CN114773226B - 一种用光电一体催化制备氘代乙腈的方法 - Google Patents
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Abstract
本发明公开了一种用光电一体催化高效制备氘代乙腈的方法,该方法是以最廉价易得的氘水为氘源,以乙腈为原料,采用多种催化剂协同作用,在室温下反应若干小时。反应结束后通过减压蒸馏并通过干燥后,即可得到氘代乙腈。经过高分辨质谱检测其氘代率大于99.8%,符合商业氘代乙腈的标准。
Description
技术领域
本发明属于化学合成领域,具体涉及新型光电一体催化制备氘代乙腈的方法。
背景技术
氘代乙腈是一种有机溶剂,可作为非质子性溶剂用于有机反应,同时,氘代乙腈也是一种最常用的核磁(NMR)检测溶剂。目前其主要制备方法是在强碱和高温的作用下,拔去乙腈中-CH3的质子,氘水中的D+发生亲电反应,从而完成H-D交换。该传统方法往往耗时长、能耗高、氘代率低等缺点,大大提高了氘代乙腈的成本。CN 114436893 A中提及了利用纳米级负载型催化剂制备氘代乙腈,然而该方法需要加热且耗时较长,此外催化剂的制备过程较为繁琐。目前国内氘代乙腈的价格普遍在5000元/100克,因此开发一种更加绿色、环保、低成本的氘代方法成为研究热点。
控制和减少温室气体排放、推动绿色低碳发展的重大创新成为目前科研和工业领域的主旋律。光电催化较于传统热催化具有对环境友好、能耗低、反应性能优越等特点,被广泛应用于各种领域的反应。二氧化钛作(TiO2)为一种优良的光敏型半导体材料,其禁带宽度为3.2eV, 当受到波长≤387.5nm的紫外光照射时,价带的电子(e-)就会获得光子的能量而被激发至导带上并在电场作用下迁移到TiO2粒子表面,相应地形成光生空穴(h+),从而产生具有高活性的空穴。空穴可以获取吸附或靠近在TiO2表面物质的电子,发生氧化还原反应。因此TiO2被广泛用于光解水和有机物C-H键的活化领域。
发明内容
本发明的目的在于提供一种快速、高效、廉价的方法制备氘代乙腈。
本发明提供的一种用光电一体催化制备氘代乙腈的方法,其特征在于,以氘水和乙腈为反应原料,以氘代DMSO、路易斯酸、TiO2、电解质、硼烷衍生物为复合催化剂,在惰性气氛保护下,一定温度下紫外光电催化反应制备氘代乙腈。
本发明涉及的一种用光电一体催化制备氘代乙腈的方法,其具体步骤如下:
(1)将一定量的乙腈加入氘水中,并加入复合催化剂,N2保护下充分搅拌均匀;
(2)功率5W-20W,波长在265-390nm之间的紫外灯照射下,C(+)/Pt(-)做电极,10-20mA电流下,15-30℃充分反应0.5-2h;
(3)反应结束后,过滤收集催化剂,40℃下减压蒸馏收集得到氘代乙腈粗品;
(4)将氘代乙腈粗品干燥得到氘代乙腈纯品。
步骤(1)乙腈和氘水之间的摩尔比为1:5~50;
步骤(1)乙腈和复合催化剂之间的摩尔比依次为:n(乙腈):n(氘代DMSO):n(路易斯酸):n(TiO2):n(电解质):n(硼烷衍生物) =1 : 0.01-0.5 : 0.0001-0.01 : 0.0001-0.01 : 0.001-0.05 : 0.0001-0.01;
步骤(1)所述惰性气氛为氮气气氛或氩气气氛,优选为氮气气氛。
步骤(4)干燥为使用干燥剂将氘代乙腈粗品干燥;所述的干燥剂选自无水CaSO4、无水CaCl2、无水MgSO4、无水Na2SO4等。
所述的路易斯酸为路易斯酸一种或几种混合,例如FeCl3、Co(NO3)2、AgNO3、Fe(NO3)3、H2SO4、HCl、CuCl2等,进一步优选为FeCl3、Co(NO3)2、AgNO3、Fe(NO3)3、H2SO4中的一种或几种。
所述的电解质选自四烷基季铵盐类电解质中的一种或几种的混合物,所述的烷基为具有1~20个碳原子的直链或支链的烷基,优选地为具有2~10个碳原子的直链或支链的烷基。所述的烷基在每种情况下独立地相同或不同。示例性的烷基包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正己基、正庚基、正辛基、正壬基、正癸基、2-乙基己基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基等。所述四烷基季铵盐阴离子包括但不限于卤素离子(例如氟、氯、溴、碘)、四氟硼酸根阴离子、六氟磷酸根阴离子等。优选地,本发明所述电解质选自四丁基四氟硼酸铵,四丁基四氟磷酸铵,四丁基溴化铵,四乙基氯化铵,四甲基氯化铵、四乙基溴化铵、十六烷基三甲基溴化铵等中的一种或几种的混合物。
所述的硼烷衍生物为BnHn 2-、BnHn+1 -、BnHn+2、CaBn−aHn−a+2中的一种或几种,其中n为6,7,8,9,10,12,20,24中的一种;a为1,2,3,4中的一种。当所述的硼烷衍生物具有前述阴离子结构时,所述的硼烷衍生物配位阳离子为碱金属或过渡族金属中的一种或几种,例如Na+,Li+,K+,Cs+,Mg2+,Cr3+,Ru3+,Al3+,Mn4+等的一种或几种。优选为Li+,Na+,Cs+,Ru3+,Al3+的一种或几种。优选地,所述的硼烷衍生物为Na2B12H12、NaB6H7、B10H14、Cs2B8H8、Li2B12H12、C2B10H12、Al2(B10H10)3、RuB10H11、Na2B24H24、Li2B12H12、Na2B6H6 、NaCB9H10中的一种或几种。
与现有技术相比,本发明具有如下优点:
(1)本发明首次采用复合催化剂在光电一体催化下实现了乙腈的氘化反应;
(2)本发明采用氘水作为氘源,极大地降低了氘代成本;
(3)与传统技术相比,本发明室温即可进行反应,且反应耗时短,产率高,具有操作容易、环境友好等优点,有助于氘代乙腈的工业化生产。
附图说明
图1是实施例1制备原料乙腈的核磁1H NMR图谱。
图2是实施例1制备的产物氘代乙腈的核磁1H NMR图谱。
图3是实施例1制备原料乙腈的核磁13C NMR图谱。
图4是实施例1制备的产物氘代乙腈的核磁13C NMR图谱。
具体实施方式
下面通过实施例对本发明作进一步详细说明,但本发明的保护范围不局限于所述内容。
实施例1:
(1)将10mmol的乙腈加入100mmol氘水中,并加入复合催化剂(氘代DMSO:5mmol,H2SO4:0.1mmol,TiO2:0.1mmol,四丁基四氟硼酸铵:0.5mmol,NaB6H7:0.1mmol),N2保护下充分搅拌均匀;
(2)功率20W,波长在365nm的紫外灯照射下,C(+)/Pt(-)做电极,10mA电流下,25℃充分反应0.5 h;
(3)反应结束后,过滤收集催化剂,滤液在40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水Na2SO4干燥24 h即可得到氘代乙腈纯品,收率为99.10%,高分辨质谱检测其氘代率为99.92%。乙腈氘代前后的核磁对比谱图见附图(图1、图2、图3、图4,溶剂为D2O)。
实施例2:
(1)将1mmol的乙腈加入5mmol氘水中,并加入复合催化剂(氘代DMSO:0.08 mmol,FeCl3:0.02 mmol,TiO2:0.05 mmol,四甲基氯化铵:0.03 mmol,Cs2B8H8:0.025 mmol,B10H14:0.025 mmol),N2保护下充分搅拌均匀;
(2)功率5W,波长在390nm的紫外灯照射下,C(+)/Pt(-)做电极,15mA电流下,20℃充分反应1 h;
(3)反应结束后,过滤收集催化剂,滤液在40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水MgSO4干燥24 h即可得到氘代乙腈纯品,收率为99.21%,高分辨质谱检测其氘代率为99.86%。
实施例3:
(1)将5mmol的乙腈加入100mmol氘水中,并加入复合催化剂(氘代DMSO:0.25mmol,AgNO3:0.025mmol,TiO2:0.05mmol,四丁基六氟磷酸铵:0.025mmol,C2B10H12:0.05mmol),N2保护下充分搅拌均匀;
(2)功率25W,波长在265nm的紫外灯照射下,C(+)/Pt(-)做电极,20mA电流下,15℃充分反应2 h;
(3)反应结束后,过滤收集催化剂,滤液在40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水CaCl2干燥24 h即可得到氘代乙腈纯品,收率为99.43%,高分辨质谱检测其氘代率为99.91%。
实施例4:
(1)将0.5mmol的乙腈加入20mmol氘水中,并加入复合催化剂(氘代DMSO:0.08mmol,Co(NO3)2:0.025 mmol,TiO2:0.025 mmol,四乙基溴化铵:0.03 mmol,Li2B12H12:0.05mmol),N2保护下充分搅拌均匀;
(2)功率20W,波长在300nm的紫外灯照射下,C(+)/Pt(-)做电极,20mA电流下,30℃充分反应0.5 h;
(3)反应结束后,过滤收集催化剂,滤液在40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水Na2SO4干燥24 h即可得到氘代乙腈纯品,收率为99.16%,高分辨质谱检测其氘代率为99.95%。
实施例5:
(1)将2mmol的乙腈加入100mmol氘水中,并加入复合催化剂(氘代DMSO:0.2mmol,Co(NO3)2:0.03 mmol,H2SO4:0.025mmol,CuCl2: 0.05mmol, TiO2:0.04 mmol,四乙基溴化铵:0.015 mmol,四丁基四氟硼酸铵:0.02 mmol,RuB10H11:0.03 mmol,Na2B24H24:0.02mmol),N2保护下充分搅拌均匀;
(2)功率10W,波长在375nm的紫外灯照射下,C(+)/Pt(-)做电极,10mA电流下,25℃充分反应1 h;
(3)反应结束后,过滤除去催化剂,40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水CaSO4干燥即可得到氘代乙腈纯品,收率为99.55%,高分辨质质谱测其氘代率为99.98%。
实施例6:
(1)将50mmol的乙腈加入1250mmol氘水中,并加入复合催化剂(氘代DMSO:25mmol,Fe(NO3)3:0.025mmol,ZnCl2:0.1mmol,TiO2:0.375mmol,十六烷基三甲基溴化铵:0.5mmol,四丁基溴化铵:0.5mmol,Al2(B10H10)3:0.125mmol),N2保护下充分搅拌均匀;
(2)功率20W,波长在265nm的紫外灯照射下,C(+)/Pt(-)做电极,15mA电流下,20℃充分反应1.5 h;
(3)反应结束后,过滤收集催化剂,滤液在40℃下减压蒸馏得到氘代乙腈粗品;
(4)利用无水Na2SO4干燥24 h即可得到氘代乙腈纯品,收率为99.8%,高分辨质谱检测其氘代率为99.96%。
以上列举的仅是本发明的具体实施例。显然本发明不限于以上实施例,还可以有许多变化。在氘代合成领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变化,如复合催化剂中路易斯酸,电解质,硼烷衍生物也可以是两种或者两种以上。此外,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种用光电一体催化制备氘代乙腈的方法,其特征在于,具体步骤如下:
(1)将一定量的乙腈加入氘水中,并加入复合催化剂,惰性气氛保护下充分搅拌均匀;
(2)功率5W-20W,波长在265-390nm之间的紫外灯照射下,C(+)/Pt(-)做电极,10-20mA电流下,15-30℃充分反应0.5-2h;
(3)反应结束后,过滤收集催化剂,40℃下减压蒸馏收集得到氘代乙腈粗品;
(4)将氘代乙腈粗品干燥得到氘代乙腈纯品;
其中,所述复合催化剂由氘代DMSO、路易斯酸、TiO2、电解质和硼烷衍生物构成;
路易斯酸选自FeCl3、Co(NO3)2、AgNO3、Fe(NO3)3、H2SO4、HCl、CuCl2中的一种或几种;
电解质选自四烷基季铵盐类电解质中的一种或几种;
所述的硼烷衍生物为BnHn 2-、BnHn+1 -、BnHn+2、CaBn−aHn−a+2中的一种或几种,其中n为6,7,8,9,10,12,20,24中的一种;a为1,2,3,4中的一种;当所述的硼烷衍生物具有前述阴离子结构时,所述的硼烷衍生物配位阳离子为碱金属或过渡族金属中的一种或几种。
2.根据权利要求1所述的方法,其特征在于,所述四烷基季铵盐类电解质中的的烷基为具有1~20个碳原子的直链或支链的烷基,所述四烷基季铵盐阴离子选自卤素离子、四氟硼酸根阴离子、六氟磷酸根阴离子。
3.根据权利要求2所述的方法,其特征在于,所述的电解质选自四丁基四氟硼酸铵,四丁基四氟磷酸铵,四丁基溴化铵,四乙基氯化铵,四甲基氯化铵、四乙基溴化铵、十六烷基三甲基溴化铵中的一种或几种的混合物。
4.根据权利要求1所述的方法,其特征在于,所述配位阳离子选自Na+,Li+,K+,Cs+,Mg2+,Cr3+,Ru3+,Al3+,Mn4+中的一种或几种。
5.根据权利要求4所述的方法,其特征在于,所述的硼烷衍生物为Na2B12H12、NaB6H7、B10H14、Cs2B8H8、Li2B12H12、C2B10H12、Al2(B10H10)3、RuB10H11、Na2B24H24、Li2B12H12、Na2B6H6、NaCB9H10中的一种或几种。
6.根据权利要求1所述的方法,其特征在于,步骤(1)乙腈和氘水之间的摩尔比为1:5~50。
7.根据权利要求1所述的方法,其特征在于,步骤(1)乙腈和复合催化剂之间的摩尔比依次为:n乙腈:n氘代DMSO:n路易斯酸:nTiO2:n电解质:n硼烷衍生物)=1 : 0.01-0.5 :0.0001-0.01 : 0.0001-0.01 : 0.001-0.05 : 0.0001-0.01。
8.根据权利要求1所述的方法,其特征在于,步骤(4)干燥为使用干燥剂将氘代乙腈粗品干燥;所述的干燥剂选自无水CaSO4、无水CaCl2、无水MgSO4、无水Na2SO4中的一种或几种。
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