CN113333028A - 一种亚磷酰胺羰基氢化铑催化剂及制备方法和应用 - Google Patents
一种亚磷酰胺羰基氢化铑催化剂及制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 6
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- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
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- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 3
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Abstract
本发明公开了一种亚磷酰胺羰基氢化铑催化剂及制备方法和应用,属于有机化学金属化合物合成技术领域。本发明将铑化合物与亚磷酰胺类双膦或四膦配体在合成气的条件下进行反应,制备出亚磷酰胺羰基氢化铑催化剂,然后将催化剂应用于底物为烯烃或炔烃的氢甲酰化反应。本发明制备得到多种含有不同结构配体络合的活性催化剂,其在烯烃或炔烃氢甲酰化反应中可以通过调节配体的结构来改变产物的区域选择性,对于端位烯烃,可以实现直链醛的高效选择转化,对于内烯烃或特殊烯烃,可以高化学选择性的实现醛的生成,芳香烯烃或者炔烃的氢甲酰化反应能高效、高化学选择性的转化为醛。
Description
技术领域
本发明涉及有机化学金属化合物合成技术领域,具体涉及一种亚磷酰胺羰基氢化铑催化剂及制备方法和应用。
背景技术
氢甲酰化反应是指烯烃或者炔烃在过渡金属催化下,与合成气(CO+H2)反应生成多一个碳的醛的反应,原子经济型反应,原子利用率100%,世界的醛产量超千万吨/年,是如今工业中最重要的应用之一。烯烃氢甲酰化反应中所用的金属铑催化前体一般为[Rh(CO)2Cl]2、Rh(COD)2BF4、[Rh(Cp*)Cl2]2、Rh(COD)(acac)、Rh(acac)(CO)2、RhCl3、[Rh(COD)Cl]2、Rh(C2H4)(acac)和[Rh(C2H4)Cl]2,为非活性物种,需要在反应中加入合成气和配体进行预活化,导致反应的效率低下,效果比较差。
发明内容
针对现有技术中存在的上述问题,本发明提供一种亚磷酰胺羰基氢化铑催化剂,该催化剂通式为HRh(L)(CO)2,其中Rh来自于Rh化合物前体,L为亚磷酰胺类膦配体,其中亚磷酰胺类膦配体的通式为式1、式2、式3或式4所示,其中,R1为氢、卤素、叔丁基、苯基、甲氧基、乙氧基、苯氧基、乙酰基、乙酰氧基或三氟甲基,R2为氢、甲基、甲氧酰基或三氟乙酰基,R3为氢、卤素、叔丁基、苯基、甲氧基、乙氧基、苯氧基、乙酰基、乙酰氧基或三氟甲基。
优选的,亚磷酰胺类膦配体为
优选的,铑化合物中金属铑与亚磷酰胺类配体的摩尔比为1:1。
优选的,铑化合物前体为[Rh(CO)2Cl]2、Rh(COD)2BF4、[Rh(Cp*)Cl2]2、Rh(COD)(acac)、Rh(acac)(CO)2、RhCl3、[Rh(COD)Cl]2、Rh(C2H4)(acac)和[Rh(C2H4)Cl]2中的至少一种,其中,acac为乙酰丙酮,COD代表1,4-环辛二烯。
本发明进一步公开了上述亚磷酰胺羰基氢化铑催化剂的制备方法,将铑化合物与亚磷酰胺类配体溶解于有机溶剂中,在25-100℃的条件下与合成气进行反应,制备得到亚磷酰胺羰基氢化铑催化剂。
优选的,有机溶剂为甲苯、二甲苯、三甲苯、四氢呋喃、1,4-二氧六环、二氯甲烷、氯仿、混合烷烃、乙醚或乙腈中的一种或多种。
优选的,合成气压力为0.5MPa-4MPa。
本发明还公开了上述亚磷酰胺羰基氢化铑催化剂在烯烃或炔烃氢甲酰化中的应用,以烯烃或炔烃为底物,在亚磷酰胺羰基氢化铑催化剂作用下生成甲酰化产物。
其中烯烃可以为C2-C16的端烯、内烯、特殊烯烃或芳香烯烃。
其中炔烃可以为C2-C16的内炔、端炔或芳香炔烃。
具体的,C2-C16的端烯结构为乙烯、丙烯、1-丁烯、戊烯、1-己烯、1-庚烯、1-辛烯、混合内辛烯、1-壬烯、1-癸烯中的一种;内烯烃结构为混合2-丁烯、混合内戊烯、2-己烯、混合内庚烯、混合内壬烯、混合内癸烯中的一种;特殊烯烃结构为乙烯基乙醚、甲基丙烯、醋酸乙烯酯、丙烯酸酯、环己烯、降冰片烯、双环戊二烯、降冰片二烯、丁烯酸酯、坎烯、蒎烯中的一种。
具体的,C2-C16的端炔结构为乙炔、丙炔、丁炔、戊炔、己炔、庚炔、辛炔、癸炔中的一种;C2-C16的内炔结构为内丁炔、内戊炔、内己炔、内庚炔、内辛炔、内癸炔中的一种。
具体的,芳香烯烃为苯乙烯、苯丙烯、甲基苯乙烯、苯丁烯以及芳环上官能化取代的上述芳香烯烃。
本发明所产生的有益效果为:
1、提供一种新的亚磷酰胺羰基氢化铑催化剂的制备和应用;
2、C2-C16的端烯和端炔,能高活性高直链选择性的转化为醛;
3、对于特殊烯烃和芳香烯烃、炔烃,能高活性高化学选择性的转化为醛;
4、此催化剂可以循环使用,且可以不需另外补充膦配体。
附图说明
图1为实施例1亚磷酰胺羰基氢化铑催化剂核磁共振(NMR)的P谱(31P NMR);
图2为实施例1亚磷酰胺羰基氢化铑催化剂核磁共振(NMR)的H谱(1H NMR);
图3为实施例2亚磷酰胺羰基氢化铑催化剂核磁共振(NMR)的P谱(31P NMR);
图4为实施例2亚磷酰胺羰基氢化铑催化剂核磁共振(NMR)的P谱(31P NMR)。
具体实施方式
本发明可以制备得到多种含有不同结构配体络合的活性催化剂,其在烯烃或炔烃氢甲酰化反应中的反应效果不同,如可以调节配体的结构来改变产物的区域选择性。
对于端位烯烃,可以实现直链醛的高效选择转化;对于内烯烃或特殊烯烃,可以高化学选择性的实现醛的生成。
芳香烯烃或者炔烃的氢甲酰化反应能高效、高化学选择性的转化为醛。
实施例1
本实施例提供了一种亚磷酰胺羰基氢化铑催化剂的制备方法,包括以下步骤:
将膦配体联萘酚双吲哚基膦L1与金属铑前体Rh(acac)(CO)2以摩尔比为1:1的比例加入高压反应釜,再加入甲苯溶剂后,用合成气置换后充入1MPa合成气并在常温下搅拌2小时,反应液体取出并除掉溶剂可得黄色固体的目标产物HRh(L1)(CO)2,将产物进行核磁共振(NMR)的P谱(31P NMR)和H谱(1H NMR)测试,结果如图1和图2所示,31P NMR中P信号为137.09,JRh-P为217.08,1H NMR中特征的负氢信号为-10.39。
实施例2
本实施例提供了一种亚磷酰胺羰基氢化铑催化剂的制备方法,包括以下步骤:
将膦配体联苯酚双(6-甲氧基)-吲哚基膦L2与金属铑前体Rh(acac)(CO)2以摩尔比为1:1的比例加入高压反应釜,再加入甲苯溶剂后,用合成气置换后充入2MPa合成气并在常温下搅拌2小时,反应液体取出并除掉溶剂可得黄色固体的目标产物HRh(L2)(CO)2,将产物进行核磁共振(NMR)的P谱(31P NMR)和H谱(1H NMR)测试,结果如图3和图4所示,31P NMR中P信号为136.74、135.40,JRh-P为217.08,1H NMR中特征的负氢信号为-10.85。
实施例3
本实施例提供本发明催化剂在烯烃氢甲酰化反应中的应用实例,操作如下:
将实施例1制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L1)(CO)2]0.02mmol,其中L1为亚磷酰胺类配体,加入高压釜,并按照物质的量烯烃:催化剂为1000的比例加入1-己烯进行氢甲酰化,在80℃、10bar合成气下反应2小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例4
本实施例提供本发明催化剂在烯烃氢甲酰化反应中的应用实例,操作如下:
将实施例1制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L1)(CO)2]0.02mmol,其中L1为亚磷酰胺类配体,加入高压釜,并按照物质的量烯烃:催化剂为1000的比例加入2-丁烯进行氢甲酰化,在80℃、20bar合成气下反应2小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例5
本实施例提供本发明催化剂在烯烃氢甲酰化反应中的应用实例,操作如下:
将实施例1制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L1)(CO)2]0.02mmol,其中L1为亚磷酰胺类配体,加入高压釜,并按物质的量照烯烃:催化剂为1000的比例加入2-戊烯进行氢甲酰化,在100℃、30bar合成气下反应4小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例6
本实施例提供本发明催化剂在特殊烯烃氢甲酰化反应中的应用实例,操作如下:
将实施例2制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L2)(CO)2]0.02mmol,其中L2为亚磷酰胺类配体,加入高压釜,并按照物质的量烯烃:催化剂为2000的比例加入乙烯基乙醚进行氢甲酰化,在80℃、10bar合成气下反应2小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例7
本实施例提供本发明催化剂在特殊烯烃氢甲酰化反应中的应用实例,操作如下:
将实施例2制备的催化剂——亚磷酰胺羰基氢化铑0.02mmol[HRh(L2)(CO)2],其中L2为亚磷酰胺类配体,加入高压釜,并按照物质的量烯烃:催化剂为1000的比例加入降冰片烯进行氢甲酰化,在100℃、20bar合成气下反应6小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例8
本实施例提供本发明催化剂在特殊烯烃氢甲酰化反应中的应用实例。操作如下:
将实施例1制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L1)(CO)2]0.02mmol,其中L1为亚磷酰胺类配体,加入高压釜,并按照物质的量烯烃:催化剂为1000的比例加入苯乙烯进行氢甲酰化,在80℃、10bar合成气下反应2小时后,通过气相色谱法进行分析产物含量,结果如下:
实施例9
本实施例提供本发明催化剂在炔烃氢甲酰化反应中的应用实例,操作如下:
将实施例1制备的催化剂——亚磷酰胺羰基氢化铑[HRh(L1)(CO)2]0.02mmol,其中L1为亚磷酰胺类配体,加入高压釜,并按照物质的量炔:催化剂为1000的比例加入苯乙炔进行氢甲酰化,在40℃、10bar合成气下反应2小时后,通过气相色谱法进行分析产物含量,结果如下:
以上内容是结合具体/优选的实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。在不脱离本发明构思的前提下,其还可以对这些已描述的实施方式做出若干替代或变型,而这些替代或变型方式都应当视为属于本发明的保护范围。
Claims (10)
3.根据权利要求1或2所述的一种亚磷酰胺羰基氢化铑催化剂,其特征在于:所述铑化合物中金属铑与亚磷酰胺类配体的摩尔比为1:1。
4.根据权利要求1~3任一项所述的一种亚磷酰胺羰基氢化铑催化剂,其特征在于:所述铑化合物前体为[Rh(CO)2Cl]2、Rh(COD)2BF4、[Rh(Cp*)Cl2]2、Rh(COD)(acac)、Rh(acac)(CO)2、RhCl3、[Rh(COD)Cl]2、Rh(C2H4)(acac)和[Rh(C2H4)Cl]2中的至少一种,其中,acac为乙酰丙酮,COD代表1,4-环辛二烯。
5.权利要求1~4任一项所述的一种亚磷酰胺羰基氢化铑催化剂的制备方法,其特征在于:将铑化合物与亚磷酰胺类配体溶解于有机溶剂中,在25~100℃的条件下与合成气进行反应,制备得到亚磷酰胺羰基氢化铑催化剂。
6.权利要求5所述的一种亚磷酰胺羰基氢化铑催化剂的制备方法,其特征在于:所述有机溶剂为甲苯、二甲苯、三甲苯、四氢呋喃、1,4-二氧六环、二氯甲烷、氯仿、混合烷烃、乙醚或乙腈中的一种或多种。
7.权利要求5或6所述的一种亚磷酰胺羰基氢化铑催化剂的制备方法,其特征在于:所述合成气压力为0.5MPa~4MPa。
8.权利要求1~4任一项所述的一种亚磷酰胺羰基氢化铑催化剂在烯烃或炔烃氢甲酰化中的应用,其特征在于:以烯烃或炔烃为底物,在亚磷酰胺羰基氢化铑催化剂作用下生成甲酰化产物。
9.权利要求8所述的一种亚磷酰胺羰基氢化铑催化剂在烯烃或炔烃氢甲酰化中的应用,其特征在于:所述烯烃为C2-C16的端烯、内烯、特殊烯烃或芳香烯烃;所述C2-C16的端烯结构为乙烯、丙烯、1-丁烯、戊烯、1-己烯、1-庚烯、1-辛烯、混合内辛烯、1-壬烯、1-癸烯中的一种;内烯烃结构为混合2-丁烯、混合内戊烯、2-己烯、混合内庚烯、混合内壬烯、混合内癸烯中的一种;特殊烯烃结构为乙烯基乙醚、甲基丙烯、醋酸乙烯酯、丙烯酸酯、环己烯、降冰片烯、双环戊二烯、降冰片二烯、丁烯酸酯、坎烯、蒎烯中的一种;所述芳香烯烃为苯乙烯、苯丙烯、甲基苯乙烯、苯丁烯以及芳环上官能化取代的上述芳香烯烃。
10.权利要求8所述的一种亚磷酰胺羰基氢化铑催化剂在烯烃或炔烃氢甲酰化中的应用,其特征在于:所述炔烃为C2-C16的内炔、端炔或芳香炔烃;所述C2-C16的端炔结构为乙炔、丙炔、丁炔、戊炔、己炔、庚炔、辛炔、癸炔中的一种;C2-C16的内炔结构为内丁炔、内戊炔、内己炔、内庚炔、内辛炔、内癸炔中的一种。
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