CN117447438A - Preparation method of cyclic carbonate compound - Google Patents
Preparation method of cyclic carbonate compound Download PDFInfo
- Publication number
- CN117447438A CN117447438A CN202311396895.0A CN202311396895A CN117447438A CN 117447438 A CN117447438 A CN 117447438A CN 202311396895 A CN202311396895 A CN 202311396895A CN 117447438 A CN117447438 A CN 117447438A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- solution
- formula
- epoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 cyclic carbonate compound Chemical class 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 144
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 46
- 150000002118 epoxides Chemical class 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 81
- 239000001257 hydrogen Substances 0.000 claims description 76
- 229910052739 hydrogen Inorganic materials 0.000 claims description 76
- 239000000047 product Substances 0.000 claims description 67
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000011668 ascorbic acid Substances 0.000 claims description 33
- 235000010323 ascorbic acid Nutrition 0.000 claims description 33
- 229960005070 ascorbic acid Drugs 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000011261 inert gas Substances 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 18
- 150000000996 L-ascorbic acids Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZKWVTFAQXGVDQV-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;methanol Chemical class OC.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O ZKWVTFAQXGVDQV-RXSVEWSESA-N 0.000 claims description 10
- YXBZNMSPFZDRFZ-UHFFFAOYSA-M methanol;tetrabutylazanium;hydroxide Chemical compound [OH-].OC.CCCC[N+](CCCC)(CCCC)CCCC YXBZNMSPFZDRFZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 9
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002152 alkylating effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006352 cycloaddition reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 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 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 5
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 65
- 238000001228 spectrum Methods 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 239000011259 mixed solution Substances 0.000 description 33
- 150000005676 cyclic carbonates Chemical class 0.000 description 31
- 238000004440 column chromatography Methods 0.000 description 30
- 238000003756 stirring Methods 0.000 description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 230000005311 nuclear magnetism Effects 0.000 description 17
- 239000007787 solid Substances 0.000 description 11
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Substances [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- 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
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The patent belongs to the technical field of organic catalysis, and particularly discloses a method for catalyzing and fixing carbon dioxide, which adopts epoxide and carbon dioxide to generate cyclic carbonate compounds under the catalysis of the catalyst at the temperature of 60-140 ℃. The method for fixing carbon dioxide has high conversion efficiency, no metal residue in the reaction, mild reaction conditions, easy preparation of the catalyst and great potential for commercial application in the fields of biological medicine, polymer preparation and the like.
Description
Technical Field
The invention belongs to the technical field of organic catalysis, and particularly relates to a preparation method for synthesizing a cyclic carbonate compound by fixing carbon dioxide.
Background
Over the past decades, the artificial emission of carbon dioxide has attracted considerable attention worldwide due to its dramatic increase in atmospheric concentration, which has led to sea level rises, glaciers and ice shelves melting, desertification and increasingly frequent extreme weather. Therefore, the development of chemical processes that efficiently fix and utilize carbon dioxide is a current research focus. Chemical immobilization of carbon dioxide into chemicals with higher added value has received extensive attention in the context of sustainable chemistry, and synthesis of cyclic carbonates from carbon dioxide and epoxides has been widely studied because cyclic carbonates can be used as monomers for polycarbonates, electrolytes for lithium ion batteries, polar aprotic solvents, and intermediates for many chemicals and pharmaceuticals.
The kinetic and thermodynamic stability of carbon dioxide is a major limitation of its use as a chemical feedstock, and thus catalysts capable of activating carbon dioxide and epoxide simultaneously are needed. Most efforts to synthesize cyclic carbonates from carbon dioxide and epoxides have focused on metal-based homogeneous catalysts, which are capable of exhibiting high catalytic activity and selectivity. Organic catalysts have also begun to attract researchers' interest in synthesizing cyclic carbonates because organic catalysts are generally more cost effective, more sustainable and less toxic than metal-based catalysts. Many organic catalysts have been studied, including ammonium salts, phosphonates, imidazolium salts and imidazolyl ionic liquids, two-component systems consisting of polyols and quaternary ammonium salts have also been developed, and the like. The systems have the characteristics of low energy consumption and environmental friendliness, and the atomic utilization rate is 100%, so that the system accords with the idea of green chemistry.
Organic catalysts that catalyze the synthesis of cyclic carbonates from carbon dioxide and epoxides are mostly salts of anions and cations. Wherein the cation and the epoxy substrate form a hydrogen bond, the anion attacks the epoxy to open the ring, then the carbon dioxide is intercalated, and the ring is closed to form the cyclic carbonate. For example, zhang et al (ACS Sustainable chem. Eng.2017,5, 2841-2846) use [ DMAPH ] Br to convert diluted carbon dioxide to carbonate at atmospheric pressure in yields up to 96% selectivity, with other pyridinium salts (Green chem.2009,11,1876), imidazolium salts (Green chem.2013,15,1584), ammonium salts (catalyst. Sci. Technologies.2014, 4,1585), phosphonium salts (chemsuschem chem.2015,8,2655), and azacyclo-carbene (chemsuschem chem.2014,7,962) all yielding high yields, high selectivity carbonate products.
However, these catalysts are expensive in raw materials, complicated in purification methods, and too many synthetic steps result in a decrease in productivity, thereby limiting the range of applications thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for synthesizing a cyclic carbonate compound by catalyzing and fixing carbon dioxide. The invention adopts a brand new organic ion pair catalyst to realize the [3+2] cycloaddition reaction of epoxide and carbon dioxide, and the cyclic carbonate compound is obtained with high selectivity. The catalyst has the advantages of simple and convenient synthesis method, mild catalytic reaction condition and wide substrate application range, and the obtained cyclic carbonate compound has no metal residue and has great potential for commercial application in the fields of microelectronics, polymer preparation and the like with strict control on the content of the metal residue.
The invention provides a novel bifunctional catalyst for the first time, namely a bifunctional organic catalyst which takes hydroxyl on carbon number 2 or hydroxyl on carbon number 3 of ascorbic acid as a hydrogen bond donor after alkylation of different substituents and tetrabutylammonium hydroxide cation as a nucleophilic cocatalyst, and is used for catalyzing epoxide and carbon dioxide to generate cyclic carbonate with high selectivity. Ascorbic acid acts as a hydrogen bond donor to activate the epoxide and stabilize the ionic intermediate, tetrabutylammonium hydroxide cation, which attacks the epoxide to open it due to its exclusive interaction with cyclopropenyl cations, enhancing nucleophilicity. The target catalyst can be obtained by dripping the methanol solution of tetrabutylammonium hydroxide into the alkylated ascorbic acid at the temperature of 0 ℃, and the post-treatment is simple and easy to operate.
The present invention addresses and solves the problems found in the actual need by catalyzing the synthesis of epoxides of different substituents using bifunctional ascorbate ion pairs as hydrogen bond donors and nucleophilic anions. The organic molecular catalytic system is firstly applied to cycloaddition reaction of epoxide and carbon dioxide, and has mild condition, high conversion rate and high selectivity.
The technical scheme for achieving the above-mentioned goal is as follows:
a method for synthesizing cyclic carbonate adopts a catalyst shown in a formula I or a formula II to catalyze epoxide shown in a formula III and carbon dioxide to generate cyclic carbonate compounds:
wherein,
Bu 4 N + is tetrabutylammonium hydroxide cation;
R 1 independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, allyl, benzyl;
R 2 ，R 3 independently selected from hydrogen, C 1 ～C 4 Straight-chain or branched alkyl, halogenated C 1 ～C 4 Straight-chain or branched alkyl, phenyl, substituted phenyl or R 4 -O-CH 2 -; the substituent in the substituted phenyl is selected from halogen or C 1 ～C 5 Straight or branched alkyl of (a); the said "R 4 -O-CH 2 R in- - " 4 Selected from phenyl, quilt C 1 ～C 3 Phenyl, allyl or C substituted by straight-chain or branched alkyl groups 1 ～C 4 Straight or branched alkyl groups of (a).
Preferably, the catalyst of formula I is selected from the following structures:
preferably, the preparation method of the catalyst with the number of 1 to 8 comprises the following steps:
(1) Ascorbic acid (1.98 mmol) is weighed, mixed with alkylating reagent (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then alkylated ascorbic acid is obtained by column chromatography (dichloromethane/methanol 15-25:1);
(2) Dissolving the alkylated ascorbic acid obtained in the step (1) in 50ml of methanol solution;
(3) At 0 ℃, uniformly mixing the alkylated ascorbic acid methanol solution and the tetrabutylammonium hydroxide methanol solution according to the molar ratio of (2-1.5:1), and stirring for 15-28h at room temperature;
(4) After the reaction, spin-drying the reaction solution under reduced pressure, adding 100ml of acetonitrile, filtering to remove unreacted alkylated ascorbic acid, collecting the filtered solution, spin-drying under reduced pressure, and drying in a vacuum oven at 70 ℃ overnight to obtain the catalyst.
Preferably, the preparation method of the catalysts 9 to 16 comprises the following steps:
(1) Ascorbic acid (2 mol) was weighed in acetone, acetyl chloride (0.1 mol) was added to the rapidly stirred suspension, the mixed solution was stirred at room temperature for 15-20 h, the precipitate was collected by filtration and washed three times with ethyl acetate, and the precipitate was dried overnight in a vacuum oven;
(2) Weighing the product (4.63 mmol) obtained in the step 1 into a mixed solution of dimethyl sulfoxide/tetrahydrofuran (3:2);
(3) Organic bases (9.26 mmol) such as potassium tert-butoxide and the like are weighed into a mixed solution of dimethyl sulfoxide/tetrahydrofuran (3:2);
(4) Slowly dripping the mixed solution obtained in the step 3 into the mixed solution obtained in the step 2 at the temperature of minus 15 ℃ to minus 10 ℃ for reaction for 7 to 10min;
(5) Weighing alkylating reagent (5.09 mmol) and dripping the alkylating reagent into the mixed solution in the step 4 in 3min, and stirring the mixed solution at room temperature for 3-5 h;
(6) The reaction was quenched with 0.25M hydrochloric acid (20 ml) and the product was extracted three times with ethyl acetate;
(7) The organic layer was dried over anhydrous sodium sulfate, the solvent removed under reduced pressure, and the product purified by column chromatography (n-hexane/ethyl acetate 3:1).
Wherein, the alkylating reagent for preparing the catalyst is methyl iodide, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, isoamyl alcohol, hexyl alcohol, isohexyl alcohol, heptanol, isoheptanol, octyl alcohol, isooctyl alcohol, allyl alcohol, vinyl alcohol and benzyl alcohol, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, octyl iodide, allyl bromide and benzyl bromide.
Preferably, the epoxide of formula III is selected from the group consisting of styrene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, butyl oxirane, 2-toluene glycidyl ether, phenyl glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, methyl acrylate glycidyl ether.
The structure of the epoxide is shown in the following table:
preferably, the specific method for fixing carbon dioxide comprises the following steps: under the anhydrous and anaerobic condition, adding the catalyst shown in the formula I or the formula II and the epoxide shown in the formula III into a reaction container in an inert gas or nitrogen atmosphere, introducing carbon dioxide, heating the reaction container, and separating after the reaction is finished to obtain a product.
The molar ratio of the epoxy compound shown in the formula III to the catalyst shown in the formula I or the formula II is 200-1000:1, the reaction temperature is 60-140 ℃, the reaction time is 6-24 h, and the initial pressure of the reaction is 0.1-1.5MPa
The post-treatment is that the reacted solution is cooled and subjected to column chromatography (petroleum ether: ethyl acetate=5:1) and is dried by spin to obtain the product.
The structure of the cyclic carbonate is shown in the following figure
Advantageous effects
The following effects can be achieved by adopting the technical scheme of the invention:
(1) Compared with the method for synthesizing the cyclic carbonate by using a metal catalyst in the prior art, the catalyst provided by the invention has the characteristics of high selectivity (more than 99%), no metal residue, mild conditions and the like.
(2) The invention provides a novel bifunctional catalyst for the first time, namely a bifunctional organic catalyst which takes hydroxyl on carbon number 2 or hydroxyl on carbon number 3 of ascorbic acid as a hydrogen bond donor after alkylation of different substituents and tetrabutylammonium hydroxide cation as a nucleophilic cocatalyst, and is used for catalyzing epoxide and carbon dioxide to generate cyclic carbonate with high selectivity.
(3) The invention can catalyze and synthesize the cyclic carbonate compound under the conditions of normal pressure and low catalytic load, has short time and low temperature, and can obtain the cyclic carbonate with extremely high reaction selectivity. Compared with other conditions such as high temperature, high pressure, long reaction time, high catalyst loading and the like, the reaction condition of the invention is very mild.
(4) The catalyst has the advantages of low raw material price, complex purification method, few synthesis steps and improved yield, and meanwhile, the reaction substrate has wide applicability and can have great commercial application potential in the fields of biological medicine, polymer preparation and the like.
In conclusion, compared with other existing catalytic systems, the catalyst has the obvious advantages of mildness, high efficiency, easiness in preparation, no metal residue and the like.
Drawings
Fig. 1: the hydrogen spectrum of the cyclic carbonate product obtained in example 1
Fig. 2: the hydrogen spectrum of the cyclic carbonate product obtained in example 2
Fig. 3: the hydrogen spectrum of the cyclic carbonate product obtained in example 3
Fig. 4: the hydrogen spectrum of the cyclic carbonate product obtained in example 4
Fig. 5: the hydrogen spectrum of the cyclic carbonate product obtained in example 5
Fig. 6: the hydrogen spectrum of the cyclic carbonate product obtained in example 6
Fig. 7: the hydrogen spectrum of the cyclic carbonate product obtained in example 7
Fig. 8: the hydrogen spectrum of the cyclic carbonate product obtained in example 8
Fig. 9: the hydrogen spectrum of the cyclic carbonate product obtained in example 9
Fig. 10: the hydrogen spectrum of the cyclic carbonate product obtained in example 10
Fig. 11: hydrogen profile of Cyclic carbonate product obtained in example 11
Fig. 12: the hydrogen spectrum of the cyclic carbonate product obtained in example 12
Fig. 13: hydrogen profile of Cyclic carbonate product obtained in example 13
Fig. 14: hydrogen profile of Cyclic carbonate product obtained in example 14
Fig. 15: hydrogen profile of Cyclic carbonate product obtained in example 15
Fig. 16: hydrogen profile of Cyclic carbonate product obtained in example 16
Fig. 17: hydrogen profile of Cyclic carbonate product obtained in example 17
Fig. 18: hydrogen spectrum of cyclic carbonate product obtained in example 18
Fig. 19: the hydrogen spectrum of the cyclic carbonate product obtained in example 19
Fig. 20: hydrogen profile of catalyst No. 1
Fig. 21: hydrogen spectrum of catalyst No. 2
Fig. 22: hydrogen spectrum of catalyst No. 3
Fig. 23: hydrogen spectrum of catalyst No. 5
Fig. 24: hydrogen spectrum of catalyst No. 6
Fig. 25: hydrogen spectrum of catalyst No. 8
Fig. 26: hydrogen profile of catalyst No. 9
Detailed Description
The invention will be further illustrated by the following examples, which are intended to illustrate, but not to limit, the invention. It will be understood by those of ordinary skill in the art that these examples are not limiting of the invention in any way and that appropriate modifications and data changes may be made thereto without departing from the spirit and scope of the invention.
The nuclear magnetic resonance hydrogen and carbon spectra involved in the examples were determined using a Bruker Assetnd TM-400 nuclear magnetic resonance analyzer from Bruker, inc. (Bruker), and the deuterating reagent used was deuterated chloroform (CDCl) 3 ) And deuterated methanol (CD) 3 OD)。
The starting materials used in the examples below were all purchased from AlfaAesar.
The catalytic system used in the examples had the following structure:
the epoxide used in the examples had the following structure:
1. preparation examples of the catalyst
The preparation method of the catalyst with the number of 1 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with methanol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after the number 3 hydroxy methylation is obtained by column chromatography (dichloromethane/methanol 15:1);
step two: 25.0mmol of the methylated ascorbic acid obtained in the step one is dissolved in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the methylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.5:1), and stirring for 15 hours at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted methylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 1.
The preparation method of the catalyst with the number of 2 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with ethanol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after No. 3 hydroxyethylation is obtained by column chromatography (dichloromethane/methanol 15:1);
step two: dissolving 25.0mmol of the ethylated ascorbic acid obtained in the step one in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the ethylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.5:1), and stirring for 15 hours at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted ethylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 2.
The preparation method of the catalyst with the number of 3 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with propanol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after No. 3 hydroxypropyl is obtained by column chromatography (dichloromethane/methanol 15:1);
step two: dissolving 25.0mmol of the propylated ascorbic acid obtained in the step one in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the propylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.7:1), and stirring for 15 hours at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted propylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 3.
The preparation method of the catalyst with the number of 4 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with amyl alcohol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after No. 3 hydroxyl amyl is obtained by column chromatography (dichloromethane/methanol 20:1);
step two: dissolving 25.0mmol of the amyl ascorbic acid obtained in the step one in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the amyl-based ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.5:1), and stirring for 15 hours at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted pentylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 4.
The preparation method of the catalyst with the number of 5 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with heptanol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and after reaction, column chromatography (dichloromethane/methanol 20:1) is carried out to obtain No. 3 hydroxyl-heptylated ascorbic acid;
step two: 25.0mmol of the heptylated ascorbic acid obtained in the first step is dissolved in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the heptylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.5:1), and stirring for 15h at room temperature;
step four: after the reaction was completed, the reaction mixture was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted heptylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 5.
The preparation method of the catalyst with the number of 6 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with octanol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after No. 3 hydroxyoctylation is obtained by column chromatography (dichloromethane/methanol 20:1);
step two: dissolving 25.0mmol of the octylated ascorbic acid obtained in the first step in 50ml of methanol solution;
step three: mixing the octylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to a molar ratio (2:1) at 0 ℃, and stirring for 15h at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted octylated ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 6.
The preparation method of the catalyst with the number of 8 comprises the following steps:
step one: preparation of alkylated ascorbic acid: ascorbic acid (1.98 mmol) is mixed with benzyl alcohol (2.49 mmol), triphenylphosphine (2.25 mmol) and diethyl azodicarboxylate (2.22 mmol) in tetrahydrofuran solution (10-40 ml) at-78 ℃ for 15-28h, and then the ascorbic acid after No. 3 hydroxybenzylation is obtained by column chromatography (dichloromethane/methanol 20:1);
step two: 25.0mmol of the benzylated ascorbic acid obtained in the step one is dissolved in 50ml of methanol solution;
step three: at 0 ℃, uniformly mixing the benzyl-methylated ascorbic acid methanol solution and the 40% tetrabutylammonium hydroxide methanol solution according to the molar ratio (1.8:1), and stirring for 15 hours at room temperature;
step four: after the reaction, the reaction solution was dried under reduced pressure, 100ml of acetonitrile was added to remove unreacted benzyl ascorbic acid by filtration, and the filtered solution was collected and dried under reduced pressure, and dried under vacuum in a vacuum oven at 70℃overnight to give catalyst No. 8. Preparation method of catalyst No. 9:
step one: weighing 2mol of ascorbic acid in acetone, adding acetyl chloride (0.1 mol) into the suspension which is rapidly stirred, stirring the mixed solution for 15-20 hours at room temperature, filtering and collecting precipitate, washing the precipitate with ethyl acetate three times, and drying the precipitate in a vacuum drying oven overnight;
step two: weighing the product (1 g,4.63 mmol) obtained in the step one into a mixed solution of dimethyl sulfoxide/tetrahydrofuran (3:2);
step three: organic bases (1.04 g,9.26 mmol) such as potassium tert-butoxide and the like are weighed into a mixed solution of dimethyl sulfoxide/tetrahydrofuran (3:2);
step four: slowly dripping the mixed solution obtained in the step 3 into the mixed solution obtained in the step 2 at the temperature of minus 15 ℃ to minus 10 ℃ for reaction for 7 to 10min;
step five: methyl iodide (5.09 mmol) is weighed and added dropwise to the mixed solution in the step 4 in 3min, and the mixed solution is stirred for 3-5 h at room temperature;
step six: the reaction was quenched with 0.25M hydrochloric acid (20 ml) and the product was extracted three times with ethyl acetate;
step seven: the organic layer was dried over anhydrous sodium sulfate, the solvent removed under reduced pressure, and the product purified by column chromatography (n-hexane/ethyl acetate 3:1) to give catalyst No. 9.
2. Preparation examples of cyclic carbonate compounds
Example 1:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under nitrogen, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, followed by epoxide A (1.12 ml,10mmol,1.0 equiv) and carbon dioxide (1 MPa). The reactor was reacted at 120℃for 12 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight, and the conversion rate of 92% was calculated by nuclear magnetism, and the selectivity was calculated>99% of the product has a hydrogen spectrum as shown in FIG. 1, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 2:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 2 (11.71 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (1.12 ml,10mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 120℃for 12 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight, and the conversion rate of 85% was calculated by nuclear magnetism, and the selectivity was calculated>The hydrogen spectrum of the product is shown in figure 2, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 3:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 3 (11.50 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (10 mmol,1.0 equiv) was further added and carbon dioxide (1 MPa) was introduced. The reactor was reacted in an oil bath at a stirring rate of 400 rpm at 120℃for 24 hours. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight, and the conversion rate of 86% was calculated by nuclear magnetism, and the selectivity was calculated>The hydrogen spectrum of the product is shown in figure 3, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 4:
standard Schlenk operation is carried out on the reaction bottle to remove water and water in the reaction systemOxygen. Under inert gas, catalyst No. 5 (12.8 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 100℃for 18 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight, and the conversion rate of 66% was calculated by nuclear magnetism, and the selectivity was obtained>The hydrogen spectrum of 80% of the product is shown in FIG. 4, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 5:
the reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 6 (53.2 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 120℃for 8 hours in an oil bath at a stirring rate of 300 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight, and the conversion rate of 65% was calculated by nuclear magnetism, and the selectivity was calculated>60% of the product has a hydrogen spectrum as shown in FIG. 5, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 6
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 8 (12.7 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (10 mmol,1.0 equiv) was further added to charge carbon dioxide (1 MPa). The reactor was reacted in an oil bath at a stirring rate of 500 rpm at 140℃for 24 hours. After the reaction, the reaction tube was taken out and allowed to cool naturally, followed by column chromatography (stoneOil ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight, and the conversion rate was 52% by nuclear magnetism, selectivity was calculated>The hydrogen spectrum of the product is shown in FIG. 6, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 7
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 4 (12.2 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (5 mmol,1.0 equiv) was further added to charge carbon dioxide (0.5 MPa). The reactor was reacted at 120℃for 18 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight, and the conversion rate of 85% was calculated by nuclear magnetism, and the selectivity was calculated>90% of the product has a hydrogen spectrum 7 as shown, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 8
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 9 (11.4 mg,0.025mmol,0.0025 equiv) was added, and epoxide A (5 mmol,1.0 equiv) was further added to charge carbon dioxide (1 MPa). The reactor was reacted at 120℃for 12 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight, and the conversion rate of 86% was calculated by nuclear magnetism, and the selectivity was calculated>The hydrogen spectrum of the product is shown in FIG. 8, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are:δ7.49–7.40(m,3H),7.40–7.28(m,2H),5.67(t,J＝8.0Hz,1H),4.79(t,J＝8.4Hz,1H),4.33(dd,J＝8.7,7.8Hz,1H)。
example 9
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, and epoxide B (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 120℃for 18 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and naturally cooled, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless transparent oil, which was dried to constant weight, the conversion rate was 71%, the hydrogen spectrum of the product was as shown in fig. 9, (nuclear magnetic resonance hydrogen spectrum, 400hz, cdcl) 3 ). The spectrogram data are: δ4.98 (dq, j=9.3, 4.9,4.5hz, 1H), 4.58 (td, j=8.6, 1.4hz, 1H), 4.43-4.35 (m, 1H), 3.79 (ddd, j=12.3, 5.3,1.4hz, 1H), 3.71 (ddd, j=12.2, 3.7,1.2hz, 1H).
Example 10
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, and epoxide C (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 120℃for 16 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless transparent oil, and dried to constant weight, and the conversion rate of 78% was calculated by nuclear magnetism, selectivity was obtained>The hydrogen spectrum of the product is shown in FIG. 10, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: δ4.97 (dq, j=8.2, 5.3hz,1 h), 4.62 (dd, j=8.9, 8.2hz,1 h), 4.37 (dd, j=8.9, 5.9hz,1 h), 3.60 (d, j=5.2 hz,2 h).
Example 11
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Adding under the condition of introducing inert gasNo. 1 catalyst (10.7 mg,0.025mmol,0.0025 equiv) was added to epoxide D (10 mmol,1.0 equiv) and carbon dioxide (1.5 MPa) was charged. The reactor was reacted at 100℃for 12 hours in an oil bath with a stirring rate of 400 rpm. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless transparent oil, and dried to constant weight, and the conversion rate of 86% was calculated by nuclear magnetism, selectivity was obtained>The hydrogen spectrum of the product is shown in FIG. 11, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 5.89-5.73 (m, 1H), 5.24-5.12 (m, 2H), 4.83-4.73 (m, 1H), 4.45 (t, j=8.4 hz, 1H), 4.36-4.28 (m, 1H), 4.05-3.92 (m, 2H), 3.64 (dd, j=11.2, 3.4hz, 1H), 3.54 (dd, j=11.2, 3.7hz, 1H).
Example 12
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7m g,0.025mmol,0.0025equiv) was added, and then epoxide E (10 mmol,1.0 equiv) was added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted in an oil bath at 60℃for 18 hours with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless oily liquid, which was dried to constant weight, and the conversion was 75% by nuclear magnetism, selectivity was calculated>The hydrogen spectrum of the product is shown in FIG. 12, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: δ4.69 (qd, j=7.5, 5.4hz, 1H), 4.55-4.47 (m, 1H), 4.05 (dd, j=8.4, 7.2hz, 1H), 1.78 (dddd, j=14.0, 10.2,7.5,4.8hz, 1H), 1.72-1.62 (m, 1H), 1.47-1.27 (m, 4H), 0.99-0.81 (m, 3H).
Example 13
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (4.28 mg,0.01mmol, 0.001equiv) was added and epoxide F (10 mmol,1.0 equiv) was further added and carbon dioxide (1 MPa) was introduced. The reactor was stirred at a stirring rate of 400 rpm for oilThe reaction is carried out for 12 hours at 120 ℃ in a bath. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless oily liquid, which was dried to constant weight, and the conversion rate of 86% was calculated by nuclear magnetism, selectivity was obtained>The hydrogen spectrum of the product is shown in FIG. 13, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.16 (ddd, j=7.3, 4.1,2.7hz, 2H), 6.93 (td, j=7.4, 1.0hz, 1H), 6.81-6.75 (m, 1H), 5.05 (ddt, j=8.6, 5.5,3.3hz, 1H), 4.67-4.54 (m, 2H), 4.26 (dd, j=10.6, 3.6hz, 1H), 4.13 (dd, j=10.6, 3.1hz, 1H), 2.22 (s, 3H).
Example 14
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, and epoxide G (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 80℃for 12 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a white solid, which was dried to a constant weight, and the conversion rate of 72% was calculated by nuclear magnetism, and the selectivity was calculated>The hydrogen spectrum of the product is shown in FIG. 14, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.38-7.26 (m, 2H), 7.05-6.97 (m, 1H), 6.94-6.87 (m, 2H), 5.07-4.97 (m, 1H), 4.60 (t, j=8.5 hz, 1H), 4.52 (dd, j=8.5, 5.9hz, 1H), 4.23 (dd, j=10.6, 4.0hz, 1H), 4.13 (dd, j=10.7, 3.6hz, 1H).
Example 15
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, and then epoxide H (10 mmol,1.0 equiv) was added to charge carbon dioxide (0.5 MPa). The reactor was reacted at 120℃for 6 hours in an oil bath with a stirring rate of 400 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, and after column chromatography (petroleum ether: ethyl acetate=5:1), a solution was obtainedThe mixed solution with the product is dissolved, the solution is dried by spin-drying on a spin-steaming instrument to obtain colorless oily liquid, the colorless oily liquid is dried to constant weight, the conversion rate is 64 percent by nuclear magnetism, and the selectivity is calculated>The hydrogen spectrum of the product is shown in FIG. 15, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: δ4.79 (ddt, j=8.4, 6.0,3.7hz, 1H), 4.47 (t, j=8.4 hz, 1H), 4.35 (dd, j=8.3, 6.0hz, 1H), 3.62 (dd, j=11.1, 3.6hz, 1H), 3.53 (dd, j=11.1, 3.8hz, 1H), 3.39 (s, 3H).
Example 16
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under inert gas, catalyst No. 1 (10.7 mg,0.025mmol,0.0025 equiv) was added, and epoxide I (10 mmol,1.0 equiv) was further added and carbon dioxide (0.5 MPa) was introduced. The reactor was reacted at 100℃for 6 hours in an oil bath with a stirring rate of 350 revolutions per minute. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless oily liquid, which was dried to constant weight, and the conversion rate of 56% was calculated by nuclear magnetism, selectivity was obtained>50% of the product has a hydrogen spectrum as shown in FIG. 16, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: δ4.81-4.71 (m, 1H), 4.47 (t, j=8.2 hz, 1H), 4.38 (dd, j=8.3, 5.8hz, 1H), 3.61 (dd, j=10.3, 4.6hz, 1H), 3.57-3.51 (m, 1H), 1.19 (s, 9H).
Example 17
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under the condition of introducing inert gas, adding the catalyst (No. 1, 10.7mg,0.025mmol,0.0025 equiv), adding epoxide J (10 mmol,1.0 equiv), pumping the inert gas in the reaction bottle, charging carbon dioxide, and repeating for three times. A balloon filled with carbon dioxide was inserted, and the reactor was reacted in an oil bath at a stirring rate of 400 rpm at 100℃for 6 hours. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a colorless oily liquid, which was dried to constant weight, the conversion was 36% by nuclear magnetism calculation, and selection was madeSelectivity of>40% of the product has a hydrogen spectrum as shown in FIG. 17, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 6.14 (t, j=1.1 hz, 1H), 5.64 (p, j=1.5 hz, 1H), 4.97 (ddt, j=8.7, 5.6,3.4hz, 1H), 4.58 (t, j=8.6 hz, 1H), 4.42 (dd, j=12.6, 3.1hz, 1H), 4.36-4.28 (m, 1H), 1.94 (t, j=1.2 hz, 3H).
Example 18
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under the condition of introducing inert gas, adding the catalyst (10.7 mg,0.025mmol,0.0025 equiv) with the number of 1, adding the epoxide A (10 mmol,1.0 equiv), pumping the inert gas in the reaction bottle, charging carbon dioxide, and repeating the process for three times. A balloon filled with carbon dioxide was inserted and the reactor was reacted in an oil bath at a stirring rate of 400 rpm at 100 c for 24 hours. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to constant weight with a conversion of 61%, selectivity>80%. The hydrogen spectrum of the product is shown in FIG. 18, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Example 19
The reaction flask was subjected to standard Schlenk procedure to remove water and oxygen from the reaction system. Under the condition of introducing inert gas, adding the catalyst (10.7 mg,0.025mmol,0.0025 equiv) with the number of 1, adding the epoxide A (10 mmol,1.0 equiv), pumping the inert gas in the reaction bottle, charging carbon dioxide, and repeating the process for three times. A balloon filled with carbon dioxide was inserted and the reactor was reacted in an oil bath at a stirring rate of 500 rpm at 120 c for 24 hours. After the reaction, the reaction tube was taken out and cooled naturally, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, the solution was spin-dried on a spin-evaporator to obtain a yellow solid, which was dried to a constant weight, and the conversion rate of 72% was calculated by nuclear magnetism, and the selectivity was obtained>80% of the product has a hydrogen spectrum as shown in FIG. 19, (nuclear magnetic resonance hydrogen spectrum, 400Hz, CDCl) 3 ). The spectrogram data are: delta 7.49-7.40 (m, 3H), 7.40-7.28 (m, 2H), 5.67 (t, j=8.0 hz, 1H), 4.79 (t, j=8.4 hz, 1H), 4.33 (dd, j=8.7, 7.8hz, 1H).
Claims (8)
1. A preparation method of a cyclic carbonate compound is characterized in that a catalyst shown in a formula I or a formula II is adopted to catalyze an epoxide shown in a formula III to carry out cycloaddition reaction with carbon dioxide, so as to obtain the cyclic carbonate compound
R in the catalyst shown in formula I or formula II 1 Independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, allyl, or benzyl;
r in the epoxide of formula III 2 、R 3 Independently selected from hydrogen, C 1 ～C 4 Straight-chain or branched alkyl, halogenated C 1 ～C 4 Straight-chain or branched alkyl, phenyl, substituted phenyl or R 4 -O-CH 2 -；
The substituent in the substituted phenyl is selected from halogen or C 1 ～C 5 A linear or branched alkyl group of (a) and (b),
the said "R 4 -O-CH 2 R in- - " 4 Selected from phenyl, quilt C 1 ～C 3 Phenyl, allyl or C substituted by straight-chain or branched alkyl groups 1 ～C 4 Straight or branched alkyl groups of (a).
2. The process according to claim 1, wherein the bifunctional catalyst of formula I is selected from compounds numbered 1 to 8 and the bifunctional catalyst of formula II is selected from compounds numbered 9 to 16:
3. the process of claim 1, wherein the catalyst of formula I is prepared by:
dissolving ascorbic acid, an alkylating reagent, triphenylphosphine and diethyl azodicarboxylate in tetrahydrofuran solution for reaction, and separating after the reaction to obtain alkylated ascorbic acid;
dissolving the alkylated ascorbic acid in a methanol solution to obtain an alkylated ascorbic acid methanol solution;
step three, preparing tetrabutylammonium hydroxide methanol solution, and adding the tetrabutylammonium hydroxide methanol solution into the alkylated ascorbic acid methanol solution for reaction;
and step four, after the reaction is finished, separating and drying to obtain the catalyst.
4. The process of claim 1, wherein the catalyst of formula II is prepared by:
step one, mixing ascorbic acid, acetone and acetyl chloride, washing a precipitate obtained by the reaction with ethyl acetate after the reaction, and performing vacuum drying treatment after the washing;
step two, mixing the product obtained in the step one, dimethyl sulfoxide and tetrahydrofuran solution to obtain solution A;
step three, dissolving potassium tert-butoxide in dimethyl sulfoxide and tetrahydrofuran solution to obtain solution B;
step four, adding the solution B into the solution A to obtain a solution C;
step five, adding an alkylating reagent into the solution C for reaction;
and step six, adding hydrochloric acid into the solution C, and extracting, separating and purifying after the reaction is finished to obtain the catalyst.
5. The process of claim 1, wherein R is an epoxide of formula III 2 Is hydrogen, R 3 Independently selected from hydrogen, C 1 ～C 4 Straight-chain or branched alkyl, halogenated C 1 ～C 4 Straight-chain or branched alkyl, phenyl, substituted phenyl or R 4 -O-CH 2 -；
Or R is 3 Is hydrogen, R 2 Independently selected from hydrogen, C 1 ～C 4 Straight-chain or branched alkyl, halogenated C 1 ～C 4 Straight-chain or branched alkyl, phenyl, substituted phenyl or R 4 -O-CH 2 -；
The substituent in the substituted phenyl is selected from halogen or C 1 ～C 5 A linear or branched alkyl group of (a) and (b),
the said "R 4 -O-CH 2 R in- - " 4 Selected from phenyl, quilt C 1 ～C 3 Phenyl, allyl or C substituted by straight-chain or branched alkyl groups 1 ～C 4 Straight or branched alkyl groups of (a).
6. The method of claim 1, wherein the epoxide of formula III is selected from the group consisting of compounds numbered a-J:
7. the preparation method of claim 1, wherein the catalyst shown in the formula I or the formula II is adopted to catalyze the epoxide shown in the formula III to react with carbon dioxide, a reaction vessel is heated, and after the reaction is finished, the cyclic carbonate compound is obtained by separation;
wherein the catalyst shown in the formula I is a catalyst shown in a number 1, and the epoxide shown in the formula III is any one of epoxide shown in a number A to a number J;
or the catalyst shown in the formula I adopts the catalyst shown in the numbers 1-8, and the epoxide shown in the formula III adopts the epoxide shown in the number A;
alternatively, the catalyst shown in the formula II adopts a catalyst shown in a number 9, and the epoxide shown in the formula III adopts an epoxide shown in a number A;
8. the process according to claim 7, wherein the reaction is carried out under anhydrous and anaerobic conditions under an inert gas or nitrogen atmosphere; the molar ratio of the epoxide to the catalyst is 200-1000:1; the temperature of the reaction is 60-140 ℃; the reaction time is 6-24 hours; the initial pressure of the reaction is 0.1-1.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311396895.0A CN117447438A (en) | 2023-10-25 | 2023-10-25 | Preparation method of cyclic carbonate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311396895.0A CN117447438A (en) | 2023-10-25 | 2023-10-25 | Preparation method of cyclic carbonate compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117447438A true CN117447438A (en) | 2024-01-26 |
Family
ID=89581141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311396895.0A Pending CN117447438A (en) | 2023-10-25 | 2023-10-25 | Preparation method of cyclic carbonate compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117447438A (en) |
-
2023
- 2023-10-25 CN CN202311396895.0A patent/CN117447438A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11292777B2 (en) | Method for preparing cyclic carbonate | |
| CN111303112A (en) | Method for fixing carbon dioxide | |
| EP3668851A1 (en) | Method for the preparation of thiocarbonates | |
| BRPI0813704B1 (en) | Cyclic Ether Preparation Process | |
| CN108772102B (en) | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide | |
| CN103641811B (en) | Method for preparing cyclic carbonate | |
| CN111233816B (en) | Preparation method of cyclic carbonate | |
| CN112812045A (en) | Onium salt organic catalyst and preparation method and application thereof | |
| JP5596258B2 (en) | Calixarene dimer compound and method for producing the same | |
| CN102391241A (en) | Method for preparing cyclic carbonate with chitosan loading type catalyst | |
| CN113061077B (en) | Alpha, alpha-dideuteroalcohol compounds, deuterated drugs and preparation method thereof | |
| CN112812091A (en) | Synthetic method of cyclic carbonate | |
| CN117447438A (en) | Preparation method of cyclic carbonate compound | |
| CN109535120B (en) | Preparation method of 7-substituted-3, 4,4, 7-tetrahydrocyclobutane coumarin-5-ketone | |
| CN101525320B (en) | Preparation method of 3, 4-epoxycyclohexyl formate-3'4'-epoxycyclohexyl methyl ester | |
| CN113200954B (en) | Preparation method of cyclic carbonate | |
| CN113072517B (en) | Synthetic method of five-membered oxygen heterocyclic compound | |
| CN113461629B (en) | Preparation method of 5-hydroxymethyl-oxazolidine-2-ketone compound | |
| CN113996339A (en) | Catalyst for preparing cyclic carbonate and preparation method of cyclic carbonate | |
| CN110156730B (en) | Synthesis method of chiral tricyclic benzofuran compound | |
| CN113563189A (en) | One-step method for efficiently catalyzing CO2Method for converting dimethyl carbonate catalyst | |
| CN111732552A (en) | Method for synthesizing 1, 3-oxazole-2-thioketone by palladium catalysis | |
| CN105801328B (en) | A kind of preparation method of coronene | |
| CN116768842A (en) | Method for synthesizing cyclic carbonate | |
| CN117358301A (en) | Catalyst for synthesizing cyclic carbonate compound by epoxide carbon fixation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |