CN111517952B - 一种基于磺化binap和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称氢化方法 - Google Patents
一种基于磺化binap和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称氢化方法 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
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- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明涉及一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,在不对称加氢反应中,只需要催化量的手性膦配体和离子液体一体化的催化剂就可以同时发挥手性催化剂、离子液体和有机溶剂的三重功能,实现高效催化氢化反应和手性催化剂的回收与循环,从而无需再额外添加溶剂离子液体和助有机溶剂,最大程度的降低离子液体和有机溶剂的负效应,实现了高效、绿色和经济的不对称氢化反应,从而克服了现有技术中必须添加大量离子液体和辅助有机溶剂的难题。
Description
技术领域
本发明涉及化学化工技术领域,具体地涉及一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法。
背景技术
在过去的几十年中,均相不对称催化加氢反应由于具有高的催化活性、好的立体选择性及温和的反应条件,已成为获得手性药物、农药和香料等精细化学品的最高效和最原子经济的手段之一。然而,长期以来,手性贵金属催化剂(主要是手性膦配体–金属配合物)与氢化产物难以分离的问题限制了其在工业上的大规模应用。因此,开发可回收和可循环的手性催化剂一直是均相不对称加氢领域的研究焦点。
近年来,随着对绿色化学的日益重视以及对环境友好溶剂的需求,绿色溶剂离子液体吸引了人们的极大关注。与传统的有机溶剂不同,离子液体具有极低的饱和蒸气压、高的热和化学稳定性、对过渡金属催化剂良好的溶解性以及结构的可设计性等优点,因此应用离子液体作为催化剂载体成为一种分离、回收和循环手性催化剂的有效手段。尽管离子液体在不对称氢化反应中用于分离手性催化剂取得了一些成功的应用,但一个难以调和的问题也显现出来,即为了抑制催化剂的流失,通常大量的溶剂离子液体被应用于催化反应中以充分地溶解和固载手性催化剂(达到金属催化剂的140–5000倍(mol/mol),相当于底物的15–2100%,mol%),这既不符合绿色化学的要求,也导致了资源的浪费。而且大量溶剂离子液体的应用也使得离子液体中难以除去的微量杂质对金属催化剂产生的负效应(如使催化剂中毒)变得更加显著,导致催化效率的降低。因此,如何更绿色和经济地应用离子液体以构建高效和可循环的离子液体不对称氢化体系是当前迫切需要解决的难题。
另一方面,在离子液体体系下的不对称氢化反应中,有机溶剂作为溶解离子液体、催化剂、底物和氢化产物的助溶剂一直是必不可少的。有机溶剂作为辅助溶剂不仅可以改善反应的传质,同时也通过参与催化循环促进不对称氢化反应的速率和对映选择性,然而,大量有机溶剂的使用也必然导致潜在的环境问题。因此,如何构建高效的、无溶剂的离子液体不对称氢化体系也是当前亟待解决的问题。
发明内容
本发明所述的一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其发明目的在于针对上述现有技术中存在的局限性,利用离子液体的可设计性和易功能化的特点,将手性双膦配体磺化BINAP的过渡金属配合物与聚醚功能化离子液体进行集成,得到一类磺化BINAP和聚醚功能化离子液体一体化手性催化剂,这种一体化手性催化剂不仅具备手性催化剂的手性诱导能力,同时也是离子液体,具有离子液体的溶解和载体功能。与现有技术中使用的传统的手性催化剂相比,这种一体化手性催化剂的优点是:(1)具有较低的熔点(一般10–60℃,或无熔点),属于一类功能化离子液体,而传统的手性催化剂熔点较高(一般高于100℃),不是离子液体;(2)具备溶解和载体功能,可实现手性催化剂的分离、回收和循环,而传统的手性催化剂不具备这一能力。
本发明的目的,是创建一个高效、无溶剂、经济,可循环的绿色不对称加氢催化体系。在本发明的不对称加氢反应中,只需要催化量的磺化BINAP和聚醚功能化离子液体一体化手性催化剂就可以同时发挥手性催化剂和溶剂离子液体的双重功能,实现手性催化剂的回收与循环,同时无需再额外添加任何溶剂离子液体,最大程度的降低溶剂离子液体的负效应,实现离子液体的绿色、经济的利用;也无需再添加助有机溶剂,实现无溶剂反应,从而克服了现有技术中不对称加氢反应需要大量辅助有机溶剂的难题。
为实现上述发明的目的,一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其特征在于:催化反应体系是由磺化BINAP和聚醚功能化离子液体一体化的手性催化剂和底物组成,不对称加氢反应在一定的反应温度和氢气压力下进行,其中,磺化BINAP和聚醚功能化离子液体一体化手性催化剂的结构式为:
手性催化剂7为M(X)2(BINAP-(SO3A)k),其是3和4以任意比例组成的混合物,3<k<4;
手性催化剂8为[M(X)n(Q)(BINAP-(SO3A)k)]Y,其是5和6以任意比例组成的混合物,3<k<4;
1或2中BINAP-(SO3A)2表示手性膦配体,其结构式如下:
3和5中BINAP-(SO3A)4表示手性膦配体,其结构式如下:
4和6中BINAP-(SO3A)3表示手性膦配体,其结构式如下:
其中,手性膦配体的立体构型为S型或R型;
A表示有机鎓盐阳离子,其结构式如下:
其中,m=4–140,R1为C1–C12烷基或苯基,l=0–140,R2为C1–C12烷基或苯基;R3为C1-C4直链烷基;R4为H或C1-C4直链烷基;
在1、3、4和7中:M为正二价RuⅡ,X=Cl,Br或I;
在2、5、6和8中:n=1,M为正二价RuⅡ,X=Cl,Br或I,Q是苯(C6H6)配体或对-甲基异丙基苯(p-MeC6H4CHMe2)配体,Y=Cl,Br或;
底物是β-酮酸酯,其结构式如下:
其中,R5是苯基、取代苯基或C1-C15的直链烷基;R6是甲基、乙基、异丙基或叔丁基。
磺化BINAP和聚醚功能化离子液体一体化手性催化剂的分离、回收和循环方法如下:不对称氢化反应结束后用溶剂萃取产物,催化体系分成两相,上层为萃取溶剂和产物组成的有机相,下层为手性催化剂相,通过简单的两相分离实现手性催化剂的回收和循环使用。
一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其特征在于:将手性催化剂1、2、3、4、5、6、7或8和底物加入反应器,底物与手性催化剂的摩尔比是100:1–30000:1,氢气压力为0.1–10MPa,反应温度为20–100℃,反应时间为5–72小时,结束反应后加入溶剂萃取产物,上层为萃取溶剂和产物组成的有机相,下层为手性催化剂相,通过简单的两相分离实现手性催化剂的回收,然后补加新的底物进行下一个催化循环;底物是β-酮酸酯,其结构式如下:
其中,R5是苯基、取代苯基或C1-C15的直链烷基;R6是甲基、乙基、异丙基或叔丁基;
萃取溶剂是乙醚、甲基叔丁基醚、C6–C10的烷烃、30–60℃沸程的石油醚、60–90℃沸程的石油醚和90–120℃沸程的石油醚中的任意一种或任意几种的混合溶剂。
与现有技术相比,本发明涉及一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称氢化的方法,在不对称加氢反应中,只需要催化量的磺化BINAP和聚醚功能化离子液体一体化手性催化剂就可以同时发挥手性催化剂、溶剂离子液体和有机溶剂的三重功能,实现手性催化剂的回收与循环,从而无需再额外添加溶剂离子液体和有机溶剂,最大程度的降低溶剂离子液体和有机溶剂的负效应,实现了高效、绿色和经济的不对称氢化反应,从而克服了现有技术中回收手性催化剂需要大量溶剂离子液体和有机溶剂的难题。
本发明具有的优点和显著的技术进步是:
1、高活性:磺化BINAP和聚醚功能化离子液体一体化的手性催化剂具有高催化活性,在无溶剂条件下,催化β-酮酸酯的不对称加氢反应,TOF值最高达到200h-1以上,与BINAP在甲醇中的活性相当;而而在无溶剂条件下,BINAP的活性仅为40h-1左右。
2、高对映选择性:磺化BINAP和聚醚功能化离子液体一体化的手性催化剂在无溶剂条件下对β-酮酸酯的不对称加氢反应具有很高的对映选择性,而传统的BINAP型手性催化剂必须在有机溶剂存在下才能获得较高的对映选择性。
3、高稳定性、低流失、无溶剂离子液体和无助溶剂:本发明所述的一种基于磺化BINAP和聚醚功能化离子液体一体化的手性催化剂的无溶剂不对称氢化的方法用于β-酮酸酯的不对称加氢反应,磺化BINAP和聚醚功能化离子液体一体化的手性催化剂的用量仅为底物的0.01%–1%(mol/mol),经5-7次循环后活性和对映选择性没有明显降低,贵金属的流失率仅为0.05%–0.3%,证明只需要催化量的磺化BINAP和聚醚功能化离子液体一体化的手性催化剂即可实现催化反应及手性催化剂的分离、回收和循环,而无需添加任何溶剂离子液体作为催化剂载体以及任何的有机溶剂作为助溶剂,从而实现了离子液体和有机溶剂在不对称氢化反应中高效、绿色和经济的利用;而传统的Ru-BINAP手性催化剂在相同条件下无法进行催化剂的分离、回收和循环。
具体实施方式
实施例1
催化剂1a-1/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1a-1为Ru(Br)2(S-BINAP-(SO3A)2)(A=[Ph(OCH2CH2)16IMCH3]+,m=16,l=0,R1=Ph,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1a-1和乙酰乙酸甲酯,催化剂1a-1和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.0%;压降法测定反应初始TOF值为165.2h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.1%(2);100%,96.1%(3);100%,95.7%(4);100%,95.8%(5),每次循环钌的流失率为0.1%–0.3%。
实施例2
催化剂1a-2/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1a-2为Ru(Br)2(S-BINAP-(SO3A)2)(A=[Ph(OCH2CH2)70IMCH3]+,m=16,l=0,R1=Ph,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1a-2和乙酰乙酸甲酯,催化剂1a-2和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.2%;压降法测定反应初始TOF值为156.6h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.2%(2);100%,96.1%(3);100%,96.1(4);100%,96.0(5),每次循环钌的流失率为0.05%–0.1%。
实施例3
催化剂1a-3/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1a-3为Ru(Br)2(S-BINAP-(SO3A)2)(A=[n-C12H25(OCH2CH2)16IMCH3]+,m=16,l=0,R1=n-C12H25,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1a-3和乙酰乙酸甲酯,催化剂1a-3和乙酰乙酸甲酯的摩尔比是1:10000,然后在80℃,4.0MPa的氢气压力下反应72h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率73%,ee(S)值95.0%。
实施例4
催化剂1a-4/乙酰乙酸乙酯体系下催化不对称氢化反应
催化剂1a-4为Ru(Br)2(R-BINAP-(SO3A)2)(A=[Ph(OCH2CH2)16IMCH3]+,m=16,l=0,R1=Ph,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1a-4和乙酰乙酸乙酯,催化剂1a-4和乙酰乙酸乙酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(R)值92.0%;压降法测定反应初始TOF值为155.8h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸乙酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,92.0%(2);100%,92.0%(3);100%,91.8(4);100%,91.8(5),每次循环钌的流失率为0.1%–0.2%。
实施例5
催化剂1a-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1a-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[CH3(OCH2CH2)16IMCH3]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1a-5和乙酰乙酸甲酯,催化剂1a-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.5%;压降法测定反应初始TOF值为181.0h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.5%(2);100%,95.4%(3);100%,95.2(4);100%,94.8(5),100%,94.6(6),每次循环钌的流失率为0.1%–0.2%。
实施例6
催化剂2a-1/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂2a-1为[RuI(p-Cymene)(S-BINAP-(SO3A)2)]I(A=[CH3(OCH2CH2)16IMCH3]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂2a-1和乙酰乙酸甲酯,催化剂2a-1和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.0%;压降法测定反应初始TOF值为175.6h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.0%(2);100%,96.0%(3);100%,95.8(4),100%,95.8%(5),每次循环钌的流失率为0.1%–0.2%。
实施例7
催化剂1a-5/β-酮酸酯(R5=Et,R6=Me)体系下催化不对称氢化反应
在氩气氛下,在高压反应釜中加入催化剂1a-5和β-酮酸酯(R5=Et,R6=Me),催化剂1a-5和β-酮酸酯(R5=Et,R6=Me)的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后,加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.8%。下层的催化剂相经两相分离后继续补加β-酮酸酯(R5=Et,R6=Me),进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.5%(2);100%,96.4%(3);100%,96.1%(4);100%,96.1%(5),每次循环钌的流失率为0.1%–0.2%。
实施例8
催化剂1a-5/β-酮酸酯(R5=Ph,R6=Et)体系下催化不对称氢化反应
在氩气氛下,在高压反应釜中加入催化剂1a-5和β-酮酸酯(R5=Ph,R6=Et),催化剂1a-5和β-酮酸酯(R5=Ph,R6=Et)的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应40h,反应结束后,加入正庚烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率95.5%,ee(S)值83.0%。
实施例9
催化剂1a-5/β-酮酸酯(R5=n-C15H31,R6=Me)体系下催化不对称氢化反应
在氩气氛下,在高压反应釜中加入催化剂1a-5和β-酮酸酯(R5=n-C15H31,R6=Me),催化剂1a-5和β-酮酸酯(R5=n-C15H31,R6=Me)的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应40h,反应结束后,加入甲基叔丁基醚萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率90.5%,ee(S)值95.0%。
实施例10
催化剂1b-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1b-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[(N-(CH2CH2O)16CH3)Py]+,m=16,R1=CH3)。在氩气氛下,在高压反应釜中加入催化剂1b-5和乙酰乙酸甲酯,催化剂1b-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.0%;压降法测定反应初始TOF值为195.6h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.0%(2);100%,96.0%(3);100%,95.6%(4);100%,95.5%(5),每次循环钌的流失率为0.1%–0.3%。
实施例11
催化剂1c-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1c-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[CH3(OCH2CH2)16NEt3]+,m=16,R1=CH3,R3=Et)。在氩气氛下,在高压反应釜中加入催化剂1c-5和乙酰乙酸甲酯,催化剂1c-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.6%;压降法测定反应初始TOF值为169.0h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.5%(2);100%,95.2%(3);100%,95.3%(4);100%,95.0%(5),每次循环钌的流失率为0.1%–0.2%。
实施例12
催化剂1d-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1d-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[CH3(OCH2CH2)16PEt3]+,m=16,R1=CH3,R3=Et)。在氩气氛下,在高压反应釜中加入催化剂1d-5和乙酰乙酸甲酯,催化剂1d-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.8%;压降法测定反应初始TOF值为173.0h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.6%(2);100%,95.4%(3);100%,95.2%(4);100%,95.0%(5),每次循环钌的流失率为0.1%–0.2%。
实施例13
催化剂1e-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1e-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[CH3(OCH2CH2)16TMG]+,m=16,R1=CH3,R4=H)。在氩气氛下,在高压反应釜中加入催化剂1e-5和乙酰乙酸甲酯,催化剂1e-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.3%;压降法测定反应初始TOF值为181.4h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.3%(2);100%,96.4%(3);100%,96.0%(4);100%,95.7%(5),每次循环钌的流失率为0.1%–0.2%。
实施例13
催化剂1f-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1f-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[(N-(CH2CH2O)16CH3)(N-CH3)Pi]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1f-5和乙酰乙酸甲酯,催化剂1f-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.6%;压降法测定反应初始TOF值为186.5h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.5%(2);100%,95.4%(3);100%,95.4%(4);100%,95.2%(5),每次循环钌的流失率为0.1%–0.2%。
实施例14
催化剂1g-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1g-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[(N-(CH2CH2O)16CH3)(N-CH3)Mor]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1g-5和乙酰乙酸甲酯,催化剂1g-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.0%;压降法测定反应初始TOF值为194.5h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.0%(2);100%,96.1%(3);100%,95.8%(4);100%,95.8%(5),每次循环钌的流失率为0.1%–0.2%。
实施例15
催化剂1h-5/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂1h-5为Ru(Br)2(S-BINAP-(SO3A)2)(A=[(N-(CH2CH2O)16CH3)(N-CH3)Pyrr]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂1h-5和乙酰乙酸甲酯,催化剂1h-5和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.8%;压降法测定反应初始TOF值为179.8h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.8%(2);100%,95.7%(3);100%,95.6%(4);100%,95.5%(5),每次循环钌的流失率为0.1%–0.2%。
实施例16
催化剂7a-1/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂7a-1为Ru(Br)2(S-BINAP-(SO3A)3.5)(k=3.5,A=[Ph(OCH2CH2)16IMCH3]+,m=16,l=0,R1=Ph,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂7a-1和乙酰乙酸甲酯,催化剂7a-1和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值96.1%;压降法测定反应初始TOF值为139.2h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,96.1%(2);100%,96.0%(3);100%,96.0%(4);100%,95.8%(5),每次循环钌的流失率为0.1%–0.2%。
实施例17
催化剂7a-2/乙酰乙酸甲酯体系下催化不对称氢化反应
催化剂7a-2为Ru(Br)2(S-BINAP-(SO3A)3.5)(k=3.5,A=[CH3(OCH2CH2)16IMCH3]+,m=16,l=0,R1=CH3,R2=CH3)。在氩气氛下,在高压反应釜中加入催化剂7a-2和乙酰乙酸甲酯,催化剂7a-2和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后加入正己烷萃取,上层有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值95.3%;压降法测定反应初始TOF值为222.8h-1;下层的催化剂相经两相分离后继续补加乙酰乙酸甲酯,进行下一次循环,经5次循环转化率和ee值均无明显降低,分别为:100%,95.2%(2);100%,95.2%(3);100%,95.0%(4);100%,95.0%(5),每次循环钌的流失率为0.1%–0.2%。
实施例18
对比实验-1:Ru(Br)2(S-BINAP)/乙酰乙酸甲酯体系下催化不对称氢化反应
在氩气氛下,在高压反应釜中加入催化剂Ru(Br)2(S-BINAP)和乙酰乙酸甲酯,Ru(Br)2(S-BINAP)和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后,加入正己烷萃取,萃取液进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值87.4%;压降法测定反应初始TOF值为40.3h-1;手性催化剂Ru(Br)2(S-BINAP)无法分离、回收和循环。
实施例19
对比实验-2:Ru(Br)2(S-BINAP)/乙酰乙酸甲酯/甲醇体系下不对称氢化反应
在氩气氛下,在高压反应釜中加入催化剂Ru(Br)2(S-BINAP)、乙酰乙酸甲酯和甲醇,Ru(Br)2(S-BINAP)和乙酰乙酸甲酯的摩尔比是1:1000,然后在60℃,4.0MPa的氢气压力下反应20h,反应结束后减压除去甲醇,有机相进气相色谱分析(lipodex A 25m×0.25mm手性毛细管柱),底物转化率100%,ee(S)值98.4%。;压降法测定反应初始TOF值为207h-1。催化剂无法实现分离、回收和循环利用。
Claims (3)
1.一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其特征在于:催化反应体系是由磺化BINAP和聚醚功能化离子液体一体化的手性催化剂和底物组成,底物与手性催化剂的摩尔比是100:1–30000:1,氢气压力为4.0MPa,反应温度为20–100℃,反应时间为5–72小时,其中,磺化BINAP和聚醚功能化离子液体一体化手性催化剂的结构式为:
手性催化剂7为M(X)2(BINAP-(SO3A)k),其是3和4以任意比例组成的混合物,3<k<4;
手性催化剂8为[M(X)n(Q)(BINAP-(SO3A)k)]Y,其是5和6以任意比例组成的混合物,3<k<4;1或2中BINAP-(SO3A)2表示手性膦配体,其结构式如下:
3和5中BINAP-(SO3A)4表示手性膦配体,其结构式如下:
4和6中BINAP-(SO3A)3表示手性膦配体,其结构式如下:
其中,手性膦配体的立体构型为S型或R型;
A表示有机鎓盐阳离子,其结构式如下:
其中,m=4–140,R1为C1–C12烷基或苯基,l=0–140,R2为C1–C12烷基或苯基;R3为C1-C4直链烷基;R4为H或C1-C4直链烷基;
在1、3、4和7中:M为正二价RuⅡ,X=Cl,Br或I;
在2、5、6和8中:n=1,M为正二价RuⅡ,X=Cl,Br或I,Q是苯(C6H6)配体或对-甲基异丙基苯(p-MeC6H4CHMe2)配体,Y=Cl,Br或I;
底物是β-酮酸酯,其结构式如下:
其中,R5是苯基或C1-C15的直链烷基;R6是甲基、乙基、异丙基或叔丁基。
2.按照权利要求1的一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其特征在于:不对称氢化反应结束后用溶剂萃取产物,催化体系分成两相,上层为萃取溶剂和产物组成的有机相,下层为手性催化剂相,通过简单的两相分离实现手性催化剂的回收和循环使用。
3.按照权利要求1的一种基于磺化BINAP和聚醚功能化离子液体一体化手性催化剂的无溶剂不对称催化氢化的方法,其特征在于:将手性催化剂1、2、3、4、5、6、7或8和底物加入反应器,底物与手性催化剂的摩尔比是100:1–30000:1,氢气压力为4.0MPa,反应温度为20–100℃,反应时间为5–72小时,结束反应后加入溶剂萃取产物,上层为萃取溶剂和产物组成的有机相,下层为手性催化剂相,通过简单的两相分离实现手性催化剂的回收,然后补加新的底物进行下一个催化循环;底物是β-酮酸酯,其结构式如下:
其中,R5是苯基或C1-C15的直链烷基;R6是甲基、乙基、异丙基或叔丁基;
萃取溶剂是乙醚、甲基叔丁基醚、C6–C10的烷烃、30–60℃沸程的石油醚、60–90℃沸程的石油醚和90–120℃沸程的石油醚中的任意一种或任意几种的混合溶剂。
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