CN115141159A - Application of bis (fluorosulfonyl) imide as catalyst - Google Patents
Application of bis (fluorosulfonyl) imide as catalyst Download PDFInfo
- Publication number
- CN115141159A CN115141159A CN202210754232.0A CN202210754232A CN115141159A CN 115141159 A CN115141159 A CN 115141159A CN 202210754232 A CN202210754232 A CN 202210754232A CN 115141159 A CN115141159 A CN 115141159A
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- Prior art keywords
- solvent
- formula
- compound shown
- alkyl
- aryl
- 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.)
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- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- -1 bis-fluorosulfonyl imide Chemical class 0.000 claims abstract description 88
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 25
- 238000006266 etherification reaction Methods 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 320
- 150000001875 compounds Chemical class 0.000 claims description 277
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 171
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 160
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 156
- 238000002360 preparation method Methods 0.000 claims description 125
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 99
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 99
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 73
- 125000000217 alkyl group Chemical group 0.000 claims description 59
- 229910052736 halogen Inorganic materials 0.000 claims description 58
- 150000002367 halogens Chemical group 0.000 claims description 58
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 57
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 57
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 56
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 55
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 52
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 49
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 44
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 43
- 229910052801 chlorine Inorganic materials 0.000 claims description 43
- 239000000460 chlorine Substances 0.000 claims description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 42
- 238000006467 substitution reaction Methods 0.000 claims description 31
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 30
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 29
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 29
- 229910052794 bromium Inorganic materials 0.000 claims description 29
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 26
- 150000001408 amides Chemical class 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 24
- 150000003462 sulfoxides Chemical class 0.000 claims description 24
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 23
- 230000009471 action Effects 0.000 claims description 23
- 150000002576 ketones Chemical class 0.000 claims description 23
- 150000002825 nitriles Chemical class 0.000 claims description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006462 rearrangement reaction Methods 0.000 claims description 21
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 20
- 101100025412 Arabidopsis thaliana XI-A gene Proteins 0.000 claims description 19
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 15
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000002829 reductive effect Effects 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 101100347612 Arabidopsis thaliana VIII-B gene Proteins 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 238000007259 addition reaction Methods 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 101100347605 Arabidopsis thaliana VIII-A gene Proteins 0.000 claims description 6
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 12
- 125000003118 aryl group Chemical group 0.000 claims 2
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 claims 1
- HNUALPPJLMYHDK-UHFFFAOYSA-N C[CH]C Chemical compound C[CH]C HNUALPPJLMYHDK-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 125000000304 alkynyl group Chemical group 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 150000002596 lactones Chemical group 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 22
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 18
- 238000001514 detection method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 230000008034 disappearance Effects 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 9
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- KJHHAPASNNVTSN-KPKJPENVSA-N 4'-Methoxychalcone Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC=CC=C1 KJHHAPASNNVTSN-KPKJPENVSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FEWIGMWODIRUJM-HWKANZROSA-N (E)-4-hexen-3-one Chemical compound CCC(=O)\C=C\C FEWIGMWODIRUJM-HWKANZROSA-N 0.000 description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 4
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 4
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
- FEWIGMWODIRUJM-UHFFFAOYSA-N hex-4-en-3-one Natural products CCC(=O)C=CC FEWIGMWODIRUJM-UHFFFAOYSA-N 0.000 description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-M phenylacetate Chemical compound [O-]C(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-M 0.000 description 4
- 229940049953 phenylacetate Drugs 0.000 description 4
- HVAPLSNCVYXFDQ-UHFFFAOYSA-N 3,3-dimethyl-1-(trifluoromethyl)-1$l^{3},2-benziodoxole Chemical compound C1=CC=C2C(C)(C)OI(C(F)(F)F)C2=C1 HVAPLSNCVYXFDQ-UHFFFAOYSA-N 0.000 description 3
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 3
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 3
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 150000007960 acetonitrile Chemical class 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940029284 trichlorofluoromethane Drugs 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- PUJDIJCNWFYVJX-UHFFFAOYSA-N benzyl carbamate Chemical compound NC(=O)OCC1=CC=CC=C1 PUJDIJCNWFYVJX-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PPFAPKNCEXDZNN-UHFFFAOYSA-N N=[SH2].F.F Chemical compound N=[SH2].F.F PPFAPKNCEXDZNN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 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
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate 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
- 150000003536 tetrazoles Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses an application of bis (fluorosulfonyl) imide as a catalyst. According to the invention, the bis-fluorosulfonyl imide is used as a catalyst, so that the Friedel-Crafts reaction, esterification reaction, lactone ring-opening polymerization reaction, silyl ether polymerization reaction, carbonyl compound reduction etherification, alkynyl hydrolysis and other reactions can be effectively catalyzed, the reaction conditions are mild, and the atom economy is high.
Description
Technical Field
The invention relates to application of bis (fluorosulfonyl) imide as a catalyst.
Background
Bis (fluorosulfonyl) imide (HN (SO) 2 F) 2 ) The N-containing strong acid is a nitrogen-containing strong acid and is mainly applied to the field of lithium batteries, such as lithium bis (fluorosulfonyl) imide, imidazole ionic liquid and the like. The lithium bis (fluorosulfonyl) imide as the lithium battery electrolyte has higher thermal stability and hydrolytic stability compared with the traditional lithium hexafluorophosphate. Para-bis (fluorosulfonyl) imide (HN (SO) 2 F) 2 ) The structure is analyzed, and under the strong electron-withdrawing action of the fluorosulfonyl group, the negative charge on the N atom can beHighly delocalised by resonance dispersion over the entire O-S-N framework, and thus greatly enhanced (FSO) 2 ) 2 N - Secondly, the fluorosulfonyl group has larger steric hindrance and strong electron withdrawing effect, so that the coordination capability of the ion is greatly reduced.
The difluo-sulfonimide belongs to nitrogen-containing superacid, is a novel super strong Bronsted acid, and has the strength higher than concentrated sulfuric acid. Among known super acids, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid and the like are widely used as catalysts in the synthesis of intermediates for medicines, pesticides, polymers and the like.
The application of the bis-fluorosulfonyl imide as a catalyst in organic synthesis is not found at present, mainly because the acid is not commercially produced at present, and the synthetic route is not mature. At present, a large amount of fluorosulfonic acid is generally needed to be used as a solvent in the synthesis of bis-fluorosulfonyl imide, the fluorosulfonic acid is expensive, and the synthesis cost is high, and in addition, the boiling point of fluorosulfonic acid is very close to that of bis-fluorosulfonyl imide, so that the separation and purification of products are difficult.
In the earlier research on the acidification process of potassium (or sodium) bis (fluorosulfonyl) imide, the applicant finds that bis (fluorosulfonyl) imide can be obtained by rapid and simple separation with high yield under the conditions of using concentrated sulfuric acid as acid and using sulfur dioxide as solvent at low temperature, and has the advantages of low price, simple post-treatment, easy separation and purification, and the synthetic route has the possibility of industrial production.
Disclosure of Invention
The invention aims to overcome the defect of narrow application field of the existing bis (fluorosulfonyl) imide and provides the application of the bis (fluorosulfonyl) imide as the catalyst, and the bis (fluorosulfonyl) imide can be used as the catalyst to efficiently catalyze Friedel-Crafts reaction, esterification reaction, lactone ring-opening polymerization reaction, silicon ether polymerization reaction, carbonyl compound reduction etherification, alkynyl hydrolysis and other reactions, and has the advantages of mild reaction conditions and high atom economy.
The invention provides an application of bis (fluorosulfonyl) imide as a catalyst in preparation of polylactone shown in a formula (I), which comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, carrying out polymerization reaction on a compound shown as a formula (I-A) and a compound shown as a formula (I-B) to obtain polylactone shown as a formula (I);
wherein n is 1 Is an integer of 1 to 7;
R 1 is C1-C16 alkyl or- (CH) 2 ) n2 -Ar，n 2 Is an integer of 1 to 6, ar is a C6-C10 aryl or R A Substituted C6-C10 aryl; r A Is halogen, C1-C6 alkyl or C1-C6 alkoxy;
m 1 is an integer of 50-200.
Preferably, n 1 Is 1,2 or 3, for example 3.
Preferably, R 1 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group.
Preferably, R 1 In, n 2 May be 1,2 or 3, for example 3.
Preferably, in Ar, said C6-C10 aryl and said R A The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, in Ar, the R A R in substituted C6-C10 aryl A The number of substitution(s) may be 1 to 3 (e.g., 1), each R A The same or different.
Preferably, R A Wherein said halogen is fluorine, chlorine, bromine or iodine.
Preferably, R A The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R A The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 1 In which Ar is phenyl or R A A substituted phenyl group.
Preferably, it isThe compound shown as the formula (I-B) is
In the preparation of the polylactone represented by the formula (I), the amount of the bis-fluorosulfonyl imide is preferably 0.1 to 10% (e.g., 0.1%) of the molar amount of the compound represented by the formula (I-A).
In the preparation of the polylactone represented by the formula (I), the dosage ratio of the compound represented by the formula (I-A) and the compound represented by the formula (I-B) can be the dosage ratio commonly used in the reaction in the field, for example, the molar ratio of the compound represented by the formula (I-A) to the compound represented by the formula (I-B) is (50-200): 1, and is 100 for example.
In the preparation of the polylactone shown in the formula (I), the solvent can be a solvent commonly used in the reaction in the field, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; further examples include tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc.; and for example methylene chloride.
In the preparation of the polylactone of formula (I), the temperature of the polymerization reaction can be a temperature commonly used in the art for such reactions, such as 20 deg.C to the reflux temperature of the solvent, such as room temperature.
In the preparation of the polylactone of formula (I), the progress of the polymerization reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and is generally determined as the end point of the reaction when the compound of formula (I-A) disappears. The time for the polymerization reaction is preferably 4 to 12 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of silicone oil shown in the formula (II), which comprises the following steps:
under the action of bis (fluorosulfonyl) imide, carrying out polymerization reaction on a compound shown as a formula (II-A) and a compound shown as a formula (II-B) to obtain silicone oil shown as a formula (II);
wherein R is 2 、R 3 、R 4 And R 5 Independently is a C1-C16 alkyl group or a C6-C10 aryl group;
m 2 is an integer of 50-200.
Preferably, R 2 、R 3 、R 4 Or R 5 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (e.g., a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group).
Preferably, R 2 、R 3 、R 4 Or R 5 In (e), the C6-C10 aryl group may be phenyl.
Preferably, R 2 、R 3 、R 4 And R 5 Independently of one another, C1-C10 alkyl, and further independently of one another, C1-C6 alkyl (for example C1-C3 alkyl, and further for example methyl, ethyl, n-propyl or isopropyl). More preferably, R 2 、R 3 、R 4 And R 5 Are each C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl, and further such as methyl.
In the preparation of the silicone oil represented by the formula (II), the bis-fluorosulfonyl imide is preferably used in an amount of 1 to 10% (e.g., 4%) by mole based on the compound represented by the formula (II-A).
In the preparation of the silicone oil represented by the formula (II), the dosage ratio of the compound represented by the formula (II-A) and the compound represented by the formula (II-B) can be the dosage ratio commonly used in the reaction in the field, for example, the molar ratio of the compound represented by the formula (II-A) to the compound represented by the formula (II-B) is (30-200): 1, and further 39.9.
In the preparation of the silicone oil shown in formula (II), the polymerization reaction may be performed in a solvent or in a solvent, and the solvent may be a solvent commonly used in the art, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide and 1,4-dioxane, etc. Preferably, the polymerization is carried out in the absence of a solvent.
In the preparation of the silicone oil represented by the formula (II), the temperature of the polymerization reaction may be a temperature commonly used in the art for such a reaction, for example, 20 ℃ to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the silicone oil of formula (II), the progress of the polymerization reaction can be monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and is generally determined as the end point of the reaction when the compound of formula (II-A) disappears. The time for the polymerization reaction is preferably 2 to 12 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a tetrazole compound shown as a formula (III), which comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (III-A), an orthoformate compound shown as a formula (III-B) and sodium azide to obtain a tetrazole compound shown as a formula (III);
wherein R is 6 Is C1-C16 alkyl, C6-C10 aryl or R B Substituted C6-C10 aryl, R B Is halogen or C2-C4 alkynyl;
R 6-1 is methyl or ethyl.
Preferably, R 6 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group.
Preferably, R 6 Wherein said C6-C10 aryl and said R B The C6-C10 aryl group of the substituted C6-C10 aryl groups may independently be a phenyl group。
Preferably, R 6 In (1), the R B R in substituted C6-C10 aryl B The number of substitution(s) may be 1 to 3 (e.g., 1), each R B The same or different.
Preferably, R B The halogen may be fluorine, chlorine, bromine or iodine, for example bromine.
Preferably, R B In (e), the C2-C4 alkynyl group may be an ethynyl group.
Preferably, R is 6 Is R B Substituted phenyl radicals, R B Is halogen or ethynyl, e.g. the R 6 Is composed of
In the preparation of the tetrazole-type compound shown in the formula (III), the bis-fluorosulfonyl imide is preferably used in an amount of 1 to 10% (e.g., 5%) of the molar amount of the compound shown in the formula (III-a).
In the preparation of the tetrazole compound represented by the formula (III), the dosage ratio of the compound represented by the formula (III-a) and the orthoformate compound represented by the formula (III-B) may be a dosage ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (III-a) to the orthoformate compound represented by the formula (III-B) is 1: (1-2), further example 1:1.2.
in the preparation of the tetrazole compound represented by the formula (III), the amount ratio of the compound represented by the formula (III-a) to the sodium azide may be an amount ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (III-a) to the sodium azide is 1: (1-3), for example, 1:1 or 1:1.1.
in the preparation of the tetrazole compound shown in the formula (III), the solvent may be a solvent commonly used in the field such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples of the solvent include glycerol, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc.; for example, glycerol.
In the preparation of the tetrazole-based compound represented by the formula (III), the reaction temperature may be a temperature commonly used in the art for such reactions, for example, 20 ℃ to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the tetrazole compound represented by the formula (III), the progress of the reaction can be monitored by a detection method (such as TLC, HPLC or GC) which is conventional in the art, and the end point of the reaction is generally determined when the compound represented by the formula (III-a) disappears. The reaction time is preferably 2 to 12 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (IV), which comprises the following steps:
in Sup>A solvent, under the action of bis (fluorosulfonyl) imide, carrying out addition reaction on Sup>A compound shown as Sup>A formulSup>A (IV-A) and Sup>A compound shown as Sup>A formulSup>A (IV-B) to obtain Sup>A compound shown as Sup>A formulSup>A (IV);
wherein the content of the first and second substances,
x is NH, S or O;
R 7 、R 8 and R 9 Independently is C1-C16 alkyl, C6-C10 aryl, R C Substituted C6-C10 aryl or
R C Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, R 7 、R 8 Or R 9 The C1-C16 alkyl group is, for example, C1-C10 alkyl, and further, for example, C1-C6 alkyl (for example, C1-C3 alkyl, further, for example, methyl, ethyl, n-propyl orIsopropyl).
Preferably, R 7 、R 8 Or R 9 Wherein said C6-C10 aryl and said R C The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R 7 、R 8 Or R 9 In (1), the R C R in substituted benzyl C The number of substitution(s) may be 1 to 3 (e.g., 1), each R C The same or different.
Preferably, R C Wherein said halogen is fluorine, chlorine, bromine or iodine.
Preferably, R C The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R C The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 7 And R 8 Independently C1-C16 alkyl, for example C1-C10 alkyl, and further for example C1-C6 alkyl (for example C1-C3 alkyl, further for example methyl, ethyl, n-propyl or isopropyl).
Preferably, R 9 Is composed of
Preferably, X is NH.
Preferably, the compound shown in the formulSup>A (IV-A) is
Preferably, the compound shown in the formula (IV-B) is
In the preparation of the compound represented by the formulSup>A (IV), the bis-fluorosulfonyl imide is preferably used in an amount of 1 to 10% (e.g., 5%) based on the molar amount of the compound represented by the formulSup>A (IV-A).
In the preparation of the compound shown in the formulSup>A (IV), the dosage ratio of the compound shown in the formulSup>A (IV-A) and the compound shown in the formulSup>A (IV-B) can be the dosage ratio commonly used in the reaction in the field, for example, the molar ratio of the compound shown in the formulSup>A (IV-A) and the compound shown in the formulSup>A (IV-B) is 1 (1-10), and further, for example, 1:1.
In the preparation of the compound represented by the formula (IV), the solvent may be a solvent commonly used in the art for such reactions, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, further examples are acetonitrile.
In the preparation of the compound represented by the formula (IV), the temperature of the addition reaction may be a temperature commonly used in the art for such a reaction, for example, 20 ℃ to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the compound represented by the formulSup>A (IV), the progress of the addition reaction can be monitored by Sup>A detection method (such as TLC, HPLC or GC) which is conventional in the art, and the progress is generally determined as an end point of the reaction when the compound represented by the formulSup>A (IV-A) disappears. The time of the addition reaction is preferably 10 minutes to 12 hours, for example 0.5 hour.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (V), which comprises the following steps:
in Sup>A solvent, under the action of bis (fluorosulfonyl) imide, carrying out Friedel-crafts reaction on Sup>A compound shown as Sup>A formulSup>A (V-A) and Sup>A compound shown as Sup>A formulSup>A (V-B) to obtain Sup>A compound shown as Sup>A formulSup>A (V);
wherein Y is halogen,
R 10 Is C1-C16 alkyl, benzyl, C6-C10 aryl, R D Substituted C6-C10 aryl or R E Substituted benzyl, R D And R E Independently halogen, C1-C6 alkyl or C1-C6 alkoxy;
R 11 is C1-C6 alkyl or C1-C6 alkoxy.
Preferably, in Y, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine, bromine or iodine.
Preferably, R 10 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 10 Wherein said C6-C10 aryl group and said R D The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R 10 In (1), the R D R in substituted C6-C10 aryl D The number of substitutions (C) may be 1 to 3 (e.g. 1), each R D The same or different.
Preferably, R 10 In (1), the R E R in substituted benzyl E The number of substitution(s) may be 1 to 3 (e.g., 1), each R E The same or different.
Preferably, R D Or R E Wherein said halogen is fluorine, chlorine, bromine or iodine.
Preferably, R D 、R E Or R 11 The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R D 、R E Or R 11 The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R D 、R E And R 11 Independently a C1-C6 alkoxy group.
Preferably, Y is
Preferably, R 10 Is benzyl, phenyl, R D Substituted phenyl or R E Substituted benzyl, R D And R E Independently is a C1-C6 alkoxy group.
Preferably, the compound represented by the formulSup>A (V-A) is
Preferably, the compound represented by the formula (V-B) is
In the preparation of the compound represented by the formula (V), the bis-fluorosulfonyl imide is preferably used in an amount of 0.1 to 10% (e.g., 5%) by mole based on the compound represented by the formula (V-B).
In the preparation of the compound shown in the formulSup>A (V), the dosage ratio of the compound shown in the formulSup>A (V-A) and the compound shown in the formulSup>A (V-B) can be the dosage ratio commonly used in the reaction in the field, for example, the molar ratio of the compound shown in the formulSup>A (V-A) and the compound shown in the formulSup>A (V-B) is (1-10): 1, and further, for example, 1:1.
In the preparation of the compound shown in the formula (V), the solvent may be a solvent commonly used in the reaction in the field, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; further examples are dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, further examples are dichloromethane.
In the preparation of the compound represented by the formula (V), the temperature of the friedel-crafts reaction may be a temperature commonly used in the art for such reactions, for example, 20 ℃ to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the compound of formula (V), the progress of the friedel-crafts reaction can be monitored by detection methods conventional in the art (e.g. TLC, HPLC or GC), and the end point of the reaction is generally determined when the compound of formula (V-B) disappears. The time of the Friedel-crafts reaction is preferably between 5 minutes and 12 hours, for example 0.5 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (VI), which comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, performing hydrolysis reaction on a compound shown as a formula (VI-A) and water to obtain a compound shown as a formula (VI);
wherein R is 12 Is C1-C16 alkyl, C6-C10 aryl or R F Substituted C6-C10 aryl, R F Is an amino group.
Preferably, R 12 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 12 Wherein said C6-C10 aryl and said R F The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R 12 In (1), the R F R in substituted C6-C10 aryl F The number of substitution(s) may be 1 to 3 (e.g., 1), each R F The same or different.
Preferably, R 12 Is phenyl or phenyl substituted by amino.
In the preparation of the compound represented by the formula (VI), the bis-fluorosulfonyl imide is preferably used in an amount of 5 to 30% (e.g., 10%) by mole based on the compound represented by the formula (VI-A).
In the preparation of the compound represented by the formula (VI), the amount ratio of the compound represented by the formula (VI-A) to water can be the amount ratio commonly used in the reaction in the field, for example, the molar ratio of the compound represented by the formula (VI-A) to water is 1 (1-10), and further 1.9.
In the preparation of the compound shown in the formula (VI), the solvent may be a solvent commonly used in the reaction in the field, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are methylene chloride, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc., further examples are 1,4-dioxane.
In the preparation of the compound represented by the formula (VI), the temperature of the hydrolysis reaction may be a temperature commonly used in the art for such a reaction, for example, 20 ℃ to the reflux temperature of the solvent, for example, 100 ℃.
In the preparation of the compound represented by the formula (VI), the progress of the hydrolysis reaction can be monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and is generally determined as the end point of the reaction when the compound represented by the formula (VI-A) disappears. The time of the hydrolysis reaction is preferably 2 to 12 hours, for example 8 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (VII), which comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (VII-A) with allyl trimethylsilane to obtain a compound shown as a formula (VII);
wherein R is 13 And R 14 Independently is C1-C16 alkyl, C6-C10 aryl or R G Substituted C6-C10 aryl, R G Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, R 13 Or R 14 The C1-C16 alkyl group is, for example, C1-C10 alkyl, and further, for example, C1-C6 alkyl (for example, C1-C3 alkyl, further, for example, methyl, ethyl, n-propyl orIsopropyl).
Preferably, R 13 Or R 14 Wherein said C6-C10 aryl group and said R G The C6-C10 aryl group of the substituted C6-C10 aryl group is independently a phenyl group.
Preferably, R G In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R G The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R G The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 13 Or R 14 In (1), the R G R in substituted C6-C10 aryl G The number of substitution(s) may be 1 to 3 (e.g., 1), each R G The same or different.
Preferably, R 13 And R 14 Independently is phenyl or R G Substituted phenyl radicals, R G Is C1-C3 alkoxy.
Preferably, the compound shown in the formula (VII-A) is
In the preparation of the compound shown in the formula (VII), the usage amount of the bis-fluorosulfonyl imide is preferably 5-30%, for example 10% of the molar amount of the compound shown in the formula (VII-A).
In the preparation of the compound represented by the formula (VII), the amount ratio of the compound represented by the formula (VII-A) and the allyltrimethylsilane may be the amount ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (VII-A) and the allyltrimethylsilane is 1 (1-10), for example, 1.2.
In the preparation of the compound shown in the formula (VII), the solvent may be a solvent commonly used in the reaction in the field, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, further examples are dichloromethane.
In the preparation of the compound represented by the formula (VII), the temperature of the reaction may be a temperature commonly used in the art for such a reaction, for example, -20 ℃ to room temperature, for example, room temperature.
In the preparation of the compound represented by the formula (VII), the progress of the reaction can be monitored by detection methods generally used in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally defined as the time when the compound represented by the formula (VII-A) disappears. The reaction time is preferably 2 to 12 hours, for example 2 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (VIII), which comprises the following steps:
under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (VIII-A), a compound shown as a formula (VIII-B) and a compound shown as a formula (VIII-C) to obtain a compound shown as a formula (VIII);
wherein R is 15 、R 16 、R 17 、R 18 、R 19 And R 20 Independently is H, C-C16 alkyl, C6-C10 aryl or R H Substituted C6-C10 aryl, R H Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, R 15 、R 16 、R 17 、R 18 、R 19 Or R 20 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 15 、R 16 、R 17 、R 18 、R 19 Or R 20 Wherein said C6-C10 aryl and said R H The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R H In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R H The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R H The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 15 、R 16 、R 17 、R 18 、R 19 Or R 20 In (1), the R H R in substituted C6-C10 aryl H The number of substitution(s) may be 1 to 3 (e.g., 1), each R H The same or different.
Preferably, R 15 、R 16 、R 17 、R 18 、R 19 And R 20 Independently H, C-C6 alkyl, phenyl or R H Substituted phenyl radicals, R H Is halogen, C1-C3 alkyl or C1-C3 alkoxy.
Preferably, the compound shown in the formula (VIII-A) is
Preferably, the compound represented by the formula (VIII-B) is
Preferably, the compound represented by the formula (VIII-C) is
In the preparation of the compound shown in formula (VIII), the amount of the bis-fluorosulfonyl imide used is preferably 1% to 100%, for example 10% to 50%, and further for example 30% of the molar amount of the compound shown in formula (VIII-B).
In the preparation of the compound represented by the formula (VIII), the amount ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-B) can be the amount ratio commonly used in such reactions in the field, for example, the molar ratio of the compound represented by the formula (VII-A) to the compound represented by the formula (VIII-B) is (1-2): 1, for example, 1.1 or 1.3.
In the preparation of the compound represented by the formula (VIII), the amount ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-C) may be an amount ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (VII-A) to the compound represented by the formula (VIII-C) is 1: (1-3), for example 1.3, 1.8 or 1:2.
In the preparation of the compound represented by the formula (VIII), the reaction may be carried out in the absence of a solvent or in a solvent, and the solvent may be a solvent commonly used in the art for such a reaction, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc. Preferably, the reaction is carried out in the absence of a solvent.
In the preparation of the compound represented by the formula (VIII), the reaction temperature may be a temperature commonly used in the art for such a reaction, for example, room temperature to 50 ℃, for example, room temperature.
In the preparation of the compound represented by the formula (VIII), the progress of the reaction can be monitored by a detection method (such as TLC, HPLC or GC) which is conventional in the art, and the end point of the reaction is generally determined when the compound represented by the formula (VIII-B) disappears. The reaction time is preferably 2 to 12 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in a rearrangement reaction of a compound shown as a formula (IX), which comprises the following steps:
in a solvent, carrying out rearrangement reaction on the compound shown in the formula (IX) under the action of bis (fluorosulfonyl) imide to obtain the compound shown in the formula (IX-A) and/or the compound shown in the formula (IX-B);
wherein R is 21 Is C1-C16 alkyl, C6-C10 aryl or R I Substituted C6-C10 aryl, R I Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, R 21 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 21 Wherein said C6-C10 aryl and said R I The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R I In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R I The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R I The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 21 In (1), the R I R in substituted C6-C10 aryl I The number of substitutions (C) may be 1 to 3 (e.g. 1), each R I The same or different.
Preferably, R 21 C1-C10 alkyl, and further for example C1-C6 alkyl (for example C1-C3 alkyl, and further for example methyl, ethyl, n-propyl or isopropyl).
In the rearrangement reaction of the compound represented by the formula (IX), the bis-fluorosulfonyl imide is preferably used in an amount of 20 to 150%, for example 100 to 150%, and further for example 123% or 124% of the molar amount of the compound represented by the formula (IX).
In the rearrangement reaction of the compound represented by the formula (IX), the rearrangement reaction may be performed in no solvent or in a solvent, and the solvent may be a solvent commonly used in the art, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc. Preferably, the rearrangement reaction is carried out in the absence of a solvent.
In the rearrangement reaction of the compound represented by the formula (IX), the temperature of the rearrangement reaction may be a temperature commonly used in such reactions in the art, for example, 20 ℃ to 150 ℃, for example, room temperature, 60 ℃.
In the rearrangement reaction of the compound represented by the formula (IX), the progress of the rearrangement reaction can be monitored by a detection method (such as TLC, HPLC or GC) which is conventional in the art, and the end point of the reaction is generally determined when the compound represented by the formula (IX) disappears. The time for the rearrangement reaction is preferably 2 to 12 hours, for example 3 hours.
The invention also provides an application of the bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as the formula (X), which comprises the following steps:
under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (X-A) with a compound shown as a formula (X-B) to obtain a compound shown as a formula (X);
wherein R is 22 Is H, C-C16 alkyl, C6-C10 aryl or R J Substituted C6-C10 aryl; r is 23 Is C1-C16 alkyl, C6-C10 aryl or R K Substituted C6-C10 aryl, R J And R K Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, R 22 Or R 23 In (A), the C1-C16 alkyl is, for example, C1-C10 alkyl, further for example C1-C6 alkyl (e.g. C1-C3 alkyl, further for example methyl)Alkyl, ethyl, n-propyl or isopropyl).
Preferably, R 22 Or R 23 Wherein said C6-C10 aryl, said R J Substituted C6-C10 aryl and said R K The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R J Or R K In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R J Or R K The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R J Or R K The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 22 In (1), the R J R in substituted C6-C10 aryl J The number of substitutions (c) may be 1 to 3 (e.g. 1), each R J The same or different.
Preferably, R 23 In (1), the R K R in substituted C6-C10 aryl K The number of substitution(s) may be 1 to 3 (e.g., 1), each R K The same or different.
Preferably, R 22 Is phenyl or R J A substituted phenyl group.
Preferably, R 23 Is C1-C16 alkyl, for example C1-C10 alkyl, and further for example C1-C6 alkyl (for example C1-C3 alkyl, further for example methyl, ethyl, n-propyl or isopropyl).
In the preparation of the compound shown in the formula (X), the amount of the bis-fluorosulfonyl imide used is preferably 0.1 to 10%, for example 10%, of the molar amount of the compound shown in the formula (X-a).
In the preparation of the compound represented by the formula (X), the dosage ratio of the compound represented by the formula (X-A) and the compound represented by the formula (X-B) can be the dosage ratio commonly used in the reaction in the field, for example, the molar ratio of the compound represented by the formula (X-A) to the compound represented by the formula (X-B) is 1 (1-10), for example, 1.
In the preparation of the compound represented by the formula (X), the reaction may be carried out in a solvent or in a solvent, and the solvent may be a solvent commonly used in the art for such a reaction, for example, one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are toluene, tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, further examples are toluene. Preferably, the reaction is carried out in the absence of a solvent.
In the preparation of the compound represented by the formula (X), the temperature of the reaction may be a temperature commonly used in the art for such a reaction, for example, room temperature — the reflux temperature of the solvent used, for example, 85 ℃.
In the preparation of the compound represented by the formula (X), the progress of the reaction can be monitored by a detection method (such as TLC, HPLC or GC) which is conventional in the art, and the end point of the reaction is generally determined when the compound represented by the formula (X-A) disappears. The reaction time is preferably 2 to 12 hours, for example 12 hours.
The invention also provides an application of the bis-fluorosulfonyl imide as a catalyst in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), which comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide and a silane compound shown in a formula (XI-B), a carbonyl compound shown in a formula (XI-A) is subjected to reduction etherification reaction to prepare a compound shown in a formula (XI);
wherein R is 24 And R 25 Independently is H, C-C16 alkyl, C6-C10 aryl or R L Substituted C6-C10 aryl, R L Is halogen, C1-C6 alkyl or C1-C6 alkoxy; r 24-1 Is C1-C3 alkyl.
Preferably, R 24 Or R 25 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 24 Or R 25 Wherein said C6-C10 aryl and said R L The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R L In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R L The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R L The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 24 Or R 25 In (1), the R L R in substituted C6-C10 aryl L The number of substitution(s) may be 1 to 3 (e.g., 1), each R L The same or different.
Preferably, R 24 And R 25 Independently is H, phenyl or R L A substituted phenyl group.
Preferably, R 24-1 Is methyl, ethyl, n-propyl or isopropyl.
Preferably, the carbonyl compound represented by the formula (XI-A) is
In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the amount of the bis-fluorosulfonyl imide is preferably 0.1 to 10%, for example 0.1 to 5%, and further for example 1%, of the molar amount of the carbonyl compound represented by the formula (XI-A).
In the reductive etherification reaction of the carbonyl compound shown in the formula (XI-A), the amount of the silane compound shown in the formula (XI-B) can be the amount commonly used in such reactions in the art, for example, the molar ratio of the carbonyl compound shown in the formula (XI-A) to the silane compound shown in the formula (XI-B) is 1 (1-2), for example, 1.
In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-a), the solvent may be a solvent commonly used in such reactions in the art, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent, and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, such as dichloromethane.
In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-a), the temperature of the reductive etherification reaction may be a temperature commonly used in such reactions in the art, for example, 0 ℃ to room temperature, for example, room temperature.
In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the progress of the reductive etherification reaction can be monitored by a detection method (such as TLC, HPLC or GC) which is conventional in the art, and the progress is generally used as the end point of the reaction when the carbonyl compound represented by the formula (XI-A) disappears. The time for the reductive etherification reaction is preferably 5 minutes to 12 hours, for example, 0.5 hour, 1 hour.
The invention also provides a preparation method of the silicon ester bis (fluorosulfonyl) imide shown in the formula (XII), which comprises the following steps:
reacting the compound shown in the formula (XII-A) with bis (fluorosulfonyl) imide to obtain bis (fluorosulfonyl) imide acid silicone ester shown in the formula (XII);
wherein Z is H, halogen, C1-C16 alkyl, C6-C10 aryl or R N Substituted C6-C10 aryl, R 26 、R 27 And R 28 Independently is C1-C16 alkyl, C6-C10 aryl, R M Substituted C6-C10 aryl or
R 29 、R 30 And R 31 Independently is C1-C6 alkyl, R M And R N Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably Z, R 26 、R 27 Or R 28 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably Z, R 26 、R 27 Or R 28 Wherein said C6-C10 aryl, said R N Substituted C6-C10 aryl and said R M The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably Z, R M Or R N In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R M Or R N The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, R M Or R N The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 26 、R 27 Or R 28 In (1), the R M R in substituted C6-C10 aryl M The number of substitutions (C) may be 1 to 3 (e.g. 1), each R M The same or different.
Preferably, R 29 、R 30 Or R 31 The C1-C6 alkyl group is a C1-C3 alkyl group such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in Z, the R N R in substituted C6-C10 aryl N The number of substitution(s) may be 1 to 3 (e.g., 1), each R N The same or different.
Preferably, R 26 、R 27 And R 28 Independently is
R 29 、R 30 And R 31 Independently a C1-C3 alkyl group (e.g., methyl, ethyl, n-propyl, or isopropyl).
Preferably, Z is H or halogen, more preferably, Z is H.
Preferably, the compound shown in the formula (XII-A) is
In the preparation method of the silicon bis (fluorosulfonyl) imide acid ester shown in the formula (XII), the dosage ratio of the compound shown in the formula (XII-a) and the bis (fluorosulfonyl) imide can be the dosage ratio commonly used in such reactions in the field, for example, the molar ratio of the compound shown in the formula (XII-a) to the bis (fluorosulfonyl) imide is (1-10): 1, for example 1:1.
In the preparation method of the silicon bis (fluorosulfonyl) imide ester shown in the formula (XII), the reaction can be carried out in no solvent or in a solvent, and the solvent can be a solvent commonly used in the reaction in the field, such as one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1,4-dioxane, and the like, further examples are acetonitrile or dichloromethane. Preferably, the reaction is carried out in the absence of a solvent.
In the method for preparing the silicon bis (fluorosulfonyl) imide ester represented by the formula (XII), the reaction temperature may be a temperature commonly used in the art for such a reaction, for example, 0 ℃ to room temperature, for example, room temperature.
In the preparation method of the silicon bis (fluorosulfonyl) imide ester shown in the formula (XII), the progress of the reaction can be monitored by a detection method (such as TLC, HPLC, or GC or NMR) which is conventional in the art, and the end point of the reaction is generally determined when bis (fluorosulfonyl) imide disappears. The reaction time is preferably 30 minutes to 2 hours, for example 1 hour.
The invention also provides an application of the bis-fluorosulfonyl imide in preparation of a compound shown as a formula (XIII) as a catalyst, which comprises the following steps:
under the action of difluoride sulfimide, reacting a compound shown as a formula (XIII-A), a compound shown as a formula (XIII-B) and a compound shown as a formula (XIII-C) to obtain a compound shown as a formula (XIII);
wherein Q is CH or N;
R 32 is halogen, C1-C16 alkyl, C6-C10 aryl or R O Substituted C6-C10 aryl;
m 3 is 0, 1,2, 3 or 4;
R 33 is C1-C16 alkyl, C6-C10 aryl or R P Substituted C6-C10 aryl;
R O and R P Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, m 3 Is 0 or 1 (e.g. m) 3 Is 0).
Preferably, Q is N.
Preferably, R 32 In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R 32 Or R 33 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group).
Preferably, R 32 Or R 33 Wherein said C6-C10 aryl, said R O Substituted C6-C10 aryl and said R P The C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl.
Preferably, R O Or R P In (b), the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, R O Or R P Wherein said C1-C6 alkyl is C1-C3 alkyl, for exampleMethyl, ethyl, n-propyl or isopropyl.
Preferably, R O Or R P The C1-C6 alkoxy group is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R 32 In (1), the R O R in substituted C6-C10 aryl O The number of substitutions (C) may be 1 to 3 (e.g. 1), each R O The same or different.
Preferably, R 33 In (1), the R P R in substituted C6-C10 aryl P The number of substitution(s) may be 1 to 3 (e.g., 1), each R P The same or different.
Preferably, R 33 C1-C6 alkyl, for example C1-C3 alkyl, and further for example methyl, ethyl, n-propyl or isopropyl.
In the preparation of the compound shown in the formula (XIII), the bis-fluorosulfonyl imide is preferably used in an amount of 5 to 20 mol%, for example 10 mol%, based on the compound shown in the formula (XIII-B).
In the preparation of the compound represented by the formula (XIII), the amount ratio of the compound represented by the formula (XIII-A) to the compound represented by the formula (XIII-B) may be an amount ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (XIII-A) to the compound represented by the formula (XIII-B) is (1-2): 1, for example, 1.1.
In the preparation of the compound represented by the formula (XIII), the amount ratio of the compound represented by the formula (XIII-C) to the compound represented by the formula (XIII-B) may be an amount ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formula (XIII-C) to the compound represented by the formula (XIII-B) is (1-200): 1, for example 192.5:1.
in the preparation of the compound represented by the formula (XIII), the reaction can be carried out in no solvent or in a solvent, and the solvent can be one or more of solvents commonly used in the reaction in the field, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, halogenated alkane solvents and alkane solvents; further examples are tetrahydrofuran, dichloromethane, ethyl acetate, dimethyl sulfoxide, N, N-dimethylformamide, 1,4-dioxane, etc., further examples are acetonitrile or dichloromethane. Preferably, the reaction is carried out in the absence of a solvent.
In the preparation of the compound represented by the formula (XIII), the reaction temperature may be a temperature commonly used in the art for such reactions, for example, 50 ℃ to 120 ℃, and further for example, 60 ℃.
In the preparation of the compound of formula (XIII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC or NMR), and the end point of the reaction is generally determined as the time at which the compound of formula (XIII-B) disappears. The reaction time is preferably 1 to 5 hours, for example 3.5 hours.
In the present invention, room temperature means 20 ℃ to 30 ℃.
Unless otherwise defined, the terms used in the present invention have the following meanings:
the term "alkyl" refers to a straight or branched chain alkyl group having the indicated number of carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like.
Examples of the term "sulfoxide-based solvent" include, but are not limited to, dimethyl sulfoxide.
Examples of the term "ketone-based solvent" include, but are not limited to, acetone or N-methylpyrrolidone, and the like.
Examples of the term "alcohol solvent" include, but are not limited to, methanol, ethanol, glycerol, t-butanol, or the like.
Examples of the term "ethereal solvent" include, but are not limited to, diethyl ether, tetrahydrofuran, methyl tert-butyl ether, or 1,4-dioxane, and the like.
Examples of the term "ester solvent" include, but are not limited to, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, ethyl butyrate, and the like.
Examples of the term "nitrile based solvent" include, but are not limited to, acetonitrile and the like.
Examples of the term "aromatic hydrocarbon solvent" include, but are not limited to, benzene, toluene, xylene, trifluorotoluene, fluorobenzene, or the like.
Examples of the term "amide-based solvent" include, but are not limited to, N-dimethylformamide or N, N-dimethylacetamide, and the like.
Examples of the term "haloalkane solvent" include, but are not limited to, dichloromethane, trichloromethane or 1,2-dichloroethane and the like.
Examples of the term "alkane solvent" include, but are not limited to, petroleum ether or n-hexane, and the like.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the bis-fluorosulfonyl imide is innovatively applied to organic synthesis reaction, can be used as a catalyst to efficiently catalyze various reactions, such as Friedel-Crafts reaction, esterification reaction, lactone ring-opening polymerization reaction, silyl ether polymerization reaction, carbonyl compound reduction etherification, alkynyl hydrolysis and the like, and has the advantages of mild reaction conditions, strong substrate adaptability and high atom economy.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Preparation of example 1
10g of potassium bis (fluorosulfonyl) imide (45.6 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) are added into an autoclave, 60 g of sulfur dioxide is introduced at the temperature of 70 ℃, the temperature is slowly increased to the room temperature, a white solid is generated after the reaction for half an hour, then sulfur dioxide gas is slowly released, 50ml of dichloromethane is added, the solid is filtered, the solid is washed by 50ml of dichloromethane, the filtrate is dried in a spinning mode, reduced pressure distillation is carried out, a fraction of 85 ℃/20mm Hg is collected, 7.7g (42.5 mmol) of bis (fluorosulfonyl) imide is obtained, and a colorless liquid is obtained, and the yield is 93%.
19 F NMR (dichloromethane as solvent, trichlorofluoromethane as internal standard) +57.3.
Preparation of example 2
10g of sodium bis (fluorosulfonyl) imide (49.26 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) are added into an autoclave, 60 g of sulfur dioxide is introduced at the temperature of 70 ℃, the temperature is slowly raised to the room temperature, a white solid is generated after reaction for half an hour, then sulfur dioxide gas is slowly released, 50ml of dichloromethane is added, the solid is filtered, the solid is washed by 50ml of dichloromethane, the filtrate is dried in a spinning mode, reduced pressure distillation is carried out, 85 ℃/20mm Hg fractions are collected, 8.1g of bis (fluorosulfonyl) imide (44.75 mmol) is obtained, and colorless liquid is obtained, wherein the yield is 91%.
19 F NMR (dichloromethane as solvent, trichlorofluoromethane as internal standard) +57.3.
Example 1
1.9998g (17.54mmol, 1eq) caprolactone, 5ml dichloromethane, 175ul phenylpropanol dichloromethane solution (1 eq) with concentration of 1mol/L are added into a 25ml three-neck flask, 35ul bis (fluorosulfonyl) imide acid dichloromethane solution (0.1 eq) with concentration of 0.5mol/L is added under nitrogen protection, the mixture is reacted at room temperature overnight, the reaction solution is poured into 50ml cold n-hexane, solid is precipitated, filtered and dried to obtain 1.86g white polycaprolactone solid (yield 93%) which is detected by GPC, and Mn is detected PS ＝25267,PDI＝1.03。
Example 2
A25 ml single neck flask was charged with 5.01g (16.92 mmol) octamethylcyclotetrasiloxane, hexamethylsilyl 0.0687g (0.424 mmol), magnetically stirred, charged with 0.12g bis-fluorosulfonylimide (0.66mmol, 4% mole relative to octamethylcyclotetrasiloxane) under nitrogen, and reacted overnight at room temperature to give a colorless viscous liquid as dimethylsilicone oil. Mn by GPC PS ＝9820,PDI＝1.0。
Example 3
In a 20ml single-neck bottle were charged 3-ethynylaniline (0.1068g, 0.912mmol), sodium azide (0.065g, 1mmol), triethyl orthoformate (0.162g, 1.1mmol), glycerol (4 ml), bis-fluorosulfonylimide (91ul, 0.5m in dcm,5% mol, relative to 3-ethynylaniline), reacted overnight at room temperature, TLC (petroleum ether: ethyl acetate = 10) detected completion of the reaction of the starting material (3-ethynylaniline), 15ml of water was added, a solid was precipitated, and after filtration, washing with water, and drying, 0.13g (0.76 mmol) of a pale yellow solid was obtained in 84% yield. Melting point 98.6-100 deg.C.
1 H NMR(400MHz,CD 3 CN):3.38(s，1H),7.17-7.32(m,4H),8.10(s,1H).
Example 4
In a 20ml single neck flask were added 3-bromoaniline (0.1g, 0.58mmol), sodium azide (0.038g, 0.58mmol), triethyl orthoformate (0.104g, 0.7mmol), glycerol (4 ml), bis-fluorosulfonylimide (58ul, 0.5m in dcm,5% mol, relative to 3-bromoaniline), reacted overnight at room temperature, TLC (petroleum ether: ethyl acetate = 10) detected completion of the reaction of the starting material (3-bromoaniline), 15ml of water was added, a solid was precipitated, filtered, washed with water, and dried to give 0.113g (0.5 mmol) of a pale yellow solid in 86% yield. Melting point 184-186 ℃.
1 H NMR(400MHz,CDCl 3 ):6.91-6.93(d，2H),7.4-7.42(d,2H),8.08(s,1H)。
Example 5
In a 20ml single neck flask were charged 4-hexen-3-one (0.3095g, 3.15mmol), benzyl carbamate (0.476g, 3.15mmol), acetonitrile (6 ml), bis-fluorosulfonylimide (315ul, 0.5M in CH) 3 CN,5 mol%, relative to 4-hexen-3-one), reaction at room temperature for half an hour, TLC (petroleum ether: ethyl acetate = 10), rf =0.4, the starting material (4-hexen-3-one) was detected to be absent, and column chromatography purification gave 0.74g of a white solid with a yield of 95%.
1 H NMR(400MHz,CDCl 3 ):0.94-1.26(m,6H),2.28-2.68(m,4H),3.91-4.17(m,1H),5.08(m,3H),7.3-7.34(m,5H)
LC-MS：272(M+Na)。
Example 6
To a 20ml single-neck flask were added benzyl p-methoxyacetate (0.792g, 4.4mmol), methoxybenzene (0.476g, 4.4mmol) and methylene chloride (6 ml), and bis-fluorosulfonylimide (440ul, 0.5M in CH) 3 CN,5% mol, relative to benzyl p-methoxyacetate), reaction at room temperature for half an hour, TLC (petroleum ether: ethyl acetate = 10), rf =0.4, and the disappearance of the starting material (benzyl p-methoxyacetate) was detected, and spin-drying gave 0.95g (4.17 mmol) of a yellow oily body with a yield of 95%.
1 H NMR(400MHz,CDCl 3 ):3.80(s,6H),3.89(s,2H),6.83-7.13(m,8H)。
Example 7
P-aminophenylacetylene (0.2265g, 1.935mmol), water (0.1g, 5.56mmol), 1,4-dioxane (2.5 ml) were charged into a 20ml single-neck flask, bis-fluorosulfonylimide (35mg, 0.193mmol,10% mole, relative to p-aminophenylacetylene) was added, reaction was carried out at 100 ℃ for 8 hours, TLC (petroleum ether: ethyl acetate =5:2, rf = 0.3), detection of disappearance of the starting material (p-aminophenylacetylene) was detected, extraction was performed by adding ethyl acetate (20 ml), washing with water (20ml × 3), washing with saturated sodium chloride, drying over anhydrous sodium sulfate, and spin-drying to give 0.23g (1.7 mmol) of a yellow solid in 88% yield.
LC-MS：136(M+1)。
1 H NMR(400MHz,CD 3 CN):2.42(s,3H),4.79(s,2H),6.58-6.69(d,2H),7.68-7.79(d,2H)。
Example 8
In a 20ml single vial was added 4' -methoxychalcone (0.1157g, 0.486mmol), dichloromethane (3 ml), allyltrimethylsilane (66.4 mg,0.58mmol, 1.2eq), bis-fluorosulfonylimide (9mg, 0.0497mmol,10% mole, relative to 4' -methoxychalcone) was added under ice-bath conditions, slowly returned to room temperature for two hours, TLC (petroleum ether: ethyl acetate = 10), detection of disappearance of starting material (4 ' -methoxychalcone), washing with water (20ml × 3), washing with saturated sodium chloride, drying over anhydrous sodium sulfate, column chromatography purification (petroleum ether: ethyl acetate =10, rf = 0.4) to give 0.11g (0.393 mmol) of a pale yellow solid in 81% yield.
1 H NMR(400MHz,CDCl 3 ):2.4-2.48(m,2H),3.21-3.23(m,2H),3.41-3.48(m,1H),3.83(s,3H),4.92-5.00(m,2H),5.62-5.72(m,1H),6.86-6.89(m,2H),7.14-7.28(m,5H),7.85-7.88(m,2H)。
Example 9
A20 ml single-neck flask was charged with aniline (213mg, 2.29mmol), benzaldehyde (192mg, 1.81mmol) and bis-fluorosulfonylimide (98mg, 0.54mmol,30% mol, relative to benzaldehyde) and stirred for 5 minutes, followed by addition of acetophenone (360mg, 3mmol) and stirring at room temperature overnight. Column chromatography purification (n-hexane: ethyl acetate =10, 1, rf = 0.4) gave the product as a white solid 210mg (0.69 mmol) with a yield of 38%.
1 H NMR(400HMz,CDCl 3 ):3.39-3.53(m,2H),4.56(s,1H),4.99-5.02(q,1H),6.55-6.57(d,2H),6.64-6.68(t,2H),7.07-7.09(t,2H),7.21-7.26(m,2H),7.30-7.34(t,2H),7.43-7.46(m,3H),7.54-7.58(t,1H),7.90-7.92(d,2H)。
Example 10
Aniline (106mg, 1.14mmol), p-chlorobenzaldehyde (140mg, 1mmol) and acetophenone (240mg, 2mmol) were added to a 20ml single-neck flask, stirred well and bis-fluorosulfonylimide (54mg, 0.298mmol,30% mol relative to p-chlorobenzaldehyde) was added and reacted overnight at room temperature. TLC (n-hexane: ethyl acetate =10 = 1) detects disappearance of aniline and formaldehyde, and column chromatography purification (n-hexane: ethyl acetate =10, rf = 0.4) gives 100mg (0.298 mmol) of the product as a white solid with a yield of 30%.
1 H NMR(400MHz,CDCl3):3.37-3.49(m,2H),4.44(brs,1H),4.94-4.97(t,1H),6.51-6.52(d,2H),6.66-6.68(t,1H),7.06-7.10(t,2H),7.24-7.28(t,2H),7.36-7.38(d,2H),7.42-7.46(t,2H),7.78-7.79(d,2H)。
Example 11
Phenyl acetate (220mg, 1.62mmol) and bis-fluorosulfonylimide (360mg, 1.99mmol) were added to a 10ml single-necked flask, the reaction was stirred at room temperature overnight, phenyl acetate disappeared by TLC (petroleum ether: ethyl acetate = 3:1) and column chromatography purification (petroleum ether: ethyl acetate =3, rf = 0.3) gave 50mg (0.367 mmol) of a yellow solid in 23% yield.
1 H NMR(400MHz,d-DMSO):2.43(s,3H),6.79-6.81(d,2H),7.78-7.80(d,2H),10.30(s,1H)。
Example 12
Phenyl acetate (330mg, 2.4 mmol) and bis-fluorosulfonylimide (540mg, 2.98mmol) were added to a 10ml single-necked flask, and the reaction was stirred at 60 ℃ for 3h, disappearance of phenyl acetate was detected by tlc (petroleum ether: ethyl acetate = 3:1), and column chromatography purification (petroleum ether: ethyl acetate =3, rf = 0.3) gave 100mg (0.735 mmol) of a yellow solid in 30% yield.
1 H NMR(400MHz,d-DMSO):2.43(s,3H),6.79-6.81(d,2H),7.78-7.80(d,2H),10.30(s,1H)。
Example 13
In a 25ml three-necked flask were added benzoic acid (0.21g, 1.72mmol), anhydrous methanol (0.3g, 9.375mmol) and toluene (1 ml) under nitrogen protection and bis-fluorosulfonylimide (31mg, 0.171mol,10% mol, relative to benzoic acid), the reaction was stirred at 85 ℃ for 12h, disappearance of benzoic acid was detected by tlc (petroleum ether: ethyl acetate = 30), column chromatography purification (petroleum ether: ethyl acetate =30, rf = 0.4) gave 160mg (1.18 mmol) of colorless oily liquid, yield 68.6%.
1 H NMR(400MHz,CDCl 3 ):3.92(s,3H),7.42-7.45(t,2H),7.53-7.55(t,2H),8.03-8.05(d,2H)。
Example 14
In a 25ml single vial was added benzaldehyde (0.2198g, 2.07mmol), triethylsilane (0.27g, 2.327mmol) and dichloromethane (1 ml) under nitrogen protection and bis-fluorosulfonylimide (42ul, 0.5m in dichloromethane, 1% mol, relative to benzaldehyde) was added, the reaction was stirred at room temperature for 30 minutes, disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate = 30), column chromatography purification (petroleum ether: ethyl acetate =30, rf = 0.4) gave 160mg (0.808 mmol) as a colorless oily liquid with a yield of 78%.
1 H NMR(400MHz,CDCl 3 ):4.59(s,4H),7.38-7.40(m,10H)。
Example 15
In a 25ml single neck flask were added 4-chlorobenzaldehyde (0.32g, 2.286 mmol), triethylsilane (0.2927g, 2.52mmol) and dichloromethane (1 ml) under nitrogen protection and bis-fluorosulfonylimide (45ul, 0.5m in dichloromethane, 1% mole, relative to 4-chlorobenzaldehyde) and the reaction was stirred at room temperature for 30 minutes, TLC (petroleum ether: ethyl acetate = 30) detected disappearance of benzaldehyde and column chromatography purification (petroleum ether: ethyl acetate =30, rf = 0.4) gave 260mg (0.974 mmol) of white solid in 86% yield.
1 H NMR(400MHz,CDCl 3 ):4.52(s,4H),7.28-7.35(m,8H)。
Example 16
In a 25ml single vial was added 3-methylbenzaldehyde (0.1387 g, 1.156mmol), triethylsilane (0.151g, 1.3 mmol) and dichloromethane (1 ml) under nitrogen protection, bis-fluorosulfonylimide (23ul, 0.5m dichloromethane solution, 1% mol, relative to 3-methylbenzaldehyde) was added, the reaction was stirred at room temperature for 30 minutes, disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate = 30), and column chromatography purification (petroleum ether: ethyl acetate =30, rf = 0.6) gave 130mg (0.575 mmol) of a white solid with a yield of 99%.
1 H NMR(400MHz,CDCl 3 ):2.35(s,6H),4.52(s,4H),7.09-7.26(m,8H)。
Example 17
In a 25ml single vial was added 4-methylbenzaldehyde (0.1507g, 1.256 mmol), triethylsilane (0.16g, 1.38mmol) and dichloromethane (1 ml) under nitrogen protection, bis-fluorosulfonylimide (25ul, 0.5m in dichloromethane, 1% mol, relative to 4-methylbenzaldehyde) was added, the reaction was stirred at room temperature for 1 hour, disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate = 30), column chromatography purification (petroleum ether: ethyl acetate =30, rf = 0.5) gave 131mg (0.58 mmol) of a white solid in 92% yield.
1 H NMR(400MHz,CDCl 3 ):2.35(s,6H),4.5(s,4H),7.14-7.17(d,4H),7.24-7.26(d,4H)。
Example 19
250ul of a deuterated acetonitrile solution of tris (trimethylsilyl) silane (0.5M) was added to a 10ml single-neck flask, and then 250ul of a deuterated acetonitrile solution of bis (fluorosulfonyl) imide (0.5M) was slowly added thereto under ice-cooling, and the reaction was carried out for 1 hour after slowly returning to room temperature. Thus obtaining the target product solution.
19 F NMR (deuterated acetonitrile as solvent, monofluorotrichloromethane as internal standard): +54
1 H NMR(400MHz,d-CD 3 CN):0.17(S)。
Example 19
Benzotriazole (0.111g, 0.933mmol), 1- (trifluoromethyl) -3,3-dimethyl-1,2-benziodoxolane (0.2g, 0.6 mmol), acetonitrile (6 ml), bis-fluorosulfonylimide (12mg, 0.066mmol,10 mol%, relative to 1- (trifluoromethyl) -3,3-dimethyl-1,2-benziodoxolane), was added to a 20ml single-neck flask and reacted at 60 ℃ for 3.5 hours, TLC (petroleum ether: ethyl acetate = 5:2), 1- (trifluoromethyl) -3,3-dimethyl-1,2-benziodoxolane was detected to disappear, and the product was quantified by fluorine spectrometry in 83% yield (using trifluorotoluene as an internal standard).
19 F NMR (acetonitrile as solvent, trichlorofluoromethane as internal standard): 53;
LC-MS：229(M+1)。
comparative example 1
This comparative example is selected from the document org.lett., vol.5, no.12,2003.
4-hexen-3-one (0.5mmol, 1.0eq) with benzyl carbamate (0.75mmol, 1.5eq), acetonitrile (1 ml), bis (trifluoromethane) sulfonimide (0.05mmol, 10 eq) was added, reacted at-20 ℃ for 10min to give 117mg of product in 95% yield. The bis (trifluoromethanesulfonyl) imide has large using amount and harsh reaction conditions, and needs to be carried out at the temperature of minus 20 ℃.
Comparative example 2
This comparative example was selected from J.org.chem.1987,52,4314-4319.
In the reductive etherification of a carbonyl compound, trimethylsilyl trifluoromethanesulfonate (Trimethylsilyl Triflate,44.45mg,0.20mmol,10% eq) and triethylsilylhydride (0.465g, 4mmol, 2eq) were dissolved in 4ml of dichloromethane as described in experimental method a on page 4318 of this document, benzaldehyde (0.212g, 2mmol, 1eq) was added under ice bath, reacted at room temperature for 2 hours, and purified by column chromatography (petroleum ether: ethyl acetate =30, rf = 0.4) to give 0.1299g of a colorless oily liquid in a yield of 65.6%.
1 H NMR(400MHz,CDCl 3 ):4.59(s,4H),7.38-7.40(m,10H)。
Claims (30)
1. The application of the bis (fluorosulfonyl) imide as a catalyst in the preparation of tetrazole compounds shown in the formula (III) comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (III-A), an orthoformate compound shown as a formula (III-B) and sodium azide to obtain a tetrazole compound shown as a formula (III);
wherein R is 6 Is C1-C16 alkyl, C6-C10 aryl or R B Substituted C6-C10 aryl, R B Is halogen or C2-C4 alkynyl;
R 6-1 is methyl or ethyl.
2. The use according to claim 1, wherein R is 6 Wherein said C1-C16 alkyl is C1-C10 alkyl, such as C1-C6 alkyl;
and/or, R 6 Wherein said C6-C10 aryl and said R B C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R 6 In (1), the R B R in substituted C6-C10 aryl B The number of substitution(s) is 1 to 3 (e.g., 1), and each R B The same or different;
and/or, R B Wherein said halogen is fluorine, chlorine, bromine or iodine, for example bromine;
and/or, R B Wherein said C2-C4 alkynyl is ethynyl;
and/or in the preparation of the tetrazole compound shown in the formula (III), the usage amount of the bis (fluorosulfonyl) imide is 1% -10% (for example, 5%) of the molar amount of the compound shown in the formula (III-A);
and/or in the preparation of the tetrazole compound shown in the formula (III), the molar ratio of the compound shown in the formula (III-A) to the orthoformate compound shown in the formula (III-B) is 1: (1-2), further example 1:1.2
And/or in the preparation of the tetrazole compound shown in the formula (III), the molar ratio of the compound shown in the formula (III-A) to the sodium azide is 1: (1-3), for example, 1:1 or 1:1.1;
and/or in the preparation of the tetrazole compound shown in the formula (III), the solvent is one or more of a propyl sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; preferably one or more of glycerol, tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and 1,4-dioxane, such as glycerol;
and/or, in the preparation of the tetrazole compound shown in the formula (III), the reaction temperature is 20 ℃ to the reflux temperature of the solvent, such as room temperature;
and/or in the preparation of the tetrazole compound shown in the formula (III), the reaction time is 2-12 hours.
3. The use of claim 1, wherein R is 6 Is R B Substituted phenyl radicals, R B Is halogen or ethynyl; preferably, R is 6 Is composed of
4. The application of bis (fluorosulfonyl) imide as a catalyst in the preparation of a compound shown as a formula (IV) comprises the following steps:
in Sup>A solvent, under the action of bis (fluorosulfonyl) imide, carrying out addition reaction on Sup>A compound shown as Sup>A formulSup>A (IV-A) and Sup>A compound shown as Sup>A formulSup>A (IV-B) to obtain Sup>A compound shown as Sup>A formulSup>A (IV);
wherein the content of the first and second substances,
x is NH, S or O;
R 7 、R 8 and R 9 Independently is C1-C16 alkyl, C6-C10 aryl, R C Substituted C6-C10 aryl or
R C Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
5. The use of claim 4, wherein R is 7 、R 8 Or R 9 The C1-C16 alkyl group is a C1-C10 alkyl group, preferably a C1-C6 alkyl group (e.g., a C1-C3 alkyl group, further e.g., a methyl group, an ethyl group, an n-propyl group or an isopropyl group);
and/or, R 7 、R 8 Or R 9 Wherein said C6-C10 aryl and said R C C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R 7 、R 8 Or R 9 In (1), the R C R in substituted benzyl C The number of substitution(s) is 1 to 3 (e.g., 1), and each R C The same or different;
and/or, R C Wherein said halogen is fluorine, chlorine, bromine or iodine;
and/or, R C Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R C Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, X is NH;
and/or, in the preparation of the compound shown in the formulSup>A (IV), the usage amount of the bis-fluorosulfonyl imide is 1% -10% (for example, 5%) of the molar amount of the compound shown in the formulSup>A (IV-A);
and/or in the preparation of the compound shown as the formulSup>A (IV), the molar ratio of the compound shown as the formulSup>A (IV-A) to the compound shown as the formulSup>A (IV-B) is 1 (1-10), and further for example, 1:1;
and/or in the preparation of the compound shown in the formula (IV), the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as acetonitrile;
and/or, in the preparation of the compound shown in the formula (IV), the temperature of the addition reaction is 20 ℃ to the reflux temperature of the solvent, such as room temperature;
and/or in the preparation of the compound shown in the formula (IV), the time of the addition reaction is 10 minutes to 12 hours, such as 0.5 hour.
6. The use of claim 4, wherein R is 7 And R 8 Independently C1-C16 alkyl, for example C1-C10 alkyl, further for example C1-C6 alkyl (for example C1-C3 alkyl, further for example methyl, ethyl, n-propyl or isopropyl); preferably, the compound shown in the formulSup>A (IV-A) is
And/or, R 9 Is composed of
Preferably, the compound shown in the formula (IV-B) is
7. The application of the bis (fluorosulfonyl) imide as a catalyst in the preparation of a compound shown as a formula (V) comprises the following steps:
in Sup>A solvent, under the action of bis (fluorosulfonyl) imide, carrying out Friedel-crafts reaction on Sup>A compound shown as Sup>A formulSup>A (V-A) and Sup>A compound shown as Sup>A formulSup>A (V-B) to obtain Sup>A compound shown as Sup>A formulSup>A (V);
wherein Y is halogen,
R 10 Is C1-C16 alkyl, benzyl, C6-C10 aryl, R D Substituted C6-C10 aryl or R E Substituted benzyl, R D And R E Independently is halogen, C1-C6 alkyl or C1-C6 alkoxy;
R 11 is C1-C6 alkyl or C1-C6 alkoxy.
8. Use according to claim 7, wherein in Y the halogen is fluorine, chlorine, bromine or iodine, for example chlorine, bromine or iodine;
and/or, R 10 Wherein said C1-C16 alkyl is C1-C10 alkyl, such as C1-C6 alkyl (e.g., C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl);
and/or, R 10 Wherein said C6-C10 aryl and said R D C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R 10 In (1), the R D R in substituted C6-C10 aryl D The number of substitution(s) is 1 to 3 (e.g., 1), and each R D The same or different;
and/or, R 10 In (1), the R E R in substituted benzyl E The number of substitution(s) is 1 to 3 (e.g., 1), and each R E The same or different;
and/or, R D Or R E Wherein said halogen is fluorine, chlorine, bromine or iodine;
and/or, R D 、R E Or R 11 Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R D 、R E Or R 11 Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or Y is
And/or, in the preparation of the compound shown in the formula (V), the usage amount of the bis-fluorosulfonyl imide is 0.1% -10% (for example, 5%) of the molar amount of the compound shown in the formula (V-B);
and/or, in the preparation of the compound shown as the formulSup>A (V), the molar ratio of the compound shown as the formulSup>A (V-A) to the compound shown as the formulSup>A (V-B) is (1-10): 1, such as 1:1;
and/or in the preparation of the compound shown in the formula (V), the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as dichloromethane;
and/or, in the preparation of the compound shown in the formula (V), the temperature of the Friedel-crafts reaction is 20 ℃ to the reflux temperature of the solvent, such as room temperature;
and/or in the preparation of the compound shown in the formula (V), the time of the Friedel-crafts reaction is 5 minutes to 12 hours, such as 0.5 hour.
9. The use of claim 7, wherein R is D And R E Independently is a C1-C6 alkoxy group; preferably, R 10 Is benzyl, phenyl, R D Substituted phenyl or R E A substituted benzyl group; more preferably, the compound represented by the formulSup>A (V-A) is
And/or, R 11 Is C1-C6 alkoxy; preferably, the compound represented by the formula (V-B) is
10. The application of bis (fluorosulfonyl) imide as a catalyst in the preparation of a compound shown as a formula (VI) comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, performing hydrolysis reaction on a compound shown as a formula (VI-A) and water to obtain a compound shown as a formula (VI);
wherein R is 12 Is C1-C16 alkyl, C6-C10 aryl or R F Substituted C6-C10 aryl, R F Is an amino group.
11. The use according to claim 10, wherein R is 12 C1-C16 alkyl is C1-C10 alkyl, for example C1-C6 alkyl (e.g. C1-C3 alkyl, again for example methyl, ethyl, n-propyl or isopropyl);
and/or, R 12 Wherein said C6-C10 aryl and said R F C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R 12 In (1), the R F R in substituted C6-C10 aryl F The number of substitution(s) is 1 to 3 (e.g., 1), and each R F The same or different;
and/or, in the preparation of the compound shown in the formula (VI), the usage amount of the bis-fluorosulfonyl imide is 5% -30% (for example, 10%) of the molar amount of the compound shown in the formula (VI-A);
and/or, in the preparation of the compound shown in the formula (VI), the molar ratio of the compound shown in the formula (VI-A) to water is 1 (1-10), such as 1;
and/or in the preparation of the compound shown in the formula (VI), the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as 1,4-dioxane;
and/or, in the preparation of the compound shown in the formula (VI), the temperature of the hydrolysis reaction is 20 ℃ to the reflux temperature of the solvent, such as 100 ℃;
and/or in the preparation of the compound shown in the formula (VI), the hydrolysis reaction time is 2-12 hours, such as 8 hours.
12. The application of bis (fluorosulfonyl) imide as a catalyst in the preparation of a compound shown as a formula (VII) comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (VII-A) with allyl trimethylsilane to obtain a compound shown as a formula (VII);
wherein R is 13 And R 14 Independently is C1-C16 alkyl, C6-C10 aryl or R G Substituted C6-C10 aryl, R G Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
13. The use of claim 12, wherein R is 13 Or R 14 In (1-16), the C1-C10 alkyl group is a C1-10 alkyl group, for exampleIs C1-C6 alkyl (e.g., C1-C3 alkyl, further e.g., methyl, ethyl, n-propyl, or isopropyl);
and/or, R 13 Or R 14 Wherein said C6-C10 aryl and said R G C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R G Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R G Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R G Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 13 Or R 14 In (1), the R G R in substituted C6-C10 aryl G The number of substitution(s) is 1 to 3 (e.g., 1), and each R G The same or different;
and/or in the preparation of the compound shown in the formula (VII), the usage amount of the bis-fluorosulfonyl imide is 5% -30%, for example 10% of the molar weight of the compound shown in the formula (VII-A);
and/or, in the preparation of the compound shown in the formula (VII), the molar ratio of the compound shown in the formula (VII-A) to the allyltrimethylsilane is 1 (1-10), such as 1.2;
and/or in the preparation of the compound shown in the formula (VII), the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as dichloromethane;
and/or, in the preparation of the compound represented by the formula (VII), the reaction temperature is-20 ℃ to room temperature, such as room temperature;
and/or in the preparation of the compound shown as the formula (VII), the reaction time is 2-12 hours, such as 2 hours.
14. The use of claim 12, wherein R is 13 And R 14 Independently is phenyl or R G Substituted phenyl radicals, R G Is C1-C3 alkoxy; preferably, the compound shown in the formula (VII-A) is
15. The application of bis (fluorosulfonyl) imide as a catalyst in preparation of a compound shown as a formula (VIII) comprises the following steps:
under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (VIII-A), a compound shown as a formula (VIII-B) and a compound shown as a formula (VIII-C) to obtain a compound shown as a formula (VIII);
wherein R is 15 、R 16 、R 17 、R 18 、R 19 And R 20 Independently H, C, C6-C10 alkyl, C1-C16 aryl or R H Substituted C6-C10 aryl, R H Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
16. The use of claim 15, wherein R is 15 、R 16 、R 17 、R 18 、R 19 Or R 20 Wherein said C1-C16 alkyl is C1-C10 alkyl, such as C1-C6 alkyl (e.g., C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl);
and/or, R 15 、R 16 、R 17 、R 18 、R 19 Or R 20 Wherein said C6-C10 aryl and said R H C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R H Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R H Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R H Wherein said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 15 、R 16 、R 17 、R 18 、R 19 Or R 20 In (1), the R H R in substituted C6-C10 aryl H The number of substitution(s) is 1 to 3 (e.g., 1), and each R H The same or different;
and/or in the preparation of the compound shown in the formula (VIII), the usage amount of the bis-fluorosulfonyl imide is 1% -100%, such as 10% -50%, and further such as 30% of the molar weight of the compound shown in the formula (VIII-B);
and/or, in the preparation of the compound of formula (VIII), the molar ratio of the compound of formula (VII-A) to the compound of formula (VIII-B) is (1-2): 1, e.g. 1.1 or 1.3;
and/or in the preparation of the compound shown in the formula (VIII), the molar ratio of the compound shown in the formula (VII-A) to the compound shown in the formula (VIII-C) is 1: (1-3), such as 1.3, 1.8, or 1:2;
and/or, in the preparation of the compound represented by the formula (VIII), the reaction is carried out in a solvent or in the absence of a solvent, wherein the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent, such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and 1,4-dioxane; preferably, the reaction is carried out in the absence of a solvent;
and/or, in the preparation of the compound shown in the formula (VIII), the reaction temperature is between room temperature and 50 ℃, for example, room temperature;
and/or in the preparation of the compound shown in the formula (VIII), the reaction time is 2-12 hours.
17. The use of claim 15, wherein R is 15 、R 16 、R 17 、R 18 、R 19 And R 20 Independently is H, C-C6 alkyl, phenyl or R H Substituted phenyl radicals, R H Is halogen, C1-C3 alkyl or C1-C3 alkoxy;
preferably, the compound shown in the formula (VIII-A) is
Preferably, the compound represented by the formula (VIII-B) is
Preferably, the compound represented by the formula (VIII-C) is
18. The application of bis (fluorosulfonyl) imide as a catalyst in the preparation of a compound shown as a formula (X) comprises the following steps:
under the action of bis (fluorosulfonyl) imide, reacting a compound shown as a formula (X-A) with a compound shown as a formula (X-B) to obtain a compound shown as a formula (X);
wherein R is 22 Is H, C-C16 alkyl, C6-C10 aryl or R J Substituted C6-C10 aryl; r 23 Is C1-C16 alkyl, C6-C10 aryl or R K Substituted C6-C10 aryl, R J And R K Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
19. The use of claim 18, wherein R is 22 Or R 23 Wherein said C1-C16 alkyl is C1-C10 alkyl, such as C1-C6 alkyl (e.g., C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl);
and/or, R 22 Or R 23 Wherein said C6-C10 aryl, said R J Substituted C6-C10 aryl and said R K C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R J Or R K Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R J Or R K Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R J Or R K Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 22 In (1), the R J R in substituted C6-C10 aryl J The number of substitution(s) is 1 to 3 (e.g., 1), and each R J The same or different;
and/or, R 23 In (1), the R K R in substituted C6-C10 aryl K The number of substitution(s) is 1 to 3 (e.g., 1), and each R K The same or different;
and/or in the preparation of the compound shown in the formula (X), the usage amount of the bis-fluorosulfonyl imide is 0.1-10%, for example 10% of the molar weight of the compound shown in the formula (X-A);
and/or, in the preparation of the compound shown in the formula (X), the molar ratio of the compound shown in the formula (X-A) to the compound shown in the formula (X-B) is 1 (1-10), such as 1;
and/or, in the preparation of the compound represented by formula (X), the reaction is carried out in a solvent or in the absence of a solvent, the solvent being one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent, such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and 1,4-dioxane, such as toluene; preferably, the reaction is carried out in the absence of a solvent;
and/or, in the preparation of the compound represented by formula (X), the temperature of the reaction is room temperature — the reflux temperature of the solvent used, for example 85 ℃;
and/or, in the preparation of the compound shown in the formula (X), the reaction time is 2-12 hours, such as 12 hours.
20. The application of the bis (fluorosulfonyl) imide as a catalyst in the reduction etherification reaction of a carbonyl compound shown in a formula (XI-A) comprises the following steps:
in a solvent, under the action of bis (fluorosulfonyl) imide and a silane compound shown in a formula (XI-B), a carbonyl compound shown in a formula (XI-A) is subjected to reduction etherification reaction to prepare a compound shown in a formula (XI);
wherein R is 24 And R 25 Independently is H, C-C16 alkyl, C6-C10 aryl or R L Substituted C6-C10 aryl, R L Is halogen, C1-C6 alkyl or C1-C6 alkoxy; r is 24-1 Is C1-C3 alkyl.
21. The use of claim 20, wherein R is 24 Or R 25 C1-C16 alkyl is C1-C10 alkyl, for example C1-C6 alkyl (e.g. C1-C3 alkyl, again for example methyl, ethyl, n-propyl or isopropyl);
and/or, R 24 Or R 25 Wherein said C6-C10 aryl and said R L Of substituted C6-C10 aryl groupsC6-C10 aryl is independently phenyl;
and/or, R L Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R L Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R L Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 24 Or R 25 In (1), the R L R in substituted C6-C10 aryl L The number of substitution(s) is 1 to 3 (e.g., 1), and each R L The same or different;
and/or, R 24-1 Is methyl, ethyl, n-propyl or isopropyl;
and/or in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the usage amount of the bis-fluorosulfonyl imide is 0.1-10%, for example 0.1-5%, and further for example 1% of the molar weight of the carbonyl compound shown in the formula (XI-A);
and/or in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the molar ratio of the carbonyl compound shown in the formula (XI-A) to the silane compound shown in the formula (XI-B) is 1 (1-2), such as 1;
and/or in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, such as dichloromethane;
and/or, in the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the temperature of the reduction etherification reaction is 0-room temperature, such as room temperature;
and/or in the reductive etherification reaction of the carbonyl compound shown in the formula (XI-A), the time of the reductive etherification reaction is 5 minutes to 12 hours, such as 0.5 hour or 1 hour.
22. The use of claim 20, wherein R is 24 And R 25 Independently is H, phenyl or R L Substituted phenyl, preferably said carbonyl compound of formula (XI-A) is
23. A preparation method of silicon bis (fluorosulfonyl) imide shown in formula (XII) comprises the following steps:
reacting the compound shown in the formula (XII-A) with bis (fluorosulfonyl) imide to obtain bis (fluorosulfonyl) imide acid silicone ester shown in the formula (XII);
wherein Z is H, halogen, C1-C16 alkyl, C6-C10 aryl or R N Substituted C6-C10 aryl, R 26 、R 27 And R 28 Independently is C1-C16 alkyl, C6-C10 aryl, R M Substituted C6-C10 aryl or
R 29 、R 30 And R 31 Independently is C1-C6 alkyl, R M And R N Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
24. The method of claim 23, wherein Z, R is prepared 26 、R 27 Or R 28 In (1), the C1-C16 alkyl group is a C1-C10 alkyl group, for example, a C1-C6 alkyl group (e.g., a C1-C3 alkyl group)Radicals such as the methyl, ethyl, n-propyl or isopropyl radical);
and/or, Z, R 26 、R 27 Or R 28 Wherein said C6-C10 aryl, said R N Substituted C6-C10 aryl and said R M C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, Z, R M Or R N Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R M Or R N Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R M Or R N Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 26 、R 27 Or R 28 In (1), the R M R in substituted C6-C10 aryl M The number of substitution(s) is 1 to 3 (e.g., 1), and each R M The same or different;
and/or, in Z, the R N R in substituted C6-C10 aryl N The number of substitution(s) is 1 to 3 (e.g., 1), and each R N The same or different;
and/or, R 29 、R 30 Or R 31 Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or in the preparation method of the bis (fluorosulfonyl) imide silicon ester shown in the formula (XII), the molar ratio of the compound shown in the formula (XII-A) to the bis (fluorosulfonyl) imide is (1-10): 1, such as 1:1;
and/or in the preparation method of the bis-fluorosulfonyl imidic acid silicone ester shown in the formula (XII), the reaction is carried out in a solvent or in the absence of a solvent, wherein the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as acetonitrile or dichloromethane; preferably, the reaction is carried out in the absence of a solvent;
and/or in the preparation method of the bis (fluorosulfonyl) imide silicon ester shown in the formula (XII), the reaction temperature is 0-room temperature, such as room temperature;
and/or in the preparation method of the bis (fluorosulfonyl) imide silicon ester shown in the formula (XII), the reaction time is 30 minutes to 2 hours, such as 1 hour.
25. The method of claim 23, wherein R is 26 、R 27 And R 28 Independently is
R 29 、R 30 And R 31 Independently a C1-C3 alkyl group (e.g., methyl, ethyl, n-propyl, or isopropyl);
and/or, Z is H or halogen, preferably, Z is H.
26. Use of a bis-fluorosulfonyl imide as a catalyst in a rearrangement reaction of a compound of formula (IX), comprising the steps of:
in a solvent, carrying out rearrangement reaction on the compound shown in the formula (IX) under the action of bis (fluorosulfonyl) imide to obtain the compound shown in the formula (IX-A) and/or the compound shown in the formula (IX-B);
wherein R is 21 Is C1-C16 alkyl, C6-C10 aryl or R I Substituted C6-C10 aryl, R I Is halogen, C1-C6 alkyl or C1-C6 alkoxy.
27. The use of claim 26, wherein R is 21 In (1), the C1-C16 alkyl groupIs C1-C10 alkyl, for example C1-C6 alkyl (for example C1-C3 alkyl, for example methyl, ethyl, n-propyl or isopropyl);
and/or, R 21 Wherein said C6-C10 aryl group and said R I C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R I Wherein said halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R I Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R I Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 21 In (1), the R I R in substituted C6-C10 aryl I The number of substitution(s) is 1 to 3 (e.g., 1), and each R I The same or different;
and/or, in the rearrangement reaction of the compound shown as the formula (IX), the usage amount of the bis-fluorosulfonyl imide is 20% -150%, such as 100% -150%, and 123% or 124% of the molar amount of the compound shown as the formula (IX);
and/or in the rearrangement reaction of the compound shown in the formula (IX), the rearrangement reaction is carried out in a solvent or in the absence of a solvent, wherein the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, a nitrile solvent, an aromatic hydrocarbon solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane; preferably, the rearrangement reaction is carried out in the absence of a solvent;
and/or, in the rearrangement reaction of the compound shown in the formula (IX), the temperature of the rearrangement reaction is 20-150 ℃, such as room temperature and 60 ℃;
and/or, in the rearrangement reaction of the compound shown in the formula (IX), the time of the rearrangement reaction is 2 to 12 hours, such as 3 hours.
28. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (XIII), comprising the steps of:
under the action of bis-fluorosulfonyl imide, reacting a compound shown as a formula (XIII-A), a compound shown as a formula (XIII-B) and a compound shown as a formula (XIII-C) to obtain a compound shown as a formula (XIII);
wherein Q is CH or N;
R 32 is halogen, C1-C16 alkyl, C6-C10 aryl or R O Substituted C6-C10 aryl;
m 3 is 0, 1,2, 3 or 4;
R 33 is C1-C16 alkyl, C6-C10 aryl or R P Substituted C6-C10 aryl;
R O and R P Independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
29. The use of claim 28, wherein R is 32 Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R 32 Or R 33 The C1-C16 alkyl group is, for example, a C1-C10 alkyl group, and further, for example, a C1-C6 alkyl group (for example, a C1-C3 alkyl group, and further, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group);
and/or, R 32 Or R 33 Wherein said C6-C10 aryl, said R O Substituted C6-C10 aryl and said R P C6-C10 aryl of the substituted C6-C10 aryl is independently phenyl;
and/or, R O Or R P Halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
and/or, R O Or R P Wherein said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, R O Or R P Wherein said C1-C6 alkoxy is a C1-C3 alkoxy group such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, R 32 In (1), the R O R in substituted C6-C10 aryl O The number of substitution(s) may be 1 to 3 (e.g., 1), each R O The same or different;
and/or, R 33 In (1), the R P R in substituted C6-C10 aryl P The number of substitution(s) may be 1 to 3 (e.g., 1), each R P The same or different;
and/or, in the preparation of the compound shown in the formula (XIII), the usage amount of the bis-fluorosulfonyl imide is preferably 5 to 20 percent, for example 10 percent of the molar amount of the compound shown in the formula (XIII-B);
and/or, in the preparation of the compound shown in the formula (XIII), the molar ratio of the compound shown in the formula (XIII-A) to the compound shown in the formula (XIII-B) is (1-2): 1, for example 1;
and/or in the preparation of the compound shown in the formula (XIII), the molar ratio of the compound shown in the formula (XIII-C) to the compound shown in the formula (XIII-B) is (1-200): 1;
and/or in the preparation of the compound shown as the formula (XIII), the reaction is carried out in a solvent or in the absence of a solvent, wherein the solvent is one or more of a sulfoxide solvent, a ketone solvent, an alcohol solvent, an ether solvent, an ester solvent, an aromatic solvent, an amide solvent, a halogenated alkane solvent and an alkane solvent; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, dimethyl sulfoxide, N-dimethylformamide, and 1,4-dioxane, further such as acetonitrile or dichloromethane; preferably, the reaction is carried out in the absence of a solvent;
and/or, in the preparation of the compound shown in the formula (XIII), the reaction temperature is 50-120 ℃, such as 60 ℃;
and/or, in the preparation of the compound shown in the formula (XIII), the reaction time is 1-5 hours, such as 3.5 hours.
30. The use of claim 28, wherein m is 3 Is 0 or 1, preferably m 3 Is 0;
and/or, Q is N;
and/or, R 33 C1-C6 alkyl, for example C1-C3 alkyl, and further for example methyl, ethyl, n-propyl or isopropyl.
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| ATTILA EGYED等: "The impact of binding site waters on the activity/selectivity trade-off of Janus kinase 2 (JAK2) inhibitors", BIOORGANIC & MEDICINAL CHEMISTRY, vol. 27, pages 1497 - 1508 * |
| GURMEET KAUR等: "Bis(fluorosulfuryl)imide: a Bronsted acid catalyst for the coupling of allylic and benzylic alcohols with allyltrimethylsilane", TETRAHEDRON LETTERS, vol. 38, no. 14, pages 2521 - 2524, XP004056750, DOI: 10.1016/S0040-4039(97)00390-0 * |
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