CN101010291B - 有机阳离子的三氰基甲基化合物的制备方法 - Google Patents
有机阳离子的三氰基甲基化合物的制备方法 Download PDFInfo
- Publication number
- CN101010291B CN101010291B CN2005800284784A CN200580028478A CN101010291B CN 101010291 B CN101010291 B CN 101010291B CN 2005800284784 A CN2005800284784 A CN 2005800284784A CN 200580028478 A CN200580028478 A CN 200580028478A CN 101010291 B CN101010291 B CN 101010291B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- formula
- randomly
- charged ion
- alkaline earth
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/05—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing at least three cyano groups bound to the carbon skeleton
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/18—Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- 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
- C07D295/02—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 containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—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 containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
Abstract
本发明涉及基于通式I表示的三氰基甲烷盐的离子液体的制备方法以及基于该三氰基甲烷盐的离子液体,式中Q+是含有选自氮、磷、硫和氧的至少一个杂原子的有机阳离子。
Description
本发明涉及通式I表示的离子液体的制备方法
式中Q+是含有选自氮、磷、硫和氧的至少一个杂原子的有机阳离子。
通式I表示的离子液体是三氰基甲烷盐或三氰基甲基化合物。三氰基甲烷金属盐及其制备方法已公开在Schmidtmann,H.Ber.29,1896,1172和Trofimenko,S等人,J.Org.Chem.27,1962,433-438页中。另外,三氰基甲烷金属盐与有机配体的配合物公开在Batten,S.R.等人,Chem.Commun.1998,439-440页中。在按照Trofimenko等人的方法由二溴代丙二腈、氰化钾和溴化钾合成三氰基甲烷金属盐(如三氰基甲基化钾)时,形式上每摩尔三氰基甲基化合物与1.5摩尔Br2反应。
不同的三氰基甲烷盐例如还记载于EP-A0850921、US3981899、Jaeger.L.等人,Z.Anorg.allg.Chem.611,1992,62-72页、Cioslowski,J.等人,Chem.Phys.Lett.170,1990,297-300页、Elvidge,L.A.等人,J.Chem.Soc.Perkin Trans.1,8,1983,1741-1744页和Markhon’kov,D.I.等人,Zh.Org.Khim.15,1979,2441-2445页。但这里仅涉及固体。EP-A 0010396中公开了不同的液态三氰基甲基化铵,它们可用作杀真菌剂和除草剂。
有机阳离子盐具有低的蒸汽压,并通常具有低的熔点。当有机阳离子盐在室温下是液体时,它称为离子液体。近年来,离子液体已知为“绿色化学”的环境友好的溶剂。通过改变阴离子和阳离子可以影响离子液体的熔点以及用作溶剂的温度范围。目前有各种使用范围为-60℃至300℃的离子液体可供使用。
离子液体的有机阳离子通常是单价的季铵或鏻碱或者芳族且大多数含氮碱的阳离子。这些阳离子任选地被烷基、卤原子或氰基取代,且还含有磷、硫或氧之类的杂原子。常用的有机阳离子例如是咪唑鎓、恶唑鎓、吡嗪鎓、吡唑鎓、哒嗪鎓、吡咯烷鎓、嘧啶鎓、噻唑鎓和三唑鎓阳离子。咪唑鎓和吡咯烷鎓是最常用的。这些阳离子具有位于至少一个杂原子的电荷或位于环中心的电荷或位于配合物中的电荷。在本申请中,所有的描述方式都是相互等价使用的。
离子液体中的常用阴离子是乙酸根、AlCl4 -、AsF6 -、BF4 -、溴离子、CF3SO3 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、氯离子、CN-、FeCl3 -、NO3 -、pF6 -、丙酮酸根、草酸根或SCN-。最常用的是AlCl4 -、AsF6 -、BF4 -和PF6 -。
用于制备离子液体的原料例如可购自Merck KGaA,Darmstadt或IoLiTec,A.Bosmann,Dr.T.Schubert G.b.R.,Freiburg。
本发明的任务是提供一种制备三氰基甲基化合物的新的低成本方法。这种方法在使用后可对环境无害地清除垃圾。
这个任务可根据权利要求1加以解决。
据此要求一种通式I表示的离子液体的制备方法
式中Q+是选自如下通式表示的有机阳离子:
a)[WR1R2R3R4]+,式中W表示氮原子或磷原子,且
i)R1-R3各自独立地为C1-20烷基,R4为C1-20烷基、C3-10环烷基或C6-10芳基,其中R1-R4各自任选地含有一个或多个卤原子,或
ii)R1和R2与W一起形成5-7元环,且R3和R4各自独立地为C1-20烷基,其中R3和R4各自任选地含有一个或多个卤原子,或
iii)R1和R2以及R3和R4各自与W一起形成5-7元环,或
b)[NR5R6R7]+,式中N表示氮原子,R5和R6与N一起形成一个环,其中N形式上与R5和R6具有一个单键和双键,且R7为C1-20烷基、C3-10环烷基或C6-10芳基,其中R7任选地含有一个或多个卤原子,或
c)[SR8R9R10]+,式中S表示硫原子,且
i)R8和R9各自独立地为C1-20烷基,R10为C1-20烷基、C3-10环烷基或C6-10芳基,其中R8和R9各自任选地含有一个或多个卤原子,或
ii)R8和R9与S一起形成5-7元环,且R10为C1-20烷基、C3-10环烷基或C6-10芳基,其中R10各自任选地含有一个或多个卤原子或
d)[ZR11R12]+,式中Z表示氧或硫原子,R11和R12与Z一起形成一个环,其中Z形式上与R5和R6具有一个单键和双键,且
其中每一个由取代基R1-R12形成的环任选地连接一个或多个选自C1-20烷基、C3-10环烷基或C6-10芳基、卤素和氰基的取代基,其中C1-20烷基、C3-10环烷基和C6-10芳基各自任选地含有一个或多个卤原子,且
其中每一个由取代基R1-R12形成的环还任选地含有一个或两个选自氮、硫和氧的杂原子,和/或稠合另一个芳族或非芳族5-7元环,
该方法包括:
在碱的存在下,任选地在溶剂的存在下混合丙二腈与通式为RCN的氰基化合物,式中R选自氯、溴、碘和氰基,然后加入盐(Q+)nXn-,其中n=1或2,Q+如上定义,且Xn-是选自卤化物、拟卤化物、硫酸根和有机酸阴离子的阴离子,从而在水相中使阴离子Xn-与由丙二腈与RCN现场形成的三氰基甲基化合物阴离子进行交换。
在一个优选的方法变化形式中,丙二腈、氰基化合物RCN和盐(Q+)nXn-在碱的存在下,任选地在另一种溶剂的存在下在水相中混合,从而在单釜反应中形成和交换三氰基甲基化合物阴离子。
没有绝对必要规定丙二腈、氰基化合物RCN、碱和盐(Q+)nXn-的一定加料次序。实施例中加料次序在工艺流程中经受了考验,但在实验室中每一种其它加料次序同样能形成本发明的化合物。
不仅通式为RCN的氰基化合物,而且碱和/或通式为(Q+)nXn-的盐(式中R、Q+、Xn-和n如下所述)可以以纯的形式或以溶液形式使用,例如水溶液和/或甲醇溶液。
其它合适的溶剂和/或溶媒(Loesungsvermittler)可选自丙酮、乙腈、C1-4醇、氯仿、二氯乙烷、乙醚、DMSO、乙酸乙酯、己烷、二氯甲烷、碳酸亚丙酯、二硫化碳、THF、甲苯、二甲苯或其合适的混合物。优选使用可与水混合的溶剂。
在一个优选的实施方式中,氰基化合物RCN选自氯化氰、溴化氯和二氰,特别优选的是氯化氰或二氰。
在一个更优选的实施方式中,丙二腈与氰基化合物RCN的摩尔比为0.2∶1-2∶1,优选为0.9∶1-1.1∶1,更优选为0.95∶1-1.05∶1。
适用于本发明方法的碱选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、氨、伯胺、仲胺、叔胺。优选的碱是碱金属氢氧化物和碱土金属氢氧化物,特别优选的是氢氧化钠和/或氢氧化钾。
在一个优选的方法中,反应过程的pH值保持在大于4,优选大于7,更优选7-9。
适用作盐(Q+)nXn-的阴离子Xn-的卤离子可选自氟、氯、溴和碘。特别优选的是氯。
由至少两个电负性原子组成且化学性质与卤素相似的阴离子可用作盐(Q+)nXn-中的拟卤阴离子Xn-。拟卤阴离子优选选自CN-、OCN-、SCN-和N3-。特别优选的是CN-。
合适的有机酸阴离子例如是一元或二元非芳族酸和芳族酸的阴离子,如乙酸根、油酸根、富马酸根、马来酸根、丙酮酸根、草酸根和苯甲酸根,特别优选的是乙酸根和丙酮根。
在一个优选的方法中,形成的通式I三氰基甲烷盐(式中Q+如上所述)与未反应的原料化合物相分离,并通过萃取法提纯。
本发明方法可以形成氯化物含量很低的离子液体。
本发明方法的一个优点是可以制备基本上不含氯和钠的离子液体。
在上下文中,术语“C1-n烷基”表示含1-n个碳原子的直链或支链烷基。因此,C1-20烷基例如表示甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、1,4-二甲基戊基、己基、庚基、辛基、1,5-二甲基己基、壬基、癸基、4-乙基-1,5-二甲基己基、十一烷基、十二烷基、十三烷基、十四烷基或二十烷基之类的基团。
在上下文中,术语“C3-n环烷基”表示含有3-n个碳原子的环烷基。因此,C3-10环烷基例如表示环丙基、环丁基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基或环癸基之类的基团。
在上下文中,术语“C6-10芳基”表示含6-10个碳原子的芳基。因此,C6-10芳基例如表示苯基、苄基、甲基苯基、二甲基苯基、乙基甲基苯基、二乙基苯基或萘基之类的基团。
在上下文中,术语“C1-n烷氧基”表示含1-n个碳原子的直链或支链烷氧基。因此,C1-20烷氧基例如表示甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、戊氧基、1,4-二甲基戊氧基、己氧基、庚氧基、辛氧基、1,5-二甲基己氧基、壬氧基、癸氧基、4-乙基-1,5-二甲基己氧基、十一烷氧基、十二烷氧基、十三烷氧基、十四烷氧基或二十烷氧基之类的基团。
在上下文中,术语“卤素”表示氟、氯、溴或碘。
在一个优选的实施方式中,阳离子Q+含有至少一个5-7元芳环或非芳环。
在一个更优选的实施方式中,有机阳离子Q+中的芳环或非芳环还含有一至二个选自氮、硫或氧的杂原子。阳离子Q+更好还含有氮原子或硫原子。
更优选地,有机阳离子Q+中的芳环或非芳环含有选自C1-20烷基、C3-10环烷基或C6-10芳基、卤素和氰基的一个或多个取代基,其中C1-20烷基、C3-10环烷基和C6-10芳基各自任选地含有一个或多个卤原子。
在本发明方法中,阳离子Q+特别优选地选自有机铵、鏻和锍阳离子、吡咯烷鎓、吡咯鎓、吡唑鎓、吡唑鎓、咪唑鎓、三唑鎓、恶唑鎓、噻唑鎓、哌啶鎓、哌嗪鎓、吗啉鎓、吡啶鎓、哒嗪鎓、嘧啶鎓、吡嗪鎓、1,3-二恶鎓、吡喃鎓、噻喃鎓、氮鎓螺(azoniaspiro)和磷鎓螺(phosphoniaspiro)阳离子。
在另一个更优选的实施方式中,阳离子Q+选自N,N-二(C1-20烷基)-N,N-二甲基铵、N-(C6-10芳基)-N,N,N-三(C1-20烷基)铵、N,N-二(C6-10芳基)-N,N-二甲铵、四甲基鏻、四丁基鏻、三甲基锍、三丁基锍、1-(C1-20烷基)-1-甲基吡咯烷鎓、1-(C1-20烷基)-1,3-二甲基哌啶鎓、1-(C1-20烷基)-1-甲基咪唑鎓、1-(C1-20烷基)-3-甲基吡啶鎓、4,5-二甲基-2-(二苯基甲基)-1,3-恶唑鎓、2-(二苯基甲基)-4,5-二苯基-1,3-恶唑鎓、6-氮鎓螺[5.5]十二烷阳离子和5-磷鎓螺[4.4]壬烷阳离子。
通式I(Q+如上所述)的离子液体可任选地与一种或多种其它离子液体、水或有机溶剂(用作溶剂,特别是用作极性溶剂的组分)混合使用。特别合适的是,三氰基甲基化合物在电化学或电合成中可用作导电溶剂。在导电溶剂中,可以还原加入的导电盐或将其完全弃用。
基于三氰基甲基化合物的离子液体的极性低于常规的离子液体,但高于常规的有机溶剂,从而形成了新的应用范围。
基于三氰基甲基化合物的离子液体是较非极性的离子液体,与其它离子液体相比,它具有低的水溶性和低的粘度。
与许多其它离子液体相比,使用基于三氰基甲基化合物的离子液体的优点是在燃烧清除垃圾时不会产生含金属的残渣。用本发明方法得到的化合物具有特别低的卤化物含量。
如下实施例用于解释本发明,但不应对其进行限制。
实施例1:氯化1-丁基-1-甲基吡咯烷鎓
提供甲基吡咯烷(150克,1.76摩尔),并在室温下与丁基氯(163克,1.76摩尔)混合。将所得的反应混合物加热回流24小时(反应温度约为77℃),这样形成淡黄色悬浮液。然后将反应混合物冷却至室温,并进行过滤。残渣用少许MTBE洗涤,接着在50℃真空干燥,产生纯的氯化1-丁基-1-甲基吡咯烷鎓(27克,0.09摩尔,8.6%转化率)。反应混合物的剩余物质仅由未反应的原料甲基吡咯烷和丁基氯构成。这些原料可以完全回收。所得氯化1-丁基-1-甲基吡咯烷鎓的熔点为199.5℃.
1H-NMR(d6-DMSO):δ=3.50(m,4H),3.36(m,2H),3.02(s,3H),2.08(s br,4H),1.68(m,2H),1.33(sext,J=7.3Hz,2H),0.94ppm(5,J=7.6Hz,3H);
13C-NMR(d6-DMSO):δ=64.0(CH2),63.4(CH2),48.1(CH3),25.6(CH2),21.8(CH2),20.0(CH2),14.2ppm(CH3).
实施例2:三氰基甲基化1-丁基-1-甲基吡咯烷鎓
将丙二腈(17.8克,264毫摩尔)加入水(300毫升)中,在0-5℃向反应溶液中通入氯化氰(16.5克,0.268毫摩尔),在通入氯化氰过程中通过相应地加入30%氢氧化钠溶液把反应溶液的pH值保持在8.5。在通入氯化氰过程中把溶液的反应温度在0-5℃保持1小时左右。向反应混合物中加入氯化1-丁基-1-甲基吡咯烷鎓(47.5克,0.267毫摩尔)和水(150毫升)的混合物。分离有机相,水相用二氯甲烷萃取。合并的有机相用水(4×75毫升)萃取。有机相中加入活性炭(3克),在室温下搅拌30分钟。然后过滤有机相,用旋转蒸发仪在40-60℃进行浓缩(约500毫巴-20毫巴)。这样得到三氰基甲基化1-丁基-1-甲基吡咯烷鎓(46.8克,201毫摩尔,产率为76%,氯化物含量<0.1%。20℃时的粘度为33mPas。
1H-NMR(d6-DMSO):δ=3.44(m,4H),3.28(m,2H),2.98(s,3H),2.08(s br,4H),1.69(m,2H),1.32(sext,J=7.3Hz,2H),0.94ppm(t,J=7.6Hz,3H);
13C-NMR(d6-DMSO):δ=120.5(Cq),63.5(CH2),63.0(CH2),47.6(CH3),24.9(CH2),21.1(CH2),19.3(CH2),13.4(CH3),4.7ppm(Cq).
实施例3:三氰基甲基化1-丁基-3-甲基咪唑鎓
如实施例2所述,将氯化1-丁基-3-甲基咪唑鎓(43.1克,178毫摩尔)在水(100毫升)中的溶液加入丙二腈与氯化氰的混合物中,这样得到三氰基甲基化1-丁基-3-甲基咪唑鎓(33.6克,147毫摩尔,82%产率),其氯化物含量<0.1%,20℃时的粘度为30mPas。
1H-NMR(d6-DMSO):δ=9.05(s,1H),7.67(t,J=1.8Hz,1H),7.61(t,J=1.8Hz,1H),4.07(t,J=7.2Hz,2H),3.83(s,3H),1.80(t-sept,1J=12.4Hz,2J=1.8Hz,2H),1.26(t-sext,1J=7.5Hz,2J=1.8Hz,2H),0.89ppm(t,J=7.4Hz,3H);
13C-NMR(d6-DMSO):δ=136.5(CH),123.5(CH),122.2(CH),120.5(Cq),48.6(CH2),35.7(CH3),31.3(CH2),18.8(CH2),13.1(CH3),4.8ppm(Cq)。
实施例4:三氰基甲基化1-乙基-3-甲基咪唑鎓
如实施例2所述,将氯化1-乙基-3-甲基咪唑鎓(178.4克,1.22摩尔)在水(180毫升)中的溶液加入丙二腈(84.6克,1.28摩尔)与氯化氰(79.9克,1.30摩尔)的混合物中,这样得到的反应混合物不分相,如实施例2那样先用活性炭(3%)处理,然后用二氯甲烷(300毫升)萃取。有机相然后用水(2×200毫升)洗涤。在40-60℃用旋转蒸发仪浓缩(约500毫巴-20毫巴)后,得到169.5克(69%产率)三氰基甲基化1-乙基-3-甲基咪唑鎓,其氯化物含量和含钠量都<10ppm。
1H-NMR(d6-DMSO):δ=9.09(s,1H),7.72(t,J=1.7Hz,1H),7.64(t,J=1.7Hz,1H),4.21(t,J=7.4Hz,2H),3.86(s,3H),1.45ppm(t,J=7.4Hz,3H);
13C-NMR(d6-DMSO):δ=136.5(CH),124.4(CH),122.8(CH),121.7(Cq),45.4(CH2),36.7(CH3),15.8(CH3),6.7ppm(Cq)。
实施例5:三氰基甲基化1-丁基-3-甲基吡啶鎓
如实施例2所述,将氯化1-丁基-3-甲基吡啶鎓(939.6克,5.06摩尔)在水(813毫升)中的溶液加入丙二腈(351.0克,5.31摩尔)与氯化氰(333.1克,5.42摩尔)的混合物中,反应溶液分成两相。分离掉水相后,用二氯甲烷(1290毫升)进行萃取。合并有机相,用活性炭(3%)处理,然后用水(4×900毫升)洗涤。在40-60℃用旋转蒸发仪浓缩(约500毫巴-20毫巴)后,得到1118克(92%产率)三氰基甲基化1-丁基-3-甲基吡啶鎓,其氯化物含量和含钠量都<10ppm。
1H-NMR(d6-DMSO):δ=8.95(s,1H),8.87(d,J=6.1Hz,1H),8.40(d,J=8.0Hz,1H),8.01(t,J=7.1Hz,2H),4.53(t,J=7.4Hz,2H),2.49(s,3H),1.90(m,2H),1.29(t-sext,J=7.5Hz,2H),0.90ppm(t,J=7.4Hz,3H);
13C-NMR(d6-DMSO):δ=145.5(CH),144.4(CH),141.8(CH),138.7(C,q),127.2(CH),120.4(Cq),60.4(CH2),32.4(CH2),18.7(CH2),13.10(CH3),4.6ppm(Cq)。
实施例6:三氰基甲基化1-辛基-3-甲基吡啶鎓
如实施例2所述,将氯化1-辛基-3-甲基吡啶鎓(125.8克,520毫摩尔)在水(300毫升)中的溶液加入丙二腈(36.0克,534毫摩尔)与氯化氰(31.4克,537毫摩尔)的混合物中,反应溶液分成两相。分离掉水相后,用二氯甲烷(300毫升)进行萃取。合并有机相,用活性炭(3%)处理,然后用水(4×125毫升)洗涤。在40-60℃用旋转蒸发仪浓缩(约500毫巴-20毫巴)后,得到137.8克(89%产率)三氰基甲基化1-辛基-3-甲基吡啶鎓,其氯化物含量和含钠量都<100ppm。
1H-NMR(d6-DMSO):δ=8.96(s,1H),8.88(d,J=6.3Hz,1H),8.40(d,J=8.0Hz,1H),8.01(t,1J=8.2Hz,2J=6.2Hz,2H),4.52(t,J=7.4Hz,2H),2.49(s,3H),1.90(p,J=7.1Hz,2H),1.26(m,10H),0.83ppm(m,3H);
13C-NMR(d6-DMSO):δ=145.5(CH),144.4(CH),141.8(CH),138.7(Cq),127.2(CH),120.3(Cq),60.6(CH2),31.0(CH2),30.5(CH2),28.3(CH2),28.2(CH2),25.3(CH2),21.9(CH2),17.7(CH2),13.7(CH3),4.6ppm(Cq)。
Claims (9)
1.通式I表示的离子液体的制备方法
式中Q+是选自如下通式表示的有机阳离子:
a)(WR1R2R3R4)+,式中W表示氮原子或磷原子,且
i)R1-R3各自独立地为C1-20烷基,R4为C1-20烷基、C3-10环烷基或C6-10芳基,其中R1-R4各自任选地含有一个或多个卤原子,或
ii)R1和R2与W一起形成5-7元环,且R3和R4各自独立地为C1-20烷基,其中R3和R4各自任选地含有一个或多个卤原子,或
iii)R1和R2以及R3和R4各自与W一起形成5-7元环,或
b)(NR5R6R7)+,式中N表示氮原子,R5和R6与N一起形成一个环,其中N形式上与R5和R6具有一个单键和双键,且R7为C1-20烷基、C3-10环烷基或C6-10芳基,其中R7任选地含有一个或多个卤原子,或
c)(SR8R9R10)+,式中S表示硫原子,且
i)R8和R9各自独立地为C1-20烷基,R10为C1-20烷基、C3-10环烷基或C6-10芳基,其中R8和R9各自任选地含有一个或多个卤原子,或
ii)R8和R9与S一起形成5-7元环,且R10为C1-20烷基、C3-10环烷基或C6-10芳基,其中R10各自任选地含有一个或多个卤原子或
d)(ZR11R12)+,式中Z表示氧或硫原子,R11和R12与Z一起形成一个环,其中Z形式上与R5和R6具有一个单键和双键,且
其中每一个由取代基R1-R12形成的环任选地连接一个或多个选自C1-20烷基、C3-10环烷基或C6-10芳基、卤素和氰基的取代基,其中C1-20烷基、C3-10环烷基和C6-10芳基各自任选地含有一个或多个卤原子,且
其中每一个由取代基R1-R12形成的环还任选地含有一个或两个选自氮、硫和氧的杂原子,和/或稠合另一个芳族或非芳族5-7元环,
该方法包括:
在碱的存在下,任选地在溶剂的存在下混合丙二腈与通式为RCN的氰基化合物,式中R选自氯、溴、碘和氰基,然后加入盐(Q+)nXn-,其中n=1或2,Q+如上定义,且Xn-是选自卤化物、拟卤化物、硫酸根和有机酸阴离子的阴离子,从而在水相中使阴离子Xn-与由丙二腈与RCN现场形成的三氰基甲基化合物阴离子进行交换。
2.如权利要求1所述的方法,其特征在于在碱的存在下,任选地在另一种溶剂的存在下在水相中混合丙二腈、氰基化合物RCN和盐(Q+)nXn-,从而在单釜反应中形成和交换三氰基甲基化合物阴离子。
3.如权利要求1或2所述的方法,其特征在于丙二腈与氰基化合物RCN的摩尔比为0.2∶1-2∶1。
4.如权利要求1或2所述的方法,其特征在于所述的碱选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、氨、伯胺、仲胺、叔胺、吡啶和咪唑。
5.如权利要求1或2所述的方法,其特征在于,丙二腈与氰基化合物RCN的摩尔比为0.2∶1-2∶1,且所述的碱选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、氨、伯胺、仲胺、叔胺、吡啶和咪唑。
6.如权利要求1或2所述的方法,其特征在于反应过程的pH值保持在大于4。
7.如权利要求1或2所述的方法,其特征在于,反应过程的pH值保持在大于4,且所述的碱选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、氨、伯胺、仲胺、叔胺、吡啶和咪唑。
8.如权利要求1或2所述的方法,其特征在于所述的阴离子Xn-选自氯、溴和氰基。
9.如权利要求1或2所述的方法,其特征在于,所述的阴离子Xn-选自氯、溴和氰基,且所述的碱选自碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、氨、伯胺、仲胺、叔胺、吡啶和咪唑。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04020116.2 | 2004-08-25 | ||
EP04020116A EP1634867A1 (de) | 2004-08-25 | 2004-08-25 | Tricyanomethansalze organischer Kationen |
PCT/EP2005/009026 WO2006021390A1 (de) | 2004-08-25 | 2005-08-20 | Verfahren zur herstellung von tricyanomethaniden organischer kationen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101010291A CN101010291A (zh) | 2007-08-01 |
CN101010291B true CN101010291B (zh) | 2010-12-22 |
Family
ID=34926287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2005800284784A Expired - Fee Related CN101010291B (zh) | 2004-08-25 | 2005-08-20 | 有机阳离子的三氰基甲基化合物的制备方法 |
Country Status (7)
Country | Link |
---|---|
EP (2) | EP1634867A1 (zh) |
JP (1) | JP5019456B2 (zh) |
KR (1) | KR101198060B1 (zh) |
CN (1) | CN101010291B (zh) |
HK (1) | HK1106222A1 (zh) |
SG (1) | SG155204A1 (zh) |
WO (1) | WO2006021390A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200710070A (en) * | 2005-07-27 | 2007-03-16 | Nippon Catalytic Chem Ind | Solvent for reaction and production method using the same |
KR101375675B1 (ko) * | 2006-07-27 | 2014-03-19 | 니치콘 가부시키가이샤 | 이온성 화합물 |
CA2694473C (en) * | 2007-08-16 | 2013-10-01 | Harald Strittmatter | Process for preparation and purification of alkali metal and alkaline earth metal tricy anomethanides |
BRPI0914748A2 (pt) * | 2008-07-01 | 2015-10-20 | Merck Patent Gmbh | aplicação de líquidos iônicos contendo ânions de tricianometida como solvente para extrair alcoóis de soluções aquosas |
ES2442915T3 (es) | 2009-02-02 | 2014-02-14 | Lonza Ltd | Nuevos tricianoboratos |
EP2465849A1 (en) | 2010-12-08 | 2012-06-20 | Lonza Ltd. | 3-cyanopyridinium tricyanomethanides as ionic liquids |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3981899A (en) * | 1968-07-25 | 1976-09-21 | The United States Of America As Represented By The Secretary Of The Army | Triaminoguanidine cyanoformate |
EP0010396A1 (en) * | 1978-10-24 | 1980-04-30 | Fbc Limited | Fungicidal and herbicidal compositions, certain cyanomethane and cyanoethene derivatives being active agents thereof, the preparation of these derivatives and methods for combating fungi and weeds |
EP0850921B1 (fr) * | 1996-12-30 | 2002-09-25 | Centre National De La Recherche Scientifique (Cnrs) | Matériaux à conduction ionique comprenant un composé ionique dérivé du malononitrile et leurs utilisations |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4152773B2 (ja) | 2003-03-03 | 2008-09-17 | 日信工業株式会社 | ブレーキペダルの操作量に対応した操作フィーリングを演出するブレーキ操作量検出装置 |
-
2004
- 2004-08-25 EP EP04020116A patent/EP1634867A1/de not_active Withdrawn
-
2005
- 2005-08-20 EP EP05772429A patent/EP1786761A1/de not_active Withdrawn
- 2005-08-20 WO PCT/EP2005/009026 patent/WO2006021390A1/de active Application Filing
- 2005-08-20 CN CN2005800284784A patent/CN101010291B/zh not_active Expired - Fee Related
- 2005-08-20 KR KR1020077005968A patent/KR101198060B1/ko not_active IP Right Cessation
- 2005-08-20 JP JP2007528711A patent/JP5019456B2/ja not_active Expired - Fee Related
- 2005-08-20 SG SG200905311-7A patent/SG155204A1/en unknown
-
2007
- 2007-10-31 HK HK07111748.5A patent/HK1106222A1/xx not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3981899A (en) * | 1968-07-25 | 1976-09-21 | The United States Of America As Represented By The Secretary Of The Army | Triaminoguanidine cyanoformate |
EP0010396A1 (en) * | 1978-10-24 | 1980-04-30 | Fbc Limited | Fungicidal and herbicidal compositions, certain cyanomethane and cyanoethene derivatives being active agents thereof, the preparation of these derivatives and methods for combating fungi and weeds |
EP0850921B1 (fr) * | 1996-12-30 | 2002-09-25 | Centre National De La Recherche Scientifique (Cnrs) | Matériaux à conduction ionique comprenant un composé ionique dérivé du malononitrile et leurs utilisations |
US6576159B1 (en) * | 1996-12-30 | 2003-06-10 | Hydro-Quebec | Malononitrile-derivative anion salts, and their uses as ionic conducting materials |
Also Published As
Publication number | Publication date |
---|---|
EP1786761A1 (de) | 2007-05-23 |
JP5019456B2 (ja) | 2012-09-05 |
HK1106222A1 (en) | 2008-03-07 |
SG155204A1 (en) | 2009-09-30 |
CN101010291A (zh) | 2007-08-01 |
KR101198060B1 (ko) | 2012-11-07 |
WO2006021390A1 (de) | 2006-03-02 |
EP1634867A1 (de) | 2006-03-15 |
JP2008510753A (ja) | 2008-04-10 |
KR20070047347A (ko) | 2007-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101010291B (zh) | 有机阳离子的三氰基甲基化合物的制备方法 | |
CN102300631A (zh) | 新型三氰基硼酸盐 | |
US4173616A (en) | Extraction of copper values from aqueous solution | |
CN107004906B (zh) | 含镁电解液 | |
Belhocine et al. | Azepanium ionic liquids | |
Beer et al. | Anion recognition by acyclic redox-responsive amide-linked cobaltocenium receptors | |
JP5583899B2 (ja) | イオン性化合物の製造方法 | |
Holm et al. | Preparation and N-Alkylation of 4-Aryl-1, 2, 4-triazoles | |
Buvaylo et al. | Hybrid organic–inorganic chlorozincate and a molecular zinc complex involving the in situ formed imidazo [1, 5-a] pyridinium cation: Serendipitous oxidative cyclization, structures and photophysical properties | |
Anderson et al. | Unusual variations in the incidence of Z′> 1 in oxo-anion structures | |
Yang et al. | Structural insights into the coordination and selective extraction of copper (II) by tertiary amine ligands derived from 2-aminomethylpyridine | |
Beer et al. | A ferrocene functionalised macrocyclic receptor for cations and anions | |
Harada et al. | Preparation and redox chemistry of novel carbonato-bridged cobalt (II) complexes with 1, 4, 8, 11-tetrakis (2-aminoethyl)-1, 4, 8, 11-tetraazacyclotetradecane and 1, 4, 8, 11-tetrakis (pyridylmethyl)-1, 4, 8, 11-tetraazacyclotetradecane | |
Amoroso et al. | Functionalisation of terpyridine complexes containing the Re (CO) 3+ moiety | |
Ohashi et al. | Effect of hydrophobic substituent on solvent extraction of copper (II) with 5-alkyloxymethyl-8-quinolinol or 5-dialkylaminomethyl-8-quinolinol and separation of copper (II) | |
Yoshida et al. | Progress in paramagnetic ionic liquids | |
Weiner et al. | Et3P+-and nitro-substituted pyridines and bipyridines. Their behavior as ligands in iron (II), cobalt (II), and ruthenium (II) complexes | |
EP0080478B1 (en) | N-hydroxyethylated macrocyclic polyamines, the preparation of such amines and their use | |
Schmittel et al. | Tris (1, 10‐phenanthroline) iron (II) Complexes—Broad Variation of the Redox Potential by 4, 7‐Substitution at the Phenanthroline Ligands [1] | |
Balamurugan et al. | Supramolecular architectures with ladder and lamellar topologies using metal-ligand coordination units via C–H··· Cl and O–H··· Cl hydrogen bonding | |
Novikova et al. | Neutral Mo 6 Q 8-clusters with terminal phosphane ligands–a route to water-soluble molecular units of Chevrel phases | |
Usón et al. | Mono-, bi-, and tri-nuclear bis (diphenylphosphino) methane gold complexes. Crystal and molecular structures of [bis (diphenylphosphino) methane] bis (pentafluorophenyl) gold (III) perchlorate and 1, 2; 2, 3-di-µ-[bis (diphenylphosphino) methane]-1, 3-dichlorotrigold (I) chlorotris (pentafluorophenyl) aurate (III) | |
Recatalá et al. | Dithiolene dimetallic molybdenum (V) complexes displaying intraligand charge transfer (ILCT) emission | |
Saad et al. | Co-ordination behaviour of a novel tristhiourea tripodal ligand; structural variations in a series of transition metal complexes | |
Mabrouk et al. | Coordination compounds of indium. Part 45. Indium (I) derivatives of aromatic diols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1106222 Country of ref document: HK |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1106222 Country of ref document: HK |
|
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101222 Termination date: 20150820 |
|
EXPY | Termination of patent right or utility model |