CN112047839B - 一种1-碘-3-全氟烷基烯烃化合物及其制备方法 - Google Patents
一种1-碘-3-全氟烷基烯烃化合物及其制备方法 Download PDFInfo
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- CN112047839B CN112047839B CN202010801423.9A CN202010801423A CN112047839B CN 112047839 B CN112047839 B CN 112047839B CN 202010801423 A CN202010801423 A CN 202010801423A CN 112047839 B CN112047839 B CN 112047839B
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- alkenyl
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- -1 alkenyl iodine, Chemical compound 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical group [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- ICQCKUWOLNVWEA-UHFFFAOYSA-N 1,1,2-trifluoropropan-2-ol Chemical compound CC(O)(F)C(F)F ICQCKUWOLNVWEA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 7
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
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- 238000000926 separation method Methods 0.000 abstract description 4
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 150
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 25
- 238000004293 19F NMR spectroscopy Methods 0.000 description 25
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 235000019439 ethyl acetate Nutrition 0.000 description 17
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000003480 eluent Substances 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- UDWBMXSQHOHKOI-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-henicosafluoro-10-iododecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I UDWBMXSQHOHKOI-UHFFFAOYSA-N 0.000 description 2
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 2
- XTGYEAXBNRVNQU-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-iodopropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)I XTGYEAXBNRVNQU-UHFFFAOYSA-N 0.000 description 2
- BBZVTTKMXRPMHZ-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-iodopropane Chemical compound FC(F)(F)C(F)(I)C(F)(F)F BBZVTTKMXRPMHZ-UHFFFAOYSA-N 0.000 description 2
- RXBQTZHAUYILQJ-UHFFFAOYSA-N 2,2-difluoro-2-iodo-1-phenylethanone Chemical compound FC(F)(I)C(=O)C1=CC=CC=C1 RXBQTZHAUYILQJ-UHFFFAOYSA-N 0.000 description 2
- SCDQTGKHEDZXKO-UHFFFAOYSA-N OC(C(I)=CCC(F)(F)F)=O Chemical compound OC(C(I)=CCC(F)(F)F)=O SCDQTGKHEDZXKO-UHFFFAOYSA-N 0.000 description 2
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 description 2
- LIPDDCLPIKKOTB-UHFFFAOYSA-N [difluoro(iodo)methyl]sulfonylbenzene Chemical compound FC(F)(I)S(=O)(=O)C1=CC=CC=C1 LIPDDCLPIKKOTB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- HGWXXIZVRRTDKT-UHFFFAOYSA-N ethyl 2,2-difluoro-2-iodoacetate Chemical compound CCOC(=O)C(F)(F)I HGWXXIZVRRTDKT-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NZXVPCQHQVWOFD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1,2-diiodoethane Chemical compound FC(F)(I)C(F)(F)I NZXVPCQHQVWOFD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KAJIIHOYBGUPIP-UTCJRWHESA-N C#CCOC(/C(\I)=C/CC(F)(F)F)=O Chemical compound C#CCOC(/C(\I)=C/CC(F)(F)F)=O KAJIIHOYBGUPIP-UTCJRWHESA-N 0.000 description 1
- NFVRUONLKHJOMB-UHFFFAOYSA-N C(C)(=O)[Mn]C1C=CC=C1 Chemical compound C(C)(=O)[Mn]C1C=CC=C1 NFVRUONLKHJOMB-UHFFFAOYSA-N 0.000 description 1
- UERIFOFTJVGNMY-AATRIKPKSA-N CCOC(/C(\I)=C(/C)\CC(F)(F)F)=O Chemical compound CCOC(/C(\I)=C(/C)\CC(F)(F)F)=O UERIFOFTJVGNMY-AATRIKPKSA-N 0.000 description 1
- JQMHEOWAJDTXQM-VQHVLOKHSA-N CCOC(/C(\I)=C(/CCCC1)\C1C(F)(F)F)=O Chemical compound CCOC(/C(\I)=C(/CCCC1)\C1C(F)(F)F)=O JQMHEOWAJDTXQM-VQHVLOKHSA-N 0.000 description 1
- UERIFOFTJVGNMY-WAYWQWQTSA-N CCOC(/C(\I)=C(\C)/CC(F)(F)F)=O Chemical compound CCOC(/C(\I)=C(\C)/CC(F)(F)F)=O UERIFOFTJVGNMY-WAYWQWQTSA-N 0.000 description 1
- JQMHEOWAJDTXQM-CLFYSBASSA-N CCOC(/C(\I)=C(\CCCC1)/C1C(F)(F)F)=O Chemical compound CCOC(/C(\I)=C(\CCCC1)/C1C(F)(F)F)=O JQMHEOWAJDTXQM-CLFYSBASSA-N 0.000 description 1
- 229910020323 ClF3 Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000006411 Negishi coupling reaction Methods 0.000 description 1
- JZEOHEWKSCRPGI-UHFFFAOYSA-N O=C(C(I)=CCC(F)(F)F)OC1OCOCC1 Chemical compound O=C(C(I)=CCC(F)(F)F)OC1OCOCC1 JZEOHEWKSCRPGI-UHFFFAOYSA-N 0.000 description 1
- BXEFQPCKQSTMKA-UHFFFAOYSA-N OC(=O)C=[N+]=[N-] Chemical compound OC(=O)C=[N+]=[N-] BXEFQPCKQSTMKA-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJRHHHMUGQMPCB-DAXSKMNVSA-N butyl (Z)-5,5,5-trifluoro-2-iodopent-2-enoate Chemical compound CCCCOC(=O)/C(=C/CC(F)(F)F)/I CJRHHHMUGQMPCB-DAXSKMNVSA-N 0.000 description 1
- GCYWNXHVHGPDGF-UHFFFAOYSA-N butyl 5-(benzenesulfonyl)-5,5-difluoro-2-iodopent-2-enoate Chemical compound CCCCOC(=O)C(=CCC(F)(F)S(=O)(=O)C1=CC=CC=C1)I GCYWNXHVHGPDGF-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001840 cholesterol esters Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 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
- 238000001308 synthesis method Methods 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
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- RQCNHUCCQJMSRG-UHFFFAOYSA-N tert-butyl piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1 RQCNHUCCQJMSRG-UHFFFAOYSA-N 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
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
本发明公开一种1‑碘‑3‑全氟烷基烯烃化合物及其制备方法。本发明的化合物具有如式(Ⅰ)所示结构,该1‑碘‑3‑全氟烷基烯烃化合物因其具有高的化学活性和丰富的反应性可广泛应用于偶联反应或自由基环加成反应中。本发明的制备方法具有非常广泛的底物适应性,可合成多种1‑碘‑3‑全氟烷基烯烃化合物;且原料廉价易得、副产物只有氮气,符合绿色合成理念,反应过程操作简单,对空气、水分不敏感,产率高,产物分离纯化简单,烯基碘顺反选择性高,适合大规模的合成,具有很好的应用前景。
Description
技术领域
本发明属于有机合成技术领域,具体涉及1-碘-3-全氟烷基烯烃化合物及其制备方法。
背景技术
氟原子具有很高的电负性,极大地影响含氟化合物的电子云分布、酸碱性、偶极距,使得含氟化合物的物理化学性质发生显著改变。从上世纪开始,许多含氟有机物被逐渐应用于药物和材料中。因此科学家开展了大量的研究以寻找将氟原子或含氟官能团引入到有机分子的新方法,其中引入全氟烷基,特别是三氟甲基的新方法尤为引人关注。在过去的十几年,可见光促进的全氟烷基碘代物与烯烃或炔烃的1,2-全氟烷基烯碘化反应取得了巨大的进展。除了传统的光敏剂Ru,Ir络合物外,近年来,人们又发展了使用有机染料,Cu(dap)2Cl,和无机材料等作为光敏剂高效地引发全氟烷基自由基。此外,RfI化合物由于全氟烷基的强吸电子作用以及碘原子较大的原子半径和较好的离去能力,它可以与富电子的添加剂,例如三级胺化合物,形成电子给体-受体复合物(EDA complexes)。这类复合物在光或者热的作用下也能产生全氟烷基自由基,从而实现无需外加光催化剂的自由基转化。
烯基碘化合物因其具有高的化学活性和丰富的反应性,在有机合成、点击化学、医药、生物以及材料多个领域中有着广泛地应用。它们可以参与多种形式的偶联反应,如:Kumada偶联反应,Negishi偶联反应,Sonogashira偶联反应,也可以作为烯基自由基的前体参与到一系列自由基环加成反应中。
但是,现有的烯基碘化物的合成方法中,通常需要引入引发剂以及添加剂,如中国专利CN106832256A公开采用全氟烷基碘化物Rf-I与含乙烯基或丙烯基的聚氧乙烯醚反应得到一种含氟非离子表面活性剂,在制备过程中,分两次加入引发剂,在应用过程中存在一定局限性。
因此,发展一种简洁高效、高选择性的烯基碘化合物的制备方法具有重要的理论和现实意义。
发明内容
本发明的目的在于克服现有技术的不足,提供一种1-碘-3-全氟烷基烯烃化合物。本发明提供的1-碘-3-全氟烷基烯烃化合物含有具有重要应用价值的全氟烷基和高合成价值的烯基碘化合物,具有高的化学活性和丰富的反应性,可广泛应用于偶联反应或自由基环加成反应中。
本发明的另一目的在于提供所述1-碘-3-全氟烷基烯烃化合物的制备方法。本发明的制备方法具有非常广泛的底物适应性,可合成多种1-碘-3-全氟烷基烯烃化合物;本发明使用的原料廉价易得、副产物只有氮气,符合绿色合成理念,反应过程操作简单,对空气、水分不敏感,产率高,产物分离纯化简单,烯基碘顺反选择性高,适合大规模的合成。
本发明的另一目的在于提供所述1-碘-3-全氟烷基烯烃化合物在偶联反应或自由基环加成反应中的应用。
为实现上述目的,本发明采用如下技术方案:
一种1-碘-3-全氟烷基烯烃化合物,具有如式(Ⅰ)所示结构:
其中,R1、R2独立地选自氢原子、烷基、环烷基、芳基或杂环基,R1、R2为独立地取代基或相连成环烷基;Rf选自全氟烷基、2-二氟-1-酰基、2-二氟-1-酯基;EWG为吸电子基团。
本发明提供的1-碘-3-全氟烷基烯烃化合物有具有重要应用价值的全氟烷基和高合成价值的烯基碘化合物,具有高的化学活性和丰富的反应性,可广泛应用于偶联反应或自由基环加成反应中。
优选地,所述烷基为C1~10烷基。进一步优选地,所述烷基为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基等。进一步优选地,所述烷基为C1~6烷基,特别优选为甲基、乙基、丙基、丁基和己基。
优选地,所述环烷基为C5~8的环烷基。
优选地,所述芳基为苯基或含取代基的苯基。取代基可以是一个或者多个,位置可以是邻位、对位和间位。常见的取代基例如烷基、烷氧基、三氟甲基、烯基、芳香基、酯基、硝基、羟基或卤素等都可作为苯基的取代基。
优选地,所述杂环基为噻吩基、呋喃基、吡啶基、噻唑基、噁唑基、哌嗪基,四氢呋喃基。
优选地,所述全氟烷基为C1~10全氟烷基、2-二氟-1-酰基、2-二氟-1-酯基。
进一步优选地,所述2-二氟-1-酰基为2-二氟-1-芳基甲酰基、2-二氟-1-芳基磺酰基。
进一步优选地,所述2-二氟-1-乙酸烷基酯基、2-二氟-1-乙酸芳基酯基。
优选地,所述EWG为甲酸酯基。
进一步优选地,所述EWG为甲酸烷基酯基、甲酸芳基酯基。
所述1-碘-3-全氟烷基烯烃化合物的制备方法,包括如下步骤:
S1.在可见光照条件下,式(Ⅱ)所示的烯基重氮化合物和式(Ⅲ)所示的全氟烷基碘代物于有机溶剂中发生ATRA反应得到1-碘-3-全氟烷基烯烃化合物异构体混合物;
S2.将S1得到的1-碘-3-全氟烷基烯烃化合物异构体混合物,在锰催化剂条件下进行异构化反应,得到所述顺式1-碘-3-全氟烷基烯烃化合物。
本发明的制备方法具有非常广泛的底物适应性,可合成多种1-碘-3-全氟烷基烯烃化合物;本发明使用的原料廉价易得、副产物只有氮气,符合绿色合成理念,反应过程操作简单,对空气、水分不敏感,产率高,产物分离纯化简单,烯基碘顺反选择性高,适合大规模的合成。
优选地,所述烯基重氮乙酸酯与全氟烷基碘化物的摩尔比为1:1~5。
优选地,所述ATRA反应的温度为0~80℃。
优选地,所述ATRA反应的时间为0.5~72h。
优选地,所述有机溶剂为二氯甲烷、二氯乙烷、乙酸乙酯、乙醇、甲醇、三氟异丙醇、异丙醇、乙腈、二甲基亚砜、N,N-二甲基甲酰胺、二氧六环、四氢呋喃、甲苯或氯苯中的一种或几种的组合。
进一步优选地,所述有机溶剂为二氯甲烷、乙酸乙酯、乙醇、三氟异丙醇、乙腈、四氢呋喃、甲苯或氯苯中的一种或几种的组合。
优选地,所述可见光为CFL、LED白光、LED蓝光或太阳光中的一种。
优选地,所述锰催化剂为甲基环戊二烯三羰基锰、十羰基二锰、三羰基环戊二烯锰、乙酰基环戊二烯三羰基锰I或环戊二烯三羰基锰中的一种或几种的组合。
进一步优选地,所述锰催化剂为十羰基二锰催化剂。
优选地,所述锰催化剂的加入量为按照烯基重氮乙酸酯与锰催化剂的摩尔比1:0.025~1。
优选地,所述异构化反应的时间为1~20h。
所述1-碘-3-全氟烷基烯烃化合物在偶联反应或自由基环加成反应中的应用。
与现有技术相比,本发明具有如下有益效果:
本发明提供的1-碘-3-全氟烷基烯烃化合物有具有重要应用价值的全氟烷基和高合成价值的烯基碘化合物,具有高的化学活性和丰富的反应性,可广泛应用于偶联反应或自由基环加成反应中。
本发明的制备方法具有非常广泛的底物适应性,可合成多种1-碘-3-全氟烷基烯烃化合物;本发明使用的原料廉价易得、副产物只有氮气,符合绿色合成理念,反应过程操作简单,对空气、水分不敏感,产率高,产物分离纯化简单,烯基碘顺反选择性高,适合大规模的合成。
具体实施方式
下面结合实施例进一步阐述本发明。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。下例实施例中未注明具体条件的实验方法,通常按照本领域常规条件或按照制造厂商建议的条件;所使用的反应物、试剂等,如无特殊说明,均为可从常规市场等商业途径得到的反应物和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例合成1-碘-3-全氟烷基烯烃化合物的通用公式如下:
具体步骤为:
S1.将1份烯基重氮乙酸酯式(Ⅱ)与1~5份全氟烷基碘化物式(Ⅲ)加入到合适量的有机溶剂中,置于密封的反应试管,光照条件下发生ATRA反应0.5~72h,生成1-碘-3-全氟烷基烯烃化合物的Z/E混合物。
S2.减压蒸馏旋走多余的全氟烷基碘化物,向Z/E混合物中加入合适量的有机溶剂和0.025~1份锰催化剂,在相同光源照射下继续反应1~20h即可得到所述1-碘-3-全氟烷基烯烃化合物式(Ⅰ)。
所述份数为摩尔份。
实施例1(Z)-5,5,5-三氟-2-碘戊-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的乙腈以及0.8mmol三氟碘甲烷,在室温下用18W CFL光照射搅拌反应1h。随后将反应液浓缩除掉多余的三氟碘甲烷,再往反应试管中加入适量的乙腈和0.06mmol十羰基二锰催化剂,在相同光源照射下继续反应9h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到(Z)-5,5,5-三氟-2-碘戊-2-烯酸丁酯,收率为85%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.26(t,J=6.4Hz,1H),4.25(t,J=6.5Hz,2H),3.22–3.06(m,2H),1.76–1.66(m,2H),1.49–1.38(m,2H),0.96(t,J=7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.9(q,J=3.6Hz),125.2(q,J=277.0Hz),101.1,71.02–67.3,42.1(q,J=30.7Hz),30.6,19.24,13.79。
19F NMR(376MHz,CDCl3)δ-64.83(s,3F)。
HRMS(EI):calcd.for C9H12F3IO2[M]+:335.98286,Found:335.98290。
实施例2(Z)-5,5,6,6,7,7-七氟-2-碘庚-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的乙腈以及1.6mmol全氟碘丙烷,在室温下用太阳光照射搅拌反应5h。随后将反应液浓缩除掉多余的七氟碘丙烷,再往反应试管中加入适量的乙腈和0.01mmol十羰基二锰催化剂,在相同光源照射下继续反应1h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到(Z)-5,5,6,6,7,7-七氟-2-碘庚-2-烯酸丁酯,收率为86%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.31(t,J=6.6Hz,1H),4.25(t,J=6.6Hz,2H),3.14(td,J=17.8,6.6Hz,2H),1.75–1.66(m,2H),1.49–1.38(m,2H),0.97(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1(t,J=4.5Hz),119.2,118.9,116.6,116.4,116.3,116.0,113.8,101.7,67.2,39.5(t,J=22.1Hz),30.6,19.3,13.8。
19F NMR(376MHz,CDCl3)δ-80.48(t,J=9.5Hz,3F),-112.22–-112.31(m,2F),-127.32(d,J=2.4Hz,2F)。
HRMS(ESI):calcd.for C11H11F7IO2[M-H]-:434.96974,Found:434.97014。
实施例3(Z)-5,5,6,6,7,7,8,8,8-九氟-2-碘-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的二氯甲烷以及2.0mmol九氟正丁基碘,在室温下用5W LED白光照射搅拌反应10h。随后将反应液浓缩除掉多余的九氟正丁基碘,再往反应试管中加入适量的二氯甲烷和0.15mmol十羰基二锰催化剂,在相同光源照射下继续反应12h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到(Z)-5,5,6,6,7,7,8,8,8-九氟-2-碘-2-烯酸丁酯,收率为85%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.31(t,J=6.6Hz,1H),4.25(t,J=6.6Hz,2H),3.16(td,J=17.8,6.5Hz,2H),1.75–1.65(m,2H),1.51–1.38(m,2H),0.97(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1(t,J=4.5Hz),119.4,118.9,118.6,117.2,116.9,116.6,116.0,114.0,101.7,67.2,39.5(t,J=22.2Hz),30.6,19.2,13.8。
19F NMR(376MHz,CDCl3)δ-81.04–-81.09(m,3F),-111.53(ddd,J=13.0,5.7,2.2Hz,2F),-123.96–-124.07(m,2F),-126.03(dd,J=14.9,10.3Hz,2F)。
HRMS(ESI):calcd.for C12H11F9IO2[M-H]-:484.96655,Found:484.96694。
实施例4(Z)-4-全氟己基-2-碘代-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的四氢呋喃以及1.2mmol十三氟正己基碘化物,在40℃下用5W LED蓝光照射搅拌反应3h后,将反应液浓缩除掉多余的十一氟正己基碘化物,然后再往反应试管中加入适量的二氯甲烷和0.02mmol十羰基二锰催化剂,在相同光源照射下继续反应20h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到异构化的1-碘-3-全氟己基烯烃化合物,收率为85%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.31(t,J=6.6Hz,1H),4.25(t,J=6.6Hz,2H),3.16(td,J=17.8,6.6Hz,2H),1.75–1.65(m,2H),1.50–1.38(m,2H),0.97(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.1,101.7,100.2,67.2,39.6(t,J=22.4Hz),30.6,19.3,13.8。
19F NMR(376MHz,CDCl3)δ-80.83–-80.92(m,3F),-111.24–-111.31(m,2F),-121.88(s,2F),-122.70–-123.14(m,4F),-126.13–-126.20(m,2F)。
HRMS(ESI):calcd.for C14H11F13IO2[M-H]-:584.96016,Found:584.96082。
实施例5(Z)-4-全氟癸烷基-2-碘-丙烯酸正丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的甲苯以及1.6mmol全氟癸烷基碘化物,在50℃下用10W LED蓝光照射搅拌反应2h后,除掉多余的全氟癸烷基碘化物。随后再往反应试管中加入适量的乙醇和0.04mmol的十羰基二锰催化剂,于相同光源的光照下继续反应6h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到异构化的(Z)-4-全氟癸烷基-2-碘-丙烯酸正丁酯,收率为83%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.31(td,J=6.6,2.2Hz,1H),4.25(td,J=6.6,3.3Hz,2H),3.15(tdd,J=17.8,5.5,3.7Hz,2H),1.75–1.65(m,2H),1.50–1.39(m,2H),0.96(td,J=7.4,3.9Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.0(d,J=5.3Hz),138.9,119.7,119.4,119.1,118.8,118.5,118.2,117.2,116.9,116.5,116.0,115.6,115.3,114.6,114.3,114.0,113.8,113.5,113.2,112.9,112.6,111.1,110.8,110.5,110.2,109.8,108.9,108.5,108.3,108.2,108.0,107.8,107.7,107.5,101.4(d,J=5.3Hz),77.3,76.9,76.6,67.2,39.4(t,J=22.3Hz),30.4,19.0,13.6。
19F NMR(376MHz,CDCl3)δ-81.22–-81.70(m,3F),-111.69(d,J=43.8Hz,2F),-121.93–-122.47(m,10F),-123.27(s,4F),-126.69(d,J=54.2Hz,2F)。
HRMS(ESI):calcd.for C18H11F21IO2[M-H]-:784.94739,Found:784.94812。
实施例6(Z)-5,6,6,6-四氟-2-碘-5-(三氟甲基)六-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸酯,适量的乙酸乙酯以及1.2mmol七氟异丙基碘,在80℃下用15W LED蓝光照射搅拌反应0.5h后,除掉多余的七氟异丙基碘,然后再往反应试管中加入适量的乙醇和0.08mmol十羰基二锰催化剂,在相同光源下照射下继续反应10h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到(Z)-5,6,6,6-四氟-2-碘-5-(三氟甲基)六-2-烯酸丁酯,收率为86%,Z/E>30:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.27(t,J=6.7Hz,1H),4.25(t,J=6.6Hz,2H),3.14(dd,J=19.5,6.8Hz,2H),1.75–1.65(m,2H),1.49–1.37(m,2H),0.96(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.2,139.7(d,J=6.5Hz),115.7(qd,J=286.0,27.0Hz),100.9,91.9(dt,J=64.8,32.3Hz),89.8(dt,J=64.9,32.4Hz),67.2,36.7(d,J=19.8Hz),30.6,19.2,13.8。
19F NMR(376MHz,CDCl3)δ-76.65–-76.75(m,7F)。
HRMS(APCI):calcd.for C11H13F7IO2[M+H]+:436.98430,Found:436.98438。
实施例7(Z)-5,5-二氟-2-碘代己二-2-烯二酸酯1-乙基6-丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的三氟异丙醇以及0.4mmol二氟碘乙酸乙酯,在室温下用3W LED蓝光照射搅拌反应8h后,除掉多余的二氟碘乙酸乙酯,然后再往反应试管中加入适量的乙酸乙酯和0.2mmol份的十羰基二锰催化剂,在相同光源下照射下继续反应10h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到5,5-二氟-2-碘代己二-2-烯二酸酯1-乙基6-丁酯,收率为86%,Z/E=19:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.26(t,J=6.7Hz,0.95×1H),6.93(t,J=7.2Hz,0.05×1H),4.36(q,J=7.2Hz,2H),4.23(t,J=6.6Hz,2H),3.34(td,J=16.7,7.1Hz,0.1×2H),3.12(td,J=16.2,6.7Hz,1.9×2H),1.74–1.64(m,2H),1.50–1.32(m,5H),0.96(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ163.3(t,J=32.1Hz),162.3,141.2(t,J=5.4Hz),114.2(t,J=252.9Hz),100.6,67.0,66.6,63.5,63.3,42.6(t,J=24.3Hz),30.6,19.2,14.03,13.8。
19F NMR(376MHz,CDCl3)δ-104.00(s,0.95×2F),-105.62(s,0.05×2F)。
HRMS(ESI):calcd.for C12H18F2IO4[M+H]+:391.02123,Found:391.02140。
实施例8(Z)-5,5-二氟-2-碘-5-(苯磺酰)戊-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的氯苯以及0.8mmol二氟碘甲基苯基砜,在室温下用36W CFL照射搅拌反应8h后,除掉多余的二氟碘甲基苯基砜,然后再往反应试管中加入适量的乙酸乙酯和0.4mmol十羰基二锰催化剂,在相同光源下照射下继续反应10h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到5,5-二氟-2-碘-5-(苯磺酰)戊-2-烯酸丁酯,收率为81%,Z/E=9:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ8.00(t,J=8.4Hz,2H),7.84–7.76(m,1H),7.69–7.60(m,2H),7.34(t,J=6.7Hz,0.9×1H),6.98(t,J=7.1Hz,0.1×1H),4.27–4.19(m,2H),3.64(td,J=17.4,7.1Hz,0.2×1H),3.39(td,J=17.1,6.7Hz,1.8×1H),1.73–1.64(m,2H),1.48–1.37(m,2H),0.95(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.1,139.5(t,J=4.3Hz),135.7,131.8,130.9,129.5,122.6(t,J=288.0Hz),67.0,38.1(t,J=20.6Hz),30.5,19.1 13.7。
19F NMR(376MHz,CDCl3)δ-101.38(t,J=18.1Hz,0.9×2F),-102.66(t,J=17.9Hz,0.1×2F)。
HRMS(ESI):calcd.for C15H18F2IO4S[M+H]+458.99331,Found:458.99352。
实施例9(Z)-5,5-二氟-2-碘-5-(苯甲酰)戊-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的氯苯以及1.2mmol一碘二氟苯乙酮,在室温下用10W白光LED照射搅拌反应20h后,除掉多余的一碘二氟苯乙酮,然后再往反应试管中加入适量的乙酸乙酯和0.06mmol十羰基二锰催化剂,在相同光源下照射下继续反应10h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到5,5-二氟-2-碘-5-(苯甲酰)戊-2-烯酸丁酯,收率为89%,Z/E=5.4:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ8.16–8.08(m,2H),7.69–7.62(m,1H),7.55–7.47(m,2H),7.36(t,J=6.6Hz,0.84×1H),7.02(t,J=7.2Hz,0.16×1H),4.27–4.17(m,2H),3.48(td,J=17.5,7.2Hz,0.32×2H),3.24(td,J=17.2,6.6Hz,1.68×2H),1.74–1.62(m,2H),1.49–1.37(m,2H),0.96(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ188.1(t,J=30.8Hz),163.4,162.5,144.2(t,J=5.7Hz),142.3(t,J=5.3Hz),134.8 134.7,131.4,130.4,128.9,118.3(t,J=256.2Hz),100.2 89.8 67.0,66.6,42.0(t,J=23.6Hz),37.4(t,J=23.5Hz),30.6,30.5,19.213.8(d,J=4.6Hz)。
19F NMR(376MHz,CDCl3)δ-97.33(t,J=18.3Hz,0.84×2F),-98.92(t,J=18.6Hz,0.16×2F)。
HRMS(ESI):calcd.for C16H18F2IO3[M+H]+:423.02632,Found:423.02639。
实施例10(Z)-6,6,6-三氟-2-碘代-2-烯酸丁酯
在Schlenk瓶中加入0.4mmol烯基重氮乙酸正丁酯,适量的氯苯以及2.0mmol 2-碘-1,1,1-三氟乙烷,在50℃用1W白光LED照射搅拌反应50h后,除掉多余的2-碘-1,1,1-三氟乙烷,然后再往反应试管中加入适量的乙酸乙酯和0.1mmol十羰基二锰催化剂,在相同光源下照射下继续反应10h后,将反应液浓缩,石油醚/乙酸乙酯=50:1混合溶剂作为洗脱剂柱层析纯化即可得到异构化的6,6,6-三氟-2-碘代-2-烯酸丁酯,收率为71%,Z/E=13:1。其结构如下所示:
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.21(t,J=7.0Hz,0.93×1H),6.89(t,J=7.2Hz,0.07×1H),4.22(t,J=6.6Hz,1.88×2H),4.14(t,J=6.7Hz,0.12×2H),2.57(dd,J=15.1,7.4Hz,2H),2.38–2.24(m,2H),1.73–1.61(m,2H),1.49–1.36(m,2H),0.96(t,J=7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ166.2,162.6,148.6,144.7,126.4(q,J=276.7Hz),124.6,123.1,121.9,119.2,100.1,97.6,66.8,64.5,31.8(q,J=29.3Hz),30.6,29.8(q,J=3.1Hz),19.2,13.8。
19F NMR(376MHz,CDCl3)δ-66.51(s,0.93×3F),-66.55(s,0.07×3F)。
HRMS(APCI):calcd.for C10H13F3IO2[M-H]-:348.99178,Found:348.99176。
实施例11(Z)-5,5,6,6-四氟-2,6-二碘-2-烯酸丁酯
以烯基重氮乙酸正丁酯和1,2-二碘四氟代乙烷为原料,按照实施例1的方法,合成具有如下结构的化合物:
产率:76%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.36(t,J=8.6Hz,1H),4.22(t,J=6.6Hz,2H),4.04(d,J=8.6Hz,2H),1.74–1.64(m,2H),1.50–1.36(m,2H),0.96(t,J=7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ162.5,146.8,99.0,67.0,30.7,19.3,13.8,5.8.19F NMR(376MHz,CDCl3)δ-59.99(s,2F),-104.86(s,2F)。
HRMS(APCI):calcd.for C10H11F4I2O2[M-H]-:492.87900,Found:492.87911。
实施例12(Z)-5,5,5-三氟-2-碘戊-2-烯酸叔丁酯
以烯基重氮乙酸叔丁酯和三氟碘甲烷为原料,按照实施例2的方法,合成具有如下结构的化合物:
产率:85%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.13(t,J=6.6Hz,1H),3.11(qd,J=10.5,6.8Hz,2H),1.53(s,9H)。
13C NMR(100MHz,CDCl3)δ161.0,138.8(q,J=3.6Hz),125.3(q,J=277.1Hz),104.0,83.9,42.2(q,J=30.6Hz),28.0。
19F NMR(376MHz,CDCl3)δ-64.85(s,3F)。
HRMS(APCI):calcd.for C9H11F3IO2[M-H]-:334.97613,Found:334.97622。
实施例13(Z)-6-氯己基5,5,5-三氟-2-碘戊-2-烯酸酯
以6-氯烯基重氮乙酸己酯和三氟碘甲烷为原料,按照实施例3的方法,合成具有如下结构的化合物:
产率:78%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.26(t,J=6.6Hz,1H),4.25(t,J=6.6Hz,2H),3.54(t,J=6.6Hz,2H),3.14(qd,J=10.5,6.7Hz,2H),1.85–1.69(m,4H),1.55–1.40(m,4H)。
13C NMR(100MHz,CDCl3)δ162.0,139.9(q,J=3.7Hz),125.1(q,J=277.1Hz),100.9,67.2,45.0,41.9(q,J=30.7Hz),32.5,28.4,26.6,25.3。
19F NMR(376MHz,CDCl3)δ-64.79(s,3F)。
HRMS(APCI):calcd.for C11H14ClF3IO2[M-H]-:396.96846,Found:396.96896。
实施例14(Z)-5,5,5-三氟-2-碘戊-2-烯酸烯丙酯
以烯基重氮乙酸烯丙酯和三氟碘甲烷为原料,按照实施例4的方法,合成具有如下结构的化合物:
产率:65%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.30(t,J=6.6Hz,1H),6.02–5.91(m,1H),5.40(dd,J=17.2,1.4Hz,1H),5.31(dd,J=10.4,1.2Hz,1H),4.74(dt,J=5.7,1.3Hz,2H),3.14(qd,J=10.5,6.6Hz,2H)。
13C NMR(100MHz,CDCl3)δ161.9,140.4(q,J=3.7Hz),131.4,125.2(q,J=277.1Hz),119.3,100.7,67.8,42.2(q,J=30.7Hz)。
19F NMR(376MHz,CDCl3)δ-64.67(s,3F)。
HRMS(APCI):calcd.for C8H7F3IO2[M-H]-:318.94483,Found:318.94478。
实施例15(Z)-5,5,5-三氟-2-碘戊-2-烯酸炔丙酯
以烯基重氮乙酸炔丙酯和三氟碘甲烷为原料,按照实施例5的方法,合成具有如下结构的化合物:
产率:53%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.33(t,J=6.5Hz,1H),4.84(d,J=1.1Hz,2H),3.15(qd,J=10.4,6.6Hz,2H),2.55(t,J=2.2Hz,1H)。
13C NMR(100MHz,CDCl3)δ161.4,141.4(q,J=3.6Hz),125.1(q,J=277.1Hz),99.7,76.0,54.5,42.2(q,J=30.8Hz)。
19F NMR(376MHz,CDCl3)δ-64.72(s,3F)。
HRMS(APCI):calcd.for C8H5F3IO2[M-H]-:316.92918,Found:316.92941。
实施例16(Z)-(3s,5s,7s)-金刚烷-1-基5,5,5-三氟-2-碘戊-2-烯酸酯
以烯基重氮乙酸金刚烷酯和三氟碘甲烷为原料,按照实施例6的方法,合成具有如下结构的化合物:
1H NMR(400M产率:85%,Z/E>30:1。
化合物核磁和高分辨数据如下:
Hz,CDCl3)δ7.12(td,J=6.6,1.0Hz,1H),3.17–3.05(m,2H),2.21(s,3H),2.17(s,6H),1.68(s,6H)。
13C NMR(100MHz,CDCl3)δ160.6,138.7(q,J=3.6Hz),125.3(q,J=277.1Hz),104.2,83.9,42.2(q,J=30.5Hz),41.2,36.21,31.1。
19F NMR(376MHz,CDCl3)δ-64.83(s,3F)。
HRMS(ESI):calcd.for C15H18F3INaO2[M+Na]+:437.01958,Found:437.020039。
实施例17(Z)-(R)-2,5,7,8-四甲基-2-((4R,8R)-4,8,12-三甲基十三烷基)苯并吡喃-6-基5,5,5-三氟-2-碘戊-2-烯酸酯
以烯基重氮乙酸维生素E酯和三氟碘甲烷为原料,按照实施例7的方法,合成具有如下结构的化合物:
产率:74%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.43(t,J=6.5Hz,1H),3.13(qd,J=10.4,6.7Hz,2H),2.52(t,J=6.6Hz,2H),2.02(s,3H),1.94(s,3H),1.90(s,3H),1.79–1.64(m,2H),1.57–1.39(m,3H),1.38–1.11(m,15H),1.10–0.93(m,6H),0.82–0.74(m,12H)。
13C NMR(100MHz,CDCl3)δ160.8,149.9,141.3(d,J=3.6Hz),141.0,126.6,124.9,123.4,117.7,99.4,75.3,42.2(q,J=30.8Hz),39.5,37.7,37.6,37.5,37.4,32.9,32.8,28.1,25.0,24.6,22.9,22.8,21.2,20.8,19.9,19.84,19.81,19.18,19.75,13.1,12.3,12.0。
19F NMR(376MHz,CDCl3)δ-64.69(s,3F)。
HRMS(APCI):calcd.for C34H51F3IO3[M-H]-:691.28405,Found:691.28391。
实施例18(Z)-(3aS,5S,6R,6aS)-5-((S)-2,2-二甲基-1,3-二氧戊环-4-基)-2,2-二甲基四氢呋喃[2,3-d][1,3]二恶酚-6-基5,5,5-三氟-2-碘戊-2-烯酸酯
以(3aS,5S,6R,6aS)-5-((S)-2,2-二甲基-1,3-二氧戊环-4-基)-2,2-二甲基四氢呋喃[2,3-d][1,3]dioxol-6-基2-重氮基-3-烯酸酯和三氟碘甲烷为原料,按照实施例8的方法,合成具有如下结构的化合物:
产率:61%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.31(t,J=6.5Hz,1H),5.93(d,J=3.5Hz,1H),5.32(d,J=2.7Hz,1H),4.57(d,J=3.5Hz,1H),4.37–4.27(m,1H),4.24(dd,J=8.2,2.7Hz,1H),4.14(dd,J=8.4,5.9Hz,1H),4.02(dd,J=8.5,4.9Hz,1H),3.22–3.10(m,2H),1.54(s,3H),1.41(s,3H),1.31(d,J=3.5Hz,6H)。
13C NMR(100MHz,CDCl3)δ161.0,141.3(d,J=3.1Hz),125.1(q,J=277.1Hz),112.6(d,J=2.7Hz),109.6(d,J=2.5Hz),105.2,99.0,83.1,80.1,79.0,72.5,67.7,42.0(q,J=30.8Hz),26.9,26.8,26.3,25.2。
19F NMR(376MHz,CDCl3)δ-64.72(s,3F)。
HRMS(APCI):calcd.for C17H21F3IO7[M-H]-:521.02895,Found:521.02946。
实施例19(Z)-5,5,5-三氟-2-碘戊-2-烯酸胆固醇酯
以烯基重氮乙酸胆固醇酯和三氟碘甲烷为原料,按照实施例9的方法,合成具有如下结构的化合物:
产率:47%,Z/E>30:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.23(t,J=6.6Hz,1H),5.40(d,J=4.1Hz,1H),4.80–4.65(m,1H),3.13(qd,J=10.5,6.8Hz,2H),2.40(d,J=7.6Hz,2H),2.05–1.79(m,5H),1.74(s,1H),1.61–1.44(m,5H),1.40–0.95(m,18H),0.92(d,J=6.5Hz,3H),0.87(d,J=6.6Hz,6H),0.68(s,3H)。
13C NMR(100MHz,CDCl3)δ161.5,139.6(q,J=3.4Hz),139.4,125.3(q,J=277.1Hz),123.3,102.2,77.4,56.8,56.3,50.2,42.5,42.2(q,J=30.6Hz),39.9,39.7,38.0,37.1,36.8,36.3,35.9,32.1,32.0,29.9,28.4,28.2,27.8,24.4,24.0,23.0,22.7,21.2,19.5,18.9,12.0。
19F NMR(376MHz,CDCl3)δ-64.75(s,3F)。
HRMS(APCI):calcd.for C32H47F3IO2[M-H]-:647.25783,Found:647.25838。
实施例20(Z)-2-碘-4-(三氟甲基)十一碳二烯酸乙酯
以(E)-2-重氮基-3-烯酸乙酯和三氟碘甲烷为原料,按照实施例10的方法,合成具有如下结构的化合物:
产率:66%,Z/E=12:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.00(d,J=10.1Hz,0.92×1H),6.65(d,J=10.6Hz,0.08×1H),4.36–4.26(m,2H),3.97–3.84(m,0.08×1H),3.42–3.28(m,0.92×1H),1.88–1.78(m,1H),1.69–1.56(m,1H),1.40–1.18(m,11H),0.88(t,J=6.2Hz,3H)。
13C NMR(100MHz,,CDCl3)δ163.3,162.4,162.4,147.1(d,J=2.4Hz),145.4(d,J=2.3Hz),126.2(q,J=280.4Hz),101.1,100.1,63.3,62.8,51.5(q,J=27.0Hz),46.8(q,J=27.0Hz),31.6,31.6,29.3,29.1,27.8,26.3,22.7。
19F NMR(376MHz,CDCl3)δ-69.23(s,0.92×3F),-70.14(s,0.08×3F)。
HRMS(APCI):calcd.for C13H19F3IO2[M-H]-:391.03873,Found:391.03852。
实施例21(Z)-4-(5-丁氧基-1,1,1-三氟-4-碘-5-氧-3-烯-2-基)哌啶-1-羧基酯
以(E)-4-(3-重氮-4-乙氧基-4-氧丁-1-烯-1-基)哌啶-1-甲酸叔丁酯和三氟碘甲烷为原料,按照实施例1的方法,合成具有如下结构的化合物:
产率:71%,Z/E=20:1。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ7.03(d,J=10.6Hz,1H),4.31(q,J=7.1Hz,2H),4.21–4.07(m,2H),3.35(dqd,J=17.9,8.9,5.8Hz,1H),2.68(dd,J=27.0,13.2Hz,2H),2.13–2.02(m,1H),1.78(dd,J=29.5,15.8Hz,2H),1.46(s,9H),1.41–1.28(m,5H)。
13C NMR(100MHz,CDCl3)δ162.2,154.7,143.1,125.9(q,J=281.7Hz),102.8,79.8,63.4 55.9(q,J=26.1Hz),43.7,36.5,30.2,28.7,28.5,14.2。
19F NMR(376MHz,CDCl3)δ-65.16(s,3F)。
HRMS(ESI):calcd.for C17H25F3INO4Na[M+Na]+:514.06726,Found:514.06714。
实施例22
以三氟碘甲烷和α-甲基烯基重氮乙酸乙酯为原料,按照实施例1的方法,反应得到两个可以分离的顺反异构体,Z/E=3:1,分别具有如下结构的化合物:
(Z)-5,5,5-三氟-2-碘-3-碘-3-甲基戊-2-烯酸乙酯
产率:53%。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ4.29(q,J=7.1Hz,2H),3.25(q,J=10.4Hz,2H),2.13(s,3H),1.34(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ165.9,140.7(d,J=2.2Hz),125.4(q,J=277.0Hz),90.8,62.5,47.0(q,J=29.6Hz),21.0,14.1.19F NMR(376MHz,CDCl3)δ-62.47(s,3F).HRMS(APCI):calcd.for C8H9F3IO2[M-H]-:320.96048,Found:320.96051。
(E)-5,5,5-三氟-2-碘-3-碘-3-甲基戊-2-烯酸乙酯
产率:18%。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ4.27(q,J=7.1Hz,2H),3.45(q,J=10.5Hz,2H),2.19(s,3H),1.32(t,J=7.1Hz,3H)。
13C NMR(100MHz,CDCl3)δ165.0,142.1(d,J=2.4Hz),124.7(q,J=278.5Hz),93.4,62.4,38.4(q,J=29.9Hz),30.5,13.9。
19F NMR(376MHz,CDCl3)δ-63.59(s,3F)。
HRMS(APCI):calcd.for C8H9F3IO2[M-H]-:320.96048,Found:320.96053。
对比例23
以1-环已烯基重氮乙酸乙酯和三氟碘甲烷为原料,按照实施例1的方法,反应得到两个可以分离的顺反异构体,Z/E=5:1,分别具有如下结构的化合物:
(Z)-乙基2-碘-2-(2-(三氟甲基)环己亚基)乙酸乙酯
产率:55.8%。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ4.35–4.20(m,2H),4.00(qd,J=10.5,5.2Hz,1H),2.89(d,J=14.6Hz,1H),2.33(td,J=14.1,4.8Hz,1H),2.12–2.03(m,1H),1.96–1.88(m,1H),1.75–1.57(m,3H),1.48–1.35(m,1H),1.31(t,J=7.1Hz,3H)。
13C NMR(100MHz,CDCl3)δ165.6 146.4,126.2(q,J=282.5Hz),89.9,62.3,42.2(q,J=27.2Hz),37.3,26.1,25.9,21.0,13.9。
19F NMR(376MHz,CDCl3)δ-64.47(s,3F)。
HRMS(ESI):calcd.for C11H15F3IO2[M+H]+:363.00633,Found:363.00652。
(E)-乙基2-碘-2-(2-(三氟甲基)环己亚基)乙酸乙酯
产率:11.2%。
化合物核磁和高分辨数据如下:
1H NMR(400MHz,CDCl3)δ4.30(q,J=7.1Hz,2H),3.61(qd,J=10.3,5.1Hz,1H),2.85(d,J=14.3Hz,1H),2.33–2.14(m,2H),1.88–1.75(m,1H),1.76–1.56(m,3H),1.35(t,J=7.1Hz,3H),1.32–1.27(m,1H)。
13C NMR(100MHz,CDCl3)δ166.3,145.6,126.92(d,J=283.2Hz),88.6,62.5,49.6(q,J=26.9Hz),30.7,26.7 26.0,21.0,14.1。
19F NMR(376MHz,CDCl3)δ-64.87(s,3F)。
HRMS(ESI):calcd.for C11H15F3IO2[M+H]+:363.00633,Found:363.00656。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,包括如下步骤:
S1.在可见光照条件下,式(Ⅱ)所示的烯基重氮化合物和式(Ⅲ)所示的全氟烷基碘代物于有机溶剂中,在室温至80℃,密闭条件下发生ATRA反应得到1-碘-3-全氟烷基烯烃化合物异构体混合物;
S2.将S1得到的1-碘-3-全氟烷基烯烃化合物异构体混合物,在相同光源以及锰催化剂条件下进行异构化反应,得到如式(I)所述1-碘-3-全氟烷基烯烃化合物,其中所述锰催化剂为十羰基二锰;
式(I)中,R1、R2独立地选自氢原子、C1~10烷基、C5~8环烷基、芳基或杂环基,其中,芳基为苯基或含取代基的苯基,所述取代基选自烷基、烷氧基、三氟甲基、芳香基中的一种或几种;所述杂环基选自噻吩基、呋喃基、吡啶基、噻唑基、噁唑基、哌嗪基或四氢呋喃基;
R1、R2为独立地取代基或相连成环烷基;Rf选自C1~10全氟烷基、2-二氟-1-酰基、2-二氟-1-酯基;EWG为甲酸烷基酯基或甲酸芳基酯基。
2.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述烯基重氮化合物为烯基重氮乙酸酯,烯基重氮乙酸酯与全氟烷基碘代物的摩尔比为1:1~5。
3.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述ATRA反应的时间为0.5~72h。
4.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述异构化反应的时间为1~20h。
5.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述有机溶剂为二氯甲烷、二氯乙烷、乙酸乙酯、乙醇、甲醇、三氟异丙醇、异丙醇、乙腈、二甲基亚砜、N,N-二甲基甲酰胺、二氧六环、四氢呋喃、甲苯或氯苯中的一种或几种的组合。
6.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述可见光为CFL、LED白光、LED蓝光或太阳光中的一种。
7.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,所述烯基重氮化合物为烯基重氮乙酸酯,烯基重氮乙酸酯与锰催化剂的摩尔比1:0.025~1。
8.根据权利要求1所述1-碘-3-全氟烷基烯烃化合物的制备方法,其特征在于,式(I)中所述R1、R2独立地选自氢原子、烷基;Rf选自C1~10全氟烷基、2-二氟-1-酰基、2-二氟-1-酯基。
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