CN107445795B - 一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 - Google Patents
一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 Download PDFInfo
- Publication number
- CN107445795B CN107445795B CN201710692303.8A CN201710692303A CN107445795B CN 107445795 B CN107445795 B CN 107445795B CN 201710692303 A CN201710692303 A CN 201710692303A CN 107445795 B CN107445795 B CN 107445795B
- Authority
- CN
- China
- Prior art keywords
- compound
- bromo
- tetrafluoroethyl
- formula
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 155
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 1, 2-dibromotetrafluoroethane compound Chemical class 0.000 claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 96
- 239000011941 photocatalyst Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002390 heteroarenes Chemical class 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical class P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 150000001448 anilines Chemical group 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- KVBKAPANDHPRDG-UHFFFAOYSA-N dibromotetrafluoroethane Chemical compound FC(F)(Br)C(F)(F)Br KVBKAPANDHPRDG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- RZXZIZDRFQFCTA-UHFFFAOYSA-N teflurane Chemical group FC(Br)C(F)(F)F RZXZIZDRFQFCTA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 36
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 239000000460 chlorine Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 238000003756 stirring Methods 0.000 description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 description 18
- 238000006073 displacement reaction Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical group FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 description 2
- KOFLVDBWRHFSAB-UHFFFAOYSA-N 1,2,4,5-tetrahydro-1-(phenylmethyl)-5,9b(1',2')-benzeno-9bh-benz(g)indol-3(3ah)-one Chemical compound C1C(C=2C3=CC=CC=2)C2=CC=CC=C2C23C1C(=O)CN2CC1=CC=CC=C1 KOFLVDBWRHFSAB-UHFFFAOYSA-N 0.000 description 1
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005071 nonynyl group Chemical group C(#CCCCCCCC)* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/25—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
- C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
- C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon 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
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0081—Substituted in position 17 alfa and 17 beta
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本专利公开了一种简便条件下制备2‑溴‑1,1,2,2‑四氟乙基取代的芳基砌块的合成方法,该方法由苯胺和1,2‑二溴四氟乙烷化合物出发,在蓝色可见光LED照射下,以铱,钌等过渡金属为核心的配合物充当催化剂,高效率地得到各种溴四氟乙烷取代的苯胺结构,进一步在对氨基进行衍生化从而制备多种2‑溴‑1,1,2,2‑四氟乙基芳烃化合物。该方法使用廉价易得的苯胺及其衍生物和二溴四氟乙烷为原料,具有催化剂用量少,底物适用范围广,操作简便,反应效率高等优点,反应结束后另一个溴原子得到了很好的保留,同时,这些产品可以很容易转化成1,1,2,2‑四氟乙基桥连的化合物,在农药,液晶材料,分子影像等领域有着十分广泛而重要的用途。
Description
技术领域
本发明涉及化学合成技术领域,具体涉及一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法。
背景技术
由于引入的氟烷基能改变有机化合物的化学,物理和生物活性的能力,氟代烷基化反应的发展引起了广泛的关注。四氟乙基是一类重要的氟代烷基,四氟乙烯桥(-CF2CF2-)在材料和农用化学研究中都有许多应用。通常,通过氟化方法制备ArCF2CF2Ar的结构,例如氟加成芳基乙炔或1,2-二羰基化合物的脱氧氟化。最近,Gouverneur,Togni,Beier和Hu使用氟代烷基转移方法。在这些反应中,使用芳基CF2CF2Br,芳基CF2CF2SiMe3和高价碘试剂作为氟烷基化试剂。而这些试剂最基本的原料是ArCF2CF2Br,因此,高效的制备ArCF2CF2Br对于这些四氟乙烯基团转移反应是必不可少的。传统上,按照两步法,由芳基溴制备ArCF2CF2Br。方法制备过程中必须使用格氏试剂和二乙氨基三氟化硫(DAST),因此这种方法具有底物范围窄和环境不友好的特点,从而限制了其在有机合成中的广泛应用。
BrCF2CF2Br是一类十分廉价的工业原料,由于氟原子的存在,该化合物十分稳定,很难发生亲核取代反应之外的其他反应。因此利用该原料探索一种高效、简洁、普遍适用的2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法具有显著的意义。
发明内容
本发明意在提供一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,以解决现有技术无法高效、简洁的合成该类化合物的缺陷。
本方案中的一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,包括以下步骤:于乙腈溶剂中,在可见光的照射下,以含钌或铱的络合物为光催化剂,在碱存在的条件下,将式A化合物与式B化合物进行反应,从而形成式C化合物,化合物C经过转化得到化合物D;化学式如下:
上述各式中,R1为氢、C1-10的烷基、烷基-羰基或甲酰基;
R2、R3、R4、R5各自独立地为H、C1-10烷基、卤代的C1-10烷基、C2-10烯基、卤代的C2-10烯基、C2-10炔基、被卤素或者苯基取代的C2-10炔基或卤素中的一种;
R6为H、C1-10烷基、C2-10烯基、C2-10炔基、-COOC1-10烷基、C1-10烷基-羰基、取代或未取代的苯基、取代或未取代的杂芳烃、C1-10烷基取代的膦酸基、C1-10烷基取代的亚膦酸基或卤素的一种。
化合物C转化成其他种类的2-溴-1,1,2,2-四氟乙基化试剂,如下所示:
式2.1在稀盐酸水溶液中,加入亚硝酸钠,碘化钾在-10℃至室温下,将C-1化合物反应为式D化合物;
化合物D是一类十分有用的化合物,可以通过各种经典的反应得到多种其他种类的2-溴-1,1,2,2-四氟乙基化试剂,具体实施例如下所示:
优选的,所述式A化合物、光催化剂、碱、式B化合物的摩尔比为1~8:0.001~0.1:1~8:1~8。
优选的,所述式A化合物、光催化剂、碱、式B化合物的摩尔比为1~3:0.005~0.01:1~3:1~3。更具体的,所述式A化合物、光催化剂、碱、式B化合物的摩尔比为1~3:0.005~0.01:0.5~2:1~3
优选的,所述的反应在0℃~60℃下进行,进一步优选的,所述的反应在10℃~50℃下进行。
优选的,所述的光催化剂选自:Ir(PPy)3、Ru(bpy)3PF6、Ru(bpy)3Cl2或者Ir(PPy)2(dtbbpy)PF6。
优选的,所述的碱选自:碳酸盐、羧酸盐、磷酸盐、亚磷酸盐、氟盐或者有机胺。
优选的,所述的溶剂选自:N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、乙腈、1,4-二氧六环、N,N-二甲基乙酰胺或其组合。
本发明的工作原理:本发明的发明人通过长期深入的研究,发现了一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,于溶剂中,在蓝光或者绿光照射下,以含铱,钌的络合物为光催化剂,在碱存在下,将式A化合物与式B化合物进行反应,从而形成式二溴四氟乙烷取代的苯胺及其衍生物的简便方法。该方法具有原料简单、易得,催化剂用量少,底物适用范围广,操作简便,反应效率高等优点。
本发明的有益效果:(1)本发明的方法使用光来促进反应,来源绿色,环保。同时反应步骤短,原料和试剂简单易得,且无需经过预活化处理,与现有方法相比,更具经济性和简洁性。
(2)本发明的方法中,可选用价格低廉工业原料苯胺,BrCF2CF2Br,以及较为低廉的催化剂(Ru(bpy)3Cl2150元/g,用量小于等于千分之五),底物适用范围广,操作简便,反应效率高,适合较大量的生产,
(3)本发明制得的二溴四氟乙烷取代的苯胺及其衍生物在生物医药领域和材料中有着十分重要的应用前景。
如本文所用,术语“C1-10烷基”指具有1-10个碳原子的直链或支链烷基,例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基或类似基团。
术语“C2-10烯基”指具有2-10个碳原子的直链或支链的烯基,例如乙烯基、烯丙基、1-丙烯基、异丙烯基、1-丁烯基、2-丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、或类似基团。
术语“C2-10炔基”是指具有2-10个碳原子的直链或支链的炔基,例如乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基、癸炔基、或类似基团。
术语“C1-10烷氧基”指具有1-10个碳原子的直链或支链烷氧基,例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
术语“卤素”指氟、氯、溴、或碘。
术语“卤代的”指基团中的H被相同或不同的一个或多个卤素原子所取代,例如三氟甲基、五氟乙基、三氟甲氧基、二氟乙烯基、或类似基团。
术语“C1-10烷基-羰基”指C1-10烷基-(C=O)-。
具体实施方式
下面通过具体实施方式对本发明作进一步详细的说明:
本发明提供了一种二溴四氟乙烷取代的苯胺及其衍生物的合成方法。优选地,所述方法包括步骤:于有机溶剂中,一定温度下(如0℃-80℃;较佳地10℃-50℃),在可见光中的蓝光或者绿光的照射下,以含铱,钌的络合物为光催化剂,将式A化合物(即苯胺或其衍生物)与式B化合物)反应一段时间(如1~40小时)从而形成式C化合物(二溴四氟乙烷取代的苯胺及其衍生物),并可通过一些经典的有机反应得到D化合物;
各式中,R1、R2、R3、R4、R5、R6定义如前所述。
更优选地,所述的式A化合物为选自下组的化合物:
本发明式A和式B化合物可通过市售或本发明所属领域技术人员所熟知的方法制备获得,然而该方法的具体条件,例如反应物、溶剂、所用化合物的量、反应温度、反应所需时间等不限于下面的解释。
作为光催化剂可以选用本领域技术人员所熟知的光催化剂,Ir(PPy)3、Ru(bpy)3PF6、Ru(bpy)3Cl2、Ir(PPy)2(dtbbpy)PF6,其中,Ru(bpy)3PF6的学名是三(2,2'-联吡啶)钌二(六氟磷酸)盐,Ru(bpy)3Cl2的学名是三联吡啶氯化钌。最优选为Ru(bpy)3Cl2。
该反应体系中,所使用的光催化剂的摩尔百分比为式A化合物摩尔量的0.01~10%,优选为0.5~1%。
本发明所述的碱包括:碳酸盐、磷酸盐、乙酸盐、亚磷酸盐、氟盐或者有机胺盐,优选为碳酸盐。
所述的溶剂包括选自下组的溶剂:乙腈、N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺、二甲基亚砜、1,3-二甲基-3,4,5,6-四氢-2-嘧啶酮(DMPU)、1,4-二氧六环、N,N-二甲基乙酰胺或其组合。优选地,采用乙腈。
所述的反应体系中,式A化合物或式B化合物的反应浓度为0.01~1mmol/mL;优选地,为0.1~0.5mmol/mL。
可以根据需要对本发明制备得到的式C化合物进行进一步的修饰从而制备得到各类功能性化合物。
本发明制备方法制得的产物可以通过多种方法进行分离纯化,所述方法包括:重结晶、薄层层析、柱层析等。以上纯化方法均为本领域的常规方法,例如,进行重结晶时,可采用极性溶剂与非极性溶剂的混合溶剂,优选为乙酸乙酯-石油醚,乙醇-石油醚等混和溶剂。使用薄层层析和柱层析时,所用的展开剂可单一的溶剂,也可采用混合溶剂,例如石油醚或乙酸乙酯-石油醚的混合溶剂等。
本发明提到的上述特征,或实施例提到的特征可以任意组合。本案说明书所揭示的所有特征可与任何组合物形式并用,说明书中所揭示的各个特征,可以被任何提供相同、均等或相似目的的替代性特征取代。因此除有特别说明,所揭示的特征仅为均等或相似特征的一般性例子。
下面结合具体实施,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件,或按照制造厂商所建议的条件。除非另外说明,否则百分比和份数按重量计算。
以下实施例中均采用本领域常规的后处理方法进行纯化。
实施例1
向25mL的反应管中,加入1.3mg(0.5mol%)Ir(PPy),Na2CO3(0.4mmol),化合物A-1(102mmol,3当量),氩气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌24小时后,得化合物C-1,产率为78%。1HNMR(400MHz,CDCl3)δ7.13(1H),7.10(d,J=8.4Hz,1H),6.62(d,J=8.4Hz,1H),3.81(br,2H),2.26(s,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.6Hz,2F),-105.4(t,J=5.6Hz,2F)。
实施例2
向25mL的反应管中,加入1.3mg(0.5mol%)Ir(PPy)3,K3PO4(0.4mmol),化合物A-1(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌24小时后,得化合物C-1,产率为65%。1HNMR(400MHz,CDCl3)δ7.13(1H),7.10(d,J=8.4Hz,1H),6.62(d,J=8.4Hz,1H),3.81(br,2H),2.26(s,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.6Hz,2F),-105.4(t,J=5.6Hz,2F)。
实施例3
向25mL的反应管中,加入2.6mg(1mol%)Ir(PPy)3,K2CO3(0.4mmol),化合物A-1(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌24小时后,得化合物C-1,产率为74%。1HNMR(400MHz,CDCl3)δ7.13(1H),7.10(d,J=8.4Hz,1H),6.62(d,J=8.4Hz,1H),3.81(br,2H),2.26(s,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.6Hz,2F),-105.4(t,J=5.6Hz,2F)。
实施例4
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-1(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌24小时后,得化合物C-1,产率为79%。1HNMR(400MHz,CDCl3)δ7.13(1H),7.10(d,J=8.4Hz,1H),6.62(d,J=8.4Hz,1H),3.81(br,2H),2.26(s,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.6Hz,2F),-105.4(t,J=5.6Hz,2F)。
实施例5
向25mL的反应管中,加入1.5mg(1mol%)Ru(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-1(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-1,产率为91%。1HNMR(400MHz,CDCl3)δ7.13(1H),7.10(d,J=8.4Hz,1H),6.62(d,J=8.4Hz,1H),3.81(br,2H),2.26(s,3H).19F-NMR(376MHz,CDCl3)δ–64.5(t,J=5.6Hz,2F),-105.4(t,J=5.6Hz,2F)。
实施例6-20
向25mL的反应管中,加入光催化剂(0.5mol%),碱(1.0当量),化合物A-2(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-2,产率如下(氟谱产率,括号内为分离产率)。δ7.20(d,J=8.8Hz,1H),7.14(s,1H),6.63(d,J=8.4Hz,1H),4.49(br,1H),2.84(s,3H),2.26(s,3H).19FNMR(376MHz,CDCl3)δ–64.3(t,J=5.45Hz,2F),-105.4(t,J=5.45Hz,2F)。C-2为新化合物。
实施例21
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-3(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-3,产率为73%。1HNMR(400MHz,CDCl3)δ7.14(1H),7.12(1H),6.64(d,J=8.4Hz,1H),4.09(br,2H),2.56(q,J=7.6Hz,2H),1.19(t,J=7.6Hz,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.5Hz,2F),-105.4(t,J=5.6Hz,2F)。C-3为新化合物。
实施例22
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-4(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-4,产率为92%。1HNMR(400MHz,CDCl3)δ7.14(s,2H),3.87(br,2H),2.20(s,6H).19FNMR(376MHz,CDCl3)δ–64.4(t,J=5.5Hz,2F),-106.6(t,J=5.1Hz,2F)。C-4为新化合物。
实施例23
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-5(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-5,产率为83%。C-5:1HNMR(400MHz,CDCl3)δ7.06(s,1H),6.52(s,1H),3.94(br,sH),2.19(s,3H),2.17(s,3H).19FNMR(376MHz,CDCl3)δ-64.4(s,2F),-105.0(s,2F).C-5’:1HNMR(400MHz,CDCl3)δ7.05(d,J=8.4Hz,1H),6.49(d,J=8.4Hz,1H),3.94(br,sH),2.26(s,3H),2.19(s,3H).19FNMR(376MHz,CDCl3)δ-63.3(s,2F),-96.1(br,2F).C-5为新化合物。
实施例24
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-6(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-6,产率为57%。1HNMR(400MHz,CDCl3)δ6.42(s,1H),6.36(s,1H),4.12(br,2H),2.34(t,J=4.8Hz,3H),2.22(s,3H).19FNMR(376MHz,CDCl3)δ–63.8(t,J=4.7Hz,2F),-98.1(s,2F)。C-6为新化合物。
实施例25
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-7(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-7,产率为69%。1HNMR(400MHz,CDCl3)δ7.05(s,2H),4.04(br,2H),2.25(s,3H),2.17.19FNMR(376MHz,CDCl3)δ-64.2(t,J=5.4Hz,2F),-104.7(t,J=5.4Hz,2F).13CNMR(100MHz,CDCl3)δ141.6,134.9,127.0(t,J=8.2Hz),126.3,124.1,122.5-110.0(m),20.2,17.7。C-7为新化合物。
实施例26
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-2(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-8,产率为61%。1HNMR(400MHz,CDCl3)δ7.13(q,J=8.5Hz,2H),6.64(dd,J=8.8Hz,J=4Hz,1H),4.53(br,1H),2.84(s,3H).19FNMR(376MHz,CDCl3)δ–64.6(t,J=5.6Hz,2F),-105.1(t,J=5.3Hz,2F)-129.2(dd,J=12.4Hz,J=8.3Hz,1F)。C-8为新化合物。
实施例27
向25mL的反应管中,加入1.3mgIr(ppy)3Cl2(0.5mol%),Na2CO3(0.8mmol),化合物A-2(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-9,产率为37%。1HNMR(400MHz,CDCl3)δ7.08–7.01(m,2H),6.66(dd,J=8.8,4.6Hz,1H),3.99(br,2H).19FNMR(376MHz,CDCl3)δ-64.82(t,J=5.5Hz,2F),-106.20(t,J=5.4Hz,2F),-126.63(dd,J=12.7,8.4Hz,1F)。C-9为新化合物。
实施例28
向25mL的反应管中,加入1.3mgIr(ppy)3Cl2(0.5mol%),Na2CO3(0.8mmol),化合物A-10(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-10,产率为39%。1HNMR(400MHz,CDCl3)δ7.30(d,J=2.3Hz,1H),7.23(dd,J=8.7,2.4Hz,1H),6.64(d,J=8.7Hz,1H),,4.12(br,2H).19FNMR(376MHzCDCl3,)δ-64.88(t,J=5.5Hz,2F),-106.18(t,J=5.5Hz,2F)。C-10为新化合物。
实施例29
向25mL的反应管中,加入1.3mgIr(ppy)3Cl2(0.5mol%),Na2CO3(0.8mmol),化合物A-11(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-11,产率为54%。1HNMR(400MHz,CDCl3)δ7.43(s,1H),7.35(d,J=8.8Hz,1H),6.58(d,J=8.8Hz,1H),4.22(br,2H).19FNMR(376MHz,CDCl3)δ–64.9(s,2F),-106.1(s,2F)。C-11为新化合物。
实施例30
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-12(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-12,产率为56%。1HNMR(400MHz,CDCl3)δ6.92(d,J=8.8Hz,1H),δ6.87(s,1H),6.67(d,J=8.8Hz,1H),3.90(br,2H),3.75(s,3H).19FNMR(376MHz,CDCl3)δ–64.5(t,J=5.1Hz,2F),-105.7(t,J=5.5Hz,2F)。C-12为新化合物。
实施例31
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-13(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B-1,在蓝光照射下搅拌40小时后,得化合物C-13,产率为67%。1HNMR(400MHz,CDCl3)δ7.33(s,1H),7.29(d,J=8.0Hz,1H),6.64(d,J=8.0Hz,1H),4.20(br,2H),2.42(s,3H).19FNMR(376MHz,CDCl3)δ-64.7(s,2F),-105.8(s,2F).13CNMR(100MHz,CDCl3)δ144.3,134.4,130.2(t,J=8.2Hz),125.5,122.5-110.0(m),118.4,18.5.C-13为新化合物。
实施例32
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-14(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-14,产率为39%。1HNMR(400MHz,CDCl3)δ7.79(t,J=9.3Hz,2H),7.46(d,J=2.3Hz,1H),7.38(s,1H),7.05(d,J=8.8Hz,2H),6.93(d,J=9.0Hz,1H),3.81(d,J=6Hz,6H),2.16(s,3H),2.10(d,J=1.4Hz,3H).19FNMR(376MHz,CDCl3)δ-64.92(t,J=5.6Hz,2F),-103.94(d,J=2.8Hz,2F)。C-14为新化合物。
实施例33
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-15(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-15,产率为37%。1HNMR(400MHz,CDCl3)δ8.13(d,J=7.4Hz,1H),7.56(t,J=8.3Hz,3H),2.19(s,3H).19FNMR(376MHz,CDCl3)δ-65.05(s,2F),-103.62(d,J=4.9Hz,2F)。C-15为新化合物。
实施例34
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-16(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-16,产率为73%。1HNMR(400MHz,CDCl3)δ8.00(d,J=8.8Hz,1H),7.69(dd,J=16.4Hz,J=8.4Hz,2H),7.46(dd,J=8.6Hz,J=7.0Hz,1H),7.29(d,J=8.0Hz,1H),6.81(d,J=8.8Hz,1H),4.22(br,2H).δ–63.2(s,2F),-97.4(s,2F)。C-16为新化合物。
实施例35
向25mL的反应管中,加入1.5mgRu(bpy)3Cl2(0.5mol%),Na2CO3(0.4mmol),化合物A-17(1.2mmol,3当量),氮气置换三次后加入2mL乙腈(MeCN),注射50μL(0.40mmol)化合物B,在蓝光照射下搅拌40小时后,得化合物C-17,产率为49%。1HNMR(400MHz,CDCl3)δ6.98(s,1H),6.92(s,1H),4.60(br,1H),3.33(t,J=3.6Hz,2H),2.78(t,J=4.0Hz,2H),2.23(s,3H),1.91(m,2H).19FNMR(376MHz,CDCl3)δ-64.1(t,J=5.4Hz,2F),-104.1(t,J=5.4Hz,2F).13CNMR(100MHz,CDCl3)δ141.7,134.0,127.2(t,J=8.4Hz),124.2,122.9,122.5-110.0(m),41.8,27.9,21.2,20.1.C-17为新化合物。
实施例36
向100mL的圆底烧瓶中,加入1mol/L的稀盐酸5ml,再慢慢滴加C-1,715ml(2.5mmol,1当量)进行搅拌30min,再慢慢滴加NaNO2水溶液(3mmol,1.2当量),反应1小时后再加入KI(3.75mmol,1.5当量),从-10℃慢慢到室温反应6小时,得化合物D,产率为53%。1HNMR(400MHz,CDCl3)δ7.92(d,J=8.1Hz,1H),7.40(s,1H),6.99(d,J=8.1Hz,1H),2.36(s,3H).19FNMR(376MHz,cdcl3)δ-62.00(t,J=4.7Hz,2F),-102.48(t,J=4.7Hz,2F)。D为新化合物
实施例37
向25mL的反应管中,加入14mgPd(PPy3)Cl2(0.02mol,0.1当量),K2CO3(0.4mmol),化合物E1(0.4mmol,2当量)氮气置换三次后加入2mL1,4-二氧六环(dioxane),注射化合物D38uL(0.2mmol,1当量)在80℃下反应24小时候,得化合物F-1-A,产率为81%。1HNMR(400MHz,CDCl3)δ7.66–7.60(m,1H),7.51–7.44(m,2H),7.39–7.33(m,4H),7.17(d,J=7.8Hz,1H),2.47(s,3H).19FNMR(376MHz,cdcl3)δ-62.34(s,2F),-98.87(s,2F)。F-1-A为新化合物。
实施例38
向25mL的反应管中,加入14mgPd(PPy3)Cl2(0.02mol,0.1当量),K2CO3(0.4mmol),化合物E1(0.4mmol,2当量)氮气置换三次后加入2mL1,4-二氧六环(dioxane),注射化合物D38uL(0.2mmol,1当量)在80℃下反应24小时候,得化合物F-1-B,产率为93%.1HNMR(400MHz,cdcl3)δ7.77–7.67(m,1H),7.61(d,J=7.8Hz,1H),7.50(s,1H),7.37(t,J=8.6Hz,3H),7.11(d,J=7.8Hz,1H),2.48(s,3H)。F-1-B为新化合物。
实施例39
向25mL的反应管中,加入14mgPd(PPy3)Cl2(0.02mol,0.1当量),CuI(0.02mmol,0.1当量),氮气置换三次后加入1mL三乙胺(Et3N),注射化合物D38uL(0.2mmol,1当量),化合物E257uL(0.4mmol,2当量)在80℃下反应24小时候,得化合物F-2,产率为96%。1HNMR(400MHz,cdcl3)δ7.48(d,J=7.9Hz,1H),7.38(s,1H),7.27(d,J=7.1Hz,1H),2.40(s,3H),0.24(d,J=0.8Hz,9H).19FNMR(376MHz,cdcl3)δ-62.86(t,J=4.6Hz,2F),-104.03(t,J=4.5Hz,2F)。F-2为新化合物。
实施例40
向25mL的反应管中,加入14mgPd(PPy3)Cl2(0.02mol,0.1当量),CuI(0.02mmol,0.1当量),氮气置换三次后加入1mL三乙胺(Et3N),注射化合物D38uL(0.2mmol,1当量),化合物E3129mg(0.4mmol,2当量)在80℃下反应24小时候,得化合物F-3,产率为85%。1HNMR(400MHz,cdcl3)δ7.54(d,J=7.7Hz,1H),7.41(s,1H),7.33(d,J=7.7Hz,1H),7.25(d,J=8.4Hz,1H),6.75(d,J=8.5Hz,1H),6.67(s,1H),3.81(s,3H),3.52(s,3H),2.89(s,2H),2.44(s,3H),2.36(dd,J=18.4,11.8Hz,3H),2.09(dd,J=14.3,10.7Hz,3H),1.90(t,J=12.8Hz,4H),1.60–1.36(m,4H),0.93(d,J=15.8Hz,3H).19FNMR(376MHz,cdcl3)δ-62.81(s,2F),-103.89(d,J=15.8Hz,2F)。F-3为新化合物。
实施例1~实施例26合成的化合物C-1、化合物C-2、化合物C-3、化合物C-4、化合物C-5、化合物C-6、化合物C-7、化合物C-8、化合物C-9、化合物C-10、化合物C-11、化合物C-12、化合物C-13、化合物C-14和化合物C-15、化合物C-16、化合物C-17、化合物F-1-A、化合物F-1-B、化合物F-2、化合物F-3、都是新化合物,在农药,材料,以及分子影像学有着潜在的应用。
在本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献被单独引用作为参考那样。此外应理解,在阅读了本发明的上述讲授内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
应理解,在本发明范围内中,本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。限于篇幅,在此不再一一累述。
Claims (5)
1.一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,其特征在于,包括以下步骤:于溶剂中,在可见光的照射下,以含钌或铱的络合物为光催化剂,在碱存在的条件下,将式A化合物与式B化合物进行反应,从而形成式C化合物,化合物C经过转化得到化合物D;化学式如下:
上述各式中,R1为烷基-羰基或甲酰基;
R2、R3、R4、R5各自独立地为卤代的C1-10烷基、C2-10烯基、卤代的C2-10烯基、C2-10炔基、被卤素或者苯基取代的C2-10炔基或卤素中的一种;
R6为C2-10烯基、C2-10炔基、-COOC1-10烷基、C1-10烷基-羰基、取代或未取代的苯基、取代或未取代的杂芳烃、C1-10烷基取代的膦酸基、C1-10烷基取代的亚膦酸基或卤素的一种;
其中,所述的光催化剂选自:Ir(PPy)3、Ru(bpy)3PF6、Ru(bpy)3Cl2或者Ir(PPy)2(dtbbpy)PF6;
所述的碱选自:碳酸盐、羧酸盐、磷酸盐、亚磷酸盐、氟盐或者有机胺。
2.根据权利要求1所述的2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,其特征在于:所述式A化合物、光催化剂、碱、式B化合物的摩尔比为1~8:0.001~0.1:1~8:1~8。
3.根据权利要求1所述的2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,其特征在于:所述式A化合物、光催化剂、碱、式B化合物的摩尔比为1~3:0.005~0.01:1~3:1~3。
4.根据权利要求2或3所述的2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,其特征在于:所述的反应在0℃~60℃下进行。
5.根据权利要求2或3所述的2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法,其特征在于:所述的溶剂选自:N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜、乙腈、1,4-二氧六环、N,N-二甲基乙酰胺或其组合。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710692303.8A CN107445795B (zh) | 2017-08-14 | 2017-08-14 | 一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710692303.8A CN107445795B (zh) | 2017-08-14 | 2017-08-14 | 一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107445795A CN107445795A (zh) | 2017-12-08 |
CN107445795B true CN107445795B (zh) | 2020-09-18 |
Family
ID=60492315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710692303.8A Active CN107445795B (zh) | 2017-08-14 | 2017-08-14 | 一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107445795B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111018708B (zh) * | 2019-11-22 | 2022-05-27 | 浙江工业大学 | 一种光催化下二氟烷基取代芳香酮类化合物的合成方法 |
CN110803972B (zh) * | 2019-11-22 | 2022-05-20 | 浙江工业大学 | 一种光催化下二氟烷基取代芳香醛类化合物的合成方法 |
CN112574056B (zh) * | 2020-12-28 | 2022-11-04 | 浙江工业大学 | 一种α,α-二氟-γ-羟基乙酰胺衍生物的合成方法 |
CN114539022B (zh) * | 2022-01-26 | 2023-10-31 | 遵义医科大学 | 一种脂肪羧酸脱羧合成三氟甲基烷基溴的方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105669546A (zh) * | 2016-03-09 | 2016-06-15 | 遵义医学院 | 一种二氟烷基取代的吡啶酮或吡喃酮的合成方法 |
-
2017
- 2017-08-14 CN CN201710692303.8A patent/CN107445795B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105669546A (zh) * | 2016-03-09 | 2016-06-15 | 遵义医学院 | 一种二氟烷基取代的吡啶酮或吡喃酮的合成方法 |
Non-Patent Citations (2)
Title |
---|
Sodium dithionite initiated fluoroalkylation of trimethoxybenzenes, mesitylene and pyrroles with BrCF2CF2Br;Wojciech Dmowski et al.;《Journal of Fluorine Chemistry》;20100204;第131卷;第746-750页 * |
Visible-Light-Induced Direct Difluoroalkylation of Uracils,Pyridinones, and Coumarins;Chun-Yang He et al.;《J. Org. Chem.》;20161220;第82卷;第910-917页 * |
Also Published As
Publication number | Publication date |
---|---|
CN107445795A (zh) | 2017-12-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107445795B (zh) | 一种2-溴-1,1,2,2-四氟乙基取代的芳基砌块的合成方法 | |
CN103992225B (zh) | 一种水杨醛衍生物及其制备方法 | |
CN105669546A (zh) | 一种二氟烷基取代的吡啶酮或吡喃酮的合成方法 | |
CN111454286A (zh) | 一种二氟烯基硼化合物的合成方法 | |
JP2011098957A (ja) | ピリジルホスフィン化合物を有する金属錯体、及びアルキルメタクリレートの製造方法 | |
CN108864164B (zh) | 一种一级胺导向的2-炔基吲哚类化合物的合成方法 | |
CN116903499A (zh) | 无水氟磺酰基二氟乙酸铜盐及其制备方法与应用 | |
WO2016141829A1 (zh) | 应用乙酸钯合成医药中间体菲化合物的方法 | |
JPWO2019069828A1 (ja) | 光学活性な2,3−ビスホスフィノピラジン誘導体、その製造方法、遷移金属錯体及び有機ホウ素化合物の製造方法 | |
KR101363583B1 (ko) | 2-브로모-6-플루오르나프탈렌의 제조방법 | |
CN112979581B (zh) | 可见光促进的n-(2-溴苯基)硫代酰胺制备苯并噻唑类化合物的方法 | |
CN110642831B (zh) | 一种在丙酮诱导下对芳烃或者杂芳烃进行氟烷基化的方法 | |
CN110407830B (zh) | 一种合成n-芳基吩噻嗪类化合物的方法 | |
CN110950836B (zh) | 一种苯并二硫杂环戊烯类骨架化合物的制备方法 | |
CN107739342B (zh) | 一种一步合成5-二芳氨基苯并咪唑酮衍生物的方法 | |
CN112939891A (zh) | 一种制备联苯苯并噻唑化合物的方法 | |
CN109810056B (zh) | S-烷基-s-喹啉基-n-磺酰基氮硫叶立德化合物及其制备和应用 | |
RU2155185C1 (ru) | Способ получения частично фторированных бензойных кислот | |
JP2001122847A (ja) | ビナフチル誘導体の製造方法 | |
CN105669486B (zh) | 一种n‑酰基‑2,6‑二芳基苄胺衍生物的制备方法及其应用 | |
CN114773245A (zh) | 一种三氟甲基硒醚的制备方法 | |
CN113999149A (zh) | 一种基于l-半胱氨酸合成二芳基硫醚类化合物的制备方法 | |
WO2022186305A1 (ja) | アリールチオールエステル化合物の製造方法 | |
CN103922975A (zh) | 一种磺酰胺类化合物的合成方法 | |
JP2023119461A (ja) | パーフルオロアルキルピリジン化合物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 563000 Dalian Road, Guizhou, China, No. 201, No. Applicant after: ZUNYI MEDICAL University Address before: 563000 No. 201 Dalian Road, Huichuan District, Zunyi City, Guizhou Province Applicant before: ZUNYI MEDICAL University |
|
GR01 | Patent grant | ||
GR01 | Patent grant |