CN112521362B - 一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法 - Google Patents
一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法 Download PDFInfo
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- CN112521362B CN112521362B CN202011505400.XA CN202011505400A CN112521362B CN 112521362 B CN112521362 B CN 112521362B CN 202011505400 A CN202011505400 A CN 202011505400A CN 112521362 B CN112521362 B CN 112521362B
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- Prior art keywords
- quaternary phosphonium
- phosphonium salt
- functionalized
- metalloporphyrin
- mmol
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- 150000004714 phosphonium salts Chemical group 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 52
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 46
- 150000002118 epoxides Chemical class 0.000 claims description 22
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 150000004032 porphyrins Chemical class 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical group CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 51
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 22
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical group CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 abstract description 7
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- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 13
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 11
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- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- -1 porphyrin compounds Chemical class 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 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 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 2
- WLOADVWGNGAZCW-UHFFFAOYSA-N 3-phenyl-23H-porphyrin-2,18,20,21-tetracarboxylic acid Chemical compound OC(=O)C=1C(N2C(O)=O)=C(C(O)=O)C(=N3)C(C(=O)O)=CC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C2C=1C1=CC=CC=C1 WLOADVWGNGAZCW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000006278 bromobenzyl group Chemical group 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- ABCGFHPGHXSVKI-UHFFFAOYSA-O meso-tetrakis(n-methyl-4-pyridyl)porphine(4+) Chemical compound C1=C[N+](C)=CC=C1C(C1=CC=C(N1)C(C=1C=C[N+](C)=CC=1)=C1C=CC(=N1)C(C=1C=C[N+](C)=CC=1)=C1C=CC(N1)=C1C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 ABCGFHPGHXSVKI-UHFFFAOYSA-O 0.000 description 2
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- 238000007142 ring opening reaction Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NUUUANNAZVEWHM-UHFFFAOYSA-N 1,2-dibromohexane Chemical compound CCCCC(Br)CBr NUUUANNAZVEWHM-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- PJOJZHHAECOAFH-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-methoxyphenyl)-21,23-dihydroporphyrin Chemical compound COc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(OC)cc2)c2ccc([nH]2)c(-c2ccc(OC)cc2)c2ccc(n2)c(-c2ccc(OC)cc2)c2ccc1[nH]2 PJOJZHHAECOAFH-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- C07D317/10—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
- 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法。本发明将功能化金属卟啉及季鏻盐结合作为双催化体系,实现在温和条件下协同催化环氧化物与CO2环加成反应合成环碳酸酯的目的。在温和条件下不同的MTRPP与季鏻盐协同催化均具有良好的催化活性,CoClTPP因其金属中心为Lewis酸性最强的Co3+、金属框架为空间位阻最小的TPP,所以其催化活性最高。季鏻盐R3PR'X中Ph3HexPBr具有最高的催化活性。CoClTPP/Ph3HexPBr双催化剂体系在常温常压条件下催化环氧氯丙烷合成环碳酸酯的环加成反应中呈现出优异的催化活性,具有高转化率和TOF值,且CoClTPP/Ph3HexPBr双催化剂体系在温和条件下对其他环氧化物也具有良好的催化活性。
Description
技术领域
本发明涉及一种环碳酸酯的合成方法,尤其涉及一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法。
背景技术
CO2是大气成分的一部分,是造成温室效应和海平面上升等危害的主要因素。同时,它也是一种丰富、廉价、可回收的无毒C1资源,其合理应用也能够适当缓解由资源问题造成的一系列危机。经过近几十年研究,发现CO2可以与约20种基材,如环氧树脂、烷基、醛等发生反应,以制备化学原料。在这些以CO2为碳源的制备的化学原料中,以环氧底物为底物制备得到的环碳酸酯,因其原子利用率为100%、反应过程绿色和无污染等优势,已成为最具潜力CO2转化方法。环碳酸酯本身也是具备高价值的一种产品,并且大部分已广泛应用于工业过程,如锂电池电解质、聚合物材料的结构单元,以及某些重要化合物的中间体等。
CO2中的C原子以最高的氧化状态存在,使CO2具有非常高的热力学稳定性和动力学惰性,导致反应条件苛刻,因此需要高效的催化体系,使其与环氧底物在较温和条件下能够高效地反应。目前已经研究出许多均相催化体系和非均相催化体系,以促进环氧底物与CO2的环加成反应能够在温和条件下进行,主要包括希夫碱金属配合物、金属卟啉、离子液体(ILs)、有机催化剂和金属有机骨架材料(MOF)等。虽然大多数催化体系能够使环碳酸酯转化率和选择性方面表现出良好的活性,但一般情况下需要添加溶剂以及苛刻的反应条件。因此,研发高效和可循环的催化剂,使CO2的化学转化能够在相对温和的条件下进行是非常有意义的。
卟啉作为一种仿生催化剂,广泛存在于动植物中,由于其功能和结构与酶相似,例如植物中用于光合作用的叶绿素就是由金属镁卟啉化合物组成的。作为一种高效的催化剂,金属卟啉在各种催化反应中得到了应用,并且其特殊结构使其具有易于设计、功能化、与不同金属配位的优良特性,都可以提升金属卟啉作为催化剂的催化活性。1978年,Takeda等首先使用铝卟啉作为均相催化剂催化氧化环己烯与CO2进行环加成反应( N. Takeda,S. Inoue, Macromol. Chem. Phys. 179 (1978) 1377–1381)。最近,景欢旺课题组使用不同的金属卟啉协同催化体系在温和的条件下催化环氧底物与CO2的环加成反应,并获得较好的转化率及选择性(B. Dongsheng, W. Xaiaoxuan, S. Yingying, L. Bo, Z. Lilong,Y. Peng, J. Huanwang, Bifunctional metalloporphyrins-catalyzed couplingreaction of epoxides and CO2 to cyclic carbonates[J], Chin. J. Catal. 31(2010) 176–180;Li B, Zhang L, Song Y, et al. Brønsted acid improvedcycloaddition of carbon dioxide to propylene oxide[J]. Journal of MolecularCatalysis A: Chemical, 2012, 363: 26-30.)。Guo等报道了一系列Bi (III) porphyrincomplexes/TBAI(四丁基碘化铵)二元催化系统(Peng J, Geng Y, Yang H J, et al.Efficient solvent-free fixation of CO2 into cyclic carbonates catalyzed by Bi(III) porphyrin/TBAI at atmospheric pressure[J]. Molecular Catalysis, 2017,432: 37-46.)以及Ema等合成的双功能镁卟啉催化剂(Maeda C, Taniguchi T, Ogawa K,et al. Bifunctional Catalysts Based on m‐Phenylene‐Bridged Porphyrin Dimerand Trimer Platforms: Synthesis of Cyclic Carbonates from Carbon Dioxide andEpoxides[J]. AngewandteChemie International Edition, 2015, 54(1): 134-138;EmaT, Miyazaki Y, Shimonishi J, et al. Bifunctional porphyrin catalysts for thesynthesis of cyclic carbonates from epoxides and CO2: structural optimizationand mechanistic study[J]. Journal of the American Chemical Society, 2014, 136(43): 15270-15279.),两者在化学固定CO2上均可获得高的 TOF值,但是为了能够让此反应能够在常压下进行仍需要较高的温度。Qi等合成了一系列二元碳对称的金属卟啉催化剂,在常压条件下制备得到环碳酸酯具备较高的转化率及选择性(Jiang X, Gou F, Qi C.C2v-symmetric metalloporphyrin promoted cycloaddition of epoxides with CO2under atmospheric pressure, Journal of CO2 Utilization, 2019, 29: 134-139.)。
发明内容
本发明的目的是提供一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,能够在温和条件下将环氧化物与CO2转化成环碳酸酯。
季鏻盐作为离子液体具有溶解性好、热稳定性好等特点,是一种良好的亲核试剂,在绿色催化领域得到了广泛的应用,本发明设计了MTRPP/R3PR'X双组分协同催化体系,用于环境条件下无溶剂催化环氧化物和CO2环加成反应。本发明使用廉价的无毒过渡金属Co、Ni、Zn与功能化卟啉配位,在催化体系中金属离子作为Lewis酸活性中心活化环氧化物,同时合成的季鏻盐作为亲核试剂,进攻环氧化物使其开环。两者的协同作用,极大地提高了催化体系在环氧氯丙烷作为底物的情况下的催化活性,使其能够在常温常压条件下达到99%的转化率、选择性以较高的TOF值。
一、基于金属卟啉/季鏻盐双催化体系合成环碳酸酯
本发明基于金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,是以功能化金属卟啉(MTRPP)作为主催化剂,以季鏻盐(R3PR'X)作为助催化剂,以环氧化物和二氧化碳作为反应底物进行环加成反应,得到环碳酸酯;所述反应温度为25~80℃,反应时间4~24h;所述主催化剂功能化金属卟啉与环氧化物摩尔比为1:650~1:6600;所述助催化剂季鏻盐与环氧化物摩尔比为1:66~1:132;所述环加成反应中二氧化碳的压力为1atm;所述环氧化物为环氧氯丙烷、氧化苯乙烯、环氧丁烷、烯丙基缩水甘油醚、丁基缩水甘油醚、苯基缩水甘油醚、3-(2,3-环氧丙氧)丙基三甲氧基硅烷中的一种。
所述功能化金属卟啉MTRPP的结构式为:
其中,R为H、COOH 、OCH3或CH=CH2;M为Zn、Co或Ni;X为Cl;优选CoClTPP作为主催化剂。
所述季鏻盐R3PR'X的结构式为:
其中:R为苯基或丁基;R´为H、CH3、OH;X为Cl、Br或I;n=1~6;优选Ph3HexPBr作为助催化剂。
所述功能化金属卟啉的制备方法为:以DMF为溶剂,以功能化卟啉和金属盐为反应底物,在N2保护下,于140~150℃下反应4~12h,加HCl酸化,减压蒸馏、抽滤、洗涤、干燥即得功能化金属卟啉;所述功能化卟啉与金属盐摩尔比为1:5~1:10;所述功能化卟啉为5,10,15,20-四(四苯基卟啉)(TPP)、5,10,15,20-四(四羧基苯基卟啉)(TCPP)、5,10,15,20-四(四乙烯基苯基卟啉)(TVPP)或5,10,15,20-四(四甲氧基苯基卟啉)(TMPP);所述金属盐为六水氯化钴、二水醋酸锌或四水醋酸镍。
所述季鏻盐的制备方法为:将三苯基膦或三丁基膦和卤代烷烃溶于甲苯中,在 N2氛围下,与90~110℃搅拌回流12~24h,旋蒸除去溶剂,滴加到乙醚中析出白色固体,过滤、洗涤,干燥即得季鏻盐;所述三苯基膦或三丁基膦与卤代烷烃的摩尔比为0.8:1~2.5:1;所述卤代烷烃为溴乙烷、2-溴乙醇、溴代丁烷、氯代丁烷、碘代丁烷、溴代己烷、溴代辛烷、溴代十二烷、1,2-二溴己烷、溴苄中的一种。
下面制备过程中功能化卟啉以5,10,15,20-四(四羧基苯基卟啉)(TCPP)为例说明主催化剂功能化金属卟啉(MTRPP)的结构。
图1为TCPP和MTCPP(M: Ni, Zn, Co)的1H NMR谱图。可以看出,TCPP中在化学位移-2.77处出现峰,而其它MTCPP在此处并未显示相同的峰,这是由于TCPP中N-H键处于卟啉环的屏蔽区,而MTCPP中N-H由于金属离子M配位形成N-M键,所以MTCPP中-2.77处的峰消失。这表明TCPP与金属离子M成功配位,形成金属卟啉配合物MTCPP。
图2为TCPP、NiTCPP、ZnTCPP、CoClTCPP的红外光谱。很明显可以看到TCPP与金属离子配位后,在964cm-1处N-H键引起的伸缩振动峰消失,MTCPP在1000cm-1处出现了新的伸缩振动峰N-M。其它TRPP与MTRPP红外谱图中也存在类似的现象,这说明MTRPP成功的形成。
卟啉化合物在UV-Vis吸收光谱中具有两个主要吸收带,即400nm的S带和500-700nm的Q带。S带是卟啉环特征吸收带,Q带主要是卟啉环共轭体系中π-π*跃迁产生的吸收带。图3为TCPP和MTCPP(M: Ni, Zn, Co)的UV-Vis吸收光谱图。与未配位的卟啉TCPP相比,MTCPP最明显的特点是S带的吸收峰发生移位,Q带的吸收峰减少。这是因为卟啉金属化后,TCPP吡咯环内部的两个质子被金属离子所取代,MTCPP分子轨道的分裂程度变小,对称性增强,导致Q带吸收峰减少。其它功能化卟啉与金属配位后紫外谱图也呈现相似结果,这些结果进一步表明金属离子与TRPP的配位成功。
二、金属卟啉/季鏻盐双催化体系对CO2与环氧化物的环加成反应的催化性能
1、不同反应条件对催化性能的影响
下面以CoClTPP/Ph3HexPBr双催化剂体系为例探讨了反应条件对催化性能的影响。
图4a为CoClTPP/Ph3HexPBr催化体系中环氧氯丙烷(ECH)与CO2环加成反应中转化率与反应时间的关系。环氧氯丙烷(ECH)与CO2环加成反应中:CoClTPP (0.058mmol),Ph3HexPBr (0.29mmol),环氧氯丙烷 (3ml, 38.26mmol)。图4a中可以看出,在室温条件下随着时间从4h增加到24h,ECH的转化率从30%增加到99%,并且在24hECH转化率达到99%时,TON达到了653.1,TOF达到了27.2h-1。
图4b为温度对ECH的转化率的影响的影响。我们可以看到,即使在室温和常压下,ECH的转化率仍可以达到97%;当温度升至40-70℃时,转化率均可在20小时内达到100%。我们进一步增加ECH的量到30mL,反应时间为48h时,ECH的转化率达到43.7%,其TOF可以达到191.3 h-1。
2、不同功能化金属卟啉催化剂的催化性能
我们进一步研究了不同功能化金属卟啉催化剂对CO2与环氧化物的环加成反应的催化性能的影响。CO2与环氧化物的环加成反应中:主催化剂为不同功能化金属卟啉催化剂(0.058 mmol),助催化剂为Bu4PBr(0.29 mmol),反应底物为环氧氯丙烷(3mL,38.26mmol)和CO2(1atm),反应温度70℃,反应时间20h。表1为不同功能化金属卟啉催化剂的催化活性(表中1-6为不同功能化金属卟啉和Bu4PBr共同催化,7为ZnTCPP单独催化,8为Bu4PBr单独催化。)。如表1中1-3所示,不同金属的催化活性顺序为Co3+> Ni2+> Zn2+,这是因为Co3+作为金属活性中心的路易斯酸性相对其它两者金属较大。此外,我们发现给电子基团(OCH3,CH2 =CH)或吸电子基团(COOH)官能化金属卟啉催化剂的催化活性低于ZnTPP,不同功能化金属卟啉的催化活性顺序依次为ZnTPP>ZnTMPP>ZnTVPP>ZnTCPP。这是因为给电子基团(OCH3,CH2 =CH)或吸电子基团(COOH)官能化金属卟啉具有相对较高的位阻,导致它们的催化活性降低。
表1中转化率和选择性均由1H NMR测定;TON:在单位时间 (或者一段时间内)生成的产物的物质的量/催化剂的物质的量;TOF: TON/h。
3、不同季鏻盐的催化性能
此外,我们还研究了不同季鏻盐对CO2与环氧氯丙烷的环加成反应的催化性能的影响。CO2与环氧氯丙烷的环加成反应中:主催化剂为CoClTCPP(序号1-10)或CoClTPP(序号11)(0.058 mmol),助催化剂为不同季鏻盐(0.29 mmol),底物为环氧氯丙烷(3mL,38.26mmol)和CO2(1atm),反应温度50℃,反应时间20h。首先,测试了具有不同卤化物的季鏻盐。如表2中1-3所示,Bu4PI作为助催化剂的催化效果要优于Bu4PBr和Bu4PC1。这是因为与Br-和Cl-相比,I-具有更大的分子量,并且更容易离开阳离子以促进底物的开环并协助闭环步骤。我们还考察了助催化剂的链长对催化效果的影响,结果表明随着链长的增加,转化率增加(序号1,5-6和9-10),这是因为随着烷基卤化物链长的增加,季鏻盐阳离子与卤素阴离子之间的静电作用变弱,并且卤素阴离子更容易对环氧底物进行亲核攻击,使环氧底物更加容易开环。因此,Bu3HexPBr和Ph3HexPBr显示出最高的催化性能,由于苯基比丁基所占空间位阻大,更容易将两个阴离子隔开,使其充分发挥亲核进攻使底物开环的优势,所以Ph3PHexBr的催化活性要高于Bu3PHexBr。在研究季鏻盐的链长和阴离子的基础上,还研究了含有氢供体基团(序号7)和双卤素原子(序号4)的助催化剂。可以看出,带有氢供体基团或者双卤素原子的助催化剂催化活性比相应的季鏻盐(序号1、5、6)高约20%。
表2中转化率和选择性均由1H NMR测定;TON: 在单位时间 (或者一段时间内)生成的产物的物质的量/催化剂的物质的量;TOF: TON/h。
4、功能化金属卟啉/季鏻盐双催化体系对其他环氧化合物的催化性能
根据以上研究结果,我们选择Co3+作为金属活性中心,选择不含官能团的TPP作为催化剂骨架,即选择CoClTPP为主催化剂,并结合含己基的季鏻盐Ph3HexPBr作为助催化剂,进一步研究在优化后的条件下催化其他不同环氧化物与CO2环加成反应的催化性能。环氧化物与CO2环加成中:主催化剂为CoClTPP(0.058 mmol),助催化剂为Ph3hPHexBr(0.29mmol),底物为不同环氧化物(38.26mmol)和CO2(1 atm),反应温度70℃(序号1为40℃),反应时间24h。如表3所示,结果表明,无论是含有芳族还是脂族的底物,在CoClTPP/Ph3HexPBr催化体系下均具有较好的转化率和近100%的选择性,这是其他催化剂体系难以实现的。其中,1,2-环氧丁烷的沸点低,因此反应温度为40℃,但转化率仍为63.5%(序号1)。由于底物3-(2,3-环氧丙氧)丙基三甲氧基硅烷的位阻较大,所以转化率远低于其他底物。
表3中催化转化率和催化选择性均由1H NMR测定;所有物质催化选择性均为99%;TON: 在单位时间 (或者一段时间内)生成的产物的物质的量/催化剂的物质的量;TOF:TON/h。
综上所述,本发明将含有不同官能团的卟啉(MTRPP)及季鏻盐(R3PR'X)结合作为双催化体系,利用金属卟啉活性金属中心提供Lewis 酸位来活化底物,季鏻盐作为Lewis碱来进攻底物并使其开环,从而实现在温和条件下协同催化CO2与环氧底物环加成合成环碳酸酯的目的。研究结果表明,不同的MTRPP与季鏻盐协同催化环氧氯丙烷与CO2的环加成反应在温和条件下都具有良好的催化活性;MTRPP中CoClTPP因其金属中心为Lewis酸性最强的Co3+、金属框架为空间位阻最小的5,10,15,20-四苯基卟啉,所以其催化活性最高。对于季鏻盐R3PR'X,通过对其链长及官能团系统化的研究表明Ph3HexPBr具有最高的催化活性。CoClTPP/Ph3HexPBr双催化剂体系在常温常压条件下催化环氧氯丙烷合成环状碳酸酯的环加成反应中呈现出优异的催化活性,不仅转化率可以达到99%,其TOF值也能达到191.3h-1。CoClTPP/Ph3HexPBr双催化剂体系在温和条件下对其他环氧化物也具有良好的催化活性。
附图说明
图1为TCPP 和 MTCPP (M: Ni, , Zn, Co)的1H NMR谱图。
图2为TCPP和MTCPP(M: Ni, Zn, Co)的红外谱图。
图3为TCPP和 MTCPP (M: Ni, Zn, Co)的UV-Vis谱图。
图4为反应时间(a)和温度(b)对环氧氯丙烷的转化率的影响。
具体实施方式
下面通过具体实施例对本发明基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法作进一步说明。
本发明所用原料及试剂如下表:
本发明所用测试仪器如下表:
实施例1
(1)功能化金属卟啉的合成:在250ml的单口圆底烧瓶中依次加入TCPP(1 g,1mmol)、CoCl2∙6H2O(1.01 g,6mmol),最后加入150ml无水DMF,在N2氛围下,于145℃下搅拌12h。待反应体系冷却至室温后,在空气中向烧瓶中缓慢滴加60ml的3M HCl。通过减压蒸馏出去大部分溶剂后,将剩余反应体系倒入去离子水中,有紫色固体沉淀产生,用布氏漏斗抽滤收集,并用去离子水洗涤三次,放入真空干燥箱50℃干燥至恒重,得到1.3g CoClTCPP固体,产率95%。
(2)季鏻盐的合成:将三丁基基膦(2g,1mmol)和溴代丁烷(1.5g,1.1mmol)溶于100mL甲苯溶剂中,再将反应体系置于N2氛围下,110℃搅拌回流12~24h。通过旋蒸仪旋掉大部分溶剂,再将剩余反应体系滴加到乙醚中,析出白色固体。将固体分离并用乙醚洗三次后,放入真空干燥箱中干燥,得到2.3gBu4PBr,产率为85%。
(3)环碳酸酯的合成:在装有磁子的25ml 史莱克管中加入主催化剂CoClTCPP(0.058 mmol)和助催化剂Bu4PBr(0.29 mmol),再取环氧氯丙烷(3mL,38.26mmol)加入史莱克管中。密封后在50℃油浴锅内加热30min,使反应体系中的催化剂完全溶解后并形成均一体系。再将反应体系冷却至室温,与装有CO2(1atm)的气球相连,放入70℃油浴锅中,打开搅拌开始反应。反应20h后,停止搅拌,将反应体系冷却至室温,从体系中取少量反应混合液,通过1H NMR来确定底物的反应选择性及转化率。
实施例2
(1)功能化金属卟啉的合成:将CoCl2∙6H2O(6mmol)换为Zn(CH3COO)2∙2H2O(10mmol),其余条件及步骤同实施例1,得到0.97gZnTCPP,产率为90%;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将主催化剂CoClTCPP(0.058 mmol)换为ZnTCPP(0.058mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例3
(1)功能化金属卟啉的合成:将CoCl2∙6H2O(6mmol)换为Ni(CH3COO)2∙4H2O(10mmol),其余条件及步骤同实施例1,得到1.03gNiTCPP,产率为96%;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将主催化剂CoClTCPP(0.058 mmol)换为NiTCPP(0.058mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例4
(1)功能化金属卟啉的合成:将CoCl2∙6H2O(6mmol)换为Zn(CH3COO)2∙2H2O(10mmol),将TCPP(1mmol)换为TVPP(1mmol)、三乙胺(10mmol),其余条件及步骤同实施例1,得到1.03gZnTVPP,产率为95%;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将主催化剂CoClTCPP(0.058 mmol)换为ZnTVPP(0.058mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例5
(1)功能化金属卟啉的合成:将CoCl2∙6H2O(6mmol)换为Zn(CH3COO)2∙2H2O(10mmol),将TCPP(1mmol)换为TMPP(1mmol),其余条件及步骤同实施例1,得到1.06gZnTMPP,产率为98%;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将主催化剂CoClTCPP(0.058 mmol)换为ZnTMPP(0.058mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例6
(1)功能化金属卟啉的合成:将CoCl2∙6H2O(6mmol)换为Zn(CH3COO)2∙2H2O(10mmol),将TCPP(1mmol)换为TPP(1mmol),其余条件及步骤同实施例1,得到1.07gZnTPP,产率为97%;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将主催化剂CoClTCPP(0.058 mmol)换为ZnTPP(0.058mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例1-6中催化体系的催化性能依次见表1中1-6。
实施例7
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:同实施例1;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例8
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为氯代丁烷(1.1mmol),其余条件及步骤同实施例1,得到0.25gBu4PCl,产率为90%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu4PCl(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例9
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为碘代丁烷(1.1mmol),其余条件及步骤同实施例1,得到0.35gBu4PI,产率为92%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu4PI(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例10
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为1,6-二溴己烷(1mmol),三丁基膦(1mmol)换为三丁基膦(2.1mmol)其余条件及步骤同实施例1,得到0.55gBu3PBrHexBrPBu3,产率为85%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu3PBrHexBrPBu3(0.29 mmol),其余条件及步骤同实施例1,通过1HNMR来确定底物的反应选择性及转化率。
实施例11
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为溴乙烷(1.1mmol),其余条件及步骤同实施例1,得到0.24gBu3PEtBr,产率为80%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu3PEtBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例12
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为溴代己烷(1.1mmol),其余条件及步骤同实施例1,得到0.35gBu3PHexBr,产率为95%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu3PHexBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例13
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的溴代丁烷(1.1mmol)换为溴乙醇(1.1mmol),其余条件及步骤同实施例1,得到0.30gBu3PEtOHBr,产率为92%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Bu3PEtOHBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例14
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(1mmol),溴代丁烷(1.1mmol)换为溴苄(1.1mmol),其余条件及步骤同实施例1,得到0.41gPh3PBnBr,产率为96%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Ph3PBnBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例15
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(1mmol),其余条件及步骤同实施例1,得到0.38gPh3PBuBr,产率为95%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Ph3PBuBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例16
(1)功能化金属卟啉的合成:同实施例1;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(10mmol),溴代丁烷(1.1mmol)换为溴代己烷(10.1mmol),其余条件及步骤同实施例1,得到4.1gPh3PHexBr,产率为97%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将助催化剂Bu4PBr(0.29 mmol)换为Ph3PHexBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例17
(1)功能化金属卟啉的合成:将实施例1中的TCPP(1mmol)换为TPP(1mmol),其余条件及步骤同实施例1,得到1.1gCoClTPP,产率为96%;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(10mmol),溴代丁烷(1.1mmol)换为溴代己烷(10.1mmol),其余条件及步骤同实施例1,得到4.1gPh3PHexBr,产率为97%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将主催化剂CoClTCPP(0.058 mmol)换为CoClTPP(0.058 mmol),将助催化剂Bu4PBr(0.29 mmol)换为Ph3PHexBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。
实施例7-17中催化体系的催化性能依次见表2中1-11。
实施例18
(1)功能化金属卟啉的合成:将实施例1中的TCPP(1mmol)换为TPP(1mmol),其余条件及步骤同实施例1,得到1.1gCoClTPP,产率为96%;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(10mmol),溴代丁烷(1.1mmol)换为溴代己烷(10.1mmol),其余条件及步骤同实施例1,得到4.1gPh3PHexBr,产率为97%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为25℃油浴锅,反应时间改为24h,将主催化剂CoClTCPP(0.058 mmol)换为CoClTPP(0.058 mmol),将助催化剂Bu4PBr(0.29 mmol)换为Ph3PHexBr(0.29 mmol),其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。转化率为99%,选择性为99%,TON达到了653.1,TOF达到了27.2h-1。
实施例19
(1)功能化金属卟啉的合成:将实施例1中的TCPP(1mmol)换为TPP(1mmol),其余条件及步骤同实施例1,得到1.1gCoClTPP,产率为96%;
(2)季鏻盐的合成:将实施例1中的三丁基膦(1mmol)换为三苯基膦(10mmol),溴代丁烷(1.1mmol)换为溴代己烷(10.1mmol),其余条件及步骤同实施例1,得到4.1gPh3PHexBr,产率为97%;
(3)环碳酸酯的合成:将实施例1中的70℃油浴锅改为50℃油浴锅,将主催化剂CoClTCPP(0.058 mmol)换为CoClTPP(0.058 mmol),将助催化剂Bu4PBr(0.29 mmol)换为Ph3PHexBr(0.29 mmol),将反应底物环氧氯丙烷分别换为环氧丁烷、氧化苯乙烯、苯基缩水甘油醚、烯丙基缩水甘油醚、丁基缩水甘油醚、3-(2,3-环氧丙氧)丙基三甲氧基硅烷,其余条件及步骤同实施例1,通过1H NMR来确定底物的反应选择性及转化率。CoClTPP/Ph3PHexBr对不同环氧底物的催化性能见表3。
Claims (9)
2.根据权利要求1所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述主催化剂功能化金属卟啉与环氧化物摩尔比为1:650~1:6600。
3.根据权利要求1所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述助催化剂季鏻盐与环氧化物摩尔比为1:66~1:132。
4.根据权利要求1所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述环加成反应中二氧化碳的压力为1atm。
5.根据权利要求1所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述功能化金属卟啉的制备方法为:以DMF为溶剂,以功能化卟啉和金属盐为反应底物,在N2氛围下,于140~150℃下反应4~12h,加HCl酸化,减压蒸馏、抽滤、洗涤、干燥即得功能化金属卟啉;所述功能化卟啉与金属盐的摩尔比为1:5~1:10。
6.根据权利要求5所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述功能化卟啉为5,10,15,20-四苯基卟啉。
7.根据权利要求5所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述金属盐为六水氯化钴。
8.根据权利要求1所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述季鏻盐的制备方法为:将三苯基膦和卤代烷烃溶于甲苯中,在 N2氛围下,90~110℃搅拌回流12~24h,旋蒸除去溶剂,滴加到乙醚中析出白色固体,过滤、洗涤,干燥即得季鏻盐;所述三苯基膦与卤代烷烃的摩尔比为0.8:1~2.5:1。
9.根据权利要求8所述一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法,其特征在于:所述卤代烷烃为溴代己烷。
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