CN108358793B - 一种由炔烃合成的仲胺类化合物及其合成方法 - Google Patents
一种由炔烃合成的仲胺类化合物及其合成方法 Download PDFInfo
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Abstract
本发明涉及一种由炔烃合成的仲胺类化合物及其合成方法,具体结构如II所示,同时本发明公开了该化合物一种“三步一锅法”的合成方法。该方法以廉价易得的乙炔基取代的苯(I)为原料,经过步骤1):以含氟的醇和水为溶剂,在三氟甲烷磺酸催化下发生水合反应生成中间体酮;步骤2):直接在反应体系中加芳香胺类化合物,生成亚胺;步骤3):在体系中加入四羟基化二硼得到产物II。该方法无金属参与,操作简便,原料易得、反应条件温和、收率较高。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种由炔烃合成仲胺类化合物的方法。
背景技术
胺类化合物是重要的医药中间体。目前合成该类化合物的方法主要为亚胺的氢化还原,在此过程中,金属的参与是必不可少,同时,氢气作为可燃性危险气体,对操作设备的要求较高。硼试剂由于其廉价易得,无金属存在,是一类用途广泛的还原剂,同时使用硼试剂对亚胺进行还原已有报道。由于存在催化剂、溶剂、反应物共生的难题,无金属催化的炔烃合成仲胺类化合物目前尚无报到。本专利提出使用廉价易得的苯乙炔和芳香胺在无金属催化的条件下,实现“三步一锅”的策略,为仲胺类化合物在工业生产提供了绿色高效的合成方法。
发明内容
针对上述技术问题,本发明主要创新点在于从廉价易得的乙炔基取代的苯为原料,采用“三步一锅法”策略,提出了一种无金属参与的由炔烃合成仲胺类化合物的原子经济性、步骤经济性的绿色方法,该方法具有重要的应用前景。
一种仲胺类化合物,所述仲胺的结构如式II所示;
R是氢、C1-C10烷基、C1-C10烷基氧基、卤代烷基、卤素、羟基、氨基、硝基、氰基、芳基中的任意一种。
R1是氢、C1-C10烷基、C1-C10烷基氧基、卤代烷基、卤素、羟基、氨基、硝基、氰基、芳基中的任意一种。
R2是C1-C10烷基、芳基中的任意一种。
所述的仲胺类化合物的合成方法,该化合物由炔烃合成,包括如下步骤:
步骤(1):乙炔基取代的苯为原料,布朗斯特酸为催化剂,含氟醇和水的混合物为溶剂,经水合反应得到中间体酮;
步骤(2):在氮气保护下,往中间体酮直接加入芳香胺,芳香胺与中间体酮反应生成亚胺;
步骤(3):在反应体系中,往亚胺中加入硼试剂,还原亚胺得到仲胺类化合物;具体的反应路线如下:
所述的结构式I为:
R是氢、C1-C10烷基、C1-C10烷基氧基、卤代烷基、卤素、羟基、氨基、硝基、氰基、芳基中的任意一种。
R2是C1-C10烷基、芳基中的任意一种。
所述的布朗斯特酸催化剂包括三氟乙酸,三氟甲烷磺酸。进一步优选为三氟甲烷磺酸。
所述的硼试剂包括四羟基化二硼,频哪醇硼,双频哪醇硼,硼酸以及硼氢化钠。进一步优选为四羟基化二硼。
所述的以含氟醇和水的混合物为溶剂,含氟醇包括三氟乙醇或六氟异丙醇,所述的含氟醇的摩尔浓度为15-25mol%,摩尔浓度为15-25mol%的含氟醇、水的体积比为0.5-1.5:1.8-3。进一步优选为三氟乙醇与水的混合物,其中,摩尔浓度为20mol%的含氟醇、水的体积比为9: 20。
乙炔基取代苯的摩尔浓度为0.5-1.5mol%、布朗斯特酸的摩尔浓度为0.1-0.5mol%、芳香胺摩尔浓度为0.8-2mol%、硼试剂的质量比为10-30%。
所述的步骤(1)的水合反应温度为40-80℃,反应时间为4-72h。进一步优选为40℃的条件下,反应6h。
所述的步骤(2)中加入芳香胺后,反应温度控制为80℃,反应时间为0.5-1h。进一步优选为 80℃的条件下,反应1h。
所述的步骤(3)中加入四羟基化二硼后,亚胺还原反应温度控制为80℃,反应时间为1h。进一步优选为80℃的条件下,反应14h。
本发明公开了一种以炔烃为原料“三步一锅法”合成仲胺类化合物的方法。该方法以廉价易得的乙炔基取代的苯(I)为原料,经过步骤1):以含氟的醇和水为溶剂,在三氟甲烷磺酸催化下发生水合反应生成中间体酮;步骤2):直接加入芳香胺与中间体酮反应生成亚胺;步骤3):在反应体系中加入四羟基化二硼还原亚胺得到仲胺类化合物。该方法操作简便,原料易得、原子经济性高,符合绿色化学的要求。
具体实施方式
下面结合具体实施例,对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1:条件优化以及N-(1-苯乙基)苯胺的合成
序号 | 布朗斯特酸催化剂 | 硼试剂 | 溶剂 | 产率 |
1 | 三氟乙酸 | 四羟基化二硼 | 三氟乙醇 | 15% |
2 | 三氟甲烷磺酸 | 四羟基化二硼 | 三氟乙醇 | 86% |
3 | 三氟甲烷磺酸 | 频哪醇硼 | 三氟乙醇 | 10% |
4 | 三氟甲烷磺酸 | 双频哪醇硼 | 三氟乙醇 | 31% |
5 | 三氟甲烷磺酸 | 硼酸 | 三氟乙醇 | <5% |
6 | 三氟甲烷磺酸 | 硼氢化钠 | 三氟乙醇 | 65% |
7 | 三氟甲烷磺酸 | 四羟基化二硼 | 六氟异丙醇 | 57% |
8 | 三氟甲烷磺酸 | 四羟基化二硼 | 水 | 0 |
序号1-8的实施例中,其各原料的添加量依照如下具体实施例的步骤实施。
将0.5mmol的苯乙炔加入到试管中,最优条件为依次加入CF3SO3H(20mol%,9μL),H2O (2当量,20μL),CF3CH2OH(1mL),氮气保护,40℃反应6h后,加入苯胺(1.2当量,0.6mmol,55.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:86%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.47-7.38(m,4H),7.33-7.29(m,1H),7.18(dd,J1=7.2Hz,J2=8.8Hz,2H),6.75-6.71(m,1H),6.61-6.58(m,2H),4.56(q,J1=6.8Hz,J2=13.6Hz,1H),4.10(s,1H), 1.59(d,J=6.8Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=147.32,145.28,129.17,128.70, 126.93,125.90,117.27,113.33,53.51,25.14ppm.
实施例2:4-甲基-N-(1-苯乙基)苯胺的合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20 μL),CF3CH2OH(1mL),40℃反应6h后,加入4-甲基苯胺(1.2当量,0.6mmol,64.2mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3 次,合并有机相浓缩至干,分离产率:76%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz, CDCl3):δ=7.42-7.34(m,4H),7.26(t,J=7.2Hz,1H),6.95(d,J=8.0Hz,2H),6.48(d,J=8.4 Hz,2H),4.49(q,J1=6.4Hz,J2=13.6Hz,1H),2.27(s,3H),1.55(d,J=6.8Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=145.37,144.94,129.62,128.63,126.83,126.45,125.88,113.47,53.75,25.09,20.39ppm.
实施例3:3,4,5-三甲氧基-N-(1-苯乙基)苯胺的合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20 μL),CF3CH2OH(1mL),40℃反应6h后,加入3,4,5-三甲氧基苯胺(1.2当量,0.6mmol,111.6mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:89%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.38-7.32(m,4H),7.25-7.21(m,1H),5.74(s,2H),4.41(q,J1=6.8Hz,J2=13.6Hz,1H),3.96(s,1H),3.69(d,J=11.2Hz,9H),1.50(d,J=6.8Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=153.67,145.35,144.04,128.66,126.93,125.73,90.89,61.00,55.71,54.13, 24.97ppm.
实施例4:3-溴-N-(1-苯乙基)苯胺的合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20 μL),CF3CH2OH(1mL),40℃反应6h后,加入3-溴-苯胺(1.2当量,0.6mmol,102mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3 次,合并有机相浓缩至干,分离产率:81%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz, CDCl3):δ=7.37(t,J=1.6Hz,4H),6.96(t,J=8.0Hz,1H),6.80-6.77(m,1H),6.71(t,J=2.0Hz,1H),6.45-6.42(m,1H),4.49(q,J1=6.8Hz,J2=13.6Hz,1H),4.14(s,1H),1.50(d,J=6.8Hz,3H) ppm;13C NMR(100MHz,CDCl3):δ=148.50,144.47,130.39,128.76,127.11,125.76,123.06, 120.04,115.99,111.81,53.32,24.85ppm.
实施例5:N-(1-苯乙基)萘胺的合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20 μL),CF3CH2OH(1mL),40℃反应6h后,加入3-溴-苯胺(1.2当量,0.6mmol,85.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3 次,合并有机相浓缩至干,分离产率:81%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz, CDCl3):δ=7.99-7.96(m,1H),7.84-7.82(m,1H),7.54-7.46(m,4H),7.37(t,J=7.2Hz,2H), 7.30-7.22(m,3H),6.44-6.40(m,1H),4.78(s,1H),4.72(q,J1=6.8Hz,J2=13.2Hz,1H),1.71(d,J=6.8Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=144.94,142.11,134.28,128.78,128.71,126.98,126.57,125.83,125.64,124.70,123.25,119.77,117.23,106.02,53.58,25.27ppm.
实施例6:4-甲氧基-N-(对乙基-1-苯乙基)苯胺的合成
将0.5mmol的对乙基苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20μL),CF3CH2OH(1mL),40℃反应6h后,加入对甲氧基苯胺(1.2当量,0.6mmol,73.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:91%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.32(d,J=8.0Hz,2H),7.19(d,J=7.6Hz,2H),6.74(d,J=8.8Hz,2H), 6.52(d,J=9.2Hz,2H),4.43(q,J1=6.8Hz,J2=13.2Hz,1H),3.74(s,1H),2.68(q,J1=7.6Hz, J2=15.2Hz,2H),1.53(d,J=6.8Hz,3H),1.27(t,J=7.6Hz,3H)ppm;13C NMR(100MHz, CDCl3):δ=151.84,142.70,142.66,141.69,128.88,125.85,114.77,114.54,55.77,53.96,28.47, 25.08,15.50ppm.
实施例7:4-甲氧基-N-(对溴1-苯乙基)苯胺的合成
将0.5mmol的对溴苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20μL),CF3CH2OH(1mL),70℃反应12h后,加入对甲氧基苯胺(1.2当量,0.6mmol,73.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:89%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.48(d,J=8.4Hz,2H),7.29(d,J=8.8Hz,2H),6.74(d,J=9.2Hz,2H),6.48 (d,J=8.8Hz,2H),4.40(q,J1=6.8Hz,J2=13.6Hz,1H),3.74(s,1H),1.51(d,J=6.8Hz, 3H)ppm;13C NMR(100MHz,CDCl3):δ=152.09,144.65,141.21,131.72,127.71,120.44,114.80, 114.59,55.76.53.84,25.16ppm.
实施例8:4-甲氧基-N-(1,2-二苯-1-乙基)苯胺的合成
将0.5mmol的二苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量, 20μL),CF3CH2OH(1mL),40℃反应48h后,加入对甲氧基苯胺(1.2当量,0.6mmol,73.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:90%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.39-7.27(m,9H),7.19-7.17(m,2H),7.69(d,J=9.2Hz,2H),6.46(d,J=8.8Hz,2H),4.56(q,J1=5.6Hz,J2=8.4Hz,1H),3.71(s,3H),3.19-3.01(m,2H)ppm;13CNMR (100MHz,CDCl3):δ=152.04,143.72,141.55,137.84,129.23,128.58,128.56,127.04,126.71, 126.52,114.89,114.64,60.06,55.72,45.32ppm.
实施例9:4-甲氧基-N-(苯-1-己基)苯胺的合成
将0.5mmol的1-苯基已炔加入到试管中,依次加入CF3SO3H(20mol%,9μL),H2O(2当量,20μL),CF3CH2OH(1mL),40℃反应48h后,加入对甲氧基苯胺(1.2当量,0.6mmol,73.8mg),80℃反应1h,之后加入B2(OH)4(8当量),80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:84%(石油醚:乙酸乙酯=10:1)。1H NMR(400MHz,CDCl3):δ=7.40-7.34(m,4H),7.29-7.25(m,1H),6.74(d,J=8.8Hz,2H),6.52(d,J= 8.8Hz,2H),4.27(t,J=6.8Hz,1H),3.74(s,3H),1.84-1.78(s,2H),1.47-1.34(m,6H),0.93(t,J= 6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=151.78,144.64,141.83,128.53,126.82,126.46, 114.77,114.43,59.11,55.78,39.09,31.79,26.10,22.61,14.11ppm.
Claims (1)
1.一种仲胺类化合物的合成方法,其特征在于,该化合物由炔烃合成,其特征在于,包括如下步骤:
将0.5 mmol的苯乙炔加入到试管中,最优条件为依次加入CF3SO3H 20 mol%, 9 μL ,H2O 2当量, 20 μL , CF3CH2OH 1 mL,氮气保护,40℃反应6 h后,加入苯胺1.2当量, 0.6mmol, 55.8 mg,80℃反应1h,之后加入B2(OH)4 8当量,80℃反应14h,结束后用水洗,水相用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:86%,石油醚:乙酸乙酯 = 10:1。
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