CN109265489B - 一种制备环碳酸酯的方法 - Google Patents
一种制备环碳酸酯的方法 Download PDFInfo
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- CN109265489B CN109265489B CN201810720223.3A CN201810720223A CN109265489B CN 109265489 B CN109265489 B CN 109265489B CN 201810720223 A CN201810720223 A CN 201810720223A CN 109265489 B CN109265489 B CN 109265489B
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011701 zinc Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- -1 cyclic carbonate compounds Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 168
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 39
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 19
- 125000004104 aryloxy group Chemical group 0.000 claims description 18
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 9
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 6
- 235000015110 jellies Nutrition 0.000 claims description 6
- 239000008274 jelly Substances 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- MZMAVYWAMJJEKA-UHFFFAOYSA-N 2,4-ditert-butyl-6-[[(3,5-ditert-butyl-2-hydroxyphenyl)methyl-[2-(2-hydroxyethoxy)ethyl]amino]methyl]phenol Chemical compound CC(C)(C)c1cc(CN(CCOCCO)Cc2cc(cc(c2O)C(C)(C)C)C(C)(C)C)c(O)c(c1)C(C)(C)C MZMAVYWAMJJEKA-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 abstract description 13
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- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000003818 flash chromatography Methods 0.000 description 11
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
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- 230000003197 catalytic effect Effects 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 4
- 240000001414 Eucalyptus viminalis Species 0.000 description 4
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 2
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 2
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- 238000007259 addition reaction Methods 0.000 description 2
- JCWMQECJDTYOET-UHFFFAOYSA-N cyclopenta-1,3-diene;ytterbium(3+) Chemical compound [Yb+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 JCWMQECJDTYOET-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BYHHBFGJQQWWIX-UHFFFAOYSA-N C(C1=CC=CC=C1)O[Zn] Chemical compound C(C1=CC=CC=C1)O[Zn] BYHHBFGJQQWWIX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 1
- TWIIVLKQFJBFPW-UHFFFAOYSA-N acetaminosalol Chemical compound C1=CC(NC(=O)C)=CC=C1OC(=O)C1=CC=CC=C1O TWIIVLKQFJBFPW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- FXSKDNJWXMDRDI-UHFFFAOYSA-M benzyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 FXSKDNJWXMDRDI-UHFFFAOYSA-M 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ASFLJDMPHLYHLV-UHFFFAOYSA-N lanthanum zinc Chemical compound [Zn].[Zn].[Zn].[Zn].[Zn].[La] ASFLJDMPHLYHLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JLMHVMIMUYHBRQ-UHFFFAOYSA-N neodymium zinc Chemical compound [Zn].[Nd] JLMHVMIMUYHBRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VNQQJIQPDCMEMS-UHFFFAOYSA-N ytterbium zinc Chemical compound [Zn].[Yb] VNQQJIQPDCMEMS-UHFFFAOYSA-N 0.000 description 1
- ZPBLKGWQKXKXOZ-UHFFFAOYSA-N yttrium zinc Chemical compound [Zn].[Y] ZPBLKGWQKXKXOZ-UHFFFAOYSA-N 0.000 description 1
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- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开一种制备环碳酸酯的方法,属于有机化合物的制备技术领域。本发明的方法能够在温和的条件下实现二氧化碳和环氧化合物合成环碳酸酯化合物。该方法反应条件温和,在常温常压下即可实现,催化剂效率高,底物普适性广。本发明技术方案如下:在季铵盐存在下,将二氧化碳及环氧化合物通过二甘醇胺桥联双芳氧基稀土‑锌杂双金属配合物催化剂作用合成环碳酸酯化合物。
Description
技术领域
本发明属于有机化合物的制备技术领域,具体涉及一种制备碳酸酯的方法。
背景技术
随着工业的快速发展,大量二氧化碳排放引起的温室效应对地球环境造成日益严重的影响,如何有效的减少二氧化碳的排放和充分利用二氧化碳资源,已成为全球化战略性的研究热点。二氧化碳作为一种清洁、廉价的C1资源被人们所熟知,也可作为一种非常有价值的有机起始原料。二氧化碳和环氧化合物合成环碳酸酯具有100%的原子经济性,符合绿色化学原则,因而具有很重要的研究意义。
主族金属和过渡金属是应用最广泛的,具有高催化活性和选择性的均相金属催化剂,然而大多数催化剂都需要在高温高压下完成这就限制了其工业化应用与发展,所以研究更温和的催化体系,更多样化底物的底物拓展依旧是众多研究者的研究热点。
2015年,Arjan W.Kleij课题组报道的dimer-(Salen)Al配合物以四丁基溴化铵为助催化剂能够在常温常压下催化二氧化碳与单取代环氧烷的反应,反应24小时可达98%的收率,但反应催化剂用量很大(参见C.Martín,G.Fioraniand A.W.Kleij,ACS Catal.,2015,1353);2016年,Michael North课题组报道的Cr(Ⅲ)Salophen催化体系在常温常压下对单取代环氧烷有57-92%的产率,但对于双取代环氧烷则需要10个大气压,80℃的反应条件才能达到中等以上收率(参见J.A.Castro-Osma,K.J.Lamb and M.North,ACS Catal.,2016,6,5012)。2018年,兰州大学刘伟生报道的Zn-Tb杂双配合物能够高效的催化二氧化碳转化,TOF值高达26800h-1,然而该催化体系反应条件比较苛刻,为120℃和10个大气压,该催化体系在常温常压下也能进行,但是反应时间长达48h,单取代环氧烷才能达到中等以上收率,对于双取代环氧烷的反应活性却不尽人意(参见L.Wang,C.Xu,Q.Han,X.Tang,P.Zhou,R.Zhang,G.Gao,B.Xu,W.Qin and W.Liu,Chem.Commun.,2018,54,2212)。我们课题组对此反应体系也做了一系列研究,秦杰利用稀土金属配合物作为催化剂能以较少的催化剂用量实现一个大气压下的CO2转化,但是仍然需要85℃的温度(参见发明专利CN201310708187_CN103641811A_CN;J.Qin,P Wang,Q.Li,Y.Zhang,D.Yuan and Y.Yao,Chem.Commun.,2014,50,10952),屈礼叶在此基础上改进提高,合成的稀土锌杂双配合物能实现大部分环氧烷和CO2在常温常压下的转化,但是对于反应活性较差的双取代环氧烷还是需要在较高的压力和温度下才能达到中等以上收率(参见发明专利CN201711238580_CN107827855A_CN)。本发明专利的催化体系较上述体系更加温和,对部分双取代环氧烷也能实现常压转化。
发明内容
本发明旨在提供一种制备环碳酸酯的方法,该方法反应条件温和,在常温常压下即可实现,催化剂效率高,底物普适性广,不仅适用于单取代环氧烷,也适用于双取代环氧烷。
为了实现上述发明目的,本发明采用如下技术方案:
本发明的第一个目的是提供一种二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物的制备方法,通过以下几个步骤合成:
(1)以二甘醇胺、甲醛水溶液和2,4-二叔丁基苯酚为原料合成二甘醇胺双芳氧基配体前体H3L;
(2)在无水无氧条件下,将步骤(1)反应得到的二甘醇胺双芳氧基配体前体H3L与LnCp3在四氢呋喃中反应合成二甘醇胺桥联双芳氧基稀土金属配合物L2Ln2;
(3)在无水无氧条件下制备苄氧基锌[Zn(OCH2Ph)2]n,然后将苄氧基锌[Zn(OCH2Ph)2]n与步骤(2)反应得到的二甘醇胺桥联双芳氧基稀土金属配合物L2Ln2反应合成二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物L2Ln2Zn(OCH2Ph)2。
在本发明的一种实施方式中,所述稀土金属选自钇、镱、钕或镧。
在本发明的一种实施方式中,所述稀土金属优选为为镧。
在本发明的一种实施方式中,在步骤(1)中,以1:2:2的摩尔比分别加入二甘醇胺、甲醛水溶液和2,4-二叔丁基苯酚,在甲苯溶液中110℃回流24小时。
在本发明的一种实施方式中,在步骤(1)中,除去溶剂后,通过硅胶柱层析分离得到目标产物H3L。
在本发明的一种实施方式中,在步骤(2)中,无水无氧条件下,二甘醇胺双芳氧基配体前体与三茂基稀土化合物LnCp3(THF)按1:1的摩尔比在四氢呋喃溶液中常温反应24小时。
在本发明的一种实施方式中,在步骤(2)中,减压除去溶剂,用甲苯和四氢呋喃的混合溶液萃取,浓缩清液得到L2Ln2(THF)的晶体。
在本发明的一种实施方式中,在步骤(3)中,将苄氧基锌[Zn(OCH2Ph)2]n与桥联双芳氧基稀土金属配合物L2Ln2(THF)在四氢呋喃溶液50℃下反应24小时,得到L2Ln2Zn(OCH2Ph)2(THF);其中苄氧基锌与L2Ln2(THF)的摩尔比为1:2。
在本发明的一种实施方式中,在步骤(3)中,减压除去溶剂,己烷洗涤固体,用四氢呋喃和己烷萃取,低温下析出目标产物的晶体。
在本发明的一种实施方式中,在步骤(3)中,苄氧基锌[Zn(OCH2Ph)2]n的制备方法为无水无氧条件下,二乙基锌与2.0当量的苯甲醇在冰盐浴下反应4小时后得到白色胶状的苄氧基锌[Zn(OCH2Ph)2]n。
本发明的第三个目的是提供一种制备环碳酸酯的方法,包括以下步骤:环氧烷化合物与二氧化碳在季铵盐存在下在催化剂作用下发生加成反应,得到环碳酸酯化合物;所述催化剂是所述的二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物。
在本发明的一种实施方式中,所述方法具体包括以下步骤:
1)将二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物、季铵盐和环氧烷分别加入反应器,然后通入二氧化碳气体进行反应;
2)反应结束后,将反应产物经过柱层析分离得到纯净产物。
在本发明的一种实施方式中,所述季铵盐选自四丁基碘化铵、四丁基溴化铵、四辛基溴化铵、苄基三辛基溴化铵或者双(三苯基膦)氯化铵中一种或几种。
在本发明的一种实施方式中,所述加成反应的条件为:反应温度为25~100℃,反应时间为18~40小时,反应压力为0.08~0.15Mpa。
在本发明的一种实施方式中,所述二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物与环氧烷的摩尔比为1:200~500。
在本发明的一种实施方式中,所述二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物与环氧烷化合物的摩尔比优选为1∶200。
在本发明的一种实施方式中,所述季铵盐的摩尔量是二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物的1~4倍。
在本发明的一种实施方式中,所述季铵盐优选为四丁基溴化铵,其用量为桥联稀土-锌杂双金属配合物的4倍,其与环氧烷化合物的摩尔比为1∶50。
本发明的第四个目的是提供所述的二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物在二氧化碳减排中的应用。
本发明中,二甘醇胺桥联双芳氧基稀土-锌杂双金属配合物的通式为L2Ln2Zn(OCH2Ph)2(THF),L代表二甘醇胺桥联双芳氧基配体N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-2-(2-aminoethoxy)ethanol;THF为四氢呋喃;Zn为锌;Ln表示稀土金属离子,选自钇、镱、钕或镧中的一种,优选为镧。
本发明与现有技术相比具有下列优点:
1.本发明公开的稀土-锌杂双金属催化剂催化二氧化碳与环氧化合物的反应催化效率高,当催化剂用量为环氧化合物有仅0.5mol%,季铵盐用量仅2mol%;反应条件温和,常温常压下即可达到九十以上的收率。
2.本发明公开的催化剂合成步骤简单,产率高,后处理提纯简单;季铵盐来源广泛,价格低廉。
3.本发明公开的环碳酸酯合成方法简单,反应原料易得,底物适用性广,常压下不仅能够高效催化单取代环氧烷,对双取代环氧烷也有很好的催化效果。
具体实施方式
实施例1
二甘醇胺基桥联双芳氧基钇配合物L2Y2(THF)的合成:
(1)将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.31克YCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为黄色透明溶液;
(2)减压除去溶剂,加入10毫升甲苯和10毫升四氢呋喃溶液,加热到120℃萃取,离心。清液转移,低温放置直至析出无色晶体(2.00克,1.43毫摩尔),产率95%。元素分析:C,69.53;H,8.66;N,1.67;。红外光谱(cm-1):2949(w),2896(s),2859(s),1475(s),1439(s),1414(s),1369(s),1362(s),1304(s),1275(s),1240(s),1202(s),1167(s),1134(s),1099(s),1053(s),991(s),928(s),913(s),881(s),875(s),835(s),802(s),743(s),773(s),694(s),529(s),458(s)。核磁氢谱(THF-d8,δ):7.15(s,2H,ArH),7.13(s,3H,ArH),7.12(s,3H,ArH),4.18(s,4H,ArCH2N),3.69(s,8H,ArCH2NCH2),3.46(s,8H,CH2OCH2),2.75(s,4H,CH2O),1.38(s,36H,C(CH3)3,1.18(s,36H,C(CH3)3).
实施例2
二甘醇胺基桥联双芳氧基镱配合物L2Yb2(THF)的合成:
(1)将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.32克YbCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系由墨绿色变成亮黄色透明溶液;
(2)减压除去溶剂,加入15毫升甲苯和10毫升四氢呋喃溶液,加热到120℃萃取,离心。清液转移,低温放置直至析出无色晶体(1.93克,1.23毫摩尔),产率82%。元素分析:C,61.70;H,7.81;N,1.60。红外光谱(cm-1):2949(s),2897(s),2858(s),1605(s),1541(s),1475(s),1439(s),1414(s),1368(s),1361(s),1303(s),1273(s),1240(s),1202(s),1168(s),1134(s),1101(s),1054(s),993(s),973(s),946(s),915(s),875(s),836(s),804(s),781(s),744(s),734(s),694(s),671(s),645(s)。
实施例3
二甘醇胺基桥联双芳氧基钕配合物L2Nd2(THF)的合成:
(1)将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.23克NdCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为蓝色透明溶液;
(2)减压除去溶剂,加入8毫升甲苯和6毫升四氢呋喃溶液,加热到120℃萃取,离心。清液转移,低温放置直至析出蓝色晶体(1.96克,1.30毫摩尔),产率87%。元素分析:C,60.45;H,8.00;N,1.85。红外光谱(cm-1):2950(s),2882(w),2869(s),1603(s),1473(s),1436(s),1414(s),1360(s),1329(s),1298(s),1279(s),1239(s),1202(s),1166(s),1106(s),1066(s),1055(s),1029(s),997(s),958(s),910(s),890(s),877(s),833(s),803(s),783(s),769(s),739(s),697(s),644(s)。
实施例4
二甘醇胺基桥联双芳氧基配合物L2La2(THF)的合成:
(1)将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.22克LaCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为浅黄色透明溶液;
(2)减压除去溶剂,加入8毫升甲苯和6毫升四氢呋喃溶液,加热到120℃萃取,离心。清液转移,低温放置直至析出无色晶体(2.02克,1.35毫摩尔),产率90%。元素分析:C,60.85;H,8.07;N,1.86。红外光谱(cm-1):2951(s),2911(s),2871(s),1756(s),1602(s),1558(s),1472(s),1438(s),1414(s),1384(s),1360(s),1331(s),1298(s),1280(s),1238(s),1202(s),1166(s),1124(s),1101(s),1063(s),1054(s),1032(s),997(s),957(s),904(s),876(s),833(s),803(s),784(s),769(s),741(s),694(s),667(s)。核磁氢谱(THF-d8,δ):7.15(d,J=2.65Hz,4H,ArH),6.90(d,J=2.31,Hz,4H,ArH)4.18(t,J=4.13Hz,J=8.21Hz,4H,ArCH2N),4.05(d,4H,J=12.06Hz,ArCH2N),3.61-3.59(m,8H,CH2),3.53(t,J=4.43Hz,J=8.34Hz,4H,NCH2CH2O),3.27(t,4H,J=4.53Hz,J=9.42Hz,NCH2CH2O),3.14(d,J=12.24Hz,4H,OCH2CH2O),2.73(d,J=4.94Hz,J=10.36Hz,4H,OCH2CH2O),1.77-1.67(m,8H,CH2),1.47(s,36H,C(CH3)3),1.27(s,36H,C(CH3)3).
实施例5
二甘醇胺基桥联双芳氧基钇-锌配合物L2Y2Zn(OCH2Ph)2(THF)的合成:
(1)第一步:将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.31克YCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为黄色透明溶液;第二步:在冰盐浴中将1.50毫升的二乙基锌(1.00摩尔/升的己烷溶液)加入3.00毫升的苯甲醇(1.00摩尔/升的四氢呋喃溶液)中反应4小时,得到白色胶状物;第三步:将第一步的反应液原位加入第二步的白色胶状物中,50℃反应24小时,浑浊消失,体系变为黄色透明溶液。
(2)减压除去溶剂,加入4毫升四氢呋喃和5毫升己烷溶液,加热到60℃萃取,离心。清液转移,常温放置直至析出无色晶体(2.18克,1.30毫摩尔),产率87%。元素分析:C,62.12;H,7.84;N,1.41。红外光谱(cm-1):2989(s),2943(s),2883(w),2859(s),1602(s),1475(s),1439(s),1414(s),1382(s),1359(s),1331(s),1301(s),1239(s),1168(s),1117(s),1090(s),1075(s),1059(s),1027(s),1001(s),960(s),913(s),895(s),874(s),836(s),803(s),770(s),743(s),728(s),696(s),677(s),644(s),625(s)。核磁氢谱(THF-d8,δ):7.62(s,3H,ArH),7.32-7.28(m,4H,ArH),7.22(s,5H,ArH),7.10(s,1H,ArH),6.91(s,3H,ArH),6.84(s,2H,ArH),5.32(dd,J=14.52Hz,J=55.02Hz,4H,PhCH2O),4.36(s,1H,NCH2CH2O),4.22-4.01(m,8H,ArCH2N),3.62(d,J=25.46Hz,3H,NCH2CH2O),3.09-2.85(m,4H,NCH2CH2OCH2),2.74-2.65(m,4H,CH2CH2OH),1.56-1.27(m,72H,C(CH3)3).
实施例6
二甘醇胺基桥联双芳氧基镱-锌配合物L2Yb2Zn(OCH2Ph)2(THF)的合成:
(1)第一步:将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.32克YbCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系由墨绿色变成亮黄色透明溶液;第二步:在冰盐浴中将1.50毫升的二乙基锌(1.00摩尔/升的己烷溶液)加入3.00毫升的苯甲醇(1.00摩尔/升的四氢呋喃溶液)中反应4小时,得到白色胶状物;第三步:将第一步的反应液原位加入第二步的白色胶状物中,50℃反应24小时,浑浊消失,体系变为黄色透明溶液。
(2)减压除去溶剂,加入6毫升四氢呋喃和5毫升己烷溶液,加热到60℃萃取,离心。清液转移,常温放置直至析出无色晶体(2.22克,1.20毫摩尔),产率80%。元素分析:C,58.53;H,7.32;N,1.52。红外光谱(cm-1):2950(s),2900(s),2865(s),1602(s),1475(s),1438(s),1414(s),1384(s),1360(s),1326(s),1302(s),1237(s),1202(s),1166(s),1126(s),1059(s),1026(s),997(s),963(s),932(s),912(s),876(s),836(s),803(s),742(s),730(s),696(s),644(s)。
实施例7
二甘醇胺基桥联双芳氧基钕-锌配合物L2Nd2Zn(OCH2Ph)2(THF)的合成:
(1)第一步:将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.23克NdCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为蓝色透明溶液;第二步:在冰盐浴中将1.50毫升的二乙基锌(1.00摩尔/升的己烷溶液)加入3.00毫升的苯甲醇(1.00摩尔/升的四氢呋喃溶液)中反应4小时,得到白色胶状物;第三步:将第一步的反应液原位加入第二步的白色胶状物中,50℃反应24小时,浑浊消失,体系变为蓝色透明溶液。
(2)减压除去溶剂,加入4毫升四氢呋喃和6毫升己烷溶液,加热到60℃萃取,离心。清液转移,常温放置直至析出蓝色晶体(2.05克,1.15毫摩尔),产率77%。元素分析:C,60。39;H,7.55;N,1.56。红外光谱(cm-1):2951(s),2900(s),2868(s),1602(s),1576(s),1558(s),1541(s),1474(s),1436(s),1414(s),1384(s),1360(s),1326(s),1299(s),1279(s),1237(s),1201(s),1166(s),1100(s),1091(s),1058(s),1025(s),1005(s),960(s),910(s),877(s),835(s),803(s),742(s),697(s),670(s),644(s)。
实施例8
二甘醇胺基桥联双芳氧基镧-锌配合物L2La2Zn(OCH2Ph)2(THF)的合成:
(1)第一步:将1.63克H3L(3.00毫摩尔)溶解于四氢呋喃,加入到含有1.22克LaCp3(THF)(3.00毫摩尔)的四氢呋喃溶液中,室温搅拌反应24小时,体系为浅黄色透明溶液;第二步:在冰盐浴中将1.50毫升的二乙基锌(1.00摩尔/升的己烷溶液)加入3.00毫升的苯甲醇(1.00摩尔/升的四氢呋喃溶液)中反应4小时,得到白色胶状物;第三步:将第一步的反应液原位加入第二步的白色胶状物中,50℃反应24小时,浑浊消失,体系变为浅黄色透明溶液。
(2)减压除去溶剂,加入4毫升四氢呋喃和7毫升己烷溶液,加热到60℃萃取,离心。清液转移,常温放置直至析出无色晶体(2.17克,1.22毫摩尔),产率81%。元素分析:C,60.76;H,7.57;N,1.57。红外光谱(cm-1):2946(s),2875(s),1602(s),1473(s),1450(s),1434(s),1415(s),1326(s),1299(s),1281(s),1239(s),1205(s),1167(s),1133(s),1113(s),1088(s),1058(s),1025(s),994(s),958(s),912(s),878(s),834(s),741(s),728(s),696(s),625(s),607(s)。核磁氢谱(THF-d8,δ):7.60(s,4H,ArH)7.35-7.30(m,4H,ArH),7.25-7.18(m,6H,ArH),6.99(s,4H,ArH),5.33(s,4H,PhCH2O),4.20-4.05(m,8H,ArCH2N),3.56(s,4H,NCH2CH2O),3.10(s,8H,CH2OCH2),2.74(s,4H,CH2O),1.58(s,8H,C(CH3)3),1.35(s,56H,C(CH3)3).
实施例9
0.5mol%L2Y2Zn(OCH2Ph)2(THF)与1mol%四丁基溴化铵催化1,2环氧己烷与二氧化碳的反应
在反应瓶中,加1.806毫升1,2环氧己烷(15.00毫摩尔),125.7毫克L2Y2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和48.4毫克四丁基溴化铵(1.50×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为79%,利用快速柱层析分离得到纯净产物。
实施例10
0.5mol%L2Yb2Zn(OCH2Ph)2(THF)与1mol%四丁基溴化铵催化1,2环氧己烷与二氧化碳的反应
在反应瓶中,加1.806毫升1,2环氧己烷(15.00毫摩尔),138.5毫克L2Yb2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和48.4毫克四丁基溴化铵(1.50×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为85%,利用快速柱层析分离得到纯净产物。
实施例11
0.5mol%L2Nd2Zn(OCH2Ph)2(THF)与1mol%四丁基溴化铵催化1,2环氧己烷与二氧化碳的反应
在反应瓶中,加1.806毫升1,2环氧己烷(15.00毫摩尔),133.7毫克L2Nd2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和48.4毫克四丁基溴化铵(1.50×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为80%,利用快速柱层析分离得到纯净产物。
实施例12
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化1,2环氧己烷与二氧化碳的反应
在反应瓶中,加1.806毫升1,2环氧己烷(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为93%,利用快速柱层析分离得到纯净产物。
实施例13
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化氧化苯乙烯与二氧化碳的反应
在反应瓶中,加1.80克氧化苯乙烯(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为94%,利用快速柱层析分离得到纯净产物。
实施例14
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化苯基缩水甘油醚与二氧化碳的反应
在反应瓶中,加2.03毫升苯基缩水甘油醚(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为95%,利用快速柱层析分离得到纯净产物。
实施例15
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化(甲氧基甲基)环氧乙烷与二氧化碳的反应
在反应瓶中,加1.35毫升(甲氧基甲基)环氧乙烷(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为95%,利用快速柱层析分离得到纯净产物。
实施例16
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化烯丙基缩水甘油醚与二氧化碳的反应
在反应瓶中,加1.78毫升烯丙基缩水甘油醚(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,取样,通过核磁氢谱分析计算产率为98%,利用快速柱层析分离得到纯净产物。
实施例17
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化1,2环氧环戊烷与二氧化碳的反应
在反应瓶中,加1.31毫升1,2环氧环戊烷(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在80℃油浴中反应24小时,取样,通过核磁氢谱分析计算顺式环酯含量62%,反式环酯30%,聚醚7%,利用快速柱层析分离得到纯净产物。
实施例18
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化1,2环氧环己烷与二氧化碳的反应
在反应瓶中,加1.52毫升1,2环氧环己烷(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在100℃油浴中反应24小时,取样,通过核磁氢谱分析计算顺式环酯含量48%,反式环酯8%,聚碳酸酯5%,聚醚36%,环氧环己烷转化率达97%,利用快速柱层析分离得到纯净产物。
实施例19
0.5mol%L2La2Zn(OCH2Ph)2(THF)与2mol%四丁基溴化铵催化甲基环氧丙烷与二氧化碳的反应
在反应瓶中,加1.33毫升甲基环氧丙烷(15.00毫摩尔),133.3毫克L2La2Zn(OCH2Ph)2(THF)(7.50×10-2毫摩尔)和96.8毫克四丁基溴化铵(3.0×10-1毫摩尔),连接一个装有二氧化碳的气袋,在25℃油浴中反应40小时,取样,通过核磁氢谱分析计算产率87%,利用快速柱层析分离得到纯净产物。
Claims (1)
1.一种制备环碳酸酯的方法,其特征在于,包括以下步骤:
在反应瓶中,加15.00毫摩尔环氧烷化合物,7.50×10-2毫摩尔L2La2Zn(OCH2Ph)2(THF)和3.0×10-1毫摩尔四丁基溴化铵,连接一个装有二氧化碳的气袋,在25℃油浴中反应24小时,得到环碳酸酯化合物;
其中,环氧烷化合物选自1, 2环氧己烷、氧化苯乙烯、苯基缩水甘油醚、(甲氧基甲基)环氧乙烷和烯丙基缩水甘油醚;
L2La2Zn(OCH2Ph)2(THF)中,L代表二甘醇胺桥联双芳氧基配体N,N-二(3,5-二叔丁基-2-羟基苄基)-2-(2-氨基乙氧基)乙醇;THF为四氢呋喃;Zn为锌;La为镧;
所述L2La2Zn(OCH2Ph)2(THF)的制备方法,包括如下步骤:
(1)第一步:将3.00毫摩尔H3L溶解于四氢呋喃,加入到含有3.00毫摩尔LaCp3(THF)的四氢呋喃溶液中,室温搅拌反应24小时,体系为浅黄色透明溶液;第二步:在冰盐浴中将1.50毫升1.00摩尔/升的二乙基锌的己烷溶液加入3.00毫升1.00摩尔/升的苯甲醇的四氢呋喃溶液中反应4小时,得到白色胶状物;第三步:将第一步的反应液原位加入第二步的白色胶状物中,50℃反应24小时,浑浊消失,体系变为浅黄色透明溶液;
(2)减压除去溶剂,加入4毫升四氢呋喃和7毫升己烷溶液,加热到60℃萃取,离心;清液转移,常温放置直至析出无色晶体,为L2La2Zn(OCH2Ph)2(THF)。
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