CN110028504B - 2,9-二芳基取代的邻菲啰啉与其钴络合物的制备方法及其应用 - Google Patents
2,9-二芳基取代的邻菲啰啉与其钴络合物的制备方法及其应用 Download PDFInfo
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- CN110028504B CN110028504B CN201810046693.6A CN201810046693A CN110028504B CN 110028504 B CN110028504 B CN 110028504B CN 201810046693 A CN201810046693 A CN 201810046693A CN 110028504 B CN110028504 B CN 110028504B
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- Prior art keywords
- phenanthroline
- bis
- cobalt
- tert
- butyl
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical class C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000004700 cobalt complex Chemical class 0.000 title abstract description 5
- -1 phenanthroline cobalt complex Chemical class 0.000 claims abstract description 146
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 230000000536 complexating effect Effects 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000005349 anion exchange Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 125000001188 haloalkyl group Chemical group 0.000 claims 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims 1
- 125000005429 oxyalkyl group Chemical group 0.000 claims 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 150000005041 phenanthrolines Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- DNKGIDURJINUOA-UHFFFAOYSA-N 2,9-dichloro-1,10-phenanthroline Chemical compound C1=C(Cl)N=C2C3=NC(Cl)=CC=C3C=CC2=C1 DNKGIDURJINUOA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 4
- 150000001543 aryl boronic acids Chemical class 0.000 abstract description 4
- 125000002355 alkine group Chemical group 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- 239000007787 solid Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 21
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000003517 fume Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 4
- XYOUZEDTUOJHQP-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C=C(C=1OC)C(C)(C)C)C1=NC2=C3N=C(C=CC3=CC=C2C=C1)C1=CC(=C(C(=C1)C(C)(C)C)OC)C(C)(C)C Chemical compound C(C)(C)(C)C=1C=C(C=C(C=1OC)C(C)(C)C)C1=NC2=C3N=C(C=CC3=CC=C2C=C1)C1=CC(=C(C(=C1)C(C)(C)C)OC)C(C)(C)C XYOUZEDTUOJHQP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- JGSIJYSDAATDQL-UHFFFAOYSA-N CC=1C(=NC2=C3N=CC=CC3=CC=C2C1)C1=CC=CC=C1 Chemical compound CC=1C(=NC2=C3N=CC=CC3=CC=C2C1)C1=CC=CC=C1 JGSIJYSDAATDQL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
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- 239000003446 ligand Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QCQALVMFTWRCFI-UHFFFAOYSA-N oct-2-yne Chemical compound CCCCCC#CC QCQALVMFTWRCFI-UHFFFAOYSA-N 0.000 description 3
- GZTNBKQTTZSQNS-UHFFFAOYSA-N oct-4-yne Chemical compound CCCC#CCCC GZTNBKQTTZSQNS-UHFFFAOYSA-N 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DJGHSJBYKIQHIK-UHFFFAOYSA-N (3,5-dimethylphenyl)boronic acid Chemical compound CC1=CC(C)=CC(B(O)O)=C1 DJGHSJBYKIQHIK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
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- 238000012552 review Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005934 tert-pentyloxycarbonyl group Chemical group 0.000 description 1
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Abstract
本发明涉及2,9‑二芳基取代的邻菲啰啉与其钴络合物的制备方法及其应用。具体的讲是以2,9‑二氯邻菲啰啉与芳基硼酸进行Suzuki偶联反应制备取代的邻菲啰啉,将其与钴盐进行络合反应,可以制备邻菲啰啉钴络合物。该邻菲啰啉钴络合物在添加剂存在下,能够催化炔烃与硅烷的硅氢化反应,得到用途多样的烯基硅化合物,表现出很高的活性和选择性,特别是对于烷基取代的端炔的硅氢化,给出优于其它已知钴催化剂的马氏加成的选择性,具有很好的应用前景。
Description
技术领域
本发明涉及2,9-二芳基取代的邻菲啰啉与其钴络合物的制备方法及其应用。具体的讲是以2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联反应制备取代的邻菲啰啉,将其与钴盐进行络合反应,可以制备邻菲啰啉钴络合物。该邻菲啰啉钴络合物在添加剂存在下,能够催化炔烃与硅烷的硅氢化反应,得到用途多样的烯基硅化合物,表现出很高的活性和选择性,特别是对于烷基取代的端炔的硅氢化,给出优于其它已知钴催化剂的马氏加成的选择性,具有很好的应用前景。
背景技术
有机硅化合物因其独特的物理化学性质,广泛用作涂料、粘合剂、化妆品、洗涤剂等 [Ojima,I.In The Chemistry of Organic Silicon Compounds,Patai,S.,Rappoport,Z.,Eds.;Wiley: Chichester,U.K.,1989;Vol.1;Chapter 25.]。其中,烯基硅化合物作为重要的原料,可以合成丰富多样的有机硅化合物分子,可用于合成具有特殊功能的高分子材料,还可以作为试剂应用于成环反应、Hiyama偶联反应以及氧化反应中,因而发展高效合成烯基硅化合物的方法是具有非常重要的理论意义和实用价值[(1)Blumenkopf,T.A.;Overman,L.E. Vinylsilane-and Alkynylsilane-Terminated CyclizationReactions.Chem.Rev.1986,86,857.(2) Denmark,S.E.;Sweis,R.F.Design andImplementation of New Silicon-Based Cross-Coupling Reactions:Importance ofSilicon-Oxygen Bonds.Acc.Chem.Res.2002,35,835.]。
硅烷对炔烃的加成反应称为炔烃硅氢化,是合成烯基硅化合物最为高效的方法之一,具有100%的原子经济性。过渡金属催化剂可以提高炔烃硅氢化的活性、控制其区域和立体选择性。发展高活性、高选择性的过渡金属催化剂一直是炔烃硅氢化研究的重点和该反应走向实际应用的关键。
迄今,人们已经发展了许多用于炔烃硅氢化的过渡金属催化剂,有些还表现出很高的活性和选择性[Marciniec,B.(Ed.),Hydrosilylation,A Comprehensive Review onRecent Advances,Spring,2009.]。但是已知的用于炔烃硅氢化反应的过渡金属催化剂还存在一些局限。一方面,这些催化剂主要是基于稀有金属,如铂、铑、钯、钌等,这些金属储量很低,价格昂贵且浮动大,大量使用时还会带来重金属的污染等问题,不符合可持续化学和绿色化学的要求。另一方面,已知的炔烃硅氢化催化剂还存在选择性不理想的问题。比如已知的催化剂在端炔硅氢化反应中通常给出反马氏加成的选择性,即硅原子加成到炔烃的端位,得到1-硅基取代的链状内烯产物。只有少数几种基于铑、钌的金属络合物催化剂在端炔硅氢化中给出较高的马氏加成的选择性,即硅原子加成到炔烃取代的一侧,得到2-硅基取代的支状端烯产物[(1)Wada,F.;Abe,S.Yonemaru,N.;Kikukawa,K.;Matsuda,T.Catalytic Behavior of Rhodium(I)Complexes in Hydrogermylation andHydrosilylation of Phenylacetylene.Bull.Chem.Soc.Jpn.1991,64,1701.(2)Trost,B.M.;Ball,Z.T. Markovnikov Alkyne Hydrosilylation Catalyzed by RutheniumComplexes.J.Am.Chem.Soc. 2001,123,12726.]。最近发展的两种基于吡啶的钳形配体和钴的络合物实现了芳基乙炔的马氏选择性硅氢化[(1)Guo,J.;Lu,Z.Highly Chemo-,Regio-,and Stereoselective Cobalt-Catalyzed Markovnikov Hydrosilylation ofAlkynes.Angew.Chem.Int.Ed.2016,55, 10835.(2)Zuo,Z.Q.;Yang,J.;Huang,Z.Cobalt-Catalyzed Alkyne Hydrosilylation and Sequential Vinylsilane Hydroborationwith Markovnikov Selectivity.Angew.Chem.Int.Ed. 2016,55,10839.],但是这些钴催化剂对于更为普遍的烷基取代的端炔不能给出高的马氏加成选择性。因此发展用于炔烃硅氢化反应的新型过渡金属催化剂,特别是基于高丰度金属的催化剂,克服已知催化剂存在的缺点,是本领域研究的重点之一。
发明内容
本发明的目的在于提供一种2,9-二芳基取代邻菲啰啉与其钴络合物的制备方法及其应用,可以克服已有技术的缺点。
本发明所述的2,9-二芳基取代邻菲啰啉(I),其特征在于具有如下的结构式:
其中:
R1、R3为甲基,R2为H,即2,9-双-3,5-二甲基苯基-1,10-菲啰啉;
R1、R3为三甲基硅基,R2为H,即2,9-双-3,5-二(三甲基硅基)苯基-1,10-菲啰啉;
R1、R3为苯基二甲基硅基,R2为H,即2,9-双-3,5-二(苯基二甲基硅基)苯基-1,10-菲啰啉;
R1、R3为2,4,6-三甲基苯基,R2为H,即2,9-双-3,5-二(2,4,6-三甲基苯基)苯基-1,10-菲啰啉。
所述的2,9-二芳基取代邻菲啰啉的制备方法,其特征在于它是经过如下步骤制备:在甲苯与水的混合溶剂中,100~110℃下,PdCl2(dppf)为催化剂,Ba(OH)2为碱,2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联,反应10~48小时,制备得到2,9-二芳基邻菲啰啉,其反应式为:
其中:R1~R3如上述化合物(I)所定义。
所述2,9-二芳基取代邻菲啰啉钴络合物(II),其特征在于具有如下的结构式:
其中:
R2、R4、R7、R9为C1~C8烷基、取代的硅基、苯基、取代的苯基,R3、R8为氢、C1~C8烷氧基,R1、R5、R6、R10为氢;R2、R3、R4、R7、R8和R9可以相同,也可以不同;R1~R10不同时为氢;
或者R1、R3、R5、R6、R8、R10为C1~C8烷基,R2、R4、R7、R9为氢;R1、R3、R5、 R6、R8、R10可以相同,也可以不同;R1~R10不同时为氢;
所述取代的硅基,取代基为C1~C8烷基、C1~C8烷氧基、苯基、取代的苯基;
所述取代的苯基,取代基为C1~C8烷基、C2~C8酰氧基、羟基、卤素、氨基、(C1~C8酰基)氨基、二(C1~C8烷基)氨基、C1~C8酰基、C2~C8酯基、卤代烷中的一种或几种;取代基数目为0~5;
X为卤素、C1~C8的羧酸根、乙酰丙酮根、高氯酸根、四氟硼酸根或三氟甲磺酸根;
n=2,3。
所述的2,9-二芳基取代邻菲啰啉钴络合物(II),其特征在于:
所述的C1~C8烷基为甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基或叔辛基;
所述的C1~C8酰基为甲酰基、乙酰基、丙酰基、正丁酰基、异丁酰基、正戊酰基、异戊酰基、仲戊酰基、新戊酰基、正己酰基、异己酰基、新己酰基、仲己酰基、正庚酰基、异庚酰基、新庚酰基、仲庚酰基、正辛酰基、异辛酰基、新辛酰基、仲辛酰基、1-环丙基甲酰基、1-环丁基甲酰基、1-环戊基甲酰基、1-环己基甲酰基、1-环庚基甲酰基;
所述的C2~C8酰氧基为乙酰氧基、丙酰氧基、正丁酰氧基、异丁酰氧基、正戊酰氧基、异戊酰氧基、仲戊酰氧基、新戊酰氧基、正己酰氧基、异己酰氧基、新己酰氧基、仲己酰氧基、正庚酰氧基、异庚酰氧基、新庚酰氧基、仲庚酰氧基、正辛酰氧基、异辛酰氧基、新辛酰氧基、仲辛酰氧基、1-环丙基甲酰氧基、1-环丁基甲酰氧基、1-环戊基甲酰氧基、 1-环己基甲酰氧基、1-环庚基甲酰氧基;
所述的C2~C8酯基为甲氧羰基、乙氧羰基、丙氧羰基、异丙氧羰基、丁氧羰基、异丁氧羰基、正戊氧羰基、异戊氧羰基、新戊氧羰基、仲戊氧羰基、叔戊氧羰基、环戊氧羰基、正己氧羰基、异己氧羰基、新己氧羰基、仲己氧羰基、叔己氧羰基、环己氧羰基、正庚氧羰基、异庚氧羰基、新庚氧羰基、仲庚氧羰基、叔庚氧羰基、环庚氧羰基;
所述的卤代烷基为含氟、氯、溴或碘的卤代烷基。
所述的邻菲啰啉钴络合物(II),其特征在于它是:
2,9-双-3,5-二甲基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二苯基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二甲氧基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(三甲基硅基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(苯基二甲基硅基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(2,4,6-三甲基苯基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三甲基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合二氯化钴;
2-苯基-9-(2,4,6-三异丙基苯基)-1,10-菲啰啉合二氯化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二溴化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二醋酸钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合三(乙酰丙酮)钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(三氟甲磺酸)钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(高氯酸)钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(四氟硼酸)钴;
所述的邻菲啰啉钴络合物(II)的制备方法,其特征在于它是经过如下步骤制备:在甲苯、苯、二甲苯、四氢呋喃、乙醚、1,4-二氧六环中的一种或几种有机溶剂中,25~110℃下,2,9-二芳基邻菲啰啉与相应的钴盐络合12~36小时,制备得到2,9-二芳基邻菲啰啉钴络合物,其反应式为:
其中:R1~R10、n如上述化合物(II)所定义,X=Cl,Br,醋酸根。
含其它阴离子的化合物(II)可通过阴离子交换反应现场制备,其反应式为:
其中:R1~R10、n如上述化合物(II)所定义,X=三氟甲磺酸根、高氯酸根、四氟硼酸根。
所述的邻菲啰啉钴络合物(II)的应用,其特征在于它作为催化剂用于炔烃的硅氢化反应:
其中:[Co]为所述的邻菲啰啉钴络合物(II);R是苯基、取代苯基、C1~C8烷基、卤代烷基、醇氧烷基、酚氧烷基、苄基、苯乙基、官能团取代的烷基。
所述的邻菲啰啉钴络合物(II)的应用,其特征在于将催化剂加入反应管中,之后依次加入溶剂、添加剂、硅烷和炔烃,在室温搅拌下反应至结束。
所述的邻菲啰啉钴络合物(II)的应用,其特征在于所述的硅氢化反应条件是:所用溶剂是C1~C8的醚类,甲苯或烷烃;催化剂用量为0.01~5mol%;底物浓度为0.001~10.0M;添加剂为格氏试剂、四氢铝锂、三乙基硼氢化钠、有机锂试剂、叔丁醇钾、叔丁醇钠、叔丁醇锂中的一种或几种;反应温度为0~100℃;反应1~72小时。
总而言之,将2,9-二氯邻菲啰啉与芳基硼酸进行Suzuki偶联反应,可以制备2,9-二芳基取代的邻菲啰啉;将得到的配体与钴盐进行络合,可以得到不同的邻菲啰啉钴络合物。该新型邻菲啰啉钴络合物能够催化炔烃的硅氢化反应,并表现出以下特点:底物适用范围广,对芳基取代的乙炔、烷基取代的乙炔、内炔都表现出较高的催化活性和很高的收率;官能团耐受性好,卤素、烷氧基、芳氧基、硅基、硅氧基、氨基、酰胺基、酯基等取代基都不影响反应结果;选择性可控,通过改变配体2,9-位取代基,可以分别以很高的区域选择性和立体选择性得到硅氢化产物;特别是对于烷基取代的端炔的硅氢化,给出优于其它已知钴催化剂的马氏加成的选择性。上述特点表明,本发明所提供的新型邻菲啰啉钴络合物催化剂克服了已有技术的缺点,是目前催化炔烃硅氢化的最高效的钴催化剂之一,具有很好的应用前景。
具体实施方式
通过下述实施实例将有助于近一步理解本发明,但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容所实现的技术均属于本发明的范围。
一般说明:
以下实例中使用了缩写,其含义如下:
Me是甲基,Et是乙基,iPr是异丙基,tBu是叔丁基,Ph是苯基,TMS是三甲基硅基,THF是四氢呋喃,DCM是二氯甲烷,PE是石油醚,EA是乙酸乙酯,dppf是1,1-双(二苯基膦)二茂铁
TLC是薄层色谱,NMR是核磁共振,HRMS是高分辨质谱,IR是红外吸收光谱;
所用溶剂在使用前用标准操作提纯,干燥;所用试剂均为市售或按照已有文献方法合成得到,并在使用前提纯。
实施例1:2,9-二芳基取代邻菲啰啉2a-2g的制备
在装有橡胶塞、回流冷凝管、抽气头的100mL三口圆底烧瓶中依次称入反应物1(498 mg,2mmol)、3,5-二甲基苯基硼酸(900mg,6mmol)、Ba(OH)2·8H2O(3.16g,10mmol)、PdCl2(dppf)(220mg,0.3mmol),将体系置换为惰性气体氛围,随后用注射器加入已脱气的甲苯(50mL)和水(4mL),置于油浴中并开始搅拌,将体系升温至110℃后反应16 h,TLC确定反应物消耗完全,停止加热。冷却至室温,过滤除去不溶物,用30mL DCM 洗涤残余物,滤液真空脱溶后,残余的黑色固体用50mL DCM溶解,饱和食盐水洗涤,无水硫酸钠干燥,有机相真空脱溶后干法上样柱层析(PE/EA=5∶1为淋洗剂)得目标产物 2,9-双-3,5-二(甲基)苯基-1,10-菲啰啉(2a)690mg,白色固体,收率:89%,熔点:174-176℃。1H NMR(400MHz,CDCl3)δ8.28(d,J=8.4Hz,2H,4,7-H),8.18(s,4H,Ar-2,6-H),8.16(d,J =8.4Hz,2H,3,8-H),7.76(s,2H,5,6-H),7.14(s,2H,Ar-4-H),2.50(s,12H,CH3);13C NMR (101MHz,CDCl3)δ156.6,145.9,139.0,138.1,136.7,131.2,127.8,125.8,125.4,119.6,21.5; HRMS(ESI)calculated for[M+H,C28H25N2]+:389.2012,found 389.2018.
以下化合物的合成方法与实施例1相同
2,9-双-3,5-二苯基苯基-1,10-菲啰啉(2b)
白色粉末,收率:80%,熔点:283-284℃。1H NMR(400MHz,CDCl3)δ8.58(s,4H, Ar-2,6-H),8.39(d,J=8.3Hz,2H,4,7-H),8.25(d,J=8.4Hz,2H,3,8-H),7.93(s,2H,Ar-4-H),7.87(s,2H,5,6-H),7.80-7.74(m,8H,Ph-H),7.35(d,J=6.2Hz,12H,Ph-H);13C NMR(101MHz,CDCl3)δ157.4,146.2,142.3,141.0(2C),137.1,128.8,128.2,127.5,127.3,127.2,126.3, 125.7,120.9;HRMS(ESI)calculated for[M+H,C48H33N2]+:637.2638,found637.2640.
2,9-双-3,5-二甲氧基苯基-1,10-菲啰啉(2c)
白色晶体,收率:60%,熔点:171-173℃。1H NMR(400MHz,CDCl3)δ8.30(d,J=8.4Hz,2H,4,7-H),8.13(d,J=8.4Hz,2H,3,8-H),7.78(s,2H,5,6-H),7.74(s,4H,Ar-2,6-H),6.60 (s,2H,Ar-4-H),3.98(s,12H,CH3);13C NMR(101MHz,CDCl3)δ161.21,155.86,145.79,141.26,136.77,128.00,125.98,119.67,105.79,101.36,55.55;HRMS(ESI)calculatedfor [M+H,C28H25N2O4]+:453.1814,found 453.1812.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉(2d)
白色固体,收率:88%,熔点:266-267℃。1H NMR(400MHz,CDCl3)δ8.28(d,J=8.4Hz,2H,4,7-H),8.08(s,4H,Ar-H),8.00(d,J=8.4Hz,2H,3,8-H),7.78(s,2H,5,6-H),3.74(s, 6H,OCH3),1.54(s,36H,CH3);13C NMR(101MHz,CDCl3)δ160.9,158.9,146.3,143.8,136.6,135.1,127.6,126.7,125.8,121.2,64.5,35.9,32.3;HRMS(ESI)calculated for[M+H, C42H53N2O2]+:617.4102,found 617.4106.
2,9-双-3,5-二(三甲基硅基)苯基-1,10-菲啰啉(2e)
白色固体,收率:53%,熔点:232-233℃。1H NMR(400MHz,CDCl3)δ8.32(d,J=8.4Hz,2H,4,7-H),8.28(d,J=1.1Hz,4H,Ar-2,6-H),8.03(d,J=8.3Hz,2H,3,8-H),7.82(s,2H, 5,6-H),7.77(t,J=0.9Hz,2H,Ar-4-H),0.35(s,36H,CH3);13C NMR(101MHz,CDCl3)δ159.3,146.4,139.6,139.1,138.9,136.8,133.8,127.9,126.1,121.9,-0.8;HRMS(ESI)calculated for[M+H,C36H49N2Si4]+:621.2967,found 621.2970.
2,9-双-3,5-二(苯基二甲基硅基)苯基-1,10-菲啰啉(2f)
白色固体,收率:30%,熔点:184-186℃。1H NMR(400MHz,CDCl3)δ8.32(d,J=1.0Hz,4H,Ar-2,6-H),8.29(d,J=8.4Hz,2H,4,7-H),7.94(d,J=8.3Hz,2H,3,8-H),7.80(s,2H, 5,6-H),7.74(s,2H,Ar-4-H),7.49(dd,J=7.6,1.6Hz,4H,Ph-H),7.36-7.27(m,6H,Ph-H), 0.55(s,24H,CH3);13C NMR(101MHz,CDCl3)δ159.2,146.4,141.1,139.4,138.3,137.4,136.8,134.9,134.2,129.0,127.9,127.7,126.1,122.0,-2.1;HRMS(ESI)calculated for[M+H, C56H57N2Si4]+:869.3593,found 869.3598.
2,9-双-3,5-二(2,4,6-三甲基苯基)苯基-1,10-菲啰啉(2g)
白色固体,收率:63%,熔点:190-192℃。1H NMR(400MHz,CDCl3)δ8.30(d,J=8.4Hz,2H,4,7-H),8.06(d,J=8.4Hz,2H,3,8-H),7.96(d,J=1.5Hz,4H,Ar-2,6-H),7.80(s,2H,5,6-H),7.02(t,J=1.5Hz,2H,Ar-4-H),6.95(s,8H,Ar-H),2.37(s,12H,Ar-4-CH3),2.05(s, 24H,Ar-2,6-CH3);13C NMR(101MHz,CDCl3)δ158.2,146.3,141.6,140.7,138.7,136.9, 136.3,136.0,131.4,128.1,127.9,127.3,126.2,121.4,21.1,20.8;HRMS(ESI)calculated for [M+H,C60H57N2]+:805.4516,found 805.4518.
实施例2:2,9-二芳基取代邻菲啰啉钴络合物的制备1
在手套箱中,将2,9-双-3,5-二(甲基)苯基-1,10-菲啰啉2a(388mg,1mmol)和CoCl2 (130mg,1mmol)称入50mL反应瓶中,加入20mL四氢呋喃,于室温下络合24小时后,真空泵抽走部分四氢呋喃(体系剩余约5mL),随后加入15mL正己烷,有蓝色固体析出,过滤,并用正己烷(3×5mL)洗涤固体,将所得固体转移至小瓶,高真空泵抽干得 414mg目标产物2,9-双-3,5-二甲基苯基-1,10-菲啰啉合二氯化钴3a,深绿色固体,80%收率。熔点:>320℃。1HNMR(400MHz,CDCl3)δ52.61,20.68,0.47,0.09,-13.26,-26.71; IR(neat)3447b,3049w,2968w,2949w,2917w,1628w,1605m,1585s,1556s,1508s,1475m, 1420m,1358m,1214m,1158m,874m,855s,703m,619m cm-1.
以下化合物的合成方法与实施例2相同
2,9-双-3,5-二苯基苯基-1,10-菲啰啉合二氯化钴(3b)
绿色固体,82%收率。分解温度:220-222℃。1H NMR(400MHz,CDCl3)δ52.42,20.04,6.94,6.49,1.07,0.82,-14.16,-21.18;IR(neat)3448b,3047w,2918w,2849w,1595s,1553w, 1495s,1409w,1355w,1221w,1154w,880m,762s,698s cm-1.
2,9-双-3,5-二甲氧基苯基-1,10-菲啰啉合二氯化钴(3c)
绿色固体,70%收率。分解温度:301-303℃。1H NMR(400MHz,CDCl3)δ51.88,19.62,-0.58,-1.83,-14.07,-22.37;IR(neat)3750w,3490b,3004w,2940w,2840w,1596s,1557m,1508m,1456m,1420m,1349m,1207s,1155s,1062m,1040m,844m,698w cm-1.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二氯化钴(3d)
青绿色固体,85%收率。熔点:>320℃。1H NMR(400MHz,CDCl3)δ51.30,18.90,1.28, -3.69,-13.95,-17.94;IR(neat)3750w,2961s,2917m,2870w,1588w,1542w,1509m,1411s, 1362w,1321w,1227s,1115w,1008m,859m cm-1.
2,9-双-3,5-二(三甲基硅基)苯基-1,10-菲啰啉合二氯化钴(3e)
绿色固体,88%收率。熔点:278-279℃。1H NMR(400MHz,CDCl3)δ51.44,19.13,0.58, -2.97,-14.04,-23.07;IR(neat)3447b,3022w,2954m,2896w,1590m,1508m,1496m,1379w, 1250s,1145m,863s,839s,754m,693w,621m cm-1.
2,9-双-3,5-二(苯基二甲基硅基)苯基-1,10-菲啰啉合二氯化钴(3f)
浅绿色固体,69%收率。熔点:165-166℃。1H NMR(400MHz,CDCl3)δ51.03,19.64,7.47,7.27(t,J=6.6Hz),5.72,0.15,-2.82,-14.05,-22.48;IR(neat)3447b,3067w,3046w, 3020w,2955m,2896w,1589m,1508m,1495m,1427m,1378w,1250m,1140m,1109m,862s, 841s,826s,776s,733s,701s,649s cm-1.
2,9-双-3,5-二(2,4,6-三甲基苯基)苯基-1,10-菲啰啉合二氯化钴(3g)
浅绿色固体,87%收率。熔点:>320℃。1H NMR(400MHz,CDCl3)δ49.23,17.51,5.62, 2.15,-1.37,-3.17,-16.13,-23.38;IR(neat)2949m,2916s,2858m,2341w,1612s,1586s,1555m, 1498s,1485s,1443s,1378w,1354w,1225m,860s,797w,723w cm-1.
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合二氯化钴(3h)
绿色固体,88%收率。熔点:>320℃。1H NMR(400MHz,CDCl3)δ51.17,18.61,0.61,-3.99,-14.34,-20.65;IR(neat)3750s,3447b,2960s,2920m,2866w,1730m,1720m,1569s,1542m 1521s,1508s,1495s,1457m,1418m,1362m,1250w,1226w,867m cm-1.
2,9-双-2,4,6-三甲基苯基-1,10-菲啰啉合二氯化钴(3i)
蓝色固体,91收率。熔点:>320℃。1H NMR(400MHz,CDCl3)δ44.08,22.78,0.47,0.17, -0.90,-15.15;IR(neat)3503b,2969m,2918m,2858w,1614s,1588s,1543s,1481s,1456s, 1427m,1378w 1357w,1080w,905m,865s,849m cm-1.
2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉合二氯化钴(3j)
蓝色固体,90%收率。分解温度:318-319℃。1H NMR(400MHz,CDCl3)δ44.03,22.08,6.50,-0.16,-1.46,-1.47,-2.23,-3.06,-15.25;IR(neat)3482b,2984s,2932m,2873m,1622m, 1608m,1587m,1542m,1436m,1421w,867s cm-1.
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合二氯化钴(3k)
蓝色固体,97%收率。熔点:305-308℃。1H NMR(400MHz,CDCl3)δ45.10,23.17,8.21, 0.43,-1.34,-2.35,-2.36,-3.80,-4.83,-12.14;IR(neat)2958s,2928m,2868w,1618w,1588w, 1555w,1509w,1493w,1472w,1420w,1384w,1362w,1149w,1112w,871m cm-1.
2-苯基-9-(2,4,6-三异丙基苯基)-1,10-菲啰啉合二氯化钴(31)
蓝绿色固体,84%收率。熔点:>320℃。1H NMR(400MHz,CDCl3)δ50.47,47.48,22.34, 22.32,22.07,22.05,7.64,4.12,4.11,4.10,2.22,1.96,0.36,-2.27,-2.98,-2.99,-13.33,-13.77; IR(neat)3447b,2959s,2928m,2867m,2361m,2343w,1623m,1591m,1552w,1510m,1488m, 1384w,1355w,1156w,1063m,868s cm-1.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二溴化钴(3m)
青绿色固体,70%收率。熔点:269-271℃。1H NMR(400MHz,CDCl3)δ51.58,18.92,1.45,-3.81,-15.33,-21.31.IR(neat)2960s,2914m,2869m,2360w,2342w,1588m,1542m,1509m,1493m,1411s,1361w,1322w,1226s,1113m,1006m,864m cm-1.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二醋酸钴(3n)
浅紫色固体,61%收率。分解温度:150-153℃。1H NMR(400MHz,CDCl3)δ8.29,8.27,8.08,8.01,7.99,7.78,3.74,1.68,1.54.IR(neat)3853w,3735w,3649w,3335b,2961m,2869w, 2360w,2342w,1587s,1559s,1506m,1417s,1225m,1115w,1010m,850w,682w cm-1.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合三(乙酰丙酮)钴(3o)
深绿色固体,59%收率。分解温度:202-205℃。1H NMR(400MHz,CDCl3)δ8.29,8.27,8.08,8.01,7.99,7.78,5.53,3.74,2.19,1.54.IR(neat)3853w,3750w,3735w,3649w,2962m, 2921w,2869w,2360w,2331w,1576s,1520s,1388s,1225m,1013m cm-1.
实施例3:2,9-二芳基取代邻菲啰啉钴络合物的制备2
在手套箱中,将2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二氯化钴(75mg, 0.1mmol)和AgOTf(57mg,0.22mmol)称入10mL Schleck管中,加入5mL四氢呋喃,于室温下搅拌12小时后,过滤得澄清液体,真空脱溶后得2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(三氟甲磺酸)钴3p,粉红色固体,99%收率。分解温度:80-85℃。1HNMR(400MHz,CDCl3)δ8.48,8.03,7.94,7.60,3.77,3.14,1.86,1.26,0.93,-3.88.IR(neat)3510b,2965m,2918m,2874w,2360w,1507m,1411m,1248s,1225s,1031s,862m,639m cm-1.
以下化合物的合成方法与实施例3相同
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(高氯酸)钴(3q)
粉红色固体,99%收率。分解温度147-152℃。1H NMR(400MHz,CDCl3)δ8.48,8.02,7.94,7.59,3.83,3.14,2.00,1.26,0.93.IR(neat)3446b,2962m,2917m,2871w,2360w,1624m, 1507m,1410m,1224m,1110s,1005m,861m,626m cm-1.
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(四氟硼酸)钴(3r)
暗黄色固体,99%收率。分解温度120-125℃。1H NMR(400MHz,CDCl3)δ8.49,8.03,7.94,7.60,3.75,3.15,1.86,1.26,0.93.IR(neat)3567b,2964s,2917m,2872m,2360w,1625m, 1541m,1507m,1410m,1361m,1224s,1112s,1061s,1003s,862m,749w cm-1.
实施例4:不同邻菲啰啉钴络合物用于1-辛炔的硅氢化
手套箱中,将催化剂3称入10mL封管中,加入四氢呋喃(1mL),随后用微量注射器加入TMSCH2Li(0.7M,in THF,16uL,0.011mmol),搅拌5min后,依次加入Ph2SiH2 (92mg,0.5mmol)和1-辛炔(55mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌5h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表1:不同邻菲啰啉钴络合物催化1-辛炔硅氢化的实验结果
a转化率由GC测定(内标:均三甲苯);b收率为核磁收率(内标:均三甲氧基苯)
实施例5:不同溶剂中1-辛炔马氏加成硅氢化结果
手套箱中,将催化剂3d称入10mL封管中,加入溶剂(1mL),随后加入添加剂TMSCH2Li(0.011mmol),搅拌5min后,依次加入Ph2SiH2(92mg,0.5mmol)和1-辛炔(55mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌5h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表2:不同溶剂中1-辛炔马氏加成硅氢化实验结果
a转化率由GC测定(内标:均三甲苯);b收率为核磁收率(内标:均三甲氧基苯)
实施例6:不同添加剂下1-辛炔马氏加成硅氢化结果
手套箱中,将催化剂3d称入10mL封管中,加入四氢呋喃(1mL),随后加入添加剂(0.011mmol),搅拌5min后,依次加入Ph2SiH2(92mg,0.5mmol)和1-辛炔(55mg, 0.5mmol),用旋塞封好后,转移到通风橱室温搅拌5h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表3:不同添加剂下1-辛炔马氏加成硅氢化实验结果
a转化率由GC测定(内标:均三甲苯);b收率为核磁收率(内标:均三甲氧基苯);c80℃
实施例7:邻菲啰啉钴络合物催化不同烷基取代端炔马氏加成硅氢化
手套箱中,将催化剂3d和tBuOK(1.1mg,0.01mmol)称入10mL封管中,加入四氢呋喃(1mL),搅拌5min后,之后依次加入Ph2SiH2(92mg,0.5mmol)和炔烃(0.5mmol),用旋塞封好后,转移到通风橱室温搅拌5-24h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析得目标产物。
表4:邻菲啰啉钴合物催化不同长链端炔的硅氢化结果
a分离收率
实施例8:1-辛炔的反马氏加成硅氢化结果
手套箱中,将催化剂和tBuOK(1.1mg,0.01mmol)称入10mL封管中,加入四氢呋喃(1mL),搅拌5min后,依次加入硅烷(0.5mmol)和1-辛炔(55mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌12h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表5:1-辛炔反马氏加成硅氢化的实验结果
a分离收率
实施例9:不同邻菲啰啉钴络合物用于苯乙炔的硅氢化
手套箱中,将催化剂和tBuOK(1.1mg,0.01mmol)称入10mL封管中,加入四氢呋喃(1mL),搅拌5min后,依次加入硅烷(0.5mmol)和苯乙炔(51mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌12h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表6:不同邻菲啰啉钴络合物催化苯乙炔硅氢化的实验结果
a收率为核磁收率(内标:均三甲氧基苯)
实施例10:不同邻菲啰啉钴络合物用于2-辛炔的硅氢化
手套箱中,将催化剂和tBuOK(1.1mg,0.01mmol)称入10mL封管中,加入四氢呋喃(1mL),搅拌5min后,依次加入硅烷(0.5mmol)和2-辛炔(55mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌10h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表7:不同邻菲啰啉钴络合物催化2-辛炔硅氢化的实验结果
a分离收率
实施例11:不同邻菲啰啉钴络合物用于4-辛炔的硅氢化
手套箱中,将催化剂和tBuOK(1.1mg,0.01mmol)称入10mL封管中,加入四氢呋喃(1mL),搅拌5min后,依次加入硅烷(0.5mmol)和4-辛炔(55mg,0.5mmol),用旋塞封好后,转移到通风橱室温搅拌10h。反应结束后,转移至圆底烧瓶,旋去溶剂,经硅胶柱层析(淋洗剂为正戊烷)得目标产物。
表8:不同邻菲啰啉钴络合物催化4-辛炔硅氢化的实验结果
a分离收率
Claims (6)
1.一种2,9-二芳基取代邻菲啰啉钴络合物,其特征在于,具有如下的结构式:
其中:
R2、R4、R7、R9为氢、C1~C4烷基、取代的硅基、苯基、取代的苯基,R3、R8为氢、C1~C4烷氧基,R1、R5、R6、R10为氢;R2、R3、R4、R7、R8和R9可以相同,也可以不同;R1~R10不同时为氢;
或者R1、R6为氢,R3、R5、R8、R10为氢、C1~C4烷基,R2、R4、R7、R9为氢;R1、R3、R5、R6、R8、R10可以相同,也可以不同;R1~R10不同时为氢;
所述取代的硅基中的取代基为C1~C4烷基;所述取代的苯基中的取代基为C1~C4烷基;
所述的C1~C4烷基为乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;
X为卤素、醋酸根、高氯酸根、四氟硼酸根或三氟甲磺酸根;n=2。
2.按照权利要求1所述的邻菲啰啉钴络合物,其特征在于它是:
2,9-双-3,5-二甲基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二苯基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二甲氧基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(三甲基硅基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(苯基二甲基硅基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二(2,4,6-三甲基苯基)苯基-1,10-菲啰啉合二氯化钴;
2,9-双-3,5-二叔丁基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三甲基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三乙基苯基-1,10-菲啰啉合二氯化钴;
2,9-双-2,4,6-三异丙基苯基-1,10-菲啰啉合二氯化钴;
2-苯基-9-(2,4,6-三异丙基苯基)-1,10-菲啰啉合二氯化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二溴化钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二醋酸钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(三氟甲磺酸)钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(高氯酸)钴;
2,9-双-(3,5-二叔丁基-4-甲氧基苯基)-1,10-菲啰啉合二(四氟硼酸)钴;
5.按照权利要求4所述的邻菲啰啉钴络合物的应用,其特征在于将催化剂加入反应管中,之后依次加入溶剂、添加剂、硅烷和炔烃,在室温搅拌下反应至结束。
6.按照权利要求4所述的邻菲啰啉钴络合物的应用,其特征在于所述的硅氢化反应条件是:所用溶剂是C1~C8的醚类,甲苯或烷烃;催化剂用量为0.01~5mol%;底物浓度为0.001~10.0M;添加剂为EtMgBr、四氢铝锂、三乙基硼氢化钠、叔丁醇钾中的一种;反应温度为0~100℃;反应1~72小时。
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