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CN109046463B - 双齿氮杂卡宾锰催化剂及其制备方法和烷基化合成应用 - Google Patents

双齿氮杂卡宾锰催化剂及其制备方法和烷基化合成应用 Download PDF

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CN109046463B
CN109046463B CN201810932032.3A CN201810932032A CN109046463B CN 109046463 B CN109046463 B CN 109046463B CN 201810932032 A CN201810932032 A CN 201810932032A CN 109046463 B CN109046463 B CN 109046463B
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柯卓锋
黄明
李玉葵
兰小兵
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Abstract

本发明公开了一种双齿氮杂卡宾锰催化剂及其制备方法和烷基化合成应用。本发明的催化剂对底物的适应范围广，能够在较温和的条件下，催化不同结构的C‑C和C‑N键化合物的合成；反应直接以醇为原料，反应物易得，可再生；相对于传统的醛反应物而言，更稳定、易操作、低毒环保。

Description

双齿氮杂卡宾锰催化剂及其制备方法和烷基化合成应用
技术领域
本发明涉及有机合成技术领域，特别涉及一种双齿氮杂卡宾锰催化剂及其制备方法和烷基化合成应用。
背景技术
烷基化反应是一类构建C-X键(X＝C or N)非常重要的反应，在天然产物、材料和药物的合成方面有着广泛的应用。传统的烷基化反应需要使用毒性较大的有机卤试剂和过量的碱，且伴随着大量的副产物和废物，对环境影响较大。近年来，以醇为烷基化试剂，通过过渡金属催化剂催化的“借氢反应”策略，在烷基化反应方面显现出巨大的优势。该策略具体分为三步：首先，醇在金属催化剂的作用下脱氢变为醛/酮；然后醛/酮和亲核试剂胺或活泼碳反应得到C＝N或C＝C中间体；最后再双键还原形成烷基化产物。该方法的优点是使用便宜易得的醇作为烷基化试剂，且原子效率高，只产生副产物水，环境友好。自2000年以来，对这类反应的研究已经取得了很大的进展，但主要集中在钌和铱等贵金属催化剂上。近年来非贵金属如铁和钴催化剂也表现出较高的活性，引起了科学家广泛的关注。锰作为仅次于铁和钛在地壳中储量第三的过渡金属元素，在氢化反应反面表现出了优越的活性。但是目前可以应用于“借氢反应”策略烷基化反应的锰配合物比较少，而且已有的文献报道中，应用于这类反应的锰催化剂结构中均含有磷，这对环境非常不友好。因此，开发出一种简单高效、环境友好的非贵金属锰催化剂，具有广阔应用前景。
发明内容
本发明的目的在于克服现有技术中存在的缺点，提供一种双齿氮杂卡宾锰催化剂，该催化剂合成简单，并且可以在较温和的条件下以醇为原料进行催化烷基化反应。
本发明的另一目的在于提供一种上述双齿氮杂卡宾锰催化剂的制备方法。
本发明的再一目的在于提供一种上述双齿氮杂卡宾锰催化剂的烷基化合成应用，通过催化醇的烷基化反应，应用于构建C-C和C-N键的合成反应中。
本发明的目的通过下述技术方案实现：
一种双齿氮杂卡宾锰催化剂，具有如式一所示的结构：
Figure BDA0001766855780000021
其中，n为0、1或2；R1为烷基或芳基；R2为H、甲基、氯或芳基；Y为氯、溴或碘。
R1为烷基时，所述烷基优选甲基、乙基、异丙基、丁基或环己基；R1为芳基时，所述芳基优选苯基、2,6-二甲基苯基、2,6-二异丙基苯基或均三甲基苯基；R2为芳基时，所述芳基优选苯基或2,6-二甲基苯基。
上述双齿氮杂卡宾锰催化剂的制备方法，是在惰性气体条件下，将五羰基溴化锰、叔丁醇钾和双齿氮杂咪唑盐配体加入到四氢呋喃溶剂中，在25～100℃条件下反应10～24h；反应完毕，降至室温，然后将反应液旋干，得到固体；用乙醚洗固体，再溶于二氯甲烷，水洗干燥，得到双齿氮杂卡宾锰催化剂。
所述惰性气体为氮气或氩气。
所述双齿氮杂咪唑盐配体，其制备方法是将咪唑和烷基卤代物按照(2.0～3.0)：1的摩尔用量比加入到四氢呋喃溶剂中，在80～120℃下反应18～24h后，冷却至室温产生大量白色沉淀；然后用四氢呋喃洗涤白色沉淀，再用二氯甲烷洗涤得到白色固体粉末，即双齿氮杂咪唑盐配体。
五羰基溴化锰、叔丁醇钾和双齿氮杂咪唑盐配体的摩尔用量比为(1.0～1.5):(2.0～3.0):1.0。
双齿氮杂卡宾锰催化剂的制备步骤如式二所示：
Figure BDA0001766855780000022
所述双齿氮杂卡宾锰催化剂的用途，是作为金属催化剂催化醇与胺/酮的烷基化反应，用于构建C-C或C-N键化合物的合成反应。
所述C-C或C-N键化合物的通式为：
Figure BDA0001766855780000031
所述醇的通式为：
Figure BDA0001766855780000032
所述胺的通式为：
Figure BDA0001766855780000033
所述酮的通式为：
Figure BDA0001766855780000034
其中，取代基R3可以是供电子基团、吸电子基团或官能化基团，供电子基团优选甲基或甲氧基，吸电子基团优选卤素、硝基或三氟甲基，官能化基团优选酯基、不饱和烯基或不饱和炔基；取代基R4可以是芳香取代基或脂肪取代基，芳香取代基优选苯环衍生物或杂环芳香化合物，脂肪取代基优选长链脂肪烃或烯烃。
所述双齿氮杂卡宾锰催化剂催化胺的烷基化合成应用，是将双齿氮杂卡宾锰催化剂、醇、胺和碱加入到溶剂中，惰性气体保护下在30～100℃反应2～48h；反应完毕，降至室温，加水淬灭，用乙酸乙酯萃取，浓缩、纯化、干燥，得到C-N键化合物。
双齿氮杂卡宾锰催化剂、醇、胺和碱的摩尔比为(0.0075～0.03):(1.0～25.0):1.0:(0.3～1.0)；所述的碱为叔丁醇钾；所述的溶剂为苯、甲苯或者均三甲苯；所述的惰性气体是氮气或者氩气。
上述C-N键化合物的合成步骤如式三所示：
Figure BDA0001766855780000035
所述双齿氮杂卡宾锰催化剂催化酮的烷基化合成应用，是将双齿氮杂卡宾锰催化剂、醇、酮和碱加入到溶剂中，惰性气体保护下在30～130℃反应1～24h；反应完毕，降至室温，加水淬灭，用乙酸乙酯萃取，浓缩、纯化、干燥，得到C-C键化合物。
双齿氮杂卡宾锰催化剂、醇、酮和碱的摩尔比为(0.003～0.06):(1.0～25.0):1.0:(0.5～1.0)；所述的碱为氢氧化锂、氢氧化钠或氢氧化钾；所述的溶剂为苯、甲苯或者均三甲苯；所述的惰性气体是氮气或者氩气。
上述C-C键化合物的合成步骤如式四所示：
Figure BDA0001766855780000041
本发明与现有技术相比具有如下优点和效果：
(1)本发明的双齿氮杂卡宾锰催化剂的合成原料简单易得，成本低，操作步骤简单易行，并且对空气稳定，不需要使用磷配体，低毒，环境友好。
(2)本发明的催化剂对底物的适应范围广，能够在较温和的条件下，催化不同结构的C-C和C-N键化合物的合成；反应直接以醇为原料，反应物易得，可再生；相对于传统的醛反应物而言，更稳定、易操作、低毒环保。
(3)在构建C-C和C-N键化合物时，本发明的催化剂可在碱性条件下，催化醇与芳香伯胺或苯乙酮类化合物的“借氢偶联”反应，得到一系列有价值的C/N-烷基化合物。而且其可以较高效率的催化脂肪醇和芳香胺的N-烷基化反应，重要的是，该催化剂可以用于简单脂肪醇，如甲醇和乙醇等的N-烷基化反应，用于合成一些药物的关键中间体。另外，该反应温度可以是室温，是目前温度最低的催化N-烷基反应的非贵金属催化剂。
(4)在构建C-C键化合物时，反应温度也较低，能够在便宜易得的氢氧化钠或氢氧化钾的作用下，较快地催化反应进行，另外该反应选择性好，不会还原C＝O双键。
附图说明
图1为双齿氮杂卡宾锰催化剂3a的单晶结构图。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
为了在实施例中简明清楚地表述配体和配合物，说明如下：
配体2a为式五所示的双齿氮杂咪唑碘盐，其中R1为甲基，R2为氢。
配体2b为式五所示的双齿氮杂咪唑碘盐，其中R1为均三甲基苯基，R2为氢。
配体2c为式五所示的双齿氮杂咪唑碘盐，其中R1为苯基，R2为氢。
Figure BDA0001766855780000051
双齿氮杂卡宾锰催化剂3a为式六所示的双齿氮杂卡宾锰催化剂，其中R1为甲基，R2为氢。
双齿氮杂卡宾锰催化剂3b为式六所示的双齿氮杂卡宾锰催化剂，其中R1为均三甲基苯基，R2为氢。
双齿氮杂卡宾锰催化剂3c为式六所示的双齿氮杂卡宾锰催化剂，其中R1为苯基，R2为氢。
Figure BDA0001766855780000052
实施例1：合成双齿氮杂咪唑碘盐配体2a
向15mL的封管中，称取1.97g(1.91mL，24mmol)1-甲基咪唑，3.21g(0.96mL，12mmol)二碘甲烷，和5mL四氢呋喃，110℃下反应24h，反应过程中有白色固体渐渐析出；反应结束后，冷却至室温，过滤，固体用四氢呋喃洗涤，再用大量二氯甲烷冲洗，最后干燥得到5g白色固体产物，即双齿氮杂咪唑碘盐配体2a，产率为96％。
1H NMR(400MHz,DMSO-d6)δ9.40(s,2H),7.99(t,J＝1.7Hz,2H),7.81(t,J＝1.6Hz,2H),6.67(s,2H),3.90(s,6H)。
13C NMR(101MHz,DMSO-d6)δ137.96,124.31,121.83,121.74,58.06,36.37。
实施例2：合成氮杂咪唑碘盐配体2b
按照实施例1中配体2a的合成方法，4.47g(24mmol)1-均三甲基苯基咪唑代替1-甲基咪唑，其他操作条件同实施例1，反应结束后得到6.9g白色固体产物，即双齿氮杂咪唑碘盐配体2b，产率为90％。
1H NMR(400MHz,DMSO-d6)δ9.82(s,2H),8.38(t,J＝1.6Hz,2H),8.11(t,J＝1.6Hz,2H),7.18(s,4H),6.89(s,2H),2.34(s,6H),2.05(s,12H)。
13C NMR(101MHz,DMSO-d6)δ140.56,139.01,134.16,130.78,129.31,124.83,122.79,59.27,20.59,17.00。
实施例3：合成双齿氮杂咪唑碘盐配体2c
按照实施例1中配体2a的合成方法，用3.46g(24mmol)1-苯基咪唑代替1-甲基咪唑，其他操作条件同实施例1，反应结束后得到6.13g淡棕色固体，即双齿氮杂咪唑碘盐配体2c，其产率为92％。
1H NMR(400MHz,DMSO-d6)δ10.11(s,2H),8.45(s,2H),8.30(s,2H),7.82(d,J＝7.9Hz,4H),7.72(t,J＝7.7Hz,4H),7.65(t,J＝7.3Hz,2H),6.85(s,2H)。
13C NMR(101MHz,DMSO-d6)δ137.25,134.41,130.31,130.27,123.02,122.04,121.81,58.82。
实施例4：合成双齿氮杂卡宾锰催化剂3a
向带有搅拌子的150mL封管中，称取216mg(0.5mmol)双齿氮杂咪唑碘盐配体2a，175mg(0.65mmol)五羰基溴化锰，130mg(1.15mmol)叔丁醇钾和12.5mL四氢呋喃溶剂，氮气保护下，60℃避光搅拌反应16h。反应结束后，旋干，然后把所得固体用乙醚洗，抽干后再把固体加入到100mL二氯甲烷中，水洗三次。最后用无水硫酸钠干燥，旋干得到130mg黄色粉末，即双齿氮杂卡宾锰催化剂3a，产率为65％。如图1所示为双齿氮杂卡宾锰催化剂3a的单晶结构图。
1H NMR(400MHz,DMSO-d6)δ7.56(s,2H),7.44(s,2H),6.56(d,J＝11.5Hz,1H),6.08(d,J＝12.7Hz,1H),3.97(s,6H)。
13C NMR(101MHz,DMSO-d6)δ220.76,187.75,123.91,121.85,62.11,38.16。
实施例5：合成双齿氮杂卡宾锰催化剂3b
按照实施例4中双齿氮杂卡宾锰催化剂3a的合成方法，用320mg(0.5mmol)双齿氮杂咪唑碘盐配体2b代替(0.5mmol)双齿氮杂咪唑碘盐配体2a，其他操作条件同实施例4，反应结束后得到100mg黄色固体，即双齿氮杂卡宾锰催化剂3b，其产率为54％。
1H NMR(400MHz,DMSO-d6)δ7.83(s,2H),7.36(s,2H),7.00(s,4H),6.65–6.37(m,2H),2.27(s,6H),2.08(s,6H),1.82(s,6H)。
13C NMR(101MHz,DMSO-d6)δ217.71,189.87,138.29,136.87,135.90,135.03,128.71,128.43,123.54,123.00,62.45,20.57,18.22,17.39。
实施例6：合成双齿氮杂卡宾锰催化剂3c
按照实施例4中双齿氮杂卡宾锰催化剂3a的合成方法，用289mg(0.5mmol)双齿氮杂咪唑碘盐配体2c代替(0.5mmol)双齿氮杂咪唑碘盐配体2a，其他操作条件同实施例4，反应结束后得到140mg黄色固体，即双齿氮杂卡宾锰催化剂3c，其产率为56％。
1H NMR(400MHz,DMSO-d6)δ7.79–7.46(m,14H),6.80–6.37(m,2H)。
13C NMR(101MHz,DMSO-d6)δ219.55,218.87,193.59,190.70,140.39,140.23,129.84,129.73,129.50,129.34,128.76,125.18,124.82,122.79,62.94,61.98。
双齿氮杂卡宾锰催化剂在催化醇与芳香胺偶联合成N-烷基类化合物的应用，其反应通式如下：
Figure BDA0001766855780000071
实施例7：合成N-苄基苯胺
向带有搅拌子的10mL Schlenk管中，称取6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a和112mg(1mmol)叔丁醇钾，108mg(1mmol)苯甲醇，93mg(1mmol)苯胺，氩气保护下加入2mL无水甲苯，50℃反应24h。反应完全后，乙酸乙酯萃取，旋干，过柱即得163mg无色油状物，即N-苄基苯胺，其产率为90％。
1H NMR(400MHz,CDCl3)δ7.41-7.35(m,4H),7.34–7.27(m,1H),7.20(t,J＝7.5Hz,2H),6.75(t,J＝7.3Hz,1H),6.67(d,J＝7.8Hz,2H),4.35(s,2H),4.04(s,1H)。
13C NMR(100MHz,CDCl3)δ148.3,139.6,129.4,128.7,127.6,127.3,117.7,113.0,48.4。
MS(ESI)[M+H]+183.65。
实施例8：合成N-4-甲基苄基苯胺
按照实施例7中N-苄基苯胺的合成方法，用10mg(0.015mmol)双齿氮杂卡宾锰催化剂3b，122mg(1mmol)4-甲基苯甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到168mg无色油状物，即N-4-甲基苄基苯胺，其产率为86％。
1H NMR(400MHz,CDCl3)δ7.26(d,J＝8.1Hz,2H),7.17(dd,J＝11.3,8.0Hz,4H),6.71(t,J＝7.3Hz,1H),6.64(d,J＝8.0Hz,2H),4.28(s,2H),3.98(s,1H),2.35(s,3H)。
13C NMR(100MHz,CDCl3)δ148.4,137.0,136.5,129.4,129.4,127.6,117.6,113.0,48.2,21.2。
MS(ESI)[M+H]+197.65。
实施例9：合成N-4-甲氧基苄基苯胺
按照实施例7中N-苄基苯胺的合成方法，用8mg(0.015mmol)双齿氮杂卡宾锰催化剂3c，138mg(1mmol)4-甲基苯甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到163mg无色油状物，即N-4-甲氧基苄基苯胺，其产率为77％。
1H NMR(400MHz,CDCl3)δ7.30(d,J＝8.4Hz,2H),7.18(t,J＝7.8Hz,2H),6.89(d,J＝8.5Hz,2H),6.72(t,J＝7.3Hz,1H),6.64(d,J＝7.7Hz,2H),4.26(s,2H),3.95(s,1H),3.81(s,3H)。
13C NMR(100MHz,CDCl3)δ159.0,148.3,131.5,129.4,128.9,117.6,114.1,112.9,55.4,47.9。
MS(ESI)[M+H]+213.60。
实施例10：合成N-2-萘甲基苯胺
按照实施例7中N-苄基苯胺的合成方法，用12mg(0.03mmol)双齿氮杂卡宾锰催化剂3a，158mg(1mmol)2-萘甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到202mg无色油状物，即N-2-萘甲基苯胺，其产率为86％。
1H NMR(400MHz,CDCl3)δ7.85-7.81(m,4H),7.51-7.48(m,3H),7.19(t,J＝7.6Hz,2H),6.74(t,J＝7.4Hz,1H),6.69(d,J＝8.1Hz,2H),4.51(s,2H),4.14(s,1H)。
13C NMR(100MHz,CDCl3)δ148.3,137.1,133.6,132.9,129.4,128.5,127.9,127.8,126.3,126.0,125.9,117.8,113.1,48.6。
MS(ESI)[M+H]+233.65。
实施例11：合成N-4-氟-苄基苯胺
按照实施例7中N-苄基苯胺的合成方法，用20mg(0.015mmol)双齿氮杂卡宾锰催化剂3b，126mg(1mmol)4-氟苯甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到170mg无色油状物，即N-4-氟-苄基苯胺，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.36-7.33(m,2H),7.18(t,J＝7.6Hz,2H),7.03(t,J＝8.6Hz,2H),6.74(t,J＝7.3Hz,1H),6.63(d,J＝7.9Hz,2H),4.31(s,2H),4.02(s,1H)。
13C NMR(100MHz,CDCl3)δ162.2(d,JC-F＝246.4Hz),148.1,135.2(d,JC-F＝2.9Hz),129.4,129.1(d,JC-F＝8.0Hz),117.8,115.5(d,JC-F＝21.2Hz),113.0,47.7。
MS(ESI)[M+H]+201.60。
实施例12：合成N-4-氯-苄基苯胺
按照实施例7中N-苄基苯胺的合成方法，用6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a，142mg(1mmol)4-氯苯甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到129mg无色油状物，即N-4-氯-苄基苯胺，其产率为86％。
1H NMR(400MHz,CDCl3)δ7.31(s,4H),7.18(t,J＝7.4Hz,2H),6.74(t,J＝7.2Hz,1H),6.62(d,J＝7.9Hz,2H),4.32(s,2H),4.06(s,1H)。
13C NMR(100MHz,CDCl3)δ148.0,138.1,133.0,129.4,128.9,128.8,117.9,113.0,47.7。
MS(ESI)[M+H]+217.50。
实施例13：合成N-4-溴-苄基苯胺
按照实施例7中N-苄基苯胺的合成方法，用12mg(0.03mmol)双齿氮杂卡宾锰催化剂3c，186mg(1mmol)4-溴苯甲醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到234mg无色油状物，即N-4-溴-苄基苯胺，其产率为89％。
1H NMR(400MHz,CDCl3)δ7.48(d,J＝8.1Hz,2H),7.28(s,2H),7.19(t,J＝7.6Hz,2H),6.75(t,J＝7.1Hz,1H),6.63(d,J＝8.2Hz,2H),4.32(s,2H),4.07(s,1H)。
13C NMR(100MHz,CDCl3)δ147.9,138.7,131.8,129.4,129.2,121.0,117.9,113.0,47.8。
MS(ESI)[M+H]+263.30。
实施例14：合成N-3-苯基丙基苯胺
按照实施例7中N-苄基苯胺的合成方法，用6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a，136mg(1mmol)苯丙醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到157mg无色油状物，即N-3-苯基丙基苯胺，其产率为75％。
1H NMR(400MHz,CDCl3)δ7.31(t,J＝7.5Hz,2H),7.25–7.15(m,5H),6.70(t,J＝7.0Hz,1H),6.59(d,J＝8.3Hz,2H),3.61(s,1H),3.16(t,J＝6.9Hz,2H),2.75(t,J＝7.6Hz,2H),2.00-1.93(m,2H)。
13C NMR(100MHz,CDCl3)δ148.5,141.8,129.3,128.6,128.5,126.1,117.3,112.9,43.5,33.5,31.2。
MS(ESI)[M+H]+211.60。
实施例15：合成N-正辛基苯胺
按照实施例7中N-苄基苯胺的合成方法，用12mg(0.03mmol)双齿氮杂卡宾锰催化剂3a，130mg(1mmol)正辛醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到195mg无色油状物，即N-正辛基苯胺，其产率为95％。
1H NMR(400MHz,CDCl3)δ7.22–7.17(m,2H),6.71(t,J＝7.3Hz,1H),6.65–6.59(m,2H),3.60(s,1H),3.12(t,J＝7.1Hz,2H),1.67-1.60(m,2H),1.44–1.29(m,10H),0.93–0.90(m,3H)。
13C NMR(101MHz,CDCl3)δ148.67,129.33,117.19,112.81,44.14,31.97,29.73,29.56,29.41,27.33,22.80,14.24。
MS(ESI)[M+H]+206.70。
实施例16：合成N-正己基苯胺
按照实施例7中N-苄基苯胺的合成方法，用6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a，102mg(1mmol)正己醇代替苯甲醇，其他操作条件同实施例7，反应结束后得到165mg无色油状物，即N-正己基苯胺，其产率为93％。
1H NMR(400MHz,CDCl3)δ7.23–7.15(m,2H),6.71(t,J＝7.3Hz,1H),6.65–6.58(m,2H),3.60(s,1H),3.12(t,J＝7.1Hz,2H),1.67–1.60(m,2H),1.46–1.31(m,6H),0.94–0.91(m,3H)。
13C NMR(101MHz,CDCl3)δ148.67,129.33,117.18,112.81,44.14,31.79,29.69,27.00,22.76,14.17。
MS(ESI)[M+H]+178.51。
实施例17：合成N-苄基-4-甲基苯胺
按照实施例7中N-苄基苯胺的合成方法，用10mg(0.015mmol)双齿氮杂卡宾锰催化剂3b，107mg(1mmol)4-甲基苯胺代替苯胺，其他操作条件同实施例7，反应结束后得到165mg黄色油状物，即N-苄基-4-甲基苯胺，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.36(q,J＝7.6Hz,4H),7.29(d,J＝7.1Hz,1H),7.00(d,J＝7.8Hz,2H),6.58(d,J＝7.7Hz,2H),4.32(s,2H),3.91(s,1H),2.25(s,3H)。
13C NMR(100MHz,CDCl3)δ146.0,139.8,129.9,128.7,127.6,127.3,126.9,113.1,48.8,20.5。
MS(ESI)[M+H]+197.65。
实施例18：合成N-苄基-4-甲氧基苯胺
按照实施例7中N-苄基苯胺的合成方法，用18mg(0.03mmol)双齿氮杂卡宾锰催化剂3c，123mg(1mmol)4-甲氧基苯胺代替苯胺，其他操作条件同实施例7，反应结束后得到120mg棕色固体，即N-苄基-4-甲氧基苯胺，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.36(q,J＝7.5Hz,4H),7.28(d,J＝7.0Hz,1H),6.78(d,J＝8.7Hz,2H),6.61(d,J＝8.7Hz,2H),4.29(s,2H),3.75(s,3H)。
13C NMR(100MHz,CDCl3)δ152.2,142.5,139.8,128.7,127.6,127.2,115.0,114.2,55.9,49.3。
MS(ESI)[M+H]+213.60。
实施例19：合成N-苄基-4-氟苯胺
按照实施例7中N-苄基苯胺的合成方法，用20mg(0.03mmol)双齿氮杂卡宾锰催化剂3b，111mg(1mmol)4-氟苯胺代替苯胺，其他操作条件同实施例7，反应结束后得到168mg无色油状物，即N-苄基-4-氟苯胺，其产率为83％。
1H NMR(400MHz,CDCl3)δ7.45–7.32(m,4H),7.32–7.27(m,1H),6.88(t,J＝8.4Hz,2H),6.62–6.52(m,2H),4.30(s,2H)。
13C NMR(100MHz,CDCl3)δ156.0(d,JC-F＝236.3Hz),144.6,139.4,128.8,127.6,127.4,115.8(d,JC-F＝22.2Hz),113.8(d,JC-F＝7.4Hz),49.0。
MS(ESI)[M+H]+201.60。
实施例20：合成N-苄基-4-氯苯胺
按照实施例7中N-苄基苯胺的合成方法，用6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a，127mg(1mmol)4-氯苯胺代替苯胺，其他操作条件同实施例7，反应结束后得到188mg无色油状物，即N-苄基-4-氯苯胺，其产率为87％。
1H NMR(400MHz,CDCl3)δ7.35(d,J＝3.9Hz,4H),7.29(dd,J＝8.3,4.0Hz,1H),7.11(d,J＝8.1Hz,2H),6.55(d,J＝8.1Hz,2H),4.30(s,2H),4.07(s,1H)。
13C NMR(100MHz,CDCl3)δ146.8,139.1,129.2,128.8,127.5,127.5,122.2,114.0,48.5。
MS(ESI)[M+H]+217.60。
实施例21：合成N-苄基-1-萘胺
按照实施例7中N-苄基苯胺的合成方法，用10mg(0.015mmol)双齿氮杂卡宾锰催化剂3b，143mg(1mmol)1-萘胺代替苯胺，其他操作条件同实施例7，反应结束后得到204mg白色固体，即N-苄基-1-萘胺，其产率为88％。
1H NMR(400MHz,CDCl3)δ7.83(t,J＝8.5Hz,2H),7.46(t,J＝7.7Hz,4H),7.38(dd,J＝13.6,6.0Hz,2H),7.35–7.30(m,2H),7.27(d,J＝7.0Hz,1H),6.65(d,J＝7.4Hz,1H),4.71(s,1H),4.51(s,2H)。
13C NMR(100MHz,CDCl3)δ143.3,139.2,134.4,128.9,128.8,127.9,127.5,126.7,125.9,124.9,123.5,120.0,117.8,104.9,48.8。
MS(ESI)[M+H]+233.60。
实施例22：合成N-苄基吡啶-2-胺
按照实施例7中N-苄基苯胺的合成方法，用20mg(0.015mmol)双齿氮杂卡宾锰催化剂3b，94mg(1mmol)2-氨基吡啶代替苯胺，其他操作条件同实施例7，反应结束后得到130mg白色固体，即N-苄基吡啶-2-胺，其产率为70％。
1H NMR(400MHz,CDCl3)δ8.11(d,J＝4.6Hz,1H),7.44–7.30(m,5H),7.29(s,1H),6.63–6.56(m,1H),6.38(d,J＝8.4Hz,1H),4.85(s,1H),4.51(d,J＝5.8Hz,2H)。
13C NMR(100MHz,CDCl3)δ158.8,148.3,139.3,137.6,128.7,127.5,127.3,113.3,106.9,46.4。
MS(ESI)[M+H]+184.60。
双齿氮杂卡宾锰催化剂催化芳香胺与甲醇偶联合成N-烷基化合物的应用，其反应通式如下：
Figure BDA0001766855780000131
实施例23：合成N-甲基-4-甲氧基苯胺
向带有搅拌子的15mL封管中，称取6mg(0.015mmol)双齿氮杂卡宾锰催化剂3a和112mg(1mmol)叔丁醇钾，0.25mL(9.85mmol)甲醇，123mg(1mmol)4-甲氧基苯胺，氩气保护下加入2mL无水甲苯，80℃反应24h。反应完全后，过滤，旋干，过柱即得113.7mg无色油状物，即N-甲基-4-甲氧基苯胺，其产率为83％。
1H NMR(400MHz,DMSO-d6)δ6.75–6.69(m,2H),6.51–6.46(m,2H),5.14(s,1H),3.63(s,3H),2.62(s,3H)。
13C NMR(101MHz,DMSO-d6)δ150.58,144.32,114.59,112.57,55.32,30.53。
实施例24：合成N-甲基-4-溴苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用172mg(1mmol)4-溴苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到165mg白色固体，即N-甲基-4-溴苯胺，其产率为89％。
1H NMR(400MHz,CDCl3)δ7.27–7.22(m,2H),6.49–6.44(m,2H),3.71(s,1H),2.79(s,3H)。
13C NMR(101MHz,CDCl3)δ148.37,131.95,114.03,108.85,30.81。
实施例25：合成N-甲基-4-乙氧基苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用137mg(1mmol)4-乙氧基苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到85mg白色固体，即N-甲基-4-乙氧基苯胺，其产率为76％。
1H NMR(400MHz,CDCl3)δ6.83–6.77(m,2H),6.61–6.56(m,2H),3.97(q,J＝7.0Hz,2H),2.81(s,3H),1.38(t,J＝7.0Hz,3H)。
13C NMR(101MHz,CDCl3)δ151.44,143.79,115.92,113.74,64.30,31.73,15.15。
实施例26：合成N-甲基-3-乙烯基苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用119mg(1mmol)3-乙烯基苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到93mg白色固体，即N-甲基-3-乙烯基苯胺，其产率为70％。
1H NMR(400MHz,CDCl3)δ7.18(t,J＝7.8Hz,1H),6.82(d,J＝7.6Hz,1H),6.74–6.65(m,2H),6.54–6.56(m,1H),5.74(dd,J＝17.6,0.9Hz,1H),5.23(dd,J＝10.9,0.8Hz,1H),3.48(s,1H),2.86(s,3H)。
13C NMR(101MHz,CDCl3)δ149.61,138.62,137.47,129.41,115.68,113.51,112.34,110.13,30.86。
MS(ESI)[M+H]+134.19。
实施例27：合成N-甲基-3-碘苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用219mg(1mmol)3-碘苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到191mg白色固体，即N-甲基-3-碘苯胺，其产率为82％。
1H NMR(400MHz,CDCl3)δ7.03(td,J＝7.7,1.3,0.9Hz,1H),6.96–6.93(m,1H),6.89(t,J＝7.9Hz,1H),6.55(m,1H),3.72(s,1H),2.80(s,3H)。
13C NMR(101MHz,CDCl3)δ150.53,130.68,126.05,120.84,111.90,95.40,30.56。
MS(ESI)[M+H]+234.11。
实施例28：合成N-甲基-4-乙基苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用121mg(1mmol)4-乙基苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到84mg白色固体，即N-甲基-4-乙基苯胺，其产率为62％。
1H NMR(400MHz,CDCl3)δ7.06(m,J＝8.5Hz,2H),6.59(m,J＝8.5Hz,2H),2.84(s,3H),2.57(q,J＝7.6Hz,2H),1.22(t,J＝7.6Hz,3H).
13C NMR(101MHz,CDCl3)δ147.47,133.29,128.64,112.73,31.18,28.06,16.14。
实施例29：合成N-甲基-4-叔丁基苯胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用149mg(1mmol)4-叔丁基苯胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到147mg白色固体，即N-甲基-4-叔丁基苯胺，其产率为79％。
1H NMR(400MHz,CDCl3)δ7.24–7.20(m,2H),6.60–6.55(m,2H),2.81(s,3H),1.28(s,9H)。
13C NMR(101MHz,CDCl3)δ147.14,140.18,126.08,112.34,33.96,31.69,31.10。
MS(ESI)[M+H]+164.40。
实施例30：合成N-甲基-2-3-二氢苯并[b][1,4]二恶英-6-胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用151mg(1mmol)6-氨基-1,4-苯并二氧杂环代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到137mg白色固体，即N-甲基-2-3-二氢苯并[b][1,4]二恶英-6-胺，其产率为83％。
1H NMR(400MHz,CDCl3)δ6.72(dd,J＝8.3,0.5Hz,1H),6.25–6.12(m,2H),4.21(m,4H),2.77(s,3H)。
13C NMR(101MHz,CDCl3)δ144.62,144.16,135.65,117.70,106.54,101.15,64.89,64.31,31.55。
MS(ESI)[M+H]+166.29。
实施例31：合成N-甲基-2-芴胺
按照实施例23中N-甲基-4-甲氧基苯胺的合成方法，用181mg(1mmol)2-芴胺代替4-甲氧基苯胺，其他操作条件同实施例23，反应结束后得到166mg白色固体，即N-甲基-2-芴胺，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.63(dd,J＝16.7,7.9Hz,2H),7.49(d,J＝7.4Hz,1H),7.34(t,J＝7.5Hz,1H),7.20(t,J＝7.4Hz,1H),6.82(s,1H),6.65(dd,J＝8.2,1.9Hz,1H),3.84(s,2H),2.91(s,3H)。
13C NMR(101MHz,CDCl3)δ149.05,145.30,142.53,142.27,131.89,126.71,124.86,124.79,120.69,118.50,111.74,108.83,37.07,31.13。
双齿氮杂卡宾锰催化剂催化苯乙酮与醇偶联合成C–烷基化合物的应用，其反应通式如下：
Figure BDA0001766855780000161
实施例32：合成1,3-二苯基丙酮
向带有搅拌子的10mL Schlenk管中，称取18mg(0.04mmol)双齿氮杂卡宾锰催化剂3a和20mg(0.5mmol)氢氧化钠，108mg(1mmol)苯甲醇，120mg(1mmol)苯乙酮，氩气保护下加入2mL无水甲苯，110℃反应2h。反应完全后，乙酸乙酯萃取，旋干，过柱即得189mg白色固体，即1,3-二苯基丙酮，其产率为90％。
1H NMR(400MHz,CDCl3)δ7.97(d,J＝7.2Hz,2H),7.56(t,J＝7.4Hz,1H),7.46(t,J＝7.6Hz,2H),7.34–7.25(m,4H),7.22(t,J＝6.8Hz,1H),3.37–3.25(m,2H),3.12–3.03(m,2H)。
13C NMR(100MHz,CDCl3)δ199.20,141.24,136.80,133.02,128.56,128.48,128.38,127.99,126.09,40.41,30.09.
实施例33：合成1-(4-氯苯基)-3-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用198mg(1mmol)4-氯苯乙酮代替苯乙酮，其他操作条件同实施例32，反应结束后得到181mg白色固体，即1-(4-氯苯基)-3-苯基丙酮，其产率为74％。
1H NMR(400MHz,CDCl3)δ7.90(d,J＝8.6Hz,2H),7.43(d,J＝8.6Hz,2H),7.34–7.28(m,2H),7.25–7.18(m,3H),3.28(t,J＝7.7Hz,2H),3.07(t,J＝7.6Hz,2H).
13C NMR(100MHz,CDCl3)δ197.94,141.01,139.46,135.12,129.42,128.88,128.53,128.37,126.19,40.39,30.02.
实施例34：合成1-(4-溴苯基)-3-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用138mg(1mmol)4-溴苯乙酮代替苯乙酮，其他操作条件同实施例32，反应结束后得到196mg白色固体，即1-(4-溴苯基)-3-苯基丙酮，其产率为68％。
1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.5Hz,2H),7.59(d,J＝8.5Hz,2H),7.34–7.28(m,2H),7.24–7.18(m,3H),3.27(t,J＝7.7Hz,2H),3.06(t,J＝7.6Hz,2H)。
13C NMR(100MHz,CDCl3)δ198.17,141.00,135.52,131.89,129.54,128.54,128.37,128.21,126.20,40.39,30.01.
实施例35：合成1-(4-甲基苯基)-3-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用134mg(1mmol)4-甲基苯乙酮代替苯乙酮，其他操作条件同实施例32，反应结束后得到190mg白色固体，即1-(4-甲基苯基)-3-苯基丙酮，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.2Hz,2H),7.33–7.28(m,2H),7.27–7.24(m,4H),7.21(m,1H),3.36–3.17(m,2H),3.13–2.93(m,2H),2.41(s,3H)。
13C NMR(100MHz,CDCl3)δ198.89,143.81,141.37,134.37,129.25,128.48,128.40,128.14,126.07,40.32,30.21,21.61。
实施例36：合成1-(4-甲氧苯基)-3-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用150mg(1mmol)4-甲氧苯乙酮代替苯乙酮，其他操作条件同实施例32，反应结束后得到223mg白色固体，即1-(4-甲氧苯基)-3-苯基丙酮，其产率为93％。
1H NMR(400MHz,CDCl3)δ7.95(d,J＝9.0Hz,2H),7.39–7.14(m,5H),6.92(d,J＝8.9Hz,2H),3.86(s,3H),3.25(m,2H),3.11–2.96(m,2H)。
13C NMR(100MHz,CDCl3)δ197.83,163.42,141.43,130.28,129.93,128.48,128.40,126.05,113.70,55.44,40.10,30.31。
实施例37：合成3-(4-氯苯基)-1-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用143mg(1mmol)4-氯苯甲醇代替苯甲醇，其他操作条件同实施例32，反应结束后得到207mg白色固体，即3-(4-氯苯基)-1-苯基丙酮，其产率为85％。
1H NMR(400MHz,CDCl3)δ7.95(d,J＝7.1Hz,2H),7.56(m,1H),7.46(m,2H),7.30–7.23(m,2H),7.18(d,J＝8.4Hz,2H),3.28(m,2H),3.05(m,2H)。
13C NMR(100MHz,CDCl3)δ198.83,139.70,136.71,133.14,131.84,129.79,128.61,128.56,127.98,40.11,29.35。
实施例38：合成3-(4-溴苯基)-1-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用187mg(1mmol)4-溴苯甲醇代替苯甲醇，其他操作条件同实施例32，反应结束后得到230mg白色固体，即3-(4-溴苯基)-1-苯基丙酮，其产率为80％。
1H NMR(400MHz,CDCl3)δ7.95(d,J＝8.0Hz,2H),7.56(m,1H),7.49–7.36(m,4H),7.19–7.08(m,2H),3.28(m,2H),3.03(m,2H)。
13C NMR(100MHz,CDCl3)δ198.77,140.21,136.68,133.13,131.50,130.19,128.60,127.96,119.83,40.01,29.38。
实施例39：合成3-(4-甲基苯基)-1-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用122mg(1mmol)4-甲基苯甲醇代替苯甲醇，其他操作条件同实施例32，反应结束后得到210mg白色固体，即3-(4-甲基苯基)-1-苯基丙酮，其产率为94％。
1H NMR(400MHz,CDCl3)δ7.97(d,J＝7.2Hz,2H),7.56(m,1H),7.46(m,2H),7.15(m,4H),3.40–3.20(m,4H),3.14–2.89(m,4H),2.34(s,3H)。
13C NMR(100MHz,CDCl3)δ199.30,138.14,136.84,135.57,132.98,129.16,128.54,128.25,127.99,40.56,29.68,20.96。
实施例40：合成3-(4-甲氧苯基)-1-苯基丙酮
按照实施例32中1,3-二苯基丙酮的合成方法，用138mg(1mmol)4-甲氧基苯甲醇代替苯甲醇，其他操作条件同实施例32，反应结束后得到230mg白色固体，即3-(4-甲氧苯基)-1-苯基丙酮，其产率为96％。
1H NMR(400MHz,CDCl3)δ7.96(d,J＝7.1Hz,2H),7.56(m,1H),7.45(m,2H),7.18(d,J＝8.6Hz,2H),6.85(d,J＝8.6Hz,2H),3.79(s,3H),3.27(m,2H),3.02(m,2H)。
13C NMR(100MHz,CDCl3)δ199.36,157.93,136.83,133.25,132.98,129.29,128.54,127.98,113.88,55.21,40.65,29.23。

Claims (5)

1.一种双齿氮杂卡宾锰催化剂的用途，其特征在于：所述双齿氮杂卡宾锰催化剂作为金属催化剂催化醇与芳香胺类化合物、或醇与酮的烷基化反应，用于构建C-N或C-C键化合物的合成反应；所述双齿氮杂卡宾锰催化剂的结构式如下：
Figure FDA0002987716380000011
其中，n为0、1或2；R1各自独立为烷基或芳基；R2各自独立为H、甲基、氯或芳基；Y为氯、溴或碘。
2.根据权利要求1所述的双齿氮杂卡宾锰催化剂的用途，其特征在于：所述双齿氮杂卡宾锰催化剂催化芳香胺类化合物的烷基化合成应用，是将双齿氮杂卡宾锰催化剂、醇、芳香胺类化合物和碱加入到溶剂中，惰性气体保护下在30～100℃反应2～48h；反应完毕，降至室温，加水淬灭，用乙酸乙酯萃取，浓缩、纯化、干燥，得到C-N键化合物。
3.根据权利要求2所述的双齿氮杂卡宾锰催化剂的用途，其特征在于：双齿氮杂卡宾锰催化剂、醇、芳香胺类化合物和碱的摩尔比为(0.0075～0.03):(1.0～25.0):1.0:(0.3～1.0)；所述的碱为叔丁醇钾；所述的溶剂为苯、甲苯或者均三甲苯；所述的惰性气体是氮气或者氩气。
4.根据权利要求1所述的双齿氮杂卡宾锰催化剂的用途，其特征在于：所述双齿氮杂卡宾锰催化剂催化酮的烷基化合成应用，是将双齿氮杂卡宾锰催化剂、醇、酮和碱加入到溶剂中，惰性气体保护下在30～130℃反应1～24h；反应完毕，降至室温，加水淬灭，用乙酸乙酯萃取，浓缩、纯化、干燥，得到C-C键化合物。
5.根据权利要求4所述的双齿氮杂卡宾锰催化剂的用途，其特征在于：双齿氮杂卡宾锰催化剂、醇、酮和碱的摩尔比为(0.003～0.06):(1.0～25.0):1.0:(0.5～1.0)；所述的碱为氢氧化锂、氢氧化钠或氢氧化钾；所述的溶剂为苯、甲苯或者均三甲苯；所述的惰性气体是氮气或者氩气。
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