CN101137436B - 碱稳定性离子液体 - Google Patents

碱稳定性离子液体 Download PDF

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CN101137436B
CN101137436B CN2006800056693A CN200680005669A CN101137436B CN 101137436 B CN101137436 B CN 101137436B CN 2006800056693 A CN2006800056693 A CN 2006800056693A CN 200680005669 A CN200680005669 A CN 200680005669A CN 101137436 B CN101137436 B CN 101137436B
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ionic liquid
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CN101137436A (zh
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马丁·约翰·厄尔
乌特·弗勒利希
苏珊·哈克
苏哈斯·卡特戴尔
拉法尔·马尔钦·卢卡西克
埃瓦·博格尔
纳塔里拉·弗拉迪米罗夫纳·普莱科瓦
肯尼斯·理查德·塞登
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Queens University of Belfast
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Abstract

本发明涉及新型的碱稳定性离子液体及其在化学反应、特别是碱催化化学反应和包括使用强碱的反应中作为溶剂的应用。

Description

碱稳定性离子液体
本发明涉及离子液体，更具体而言，涉及新型的碱稳定性离子液体及其在化学反应中作为溶剂的应用。
在US6,552,232中描述了需要碱促进或催化的羟醛反应，其中使用1，2，3-三烷基咪唑鎓盐或1，3-二烷基咪唑鎓盐作为用于羟醛反应的溶剂和/或催化剂。US6,552,232还描述了咪唑鎓的合成及其应用。然而，1，2，3-三烷基咪唑鎓盐或1，3-二烷基咪唑鎓盐在碱性条件下不稳定，并且BF4和PF6阴离子在酸或碱的存在下分解成氢氟酸或氟化物。在US6,774,240和ACS论文集系列856，25页(其中举例说明了氢氧化咪唑鎓的不稳定性)中描述了咪唑鎓离子液体在碱性条件下的这种分解。
Davis(Chemistry Letters，2004，33，1072-1077)公开了碱性离子液体1-丁基-3-氨基丙基四氟硼酸盐与二氧化碳反应，并且所述氨基可以在化学过程中被化学结合到反应物上。公开的离子液体不是碱稳定性，因为它包含碱不稳定的咪唑环以及碱不稳定的四氟硼酸根阴离子。
Mateus，N.M.M.等在GreenChem.2003，347中描述了可以将一些咪唑鎓离子液体与碱结合使用，但是Aggarwal，V.K.等在Chem.Commun.2002，1612-1613中教导我们，因为咪唑鎓阳离子与在碱性条件下使用的试剂反应，因此咪唑鎓离子液体不适合碱催化反应(特别是Baylis-Hillman反应)。Earle，M.J.在ACS论文集华盛顿DC2001(M.J.Earle，Abstracts of Papers ofthe American Chemical Society，2001，221，161)也说明，因为如下所示的导致咪唑鎓阳离子改性的副反应，所以2-烷基化的咪唑鎓离子液体不适合碱催化反应。
Figure S06805669320070824D000011
2-烷基咪唑鎓离子液体在碱的存在下的反应
如在此所用的术语″离子液体″指能够通过熔化固体而制备，并且在如此制备时，只由离子组成的液体。离子液体可以衍生自有机盐。
离子液体可以由包含一种阳离子和一种阴离子的均相物质形成，或者可以由多于一种的阳离子和/或阴离子组成。因此，离子液体可以由多于一种的阳离子和一种阴离子组成。离子液体还可以由一种阳离子和一种或多种阴离子组成。因此，本发明的混合盐可以包括含有阴离子和阳离子的混合盐。
因此，总之，如在此所用的术语″离子液体″可以指由单一盐(一种阳离子种类和一种阴离子种类)组成的均相组合物，或者它可以指含有多于一种的阳离子和/或多于一种的阴离子的非均相混合物。
特别令人感兴趣的一类离子液体是熔点低于100℃的盐组合物的离子液体。这些组合物是在低于多种组分的各个熔点的温度下通常为液体的多种组分的混合物。
术语″碱″指具有与酸反应(中和)形成盐的能力的布朗斯台德碱。当溶解或悬浮于水时，碱的pH范围在7.0至14.0。
本发明描述了碱稳定性离子液体作为溶剂和在碱催化或促进的化学反应、分离或处理中的新应用。根据本发明，提供离子液体作为在碱催化或促进的化学反应中的溶剂的应用，所述离子液体由至少一种阳离子和至少一种阴离子组成，并且其特征在于所述离子液体是碱稳定性的。
离子液体的碱稳定性可以被定义成离子液体经受24小时的在25℃下与5MNaOD在D2O中反应的能力。
备选地，碱稳定性可以被定义成离子液体经受24小时的在25℃下与1MNaOCD3在DOCD3中反应的能力。
作为另一种选择，碱稳定性可以被定义成离子液体经受24小时的在25℃下与PhMgBr在THF中反应的能力。
优选地，根据本发明的碱稳定性离子液体可以经受24小时的在25℃下与5MNaOD在D2O中的反应和24小时的在25℃下与1MNaOCD3在DOCD3中的反应。
还更优选地，根据本发明的碱稳定性离子液体可以经受与上面详述的所有试剂的反应。
本发明的离子液体由下式表示：
[Cat+][X-]
其中：Cat+是选自铵、鏻、硼鎓(borate)、吡唑鎓、DBU和DBN中的阳离子种类；并且
X-是磺酸根、次磷酸根或卤化物阴离子种类。
在一个实施方案中，Cat+选自[NR4]+、[BR4]+和[PR4]+；其中R相同或不同，并且独立地选自H、直链或支链C1至C18烷基和直链或支链C1至C18取代烷基，其中该取代基选自-OH；＝O；-O-；-NR′R″，其中R′和R″相同或不同，并且独立地选自直链或支链C1至C6烷基；并且其中两个相邻的R基团可以一起形成环。
更优选地，Cat+选自：
Figure S06805669320070824D000031
(去质子化形成甜菜碱)
其中：R如上述定义。
优选地，其中R相同或不同，并且独立地选自H、直链或支链C2至C18取代烷基和直链或支链C1至C18取代烷基，其中取代基选自-OH；＝O；-O-；-NR′R″，其中R′和R″相同或不同，并且独立地选自直链或支链C1至C6烷基；并且其中两个相邻的R基团可以一起形成环。
还更优选地，Cat+选自：
还更优选地，Cat+选自：
Cat+还可以选自1，3，5三烷基吡唑鎓、1，2二烷基吡唑鎓和1，2，3，5四烷基吡唑鎓，并且优选选自：
Figure S06805669320070824D000042
此外，Cat+以选自：
Figure S06805669320070824D000043
而且，根据本发明，Cat+可以是：
Figure S06805669320070824D000051
其中：R如上述定义。
在本发明的离子液体中，X-优选选自[NTf2]、[OTf]、[R-SO3]、[R2PO2]、[F]、[Cl]、[Br]和[I]；其中R是C1至C18烷基或C1至C18芳基，优选C1至C6烷基或C1至C6芳基。
还更优选地，X-选自[Me-SO3]、[Ph-SO3]和[Me-Ph-SO3]。
碱催化化学反应中可以包含碱，所述碱选自碱金属、碱土金属、普通金属、有机金属化合物、格氏试剂、烷基锂有机金属化合物、碱金属氢氧化物和碱土金属氢氧化物。
优选地，所述碱选自KOH、NaOH、Ca(OH)2、Li(NTF2)、KF/Al2O3和二异丙基氨基锂。
根据本发明，所述化学反应可以选自曼尼希(Mannich)反应、罗宾逊(Robinson)成环、迈克尔(Michael)反应、赫克(Heck)反应、环氧化(epoxdation)、氢化、缩合、羟醛反应、酯交换、酯化、水解、氧化、还原、水合、脱水、取代、芳族取代、加成(包括羰基加成)、消除、聚合、解聚、低聚、二聚、偶联、电环化、异构化、卡宾形成、差向异构作用、反转(inversion)、重排、光化学反应、微波辅助反应、热反应、声化学反应和歧化反应。
在Cat+是铵或鏻时，化学反应优选选自曼尼希反应、罗宾逊成环、环氧化、氢化、缩合、羟醛反应、水解、氧化、还原、水合、脱水、取代、芳族取代、消除、聚合、解聚、低聚、二聚、异构化、卡宾形成、差向异构作用、反转、重排、光化学反应、微波辅助反应、热反应、声化学反应和歧化反应。
本发明还提供由下式表示的碱稳定性离子液体：
[Cat+][X-]
其中：Cat+是选自硼鎓、吡唑鎓、DBU和DBN中的阳离子种类；并且X-是磺酸根或次磷酸根阴离子种类。
通过使用离子液体作为反应介质(即溶剂)，可以实现产物的简化的分离或纯化，并且减少或消除挥发性溶剂。
与常规的溶剂体系不同，这些液体具有低蒸汽压、可调的极性和性能以及高的热稳定性。根据离子片段的选择，可以将反应环境设计成以最有效率的方式适应化学过程的催化和分离。通过组合碱催化和离子液体的优点，可以制备相对于现有催化剂体系而表现出选择性和再循环性的显著优点的催化剂介质。
所述离子液体还可以包含一种或多种阴离子或者备选的一种或多种阳离子的混合物。
所述离子液体还可以包含一种或多种由阳离子和阴离子组成的离子液体的混合物。
上面提及的反应通常可以在约1atm(大气压)至约1000atm(高压)的压力下进行。所述反应可以在宽的温度范围内进行，并且不受特别限制。通常反应温度在约-50℃至400℃的范围内，更典型地在0℃至250℃的范围内，如20℃至150℃。
本方案的羟醛缩合反应可以进行约0.01至1000小时，优选约0.1至100小时，并且最优选约1至10小时。
现在通过实施例并且参考下列附图进一步描述本发明，在附图中：
图1显示了N-烷基DMEA溴化物的熔点与烷基链长的关系；
图2显示了N，O-二烷基DMEA溴化物的熔点与链长的关系；
图3是在图1和2中公开的熔点之间的比较；和
图4显示了N-烷基DABCO溴化物(3a-j)的熔点随烷基链长增加的变化。
根据本发明的碱稳定性的离子材料的实例包括：
(A)卤化铵、磺酸铵、次磷酸铵和氨基铵(ammonium amide)。
(B)卤化鏻、磺酸鏻、次磷酸鏻和氨基鏻。
(C)卤化吡唑鎓、磺酸吡唑鎓、次磷酸吡唑鎓和氨基吡唑鎓。
(D)铵、鏻、第1族金属的四烷基硼酸盐。
(A)类铵盐
N，N-二甲基乙醇胺离子液体
Figure S06805669320070824D000071
N，N-二甲基-乙醇胺N-烷基-O-烷基-N，N-二甲基乙醇铵离子液体或
[N-烷基-O-烷基DMEA][X]-
R＝H，烷基。R′＝H、烷基，X＝阴离子
合成一系列铵盐以研究它们的碱稳定性。
更具体而言，由二甲基乙醇胺和烷基卤合成一系列二甲基乙醇胺盐和离子液体，随后将卤化物离子交换成其它阴离子。选择这些离子液体，原因是二甲基乙醇胺便宜、稳定，并且与类似的四烷基铵盐相比，氧的功能性将降低这些铵盐的熔点。发现这种材料是室温离子液体。
Figure S06805669320070824D000072
Figure S06805669320070824D000073
方案1.[NC3-OCODMEA][NTf2]的合成
二甲基乙醇胺的烷基化发生在氮原子。当使用至少两摩尔烷基化剂时，观察到氮和氧的二烷基化。注意：碱也是需要的。因此，合成一系列一烷基二甲基乙醇胺盐和二烷基二甲基乙醇胺盐(参见方案2)并且测定它们的熔点以发现这些盐中哪些是室温离子液体的最佳候选者。
Figure S06805669320070824D000081
Figure S06805669320070824D000082
方案2.二甲基乙醇胺离子液体的常规合成
如果需要不同的N-烷基和O-烷基，则可以用不同的烷基卤将方案2的第一步骤中的产物烷基化。这示于方案3中。
方案3.具有不同的N-和O-烷基的二甲基乙醇胺离子液体的合成
使用这种方法，合成两种等量的二甲基乙醇胺盐，其中一种含有两个在氧和氮原子上的己基，并且另一种含有N-辛基和O-丁基。这两种化合物[NC6-OC6DMEA]Br和[NC8-OC4DMEA]Br分别具有126℃和138℃的熔点。这表明这些盐的熔点明显受到结构的影响。尽管这两种化合物具有超过100℃的熔点(熔融盐)，但是该特征通过将阴离子改变为例如双三氟甲磺酰亚胺被降低，此时熔点恰好高于室温。
Figure S06805669320070824D000084
Figure S06805669320070824D000085
[NC6-OC6DMEA]Br和[NC8-OC4DMEA]Br的熔点
为了确定具有最低熔点的DMEA盐，由N-烷基溴化物和二甲基乙醇胺合成一系列溴化物。在图1中给出了通过DSC所测定的它们的熔点。可以看出，熔点最低值在C6区域，并且[NC3-DMEA]Br的值似乎是类似的。这种化合物在DSC图形中显示显著的多晶型现象。
Figure S06805669320070824D000091
[N-烷基DMEA]Br               [N，O-二烷基DMEA]Br
[N-烷基DMEA]溴化物和[N，O-二烷基DMEA]溴化物的结构
在图2和3中给出了二烷基-二甲基乙醇胺盐的熔点。可以看出，羟基烷基化的结果并没有显著提高熔点。以与溴化物类似的方法合成氯化物，并且发现该氯化物具有类似的熔点(90℃)。
Figure S06805669320070824D000092
[N-己基DMEA]Cl
Figure S06805669320070824D000093
表1.乙基和丙基DMEA盐的熔点
将乙基和丙基DMEA溴化物转化为BF4、三氟甲磺酸盐和双三氟甲磺酰亚胺盐，并且测量它们的熔点。
DABCO离子液体
烷基卤与过量二氮杂双环[2，2，2]辛烷反应得到一系列碱稳定性(和碱性的)离子液体系列。
Figure S06805669320070824D000101
[CnDabco]Br
这些一烷基DABCO溴化物具有相当高的熔点，但是己基、辛基和癸基DABCO溴化物是离子液体(熔点<100℃)。还注意到C3化合物的熔点低于预期。根据DSC，分解温度全部在220-250℃的范围内。[C6DABCO]溴化物离子液体的熔点(95℃)下降到[C6DABCO][N(SO2CF3)2](3k)的25℃，[C6DABCO][N(SO2CF3)2]在该温度下形成凝胶(参见图4)。
还由DABCO和甲磺酸乙酯或甲磺酸己酯的反应合成甲磺酸乙基DABCO即[C2DABCO][OSO2CH3](31)(熔点：81℃)和甲磺酸己基Dabco(3m)。
典型的实验方法
[CnDABCO][Br]
将二氮杂双环-[2，2，0]-辛烯(1.13g，12.5mmol)和烷基溴(10mmol)在回流(或150℃，始终在这两者中较低的那个温度)下加热1至24小时。在冷却时，形成沉淀物。对于C2至C10DABCO溴化物，将这种沉淀物溶解于极少量沸腾的乙酸乙酯/异丙醇中，而对于C12至C18DABCO溴化物，将这种沉淀物溶于沸腾的甲苯/乙酸乙酯中。将在冷却时形成的晶体滤出并且通过在真空(1mmHg)下于80℃加热4小时干燥。通过NMR和DSC分析所述化合物。
产率典型为60-80％。
[CnDABCO][OSO2CH3]
将二氮杂双环-[2，2，0]-辛烯(1.13g，12.5mmol)和甲磺酸烷基酯(10mmol)在100℃下加热1小时。在冷却时，形成沉淀物。将这种沉淀物溶解于极少量沸腾的乙酸乙酯/异丙醇中。将在冷却时形成的晶体滤出并且通过在真空(1mmHg)下于80℃加热4小时干燥。通过NMR和DSC分析所述化合物。产率典型为70-80％。
[CnDABCO][N(SO2CF3)2]
将[C6DABCO]Br(2.75g，10.0mmol)和双三氟甲磺酰亚氨基锂(lithiumbisftifluoromethanesulfinimide)(3.15g，11mmol)各自溶于水(10cm3)中。将两种溶液混合，并且形成致密的离子液体相。使用二氯甲烷(3×10cm3)萃取这种离子液体相，通过Na2SO4干燥、过滤并且蒸发溶剂以得到在25℃变成液体的无色糊状物。通过在真空(1mmHg)下于80℃加热4小时干燥这种糊状物。采用NMR和DSC分析所述化合物。
TMEDA盐
如下由TMEDA和烷基溴合成四甲基乙二胺(TMEDA)离子液体。C2、C5、C6、C8、C12和C18烷基溴已经被制备并且显示出略低于DABCO离子液体的熔点。其中N＝5、6、8、10的[CnTMEDA]Br均是室温离子液体。
TMEDA离子液体的合成
[CnTMEDA]Br
将四甲基乙二胺(TMEDA)(2.32g，20mmol)和烷基溴(25mmol)在回流(或130℃，始终在这两者中较低的那个温度)下加热1小时，从而导致致密相的形成。使这种致密相冷却至室温。对于[C2TMEDA]Br和[C4TMEDA]Br，形成结晶固体，而对于[C18TMEDA]Br，形成液晶材料。将这些产物用环己烷洗涤并且在真空下干燥(在80℃、1mmHg下进行24小时)。产率典型为60-80％。
(C)类碱稳定性吡唑鎓离子液体
由毗唑化合物和烷基碘合成吡唑鎓离子液体是可行的，但却是相当昂贵的。遇到的主要难题是吡唑是差的亲核试剂，并且仅与反应性烷基化试剂缓慢反应。还观察到在吡唑的烷基化中的副反应导致离子液体的分解(方案4、5)。在溴化物盐的情况下，这种副反应发生在低至100℃的温度，并且致使使用烷基氯的烷基化不可行。使用碘化物的最大产率约为90％，使用溴化物为60-80％，并且使用氯化物为<5％。
Figure S06805669320070824D000121
方案4.在1-甲基吡唑鎓离子液体的合成中的副反应
为了战胜这些问题，发明了吡唑鎓离子液体的一种新合成以消除分解问题。使用的方法包括使烷基甲磺酸盐与吡唑反应以得到甲磺酸盐离子液体。使用这种方法，消除副反应不再是一个显著的问题。下面以方案6显示了重新设计的合成。
方案6.吡唑鎓离子液体的一种备选合成
这种新路线比烷基卤的方法更可靠、并且产率更高。在甲磺酸盐烷基化反应中的产率典型为95％。应该指出用于这种反应的原料必须是纯的。不这么做将导致产物的产率低得多和产物的分离步骤困难。在甲磺酸盐路线的情况下，即使在140℃下6天的反应时间之后，也没有观察到消除副产物。迄今，已经合成并且表征2-烷基-1，3，5-三甲基吡唑鎓甲磺酸盐，其中n＝2、3、4、5、6、8、10、12、14、16或18。
Figure S06805669320070824D000141
表2.各种甲磺酸酸盐的熔点(括号中的数字表示其它转变温度)。
通过DSC分析(表2)，将甲磺酸烷基-1，3，5-吡唑鎓盐的熔点与相应(equivalent)的1-烷基-3-甲基咪唑和1-烷基-2，3-二甲基咪唑盐进行比较。令人惊奇的是，吡唑鎓盐通常具有更低的熔点。
使用甲磺酸盐离子液体的一个优点在于：甲磺酸根阴离子是碱稳定性的，并且它很容易与其它阳离子交换。甲磺酸盐离子液体几乎全部是亲水性的。此外，甲磺酸根离子比目前通常用于离子液体的大多数其它阴离子更亲水。因此，将需要的阴离子的酸形式或钠盐加入到吡唑鎓甲磺酸盐在水的溶液中制备疏水离子液体或可以被萃取到有机溶剂如二氯甲烷中的离子液体。这是以方案7显示的。各种阴离子的2-己基-1，3，5-三甲基吡唑鎓盐的熔点或转变温度示于表3中，并且由EwaBogel-Lusawi使用这种方法合成。
Figure S06805669320070824D000142
方案7.甲磺酸盐离子液体到PF6离子液体的转变
Figure S06805669320070824D000151
表3.各种阴离子的2-己基-1，3，5-三甲基吡唑鎓盐的熔点或转变温度甲磺酸烷基-酯还可以用于离子液体[bmim][乳酸盐]的无氯化物合成。
DMAP离子液体
按如下由DMAP和甲磺酸烷基酯合成N，N-二甲基氨基吡啶(DAMP)离子液体。
Figure S06805669320070824D000152
新型DMAP离子液体的合成
将二甲基氨基吡啶(DMAP)(2.443g，20mmol)和乙基溴或己基溴(25mmol)在回流(或130℃，始终在这两者中较低的那个温度)下加热1小时。在冷却时，形成沉淀物。对于C2至C6DMAP溴化物，将这种沉淀物溶解于极少量的沸腾乙酸乙酯/异丙醇中。将在冷却时形成的晶体滤出并且通过在真空(1mmHg)下于80℃加热4小时干燥。通过NMR和DSC分析所述化合物。产率典型为60-80％。
将二甲基氨基吡啶(DMAP)(2.443g，20mmol)和甲磺酸乙酯或甲磺酸己酯(25mmol)在100℃下加热1小时。在冷却时，形成沉淀物。对于C2至C6DMAP甲磺酸盐，将这种沉淀物溶解于极少量的沸腾乙酸乙酯/异丙醇中。将在冷却时形成的晶体滤出并且通过在真空(1mmHg)下于80℃加热4小时干燥。通过NMR和DSC分析所述化合物。产率典型为80-85％。
其它离子液体
将氢化钠(60％在油中的分散体)(45mmol，1.80g)分批加入到N，N-二甲基乙醇胺(20mmol，1.78g)的THF(100cm3)溶液中。将得到的浆液在60℃加热1小时，然后冷却。分批加入1-(N-吗啉代)-2-氯乙烷盐酸盐(20mmol，3.72g)，并且将所述浆液在25°搅拌18小时。加入乙醇(10cm3)，随后加入水(100cm3)，并且使用二氯甲烷(3×50cm3)萃取产物。将二氯甲烷萃取物通过Na2SO4干燥，过滤并且通过旋转式蒸发器浓缩。将所述产物在110-120℃、1mmHg下进行Kugelrorh蒸馏以得到2.3g无色油(N-吗啉代乙基二甲基氨基乙基醚)。
碱催化反应
实施例1
曼尼希反应包括亚氨鎓盐(iminium salt)与烯醇化物或芳族化合物的相互作用。亚氨鎓盐通常由仲胺和甲醛生成。这种反应的一个实例在下面给出，并且该实例在100℃下1小时之后，得到相应的产率为85％的曼尼希碱。在水中的类似反应得到35％的产率。
Figure S06805669320070824D000171
离子液体可以用于提高氨甲基化反应(曼尼希反应)和相关反应中的产率和选择性以及速率。优选使用碱稳定性或碱性的离子液体。
因为许多离子液体例如[bmim][PF6]在碳酸盐的存在下不稳定，所以将改进的离子液体用于这种反应。该反应在离子液体如[(CH3)2C2C5N-CH2-CH2-OC2H5][N(SO2CF3)2]中进行，并且优选在碱稳定性离子液体如[bmim][NTf2]和[C2DBU][NTf2]中。
实施例II
离子液体在曼尼希反应中的应用是在反胺苯环醇(Tramadol，一种止痛药)的合成中。
Figure S06805669320070824D000172
外消旋反胺苯环醇
实施例III
另一个经典反应是罗宾逊成环反应。这种反应包括不饱和酮与酮的迈克尔反应，随后是内羟醛缩合。所述反应典型地在溶剂如醇中进行，并且在某些情况下，偶极非质子溶剂如DMF或DMSO是必需的。罗宾逊成环反应是两步反应，并且通常不分离中间体迈克尔产物。
Figure S06805669320070824D000181
[C2DBU][NTf2]的结构
Figure S06805669320070824D000182
上述罗宾逊成环反应在离子液体[C2DBU][NTf2]中进行。在室温下，迈克尔产物是在5分钟内以高产率得到的。这种反应显著快于在乙醇中进行的类似反应。在温度上升至80℃时，在离子液体中只发生羟醛缩合。
Figure S06805669320070824D000183
该反应在离子液体如[(CH3)2C2C5N-CH2-CH2-OC2H5][N(SO2CF3)2]中进行，并且优选在碱稳定性离子液体如[bmim][NTf2]和[C2DBU][NTf2]中。
实施例IV
环己酮与MVK的反应在室温下极快并且得到迈克尔产物。相应的环化慢，通过加热至80℃发生。
Figure S06805669320070824D000184
该反应在离子液体如[(CH3)2C2C5N-CH2-CH2-OC2H5][N(SO2CF3)2]中进行，并且优选在碱稳定性离子液体如[bmim][NTf2]和[C2DBU][NTf2]中。
实施例V
Figure S06805669320070824D000191
已知脯氨酸催化2-甲基环己1，3-二酮与MVK的反应，并且据报导在35℃的DMSO中得到产率为49％的成环产物(70％ee)。在[C2DBU][NTf2]中尝试这种反应。如同在离子液体中的前面的反应一样，迈克尔反应有效地进行。
该反应在离子液体如[(CH3)2C2C5N-CH2-CH2-OC2H5][N(SO2CF3)2]中进行，并且优选在碱较不稳定的离子液体如[bmim][NTf2]和[C2DBU][NTf2]中。
实施例VI
丙酮与异佛尔酮的缩合可以在碱稳定性离子液体中进行，该反应如下：
实施例VII
环己酮的缩合对于碱稳定性离子液体是更复杂的试验。
Figure S06805669320070824D000193
BSIL＝碱稳定性离子液体
实施例VIII
通过D2O交换实验[M.J.Earle，未公布的结果]，胆碱基的离子液体对强碱显示出优异的稳定性。因此，将它们用于该研究。当水是副产物时，该离子液体的疏水性可以进一步提高促进反应。通过使用常规的均相或异相催化剂，该缩合反应以中等至高产率提供需要的产物。此外，NMR光谱表明离子液体在反应后保持完整。
Figure S06805669320070824D000202
Figure S06805669320070824D000211
实施例IX-作为离子液体中的催化剂的仲胺
发现脯氨酸对于在离子液体中的取代苯甲醛和丙酮之间的羟醛反应是有效试剂。
Figure S06805669320070824D000212
在吡咯烷作为催化剂的情况下，该反应是很快的，然而，在离子液体的存在下，转化率和选择性都急剧降低。L-脯氨酸在有或没有离子液体时显示出几乎类似的活性。可以获得几乎全部的转化以及优异的选择性。最重要的是，脯氨酸可以在不损害活性或选择性的情况下以约4％的催化量进行使用。
Figure S06805669320070824D000221
^酮/醛的摩尔比＝2
*MDJ相关产物的组合选择性(3+4+5)
用于羟醛缩合的脯氨酸催化剂的活性
Figure S06805669320070824D000222
*离子液体[C2ODMEA][NTf2]
**MDJ相关产物的组合选择性(3+4+5)
在离子液体的存在下进行这种反应具有下列优点：
1.脯氨酸在离子液体中的溶解度高，因而体系可整个再循环
2.即使涉及除去产物的蒸馏，脯氨酸的分解也得到避免。
3.原料完全转化，因而没有未反应的原料的再循环。
因此，在离子液体中通过脯氨酸催化合成二氢茉莉酮的羟醛化学路线提供产率优异的MDJ-1。还可以通过催化蒸馏获得MDJ-2，并且可以被视为一锅煮合成。

Claims (30)

1.一种离子液体在碱催化的化学反应中作为溶剂的应用，其中所述离子液体由下式表示：
[Cat+][X-]
其中：Cat+是选自铵、吡唑鎓和DBN；并且
X-是四烷基硼酸根、磺酸根、次磷酸根、NTf2或卤化物阴离子种类；
此外，其中所使用的碱选自碱金属、碱土金属、有机金属化合物、格氏试剂、碱金属氢氧化物和碱土金属氢氧化物，并且其特征在于所述离子液体具有碱稳定性。
2.根据权利要求1所述的应用，其中碱稳定性被定义成所述离子液体经受24小时的在25℃下与5MNaOD在D2O中反应的能力。
3.根据权利要求1所述的应用，其中碱稳定性被定义成所述离子液体经受24小时的在25℃下与1M NaOCD3在DOCD3中反应的能力。
4.根据权利要求1所述的应用，其中碱稳定性被定义成所述离子液体经受24小时的在25℃下与PhMgBr在THF中反应的能力。
5.根据权利要求1所述的应用，其中所述有机金属化合物是烷基锂有机金属化合物。
6.根据权利要求1至5中任一项所述的应用，其中Cat+选自[NR4]+；其中R相同或不同，并且独立地选自H、直链或支链C1至C18烷基和直链或支链C1至C18取代烷基，其中取代基选自-OH；＝O；-O-；-NR′R″，其中R′和R″相同或不同，并且独立地选自直链或支链C1至C6烷基；并且其中两个相邻的R基团可以一起形成环。
7.根据权利要求6所述的应用，其中Cat+选自：
Figure FSB00000631518400011
其中：R相同或不同，并且独立地选自H、直链或支链C2至C18烷基和直链或支链C1至C18取代烷基，其中取代基选自-OH；＝O；-O-；-NR′R″，其中R′和R″相同或不同，并且独立地选自直链或支链C1至C6烷基；并且其中两个相邻的R基团可以一起形成环。
8.根据权利要求6所述的应用，其中Cat+选自：
Figure FSB00000631518400021
9.根据权利要求1至5中任一项所述的应用，其中Cat+选自1，3，5三烷基吡唑鎓、1，2二烷基吡唑鎓和1，2，3，5四烷基吡唑鎓。
10.根据权利要求9所述的应用，其中Cat+选自：
Figure FSB00000631518400022
11.根据权利要求1至5中任一项所述的应用，其中Cat+选自：
12.根据权利要求1至5中任一项所述的应用，其中Cat+是：
Figure FSB00000631518400032
其中R相同或不同，并且独立地选自H、直链或支链C1至C18烷基和直链或支链C1至C18取代烷基，其中取代基选自-OH；＝O；-O-；-NR′R″，其中R′和R″相同或不同，并且独立地选自直链或支链C1至C6烷基；并且其中两个相邻的R基团可以一起形成环。
13.根据权利要求1至5中任一项的应用，其中X-选自[NTf2]-、[OTf]-、[R-SO3]-、[R2PO2]-、[F]-、[C1]-、[Br]-和[I]-；其中R是C1至C6烷基或C6至C18芳基。
14.根据权利要求13所述的应用，其中X-选自[Me-SO3]-、[Ph-SO3]-和[Me-Ph-SO3]-。
15.根据权利要求1至5中任一项所述的应用，其中所述碱选自KOH、NaOH、Ca(OH)2、Li(NTf2)和二异丙基氨基锂。
16.根据权利要求1至5中任一项所述的应用，其中所述化学反应选自罗宾逊成环、氢化、缩合、羟醛反应、酯交换、酯化、水解、氧化、还原、水合、脱水、取代、加成、消除、聚合、解聚、偶联、电环化、异构化、卡宾形成、差向异构作用、反转、重排和歧化反应。
17.根据权利要求16所述的应用，其中所述加成包括羰基加成。
18.根据权利要求16所述的应用，其中所述取代包括曼尼希反应和芳族取代。
19.根据权利要求16所述的应用，其中所述聚合包括低聚。
20.根据权利要求16所述的应用，其中所述加成包括迈克尔反应。
21.根据权利要求1至5中任一项所述的应用，其中所述化学反应选自光化学反应、微波辅助反应、热反应和声化学反应。
22.根据权利要求16所述的应用，其中所述氧化包括环氧化。
23.根据权利要求19所述的应用，其中所述低聚包括二聚。
24.根据权利要求1至5中任一项所述的应用，其中Cat+是铵，并且所述化学反应选自罗宾逊成环、氢化、缩合、羟醛反应、水解、氧化、还原、水合、脱水、取代、消除、聚合、解聚、异构化、卡宾形成、差向异构作用、反转、重排和歧化反应。
25.根据权利要求24所述的应用，其中所述取代包括曼尼希反应和芳族取代。
26.根据权利要求24所述的应用，其中所述聚合包括低聚。
27.根据权利要求1至5中任一项所述的应用，其中Cat+是铵，并且所述化学反应选自光化学反应、微波辅助反应、热反应和声化学反应。
28.根据权利要求24所述的应用，其中所述氧化包括环氧化。
29.根据权利要求26所述的应用，其中所述低聚包括二聚。
30.一种由下式表示的碱稳定性离子液体：
[Cat+][X-]
其中：Cat+是选自吡唑鎓和DBN中的阳离子种类；并且X-是四烷基硼酸根、磺酸根或次磷酸根的阴离子种类。
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