃。在醛添加过程中也收集蒸馏物。当添加完3-甲基硫代丁醛溶液之后，继续蒸馏另外50分钟(min)，直至内部罐温度达到26℃。这时，将真空调节至约2400Pa，继续蒸馏另外2.0min，直至内部罐温度达到24℃。停止蒸馏，用氮气保护反应容器。分离出反应性蒸馏底部物质，得到74.91g的1-(3-甲基硫代丁-l-烯基)吡咯烷，其为在甲苯中的28wt％黄色溶液。溶液混合物的质子(1H)NMR波谱分析(使用乙酸苄基酯作为内标)表明罐内收率为84％。
实施例1：制备1-(3-甲基硫代丁-1-烯基)吡咯烷。
向装备有机械搅拌、短程蒸馏头、和氮气保护的3-升三颈圆底烧瓶中装入61g(0.86mol)吡咯烷，然后装入100mL甲苯和200mL乙腈(按体积比33％甲苯在乙腈中)。将混合物在冰水浴中冷却，然后经添加漏斗历时130min连续添加在甲苯中的558g(0.78mol)的16.5wt％3-甲基硫代丁醛溶液。在添加醛的过程中，内部反应温度保持低于7℃。移开冰水浴，将约6600Pa的压力施加于系统。将反应混合物加热至15℃(罐温度)，这时开始在顶部收集蒸馏物。加热内部反应温度，直至罐温度达到33℃。蒸馏的总时间为约1小时。反应混合物用氮气保护，然后冷却至环境温度。共收集到282.4g顶部蒸馏物。收集反应蒸馏底部物质，得到在甲苯溶液中约25.0wt％的1-(3-甲基硫代丁-1-烯基)吡咯烷(收率为约89％，基于使用乙酸苄基酯作为内标的1H NMR波谱法)。

Claims (1)

1.一种制备1-(3-甲基硫基-丁-1-烯基)-吡咯烷的方法，所述方法基本上由如下步骤构成：
(A)在包含溶剂、吡咯烷和3-甲基硫基-丁醛的反应区域中使它们反应，生成1-(3-甲基硫基-丁-1-烯基)-吡咯烷和H2O，其中在所述反应区域中的所述反应在共沸蒸馏条件下进行，所述蒸馏条件包括
(1)压力为5000Pa至15,000Pa，和
(2)温度为25℃至65℃；
其中所述溶剂最初为甲苯和乙腈，然后和H2O，其中所述H2O由所述吡咯烷和所述3-甲基硫基-丁醛的制备所述1-(3-甲基硫基-丁-1-烯基)-吡咯烷的缩合反应生成，由此形成甲苯、乙腈和H2O的三元共沸物；和
(B)从所述反应区域移除蒸气相，其中所述蒸气相包括H2O；
其中所述方法中不采用干燥剂除H2O；且
其中所述方法中所述吡咯烷与3-甲基硫基-丁醛的摩尔比例大于1但小于1.1。
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