CN112961079A - 一种钴催化伯酰胺脱水成腈类的方法 - Google Patents
一种钴催化伯酰胺脱水成腈类的方法 Download PDFInfo
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- CN112961079A CN112961079A CN202110239585.2A CN202110239585A CN112961079A CN 112961079 A CN112961079 A CN 112961079A CN 202110239585 A CN202110239585 A CN 202110239585A CN 112961079 A CN112961079 A CN 112961079A
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- China
- Prior art keywords
- reaction
- primary amide
- compound
- nitrile
- dehydration
- Prior art date
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- 150000003140 primary amides Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 title description 4
- 239000010941 cobalt Substances 0.000 title description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 4
- 238000006555 catalytic reaction Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- -1 sodium triethylborohydride Chemical compound 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 150000004700 cobalt complex Chemical class 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 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
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 105
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 99
- 238000006297 dehydration reaction Methods 0.000 claims description 37
- 230000018044 dehydration Effects 0.000 claims description 35
- 239000012298 atmosphere Substances 0.000 claims description 34
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 33
- 238000010791 quenching Methods 0.000 claims description 33
- 238000010898 silica gel chromatography Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 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
- 238000007664 blowing Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 37
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 62
- 239000000203 mixture Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 33
- 239000012467 final product Substances 0.000 description 31
- 239000007858 starting material Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 28
- 238000012512 characterization method Methods 0.000 description 28
- 239000012043 crude product Substances 0.000 description 28
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 16
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 4
- QXSAKPUBHTZHKW-UHFFFAOYSA-N 4-hydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1 QXSAKPUBHTZHKW-UHFFFAOYSA-N 0.000 description 4
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 4
- UHBGYFCCKRAEHA-UHFFFAOYSA-N P-toluamide Chemical compound CC1=CC=C(C(N)=O)C=C1 UHBGYFCCKRAEHA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000005970 1-Naphthylacetamide Substances 0.000 description 2
- XFNJVKMNNVCYEK-UHFFFAOYSA-N 1-naphthaleneacetamide Chemical compound C1=CC=C2C(CC(=O)N)=CC=CC2=C1 XFNJVKMNNVCYEK-UHFFFAOYSA-N 0.000 description 2
- JHSPCUHPSIUQRB-UHFFFAOYSA-N 2,6-dichlorobenzamide Chemical compound NC(=O)C1=C(Cl)C=CC=C1Cl JHSPCUHPSIUQRB-UHFFFAOYSA-N 0.000 description 2
- AVRQBXVUUXHRMY-UHFFFAOYSA-N 2,6-difluorobenzamide Chemical compound NC(=O)C1=C(F)C=CC=C1F AVRQBXVUUXHRMY-UHFFFAOYSA-N 0.000 description 2
- XXUNIGZDNWWYED-UHFFFAOYSA-N 2-methylbenzamide Chemical compound CC1=CC=CC=C1C(N)=O XXUNIGZDNWWYED-UHFFFAOYSA-N 0.000 description 2
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 2
- YTLRWVNYANKXOW-UHFFFAOYSA-N 3,5-dimethoxybenzamide Chemical compound COC1=CC(OC)=CC(C(N)=O)=C1 YTLRWVNYANKXOW-UHFFFAOYSA-N 0.000 description 2
- WGRPQCFFBRDZFV-UHFFFAOYSA-N 3-methylbenzamide Chemical compound CC1=CC=CC(C(N)=O)=C1 WGRPQCFFBRDZFV-UHFFFAOYSA-N 0.000 description 2
- VYIBCOSBNVFEIW-UHFFFAOYSA-N 3-phenylpropanamide Chemical compound NC(=O)CCC1=CC=CC=C1 VYIBCOSBNVFEIW-UHFFFAOYSA-N 0.000 description 2
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 2
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 2
- VNDHYTGVCGVETQ-UHFFFAOYSA-N 4-fluorobenzamide Chemical compound NC(=O)C1=CC=C(F)C=C1 VNDHYTGVCGVETQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CKBZJTAMRPPVSR-UHFFFAOYSA-N adamantane-1-carboxamide Chemical compound C1C(C2)CC3CC2CC1(C(=O)N)C3 CKBZJTAMRPPVSR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PNZXMIKHJXIPEK-UHFFFAOYSA-N cyclohexanecarboxamide Chemical compound NC(=O)C1CCCCC1 PNZXMIKHJXIPEK-UHFFFAOYSA-N 0.000 description 2
- AEDIXYWIVPYNBI-UHFFFAOYSA-N heptanamide Chemical compound CCCCCCC(N)=O AEDIXYWIVPYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 2
- RMHJJUOPOWPRBP-UHFFFAOYSA-N naphthalene-1-carboxamide Chemical compound C1=CC=C2C(C(=O)N)=CC=CC2=C1 RMHJJUOPOWPRBP-UHFFFAOYSA-N 0.000 description 2
- JVXXKQIRGQDWOJ-UHFFFAOYSA-N naphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(C(=O)N)=CC=C21 JVXXKQIRGQDWOJ-UHFFFAOYSA-N 0.000 description 2
- 229960003966 nicotinamide Drugs 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
- 239000011570 nicotinamide Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- DENPQNAWGQXKCU-UHFFFAOYSA-N thiophene-2-carboxamide Chemical compound NC(=O)C1=CC=CS1 DENPQNAWGQXKCU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- YZBOZNXACBQJHI-UHFFFAOYSA-N 1-dichlorophosphoryloxyethane Chemical compound CCOP(Cl)(Cl)=O YZBOZNXACBQJHI-UHFFFAOYSA-N 0.000 description 1
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 1
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 1
- OLKQIWCQICCYQS-UHFFFAOYSA-N 2-(4-methoxyphenyl)acetamide Chemical compound COC1=CC=C(CC(N)=O)C=C1 OLKQIWCQICCYQS-UHFFFAOYSA-N 0.000 description 1
- HIJRINSXBOZPGQ-UHFFFAOYSA-N 3,3,3-triphenylpropanenitrile Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(CC#N)C1=CC=CC=C1 HIJRINSXBOZPGQ-UHFFFAOYSA-N 0.000 description 1
- NVTHWSJNXVDIKR-UHFFFAOYSA-N 3,5-dimethoxybenzonitrile Chemical compound COC1=CC(OC)=CC(C#N)=C1 NVTHWSJNXVDIKR-UHFFFAOYSA-N 0.000 description 1
- BOHCMQZJWOGWTA-UHFFFAOYSA-N 3-methylbenzonitrile Chemical compound CC1=CC=CC(C#N)=C1 BOHCMQZJWOGWTA-UHFFFAOYSA-N 0.000 description 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 1
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- ZWOSFDRLSUZDJD-UHFFFAOYSA-N 4-chlorobenzamide 4-chlorobenzonitrile Chemical compound Clc1ccc(cc1)C#N.NC(=O)c1ccc(Cl)cc1 ZWOSFDRLSUZDJD-UHFFFAOYSA-N 0.000 description 1
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 1
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 1
- GUCPYIYFQVTFSI-UHFFFAOYSA-N 4-methoxybenzamide Chemical compound COC1=CC=C(C(N)=O)C=C1 GUCPYIYFQVTFSI-UHFFFAOYSA-N 0.000 description 1
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 1
- VIPMBJSGYWWHAO-UHFFFAOYSA-N 4-tert-butylbenzamide Chemical compound CC(C)(C)C1=CC=C(C(N)=O)C=C1 VIPMBJSGYWWHAO-UHFFFAOYSA-N 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- FQFZASRJFRAEIH-UHFFFAOYSA-N adamantane-1-carbonitrile Chemical compound C1C(C2)CC3CC2CC1(C#N)C3 FQFZASRJFRAEIH-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- GHLZUHZBBNDWHW-UHFFFAOYSA-N nonanamide Chemical compound CCCCCCCCC(N)=O GHLZUHZBBNDWHW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明提供了一种伯酰胺脱水成腈的方法:在惰性气体保护下,将伯酰胺(II)、硅烷、三乙基硼氢化钠、胺吡啶亚胺三齿氮配体钴配合物(I)与反应溶剂混合,于60~100℃下反应6~24h,之后反应液经后处理,得到腈类化合物(III);本发明利用新型的胺吡啶亚胺三齿氮配体钴配合物催化剂提供了一种有效的钴催化伯酰胺脱水反应制备腈类化合物的方法,与现有方法相比,该方法操作简单,反应条件温和、反应底物适用范围广,选择性高,催化剂稳定,效率高,在合成上具有较大的实际应用价值;
Description
技术领域
本发明涉及一种钴催化伯酰胺脱水成腈的简单方法,具体涉及一种利用新型刚性骨架的三齿氮配体钴配合物催化伯酰胺脱水成腈的方法。
背景技术
腈类化合物作为一种常见化合物被广泛用于各种药物,农用化学品,聚合物,材料等的合成。也是有机合成的通用中间体,可以很容易地转化为各种其他重要的官能团,例如醛,羧酸,酯,伯胺,亚胺,杂环,酰胺等。因此,腈类化合物的合成方法研究是合成化学中重要的方向之一。
伯酰胺脱水是合成腈的途径之一。传统上,这种转化是在强酸性脱水剂(如P2O5、POCl3、SOCl2、TiCl4)[a)J.Org.Chem.,1962,27,4608.b)Org.Synth.,1963,Coll.IV,436.]的存在下进行的,但反应条件过于苛刻。最近,也开发了更复杂的试剂,如二氯磷酸乙酯和DBU的混合物[Chem.Commun.,2007,301-303.]新戊酰氯-吡啶或三氯乙酰氯[J.Am.Chem.Soc.,2003,125,2400.],它们可以在较温和的条件下使用。但是,这些试剂的使用可能会带来存储和处理问题以及大量废物的产生等新问题。
过渡金属催化的伯酰胺脱水制备腈近年来受到了关注,如Pd,Ru,Zn,Fe,U[a)Eur.J.Org.Chem.2008,4097–4100.b)Chem.Eur.J.2011,17,9316–9319]具有原子利用率高、高效简洁的特点。但目前所报道的过渡金属催化的方法仍然存在一些问题,如:1、过渡金属催化量大,例如在PdCl2催化体系下,则需要10mol%的催化量[Org.Lett.,2019,21,4767–4770.];2、反应体系对某些底物不能很好的兼容,例如在一些Zn和Fe的催化体系下,杂环吡啶环等底物无法进行拓展,底物兼容性不好[Chem.Asian J.2012,7,169–175.]。
钴作为环境友好、生物兼容性好的廉价过渡金属用于伯酰胺脱水反应得到了关注[Catalysis Communications 120(2019)72–75.]。但是配合物制备复杂,而且使用了含磷配体,导致稳定性差。因此,开发新型的稳定的钴配合物实现高效的钴催化伯酰胺脱水成腈反应具有重要的意义。
发明内容
本发明的目的是提供一种有效伯酰胺脱水成腈的方法,该方法的催化体系化学选择性和区域选择性高,底物兼容性广,催化剂稳定,效率高,操作简单。
本发明的技术方案如下:
一种伯酰胺脱水成腈的方法,所述方法为:
在惰性气体保护下,将伯酰胺(II)、硅烷、三乙基硼氢化钠、胺吡啶亚胺三齿氮配体钴配合物(I)与反应溶剂混合,于60~100℃(优选60℃)下反应6~24h(优选6h),之后反应液经后处理,得到腈类化合物(III);
其中,伯酰胺(II)为原料,硅烷为脱水剂,胺吡啶亚胺三齿氮配体钴配合物(I)为催化剂、三乙基硼氢化钠为活化剂;
所述伯酰胺(II)、硅烷、三乙基硼氢化钠、胺吡啶亚胺三齿氮配体钴配合物(I)的物质的量之比为1∶5∶0.03~0.06∶0.01;
所述反应溶剂可选自:甲苯、四氢呋喃、苯甲醚、环戊基甲醚、1,4-二氧六环、正庚烷、二甲醚中的一种或两种以上任意比例的混合溶剂,例如:甲苯与四氢呋喃、甲苯与二甲醚的混合溶剂,优选以甲苯为反应溶剂;
所述反应溶剂的体积用量以伯酰胺的物质的量计为1~5mL/mmol,优选2mL/mmol;
所述后处理的方法为:反应结束后,待反应液冷却至室温(25℃),乙酸乙酯淬灭稀释,浓缩后硅胶(200~300目)柱层析分离,以石油醚和乙酸乙酯体积比为50∶1的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到腈类化合物(III)。
本发明中,
原料伯酰胺(II)、产物腈类化合物(III)的结构式如下:
式(II)或(III)中,
R4为C5~C10烷基、C5~C10环烷基、萘基、萘甲基、苄基、苯乙基、苯乙烯基、对甲氧基苄基、杂芳基(吡啶基或噻吩基)、苯基或取代苯基,所述取代苯基的苯环上被一个或多个取代基取代,所述取代基各自独立为C1~C3烷基、C1~C3烷氧基、羟基、羟甲基、氟、氯、溴、氨基或叔丁基。
催化剂胺吡啶亚胺三齿氮配体钴配合物(I)的结构式如下:
式(I)中,
R1、R2各自独立为C1~C4烷基或C6~C10芳基;优选R1、R2为乙基;
R3为苯基或取代苯基,所述取代苯基的苯环上被一个或多个C1~C4烷基取代;优选R3为苯基或2,6-二异丙基苯基;
具体的,所述胺吡啶亚胺三齿氮配体钴配合物举例如下:
所述催化剂胺吡啶亚胺三齿氮配体钴配合物(I)可按如下方法制备得到:
在惰性氛围下,将化合物(I-a)、化合物(I-b)、CoCl2、乙酸混合均匀,回流反应8h,之后反应液经后处理,得到胺吡啶亚胺三齿氮配体钴配合物(I);
所述化合物(I-a)、化合物(I-b)、CoCl2的物质的量之比为1∶1.1∶1;
所述乙酸的体积用量以化合物(I-a)的物质的量计为20mL/mmol;
所述后处理的方法为:反应结束后,用氮气将反应液中的醋酸吹干,剩下黑色油状物,用DCM(二氯甲烷)溶解后,滴加入MTBE(甲基叔丁基醚)中搅拌,可以看见MTBE中有绿色粉末产物,过滤,洗涤,干燥,得到产物(I);
式(I-a)或(I-b)中,R1、R2、R3的定义与式(I)中相同。
脱水剂硅烷的结构式为R5R6R7SiH,其中R5、R6、R7各自独立为氢、烷基、三甲基硅基、烷氧基或芳基;具体的硅烷例如:四甲基二硅氧烷、苯硅烷、二苯基硅氧烷或聚甲基氢硅氧烷,优选聚甲基氢硅氧烷。
本发明的有益效果如下:
本发明利用新型的胺吡啶亚胺三齿氮配体钴配合物催化剂提供了一种有效的钴催化伯酰胺脱水反应制备腈类化合物的方法。与现有方法相比,该方法操作简单,反应条件温和、反应底物适用范围广,选择性高,催化剂稳定,效率高,在合成上具有较大的实际应用价值。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
以下实施例中用到的催化剂配合物Co-2结构式为:
催化剂Co-2的合成方法如下:
在惰性氛围下,向100mL的二口烧瓶中加入2-((二乙基胺基)甲基)-四氢喹啉-8-酮(232mg,1mmol)、苯胺(205mg,1.1mmol)、CoCl2(260mg,1mmol)、乙酸(20mL),并将得到的混合物搅拌均匀。在氮气氛围下回流反应8h。反应结束后,用氮气将反应液中的醋酸吹干,剩下黑色油状物,用5mL DCM溶解,缓慢滴加入事先准备好的50mL的MTBE中搅拌,明显可以看见MTBE中有绿色粉末产物。过滤,用MTBE 30mL*5洗涤,最后在油泵将多余的溶剂抽干,得到401mg粉末状产物。
以下实施例中用到的脱水剂聚甲基氢硅氧烷购自Alfa Aesar 250g FW:ca 1900,其结构式如下:
实施例1:苯甲酰胺脱水成苯甲腈:
在惰性氛围下,反应管中依次加入底物苯甲酰胺(121mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为97mg无色油状液体,收率:83%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.61(d,2H),7.58(d,1H),7.50-7.38(m,2H).13C NMR(150MHz,CDCl3)δ132.61,131.92,128.95,118.64,112.21.
实施例2:2-甲基苯甲酰胺脱水成2-甲基苯甲腈:
在惰性氛围下,反应管中依次加入底物2-甲基苯甲酰胺(135mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(1mL)与四氢呋喃(1mL)混合溶剂,并将得到的混合物搅拌均匀。60℃油浴下反应18h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为100mg无色油状液体,收率:85%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.60(d,J=7.7,1.0Hz,1H),7.48(t,J=7.7,1.3Hz,1H),7.32(m,J=7.8Hz,1H),7.28(t,1H),2.55(s,3H).13C NMR(150MHz,CDCl3)δ147.87,132.51,130.17,126.16,118.07.112.73,20.39.
实施例3:3-甲基苯甲酰胺脱水成3-甲基苯甲腈:
在惰性氛围下,反应管中依次加入底物3-甲基苯甲酰胺(135mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为94mg无色油状液体,收率:80%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.45(dd,J=3.3,2.6Hz,1H),7.40(d,J=7.7Hz,1H),7.34(t,J=7.9Hz,1H),2.39(s,3H).
实施例4:4-甲基苯甲酰胺脱水成4-甲基苯甲腈:
在惰性氛围下,反应管中依次加入底物4-甲基苯甲酰胺(135mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为110mg无色油状液体,收率:86%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.50(d,J=8.2Hz,2H),7.25(s,2H),2.41(s,3H).
实施例5:对氟苯甲酰胺脱水成对氟苯甲腈:
在惰性氛围下,反应管中依次加入底物对氟苯甲酰胺(139mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为88mg白色固体,收率:73%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.61(dd,J=7.7Hz,2H),7.18Hz(t,2H).
实施例6:对氯苯甲酰胺脱水成对氯苯甲腈:
在惰性氛围下,反应管中依次加入底物对氯苯甲酰胺(155mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为90mg无色透明液体,收率:66%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.65-7.55(m,2H),7.50-7.41(m,2H).
实施例7:对溴苯甲酰胺脱水成对溴苯甲腈:
在惰性氛围下,反应管中依次加入底物对溴苯甲酰胺(199mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(1mL)与四氢呋喃(1mL)混合溶剂,并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为142mg无色油状液,收率:78%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.66-7.61(m,2H),7.55-7.50(m,2H).
实施例8:对氨基苯甲酰胺脱水成对氨基苯甲腈:
在惰性氛围下,反应管中依次加入底物对氨基苯甲酰胺(136mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为104mg淡黄色结晶粉末,收率:88%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.44-7.38(m,2H),7.67-7.59(m,2H),4.15(s,2H).
实施例9:对甲氧基苯甲酰胺脱水成对甲氧基苯甲腈:
在惰性氛围下,反应管中依次加入底物对甲氧基苯甲酰胺(133mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应18h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为116mg白色固体,收率:87%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.58(d,2H),6.96(d,2H),3.86(s,3H).13C NMR(150MHz,CDCl3)δ162.82,133.94,119.17,114.72,103.95,55.50.
实施例10:苯乙酰胺与脱水成对苯乙腈:
在惰性氛围下,反应管中依次加入底物苯乙酰胺(135mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为95mg无色油状液体,收率:81%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.41-7.36(d,2H),7.36-7.30(m,3H),7.32(s,3H).
实施例11:1-萘甲酰胺脱水成对1-萘甲腈:
在惰性氛围下,反应管中依次加入底物1-萘甲酰胺(171mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为138mg针状结晶体,收率:90%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ8.27(dd,J=8.4,0.6Hz,1H),8.11(d,J=8.3Hz,1H),7.98-7.93(m,2H),7.73(ddd,J=8.3,6.9,1.2Hz,1H),7.65(ddd,J=8.1,7.0,1.1Hz,1H),7.56(dd,J=8.3,7.2Hz,1H).
实施例12:1-萘乙酰胺脱水成对1-萘乙腈:
在惰性氛围下,反应管中依次加入底物1-萘乙酰胺(185mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为142mg白色晶体粉末,收率:85%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.89-7.80(m,4H),7.56-7.48(m,2H),7.39(dd,J=8.4,1.8Hz,1H),3.92(s,2H).
实施例13:对羟基苯甲酰胺脱水成对羟基苯甲腈:
在惰性氛围下,反应管中依次加入底物对羟基苯甲酰胺(137mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(1mL)与四氢呋喃(1mL)混合溶剂,并将得到的混合物搅拌均匀。60℃油浴下反应18h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为84mg白色结晶,收率:71%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.59-7.52(m,2H),6.97-6.90(m,2H),6.60(s,1H).
实施例14:2-噻吩甲酰胺与脱水成对2-噻吩甲腈:
在惰性氛围下,反应管中依次加入底物2-噻吩甲酰胺(127mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应18h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为90mg淡黄色油状物,收率:83%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.66-7.53(m,2H),7.11(dd,J=5.1,3.8Hz,1H).
实施例15:3-苯基丙酰胺脱水成三苯基丙腈:
在惰性氛围下,反应管中依次加入底物3-苯基丙酰胺(149mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为98mg淡黄色液体,收率:75%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.92(t,J=7.5Hz,2H),7.26(ddd,J=8.77.4,0.8Hz,3H),2.96(t,J=7.5Hz,2H),2.62(t,J=7.4Hz,2H).
实施例16:肉桂酰胺脱水成肉桂腈:
在惰性氛围下,反应管中依次加入底物肉桂酰胺(147mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(36.6mg,0.06mmol)和甲苯(1mL)与四氢呋喃(1mL)混合溶剂,并将得到的混合物搅拌均匀。60℃油浴下反应12h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为95mg黄色透明液体,收率:74%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.47-7.44(m,2H),7.44-7.36(m,4H),5.88(d,J=16.7Hz,1H).
实施例17:2-萘甲酰胺脱水成2-萘甲腈:
在惰性氛围下,反应管中依次加入底物2-萘甲酰胺(171mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应18h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为132mg白色固体,收率:86%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ8.4(s,1H),7.91(dd,J=13.8,8.6Hz,3H),769-7.54(m,3H).
实施例18:环己甲酰胺脱水成环己甲腈:
在惰性氛围下,反应管中依次加入底物环己甲酰胺(127mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀后转出手套箱。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为104mg无色透明液体,收率:95%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.59(td,J=8.2,4.0Hz,1H),1.91-1.76(m,2H),1.74-1.57(m,4H),1.52-1.31(m,4H).
实施例19:己酰胺脱水成己腈:
在惰性氛围下,反应管中依次加入底物己酰胺(115mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为88mg无色透明液体,收率:91%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.33(t,J=7.2,2H),1.70-1.62(m,2H),1.50-1.39(m,2H),1.39-1.31(m,2H),0.92(t,J=7.1Hz,3H).
实施例20:2,6-二氯苯甲酰胺脱水成2,6-二氯苯甲腈:
在惰性氛围下,反应管中依次加入底物2,6-二氯苯甲酰胺(189mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为150mg无色结晶体,收率:87%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.49-7.41(m,2H),1.56(s,1H).
实施例21:对叔丁基苯甲酰胺脱水成对叔丁基苯甲腈:
在惰性氛围下,反应管中依次加入底物对叔丁基苯甲酰胺(177mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为124mg无色透明液体,收率:78%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.61-7.55(m,2H),7.51-7.45(m,2H),1.33(s,9H).
实施例22:3,5-二甲氧基苯甲酰胺脱水成3,5-二甲氧基苯甲腈:
在惰性氛围下,反应管中依次加入底物3,5-二甲氧基苯甲酰胺(181mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为159mg白色固体,收率:88%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.00(d,J=2.3Hz,2H),6.82(t,J=2.3Hz,1H),3.79(s,6H).
实施例23:对甲氧基苯乙酰胺脱水成对甲氧基苯乙腈:
在惰性氛围下,反应管中依次加入底物对甲氧基苯乙酰胺(165mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为118mg白色固体,收率:80%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.23(t,J=5.7Hz,2H),6.93-6.85(m,2H),3.81(s,3H),3.68(s,2H).
实施例24:2,6-二氟苯甲酰胺脱水成2,6-二氟苯甲腈:
在惰性氛围下,反应管中依次加入底物2,6-二氟苯甲酰胺(157mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为118mg白色固体,收率:85%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ7.61(tt,J=8.6,6.3Hz,1H),7.13-7.01(m,2H).
实施例25:辛酰胺与脱水成辛腈:
在惰性氛围下,反应管中依次加入底物辛酰胺(143mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为110mg无色液体,收率:88%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.36-2.29(m,2H),1.71-1.60(m,2H),1.44(ddd,J=9.8,8.0,6.5Hz,2H),1.34-1.25(m,6H),0.89(t,J=7.0Hz,3H).
实施例26:葵酰胺脱水成葵腈:
在惰性氛围下,反应管中依次加入底物葵酰胺(171mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为141mg无色液体,收率:92%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.32(t,J=7.2Hz,2H),1.70-1.59(m,2H),1.43(dd,J=10.2,4.8Hz,2H),1.34-1.17(m,10H),0.87(t,J=7.1Hz,3H).
实施例27:1-金刚烷甲酰胺脱水成1-金刚烷甲腈:
在惰性氛围下,反应管中依次加入底物1-金刚烷甲酰胺(179mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为121mg白色固体,收率:75%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ2.15-1.93(m,9H),1.81-1.66(m,6H).
实施例28:3-吡啶甲酰胺脱水成3-吡啶甲腈:
在惰性氛围下,反应管中依次加入底物3-吡啶甲酰胺(122mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.4mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和二甲醚(2mL),并将得到的混合物搅拌均匀。100℃油浴下反应24h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为80mg白色固体,收率:77%。产物表征数据如下:1H NMR(600MHz,CDCl3)δ8.88(d,J=1.4Hz,1H),8.81(dd,J=4.9,1.7Hz,1H),7.96(d,J=7.9,1.9Hz,1H),7.43(ddd,J=7.9,4.9,0.8Hz,1H).
对比例1:苯甲酰胺脱水成苯甲腈:
在惰性氛围下,反应管中依次加入底物苯甲酰胺(121mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-1催化剂(4.7mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为97mg无色油状液体,收率:61%。
对比例2:苯甲酰胺脱水成苯甲腈:
在惰性氛围下,反应管中依次加入底物苯甲酰胺(121mg,1mmol)、苯硅烷(540mg,5mmol)、Co-2催化剂(4.7mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和甲苯(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为97mg无色油状液体,收率:51%。
对比例3:苯甲酰胺脱水成苯甲腈:
在惰性氛围下,反应管中依次加入底物苯甲酰胺(121mg,1mmol)、聚甲基氢硅氧烷(1.1g,5mmol)、Co-2催化剂(4.7mg,0.01mmol)、三乙基硼氢化钠(73.2mg,0.06mmol)和THF(2mL),并将得到的混合物搅拌均匀。60℃油浴下反应6h,反应体系冷却至室温,加入乙酸乙酯稀释淬灭,浓缩,粗产物快速硅胶柱层析得到最终产物为97mg无色油状液体,收率:55%。
最后,还需要注意的是,以上列举的仅是本发明若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种伯酰胺脱水成腈的方法,其特征在于,所述方法为:
在惰性气体保护下,将伯酰胺(II)、硅烷、三乙基硼氢化钠、胺吡啶亚胺三齿氮配体钴配合物(I)与反应溶剂混合,于60~100℃下反应6~24h,之后反应液经后处理,得到腈类化合物(III);
原料伯酰胺(II)、产物腈类化合物(III)的结构式如下:
式(II)或(III)中,
R4为C5~C10烷基、C5~C10环烷基、萘基、萘甲基、苄基、苯乙基、苯乙烯基、对甲氧基苄基、杂芳基、苯基或取代苯基,所述取代苯基的苯环上被一个或多个取代基取代,所述取代基各自独立为C1~C3烷基、C1~C3烷氧基、羟基、羟甲基、氟、氯、溴、氨基或叔丁基;
催化剂胺吡啶亚胺三齿氮配体钴配合物(I)的结构式如下:
式(I)中,
R1、R2各自独立为C1~C4烷基或C6~C10芳基;
R3为苯基或取代苯基,所述取代苯基的苯环上被一个或多个C1~C4烷基取代。
2.如权利要求1所述伯酰胺脱水成腈的方法,其特征在于,所述硅烷的结构式为R5R6R7SiH,其中R5、R6、R7各自独立为氢、烷基、三甲基硅基、烷氧基或芳基。
3.如权利要求2所述伯酰胺脱水成腈的方法,其特征在于,所述硅烷为:四甲基二硅氧烷、苯硅烷、二苯基硅氧烷或聚甲基氢硅氧烷。
4.如权利要求1所述伯酰胺脱水成腈的方法,其特征在于,所述伯酰胺(II)、硅烷、三乙基硼氢化钠、胺吡啶亚胺三齿氮配体钴配合物(I)的物质的量之比为1∶5∶0.03~0.06∶0.01。
5.如权利要求1所述伯酰胺脱水成腈的方法,其特征在于,所述反应溶剂选自:甲苯、四氢呋喃、苯甲醚、环戊基甲醚、1,4-二氧六环、正庚烷、二甲醚中的一种或两种以上任意比例的混合溶剂。
6.如权利要求1所述伯酰胺脱水成腈的方法,其特征在于,所述反应溶剂的体积用量以伯酰胺的物质的量计为1~5mL/mmol。
7.如权利要求1所述伯酰胺脱水成腈的方法,其特征在于,所述后处理的方法为:反应结束后,待反应液冷却至室温,乙酸乙酯淬灭稀释,浓缩后硅胶柱层析分离,以石油醚和乙酸乙酯体积比为50∶1的混合液为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到腈类化合物(III)。
9.如权利要求8所述式(I)所示胺吡啶亚胺三齿氮配体钴配合物的制备方法,其特征在于,所述制备方法为:
在惰性氛围下,将化合物(I-a)、化合物(I-b)、CoCl2、乙酸混合均匀,回流反应8h,之后反应液经后处理,得到胺吡啶亚胺三齿氮配体钴配合物(I);
所述化合物(I-a)、化合物(I-b)、CoCl2的物质的量之比为1∶1.1∶1;
所述乙酸的体积用量以化合物(I-a)的物质的量计为20mL/mmol;
所述后处理的方法为:反应结束后,用氮气将反应液中的醋酸吹干,剩下黑色油状物,用DCM溶解后,滴加入MTBE中搅拌,可以看见MTBE中有绿色粉末产物,过滤,洗涤,干燥,得到产物(I);
式(I-a)或(I-b)中,R1、R2、R3的定义与式(I)中相同。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113943199A (zh) * | 2021-10-18 | 2022-01-18 | 浙江工业大学 | 一种以腈和二芳基甲烷为原料合成酰胺类化合物的方法 |
CN114031477A (zh) * | 2021-11-02 | 2022-02-11 | 浙江工业大学 | 一种钴催化酰胺类化合物还原成胺类化合物的方法 |
CN115745825A (zh) * | 2022-11-10 | 2023-03-07 | 浙江工业大学 | 利用三齿nno镍配合物催化酰胺烷基化反应的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111635334A (zh) * | 2020-07-13 | 2020-09-08 | 四川大学 | 一种Ru配合物催化伯胺无受体脱氢生成腈的方法 |
CN111875515A (zh) * | 2020-09-04 | 2020-11-03 | 四川大学 | 一种使用金属配合物催化伯胺生成酰胺的方法 |
CN112028793A (zh) * | 2020-08-17 | 2020-12-04 | 浙江大学衢州研究院 | 铋配合物催化酰胺脱水制备腈的方法 |
-
2021
- 2021-03-04 CN CN202110239585.2A patent/CN112961079B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111635334A (zh) * | 2020-07-13 | 2020-09-08 | 四川大学 | 一种Ru配合物催化伯胺无受体脱氢生成腈的方法 |
CN112028793A (zh) * | 2020-08-17 | 2020-12-04 | 浙江大学衢州研究院 | 铋配合物催化酰胺脱水制备腈的方法 |
CN111875515A (zh) * | 2020-09-04 | 2020-11-03 | 四川大学 | 一种使用金属配合物催化伯胺生成酰胺的方法 |
Non-Patent Citations (2)
Title |
---|
JIAXIN LI ET AL.: ""2-(N,N-Diethylaminomethyl)-6,7-trihydroquinolinyl-8-ylideneamine-Ni(ii) chlorides: application in ethylene dimerization and trimerization"", 《NEW JOURNAL OF CHEMISTRY》, vol. 44, 11 September 2020 (2020-09-11), pages 17047 - 17052 * |
宗志建: ""基于四氢喹啉骨架开发氮配体及其钴配合物的催化反应研究"", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》, no. 2021, 15 February 2021 (2021-02-15), pages 014 - 42 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113943199A (zh) * | 2021-10-18 | 2022-01-18 | 浙江工业大学 | 一种以腈和二芳基甲烷为原料合成酰胺类化合物的方法 |
CN113943199B (zh) * | 2021-10-18 | 2023-09-22 | 浙江工业大学 | 一种以腈和二芳基甲烷为原料合成酰胺类化合物的方法 |
CN114031477A (zh) * | 2021-11-02 | 2022-02-11 | 浙江工业大学 | 一种钴催化酰胺类化合物还原成胺类化合物的方法 |
CN114031477B (zh) * | 2021-11-02 | 2023-12-05 | 浙江工业大学 | 一种钴催化酰胺类化合物还原成胺类化合物的方法 |
CN115745825A (zh) * | 2022-11-10 | 2023-03-07 | 浙江工业大学 | 利用三齿nno镍配合物催化酰胺烷基化反应的方法 |
CN115745825B (zh) * | 2022-11-10 | 2024-05-03 | 浙江工业大学 | 利用三齿nno镍配合物催化酰胺烷基化反应的方法 |
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