CN107417478B - 一种催化氧化羰基化合成不对称二取代脲的方法 - Google Patents
一种催化氧化羰基化合成不对称二取代脲的方法 Download PDFInfo
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Abstract
本发明公开了一种直接合成不对称二取代脲类化合物的新方法,在溶剂聚乙二醇或聚乙二醇的水溶液中,在碱、碘化物和氧化剂的作用下,加入钯催化剂,催化伯胺与一氧化碳的直接交叉偶联反应制备不对称二取代脲类化合物。本发明的偶联反应制备不对称二取代脲类化合物的方法,具有具有氧化剂来源广泛和环境友好;底物来源广泛、廉价和易于处理;羰基源稳定、廉价和不产生废物;反应无需配体且活性好;反应条件温和且选择性高;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收的优势。在优化的反应条件之下,目标产品分离收率可高达97%左右。
Description
技术领域
本发明属于催化合成技术和精细化学品合成领域,更具体地说,涉及一种催化合成不对称二取代脲类化合物的合成方法,是一种直接利用伯胺类化合物、一氧化碳为羰基源和空气或氧气为氧化剂来交叉偶联来制备不对称二取代脲的方法。
背景技术
不对称二取代脲的骨架结构广泛存在于天然产品、杀虫剂、除草剂和医药中,因其具有广泛的药理和生理活性,其合成方法已经引起了广泛的关注。传统合成不对称二取代脲的方法是基于光气的异氰酸酯法:虽然此反应产率较高,但是这种方法由于原料具有高毒性,并且反应中生成大量强腐蚀性和污染性的含氯废物,造成设备的严重腐蚀及产品后处理上的困难;同时,异氰酸酯的活性非常高,需要在无水、无氧、氮气保护氛围下进行反应,操作比较复杂(冯胜主编,《精细化工手册》,广东科技出版社,1995年,945页)。随着碳一化学的发展,直接利用一氧化碳的羰基化反应来合成取代脲的方法被发现并得到广泛研究。硒催化的方法有效的合成了不对称芳基烷基取代脲,然而难以实现不对称芳基芳基取代脲的合成,并且反应压力较大(CN 1294123A)。最近,钯催化的氧化羰基化芳胺制备脲的方法,因为反应条件温和、选择性好、原料稳定和来源广泛,而引起了重视。尽管如此,该法仍然存在着需要使用金属氧化剂,而且难以合成不对称的二取代脲(Adv.Synth.Catal.2012,354,489-496)。因此,开发更加安全、环保、高效和通用的合成不对称二取代脲的方法具有重要的研究意义和应用价值。
发明内容
技术问题
针对传统合成脲的方法原料具有高毒性,并且反应中生成大量强腐蚀性和污染性的含氯废物,造成设备的严重腐蚀及产品后处理上的困难,同时,异氰酸酯的活性非常高,需要在无水、无氧和氮气保护氛围下进行反应,操作比较复杂;以及现有钯催化合成脲的方法需要金属氧化剂的使用,而且用于不对称二取代脲的合成存在选择性差的难题。本发明提供一种催化合成不对称二取代脲的方法,在钯催化剂作用下,空气或氧气为氧化剂,两种伯胺类化合物、与一氧化碳直接交叉偶联合成不对称二取代脲,该方法具有氧化剂来源广泛和环境友好;底物来源广泛、廉价和易于处理;羰基源稳定、廉价和不产生废物;反应无需配体且活性好;反应条件温和且选择性高;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收的优势。
技术方案
为了解决上述问题,本发明所采用的技术方案如下:
一种催化合成不对称二取代脲的方法,一种常压下直接合成不对称二取代脲类化合物的合成方法,以聚乙二醇或聚乙二醇的水溶液为溶剂,在碱、碘化物和氧化剂的作用下,加入钯催化剂,伯胺类化合物与一氧化碳直接交叉偶联反应,制得不对称二取代脲类化合物反应通式表示如下:
式中:
R’NH2表示芳基或杂芳基的伯胺,以及烷基伯胺;R”NH2表示芳基或杂芳基的伯胺,以及烷基伯胺;
本发明的方法所合成的不对称二取代脲类化合物的结构通式为:
式中:R’表示的芳基为苯基、联苯基、萘基、蒽基、菲基或芘基,R’表示的杂芳基为含N、O或S的五至十三元环的杂芳基,R’表示的烷基为C1~C12的烷基、C3~C12的环烷基或苄基;R表示的芳基为苯基、联苯基、萘基、蒽基、菲基或芘基,R”表示的杂芳基为含N、O或S的五至十三元环的杂芳基,R”表示的烷基为C1~C12的烷基、C3~C12的环烷基或苄基。
进一步地,R’NH2或R”NH2中的杂芳基为吲哚基、呋喃基、噻吩基、吡咯基、咔唑基、吡唑基、恶唑基、噻唑基、咪唑基或吡啶基。
进一步地,以R1表示R’中芳基或杂芳基上的取代基,R1单取代或多取代芳环上的氢;以R2表示R”中芳基或杂芳基上的取代基,R2单取代或多取代芳环上的氢;其中
R1任意选自氢,C1~C12的烷基,C1~C12的烷氧基,C1~C12的卤取代烷基,C3~C12的环烷基,芳基、芳氧基或芳胺基,杂芳基、杂芳氧基或杂芳胺基,C1~C12烷基取代的氨基,C1~C12的巯基,氟、氯或溴,羟基,C1~C12烷基羰基,羧基,C1~C12烷氧基羰基,C1~C12烷胺基羰基,芳基羰基,C1~C12烷磺酰基、氰基或硝基;
R2任意选自氢,C1~C12烷基,C1~C12烷氧基、C1~C12的卤取代烷基、C3~C12的环烷基,芳基、芳氧基或芳胺基,杂芳基、杂芳氧基或杂芳胺基,C1~C12烷基取代的氨基,C1~C12的巯基,氟、氯或溴,羟基,C1~C12烷基羰基,羧基,C1~C12烷氧基羰基,C1~C12烷胺基羰基,芳基羰基,C1~C12烷磺酰基,氰基或硝基。
进一步地,R’或R”中的杂芳基吡咯基、吲哚基、咔唑基、吡唑基和咪唑基,其氮原子上的取代基任意选自氢、C1~C12的烷基、C1~C12卤取代烷基、C3~C12的环烷基、芳基、杂芳基、C1~C12烷磺酰基、対甲苯磺酰基、苄基、C1~C12烷基羰基、叔丁氧酰基或芳酰基。
所述的伯胺类化合物为苯类、联苯类、萘类、蒽类、芘类、呋喃类、噻吩类、吡咯类、吲哚类、咔唑类、吡唑类、噻唑类、恶唑类、咪唑类、吡啶类、烷基类或苄基的伯胺。
进一步地,所述的钯催化剂包括但不限于钯纳米、钯粉、钯碳、醋酸钯、氯化钯、氢氧化钯碳、四三苯基膦钯、三(二亚苄基丙酮)二钯、二苯腈氯化钯、二乙腈氯化钯或四氯钯酸钠。
进一步地,所述的氧化剂为空气或氧气,压力为0.5~2.5个大气压;所述一氧化碳压力为0.5~2.5个大气压。
进一步地,所述的碱为包括但不限于磷酸钾、磷酸氢钾、磷酸氢二钾、磷酸钠、磷酸氢钠、磷酸氢二钠、氟化钠、氟化钾、氟化铯、碳酸锂、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯、特戊酸钠、特戊酸钾、特戊酸铯、甲醇钠、乙醇钠,乙醇钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铯、四丁基氟化铵、三乙二胺、三乙胺、二异丙基乙胺或吡啶。且以上各碱可以组合使用。
进一步地,所述的碘化物包括但不限于碘化氢、碘化锂、碘化钠、碘化钾、碘化铵、碘化亚铜、碘化铜、碘化锌、四甲基碘化铵、四乙基碘化铵、四丙基碘化铵、四丁基碘化铵、四正庚基碘化铵、三甲基碘化锍、三甲基碘化亚砜、甲基三苯基碘化鏻或乙基三苯基碘化鏻。
进一步地,所述的聚乙二醇包括但不限于平均分子量为100~10000的聚乙二醇。聚乙二醇的水溶液中醇与水的体积比为:1:0~100。最优选的溶剂为聚乙二醇-400。
进一步地,所述的方法中,伯胺R’NH2、伯胺R”NH2、碱、碘化物、钯催化剂的摩尔比为1:(1~10):(0.1~5):(0.1~5):(0.001~0.5);所述的伯胺底物与溶剂的重量比为1:5~1000;所述的方法中,偶联反应温度为50~200℃,反应时间为0.5~72小时。
有益效果
相比于现有技术,本发明的有益效果为:
(1)本发明提供了一种在绿色介质聚乙二醇或聚乙二醇的水溶液中钯催化空气或氧气氧化不同伯胺与一氧化碳的交叉偶联反应来制备不对称二取代脲类化合物的新方法。该方法具有氧化剂来源广泛和环境友好;底物来源广泛、廉价和易于处理;羰基源稳定、廉价和不产生废物;反应无需配体且活性好;反应条件温和且选择性高;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收的优势。
(2)本发明提供的不对称二取代脲的合成方法简单易行,一步法直接得到不对称二取代脲,在优化的反应条件之下,目标产品分离后收率可高达97%左右,是一种高效、经济、环境友好的合成不对称二取代脲类化合物的方法。
(3)本发明方法制备的不对称二取代脲可用来制备具有独特的生物、药理活性和功能的杂环化合物,在药物中间体、生物活性分子和农用化学品等方面有着广泛的用途。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,对依据本发明提出的技术方案具体实施方式、特征及其功效,详细说明如后。
实施例1
化合物1:25mL反应瓶中依次加入醋酸钯(0.005mmol),胺1a(0.5mmol),胺1a’(0.75mmol),三乙胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在25℃下反应6h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率81%。
实施例2
化合物2:25mL反应瓶中依次加入氯化钯(0.005mmol),胺1b(0.5mmol),胺1b’(1.0mmol),磷酸钾(0.1mmol),碘化钾(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在80℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率72%。
实施例3
化合物3:25mL反应瓶中依次加入钯碳(0.01mmol),胺1c(0.5mmol),胺1c’(1.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-600(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在80℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率88%。
实施例4
化合物4:25mL反应瓶中依次加入氢氧化钯碳(0.01mmol),胺1d(0.5mmol),胺1d’(1.5mmol),三乙二胺(0.1mmol),碘化铵(0.25mmol)和聚乙二醇-600(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率89%。
实施例5
化合物5:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1e(0.5mmol),胺1e’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在80℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率92%。
实施例6
化合物6:25mL反应瓶中依次加入钯纳米(0.001mmol),胺1f(0.5mmol),胺1f’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在80℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率81%。
实施例7
化合物7:25mL反应瓶中依次加入四氯钯酸钠(0.001mmol),胺1g(0.5mmol),胺1g’(2.0mmol),四丁基氟化铵(0.5mmol),碘化钠(0.25mmol)和聚乙二醇-4000(1.0g)和水(1.0g),并引入一个大气压的一氧化碳和氧气(1:1),在100℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率85%。
实施例8
化合物8:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1h(0.5mmol),胺1h’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率91%。
实施例9
化合物9:25mL反应瓶中依次加入四三苯基膦钯(0.001mmol),胺1i(0.5mmol),胺1i’(2.0mmol),磷酸氢钠(0.1mmol),四丁基碘化铵(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应9h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率79%。
实施例10
化合物10:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1j(0.5mmol),胺1j’(2.0mmol),三乙二胺(0.1mmol),碳酸钠(0.25mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率92%。
实施例11
化合物11:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1k(0.5mmol),胺1k’(2.0mmol),三乙二胺(0.1mmol),甲基三苯基碘化鏻(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率87%。
实施例12
化合物12:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1l(0.5mmol),胺1l’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率90%。
实施例13
化合物13:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1m(0.5mmol),胺1m’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率91%。
实施例14
化合物14:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1n(0.5mmol),胺1n’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率91%。
实施例15
化合物15:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1o(0.5mmol),胺1o’(2.0mmol),碳酸铯(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率79%。
实施例16
化合物16:25mL反应瓶中依次加入三(二亚苄基丙酮)二钯(0.001mmol),胺1p(0.5mmol),胺1p’(2.0mmol),氢氧化钠(0.5mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应18h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率71%。
实施例17
化合物17:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1q(0.5mmol),胺1q’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率91%。
实施例18
化合物18:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1r(0.5mmol),胺1r’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率87%。
实施例19
化合物19:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1s(0.5mmol),胺1s’(2.0mmol),三乙二胺(0.1mmol),二异丙基乙胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率97%。
实施例20
化合物20:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1t(0.5mmol),胺1t’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率90%。
实施例21
化合物21:25mL反应瓶中依次加入二乙腈氯化钯(0.001mmol),胺1u(0.5mmol),胺1u’(2.0mmol),三乙二胺(0.1mmol),二异丙基乙胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率93%。
实施例22
化合物22:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1v(0.5mmol),胺1v’(2.0mmol),醋酸钾(0.1mmol),碘化锌(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率80%。
实施例23
化合物23:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1w(0.5mmol),胺1w’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-200(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率83%。
实施例24
化合物24:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1x(0.5mmol),胺1x’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率87%。
实施例25
化合物25:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1y(0.5mmol),胺1y’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率88%。
实施例26
化合物26:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1z(0.5mmol),胺1z’(2.0mmol),碳酸氢钠(0.1mmol),碘化钾(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应12h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率81%。
实施例27
化合物27:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1aa(0.5mmol),胺1aa’(2.0mmol),三乙二胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率85%。
实施例28
化合物28:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1ab(0.5mmol),胺1ab’(2.0mmol),三乙二胺(0.1mmol),三乙胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率96%。
实施例29
化合物29:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1ac(0.5mmol),胺1ac’(2.0mmol),乙醇钠(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和氧气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率80%。
实施例30
化合物30:25mL反应瓶中依次加入醋酸钯(0.001mmol),胺1ad(0.5mmol),胺1ad’(2.0mmol),三乙二胺(0.1mmol),三乙胺(0.1mmol),碘化钠(0.25mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳和空气(1:1),在50℃下反应24h。冷却到室温,萃取,减压蒸除溶剂后柱层析分离得到产率94%。
实施例1~30不对称二取代脲的合成方法对应的实验结果列于表1:
表1钯催化的不对称二取代脲的合成反应[a]
[a]反应条件见实施例;[b]柱分离收率。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽
然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,本发明中的钯催化剂在反应中有利于活化一氧化碳与胺进行胺羰化反应,实现双电子转移过程,理论上各种价态的钯在氧化剂的作用下都应能取得类似的作用;碱是发生胺羰化反应必须的促进剂,利用的是其碱性,理论上给出的各种碱,都应能取得类似之效果;碘化物是羰基化化反应常见的促进剂,利用的是碘阴离子的作用,理论上能电离出碘阴离子的碘化物,都应能取得类似之效果;胺底物发生反应的官能团是氨基,而其周围的取代基影响的是氨基的电子云密度大小以及反应时的空间位阻大小,即取代基的修饰只是一定程度上影响反应,不对反应的发生起决定作用;任何熟悉本专业的技术人员不难理解,在不脱离本发明技术方案范围内,当可进行替换、变动或修饰得到相应的实施例,例如对于所述的取代基可在本发明范围内进行替换、改变或修饰,均可以实现本发明方法。但凡是未脱离本发明技术方案的宗旨,依据本发明的对以上实施例所作的任何修改、修饰或等同与等效的变化,均仍属于本发明技术方案的范围内。
Claims (10)
2.根据权利要求1所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述芳基为苯基、联苯基、萘基、蒽基、菲基或芘基,杂芳基为含N、O或S的五至十三元环的杂芳基,烷基为C1~C12的烷基、C3~C12的环烷基或苄基。
3.根据权利要求1所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述杂芳基为吲哚基、呋喃基、噻吩基、吡咯基、咔唑基、吡唑基、恶唑基、噻唑基、咪唑基或吡啶基。
4.根据权利要求1所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述杂芳基为吡咯基、吲哚基、咔唑基、吡唑基和咪唑基时,其氮原子上的取代基任意选自氢、C1~C12的烷基、C1~C12卤取代烷基、C3~C12的环烷基、芳基、杂芳基、C1~C12烷磺酰基、対甲苯磺酰基、苄基、C1~C12烷基羰基、叔丁氧酰基或芳酰基。
5.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的钯催化剂为钯纳米、钯粉、钯碳、醋酸钯、氯化钯、氢氧化钯碳、四三苯基膦钯、三(二亚苄基丙酮)二钯、二苯腈氯化钯、二乙腈氯化钯或四氯钯酸钠。
6.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的氧化剂为空气或氧气。
7.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的碱为磷酸钾、磷酸氢钾、磷酸氢二钾、磷酸钠、磷酸氢钠、磷酸氢二钠、氟化钠、氟化钾、氟化铯、碳酸锂、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯、特戊酸钠、特戊酸钾、特戊酸铯、甲醇钠、乙醇钠,乙醇钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铯、四丁基氟化铵、三乙二胺、三乙胺、二异丙基乙胺或吡啶,且以上各碱能够组合使用。
8.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的碘化物为碘化氢、碘化锂、碘化钠、碘化钾、碘化铵、碘化亚铜、碘化铜、碘化锌、四甲基碘化铵、四乙基碘化铵、四丙基碘化铵、四丁基碘化铵、四正庚基碘化铵、三甲基碘化锍、三甲基碘化亚砜、甲基三苯基碘化鏻或乙基三苯基碘化鏻。
9.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的聚乙二醇为平均分子量为100~10000;聚乙二醇的水溶液中的聚乙二醇与水的体积比为1:(0~100)。
10.根据权利要求1-4任一项所述的催化氧化羰基化合成不对称二取代脲的方法,其特征在于,所述的伯胺R’NH2、伯胺R”NH2、碱、碘化物、钯催化剂的摩尔比为1:(1~10):(0.1~5):(0.1~5):(0.001~0.5);伯胺底物与溶剂的重量比为1:(5~1000);所述方法中,偶联反应温度为20~200℃,反应时间为0.5~72小时。
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