CN109096109B - Synthesis method of 2-butenoic ester - Google Patents
Synthesis method of 2-butenoic ester Download PDFInfo
- Publication number
- CN109096109B CN109096109B CN201710473476.0A CN201710473476A CN109096109B CN 109096109 B CN109096109 B CN 109096109B CN 201710473476 A CN201710473476 A CN 201710473476A CN 109096109 B CN109096109 B CN 109096109B
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- CN
- China
- Prior art keywords
- rhodium
- propyne
- 50mmol
- dichloromethane
- dissolving
- 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.)
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- 238000001308 synthesis method Methods 0.000 title claims description 8
- 150000002148 esters Chemical class 0.000 title abstract description 21
- -1 cation diphosphine compound Chemical class 0.000 claims abstract description 110
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 24
- 239000010948 rhodium Substances 0.000 claims abstract description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 24
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- CNZJXEMAGREJBO-UHFFFAOYSA-L cycloocta-1,5-diene;dichlororhodium Chemical compound Cl[Rh]Cl.C1CC=CCCC=C1.C1CC=CCCC=C1 CNZJXEMAGREJBO-UHFFFAOYSA-L 0.000 claims description 2
- XZMMPTVWHALBLT-UHFFFAOYSA-N formaldehyde;rhodium;triphenylphosphane Chemical compound [Rh].O=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XZMMPTVWHALBLT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical class P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- FCQRKDSALKMOGU-UHFFFAOYSA-K rhodium(3+);triphenylphosphane;trichloride Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FCQRKDSALKMOGU-UHFFFAOYSA-K 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RJIBAVLJENHCSE-UHFFFAOYSA-N [Rh].C12=CC=C(CC1)C2.C(C)(=O)CC(C)=O Chemical compound [Rh].C12=CC=C(CC1)C2.C(C)(=O)CC(C)=O RJIBAVLJENHCSE-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 159
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 126
- 239000000243 solution Substances 0.000 description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 54
- 238000001816 cooling Methods 0.000 description 51
- 238000001914 filtration Methods 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000002904 solvent Substances 0.000 description 38
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 34
- 238000001704 evaporation Methods 0.000 description 34
- 238000003756 stirring Methods 0.000 description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 27
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 18
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000006315 carbonylation Effects 0.000 description 15
- 238000005810 carbonylation reaction Methods 0.000 description 15
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 14
- 239000003446 ligand Substances 0.000 description 14
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 12
- 229960002089 ferrous chloride Drugs 0.000 description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical class P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229940097267 cobaltous chloride Drugs 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LYLFXVKSLNCSCK-UHFFFAOYSA-N C12=CC=C(CC1)C2.[Rh] Chemical compound C12=CC=C(CC1)C2.[Rh] LYLFXVKSLNCSCK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LYEZAEXHLSEXON-UHFFFAOYSA-N [RhH3].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [RhH3].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 LYEZAEXHLSEXON-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention relates to a synthetic method of 2-butenoic ester, mainly solve the problem that propyne is low in conversion rate and 2-butenoic ester is low in selectivity in the prior art, the invention obtains 2-butenoic ester by adopting the synthetic method of 2-butenoic ester, comprising the contact reaction of materials of propyne, carbon monoxide and alcohol and a catalyst composition, and the catalyst composition comprises a technical scheme of a rhodium complex and a high-valence metallocene cation diphosphine compound, better solves the technical problem, and can be used in the industrial production of 2-butenoic ester.
Description
Technical Field
The invention relates to a synthetic method of 2-butenoic ester.
Background
2-butenoic esters are useful as fragrances and as intermediates in organic synthesis, and also as monomers in polymers. The copolymer of 20% methyl crotonate and 80% vinyl acetate is a transparent solid resin, and has the characteristics of high softening point and solubility in organic solvents such as benzene and methyl chloride. 2-butenoic esters are used as hardeners and sizing agents, paint softeners in the cap industry. The present invention fulfills this need and other needs as will become apparent to those skilled in the art from a reading of the following and the appended claims.
CN1109865 provides a process for producing α, β -unsaturated carboxylic acid esters in high yield from acetone cyanohydrin and sulfuric acid by reducing reaction by-products and recycling process intermediates. Is a method for producing a high-purity methacrylic acid ester in a high yield. The improved process reduces the waste generated in current manufacturing processes.
CN103539666A discloses a preparation method of 2-methyl-3-butenoic ester, which comprises the following steps: (1) under the action of iodine simple substance, 3-halogenated butene reacts with magnesium in an ether solvent to obtain a 3-halogenated-butene Grignard reagent; (2) and (2) dropwise adding the 3-halogenated-butylene Grignard reagent obtained in the step (1) into carbonic ester for substitution reaction to obtain the 2-methyl-3-butenoic ester. The preparation method takes 3-halogenated butene as a starting material, the 3-halogenated-butene Grignard reagent is prepared firstly, and then the 3-halogenated-butene Grignard reagent and the carbonic ester are subjected to substitution reaction, so that the reaction route is shortened, the product yield is improved, the post-treatment step is simplified, and meanwhile, the route avoids the use of virulent hydrocyanic acid and is more environment-friendly.
CN101691329 relates to a synthesis method of 3-fluoro-4-oxo-2 (trans) -butenoic ester with high stereoselectivity and regioselectivity. 2, 3-allenoic acid ester and 1-chloromethyl-4-fluorine-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) salt are stirred in anhydrous acetonitrile at the temperature of 80 ℃ to carry out electrophilic fluorination reaction, so as to synthesize the 3-fluorine-4-oxygen-2 (trans) -butenoic acid ester. The method has the advantages of simple operation, easily obtained raw materials and reagents, high regio-and stereoselectivity of the reaction, easy separation and purification of the product, and suitability for efficiently and quickly synthesizing the 3-fluoro-4-oxo-2 (trans) -butenoic ester.
Disclosure of Invention
The invention aims to solve the technical problems of low propyne conversion rate and low 2-butenoate selectivity in the preparation of 2-butenoate by a propyne route in the prior art, and provides a catalyst composition for preparing 2-butenoate by the propyne route, which has the advantages of high propyne conversion rate and high 2-butenoate selectivity.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the synthesis method of 2-butenoic ester comprises the step of carrying out contact reaction on a material of propyne, carbon monoxide and alcohol and a catalyst composition to obtain the 2-butenoic ester, wherein the catalyst composition comprises a rhodium complex and a diphosphine compound of a metallocene high-valence metal cation.
The invention adopts the high-valence metallocene cationic diphosphine compound to replace the low-valence metallocene cationic diphosphine compound in the prior art, obviously improves the conversion rate of the propyne and the selectivity of the 2-butenoate in the reaction of synthesizing the 2-butenoate by carbonylation of the propyne, and obtains unexpected technical effects.
In the above technical scheme, the reaction temperature is preferably 25 ℃ to 150 ℃, more preferably 90 ℃ to 130 ℃.
In the above-mentioned embodiment, the reaction pressure is preferably 0.01MPa to 10MPa, more preferably 0.1MPa to 2 MPa.
In the technical scheme, the molar ratio of the rhodium complex to the metallocene high-valence metal cation diphosphine compound is preferably 0.01-100; further preferably, the molar ratio of the rhodium complex to the metallocene high-valence metal cation diphosphine compound is 0.1-10, more preferably 0.2-2, and most preferably 0.5-1.
In the above technical scheme, the valence of the metal is preferably greater than 2.
In the above-mentioned technical solutions, rhodium complexes common in the art can be used in the present invention and achieve comparable technical effects, including, as non-limiting examples, rhodium salts, hydrogen complexes (hydride complexes), carbonyl compounds, halides, oxides, phosphine complexes (phosphine complexes) and mixtures thereof; more specific non-limiting examples may be selected from rhodium trichloride, rhodium acetate, rhodium dicarbonyl acetylacetonate, (acetylacetonate) (norbornadiene) rhodium, rhodium bis (1, 5-cyclooctadiene) tetrafluoroborate, rhodium bis (dicyclopentadiene) tetrafluoroborate, rhodium carbonylbis (triphenylphosphino) chloride, rhodium tris (triphenylphosphine) carbonylhydride, rhodium bis (1, 5-cyclooctadiene) dichloride, rhodium tetrakis (triphenylphosphine) hydride, rhodium tris (triphenylphosphine) chloride, rhodium phosphine complexes, or mixtures thereof.
In the above embodiment, the rhodium complex preferably comprises rhodium dicarbonyl acetylacetonate.
In the above technical solution, the metal cation is at least one metal cation selected from iron system in the periodic table. The high-valence metal cation is preferably at least one of trivalent Fe, trivalent Co and trivalent Ni.
In the above technical solution, the high valence metal cation preferably includes trivalent Fe and trivalent Co at the same time, and both have synergistic effect in improving the propyne conversion rate and the 2-butenoate selectivity.
In the above technical solution, the high valence metal cation preferably includes trivalent Fe and trivalent Ni, and both have synergistic effect in improving the conversion rate of propyne and the selectivity of 2-butenoate.
In the above technical solution, the high valence metal cation preferably includes trivalent Co and trivalent Ni, and both have synergistic effect in improving the conversion rate of propyne and the selectivity of 2-butenoate.
In the above technical scheme, the metallocene high-valence metal cation diphosphine compound preferably has the following structure:
wherein M is at least one of Fe, Co, Ni, R is some representative examples are phenyl, halophenyl such as 4-fluorophenyl, 2, 6-difluorophenyl, 2, 5-dichlorophenyl, 3, 4-dichlorophenyl, 3-chlorophenyl, 3-bromophenyl, 4-bromophenyl, 3, 4-dibromophenyl, 2-fluorophenyl, and the like; mono-or di (methyl) aryl such as 4-methylphenyl, 3-methylphenyl, 2, 4-dimethylphenyl, 3, 5-dimethylphenyl, etc., X-Is BF4 -And or PF6 -。
The above reaction is preferably carried out in a solvent, preferably those capable of dissolving the catalyst composition, saturated alcohols of C1 to C10 (as reactants and solvents; such as, but not limited to, methanol, ethanol, propanol, ethylene glycol, glycerol, etc.), ethers of C3 to C10 (such as, but not limited to, methylethyl ether, diethyl ether, tetrahydrofuran, 3-methyltetrahydrofuran, dioxane, etc.), alkyl-substituted phenyl groups containing 7 to 10 carbon atoms in the molecule (such as, but not limited to, toluene, ethylbenzene, cumene, xylene, diethylbenzene, diisopropylbenzene, trimethylbenzene, tetramethylbenzene, etc.), halogenated hydrocarbons of C1 to C10 (such as, but not limited to, dichloromethane, trichloromethane, 1, 2-dichloroethane), and mixtures thereof.
The preparation method of the catalyst composition of the invention is not particularly limited, for example, the components can be simply mixed and used for the preparation reaction of the 2-butenoic ester, or the components can be added into the reaction system sequentially or simultaneously for use, and the sequence of adding the components into the reaction system is not particularly limited, so that comparable technical effects can be obtained.
The alcohol in the technical scheme is preferably saturated alcohol of C1-C10. In this case the corresponding 2-butenoate is CH3CH-COOR, wherein R is C1-C10 alkyl.
The preparation method of the dicyclopentadienyl high-valence metal cation diphosphine compound comprises the following steps:
in the above reaction formula, LiCp and TiCp respectively represent a lithium metallocene and a titanium metallocene;
TiOEt represents titanium ethoxide;
[ O ] represents an oxidizing agent, and may be p-benzoquinone and/or perchloroethane.
Dissolving lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 deg.C, adding diaryl phosphonium chloride, and stirring at room temperature for 2 hr. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding anhydrous ether solution of titanium ethoxide dropwise, naturally recovering to room temperature, and stirring for 2 hr. Adding at least one of Fe, Co and Ni, and refluxing for 12 hr. Cooling the solution to room temperature, adding p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding fluoroboric acid or sodium fluoroborate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the high-valence metallocene diphosphine compound.
The amount of the catalyst composition used in the reaction is not particularly limited, and can be determined reasonably by those skilled in the art according to the need, for example, but not limited to, the molar ratio of the propyne to the catalyst composition is 1 to 10000.
The above reaction is preferably carried out in a solvent, preferably those capable of dissolving the catalyst composition, saturated alcohols of C1 to C10 (which may also serve as reaction raw materials, such as, but not limited to, methanol, ethanol, propanol, ethylene glycol, glycerol, etc.), ethers of C3 to C10 (such as, but not limited to, methylethyl ether, diethyl ether, tetrahydrofuran, 3-methyltetrahydrofuran, dioxane, etc.), alkyl-substituted phenyl groups having 7 to 10 carbon atoms in the molecule (such as, but not limited to, toluene, ethylbenzene, cumene, xylene, diethylbenzene, diisopropylbenzene, trimethylbenzene, tetramethylbenzene, etc.), halogenated hydrocarbons of C1 to C10 (such as, but not limited to, dichloromethane, trichloromethane, 1, 2-dichloroethane), and mixtures thereof.
No special technique is required to obtain the catalyst composition of the present invention, but in order to obtain a highly active catalyst composition, it is preferred to perform the operation of rhodium and phosphine ligands in an inert atmosphere, i.e., nitrogen, argon, etc. The catalyst composition can be mixed before being added into the applied reaction system for use, or can be simultaneously or respectively added into the applied reaction system according to the composition of the catalyst composition, and when the catalyst composition is respectively added into the applied reaction system, no special requirement is imposed on the adding sequence, and the catalyst composition can achieve the purpose of the invention and obtain comparable technical effects.
The amount of propyne in the reaction mixture may vary within wide limits. In practice, higher concentrations of feedstock in the reactor favor the reaction rate.
Unless otherwise specified, the 2-butenoic esters referred to in the present invention are all mixtures of cis and trans forms.
The present invention is described in more detail below by way of examples of embodiments of the invention, although it should be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. All percentages are by weight of the material unless otherwise indicated.
By adopting the technical scheme of the invention, the conversion rate of the propyne can reach 86.4%, the selectivity of the 2-butenoate can reach 91.2%, and a better technical effect is achieved.
Detailed Description
[ example 1 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and trivalent ferrocene cation bis (diphenyl) phosphinyl hexafluorophosphate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed 82.3% conversion of propyne and 89.5% selectivity to 2-butenoate. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
Comparative example 1
Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and the divalent ferrocenium cation bis (diphenyl) phosphine (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 36.1% and a 2-butenoate selectivity of 66.9%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 2]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of cobaltous chloride was added thereto, and the mixture was refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the trivalent cobaltocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and the trivalent cobaltocene cation bis (diphenyl) phosphine hexafluorophosphate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 74.6% and a 2-butenoate selectivity of 88.1%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 3 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of nickel chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the nickelous trivalent nickelocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and the cationic bis (diphenyl) phosphine hexafluorophosphate salt of nickelous trivalent (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 79.6% with a 2-butenoate selectivity of 85.2%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 4 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of cobaltous chloride was added thereto, and the mixture was refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the trivalent cobaltocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol), trivalent ferrocene cation bis (diphenyl) phosphino hexafluorophosphate (0.06mmol), and trivalent cobaltocene cation bis (diphenyl) phosphino hexafluorophosphate (0.04 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. The contents were analyzed by internal standard gas chromatography and showed propyne conversion/86.4% and 2-butenoate selectivity 91.2%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 5 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of nickel chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the nickelous trivalent nickelocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol), trivalent ferrocene cation bis (diphenyl) phosphino hexafluorophosphate (0.05mmol), and trivalent nickelocene cation bis (diphenyl) phosphino hexafluorophosphate (0.05 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 84.1% and a 2-butenoate selectivity of 90.0%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 6 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of cobaltous chloride was added thereto, and the mixture was refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the trivalent cobaltocene cation bis (diphenyl) phosphine hexafluorophosphate.
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol of nickel chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the nickelous trivalent nickelocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol), trivalent nickelocene cation bis (diphenyl) phosphine hexafluorophosphate (0.03mmol), and trivalent cobaltocene cation bis (diphenyl) phosphine hexafluorophosphate (0.07 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 86.1% and a 2-butenoate selectivity of 89.9%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 7 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of dinaphthyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 mL autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and trivalent ferrocene cation bis (dinaphthyl) phosphino hexafluorophosphonate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 64.0% and a 2-butenoate selectivity of 92.5%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 8 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium tetrafluoroborate, adding water, extracting with dichloromethane, dripping the solution into diethyl ether, filtering to obtain a solid, and recrystallizing with dichloromethane/diethyl ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine tetrafluoroborate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and trivalent ferrocene cation bis (diphenyl) phosphinotrifluoroborate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed 78.1% conversion of propyne and 88.7% selectivity for 2-butenoate. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 9 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 mL autoclave was charged with tetrakis (triphenylphosphine) rhodium hydride (0.05mmol), trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphineAcid salt (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 75.6% and a 2-butenoate selectivity of 95.4%. For comparison, the composition of the catalyst and the reaction results are shown in Table 1.
[ example 10 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in toluene to 2-butenoate
A150 mL autoclave was charged with rhodium dicarbonylacetylacetonate (0.05mmol), trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate (0.10 mmol). Toluene (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 83.5% and a 2-butenoate selectivity of 87.6%.
[ example 11 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.005mmol) and trivalent ferrocene cation bis (diphenyl) phosphinyl hexafluorophosphate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 120 ℃. The autoclave was stirred and maintained at 120 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 50.0% and a 2-butenoate selectivity of 81.1%.
[ example 12 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and trivalent ferrocene cation bis (diphenyl) phosphinyl hexafluorophosphate (0.10 mmol). Tetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) were added, followed by a solution of N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 150 ℃. The autoclave was stirred and maintained at 150 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed 82.1% conversion of propyne and 86.4% selectivity to 2-butenoate.
[ example 13 ]
1. Synthesis of ligands
Dissolving 50mmol of lithium cyclopentadienyl or titanium cyclopentadienyl in anhydrous ether, cooling the system to-30 ℃, adding 50mmol of diphenyl phosphine chloride, and stirring at room temperature for 2 hours. Filtering with diatomite, cooling the filtrate to-78 deg.C, adding 50mmol titanium ethoxide anhydrous ether solution dropwise, naturally returning to room temperature, and stirring for 2 hr. 25mmol ferrous chloride was added and refluxed for 12 hours. Cooling the solution to room temperature, adding 60mmol of p-benzoquinone or perchloroethane, reacting for 10 minutes, evaporating the solvent under reduced pressure, dissolving the residue with dichloromethane, filtering with diatomite, evaporating the solvent under reduced pressure, dissolving the residue in acetone, adding 75mmol of sodium hexafluorophosphate, adding water, extracting with dichloromethane, dripping the solution into ether, filtering to obtain a solid, and recrystallizing with dichloromethane/ether to obtain the trivalent ferrocene cation bis (diphenyl) phosphine hexafluorophosphate.
2. Carbonylation of propyne in tetrahydrofuran to 2-butenoate
A150 ml autoclave was charged with rhodium carbonyl acetylacetonate (0.05mmol) and trivalent ferrocene cation bis (diphenyl) phosphinyl hexafluorophosphate (0.10 mmol). Adding fourTetrahydrofuran (25mL), methanol (10g) and propyne (50mmol) then under N2And (4) replacing the reactor. The reactor was pressurized to 2.0MPa with CO and heated to 60 ℃. The autoclave was stirred and maintained at 60 ℃ for a total of 3 hours. The autoclave was then cooled, excess gas vented and the contents recovered. Analysis of the contents by internal standard gas chromatography showed a propyne conversion of 35.2% and a 2-butenoate selectivity of 93.8%.
TABLE 1
Claims (7)
- The synthesis method of 2-butenoate comprises the following steps of carrying out contact reaction on a material of propyne, carbon monoxide and alcohol and a catalyst composition to obtain the 2-butenoate, wherein the catalyst composition comprises a rhodium complex and a diphosphine compound of a metallocene high-valence metal cation; wherein the metal cation is at least one metal cation selected from iron system in the periodic table of elements; the valence of the metal is greater than 2.
- 2. The synthesis process according to claim 1, characterized in that the reaction temperature is between 25 ℃ and 150 ℃.
- 3. The synthesis method according to claim 1, wherein the reaction pressure is 0.01MPa to 10 MPa.
- 4. The synthesis method according to claim 1, wherein the molar ratio of the rhodium complex to the bis-metallocene high-valence metal cation diphosphine compound is 0.01-100.
- 5. The synthesis process according to claim 1, characterized in that the rhodium complex is selected from rhodium trichloride, rhodium acetate, rhodium dicarbonylacetylacetonate, (acetylacetone) (norbornadiene) rhodium, rhodium bis (1, 5-cyclooctadiene) tetrafluoroborate, rhodium bis (dicyclopentadiene) tetrafluoroborate, rhodium carbonylbis (triphenylphosphino) rhodium chloride, rhodium tris (triphenylphosphine) carbonylhydride, rhodium bis (1, 5-cyclooctadiene) dichloride, rhodium tetrakis (triphenylphosphine) hydride, rhodium tris (triphenylphosphine) chloride, rhodium phosphine complexes or mixtures thereof.
- 6. The method of claim 5, wherein the rhodium complex comprises rhodium dicarbonyl acetylacetonate.
- 7. The synthesis method according to claim 1, wherein the alcohol is a saturated alcohol having a carbon number of 1-10.
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