CN101239865A - 季碳上带有三氟甲基的有机化合物的制备 - Google Patents
季碳上带有三氟甲基的有机化合物的制备 Download PDFInfo
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Abstract
一种制备在季碳原子上带有三氟甲基的分子的方法,包括提供包含带有羧酸基团和吸电子基团的季碳原子的反应物;将该反应物与SF4在溶剂中发生反应,以三氟甲基取代羧酸基团,得到一种反应产物混合物,该反应产物混合物包含在季碳原子上带有三氟甲基的分子。
Description
技术领域
[0001]本发明涉及一种季碳原子上带有三氟甲基的有机化合物的制备方法。特别是可作为合成药物和液晶产品的中间体的所述有机化合物。
背景技术
[0002]制备三氟甲基(CF3)取代的有机化合物的新方法被广泛地重视。带有该结构的化合物已经应用于从染料、聚合体到药物和农用化学品的各种工业产品中。参见McClinton等人,“Trifluoromethylations and Related Reactons inOrganic Chemistry.”Tetrahedron 1992,48,6555。在药物和农用化学品领域,由CF3基团赋予的增加的亲脂性和水解稳定性,深远地影响了所述产品的生物学活性。另外,带有三氟甲基基团的有机化合物还被用作液晶显示器的组分。Paulwth等人,“Advanced Liquid Crystals for Television.”J.Mater.Chen.2004,14,1219。
[0003]虽然制备在1°碳或2°碳上带有三氟甲基的化合物的方法相对而言较为容易,但是在季碳上引入CF3基团仍是有机合成领域的一项挑战,并且只有几种方法能够实现这种转化。这些方法包括在多步骤方法中使用含有三氟甲基的构造单元或相对昂贵的三氟甲基化试剂。McBee等人描述了一种2-甲基-3,3,3-三氟丙烯与各种二烯反应制备1-三氟甲基-1’-甲基环己烯的狄尔斯-阿尔德反应(“Diels-Alder Reactions with Fluorine-containing Olefins.”J.Am.Chem.Soc.1955,77,915)。Hanzawa等人也报告了相似反应,其中使用2-烷氧羰基-1-三氟丙烯与二烯反应制备1-三氟甲基-1’-乙氧羰环己烯(“Constrution ofTrifluoromethylated Quaternary Carbons via Diels-Alder Reactions of2-(Trifluoromethyl)propenoic Acid Derivatives:Application to the Synthesis of16,16,16-Trifluororetinal.”J.Org.Chem.1991,56,1718)。Ruppert’s试剂,三氟甲基三甲基硅烷,已经被用于通过其与酮反应在有机化合物中引入三氟甲基基团,这是制备在季碳原子上带有CF3基团化合物的第一步,参见Blazejewski等人,“Radical allylation of trifuoromethylated xanthates:use of DEAD for removing theallyltributyltin excess.”Tett.Lett.2001,42,859。其它在有机化合物的季碳原子上引入CF3基团的方法包括将烷基胺与CF3NO2反应(Golitz等,“A New Method for theIntroducton of Trifluoromethyl Groups.”Chem.Int.Ed.Eng.1977,16,12,854),将负碳离子与s-(三氟甲基)二苯并噻吩盐(dibenzothiophenium salts)反应(Umemoto等,“New Method for Trifluoromethyl of Enolate Anions and Applications toRegio-,Diastereo-and Enantioselective Trifluoromethylation.”J.Org.Chem.1994,59,5692)以及将三氟甲基碘化物与烯胺反应产生α-三氟甲基酮,随后在带有CF3基团的碳原子上烷基化(Balko等,“Total synthesis of(±)8-trifluoromethylabscisic acid.”Tett.Lett.1999,40,6347)。
[0004]一种更加直接的合成在季碳原子上带有CF3基团的化合物的方法是将BrF3与二硫代碳酸酯在羧酸酯基团的α位置发生反应,参见Rozen等人,“α-Trifluoromethylation of Secondary and Sterically Hindered Carboxylates with Useof BrF3.”J.Org.Chem.2004,69,7241。Dmowski等人描述了一种将1,1-环己烷二羧酸与SF4反应制备1-氟甲酰基-1-三氟甲基环烷烃和1-三氟甲基-1-环己烷羧酸的方法(“Selective reactions of 1,1-cycloalkanedicarboxylic acids with SF4.A route to1,1-bis(trifluoromethyl)cycloalkanes,1-fluoroformyl-1-(trifluoromethyl)cycloalkanesand 1-(trifluoromethyl)-1-cycloalkanecarboxylic acids.”J.FI.Chem.2000,102,141)。
[0005]尽管有上述进展,仍需要提供制备在季碳原子上带有三氟甲基的有机化合物的新的方法。
[0006]所有在此引用的参考文献不仅包括参考文献本身,还包括这些参考文献所引用的文献。
发明内容
[0007]因此,本发明的第一个方面包括一种制备在季碳原子上带有三氟甲基的分子的方法,所述方法包括:
提供包含带有羧酸基团和吸电子基团的季碳原子的反应物;和
将反应物与SF4在溶剂中发生反应,用三氟甲基基团取代羧酸基团,提供一种反应产物混合物,该反应产物混合物中含有在季碳原子上带有三氟甲基基团的分子。
[0008]本发明的第三个方面包括一种制备在季碳原子上带有三氟甲基的分子的方法,该方法可用下述反应式表示:
其中:
(i)R1是吸电子基团,该吸电子基团选自(a)羧酸酯,COOR’,其中R’是未取代烷基、取代烷基、未取代芳基或1-20个碳原子的取代芳基;(b)NO2;(c)SOR,其中R是烷基或芳基;(d)SO2R,其中R是烷基或芳基;(e)POOR3,
其中R是烷基或芳基;(f)PR3,其中R是烷基或芳基;和(g)CN,以及
(ii)R3、R4是具有3-8个碳原子的环烷基,或者
(iii)R3和R4独立选自未取代烷基、取代烷基、未取代芳基或1-20个碳原子的取代芳基。
[0009]在此,我们记载了一种制备CF3取代的季碳的新方法。本发明的该方法用在溶剂中的SF4与带有吸电子基团的羧酸反应。在反应过程中,以好的收率得到三氟甲基取代的产物,该产物带有可进一步被修饰的取代基以制备多种可潜在用作药物或液晶化合物的产物。
[0010]下述反应式总结了本发明获得在季碳原子上带有三氟甲基基团的化合物的实施方案:
其中R1、R3和R4定义如下。
[0011]R1优选是吸电子基团,更优选地是羧酸酯,COOR’,其中R’是有或没有取代基的烷基或1-20个碳原子的芳基,包括杂原子,如O、N或S。在较少优选的实施方案中,R1不是吸电子基团。当R1不是吸电子基团时,产品的产量很低。例如,当R3、R4是4-(4’丙基环己基)环己烷,且R1不是吸电子基团时,包含CF3基团的产品的产量是5%,而当R1是COOCH3时,包含CF3基团的产品的产量是50%。
[0012]其它的合适的吸电子基团的非限制性实例包括NO2、SOR(其中R是烷基或芳基)、SO2R(其中R是烷基或芳基)、POOR3(其中R是烷基或芳基)、PR3(其中R是烷基或芳基)和CN。
[0013]在某些实施方案中,R3、R4是具有烷基、芳基和/或环脂族取代基的具有3-8个碳原子的环烷基。这些基团可进一步被例如但不限于含有或不含有杂原子取代基和卤素的烷基、芳基、环烷基(3-8个碳)和烷基环烷基取代基所取代,杂原子例如但取代基不限于O、S、N,卤素如Cl、F、Br、I。
[0014]在某些实施方案中,R3是含有或不含有杂原子取代基和卤素的烷基(至多20个碳原子)、芳基(至多20个碳原子),其中杂原子取代基例如但不限于O、S、N和卤素例如Cl、F、Br、I。
[0015]在某些实施方案中,R4是含有或不含有杂原子取代基和卤素的烷基(优选至多20个碳原子)、或芳基(优选至多20个碳原子),其中杂原子取代基例如但不限于O、S、N和卤素例如Cl、F、Br、I。
[0016]在某些实施方案中,与SF4反应的反应物由选自下列基团的结构式表示:
其中R’是C1-C10烷基,且R”是C1-C5烷基。
[0017]溶剂优选包含HF。其他适宜的溶剂包括但不限于醚类如二乙醚、THF、烃类如己烷及其组合。其他适宜的溶剂包括但不限于碳氟化合物如氟利昂113。优选溶剂不与SF4发生反应。
[0018]优选的反应温度范围为-78℃至100℃。
[0019]在某些实施方案中,反应时间从1分钟到5天,或者大约24小时。
[0020]最终产物可任选在进一步使用之前进行纯化,纯化采用标准的纯化方法,如重结晶、蒸馏或色谱。
[0021]任选地,带有CF3基团的碳上的吸电子取代基可通过它们的化学反应活性被转化成其它基团。方案1-3说明了酯官能团转化成其它基团的非限定性实例。
方案1
[0022]在方案1中,羧酸1被转变成三氟甲基衍生物2。然后酯2通过用氢化铝锂还原反应和1°醇的氧化被转化成醛3。醛上发生了维蒂希(wittig)反应后得到了乙烯基取代的产物4。
[0023]方案2给出了将酯基转变成其他基团的可替代方法。
方案2
[0024]羧酸1被转变成三氟甲基衍生物2。然后酯2通过用氢化铝锂还原和用1°醇的氧化被转化成醛。醛3与己基溴化镁反应形成醇6。
[0025]因此,在方案1和2中,本发明包括如下步骤:(1)提供一种包含与酯基处于偕位的羧基的反应物;(2)以三氟甲基取代羧基;(3)将酯转化成醛;以及(4)将醛转变成乙烯基取代的或醇取代的中间体。
[0026]在方案3中,酯官能团被转变成酮基。酯水解成酸7,随后转变成相应的酰基氯,8接下来与有机镁或有机铜酸盐试剂反应生成酮9。
方案3
[0027]因此,在方案3中,本发明包括以下步骤:(1)提供一种包含与酯基处于偕位的羧基的反应物;(2)以三氟甲基取代羧基;(3)将酯转变成酸;(4)将酸转变成酰基氯;(5)将酰基氯与有机金属试剂反应生成酮。
具体实施方式
实施例
[0028]以下更详细的实施例将进一步证明本发明,但是应理解本发明并不局限于所述实施例。
实施例1:
1-羧基-1-甲酯基-4(4’-丙基环己基)环己烷与四氟化硫的氟化反应
[0029]取4.2g 1-羧基-1-甲酯基-4(4’-丙基环己基)环己烷置于75mL的装备有磁力搅拌棒的Hoke圆筒中,将其用T形接头与减压装置、进口阀相连接。将Hoke圆筒抽真空并冷却到-78℃。在真空状态下将9.4g氟化氢和9.5摩尔当量的四氟化硫放入冷却的圆筒中。关闭圆筒上的进口阀,并将其加热至室温。在室温下搅拌反应24小时。抽去Hoke圆筒中的挥发物,残留物用二乙醚提取、碳酸氢钠中和。过滤混合物,浓缩、通过硅胶短柱,用2-4%的乙酸乙酣/己烷洗脱(体积/体积)。GC-MS色谱分析显示,具有四个产物峰,对应四个直立的/平伏的异构体,每个都具有分子离子峰(m/z=334)。蒸发溶剂后,反应产物2.0g。
实施例2:
1-三氟甲基-1-甲酯基-4-(4’-丙基环己基)环己烷与氢化铝锂的还原反应
[0030]在氮气存在的情况下,将200mg氢化铝锂置于干燥的100mL两颈圆底烧瓶中。将10mL无水四氢呋喃加入到烧瓶中,并将烧瓶放入冰水浴中冷至0℃。取1.45gl-三氟甲基-1-甲酯基-4(4’-丙基环己基)环己烷溶解于6mL无水四氢呋喃中,逐滴加入到反应烧瓶中。在0℃搅拌反应1小时,然后室温反应4小时。用二乙醚稀释反应混合物,并慢慢依次加入0.25mL水、0.25mL 15%的NaOH水溶液、0.75mL水。搅拌混合物过夜。过滤铝盐后,有机相用水洗涤两次,硫酸镁干燥,过滤、浓缩,得到1.0g产物。GC-MS色谱分析显示,具有3个不同的峰(大概第四个峰被其他三个峰中的一个掩盖了),属于直立/平伏的异构体,每个都具有分子离子峰(m/z=306)。
实施例3:
1-三氟甲基-1-羟甲基-4-(4’-丙基环己基)环己烷与铬酸酐/吡啶的氧化反应
[0031]在氮气存在的情况下,取1.0g铬酸酐置于干燥的两颈圆底烧瓶中。加入10mL无水二氯甲烷,然后加入1.7mL无水吡啶。在室温下搅拌混合物40分钟。将1.0gl-三氟甲基1-羟甲基-4-(4’-丙基环己基)环己烷加入6mL无水二氯甲烷中,并搅拌过周末。反应物用醚稀释,沉淀物用硅藻土过滤。有机相用稀盐酸洗涤两次,再分别用NaHCO3溶液和水洗涤一次,硫酸镁干燥,蒸发溶剂后得到产物0.59g。GC-MS色谱分析显示,各峰都具有一个分子离子峰(m/z=302)。
实施例4:
1-三氟甲基1-甲酰基-4-(4’-丙基环己基)环己烷的维蒂希反应
[0032]在氮气存在的情况下,取6.25g己基溴化置于干燥的两颈圆底烧瓶中。加入30mL无水四氢呋喃,冷却至-70℃。边搅拌边逐滴加入5.8mL的2.5M正丁基锂己烷溶液,所有的盐类均溶解形成橙色溶液。冷却水浴缓慢降温,将4.04gl-三氟甲基-1-甲酰基-4-(4’-丙基环己基)环己烷在10mL四氢呋喃中的溶液缓慢加入到烧瓶中,搅拌2小时。加入二乙醚,并且将反应混合物先用稀盐酸溶液洗涤,随后用饱和碳酸氢钠溶液洗涤。浓缩有机相,用己烷研磨。将该己烷溶液通过硅胶短柱,随后再用己烷洗涤。蒸发合并的己烷溶液后得到4.21g产物。GC-MS色谱分析显示分子离子峰(m/z=372)。
[0033]尽管已经参照特定的实施例详尽地描述了本发明,但不脱离本发明的精神和范围对其进行各种改变或修正对本领域技术人员来说是显而易见的。
Claims (17)
1.一种制备在季碳原子上带有三氟甲基的分子的方法,该方法包括:
提供包含带有羧酸基团和吸电子基团的季碳原子的反应物;和
将该反应物与SF4在溶剂中发生反应,以三氟甲基取代羧酸基团,得到一种反应产物混合物,该混合物包含在季碳原子上带有三氟甲基的分子。
2.如权利要求1所述的方法,其中所述吸电子基团为酯。
3.如权利要求1所述的方法,其中所述的溶剂包括选自HF、醚类、THF、烃和碳氟化合物中的至少一种。
4.如权利要求1所述的方法,其中所述的溶剂包括HF。
6.如权利要求1所述的方法,进一步包括通过重结晶、蒸馏和色谱法中的至少一种从反应产物混合物中纯化分子。
7.如权利要求1所述的方法,其中在反应步骤之后,吸电子基团被转化成选自醛、醇、酰基氯和烯烃的另一种基团。
8.如权利要求7所述的方法,其中吸电子基团是酯,该酯被转化成醛,该醛被进一步转化成醇。
9.如权利要求7所述的方法,其中吸电子基团是酯,该酯被转化成酸,该酸被转化成酰基氯,该酰基氯被转化成酮。
10.一种制备在季碳原子上带有三氟甲基和烷基的分子的方法,所述方法包括下述顺序的步骤:
提供包含带有羧酸基团和吸电子基团的季碳原子的反应物;
将反应物与SF4在溶剂中反应,以三氟甲基取代羧酸基团;且以烷基取代酯基,提供在季碳原子上带有三氟甲基和烷基的分子。
11.如权利要求10所述的方法,其中所述的溶剂包括选自HF、醚类、THF、烃和碳氟化合物中的至少一种。
12.如权利要求10所述的方法,其中所述的溶剂包括HF。
13.如权利要求10所述的方法,其中所述取代步骤包括将酯转化成醛,将醛转化成乙烯基-取代的或醇-取代的中间体,和将中间体氢化。
14.如权利要求10所述的方法,其中所述取代步骤包括将酯转化成酸,将酸转化成酰基氯,将酰基氯与有机金属试剂反应生成酮,和将酮中的羰基还原成亚甲基。
16.如权利要求15所述的方法,其中所述的溶剂包括选自HF、醚类、THF、烃和碳氟化合物中的至少一种。
17.如权利要求15所述的方法,其中所述的溶剂包括HF。
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