CN103396354A - 富勒烯吡咯烷衍生物的合成方法 - Google Patents
富勒烯吡咯烷衍生物的合成方法 Download PDFInfo
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Abstract
本发明公开了一种富勒烯吡咯烷衍生物的合成方法,以富勒烯、有机卤化物和α-氨基酸为原料,以二甲亚砜为催化剂,在有机溶剂中反应生成富勒烯吡咯烷衍生物。此方法原料价廉易得、产率高、操作简单,适合大规模生产富勒烯吡咯烷衍生物。
Description
技术领域
本发明涉及富勒烯吡咯烷衍生物的制备方法,特指一种以富勒烯、有机卤化物和α-氨基酸为原料,以二甲亚砜为催化剂,在有机溶剂中反应生成富勒烯吡咯烷衍生物的方法。
背景技术
自从富勒烯被发现和成功分离以来,对富勒烯的化学修饰就已经引起了各国学者的广泛关注,并通过各种不同的方法制备得到了大量的富勒烯衍生物,这些衍生物在材料科学和生命科学等领域有着潜在的应用价值。富勒烯吡咯烷衍生物就是其中最具有代表性的一类衍生物。最早对富勒烯进行化学修饰的报道是亚胺叶立德与富勒烯的反应,之后这种方法被大量应用于不同富勒烯吡咯烷衍生物的合成,而制备亚胺叶立德简便易行的一种方法是通过氨基酸和醛、酮反应得到亚胺盐的脱羧反应,另外也可以通过氮丙啶的开环反应或氨基酸的甲基硅衍生物的酸催化制备得到。除了上述方法外,叔胺与C60的光化学反应也可以制备富勒烯吡咯烷衍生物。而目前合成富勒烯吡咯烷衍生物最常用的方式都要用到氨基酸和醛作为原料,而这里面涉及到的某些醛价格昂贵且不易得到。因此,需要一种原料价廉易得、产率高、操作简单的方法,这样会更适合大规模生产的需要。
发明内容
本发明的目的是提供一种原料易得、产率高、操作简单、更适合大规模生产富勒烯吡咯烷衍生物的合成方法。
本发明的技术方案是,以富勒烯、有机卤化物和α-氨基酸为原料,以二甲亚砜为催化剂,在有机溶剂中反应生成富勒烯吡咯烷衍生物;其合成路线为
式中,环FL为富勒烯,R1CH2X为有机卤化物,R2NHCH(R3)COOH为α-氨基酸,R1、R2和R3独立地为任意的有机侧链;
合成步骤为:
在容器中依次加入富勒烯、有机卤化物、α-氨基酸、二甲亚砜和有机溶剂,加热反应;反应结束后,先用水洗除去二甲亚砜,然后减压除去有机溶剂,残余物用二硫化碳溶解,用洗脱剂进行硅胶柱层析分离纯化,既得产物。
所述富勒烯为富勒烯C60或富勒烯C70。
所述有机卤化物为R1CH2F,R1CH2Cl,R1CH2Br,R1CH2I之一,R1独立地为任意有机侧链。
按摩尔比,反应原料有机卤化物:富勒烯为1:(0~10),优选的,反应原料有机卤化物:富勒烯为1:0.2。
所述α-氨基酸可为R2NHCH(R3)COOH,R2和R3独立地为任意有机侧链;按摩尔比,反应原料α-氨基酸:富勒烯为1:(0~10);
所述有机溶剂为苯、甲苯、邻二甲苯、对二甲苯、间二甲苯、乙苯、氯苯、氟苯、溴苯、邻二氯苯、间二氯苯、对二氯苯之一,优选有机溶剂为氯苯或甲苯。
所述催化剂二甲亚砜用量,按体积比,有机溶剂:二甲亚砜为1:(0~2);优选的,有机溶剂:二甲亚砜为1:0.5。
所述反应的温度在50~180℃之间,优选为90℃。
所述反应时间为0.1~48小时,优选为16小时。
所述硅胶柱层析步骤中,硅胶的目数为200~400目,优选300~400目;所述洗脱剂为由体积比为1:(0~5)的甲苯和二硫化碳组成的混合溶剂或由体积比为1:(0~1)的甲苯和石油醚组成的混合溶剂。
与现有合成富勒烯吡咯烷衍生物的合成方法相比,本发明具有以下突出优点和技术效果:
1、可广泛应用于各种有机卤化物和α-氨基酸与富勒烯的反应;
2、所用催化剂为二甲亚砜,价格低廉,容易获得,而且可回收再利用;
3、操作简单,不需要超低温或超高温;
4、产物分离纯化容易,并且具有较高的产率;
5、多种有机溶剂均可以高效完成反应。
具体实施方式
以下将用实施例更详细地描述发明,实施例仅仅在于说明本发明,而不是对其进行限制。
实施例1:制备富勒烯吡咯烷衍生物F1
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入309mg N-乙基甘氨酸(3mmol)和635mg氯化苄(5mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件70℃恒温油浴加热反应24小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用体积比为1:3的甲苯和二硫化碳的混合液依次洗下未反应完的紫色带C60和棕色带产物F1,产物F1相对产率为85%。1H NMR(CDCl3,400MHz):7.79(bs,2H),7.40(t,J=7.2Hz,2H),7.32(t,J=7.2Hz,1H),5.13(d,J=9.2Hz,1H),5.08(s,1H),4.18(d,J=9.2Hz,1H),3.32-3.42(m,1H),2.60-2.69(m,1H),1.55(t,J=7.2Hz,3H).13C NMR(CDCl3,400MHz):156.42,154.22,153.53,153.45,147.35,147.34,146.84,146.52,146.39,146.32,146.27(2C),146.24,146.19,146.16,146.00(2C),145.84,145.67,145.60,145.58,145.51,145.47,145.36,145.32,145.29,145.27,145.20,144.79,144.72,144.46,143.23,143.09,142.76,142.68,142.65(2C),142.35(2C),142.23(2C),142.18,142.16,142.11,142.08,142.01,141.90,141.77,141.61,140.32,140.27,139.99,139.55,137.27(2C),136.94,136.74,135.89,135.81,129.46,128.82,128.56,82.45,76.78,68.82,66.63,47.42,13.76.MS(APCI):m/z=868(M+1)+,720(C60)+。
实施例2:制备富勒烯吡咯烷衍生物F2
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入267mg N-甲基甘氨酸(3mmol)和805mg对氯苄基氯(5mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件70℃恒温油浴加热反应16小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用体积比为1:3的甲苯与二硫化碳的混合液依次洗下未反应完的紫色带C60和棕色带产物F2,产物F2相对产率为82%。1H NMR(CDCl3,400MHz):7.75(bs,2H),7.39(d,J=8.4Hz,2H),4.99(d,J=9.2Hz,1H),4.93(s,1H),4.29(d,J=9.6Hz,1H),2.82(s,3H).13C NMR(CDCl3,400MHz):156.03,153.78,153.06,152.76,147.37(2C),146.54,146.40(2C),146.36,146.30,146.27,146.23,146.19,146.02,146.00,145.96,145.78,145.69,145.66,145.53,145.47,145.40(2C),145.37,145.34,145.31,145.26,144.78,144.70,144.47,144.43,143.25,143.11,142.80,142.72,142.69,142.67,142.34,142.30,142.24,142.22,142.17,142.13,142.11,142.08,141.95,141.78(2C),141.67,140.34,140.31,140.10,139.73,137.02,136.54,135.99,135.75,135.62(2C),134.74(2C),130.61,129.10,82.95,70.13,68.96(2C),40.03.MS(APCI):m/z=888(M+1)+,720(C60)+。
实施例3:制备富勒烯吡咯烷衍生物F3
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入345mg N-烯丙基甘氨酸(3mmol)和770mg烯丙基氯(10mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件90℃恒温油浴加热反应16小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用体积比为2:1的甲苯与二硫化碳的混合液依次洗下未反应完的紫色带C60和棕色带产物F3,产物F3相对产率为88%。1H NMR(CDCl3,400MHz):6.33-6.43(m,1H),6.25-6.33(m,1H),5.77(dd,J=1.2Hz,17.2Hz,1H),5.63(dd,J=1.6Hz,10.0Hz,1H),5.57(dd,J=1.2Hz,17.2Hz,1H),5.41(d,J=10.0Hz,1H),4.90(d,J=9.2Hz,1H),4.50(d,J=9.2Hz,1H),4.09(dd,J=1.2Hz,13.6Hz,1H),4.04(d,J=9.9Hz,1H),3.27(dd,J=8.0Hz,13.2Hz,1H).13C NMR(CDCl3,600MHz):156.03,154.27,153.45,153.52,147.34(2C),147.10,146.86,146.40,146.39,146.36,146.30,146.26,146.21,146.16,146.05,145.91,145.64,145.62(2C),145.49,145.45,145.38,145.28,145.25,144.81,144.73,144.48,143.23,143.11,142.77,142.74,142.67,142.38,142.29,142.24,142.18(2C),142.14,142.11(3C),142.05,141.82,141.74,140.37,140.27,140.21,139.68,137.49,136.55(3C),136.08,135.71,134.77(3C),121.59,118.47,80.75,75.54,69.09,66.63,55.88.MS(APCI):m/z=830(M+1)+,720(C60)+。
实施例4:制备富勒烯吡咯烷衍生物F4
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入495mg N-苄基甘氨酸(3mmol)和770mg烯丙基氯(10mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件90℃恒温油浴加热反应16小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用体积比为1:2的甲苯与二硫化碳的混合液依次洗下未反应完的紫色带C60和棕色带产物F4,产物F4相对产率为85%。
1H NMR(CDCl3,400MHz):7.66(d,J=7.6Hz,2H),7.45(t,J=7.6Hz,2H),7.35(t,J=7.6Hz,2H),6.43-6.53(m,1H),5.84(d,J=17.2Hz,1H),5.69(d,J=10.4Hz,1H),4.71(d,J=9.6Hz,1H),4.67(d,J=13.2Hz,1H),4.60(d,J=9.2Hz,1H),4.02(d,J=9.2Hz,1H),3.75(d,J=13.2Hz,1H).13C NMR(CDCl3,400MHz):155.98,154.19,153.42,152.57,147.36(2C),147.15,146.90,146.44,146.40,146.33(2C),146.27,146.23,146.17,146.07,146.04,145.92,145.68,145.61(3C),145.54,145.48,145.39(2C),145.31,145.27,144.82,144.76,144.48(2C),143.25,143.12,142.78,142.76,142.70,142.68,142.44,142.30,142.26(2C),142.22,142.13(3C),142.07,141.81,141.77,140.39,140.31,140.21,139.71,137.91(2C),137.49,136.78(3C),136.52,136.16,135.75,129.00,128.83,127.70,80.72,75.56,69.11,66.49,57.19.MS(APCI):m/z=880(M+1)+,720(C60)+。
实施例5:制备富勒烯吡咯烷衍生物F5
将720mg C60(1mmol)溶于150mL氯苯中,按计量比加入267mg N-甲基甘氨酸(3mmol)和835mg溴乙酸乙酯(5mmol),超声波超声至富勒烯完全溶解,加入75mL二甲亚砜,然后在磁力搅拌条件90℃恒温油浴加热反应1小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用甲苯依次洗下未反应完的紫色带C60和棕色带产物F5,产物F5相对产率为71%。1H NMR(CDCl3,300MHz):4.95(d,J=9.3Hz,1H),4.78(s,1H),4.49-4.42(m,2H),4.26(d,J=9.3Hz,1H),3.01(s,3H),1.28(t,J=7.2Hz,3H).MS(APCI):m/z=850(M+1)+,720(C60)+。
实施例6:制备富勒烯吡咯烷衍生物F6
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入267mg N-甲基甘氨酸(3mmol)和595mg炔丙基溴(5mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件80℃恒温油浴加热反应2小时。反应完毕后,先300mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用甲苯依次洗下未反应完的紫色带C60和棕色带产物F6,产物F6相对产率为88%。1H NMR(CDCl3,300MHz):4.96(s,1H),4.73(d,J=9.5Hz,1H),4.22(d,J=9.4Hz,1H),3.05(s,3H),2.86(t,J=1.1Hz,1H).13C NMR(CDCl3,400MHz):154.51,153.55,152.62,152.52,147.08,147.04,146.53,146.12,146.07,146.05,145.98(2C),145.85,145.80,145.74,145.71,145.44,145.40,145.28(2C),145.24(2C),145.19,145.17,145.14,145.01,144.97(2C),144.38,144.31,144.19,144.16,142.83,142.75,142.41(2C),142.36(2C),142.00,141.91(2C),141.81,141.80,141.75,141.72(2C),141.51,141.48,139.99,139.93,139.87,139.45,137.04,136.40,136.02,135.61,79.63,79.01,74.20,69.06,68.99,67.62,39.09.MS(APCI):m/z=802(M+1)+,720(C60)+。
实施例7:制备富勒烯吡咯烷衍生物F7
将720mg C60(1mmol)溶于200mL氯苯中,按计量比加入309mg N-乙基甘氨酸(3mmol)和615mg溴丙烷(5mmol),超声波超声至富勒烯完全溶解,加入100mL二甲亚砜,然后在磁力搅拌条件90℃恒温油浴加热反应4小时。反应完毕后,先200mL水洗三遍,去除二甲亚砜,然后减压去除溶剂氯苯,残余物用二硫化碳溶解后进行硅胶柱层析分离,用体积比为1:1的甲苯与二硫化碳的混合液依次洗下未反应完的紫色带C60和棕色带产物F7,产物F7相对产率为90%。1H NMR(CDCl3,600MHz):4.94(d,J=9.8Hz,1H),4.13(d,J=9.8Hz,1H),4.10(t,J=5.4Hz,1H),3.59-3.68(m,1H),2.86-2.93(m,1H),2.46-2.59(m,2H),1.57(t,J=7.7Hz,3H),1.45(t,J=7.4Hz,3H).13C NMR(CDCl3,400MHz):156.24,154.71,154.60,153.36,146.90,146.87,146.42,146.20,146.00(2C),146.59,145.89,145.86,145.78,145.74,145.69,145.67,145.50,145.33,145.28,145.17,145.15,145.04(2C),144.98(2C),144.96,144.90,144.47,144.33,144.15,144.12,142.95,142.82,142.42,142.40,142.39,142.36,141.97,141.96,141.93,141.89,141.85,141.83,141.81(2C),141.64,141.59,141.51,141.45,140.04,139.99,139.67,139.42,136.92,136.11,135.44,135.24,77.85,75.85,70.15,66.24,46.61,23.91,13.74,12.10.MS(APCI):m/z=820(M+1)+,720(C60)+。
Claims (10)
2.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述富勒烯为富勒烯C60或富勒烯C70。
3.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述有机卤化物为R1CH2F,R1CH2Cl,R1CH2Br,R1CH2I之一,R1独立地为任意有机侧链。
4.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,按摩尔比,反应原料有机卤化物:富勒烯为1:0~10,优选的,反应原料有机卤化物:富勒烯为1:0.2。
5.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述α-氨基酸可为R2NHCH(R3)COOH,R2和R3独立地为任意有机侧链。
6.如权利要求1和权利要求5所述的富勒烯吡咯烷衍生的合成方法,其特征在于,按摩尔比,反应原料α-氨基酸:富勒烯为1:0~10。
7.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于所述有机溶剂为苯、甲苯、邻二甲苯、对二甲苯、间二甲苯、乙苯、氯苯、氟苯、溴苯、邻二氯苯、间二氯苯、对二氯苯之一。
8.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述催化剂二甲亚砜用量,按体积比,有机溶剂:二甲亚砜为1:0~2。
9.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述反应的温度在50~180℃之间,反应时间为0.1~48小时。
10.如权利要求1所述的富勒烯吡咯烷衍生的合成方法,其特征在于,所述硅胶柱层析步骤中,硅胶的目数为200~400目;所述洗脱剂为由体积比为1:0~5的甲苯和二硫化碳组成的混合溶剂或由体积比为1:0~1的甲苯和石油醚组成的混合溶剂。
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