CN115368218B - Method for preparing 4-diaryl methyl substituted phenol compound - Google Patents
Method for preparing 4-diaryl methyl substituted phenol compound Download PDFInfo
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- CN115368218B CN115368218B CN202211113555.8A CN202211113555A CN115368218B CN 115368218 B CN115368218 B CN 115368218B CN 202211113555 A CN202211113555 A CN 202211113555A CN 115368218 B CN115368218 B CN 115368218B
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- Prior art keywords
- tert
- cyclohexadien
- butyl
- methylene
- mmol
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- -1 phenol compound Chemical class 0.000 title claims description 41
- 238000000034 method Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 123
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 122
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 61
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 26
- 150000002989 phenols Chemical class 0.000 claims abstract description 20
- 150000008378 aryl ethers Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 171
- 238000003756 stirring Methods 0.000 claims description 36
- HCUWXYBKPSKTAB-UHFFFAOYSA-N 4-benzylidene-2,6-ditert-butylcyclohexa-2,5-dien-1-one Chemical group C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC=C1 HCUWXYBKPSKTAB-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- NIEHEMAZEULEKB-UHFFFAOYSA-N 1-ethyl-2-methoxybenzene Chemical compound CCC1=CC=CC=C1OC NIEHEMAZEULEKB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 4
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 claims description 3
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 claims description 3
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 claims description 3
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 claims description 3
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 claims description 3
- MFJNOXOAIFNSBX-UHFFFAOYSA-N 1-fluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1 MFJNOXOAIFNSBX-UHFFFAOYSA-N 0.000 claims description 3
- RSHBAGGASAJQCH-UHFFFAOYSA-N 1-iodo-3-methoxybenzene Chemical compound COC1=CC=CC(I)=C1 RSHBAGGASAJQCH-UHFFFAOYSA-N 0.000 claims description 3
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical compound COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 claims description 3
- HWINBBUYLKWIBO-UHFFFAOYSA-N 1-methoxy-3-propan-2-ylbenzene Chemical compound COC1=CC=CC(C(C)C)=C1 HWINBBUYLKWIBO-UHFFFAOYSA-N 0.000 claims description 3
- YIQUTYFGUKCQCY-UHFFFAOYSA-N 1-tert-butyl-2-methoxybenzene Chemical group COC1=CC=CC=C1C(C)(C)C YIQUTYFGUKCQCY-UHFFFAOYSA-N 0.000 claims description 3
- ISCSZBNBHRYDHG-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(2,5-dimethoxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound COC1=C(C=C(C=C1)OC)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C ISCSZBNBHRYDHG-UHFFFAOYSA-N 0.000 claims description 3
- KYYUIWYESGCESW-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(2-methylphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C(C)(C)(C)C=1C(C(=CC(C=1)=CC1=C(C=CC=C1)C)C(C)(C)C)=O KYYUIWYESGCESW-UHFFFAOYSA-N 0.000 claims description 3
- KVVYAFNPDCBJNJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3-fluorophenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC(F)=C1 KVVYAFNPDCBJNJ-UHFFFAOYSA-N 0.000 claims description 3
- RKRMNTKNIMMDCP-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3-nitrophenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC([N+]([O-])=O)=C1 RKRMNTKNIMMDCP-UHFFFAOYSA-N 0.000 claims description 3
- HDOZCKSWZCDDIU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(4-ethylphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C(C)C1=CC=C(C=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C HDOZCKSWZCDDIU-UHFFFAOYSA-N 0.000 claims description 3
- LCPSMZHRXVCYMO-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(4-fluorophenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C(C)(C)(C)C=1C(C(=CC(C1)=CC1=CC=C(C=C1)F)C(C)(C)C)=O LCPSMZHRXVCYMO-UHFFFAOYSA-N 0.000 claims description 3
- AASIYXCYZZBJQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(4-methylphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1(=CC=C(C=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C)C AASIYXCYZZBJQU-UHFFFAOYSA-N 0.000 claims description 3
- NJIYPCPZILAPKS-UHFFFAOYSA-N 2-methoxy-1,3-di(propan-2-yl)benzene Chemical compound COC1=C(C(C)C)C=CC=C1C(C)C NJIYPCPZILAPKS-UHFFFAOYSA-N 0.000 claims description 3
- GFNZJAUVJCGWLW-UHFFFAOYSA-N 2-methoxy-1,3-dimethylbenzene Chemical compound COC1=C(C)C=CC=C1C GFNZJAUVJCGWLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 3
- KVKBXFODXZVSIX-UHFFFAOYSA-N 4-[(2-bromophenyl)methylidene]-2,6-ditert-butylcyclohexa-2,5-dien-1-one Chemical compound BrC1=C(C=C2C=C(C(C(=C2)C(C)(C)C)=O)C(C)(C)C)C=CC=C1 KVKBXFODXZVSIX-UHFFFAOYSA-N 0.000 claims description 3
- FDLNSYALUHVOFE-UHFFFAOYSA-N 4-[(3,5-ditert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]benzaldehyde Chemical compound CC(C)(C)C1=CC(=CC2=CC=C(C=C2)C=O)C=C(C1=O)C(C)(C)C FDLNSYALUHVOFE-UHFFFAOYSA-N 0.000 claims description 3
- ARGBWAVMKGOIDU-UHFFFAOYSA-N 4-benzylidene-2,6-diphenylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C=2C=CC=CC=2)C(=O)C(C=2C=CC=CC=2)=CC1=CC1=CC=CC=C1 ARGBWAVMKGOIDU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- NNZRVXTXKISCGS-UHFFFAOYSA-N 1-methoxy-2-propan-2-ylbenzene Chemical compound COC1=CC=CC=C1C(C)C NNZRVXTXKISCGS-UHFFFAOYSA-N 0.000 claims description 2
- DKQAIUAVVFPNRF-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(2-methoxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C(C)(C)(C)C=1C(C(=CC(C1)=CC1=C(C=CC=C1)OC)C(C)(C)C)=O DKQAIUAVVFPNRF-UHFFFAOYSA-N 0.000 claims description 2
- HMZXLCKUQUILES-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,4-dimethoxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C=C1C=C(C(C)(C)C)C(=O)C(C(C)(C)C)=C1 HMZXLCKUQUILES-UHFFFAOYSA-N 0.000 claims description 2
- YRLDRQMKESMMBC-UHFFFAOYSA-N 2,6-ditert-butyl-4-[[4-(trifluoromethyl)phenyl]methylidene]cyclohexa-2,5-dien-1-one Chemical compound FC(C1=CC=C(C=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C)(F)F YRLDRQMKESMMBC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000006305 3-iodophenyl group Chemical group [H]C1=C([H])C(I)=C([H])C(*)=C1[H] 0.000 claims description 2
- KLWTVMSRSYMLKS-UHFFFAOYSA-N 4-[(3-bromophenyl)methylidene]-2,6-ditert-butylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=CC(Br)=C1 KLWTVMSRSYMLKS-UHFFFAOYSA-N 0.000 claims description 2
- UWAVGFQNQOCUQH-UHFFFAOYSA-N 4-[(4-bromophenyl)methylidene]-2,6-ditert-butylcyclohexa-2,5-dien-1-one Chemical compound BrC1=CC=C(C=C2C=C(C(C(=C2)C(C)(C)C)=O)C(C)(C)C)C=C1 UWAVGFQNQOCUQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 2
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JBGVGINLCNYKLP-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3-methoxyphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound COC=1C=C(C=CC=1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C JBGVGINLCNYKLP-UHFFFAOYSA-N 0.000 claims 1
- HZYGDLBPFQGNGZ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(4-tert-butylphenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound C(C)(C)(C)C1=CC=C(C=C1)C=C1C=C(C(C(=C1)C(C)(C)C)=O)C(C)(C)C HZYGDLBPFQGNGZ-UHFFFAOYSA-N 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 114
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 94
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 56
- 238000004440 column chromatography Methods 0.000 description 55
- 229910052757 nitrogen Inorganic materials 0.000 description 47
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 4
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 4
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical compound COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 4
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- HZXKDBNTDXFOIG-UHFFFAOYSA-N 1-methoxy-2-propan-2-yloxybenzene Chemical compound COC1=CC=CC=C1OC(C)C HZXKDBNTDXFOIG-UHFFFAOYSA-N 0.000 description 2
- XAAYORJUOMYYAQ-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(2-fluorophenyl)methylidene]cyclohexa-2,5-dien-1-one Chemical compound FC1=C(C=C2C=C(C(C(=C2)C(C)(C)C)=O)C(C)(C)C)C=CC=C1 XAAYORJUOMYYAQ-UHFFFAOYSA-N 0.000 description 2
- BYLXXCGOKJOSNY-UHFFFAOYSA-N 2-butylcyclohexa-2,5-dien-1-one Chemical compound CCCCC1=CCC=CC1=O BYLXXCGOKJOSNY-UHFFFAOYSA-N 0.000 description 2
- KWVFKUXYRNZFCX-UHFFFAOYSA-N 4-benzylidene-2,6-di(propan-2-yl)cyclohexa-2,5-dien-1-one Chemical compound C1=C(C(C)C)C(=O)C(C(C)C)=CC1=CC1=CC=CC=C1 KWVFKUXYRNZFCX-UHFFFAOYSA-N 0.000 description 2
- AIJTYOKWWVAWQF-UHFFFAOYSA-N 4-benzylidene-2,6-dimethylcyclohexa-2,5-dien-1-one Chemical compound C1=C(C)C(=O)C(C)=CC1=CC1=CC=CC=C1 AIJTYOKWWVAWQF-UHFFFAOYSA-N 0.000 description 2
- KBTMGSMZIKLAHN-UHFFFAOYSA-N 4-bromo-1,2-dimethoxybenzene Chemical compound COC1=CC=C(Br)C=C1OC KBTMGSMZIKLAHN-UHFFFAOYSA-N 0.000 description 2
- BWIOURVJVDKDOC-UHFFFAOYSA-N 6-bromo-1-(chloromethyl)-2-methoxynaphthalene Chemical compound C1=C(Br)C=CC2=C(CCl)C(OC)=CC=C21 BWIOURVJVDKDOC-UHFFFAOYSA-N 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940116837 methyleugenol Drugs 0.000 description 2
- PRHTXAOWJQTLBO-UHFFFAOYSA-N methyleugenol Natural products COC1=CC=C(C(C)=C)C=C1OC PRHTXAOWJQTLBO-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 2
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 2
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JUVLYFQRUBLHEH-UHFFFAOYSA-N tert-butyl 4-(5-formyl-1,3-thiazol-2-yl)piperazine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCN1C1=NC=C(C=O)S1 JUVLYFQRUBLHEH-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 125000001617 2,3-dimethoxy phenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- AXTGHEHNZBIWGM-UHFFFAOYSA-N 3-benzylidene-1,5-ditert-butylcyclohexa-1,4-diene Chemical compound C1=C(C(C)(C)C)CC(C(C)(C)C)=CC1=CC1=CC=CC=C1 AXTGHEHNZBIWGM-UHFFFAOYSA-N 0.000 description 1
- JDILELFDHRSELN-UHFFFAOYSA-N 4-[(3,5-ditert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]benzonitrile Chemical compound C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=CC1=CC1=CC=C(C#N)C=C1 JDILELFDHRSELN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PLPHFNBDZUFZQV-UHFFFAOYSA-N FC(C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C)(F)F Chemical compound FC(C1=CC=C(C=C1)C1C=C(C(C(=C1)C(C=C)(C)C)=O)C(C)(C)C)(F)F PLPHFNBDZUFZQV-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical class O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000003430 hydroarylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- Chemical & Material Sciences (AREA)
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Abstract
本发明提供了一种高效、高选择性合成含不同取代官能团的4‑二芳基甲基取代酚类化合物的方法，其采用溴化锌和三甲基氯硅烷作为催化剂，以芳基醚与4‑芳基亚甲基‑2,6‑二烷基/芳基‑2,5‑环己二烯‑1‑酮类化合物作为反应底物，反应体系加入了有机溶剂。该方法的优点：催化剂廉价易得；底物适用性高；反应条件温和，安全可靠；所得目标产物的选择性接近100%，产率较高。该方法解决了传统合成4‑二芳基甲基取代酚类化合物的反应选择性差、反应步骤繁琐、产率低以及需要用到对环境有害试剂等不足，具有良好的工业应用前景。本发明同时还提供了对应的含不同取代官能团的4‑二芳基甲基取代酚类衍生物。The invention provides an efficient and highly selective method for synthesizing 4-diarylmethyl-substituted phenolic compounds containing different substituted functional groups, which uses zinc bromide and trimethylchlorosilane as catalysts, and uses aryl ether and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds are used as reaction substrates, and organic solvents are added to the reaction system. The advantages of this method are: the catalyst is cheap and easy to obtain; the substrate has high applicability; the reaction conditions are mild, safe and reliable; the selectivity of the target product is close to 100%, and the yield is high. This method solves the shortcomings of traditional synthesis of 4-diarylmethyl-substituted phenolic compounds such as poor reaction selectivity, cumbersome reaction steps, low yield, and the need for environmentally harmful reagents, and has good industrial application prospects. The present invention also provides corresponding 4-diarylmethyl substituted phenolic derivatives containing different substituted functional groups.
Description
技术领域Technical field
本发明涉及二芳基甲基取代酚类化合物的催化合成领域，具体地说涉及一种以芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物高效反应制备含4-二芳基甲基取代酚类衍生物的合成方法。The present invention relates to the field of catalytic synthesis of diarylmethyl-substituted phenolic compounds, specifically a method using aryl ether and 4-aryl methylene-2,6-dialkyl/aryl-2,5 -A synthetic method for preparing 4-diarylmethyl-substituted phenolic derivatives through efficient reaction of cyclohexadien-1-one compounds.
背景技术Background technique
4-二芳基甲基取代酚类化合物是一类重要的有机合成中间体。它们在医药中间体、农药、抗氧剂、光电材料、高效阻燃剂以及催化剂配体的制备等方面有着广泛应用。4-Diarylmethyl-substituted phenolic compounds are an important class of organic synthesis intermediates. They are widely used in the preparation of pharmaceutical intermediates, pesticides, antioxidants, optoelectronic materials, efficient flame retardants and catalyst ligands.
4-二芳基甲基取代酚类化合物由于其羟基的可修饰性，使得该类衍生物在有机合成及药物等其他领域的应用更加广泛，特别是含有芳杂环的4-二芳基甲基取代酚类化合物具有更大的潜在研究意义。Due to the modifiable nature of its hydroxyl group, 4-diarylmethyl-substituted phenolic compounds have become more widely used in other fields such as organic synthesis and medicine, especially 4-diarylmethyl containing aromatic heterocycles. Substituted phenolic compounds have greater potential research significance.
目前文献已报道的合成4-二芳基甲基取代酚类化合物的方法主要包括：（1）膦或布朗斯特酸催化p-QMs类化合物与萘酚类化合物的氢芳基化反应，利用萘酚类化合物α-H或β-H活性较高的优势，针对p-QMs类化合物的C=C键进行选择性活化；（2）傅克烷基化反应：利用二芳基甲基卤代烷烃类化合物与芳烃类化合物在路易斯酸（三氯化铝、氯化锌等）的催化下发生傅克烷基化反应；（3）Suzuki交叉偶联反应：利用二芳基甲基卤代烷烃类化合物与芳硼酸酯在过渡金属的催化下发生交叉偶联反应。但是，上述方法存在着反应底物结构复杂、催化剂（Pd、Ni）比较昂贵，而且还存在着实验步骤繁琐、且难以回收利用、反应条件苛刻、底物适用性较差、反应的选择性及产率较低以及对环境的污染较大等缺陷。The methods for synthesizing 4-diarylmethyl-substituted phenolic compounds currently reported in the literature mainly include: (1) Hydroarylation reaction of p -QMs compounds and naphthol compounds catalyzed by phosphine or Brönsted acid, using Naphthol compounds have the advantage of higher α-H or β-H activity, and can selectively activate the C=C bond of p -QMs compounds; (2) Friedel-Crafts alkylation reaction: using diarylmethyl halogenated alkanes Friedel-Crafts alkylation reaction occurs between compounds and aromatic hydrocarbons under the catalysis of Lewis acids (aluminum trichloride, zinc chloride, etc.); (3) Suzuki cross-coupling reaction: using diarylmethyl haloalkanes and aromatic boron Acid esters undergo cross-coupling reactions catalyzed by transition metals. However, the above methods have complex reaction substrate structures, relatively expensive catalysts (Pd, Ni), cumbersome experimental steps, difficulty in recycling, harsh reaction conditions, poor substrate applicability, and poor reaction selectivity. It has shortcomings such as lower yield and greater environmental pollution.
迄今为止，4-二芳基甲基取代酚类化合物及其衍生物的高效合成存在着原料质量、生产的安全性（路易斯酸具有较强的腐蚀性）以及产品的稳定性及纯度等几个方面的难题，合成技术难度较大，目前只有美国、德国和日本等几家公司在生产，而我国高端酚类化工产品目前的情况主要是依靠于进口。So far, the efficient synthesis of 4-diarylmethyl substituted phenolic compounds and their derivatives has several issues such as raw material quality, production safety (Lewis acids are highly corrosive), and product stability and purity. The synthesis technology is relatively difficult. At present, only a few companies such as the United States, Germany and Japan are producing it. However, my country's high-end phenolic chemical products currently mainly rely on imports.
针对现有的4-二芳基甲基取代酚类化合物合成工艺的不足，业界正着力于利用廉价催化剂高效催化研制由稳定、廉价易得的醚类化合物与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物作为合成砌块制备对应的4-二芳基甲基取代酚类化合物的新方法。In view of the shortcomings of the existing synthesis process of 4-diarylmethyl-substituted phenolic compounds, the industry is focusing on using cheap catalysts to efficiently catalyze the development of stable, cheap and easily available ether compounds and 4-arylmethylene-2 , a new method for preparing the corresponding 4-diarylmethyl substituted phenolic compounds by using 6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds as synthetic building blocks.
发明内容Contents of the invention
本发明的目的是提供一种由廉价易得的芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物作为原料的高效、高选择性合成对应的4-二芳基甲基取代酚类化合物的新方法，以克服现有技术中的上述缺陷。The object of the present invention is to provide a kind of aryl ether and 4-aryl methylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds which are cheap and easy to obtain. A new method for efficiently and highly selectively synthesizing corresponding 4-diarylmethyl-substituted phenolic compounds as raw materials to overcome the above-mentioned defects in the existing technology.
本发明包含下述步骤：取反应量的芳基醚、4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮、催化剂和有机溶剂在空气环境下置于反应容器中进行混合，在搅拌下于25~100 oC下反应1~6小时，即制得相应的含不同取代官能团的4-二芳基甲基取代酚类化合物。具体反应式如下：The invention includes the following steps: taking reaction amounts of aryl ether, 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one, catalyst and organic The solvent is placed in a reaction vessel in an air environment for mixing, and the reaction is carried out under stirring at 25 to 100 o C for 1 to 6 hours to prepare corresponding 4-diarylmethyl substituted phenolic compounds containing different substituted functional groups. . The specific reaction formula is as follows:
（I） (I)
其中，in,
所述催化剂为溴化锌和三甲基氯硅烷，有机溶剂为二氯甲烷；The catalyst is zinc bromide and trimethylchlorosilane, and the organic solvent is methylene chloride;
Ar1是选自苯基、4-甲基苯基、4-乙基苯基、4-叔丁基苯基、4-苄氧基苯基、2-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、3-甲氧基-4-羟基苯基、3,4-二甲氧基苯基、2,5-二甲氧基苯基、4-氟苯基、4-溴苯基、4-氰基苯基、4-甲酰基苯基、4-三氟甲基苯基、2-氟苯基、2-溴苯基、3-氟苯基、3-溴苯基、3-氰基苯基、3-硝基苯基、6-苯并-2,3-二氢呋喃基；Ar 1 is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-benzyloxyphenyl, 2-methylphenyl, 2-methoxy Phenyl, 3-methoxyphenyl, 3-methoxy-4-hydroxyphenyl, 3,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 4-fluorophenyl , 4-bromophenyl, 4-cyanophenyl, 4-formylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 2-bromophenyl, 3-fluorophenyl, 3- Bromophenyl, 3-cyanophenyl, 3-nitrophenyl, 6-benzo-2,3-dihydrofuryl;
R1是选自甲基、异丙基、叔丁基、苯基；R 1 is selected from methyl, isopropyl, tert-butyl, and phenyl;
Ar2是选自2-甲氧基苯基、2-异丙氧基苯基、2-叔丁基苯基、2-异丙基苯基、2-乙基苯基、2-甲基苯基、3-甲氧基苯基、3-异丙基苯基、2,6-二异丙基苯基、2,6-二甲基苯基、2,3-二甲氧基苯基、3-烯丙基-6-羟基苯基、3-烯丙基-6-甲氧基苯基、2-甲氧基-5-溴苯基、2-氟苯基、2-氯苯基、2-溴苯基、2-苯基苯基、2-甲酰基苯基、3-氟苯基、3-氯苯基、3-溴苯基、3-碘苯基；Ar 2 is selected from 2-methoxyphenyl, 2-isopropoxyphenyl, 2-tert-butylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 2-methylbenzene base, 3-methoxyphenyl, 3-isopropylphenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,3-dimethoxyphenyl, 3-allyl-6-hydroxyphenyl, 3-allyl-6-methoxyphenyl, 2-methoxy-5-bromophenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-phenylphenyl, 2-formylphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-iodophenyl;
R2是选自甲基、乙基、丙基、苄基、烯丙基、炔丙基、苯基。R 2 is selected from methyl, ethyl, propyl, benzyl, allyl, propargyl, and phenyl.
上述由芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物合成4-二芳基甲基取代酚类化合物的方法中，4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮是选自4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-乙基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-叔丁基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-苄氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（2-甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（2-甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-甲氧基-3-羟基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3,4-二甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（2,5-二甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-氰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-甲酰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（4-三氟甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（2-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（2-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-氰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（3-硝基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-（6-苯并-2,3-二氢呋喃基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、4-苯基亚甲基-2,6-二甲基-2,5-环己二烯-1-酮、4-苯基亚甲基-2,6-二异丙基-2,5-环己二烯-1-酮、4-苯基亚甲基-2,6-二苯基-2,5-环己二烯-1-酮。The above synthesis of 4-diarylmethyl substituted phenols from aryl ethers and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds In the method of the compound, 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one is selected from 4-phenylmethylene-2,6 -Di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4-methylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 4-(4-ethylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4-tert-butylbenzene methyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4-benzyloxyphenyl)methylene-2,6-di-tert-butyl methyl-2,5-cyclohexadien-1-one, 4-(2-methylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , 4-(2-methoxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(3-methoxyphenyl)methylene Methyl-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(3-methoxy-3-hydroxyphenyl)methylene-2,6-di-tert Butyl-2,5-cyclohexadien-1-one, 4-(3,4-dimethoxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien En-1-one, 4-(2,5-dimethoxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4 -Fluorophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4-bromophenyl)methylene-2,6-di-tert. Butyl-2,5-cyclohexadien-1-one, 4-(4-cyanophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 4-(4-formylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(4-trifluoromethylphenyl) Methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(2-fluorophenyl)methylene-2,6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4-(2-bromophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(3 -Fluorophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(3-bromophenyl)methylene-2,6-di-tert. Butyl-2,5-cyclohexadien-1-one, 4-(3-cyanophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 4-(3-nitrophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-(6-benzo-2,3- Dihydrofuryl)methylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 4-phenylmethylene-2,6-dimethyl-2,5 -Cyclohexadien-1-one, 4-phenylmethylene-2,6-diisopropyl-2,5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diphenyl-2,5-cyclohexadien-1-one.
上述由芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物合成4-二芳基甲基取代酚类化合物的方法中，芳基醚是选自苯甲醚、2-甲氧基苯甲醚、2-异丙氧基苯甲醚、2-叔丁基苯甲醚、2-异丙基苯甲醚、2-乙基苯甲醚、2-甲基苯甲醚、3-甲氧基苯甲醚、3-异丙基苯甲醚、2,6-二异丙基苯甲醚、2,6-二甲基苯甲醚、1,2,3-三甲氧基苯、丁香酚、甲基丁香酚、2-甲氧基-5-溴苯甲醚、2-氟苯甲醚、2-氯苯甲醚、2-溴苯甲醚、2-苯基苯甲醚、2-甲氧基苯甲醛、3-氟苯甲醚、3-氯苯甲醚、3-溴苯甲醚、3-碘苯甲醚、苯乙醚、苯丙醚、苯基苄基醚、苯基烯丙基醚、苯基炔丙基醚、二苯醚。The above synthesis of 4-diarylmethyl substituted phenols from aryl ethers and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds In the method of compound, the aryl ether is selected from anisole, 2-methoxyanisole, 2-isopropoxyanisole, 2-tert-butylanisole, 2-isopropylbenzole Ether, 2-ethylanisole, 2-methylanisole, 3-methoxyanisole, 3-isopropylanisole, 2,6-diisopropylanisole, 2, 6-Dimethylanisole, 1,2,3-trimethoxybenzene, eugenol, methyleugenol, 2-methoxy-5-bromoanisole, 2-fluoroanisole, 2- Chloroanisole, 2-bromoanisole, 2-phenylanisole, 2-methoxybenzaldehyde, 3-fluoroanisole, 3-chloroanisole, 3-bromoanisole, 3 - Iodoanisole, phenylethyl ether, phenylpropyl ether, phenyl benzyl ether, phenyl allyl ether, phenyl propargyl ether, diphenyl ether.
上述由芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物合成4-二芳基甲基取代酚类化合物的方法中，所述4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物与芳基醚的摩尔比为1：[1.0~1.2]，最优选为1：1； 4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物与溴化锌以及三甲基氯硅烷的摩尔比为1：[0.05~0.2]：[0.05~0.2]，最优选为1：0.05：0.05。The above synthesis of 4-diarylmethyl substituted phenols from aryl ethers and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds In the method of compound, the molar ratio of the 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compound and the aryl ether is 1: [1.0~1.2], most preferably 1:1; 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds and zinc bromide And the molar ratio of trimethylsilyl chloride is 1:[0.05~0.2]:[0.05~0.2], most preferably 1:0.05:0.05.
本发明所提供由基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物高效、高选择性的合成4-二芳基甲基取代酚类化合物的方法，反应过程温和易控制。在获得较高产率和100%选择性的同时，该方法简单易行，而且所用催化剂廉价易得，制备简单、具有良好的工业应用前景。The invention provides an efficient and highly selective synthesis of 4-methyl ether and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-one compounds. The method of substituting phenolic compounds with diarylmethyl has a mild and easy-to-control reaction process. While obtaining a high yield and 100% selectivity, the method is simple and easy to implement, the catalyst used is cheap and easily available, the preparation is simple, and it has good industrial application prospects.
【具体实施方式】【Detailed ways】
下面结合本发明的实施例对本发明做进一步说明：The present invention will be further described below in conjunction with the embodiments of the present invention:
一、测试与分析1. Testing and Analysis
本发明下述实施例中反应产物的结构分析采用Agilent公司生产的配置HP-5MS毛细管色谱柱(30m×0.45mm×0.8μm)的气相-质谱仪联用仪GC/MS (6890N/5973N)以及Bruker公司生产的Bruker Avance-III 500核磁共振分析仪。目标产物选择性和产率则采用由Bruker公司生产的Bruker Avance-III 500核磁共振分析仪进行分析 。The structural analysis of the reaction products in the following examples of the present invention adopts the gas chromatography-mass spectrometer GC/MS (6890N/5973N) equipped with HP-5MS capillary chromatography column (30m×0.45mm×0.8μm) produced by Agilent Company and Bruker Avance-III 500 NMR analyzer produced by Bruker. The target product selectivity and yield were analyzed using a Bruker Avance-III 500 nuclear magnetic resonance analyzer produced by Bruker Company.
二、实施例2. Embodiments
实施例1Example 1
准备一组平行反应，将54.0 mg (0.5 mmol) 的苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg(0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，分别于25 oC、40 oC、60 oC、80 oC、100 oC搅拌反应3小时。待反应结束后，经气相色谱分析，目标产物在反应温度为80 oC时产率最高，为96%（气相色谱产率，十二烷作为内标，采用归一法进行计算）。Prepare a parallel reaction by adding 54.0 mg (0.5 mmol) of anisole and 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene. -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, respectively at 25 Stir the reaction at o C, 40 o C, 60 o C, 80 o C, and 100 o C for 3 hours. After the reaction was completed, gas chromatography analysis showed that the yield of the target product was the highest when the reaction temperature was 80 o C, which was 96% (gas chromatography yield, dodecane was used as the internal standard, and the normalization method was used for calculation).
实施例2Example 2
将54.0 mg (0.5 mmol) 的苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为94%。Combine 54.0 mg (0.5 mmol) of anisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir for 3 hours at 80 ° C. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
实施例3Example 3
将54.0 mg (0.5 mmol) 的苯甲醚、154 mg (0.5 mmol)的4-（4-甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为92%。Add 54.0 mg (0.5 mmol) of anisole, 154 mg (0.5 mmol) of 4-(4-methylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
实施例4Example 4
将54.0 mg (0.5 mmol) 的苯甲醚、161 mg (0.5 mmol)的4-（4-乙基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为84%。54.0 mg (0.5 mmol) of anisole, 161 mg (0.5 mmol) of 4-(4-ethylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
实施例5Example 5
将54.0 mg (0.5 mmol) 的苯甲醚、175 mg (0.5 mmol)的4-（4-叔丁基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为91%。54.0 mg (0.5 mmol) of anisole, 175 mg (0.5 mmol) of 4-(4-tert-butylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
实施例6Example 6
将54.0 mg (0.5 mmol) 的苯甲醚、200 mg (0.5 mmol)的4-（4-苄氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为83%。54.0 mg (0.5 mmol) of anisole, 200 mg (0.5 mmol) of 4-(4-benzyloxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
实施例7Example 7
将54.0 mg (0.5 mmol) 的苯甲醚、154 mg (0.5 mmol)的4-（2-甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为87%。Add 54.0 mg (0.5 mmol) of anisole, 154 mg (0.5 mmol) of 4-(2-methylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
实施例8Example 8
将54.0 mg (0.5 mmol) 的苯甲醚、162 mg (0.5 mmol)的4-（2-甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为89%。54.0 mg (0.5 mmol) of anisole, 162 mg (0.5 mmol) of 4-(2-methoxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
实施例9Example 9
将54.0 mg (0.5 mmol) 的苯甲醚、162 mg (0.5 mmol)的4-（3-甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为85%。54.0 mg (0.5 mmol) of anisole, 162 mg (0.5 mmol) of 4-(3-methoxyphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 85%.
实施例10Example 10
将54.0 mg (0.5 mmol) 的苯甲醚、170 mg (0.5 mmol)的4-（3-甲氧基-3-羟基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg(0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为78%。54.0 mg (0.5 mmol) of anisole, 170 mg (0.5 mmol) of 4-(3-methoxy-3-hydroxyphenyl)methylene-2,6-di-tert-butyl-2,5 - Cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL dichloride was added under air condition Methane, stir and react at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 78%.
实施例11Example 11
将54.0 mg (0.5 mmol) 的苯甲醚、177 mg (0.5 mmol)的4-（3,4-二甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为79%。54.0 mg (0.5 mmol) of anisole, 177 mg (0.5 mmol) of 4-(3,4-dimethoxyphenyl)methylene-2,6-di-tert-butyl-2,5- Cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL methylene chloride was added under air condition. , stir and react at 80 o C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
实施例12Example 12
将54.0 mg (0.5 mmol) 的苯甲醚、177 mg (0.5 mmol)的4-（2,5-二甲氧基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为80%。54.0 mg (0.5 mmol) of anisole, 177 mg (0.5 mmol) of 4-(2,5-dimethoxyphenyl)methylene-2,6-di-tert-butyl-2,5- Cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL methylene chloride was added under air condition. , stir and react at 80 o C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 80%.
实施例13Example 13
将54.0 mg (0.5 mmol) 的苯甲醚、156 mg (0.5 mmol)的4-（4-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为86%。54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4-(4-fluorophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
实施例14Example 14
将54.0 mg (0.5 mmol) 的苯甲醚、186 mg (0.5 mmol)的4-（4-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为94%。54.0 mg (0.5 mmol) of anisole, 186 mg (0.5 mmol) of 4-(4-bromophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
实施例15Example 15
将54.0 mg (0.5 mmol) 的苯甲醚、159.5 mg (0.5 mmol)的4-（4-氰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为88%。Add 54.0 mg (0.5 mmol) of anisole, 159.5 mg (0.5 mmol) of 4-(4-cyanophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
实施例16Example 16
将54.0 mg (0.5 mmol) 的苯甲醚、161 mg (0.5 mmol)的4-（4-甲酰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为78%。54.0 mg (0.5 mmol) of anisole, 161 mg (0.5 mmol) of 4-(4-formylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 78%.
实施例17Example 17
将54.0 mg (0.5 mmol) 的苯甲醚、181 mg (0.5 mmol)的4-（4-三氟甲基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为88%。54.0 mg (0.5 mmol) of anisole, 181 mg (0.5 mmol) of 4-(4-trifluoromethylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexan Dien-1-one, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL dichloromethane was added under air conditions. Stir the reaction at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
实施例18Example 18
将54.0 mg (0.5 mmol) 的苯甲醚、156 mg (0.5 mmol)的4-（2-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为84%。54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4-(2-fluorophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
实施例19Example 19
将54.0 mg (0.5 mmol) 的苯甲醚、186 mg (0.5 mmol)的4-（2-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为83%。54.0 mg (0.5 mmol) of anisole, 186 mg (0.5 mmol) of 4-(2-bromophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
实施例20Example 20
将54.0 mg (0.5 mmol) 的苯甲醚、156 mg (0.5 mmol)的4-（3-氟苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为92%。54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4-(3-fluorophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
实施例21Example 21
将54.0 mg (0.5 mmol) 的苯甲醚、186 mg (0.5 mmol)的4-（3-溴苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为87%。54.0 mg (0.5 mmol) of anisole, 186 mg (0.5 mmol) of 4-(3-bromophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
实施例22Example 22
将54.0 mg (0.5 mmol) 的苯甲醚、159.5 mg (0.5 mmol)的4-（3-氰基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为93%。Add 54.0 mg (0.5 mmol) of anisole, 159.5 mg (0.5 mmol) of 4-(3-cyanophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
实施例23Example 23
将54.0 mg (0.5 mmol) 的苯甲醚、169.5 mg (0.5 mmol)的4-（3-硝基苯基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为93%。54.0 mg (0.5 mmol) of anisole, 169.5 mg (0.5 mmol) of 4-(3-nitrophenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
实施例24Example 24
将54.0 mg (0.5 mmol) 的苯甲醚、168 mg (0.5 mmol)的4-（6-苯并-2,3-二氢呋喃基）亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg(0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为81%。54.0 mg (0.5 mmol) of anisole, 168 mg (0.5 mmol) of 4-(6-benzo-2,3-dihydrofuryl)methylene-2,6-di-tert-butyl-2 ,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, add to the Schlenk tube under nitrogen environment, add 1.0 mL under air conditions Dichloromethane, stir and react at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 81%.
实施例25Example 25
将54.0 mg (0.5 mmol) 的苯甲醚、105 mg (0.5 mmol)的4-苯基亚甲基-2,6-二甲基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为82%。Combine 54.0 mg (0.5 mmol) of anisole, 105 mg (0.5 mmol) of 4-phenylmethylene-2,6-dimethyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions, and stir for 3 hours at 80 ° C. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 82%.
实施例26Example 26
将54.0 mg (0.5 mmol) 的苯甲醚、133 mg (0.5 mmol)的4-苯基亚甲基-2,6-二异丙基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为88%。Combine 54.0 mg (0.5 mmol) of anisole, 133 mg (0.5 mmol) of 4-phenylmethylene-2,6-diisopropyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir for 3 hours at 80 ° C. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
实施例27Example 27
将54.0 mg (0.5 mmol) 的苯甲醚、167 mg (0.5 mmol)的4-苯基亚甲基-2,6-二苯基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为90%。Combine 54.0 mg (0.5 mmol) of anisole, 167 mg (0.5 mmol) of 4-phenylmethylene-2,6-diphenyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen atmosphere, 1.0 mL dichloromethane was added under air conditions, and the reaction was stirred at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 90%.
实施例28Example 28
将69 mg (0.5 mmol) 的2-甲氧基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为86%。69 mg (0.5 mmol) of 2-methoxyanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
实施例29Example 29
将83 mg (0.5 mmol) 的2-异丙氧基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为95%。83 mg (0.5 mmol) of 2-isopropoxyanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene -1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane, were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirred reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 95%.
实施例30Example 30
将82 mg (0.5 mmol) 的2-叔丁基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为80%。82 mg (0.5 mmol) of 2-tert-butylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 80%.
实施例31Example 31
将75 mg (0.5 mmol) 的2-异丙基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为92%。75 mg (0.5 mmol) of 2-isopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
实施例32Example 32
将68 mg (0.5 mmol) 的2-乙基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为91%。68 mg (0.5 mmol) of 2-ethylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1 -Ketone, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, stir at 80 o C Reaction takes 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
实施例33Example 33
将61 mg (0.5 mmol) 的2-甲基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为94%。61 mg (0.5 mmol) of 2-methylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1 -Ketone, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, stir at 80 o C Reaction takes 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
实施例34Example 34
将69 mg (0.5 mmol) 的3-甲氧基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为93%。69 mg (0.5 mmol) of 3-methoxyanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
实施例35Example 35
将75 mg (0.5 mmol) 的3-异丙基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为90%。75 mg (0.5 mmol) of 3-isopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene- 1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, at 80 o C Stir the reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 90%.
实施例36Example 36
将96 mg (0.5 mmol) 的2,6-二异丙基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为87%。96 mg (0.5 mmol) of 2,6-diisopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexane Dien-1-one, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL dichloromethane was added under air conditions. Stir the reaction at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
实施例37Example 37
将68 mg (0.5 mmol) 的2,6-二甲基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为72%。68 mg (0.5 mmol) of 2,6-dimethylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 72%.
实施例38Example 38
将84 mg (0.5 mmol) 的1,2,3-三甲氧基苯、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为88%。84 mg (0.5 mmol) of 1,2,3-trimethoxybenzene, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexanedi En-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen environment, and 1.0 mL dichloromethane was added under air conditions, and the mixture was heated at 80 o C stirring reaction for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
实施例39Example 39
将82 mg (0.5 mmol) 的丁香酚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为83%。Combine 82 mg (0.5 mmol) of eugenol, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen atmosphere, 1.0 mL dichloromethane was added under air conditions, and the reaction was stirred at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
实施例40Example 40
将89 mg (0.5 mmol) 的甲基丁香酚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为87%。89 mg (0.5 mmol) of methyl eugenol, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir for 3 hours at 80 o C. . After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
实施例41Example 41
将108.5 mg (0.5 mmol) 的2-甲氧基-5-溴苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为73%。108.5 mg (0.5 mmol) of 2-methoxy-5-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclo Hexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025mmol) trimethylchlorosilane were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL dichloromethane was added under air conditions. Stir the reaction at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 73%.
实施例42Example 42
将63 mg (0.5 mmol) 的2-氟苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为76%。63 mg (0.5 mmol) of 2-fluoroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 76%.
实施例43Example 43
将71 mg (0.5 mmol) 的2-氯苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为79%。71 mg (0.5 mmol) of 2-chloroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
实施例44Example 44
将93.5 mg (0.5 mmol) 的2-溴苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为72%。93.5 mg (0.5 mmol) of 2-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 72%.
实施例45Example 45
将92 mg (0.5 mmol) 的2-苯基苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为93%。92 mg (0.5 mmol) of 2-phenylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1 -Ketone, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, stir at 80 o C Reaction takes 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
实施例46Example 46
将68 mg (0.5 mmol) 的2-甲氧基苯甲醛、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为69%。68 mg (0.5 mmol) of 2-methoxybenzaldehyde, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1 -Ketone, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air condition, stir at 80 o C Reaction takes 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 69%.
实施例47Example 47
将63 mg (0.5 mmol) 的3-氟苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为81%。63 mg (0.5 mmol) of 3-fluoroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 81%.
实施例48Example 48
将71 mg (0.5 mmol) 的3-氯苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为82%。71 mg (0.5 mmol) of 3-chloroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 82%.
实施例49Example 49
将93.5 mg (0.5 mmol) 的3-溴苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为84%。93.5 mg (0.5 mmol) of 3-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
实施例50Example 50
将117 mg (0.5 mmol) 的3-碘苯甲醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为89%。117 mg (0.5 mmol) of 3-iodoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
实施例51Example 51
将61 mg (0.5 mmol) 的苯乙醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为92%。Combine 61 mg (0.5 mmol) of phenylethyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen atmosphere, 1.0 mL dichloromethane was added under air conditions, and the reaction was stirred at 80 ° C for 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
实施例52Example 52
将68 mg (0.5 mmol) 的苯丙醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为94%。Combine 68 mg (0.5 mmol) of phenylpropyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir for 3 hours at 80 ° C. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
实施例53Example 53
将92 mg (0.5 mmol) 的苯基苄基醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为86%。92 mg (0.5 mmol) of phenyl benzyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylsilyl chloride, add to the Schlenk tube under nitrogen environment, add 1.0 mL dichloromethane under air conditions, and stir at 80 o C for reaction 3 Hour. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
实施例54Example 54
将67 mg (0.5 mmol) 的苯基烯丙基醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为78%。67 mg (0.5 mmol) of phenyl allyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 78%.
实施例55Example 55
将66 mg (0.5 mmol) 的苯基炔丙基醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为74%。66 mg (0.5 mmol) of phenyl propargyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadiene-1- Ketone, 5.6 mg (0.025 mmol) zinc bromide, and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir the reaction at 80 o C. 3 hours. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 74%.
实施例56Example 56
将85 mg (0.5 mmol) 的二苯醚、147 mg (0.5 mmol)的4-苯基亚甲基-2,6-二叔丁基-2,5-环己二烯-1-酮、5.6 mg (0.025 mmol)溴化锌、2.7 mg (0.025 mmol)三甲基氯硅烷，在氮气环境下加入Schlenk管里，在空气条件下加入1.0 mL二氯甲烷，于80 oC搅拌反应3小时。待反应结束后，经过柱层析色谱分离提纯，目标产物的产率为86%。Combine 85 mg (0.5 mmol) of diphenyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide and 2.7 mg (0.025 mmol) trimethylsilyl chloride were added to the Schlenk tube under nitrogen. Add 1.0 mL dichloromethane under air conditions and stir for 3 hours at 80 ° C. After the reaction is completed, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
由上述实施例可以看出，本发明所采用的利用芳基醚与4-芳基亚甲基-2,6-二烷基/芳基-2,5-环己二烯-1-酮类化合物高效反应制备相应的含不同取代官能团的4-二芳基甲基取代酚类化合物的方法具有反应条件温和、催化剂廉价易得以及制备简单等优点。此外，该方法还具有底物适用性广、高产率等优点，提供了一种高效合成含不同取代官能团的4-二芳基甲基取代酚类化合物的方法。It can be seen from the above examples that the method used in the present invention utilizes aryl ethers and 4-arylmethylene-2,6-dialkyl/aryl-2,5-cyclohexadien-1-ones. The method of efficiently reacting compounds to prepare corresponding 4-diarylmethyl-substituted phenolic compounds containing different substituted functional groups has the advantages of mild reaction conditions, cheap and easily available catalysts, and simple preparation. In addition, this method also has the advantages of wide substrate applicability and high yield, and provides an efficient method for synthesizing 4-diarylmethyl-substituted phenolic compounds containing different substituted functional groups.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the patent scope of the present invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112867A (en) * | 1989-04-28 | 1992-05-12 | Kyowa Hakko Gogyo Co., Ltd. | Triphenylmethane derivatives |
| WO1998057922A1 (en) * | 1997-06-17 | 1998-12-23 | Sumitomo Chemical Company, Limited | Triphenylmethane derivatives and use thereof |
| US6365765B1 (en) * | 1999-06-10 | 2002-04-02 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
| CN109879731A (en) * | 2019-02-27 | 2019-06-14 | 华东师范大学 | A class of diarylmethane halogenated olefin derivatives and preparation method thereof |
| CN114369011A (en) * | 2022-01-21 | 2022-04-19 | 湖南理工学院 | Green novel method for preparing 2-diarylmethyl substituted-1-naphthol compound |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112867A (en) * | 1989-04-28 | 1992-05-12 | Kyowa Hakko Gogyo Co., Ltd. | Triphenylmethane derivatives |
| WO1998057922A1 (en) * | 1997-06-17 | 1998-12-23 | Sumitomo Chemical Company, Limited | Triphenylmethane derivatives and use thereof |
| US6365765B1 (en) * | 1999-06-10 | 2002-04-02 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
| CN109879731A (en) * | 2019-02-27 | 2019-06-14 | 华东师范大学 | A class of diarylmethane halogenated olefin derivatives and preparation method thereof |
| CN114369011A (en) * | 2022-01-21 | 2022-04-19 | 湖南理工学院 | Green novel method for preparing 2-diarylmethyl substituted-1-naphthol compound |
Non-Patent Citations (1)
| Title |
|---|
| Sampath Thavaselvan等.《Organic Letters》/Nickel-Catalyzed Cyclization Strategy for the Synthesis of Pyrroloquinolines, Indoloquinolines, and Indoloisoquinolines.2020,第22卷(第10期),第3810–3814页. * |
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