CN114829339A - 通过使环状nh-化合物与乙炔在均相催化剂存在下反应而合成n-乙烯基化合物 - Google Patents
通过使环状nh-化合物与乙炔在均相催化剂存在下反应而合成n-乙烯基化合物 Download PDFInfo
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- CN114829339A CN114829339A CN202080087096.3A CN202080087096A CN114829339A CN 114829339 A CN114829339 A CN 114829339A CN 202080087096 A CN202080087096 A CN 202080087096A CN 114829339 A CN114829339 A CN 114829339A
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- phosphine
- acetylene
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 39
- 125000004122 cyclic group Chemical group 0.000 title claims description 13
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 239000002815 homogeneous catalyst Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 48
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 33
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 28
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 238000007172 homogeneous catalysis Methods 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- -1 Alkyl radical Chemical class 0.000 claims description 64
- 229910052760 oxygen Inorganic materials 0.000 claims description 59
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- 125000005842 heteroatom Chemical group 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910052717 sulfur Inorganic materials 0.000 claims description 32
- 125000001424 substituent group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 150000003950 cyclic amides Chemical class 0.000 claims description 7
- 150000001924 cycloalkanes Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical compound OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000012967 coordination catalyst Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910000856 hastalloy Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 5
- AXVOAMVQOCBPQT-UHFFFAOYSA-N triphos Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 AXVOAMVQOCBPQT-UHFFFAOYSA-N 0.000 description 5
- 238000006886 vinylation reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- BARUNXKDFNLHEV-UHFFFAOYSA-N [3-diphenylphosphanyl-2-(diphenylphosphanylmethyl)-2-methylpropyl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC(CP(C=1C=CC=CC=1)C=1C=CC=CC=1)(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 BARUNXKDFNLHEV-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical compound C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HBRXQSHUXIJOKV-UHFFFAOYSA-N 5-methyl-1,3-oxazolidin-2-one Chemical compound CC1CNC(=O)O1 HBRXQSHUXIJOKV-UHFFFAOYSA-N 0.000 description 2
- VMAQYKGITHDWKL-UHFFFAOYSA-N 5-methylimidazolidine-2,4-dione Chemical compound CC1NC(=O)NC1=O VMAQYKGITHDWKL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000179480 Codrus Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
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- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- AICIYIDUYNFPRY-UHFFFAOYSA-N 1,3-dihydro-2H-imidazol-2-one Chemical compound O=C1NC=CN1 AICIYIDUYNFPRY-UHFFFAOYSA-N 0.000 description 1
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 description 1
- OYELEBBISJGNHJ-UHFFFAOYSA-N 1,3-oxazinan-2-one Chemical compound O=C1NCCCO1 OYELEBBISJGNHJ-UHFFFAOYSA-N 0.000 description 1
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- WGOBPPNNYVSJTE-UHFFFAOYSA-N 1-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 WGOBPPNNYVSJTE-UHFFFAOYSA-N 0.000 description 1
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- DWEQVNFWAKJCEY-UHFFFAOYSA-N 4-methylimidazolidin-2-one Chemical compound CC1CNC(=O)N1 DWEQVNFWAKJCEY-UHFFFAOYSA-N 0.000 description 1
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- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 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 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004857 phospholes Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- FFRYUAVNPBUEIC-UHFFFAOYSA-N quinoxalin-2-ol Chemical compound C1=CC=CC2=NC(O)=CN=C21 FFRYUAVNPBUEIC-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
- C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
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Abstract
通过均相催化制备N‑乙烯基化合物的方法,其中使乙炔与环状化合物在液相中在包含至少一种膦作为配体的钌配合物(RuCat)存在下反应,所述环状化合物包含具有可取代氢基团的氮作为环成员的环状化合物(环状化合物C)。
Description
本发明的目的是一种通过均相催化制备N-乙烯基化合物的方法,其中使乙炔与包含氢取代的氮作为环成员的环状化合物在液相中在包含至少一种膦作为配体的钌配合物存在下反应。
由EP 512 656已知通过乙炔与布朗斯台德酸在包含钌的非均相负载催化剂的存在下反应来制备乙烯基化合物。
EP-A 646571公开了乙炔与氨或伯或仲氨基化合物在1-30巴下的均相催化反应;实施例中使用了20巴。公开了各种催化剂,尤其提到了基于钌的催化剂。
WO 2006/056166公开了由均相催化剂催化的取代炔烃与内酰胺、脲或氨基甲酸酯的反应。没有包括乙炔。由于使用的取代炔烃是液体,因此反应在常压下进行。
DE 19816479中描述了一种通过均相催化合成N-乙烯基化合物的方法。炔烃与氨或伯氨基或仲氨基化合物在液相中反应。提及了乙炔,但实施例中没有使用乙炔。列出了许多合适的过渡金属配合物,但没有使用钌/膦配合物来与乙炔反应。
由于乙炔是气态的,与乙炔的反应通常在压力下进行。保持压力尽可能低是经济的。
本发明的目的是提供一种合成N-乙烯基化合物,特别是环状N-乙烯基化合物的方法,所述方法可在低压下进行,并且其中以高产率和选择性获得N-乙烯基化合物。
因此,发现了上述方法。
环状化合物
环状化合物优选为具有5-8元环系的化合物,其包含具有至少一个氮作为环成员的环状化合物(环状化合物C),所述氮具有可取代的氢基团。优选地,环状化合物C具有一个或两个带有一个或两个可取代氢基团,更优选一个氢基团的氮环成员。
在特别优选的实施方案中,环状化合物C是环状酰胺、环状脲或硫脲或环状氨基甲酸酯或硫代氨基甲酸酯。
环状酰胺包含酰胺基-NH-C(=O)-CH2-作为环系的要素。
环状脲包含脲基-NH-C=(O)-NH-作为环系的要素。
环状硫脲包含硫脲基团-NH-C=(S)-NH-作为环系的要素。
环状氨基甲酸酯包含氨基甲酸酯基团-NH-C(=O)-O-作为环系的要素。
环状硫代氨基甲酸酯包含硫代氨基甲酸酯基团-NH-C(=S)-O-或-NH-C(=O)-S-作为环系的要素。
环系的其他碳原子可以是取代的或未取代的。碳原子的取代基可以是例如羰基(=O)、脂族或芳族烃基,其可以包含杂原子,特别是醚基形式的氧,两个相邻的碳原子可以是其他环系的一部分,例如脂环族或芳族环系。
在最优选的实施方案中,环状化合物C是环状酰胺。
环状化合物C的分子量通常为至多1000g/mol,优选为至多500g/mol。
优选的环状酰胺是:2-吡咯烷酮、2-哌啶酮、己内酰胺、8-辛内酰胺、2,3-二氢-1H-异吲哚-1-酮、2(1H)-喹喔啉酮、4(3H)-喹唑啉酮、2,5-哌嗪二酮、2-噻唑烷酮、2-氮杂双环[2.2.1]庚-5-烯-3-酮。
优选的环脲是:2-咪唑啉酮、4-甲基-2-咪唑啉酮、1,3-二氢-2H-咪唑-2-酮、1,3-二氢-2H-苯并咪唑-2-酮、1,3-二氢-1-甲基-2H-苯并咪唑-2-酮、2,4-咪唑烷二酮、5-甲基-2,4-咪唑烷二酮、5,5-二甲基-2,4-咪唑烷二酮、5-甲基-2,4(1H,3H)-嘧啶二酮。
优选的环状氨基甲酸酯是:2-噁唑烷酮、4-甲基-2-噁唑烷酮、5-甲基-2-噁唑烷酮、四氢-2H-1,3-噁嗪-2-酮、2(3H)-苯并噁唑酮。
在本发明的方法中,包含氢取代的氮作为环成员的环状化合物C在至少一种均相Ru金属催化剂的存在下与乙炔反应,所述催化剂具有至少一种膦作为配体(RuCat);下文也称为乙烯基化催化剂。
本发明方法的乙烯基化催化剂RuCat可以以包含Ru金属化合物和一种或多种配体的预先形成的Ru金属配合物的形式使用。或者,通过将Ru金属化合物(本文也称为前催化剂)与一种或多种合适的配体结合以在反应混合物中形成催化活性金属配合物,从而在反应混合物中原位形成催化体系。
优选的前催化剂选自钌的中性金属配合物、氧化物和盐。可用作前催化剂的钌化合物例如为[Ru(对-繖花烃)Cl2]2、[Ru(苯)Cl2]n、[Ru(CO)2Cl2]n、[Ru(CO)3Cl2]2、[Ru(COD)(烯丙基)]、[RuCl3·H2O]、[Ru(乙酰丙酮)3]、[Ru(DMSO)4Cl2]、[Ru(PPh3)3Cl2]、[Ru(环戊二烯基)(PPh3)2Cl]、[Ru(环戊二烯基)(CO)2Cl]、[Ru(环戊二烯基)(CO)2H]、[Ru(环戊二烯基)(CO)2]2、[Ru(五甲基环戊二烯基)(CO)2Cl]、[Ru(五甲基环戊二烯基)(CO)2H]、[Ru(五甲基环戊二烯基)(CO)2]2、[Ru(茚基)(CO)2Cl]、[Ru(茚基)(CO)2H]、[Ru(茚基)(CO)2]2、二茂钌、[Ru(2,2'-联吡啶)2(Cl)2·H2O]、[Ru(COD)(Cl)2H]2、[Ru(五甲基环戊二烯基)(COD)Cl]、[Ru3(CO)12]和[Ru(四苯基羟基环戊二烯基)(CO)2H]。
对于根据本发明方法的乙烯基化,可以使用本领域已知的任何配合物配体,特别是已知可用于钌催化氢化的那些。
用于根据本发明方法的乙烯基化的催化体系的合适配体例如为下文所示的式I和II的单齿、双齿、三齿和四齿膦,
其中:
n为0或1;
R4至R12彼此独立地为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
A为:
i)桥接基团,其选自未取代或至少单取代的N,O,P,C1-C6链烷烃,C3-C10环烷烃,包含至少一个选自N、O和S的杂原子的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族,其中取代基选自C1-C4烷基、苯基、F、Cl、Br、OH、OR16、NH2、NHR16或N(R16)2,
其中R16选自C1-C10烷基和C5-C10芳基;或者
ii)式(VI)或(VII)的桥接基团:
R13、R14彼此独立地选自C1-C10烷基、F、Cl、Br、OH、OR15、NH2、NHR15和N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;
X1、X2彼此独立地为NH、O或S;
X3为键、NH、NR16、O、S或CR17R18;
R16为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
R17、R18彼此独立地为未取代的或至少单取代的C1-C10烷基,C1-C10烷氧基,C3-C10环烷基,C3-C10环烷氧基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基,C5-C14芳氧基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
Y1、Y2、Y3彼此独立地为键、未取代或至少单取代的亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基或六亚甲基,
其中取代基选自:F、Cl、Br、OH、OR15、CN、NH2、NHR15、N(R15)2和C1-C10烷基,
其中R15选自C1-C10烷基和C5-C10芳基。
A为桥接基团。对于A选自未取代或至少单取代的C1-C6链烷烃、C3-C10环烷烃、C3-C10杂环烷烃、C5-C14芳族和C5-C6杂芳族的情况,对于情况(n=0),桥接基团的两个氢原子被与相邻取代基Y1和Y2的键代替。对于情况(n=1),桥接基团的三个氢原子被与相邻取代基Y1、Y2和Y3的三个键代替。
对于A为P(磷)的情况,对于情况(n=0),磷与相邻取代基Y1和Y2形成两个键,并与选自C1-C4烷基和苯基的取代基形成一个键。对于情况(n=1),磷与相邻取代基Y1、Y2和Y3形成三个键。
对于A为N(氮)的情况,对于情况(n=0),氮与相邻取代基Y1和Y2形成两个键,并且与选自C1-C4烷基和苯基的取代基形成一个键。对于情况(n=1),氮与相邻取代基Y1、Y2和Y3形成三个键。
对于A为O(氧)的情况,n=0。氧与相邻取代基Y1和Y2形成两个键。
优选包含至少一种选自钌和铱的元素的配位催化剂。
在优选实施方案中,本发明的方法在至少一种包含Ru以及至少一种通式(II)的磷供体配体的配位催化剂的存在下进行,其中:
n为0或1;
R7至R12彼此独立地为未取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基;
A为:
i)桥接基团,其选自未取代的C1-C6链烷烃,C3-C10环烷烃,包含至少一个选自N、O和S的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族;或者
ii)式(VI)或(VII)的桥接基团:
R13、R14彼此独立地选自C1-C10烷基、F、Cl、Br、OH、OR15、NH2、NHR15和N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;
X1、X2彼此独立地为NH、O或S;
X3为键、NH、NR16、O、S或CR17R18;
R16为未取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基;
R17、R18彼此独立地为未取代的C1-C10烷基,C1-C10烷氧基,C3-C10环烷基,C3-C10环烷氧基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基,C5-C14芳氧基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基;
Y1、Y2、Y3彼此独立地为键,未取代的亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基或六亚甲基。
在另一优选实施方案中,本发明的方法在至少一种包含Ru和至少一种通式(VIII)的磷供体配体的配位催化剂的存在下进行,
其中:
R7至R10彼此独立地为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
A为:
i)桥接基团,其选自未取代或至少单取代的N,O,P,C1-C6链烷烃,C3-C10环烷烃,包含至少一个选自N、O和S的杂原子的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族,
其中取代基选自:C1-C4烷基、苯基、F、Cl、Br、OH、OR15、NH2、NHR15或N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;或者
ii)式(VI)或(VII)的桥接基团:
i)桥接基团,其选自未取代或至少单取代的N,O,P,C1-C6链烷烃,
C3-C10环烷烃,包含至少一个选自N、O和S的杂原子的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族,其中取代基选自:C1-C4烷基、苯基、F、Cl、Br、OH、OR15、NH2、NHR15或N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;或者
ii)式(VI)或(VII)的桥接基团:
m、q彼此独立地为0、1、2、3或4;
R13、R14彼此独立地选自C1-C10烷基、F、Cl、Br、OH、OR15、NH2、NHR15和N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;
X1、X2彼此独立地为NH、O或S,
X3为键、NH、NR16、O、S或CR17R18;
R16为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
R17、R18彼此独立地是未取代的或至少单取代的C1-C10烷基,C1-C10烷氧基,C3-C10环烷基,C3-C10环烷氧基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基,C5-C14芳氧基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
Y1、Y2彼此独立地为键,未取代的或至少单取代的亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基或六亚甲基,
其中取代基选自:F、Cl、Br、OH、OR15、CN、NH2、NHR15、N(R15)2和C1-C10烷基,
其中R15选自C1-C10烷基和C5-C10芳基。
在另一优选实施方案中,本发明的方法在至少一种配位催化剂的存在下进行,所述配位催化剂包含至少一种选自元素周期表第8、9和10族的元素以及至少一种通式(IX)的磷给体配体:
其中:
R7至R12彼此独立地为未取代或至少单取代的C1-C10烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
A为桥接基团,其选自未取代或至少单取代的N,P,C1-C6链烷烃,C3-C10环烷烃,包含至少一个选自N、O和S的杂原子的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族,其中取代基选自:C1-C4烷基、苯基、F、Cl、Br、OH、OR15、NH2、NHR15或N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;
Y1、Y2、Y3彼此独立地为键,未取代的或至少单取代的亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基或六亚甲基,
其中取代基选自:F、Cl、Br、OH、OR15、CN、NH2、NHR15、N(R15)2和C1-C10烷基,
其中R15选自C1-C10烷基和C5-C10芳基。
在另一优选实施方案中,本发明的方法在至少一种配位催化剂的存在下进行,所述配位催化剂包含至少一种选自元素周期表第8、9和10族的元素以及至少一种通式(VIII)的磷给体配体,其中:
R7至R10彼此独立地为甲基、乙基、异丙基、叔丁基、环戊基、环己基、苯基或均三甲苯基;
A为:
i)桥接基团,其选自甲烷、乙烷、丙烷、丁烷、环己烷、苯、萘和蒽;或者
ii)式(X)或(XI)的桥接基团:
X1、X2彼此独立地为NH、O或S;
X3为键、NH、O、S或CR17R18;
R17、R18彼此独立地为未取代的C1-C10烷基;
Y1、Y2彼此独立地为键、亚甲基或亚乙基。
在特别优选的实施方案中,本发明的方法在至少一种配位催化剂的存在下进行,所述配位催化剂包含至少一种选自元素周期表第8、9和10族的元素以及至少一种通式(XII)或(XIII)的磷供体配体,
其中,对于m、q、R7、R8、R9、R10、R13、R14、X1、X2和X3,适用上文列出的定义和优选方案。
在实施方案中,本发明的方法在至少一种Ru金属配位催化剂的存在下进行,并且式I的单齿配体在本文中优选是其中R5a、R5b和R6各自是任选带有1或2个C1-C4烷基取代基的苯基或烷基的那些,以及其中R7、R8和R9各自为C5-C8环烷基或C2-C10烷基,特别是直链非支化正C2-C10烷基的那些。基团R5a至R6可不同或相同。优选地,基团R5a至R6是相同的并且选自本文所述的取代基,特别是选自指示为优选的那些。优选的单齿配体IV的实例是三苯基膦(TPP)、三乙基膦、三正丁基膦、三正辛基膦和三环己基膦。
在另一实施方案中,本发明的方法在至少一种Ru金属配位催化剂和至少一种选自如下组的磷供体配体的存在下进行:1,2-双(二苯基膦基)乙烷(dppe)、1,2-双(二苯基膦基)丙烷(dppp)、1,2-双(二苯基膦基)丁烷(dppb)、2,3-双(二环己基膦基)乙烷(dcpe)、4,5-双(二苯基膦基)-9,9-二甲基呫吨(xantphos)、双(2-二苯基膦乙基)苯基膦和1,1,1-三(二苯基膦甲基)乙烷(triphos)。
在另一个特别优选的实施方案中,本发明的方法在包含钌和至少一种选自4,5-双(二苯基膦基)-9,9-二甲基呫吨(xantphos)、双(2-二苯基膦乙基)苯基膦和1,1,1-三(二苯基膦甲基)乙烷(triphos)的磷供体配体的配位催化剂存在下进行。
在另一个特别优选的实施方案中,本发明的方法在包含铱和至少一种选自4,5-双(二苯基膦基)-9,9-二甲基呫吨(xantphos)、双(2-二苯基膦乙基)苯基膦和1,1,1-三(二苯基膦甲基)乙烷(triphos)的磷供体配体的配位催化剂存在下进行。
在本发明的上下文中,C1-C10烷基应理解为意指支化、非支化、饱和和不饱和基团。优选具有1-6个碳原子的烷基(C1-C6烷基)。更优选具有1-4个碳原子的烷基(C1-C4烷基)。
饱和烷基的实例是甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基和己基。
不饱和烷基(链烯基、炔基)的实例是乙烯基、烯丙基、丁烯基、乙炔基和丙炔基。
C1-C10烷基可未被取代或被一个或多个选自如下组的取代基取代:F,Cl,Br,羟基(OH),C1-C10烷氧基,C5-C10芳氧基,C5-C10烷芳氧基,包含至少一个选自N、O、S、氧代的杂原子的C5-C10杂芳氧基,氧代,C3-C10环烷基,苯基,包含至少一个选自N、O、S的杂原子的C5-C10杂芳基,包含至少一个选自N、O、S的杂原子的C5-C10杂环基,萘基,氨基,C1-C10烷基氨基,C5-C10芳基氨基,包含至少一个选自N、O、S的杂原子的C5-C10杂芳基氨基,C1-C10二烷基氨基,C10-C12二芳基氨基,C10-C20烷基芳基氨基,C1-C10酰基,C1-C10酰氧基,NO2,C1-C10羧基,氨基甲酰基,甲酰胺基,氰基,磺酰基,磺酰基氨基,亚磺酰基,亚磺酰基氨基,巯基,C1-C10烷基巯基、C5-C10芳基巯基或C1-C10烷基磺酰基。
C1-C10烷基的上述定义相应地适用于C1-C30烷基和C1-C6链烷烃。
在本发明的情况下,C3-C10环烷基应理解为意指饱和、不饱和的单环和多环基团。C3-C10环烷基的实例是环丙基、环丁基、环戊基、环己基或环庚基。环烷基可以是未取代的或被一个或多个如上文就基团C1-C10烷基所定义的取代基取代。
通过将配体添加到上述前体中,可以在反应混合物中原位生成活性乙烯基化催化剂。过渡金属和配体的摩尔比为2:1至1:50,优选为1:1至1:10,最优选为1:2至1:5。
除了选自上述配体组的一种或多种配体之外,本发明方法的催化体系还可以包含至少一种选自如下组的其他配体:卤化物、酰胺、羧酸盐、乙酰丙酮化物、芳基磺酸盐或烷基磺酸盐、氢化物、CO、烯烃、二烯、环烯烃、腈、芳族和杂芳族化合物、醚、PF3、磷杂环戊二烯、磷腈,以及单齿、二齿和多齿次膦酸酯、亚膦酸酯、亚磷酰胺和亚磷酸酯配体。优选地,催化剂还包含CO作为配体。
活性催化剂RuCat也可以在专门的合成步骤中预先形成。合适的预先形成的催化剂可为[Ru(PPh3)3(CO)(H)Cl]、[Ru(PPh3)3(CO)Cl2]、[Ru(PPh3)3(CO)(H)2]、[Ru(binap)(Cl)2]、[Ru(PMe3)4(H)2]、[Ru(PEt3)4(H)2]、[Ru(Pn-Pr3)4(H)2]、[Ru(Pn-Bu3)4(H)2]、[Ru(Pn-辛基3)4(H)2]、[Ru(Pn-Bu3)4(H)2]、[Ru(Pn-辛基3)4(H)2]、[Ru(PPh3)3(CO)(H)Cl]和[Ru(PPh3)3(CO)(H)2],优选[Ru(PEt3)4(H)2]、[Ru(Pn-Bu3)4(H)2]和[Ru(Pn-辛基3)4(H)2]。
在本发明的一个实施方案中,本发明方法的特征在于均相过渡RuCat选自[Ru(PPh3)3(CO)(H)Cl]、[Ru(PPh3)3(CO)Cl2]、[Ru(PPh3)3(CO)(H)2]、[Ru(binap)(Cl)2]、[Ru(PMe3)4(H)2]、[Ru(PEt3)4(H)2]、[Ru(Pn-Pr3)4(H)2]、[Ru(Pn-Bu3)4(H)2]、[Ru(Pn-辛基3)4(H)2]、[Ru(Pn-Bu3)4(H)2]、[Ru(Pn辛基3)4(H)2]、[Ru(PPh3)3(CO)(H)Cl]和[Ru(PPh3)3(CO)(H)2],优选[Ru(PPh3)3(CO)(H)Cl]、[Ru(PPh3)3(CO)Cl2]和[Ru(PPh3)3(CO)(H)2。
如果使用预先形成的活性催化剂,则将额外的式I或II的配体添加到反应混合物中也是有益的。
在本发明的方法中,基于环状化合物C的RuCat用量可以在宽范围内变化。相对于环状化合物C,RuCat通常以亚化学计量的量使用。通常,RuCat的量不超过50mol%,经常不超过20mol%,特别是不超过10mol%或不超过5mol%,基于环状化合物C的量。优选将0.001-50mol%,经常为0.001-20mol%,特别是0.005-5mol%量的RuCat用于本发明的方法,基于环状化合物C的量。优选使用0.01-5mol%量的RuCat。所示的所有RuCat量均以Ru金属计算,并且基于环状化合物C的量。
在本发明的一个实施方案中,本发明方法的特征在于均相RuCat以0.001-20mol%的量使用,以Ru金属计算,并且基于该方法中所用的环状化合物C的量。
环状化合物C与乙炔的反应主要可以根据本领域技术人员已知的适合环状化合物C与乙炔反应的所有方法进行。
用于还原反应的乙炔可以以纯形式使用,或者如果需要,也可以以与其他气体,优选惰性气体如氮气或氩气的混合物形式使用。优选使用未稀释形式的乙炔。
乙炔可以非连续地或连续地施加,例如通过使乙炔气体鼓泡通过反应混合物。
所述反应通常在0.1-10巴,优选1-5巴,更优选1-1.5巴冷压的乙炔压力下进行。
在本发明的一个实施方案中,本发明方法的特征在于环状化合物C与乙炔之间的反应在1-15巴的压力下进行。
所述反应主要可以连续、半连续或非连续地进行。优选连续方法。
本发明的乙烯基化反应在液相中进行。这可以通过添加一种或多种溶剂来实现,所述溶剂优选选自脂族和芳族烃、直链和环状醚、直链和环状酰胺、亚砜、腈和卤代烃。优选的溶剂是甲苯、DMF和二甘醇二甲醚。液相也可以由液态环状化合物C形成而无需任何额外的溶剂。
还可以将一种或多种碱,例如氮碱如三烷基胺或吡啶类,优选N,N-二甲基氨基吡啶添加到液相中,根据所用催化剂RuCat的量,优选以0.5-20当量的量添加。
所述反应主要可以在本领域技术人员已知的用于此类反应的所有反应器中进行,因此他们将相应地选择反应器。合适的反应器在相关的现有技术中进行了描述和回顾,例如K.Henkel,“Reactor Types and Their Industrial Applications”,Ullmann'sEncyclopedia of Industrial Chemistry,2005年,Wiley-VCH Verlag GmbH&Co.KGaA,第3.3章:“Reactors for gas-liquid reactions”。
本发明的方法可以在宽温度范围内进行。优选地,反应在20-200℃,更优选50-180℃,特别是100-170℃的温度下进行。
实施例
A)实施例1、9、10、11、12、14、18、21、22、23、25、27、29、30、31、32、33、38、40、42的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入CodRu(met)2(0,001-0.06mmol)、环状化合物C(1mmol)、甲苯(5.0-10.0mL)或二氯甲烷(10mL,条目9)或二甲基甲酰胺(5mL,条目20、36、37、40、41)和三正丁基膦(0,005-0,18mmol)或三辛基膦(0.1mmol,条目12)或三环己基膦(0.1mmol,条目13)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在100-140℃下加热。然后,将混合物在指定温度下搅拌14-18小时。注意:在此温度下,内部压力升至3-4巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。随后,将其溶解在1mL CH2Cl2中并涂覆在二氧化硅上。通过柱色谱法分离产物(石油醚/乙酸乙酯8/2—对于不同的产物,系统比例略有不同)。当反应在DMF中进行时,用二氯甲烷从反应混合物的水溶液中萃取产物,将有机层用水洗涤至少5次(条目40、41)或收集在圆底烧瓶中并在真空下浓缩,然后进行柱色谱法分离(石油醚/乙酸乙酯,条目20、36、37)。
B)实施例13、15、16、17、19、20、26、28、34、35、36、37、39、41的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入CodRu(met)2(0.02 0,06mmol)、环状化合物C(1mmol)、甲苯(5.0mL,条目15、17、18、19、21、22、33、35、43、47、49)或二甲基甲酰胺(5-8mL,条目42、44、45)、DMAP(0,04-0,12mmol)和三正丁基膦(0,06-0,18mmol)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在100-150℃下加热。然后,将混合物在指定温度下搅拌14-18小时。注意:在此温度下,内部压力升至4-6巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。随后,将其溶解在1mL CH2Cl2中并涂覆在二氧化硅上。通过柱色谱法分离产物(石油醚/乙酸乙酯8/2—对于不同的产物,系统比例略有不同)。
C)对比实施例2和3的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入负载在活性炭上5%钌(100mg)、2-吡咯烷酮(13,1mmol,1.116g)和二甘醇二甲醚(条目13)或甲苯(条目14)(8.0mL)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在170℃下加热。然后,将混合物在指定温度下搅拌14小时。注意:在此温度下,内部压力升至5巴(二甘醇二甲醚)/7巴(甲苯)。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。通过GC和/或NMR分析粗混合物。产物未分离。对比实施例2和3表明,使用非均相Ru催化剂仅产生少量的所需产物。
D)对比实施例4的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入负载在活性炭的5%钌(10mg)、2-吡咯烷酮(1mmol,0,085g)和甲苯(10.0mL)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在170℃下加热。然后,将混合物在指定温度下搅拌14小时。注意:在此温度下,内部压力升至7巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。通过GC和/或NMR分析粗混合物。产物未分离。对比实施例4表明,使用非均相Ru催化剂仅产生少量的所需产物。
E)对比实施例5、6、7和8的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入2mol%钌催化剂(RuCl3·3H2O—条目5;Ru(AcAc)3—条目6;Ru3(CO)12—条目7;codRumet2—条目8)、2-吡咯烷酮(1mmol,0,085g)和甲苯(5.0mL)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在100℃下加热。然后,将混合物在指定温度下搅拌16-19小时。注意:在此温度下,内部压力升至3-4巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。通过GC分析粗混合物。产物未分离。对比实施例5、6、7和8表明,仅使用不含膦配体的钌配合物,在相同条件下仅形成痕量的所需产物。
F)对比实施例43的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex)中加入20mol%三正丁基膦(0.2mmol,0,042g)、2-吡咯烷酮(1mmol,0,085g)和甲苯(10.0mL)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在100℃下加热。然后,将混合物在指定温度下搅拌16小时。注意:在此温度下,内部压力升至3-4巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。通过GC分析粗混合物。没有形成产物。对比实施例43表明,在这些条件下,仅使用膦配体而不使用钌配合物不会得到产物。
G)实施例24的一般程序:在手套箱中在氩气气氛下,在约40mL的高压釜(Premex,Hastelloy)中加入将无水氯化钌(III)(0.03mmol,条目26)或氯化钌(III)水合物(0.03-0.09mmol,条目27、29、30、31)、5-甲基-1,3-噁唑烷-2-酮(1mmol,0,101g)、甲苯(5.0mL)和三正丁基膦(0,06-0.12mmol,条目26、27、29、30)或三苯基膦(0.1mmol,条目31)。在关闭反应容器后,用乙炔吹扫体系(3次)。最后,将高压釜用乙炔加压(在室温下在1.5巴下15分钟)并在100℃下加热。然后,将混合物在指定温度下搅拌14-16小时。注意:在此温度下,内部压力升至3-4巴。然后,将反应在水浴上冷却并小心减压。将粗混合物收集在圆底烧瓶中并在真空下浓缩。通过GC和/或NMR分析粗混合物。产物未分离。
Claims (15)
1.通过均相催化制备N-乙烯基化合物的方法,其中使乙炔与环状化合物在液相中在包含至少一种膦作为配体的钌配合物(RuCat)存在下反应,所述环状化合物包含具有可取代氢基团的氮作为环成员的环状化合物(环状化合物C)。
2.根据权利要求1所述的方法,其中环状化合物C是环状酰胺、环状脲或硫脲或环状氨基甲酸酯或硫代氨基甲酸酯。
3.根据权利要求1或2所述的方法,其中环状化合物C是环状酰胺。
4.根据权利要求1-3中任一项所述的方法,其中所述膦是单齿、二齿、三齿或四齿膦。
5.根据权利要求1-4中任一项所述的方法,其中所述膦是如下所示的式I或II的膦:
其中:
n为0或1;
R4至R12彼此独立地为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
A为:
i)桥接基团,其选自未取代或至少单取代的N,O,P,C1-C6链烷烃,C3-C10环烷烃,包含至少一个选自N、O和S的杂原子的C3-C10杂环烷烃,C5-C14芳族和包含至少一个选自N、O和S的杂原子的C5-C6杂芳族,
其中取代基选自:C1-C4烷基、苯基、F、Cl、Br、OH、OR16、NH2、NHR16或N(R16)2,
其中R16选自C1-C10烷基和C5-C10芳基;或
ii)式(VI)或(VII)的桥接基团:
其中:
m、q彼此独立地为0、1、2、3或4;
R13、R14彼此独立地选自C1-C10烷基、F、Cl、Br、OH、OR15、NH2、NHR15和N(R15)2,
其中R15选自C1-C10烷基和C5-C10芳基;
X1、X2彼此独立地为NH、O或S;
X3为键、NH、NR16、O、S或CR17R18;
R16为未取代或至少单取代的C1-C10烷基,C3-C10环烷基,包含至少一个选自N、O和S的杂原子的C3-C10杂环基,C5-C14芳基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
R17、R18彼此独立地为未取代或至少单取代的C1-C10烷基,C1-C10烷氧基,C3-C10环烷基,C3-C10环烷氧基,包含至少一个选自N、O和S的杂原子的杂环基,C5-C14芳基,C5-C14芳氧基或包含至少一个选自N、O和S的杂原子的C5-C10杂芳基,
其中取代基选自:F、Cl、Br、OH、CN、NH2和C1-C10烷基;
Y1、Y2、Y3彼此独立地是为键,未取代的或至少单取代的亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基或六亚甲基,
其中取代基选自:F、Cl、Br、OH、OR15、CN、NH2、NHR15、N(R15)2和C1-C10烷基,
其中R15选自C1-C10烷基和C5-C10芳基。
6.根据权利要求1-5中任一项所述的方法,其中所述膦是式(IV)的膦。
7.根据权利要求6所述的方法,其中所述膦是三烷基膦。
8.根据权利要求1-7中任一项所述的方法,其中所述钌配合物单独制备或者在所述环状化合物与乙炔反应期间原位制备。
9.根据权利要求8所述的方法,其中使用1-10mol膦/mol钌来制备钌配合物。
10.根据权利要求1-9中任一项所述的方法,其中所述钌配合物以0.01-5mol%的量使用,基于环状化合物的量。
11.根据权利要求1-10中任一项所述的方法,其中所述环状化合物C和乙炔的反应在N-碱的存在下进行。
12.根据权利要求1-11中任一项所述的方法,其中所述液相包含溶剂。
13.根据权利要求1-12中任一项所述的方法,将乙炔以1-2巴的压力在20℃下供入到反应中。
14.根据权利要求1-13中任一项所述的方法,其中所述反应在50-200℃的温度下进行。
15.根据权利要求1-14中任一项所述的方法,其中反应期间的压力为至多10巴。
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WO2006056166A2 (de) * | 2004-11-24 | 2006-06-01 | Studiengesellschaft Kohle Mbh | Verfahren zur addition von amiden, harnstoffen. lactamen und carbamaten an alkine |
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US4981973A (en) * | 1988-06-30 | 1991-01-01 | Union Carbide Chemicals And Plastics Company, Inc. | Transvinylation reaction |
CA2131594A1 (en) * | 1993-09-30 | 1995-03-31 | Marc Heider | Preparation of n-vinyl compounds |
WO2006056166A2 (de) * | 2004-11-24 | 2006-06-01 | Studiengesellschaft Kohle Mbh | Verfahren zur addition von amiden, harnstoffen. lactamen und carbamaten an alkine |
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