CN114507252A - Synthesis method of novel aryl silane compound - Google Patents
Synthesis method of novel aryl silane compound Download PDFInfo
- Publication number
- CN114507252A CN114507252A CN202210158120.9A CN202210158120A CN114507252A CN 114507252 A CN114507252 A CN 114507252A CN 202210158120 A CN202210158120 A CN 202210158120A CN 114507252 A CN114507252 A CN 114507252A
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- China
- Prior art keywords
- novel
- hexamethyldisilane
- synthesizing
- compound according
- column chromatography
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- -1 aryl silane compound Chemical class 0.000 title claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims abstract description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 5
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims description 44
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 26
- 239000003208 petroleum Substances 0.000 claims description 24
- WDVGNXKCFBOKDF-UHFFFAOYSA-N dicyclohexyl-[3,6-dimethoxy-2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane Chemical compound COC1=CC=C(OC)C(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1P(C1CCCCC1)C1CCCCC1 WDVGNXKCFBOKDF-UHFFFAOYSA-N 0.000 claims description 22
- 239000003480 eluent Substances 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 239000012046 mixed solvent Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 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 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 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 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-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
- REWLCYPYZCHYSS-UHFFFAOYSA-N ditert-butyl-[3,6-dimethoxy-2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane Chemical compound COC1=CC=C(OC)C(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1P(C(C)(C)C)C(C)(C)C REWLCYPYZCHYSS-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 10
- 150000001875 compounds Chemical class 0.000 claims 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 80
- 239000000047 product Substances 0.000 description 61
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 20
- 229910000024 caesium carbonate Inorganic materials 0.000 description 20
- 238000012512 characterization method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 20
- 238000000746 purification Methods 0.000 description 20
- 238000000926 separation method Methods 0.000 description 20
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YFWBUVZWCBFSQN-UHFFFAOYSA-N 1,2-dimethoxy-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1OC YFWBUVZWCBFSQN-UHFFFAOYSA-N 0.000 description 1
- HFZKOYWDLDYELC-UHFFFAOYSA-N 1,2-dimethyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1C HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 description 1
- BYFNZOKBMZKTSC-UHFFFAOYSA-N 1,3-dimethyl-5-nitrobenzene Chemical compound CC1=CC(C)=CC([N+]([O-])=O)=C1 BYFNZOKBMZKTSC-UHFFFAOYSA-N 0.000 description 1
- QOZMIJZYJZQOBV-UHFFFAOYSA-N 1-methoxy-2-methyl-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1C QOZMIJZYJZQOBV-UHFFFAOYSA-N 0.000 description 1
- PXBQSCHRKSBGKV-UHFFFAOYSA-N 1-methyl-5-nitroindole Chemical compound [O-][N+](=O)C1=CC=C2N(C)C=CC2=C1 PXBQSCHRKSBGKV-UHFFFAOYSA-N 0.000 description 1
- FYRPEHRWMVMHQM-UHFFFAOYSA-N 1-nitro-3-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC(C=2C=CC=CC=2)=C1 FYRPEHRWMVMHQM-UHFFFAOYSA-N 0.000 description 1
- JDTMUJBWSGNMGR-UHFFFAOYSA-N 1-nitro-4-phenoxybenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=CC=C1 JDTMUJBWSGNMGR-UHFFFAOYSA-N 0.000 description 1
- ZKRDQLBHUZNPGZ-UHFFFAOYSA-N 1-tert-butyl-3-nitrobenzene Chemical compound CC(C)(C)C1=CC=CC([N+]([O-])=O)=C1 ZKRDQLBHUZNPGZ-UHFFFAOYSA-N 0.000 description 1
- HSDNHFOJTRMGER-UHFFFAOYSA-N 2-methoxy-1,3-dimethyl-5-nitrobenzene Chemical compound COC1=C(C)C=C([N+]([O-])=O)C=C1C HSDNHFOJTRMGER-UHFFFAOYSA-N 0.000 description 1
- ZJYJZEAJZXVAMF-UHFFFAOYSA-N 2-nitronaphthalene Chemical compound C1=CC=CC2=CC([N+](=O)[O-])=CC=C21 ZJYJZEAJZXVAMF-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- IAJDSUYFELYZCS-UHFFFAOYSA-N 4-(4-nitrophenyl)morpholine Chemical compound C1=CC([N+](=O)[O-])=CC=C1N1CCOCC1 IAJDSUYFELYZCS-UHFFFAOYSA-N 0.000 description 1
- BAJQRLZAPXASRD-UHFFFAOYSA-N 4-Nitrobiphenyl Chemical group C1=CC([N+](=O)[O-])=CC=C1C1=CC=CC=C1 BAJQRLZAPXASRD-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- NOVKHIQVXQKSRL-UHFFFAOYSA-N 5-nitro-1-benzothiophene Chemical compound [O-][N+](=O)C1=CC=C2SC=CC2=C1 NOVKHIQVXQKSRL-UHFFFAOYSA-N 0.000 description 1
- TYPKKUFDAHEIOP-UHFFFAOYSA-N 5-nitro-2,3-dihydro-1-benzofuran Chemical compound [O-][N+](=O)C1=CC=C2OCCC2=C1 TYPKKUFDAHEIOP-UHFFFAOYSA-N 0.000 description 1
- SPNVINZCDHRVAI-UHFFFAOYSA-N 9,9-dimethyl-2-nitrofluorene Chemical compound C1=C([N+]([O-])=O)C=C2C(C)(C)C3=CC=CC=C3C2=C1 SPNVINZCDHRVAI-UHFFFAOYSA-N 0.000 description 1
- CDGXAOCJQUZBID-UHFFFAOYSA-N 9-(4-nitrophenyl)carbazole Chemical compound C1=CC([N+](=O)[O-])=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 CDGXAOCJQUZBID-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- POADTFBBIXOWFJ-VWLOTQADSA-N cositecan Chemical compound C1=CC=C2C(CC[Si](C)(C)C)=C(CN3C4=CC5=C(C3=O)COC(=O)[C@]5(O)CC)C4=NC2=C1 POADTFBBIXOWFJ-VWLOTQADSA-N 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QJAIOCKFIORVFU-UHFFFAOYSA-N n,n-dimethyl-4-nitroaniline Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=C1 QJAIOCKFIORVFU-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JLAVCPKULITDHO-UHFFFAOYSA-N tetraphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JLAVCPKULITDHO-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthesis method of a novel aryl silane compound, which takes hexamethyldisilane and nitroaromatic as raw materials, and realizes one-step denitration C-Si coupling of the nitroaromatic and the hexamethyldisilane through a palladium catalyst to obtain the aryl silane compound. The method has the advantages that the nitro aromatic hydrocarbon is directly utilized to carry out one-step denitration and silicification reaction, so that steps and economic benefits are greatly improved, and the process cost is reduced; compared with silicon-based borate, hexamethyldisilane has the advantages of stable property, low price, low toxicity and the like. Therefore, compared with the existing method, the method has the advantages of simple and convenient operation, easily obtained raw materials, high efficiency, economy, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of a novel aryl silane compound.
Background
The C-Si bond has unique biological activity, physical and chemical properties, so that the organic silicon compound is widely applied to materials, medicines and the like. Organic silicon compounds such as tetraphenylsilane have been reported in the fields of luminescent materials, electron-active materials, and the like. Because the silicon-based substituent has the functions of activating, orienting, stabilizing an intermediate, protecting a functional group and the like, the biological activity of the silicon-based grafted polymer can be optimized, the toxicity can be reduced, and the therapeutic potential of the drug can be increased by grafting the silicon-based grafted polymer to the known drug skeleton. Silicon-containing drugs such as amsilatrane (Amsilatrane), zirosilone (Zifosilone), Koxitekang (Karenitecin), etc. have been widely used in drug development. In addition, the organic silicon compound is also an important synthetic intermediate, and can efficiently construct C-C and C-X bonds, for example, silicon groups can be converted into boron groups, halogens and the like, so that the molecular skeleton is modified. Therefore, the development of a novel and efficient method for constructing the C-Si bonded organosilicon compound is of great significance.
The traditional synthetic method of aryl silane is mainly obtained by coupling reaction of organic lithium reagent or Grignard reagent and halosilane. The method has harsh reaction conditions, poor functional group tolerance and limited substrate range. Transition metal catalyzed cross-coupling strategies with hydrosilanes and disilanes as silicon-based sources have been developed further in recent years. Transition metal catalyzed silica alkylation processes are largely classified into the following two categories: (1) cross-coupling of aryl halides with disilane reagents. (2) Silicon activation strategy for C-H bond activation. Compared with the traditional synthesis method, the transition metal catalysis method has the advantages of directness, high efficiency, good functional group tolerance, wide substrate range and the like. However, the preparation process of the single aryl halide is complicated industrially, the single aryl halide is usually obtained by three steps of reduction, diazotization and Sandmeyer reaction of nitroaromatic, the atom economy is not high, and the organic halide waste can pollute the environment. The C-H bond activated silica-based strategy usually requires the use of a directing group, and the introduction of the directing group into the starting material and the removal of the directing group from the product require additional process steps, which also increases the cost of the synthesis. Therefore, the development of a novel and low-cost method for constructing a C-Si bond by replacing a halide with an aryl electrophilic reagent in one step has great significance and research value in the aspects of synthetic chemistry and industrial production.
Nitroaromatic is one of basic raw materials for chemical production, and is a very valuable synthetic intermediate. From Nakao et al in Ar-NO2Since the activation of bond made a great breakthrough, many novel coupling reactions using nitroarenes as electrophilic coupling reagents were developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a practical, economical, cheap and low-toxic novel aryl silane compound synthesis method.
In order to solve the technical problems, the invention adopts the following technical scheme:
the synthesis method of the novel aryl silane compound comprises the steps of taking hexamethyldisilane and nitroaromatic as raw materials, and realizing one-step denitration C-Si coupling of the nitroaromatic and the hexamethyldisilane through a palladium catalyst to obtain the aryl silane compound.
The method conforms to the following reaction equation:
the nitroaromatic hydrocarbon is
Hexamethyldisilane is
Wherein R is1Represents alkyl, alkoxy, phenyl or phenoxy containing one or more substituents.
The palladium catalyst is Pd (PPh)3)4，Pd2(dba)3，Pd2(dba)2，Pd(TFA)2，Pd(OAc)2，[Pd(allyl)Cl]2，Pd(acac)2One or a mixture of two or more of them.
The synthesis method of the novel aryl silane compound is operated according to the following steps: adding hexamethyldisilane, nitroaromatic hydrocarbon, palladium catalyst, ligand, alkali and solvent into a reaction tube, and adding N2Stirring and reacting for 24 hours at 150 ℃ under protection, cooling to room temperature after the reaction is finished, performing suction filtration, removing the solvent under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain the aryl silane compound.
The molar ratio of nitroarene to hexamethyldisilane was 3: 2.
The ligand is Brettphos,tBuBrettPhos、XantPhos、DPPF、tOne or more than two of BuXPhos.
The alkali is one or more of potassium acetate, potassium methoxide, potassium tert-butoxide, potassium phosphate, sodium carbonate, potassium carbonate, cesium fluoride, potassium fluoride, sodium hydroxide, and potassium hydroxide.
The solvent is one or more of N-heptane, p-xylene, toluene, trifluorotoluene, 1, 4-dioxane, N-dimethylformamide, and dimethyl sulfoxide.
The reaction tube was a Schlenk tube (Schlenk tube).
The eluent in column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of (20-300): 1
Aiming at the problems in the synthesis of the aryl silane at present, the inventor establishes a novel synthesis method of the aryl silane compound, takes hexamethyldisilane and nitro-arene as raw materials, and realizes one-step denitration C-Si coupling of the nitro-arene and the hexamethyldisilane through a palladium catalyst to obtain the aryl silane compound. The method has the advantages that the nitro aromatic hydrocarbon is directly utilized to carry out one-step denitration and silicification reaction, so that steps and economic benefits are greatly improved, and the process cost is reduced; compared with silicon-based borate, hexamethyldisilane has the advantages of stable property, low price, low toxicity and the like. Therefore, compared with the existing method, the method has the advantages of simple and convenient operation, easily obtained raw materials, high efficiency, economy, environmental protection and the like.
Detailed Description
Example 1
To a Schlenk tube were added 0.3mmol of p-nitroanisole, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 50:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.49(d,J＝8.6Hz,2H),6.95(d,J＝8.6Hz,2H),3.84(s,3H),0.29(s,9H)；
13C NMR(126MHz,CDCl3)δ160.2,134.7,131.2,113.5,54.9,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 2
To a Schlenk tube were added 0.3mmol of 2-nitronaphthalene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ8.03(s,1H),7.85(ddd,J＝11.7,5.9,3.2Hz,3H),7.62(dd,J＝8.1,1.1Hz,1H),7.51–7.47(m,2H),0.37(s,9H).
13C NMR(126MHz,CDCl3)δ137.9,133.7,133.6,132.9,129.8,128.0,127.7,126.9,126.2,125.8,-1.1
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 3
To a Schlenk tube were added 0.3mmol of N, N-dimethyl-4-nitroaniline, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the conditions, the heating and stirring were stopped, and the mixture was cooled to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 40:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.46(d,J＝8.6Hz,2H),6.80(d,J＝8.6Hz,2H),3.01(s,6H),0.29(s,9H).
13C NMR(126MHz,CDCl3)δ151.1,134.5,125.8,112.1,40.4,-0.7.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 4
To a Schlenk tube were added 0.3mmol of 5-nitrobenzothiophene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the conditions, the heating and stirring were stopped, and the mixture was cooled to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ8.02(s,1H),7.91(d,J＝8.0Hz,1H),7.50(d,J＝8.5Hz,1H),7.44(d,J＝5.4Hz,1H),7.36(d,J＝5.4Hz,1H),0.35(s,9H)；
13C NMR(126MHz,CDCl3)δ140.6,139.4,135.7,128.9,128.9,126.1,124.0,122.0,-0.8.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 5
To a Schlenk tube were added 0.3mmol of 4-nitrobiphenyl, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.65–7.60(m,6H),7.46(t,J＝7.7Hz,2H),7.39–7.35(m,1H),0.33(s,9H).
13C NMR(126MHz,CDCl3)δ141.8,141.3,139.4,134.0,128.9,127.5,127.3,126.6,-0.9.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 6
To a Schlenk tube were added 0.3mmol of 4- (4-nitrophenyl) morpholine, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 20:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.54(d,J＝8.6Hz,2H),7.00(d,J＝8.6Hz,2H),3.95–3.91(m,4H),3.28–3.24(m,4H),0.35(s,9H).
13C NMR 13C NMR(126MHz,CDCl3)δ151.5,134.3,129.8,114.7,66.7,48.7,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 7
To a Schlenk tube were added 0.3mmol of 1-methyl-5-nitro-1H-indole, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After the reaction is carried out for 24 hours under the condition of stirring,stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.90(s,1H),7.45(d,J＝8.1Hz,1H),7.40(d,J＝8.1Hz,1H),7.08(d,J＝3.1Hz,1H),6.56(d,J＝3.1Hz,1H),3.82(s,3H),0.39(s,9H).
13C NMR(126MHz,CDCl3)δ137.3,129.3,128.8,128.6,126.5,126.3,109.0,101.1,32.7,-0.5.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 8
To a Schlenk tube were added 0.3mmol of 3-nitrotoluene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.33(d,J＝6.3Hz,2H),7.26(t,J＝7.6Hz,1H),7.19–7.16(m,1H),2.37(s,3H),0.27(s,9H)；
13C NMR(126MHz,CDCl3)δ140.5,137.2,134.1,130.5,129.7,127.8,21.7,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 9
To a Schlenk tube were added 0.3mmol of 4-nitrotoluene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of Brettphos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.44(d,J＝7.7Hz,2H),7.19(d,J＝7.5Hz,2H),2.36(s,3H),0.26(s,9H).
13C NMR(126MHz,CDCl3)δ138.6,136.8,133.3,128.6,21.4,-1.1.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 10
To a Schlenk tube were added 0.3mmol of 1, 3-dimethyl-5-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.16(s,2H),7.03(s,1H),2.35(s,6H),0.28(s,9H).
13C NMR(126MHz,CDCl3)δ140.2,137.0,131.0,130.6,21.4,-1.1.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 11
To a Schlenk tube were added 0.3mmol of 5-nitro-2, 3-dihydrobenzofuran, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.39(d,J＝0.6Hz,1H),7.33–7.29(m,1H),6.84(d,J＝7.8Hz,1H),4.58(t,J＝8.7Hz,2H),3.24(t,J＝8.7Hz,2H),0.28(s,9H).
13C NMR(126MHz,CDCl3)δ160.9,133.4,131.1,129.8,126.6,109.1,71.0,29.5,-0.8.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 12
To a Schlenk tube were added 0.3mmol of 1- (tert-butyl) -3-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.60(d,J＝0.9Hz,1H),7.48–7.31(m,3H),1.38(s,9H),0.32(s,9H).
13C NMR(126MHz,CDCl3)δ150.0,139.9,130.5,129.9,127.4,125.89,34.7,31.4,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 13
To a Schlenk tube were added 0.3mmol of 1, 2-dimethyl-4-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the obtained product are as follows:
1H NMR(500MHz,CDCl3)δ7.31(d,J＝10.4Hz,2H),7.17(d,J＝7.3Hz,1H),2.32(s,3H),2.30(s,3H),0.29(s,9H)；
13C NMR(126MHz,CDCl3)δ137.4,137.3,135.8,134.6,131.0,129.2,19.7,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 14
To a Schlenk tube were added 0.3mmol of 1-nitro-4-phenoxybenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.55–7.50(m,2H),7.38(dd,J＝8.6,7.4Hz,2H),7.15(s,1H),7.09–7.03(m,4H),0.32(s,9H)；
13C NMR(126MHz,CDCl3)δ158.1,156.9,134.9,134.4,129.7,123.4,119.2,118.0,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 15
To a Schlenk tube were added 0.3mmol of 1-methoxy-2-methyl-4-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 50:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.38(dd,J＝8.0,1.4Hz,1H),7.33(s,1H),6.88(d,J＝8.0Hz,1H),3.87(s,3H),2.29(s,3H),0.30(s,9H)；
13C NMR(126MHz,CDCl3)δ158.5,135.7,132.3,130.8,126.0,109.45,55.1,16.2,-0.9.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 16
To a Schlenk tube were added 0.3mmol of 3-nitro-1, 1' -biphenyl, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol BrettPhos, 0.6mmol Cesium carbonate, 1.5mL trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.78(s,1H),7.66–7.61(m,3H),7.56(dd,J＝4.8,3.6Hz,1H),7.49(dt,J＝7.2,5.3Hz,3H),7.40(d,J＝7.4Hz,1H),0.37(s,9H).
13C NMR(126MHz,CDCl3)δ141.6,141.0,140.5,132.2,132.1,128.7,128.1,127.7,127.3,127.2,-1.1.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 17
To a Schlenk tube were added 0.3mmol of 9, 9-dimethyl-2-nitro-9H-fluorene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.78–7.74(m,2H),7.62(s,1H),7.55(dd,J＝7.4,0.9Hz,1H),7.49–7.46(m,1H),7.38–7.34(m,2H),1.54(s,6H),0.37(s,9H)；
13C NMR(126MHz,CDCl3)δ153.8,152.7,139.9,139.4,139.1,132.1,127.4,127.2,126.9,122.6,120.1,119.3,46.8,27.2,-0.8.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 18
To a Schlenk tube were added 0.3mmol of 9- (4-nitrophenyl) -9H carbazole, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The eluent of column chromatography is petroleum ether.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.7Hz,2H),7.79–7.75(m,2H),7.60–7.57(m,2H),7.48(d,J＝8.2Hz,2H),7.43(dt,J＝8.2,4.1Hz,2H),7.33–7.29(m,2H),0.40(s,9H).
13C NMR(126MHz,CDCl3)δ140.8,139.8,138.1,134.8,126.2,125.9,123.4,120.3,119.9,109.9,-1.1.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 19
To a Schlenk tube were added 0.3mmol of 1, 2-dimethoxy-4-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 50:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.09(dd,J＝7.8,1.2Hz,1H),7.01(s,1H),6.90(d,J＝7.8Hz,1H),3.91(s,3H),3.89(s,3H),0.27(s,9H)；
13C NMR(126MHz,CDCl3)δ149.7,148.5,131.8,126.4,115.7,110.9,55.817,55.7,-1.0.
the structure of the resulting product is deduced from the above data as shown in the following formula:
example 20
To a Schlenk tube were added 0.3mmol of 2-methoxy-1, 3-dimethyl-5-nitrobenzene, 0.2mmol of hexamethyldisilane, 0.01mmol of palladium acetylacetonate, 0.02mmol of BrettPhos, 0.6mmol of cesium carbonate, and 1.5mL of trifluorotoluene. At 150 ℃ N2After stirring and reacting for 24 hours under the condition, stopping heating and stirring, and cooling to room temperature. And (4) carrying out suction filtration, removing the solvent under reduced pressure, and carrying out column chromatography separation and purification to obtain the target product. The volume ratio of the used column chromatography eluent is 50:1 of petroleum ether-ethyl acetate mixed solvent.
The structural characterization data of the product obtained are as follows:
1H NMR(500MHz,CDCl3)δ7.21(s,2H),3.78(s,3H),2.35(s,6H),0.30(s,9H).
13C NMR(126MHz,CDCl3)δ157.7,135.3,134.1,130.1,59.5,16.1,-1.0
the structure of the resulting product is deduced from the above data as shown in the following formula:
Claims (10)
1. a method for synthesizing a novel aryl silane compound is characterized by comprising the following steps: hexamethyldisilane and nitroaromatic are used as raw materials, and the one-step denitration C-Si coupling of the nitroaromatic and the hexamethyldisilane is realized through a palladium catalyst to obtain the aryl silane compound.
2. The method for synthesizing a novel arylsilane compound according to claim 1, wherein the method satisfies the following reaction equation:
the nitroaromatic is
Hexamethyldisilane is
Wherein R is1Represents an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, etc., having one or more substituents.
3. The method for synthesizing a novel arylsilane compound according to claim 1, wherein: the palladium catalyst is Pd (PPh)3)4，Pd2(dba)3，Pd2(dba)2，Pd(TFA)2，Pd(OAc)2，[Pd(allyl)Cl]2，Pd(acac)2One or a mixture of two or more of them.
4. The method for synthesizing a novel arylsilane compound according to claim 1, which comprises the steps of: adding hexamethyldisilane, nitroaromatic hydrocarbon, palladium catalyst, ligand, alkali and solvent into a reaction tube, and adding N2Stirring and reacting for 24 hours at 150 ℃ under protection, cooling to room temperature after the reaction is finished, performing suction filtration, removing the solvent under reduced pressure to obtain a crude product, and purifying the crude product by column chromatography to obtain the aryl silane compound.
5. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the molar ratio of the nitroarene to the hexamethyldisilane is 3: 2.
6. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the ligand is Brettphos,tBuBrettPhos、XantPhos、DPPF、tOne or more than two of BuXPhos.
7. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the alkali is one or more of potassium acetate, potassium methoxide, potassium tert-butoxide, potassium phosphate, sodium carbonate, potassium carbonate, cesium fluoride, potassium fluoride, sodium hydroxide and potassium hydroxide.
8. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the solvent is one or the mixture of more than two of N-heptane, p-xylene, toluene, benzotrifluoride, 1, 4-dioxane, N-dimethylformamide and dimethyl sulfoxide.
9. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the reaction tube is a Schlenk tube.
10. The method for synthesizing a novel arylsilane compound according to claim 4, wherein: the eluent in the column chromatography is petroleum ether or a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of (20-300): 1.
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