CN118290355A - Application of difluoro sulfimide as catalyst - Google Patents
Application of difluoro sulfimide as catalyst Download PDFInfo
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- CN118290355A CN118290355A CN202410403513.0A CN202410403513A CN118290355A CN 118290355 A CN118290355 A CN 118290355A CN 202410403513 A CN202410403513 A CN 202410403513A CN 118290355 A CN118290355 A CN 118290355A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 24
- 238000006266 etherification reaction Methods 0.000 claims abstract description 22
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 250
- 239000002904 solvent Substances 0.000 claims description 228
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 163
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 150
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 144
- 238000002360 preparation method Methods 0.000 claims description 99
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 93
- -1 bis-fluorosulfonyl imide Chemical class 0.000 claims description 72
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 68
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 55
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 53
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 53
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 53
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 52
- 229910052736 halogen Inorganic materials 0.000 claims description 52
- 150000002367 halogens Chemical class 0.000 claims description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 49
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 42
- 150000003949 imides Chemical class 0.000 claims description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 40
- 229910052801 chlorine Inorganic materials 0.000 claims description 40
- 239000000460 chlorine Substances 0.000 claims description 40
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 39
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 27
- 238000006467 substitution reaction Methods 0.000 claims description 27
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 26
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 26
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052794 bromium Inorganic materials 0.000 claims description 26
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 23
- 150000001408 amides Chemical class 0.000 claims description 23
- 150000003462 sulfoxides Chemical class 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 22
- 239000005456 alcohol based solvent Substances 0.000 claims description 21
- 239000003759 ester based solvent Substances 0.000 claims description 21
- 239000004210 ether based solvent Substances 0.000 claims description 21
- 239000005453 ketone based solvent Substances 0.000 claims description 21
- 150000002825 nitriles Chemical class 0.000 claims description 21
- 238000006462 rearrangement reaction Methods 0.000 claims description 21
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 20
- 101100025412 Arabidopsis thaliana XI-A gene Proteins 0.000 claims description 19
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 18
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 18
- 230000002829 reductive effect Effects 0.000 claims description 17
- 150000008282 halocarbons Chemical class 0.000 claims description 16
- 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
- 230000035484 reaction time Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 10
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 150000001350 alkyl halides Chemical class 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 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
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000004756 silanes Chemical class 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 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 150000002596 lactones Chemical group 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000003208 petroleum Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 20
- 230000008034 disappearance Effects 0.000 description 19
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 238000001514 detection method Methods 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 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 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 239000000243 solution 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
- 101100347612 Arabidopsis thaliana VIII-B gene Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction 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
- 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
- 101100347605 Arabidopsis thaliana VIII-A gene Proteins 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
- 230000000694 effects 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
- 238000003756 stirring Methods 0.000 description 4
- 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 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000007960 acetonitrile Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-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
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 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
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 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
- 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
- 238000005406 washing Methods 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
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- 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
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 238000007796 conventional method Methods 0.000 description 1
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- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000543 intermediate 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
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-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
- 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
- 229940083037 simethicone Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum 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
- 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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- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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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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- C08G63/78—Preparation processes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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Abstract
The invention discloses an application of difluoro sulfimide as a catalyst. The invention takes the difluoro sulfimide as the catalyst to efficiently catalyze the Friedel-Crafts reaction, the esterification reaction, the lactone ring-opening polymerization reaction, the silyl ether polymerization reaction, the reduction etherification of carbonyl compounds, the alkynyl hydrolysis and other reactions, and has mild reaction conditions and high atom economy.
Description
This patent application is a divisional application of patent application number 202210754232.0, the application date of which is 2019, 12 and 31, and the name of which is "application of bisfluorosulfonyl imide as a catalyst".
Technical Field
The invention relates to an application of bis-fluoro-sulfimide as a catalyst.
Background
The structure of the difluoro-sulfonyl imide (HN (SO 2F)2) is analyzed, negative charges on N atoms are dispersed to the whole O-S-N framework through resonance effect under the strong electron-withdrawing effect of the fluoro-sulfonyl group to generate high delocalization, SO that the stability of FSO 2)2N- is greatly enhanced, and the fluoro-sulfonyl group has larger steric hindrance and strong electron-withdrawing effect, SO that the coordination capability of the ions is greatly reduced.
The difluoro sulfimide belongs to nitrogen-containing superacid, is a novel super strong Bronsted acid, and has the strength of more than concentrated sulfuric acid. Among known superacids, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid and the like are widely used as catalysts in the synthesis of intermediates such as medicines, pesticides, polymers and the like.
The application of the difluoro-sulfonyl imide as a catalyst in organic synthesis is not found at present, mainly because commercial production of the acid is not realized at present, and the synthetic route is not mature. At present, a large amount of fluorosulfonic acid is generally required to be used as a solvent in the synthesis of the bisfluorosulfonyl imide, the fluorosulfonic acid is high in price, the synthesis cost is high, in addition, the boiling point of the fluorosulfonic acid is very close to that of the bisfluorosulfonyl imide, and the separation and purification of a product are difficult.
In the acidification process of potassium (or sodium) difluoro-sulfonyl imide studied in the prior stage, the applicant finds that the difluoro-sulfonyl imide can be obtained by rapid and simple separation with very high yield under the condition of using concentrated sulfuric acid as acid and sulfur dioxide as solvent at low temperature, the price is low, the post-treatment is simple, the separation and purification are easy, and the synthetic route has the possibility of industrialized production.
Disclosure of Invention
The invention aims to overcome the defect of narrower application field of the prior difluoro-sulfonyl imide, and provides the application of the difluoro-sulfonyl imide as a catalyst.
The invention provides an application of difluoro sulfimide as a catalyst in the preparation of polylactone shown in a formula (I), which comprises the following steps:
In a solvent, under the action of bisfluorosulfonyl imide, a compound shown in a formula (I-A) and a compound shown in a formula (I-B) are subjected to polymerization reaction to obtain polylactone shown in the formula (I);
Wherein n 1 is an integer of 1 to 7;
R 1 is C1-C16 alkyl or- (CH 2)n2-Ar,n2 is an integer from 1 to 6, ar is 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 from 50 to 200.
Preferably, n 1 is 1,2 or 3, for example 3.
Preferably, in R 1, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably, C1-C6 alkyl.
Preferably, in R 1, n 2 may be 1,2 or 3, for example 3.
Preferably, in Ar, the C6-C10 aryl group and the C6-C10 aryl group of the R A -substituted C6-C10 aryl group are independently phenyl.
Preferably, in Ar, the number of R A substituted in the C6-C10 aryl substituted by R A is 1-3 (for example 1), and each R A is the same or different.
Preferably, in R A, the halogen is fluorine, chlorine, bromine or iodine.
Preferably, in R A, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R A, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 1, ar is phenyl or R A substituted phenyl.
Preferably, the compound represented by the formula (I-B) is
In the preparation of the polylactone represented by the formula (I), the amount of the bisfluorosulfonyl 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 ratio of the compound represented by the formula (I-A) to the compound represented by the formula (I-B) may be a ratio commonly used in the art for such reactions, 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 still more example, 100:1.
In the preparation of the polylactone shown in the formula (I), the solvent can be one or more solvents commonly used in the reaction in the field, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc.; and for example dichloromethane.
In the preparation of the polylactone of formula (I), the temperature of the polymerization reaction may be a temperature commonly used in such reactions in the art, for example, 20℃to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the polylactone of formula (I), the progress of the polymerization reaction can be generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (I-A). The polymerization time is preferably 4 to 12 hours.
The invention also provides an application of the difluoro sulfimide in preparing silicone oil shown in a formula (II) as a catalyst, which comprises the following steps:
under the action of bisfluorosulfonyl imide, a compound shown as a formula (II-A) and a compound shown as a formula (II-B) are subjected to polymerization reaction to obtain silicone oil shown as a formula (II);
Wherein R 2、R3、R4 and R 5 are independently C1-C16 alkyl or C6-C10 aryl;
m 2 is an integer from 50 to 200.
Preferably, in R 2、R3、R4 or R 5, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl, isopropyl).
Preferably, in R 2、R3、R4 or R 5, the C6-C10 aryl group may be phenyl.
Preferably, R 2、R3、R4 and R 5 are independently C1-C10 alkyl, further independently C1-C6 alkyl (e.g., C1-C3 alkyl, further e.g., methyl, ethyl, n-propyl, or isopropyl). More preferably, R 2、R3、R4 and R 5 are both 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 amount of the bisfluorosulfonyl imide is preferably 1% to 10% (e.g., 4%) of the molar amount of the compound represented by the formula (II-A).
In the preparation of the silicone oil represented by the formula (II), the ratio of the compound represented by the formula (II-A) to the compound represented by the formula (II-B) may be a ratio commonly used in the art for such reactions, 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, for example, 39.9:1.
In the preparation of the silicone oil represented by the formula (II), the polymerization reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 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 formula (II), the temperature of the polymerization reaction may be a temperature commonly used in such a reaction in the art, 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 generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point at which the compound of formula (II-A) disappears. The polymerization time is preferably 2 to 12 hours.
The invention also provides an application of the difluoro sulfimide in preparing tetrazole compounds shown in a formula (III) as a catalyst, which comprises the following steps:
Under the action of difluoro-sulfonyl imide in a solvent, a compound shown as a formula (III-A), an orthoformate compound shown as a formula (III-B) and sodium azide react to obtain a tetrazole compound shown as a formula (III);
Wherein R 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, in R 6, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably, C1-C6 alkyl.
Preferably, in R 6, the C6-C10 aryl group and the C6-C10 aryl group in the R B substituted C6-C10 aryl group may independently be phenyl.
Preferably, in R 6, the number of substitution of R B in the C6-C10 aryl substituted by R B is 1-3 (for example, 1), and each R B is the same or different.
Preferably, in R B, the halogen may be fluorine, chlorine, bromine or iodine, for example bromine.
Preferably, in R B, the C2-C4 alkynyl group may be an ethynyl group.
Preferably, R 6 is R B substituted phenyl, R B is halogen or ethynyl, e.g., R 6 is
In the preparation of the tetrazole compound of formula (III), the amount of the bis-fluorosulfonyl imide is preferably 1% to 10% (e.g., 5%) of the molar amount of the compound of formula (III-A).
In the preparation of the tetrazole compound represented by formula (III), the ratio of the compound represented by formula (III-a) to the orthoformate compound represented by formula (III-B) may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by formula (III-a) to the orthoformate compound represented by formula (III-B) is 1: (1-2), for example 1:1.2.
In the preparation of the tetrazole compound represented by formula (III), the ratio of the compound represented by formula (III-a) to the sodium azide may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by 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 represented by formula (III), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents, and alkane solvents; for example, glycerol, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc.; and for example glycerol.
In the preparation of the tetrazole compound of formula (III), the temperature of the reaction may be a temperature commonly used in such a reaction in the art, for example, 20℃to the reflux temperature of the solvent, for example, room temperature.
In the preparation of the tetrazole compound of formula (III), the progress of the reaction can be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point when the compound of formula (III-A) disappears. The reaction time is preferably 2 to 12 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (IV) as a catalyst, which comprises the following steps:
in Sup>A solvent, under the action of bisfluorosulfonyl imide, performing an addition reaction between Sup>A compound shown in formulSup>A (IV-A) and Sup>A compound shown in formulSup>A (IV-B) to obtain Sup>A compound shown in formulSup>A (IV);
Wherein,
X is NH, S or O;
R 7、R8 and R 9 are independently 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, in R 7、R8 or R 9, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 7、R8 or R 9, the C6-C10 aryl group and the C6-C10 aryl group of the R C substituted C6-C10 aryl group are independently phenyl.
Preferably, in R 7、R8 or R 9, the number of substitutions of R C in the benzyl group substituted by R C may be 1 to 3 (for example, 1), and each R C may be the same or different.
Preferably, in R C, the halogen is fluorine, chlorine, bromine or iodine.
Preferably, in R C, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in 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 are 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, R 9 is
Preferably, X is NH.
Preferably, the compound represented by the formulSup>A (IV-A) is
Preferably, the compound represented by the formula (IV-B) is
In the preparation of the compound represented by the formulSup>A (IV), the amount of the bisfluorosulfonyl imide is preferably 1% to 10% (e.g., 5%) of the molar amount of the compound represented by the formulSup>A (IV-A).
In the preparation of the compound represented by the formulSup>A (IV), the ratio of the compound represented by the formulSup>A (IV-A) to the compound represented by the formulSup>A (IV-B) may be Sup>A ratio of the amounts commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formulSup>A (IV-A) to the compound represented by the formulSup>A (IV-B) is 1 (1-10), for example, 1:1.
In the preparation of the compound represented by formula (IV), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, acetonitrile.
In the preparation of the compound of formula (IV), the temperature of the addition reaction may be a temperature commonly used in such reactions in the art, for example 20 ℃ to the reflux temperature of the solvent, for example room temperature.
In the preparation of the compound of formulSup>A (IV), the progress of the addition reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formulSup>A (IV-Sup>A). The time of the addition reaction is preferably 10 minutes to 12 hours, for example 0.5 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (V) as a catalyst, which comprises the following steps:
performing 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) in Sup>A solvent under the action of difluoro sulfimide to obtain the compound shown as the 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 are 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, in R 10, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 10, the C6-C10 aryl group and the C6-C10 aryl group of the R D substituted C6-C10 aryl group are independently phenyl.
Preferably, in R 10, the number of substitution of R D in the C6-C10 aryl substituted by R D is 1-3 (for example, 1), and each R D is the same or different.
Preferably, in R 10, the number of substitutions of R E in the benzyl group substituted by R E may be 1 to 3 (for example, 1), and each R E may be the same or different.
Preferably, in R D or R E, the halogen is fluorine, chlorine, bromine or iodine.
Preferably, in R D、RE or R 11, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R D、RE or R 11, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, R D、RE and R 11 are independently C1-C6 alkoxy.
Preferably Y is
Preferably, R 10 is benzyl, phenyl, R D substituted phenyl or R E substituted benzyl, R D and R E are independently C1-C6 alkoxy.
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 amount of the bisfluorosulfonyl imide is preferably 0.1% to 10% (e.g., 5%) of the molar amount of the compound represented by the formula (V-B).
In the preparation of the compound represented by the formulSup>A (V), the ratio of the compound represented by the formulSup>A (V-A) to the compound represented by the formulSup>A (V-B) may be Sup>A ratio commonly used in such reactions in the art, for example, the molar ratio of the compound represented by the formulSup>A (V-A) to the compound represented by the formulSup>A (V-B) is (1-10): 1, for example, 1:1.
In the preparation of the compound represented by formula (V), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, dichloromethane.
In the preparation of the compound of formula (V), the temperature of the friedel-crafts reaction may be a temperature commonly used in such reactions in the art, 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 generally monitored by detection methods conventional in the art (such as TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (V-B). The time of the friedel-crafts reaction is preferably 5 minutes to 12 hours, for example 0.5 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown in a formula (VI) as a catalyst, which comprises the following steps:
in a solvent, under the action of bisfluorosulfonyl imide, a compound shown in a formula (VI-A) and water are subjected to hydrolysis reaction to obtain the compound shown in the formula (VI);
Wherein R 12 is C1-C16 alkyl, C6-C10 aryl or R F substituted C6-C10 aryl, R F is amino.
Preferably, in R 12, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 12, the C6-C10 aryl group and the C6-C10 aryl group of the R F substituted C6-C10 aryl group are independently phenyl.
Preferably, in R 12, the number of substitution of R F in the C6-C10 aryl substituted by R F is 1-3 (for example, 1), and each R F is the same or different.
Preferably, R 12 is phenyl or amino-substituted phenyl.
In the preparation of the compound of formula (VI), the amount of the bis-fluorosulfonyl imide is preferably 5% to 30% (e.g., 10%) of the molar amount of the compound of formula (VI-A).
In the preparation of the compound of formula (VI), the ratio of the compound of formula (VI-A) to water may be a ratio commonly used in such reactions in the art, for example, the molar ratio of the compound of formula (VI-A) to water may be 1 (1-10), for example, 1:2.9.
In the preparation of the compound represented by formula (VI), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, 1, 4-dioxane.
In the preparation of the compound of formula (VI), the temperature of the hydrolysis reaction may be a temperature commonly used in such reactions in the art, for example 20 ℃ to the reflux temperature of the solvent, for example 100 ℃.
In the preparation of the compound of formula (VI), the progress of the hydrolysis reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (VI-a). The hydrolysis reaction time is preferably 2 to 12 hours, for example 8 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (VII) as a catalyst, which comprises the following steps:
In a solvent, under the action of difluoro-sulfonyl imide, a compound shown as a formula (VII-A) reacts with allyl trimethyl silane to obtain the compound shown as the formula (VII);
Wherein R 13 and R 14 are independently 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, in R 13 or R 14, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 13 or R 14, the C6-C10 aryl group and the C6-C10 aryl group of the R G substituted C6-C10 aryl group are independently phenyl.
Preferably, in R G, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.
Preferably, in R G, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R G, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 13 or R 14, the number of the substitutions of R G in the C6-C10 aryl substituted by R G is 1-3 (for example, 1), and each R G is the same or different.
Preferably, R 13 and R 14 are independently phenyl or R G substituted phenyl, R G is C1-C3 alkoxy.
Preferably, the compound represented by the formula (VII-A) is
In the preparation of the compound represented by the formula (VII), the amount of the bisfluorosulfonyl imide is preferably 5% to 30%, for example, 10% of the molar amount of the compound represented by the formula (VII-A).
In the preparation of the compound represented by the formula (VII), the ratio of the compound represented by the formula (VII-A) to the allyltrimethylsilane may be a 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 allyltrimethylsilane is 1 (1-10), for example, 1:1.2.
In the preparation of the compound represented by formula (VII), the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, dichloromethane.
In the preparation of the compound of formula (VII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example, -20 ℃ to room temperature, for example room temperature.
In the preparation of the compound of formula (VII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (VII-A). The reaction time is preferably 2 to 12 hours, for example 2 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (VIII) as a catalyst, which comprises the following steps:
Under the action of bisfluorosulfonyl imide, 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) react to obtain a compound shown as a formula (VIII);
Wherein R 15、R16、R17、R18、R19 and R 20 are independently H, C C16 alkyl, C6C 10 aryl or R H substituted C6C 10 aryl, R H is halogen, C1C 6 alkyl or C1C 6 alkoxy.
Preferably, in R 15、R16、R17、R18、R19 or R 20, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 15、R16、R17、R18、R19 or R 20, the C6-C10 aryl group and the C6-C10 aryl group of the R H substituted C6-C10 aryl group are independently phenyl.
Preferably, in R H, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.
Preferably, in R H, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R H, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 15、R16、R17、R18、R19 or R 20, the number of the substitutions of R H in the C6-C10 aryl substituted by R H is 1-3 (for example, 1), and each R H is the same or different.
Preferably, R 15、R16、R17、R18、R19 and R 20 are independently H, C C6 alkyl, phenyl or R H substituted phenyl, R H is halogen, C1C 3 alkyl or C1C 3 alkoxy.
Preferably, the compound represented by 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 represented by the formula (VIII), the amount of the bisfluorosulfonyl imide is preferably 1% to 100%, for example 10% to 50%, still more for example 30% of the molar amount of the compound represented by the formula (VIII-B).
In the preparation of the compound represented by the formula (VIII), the ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-B) may be a ratio of the amounts 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-B) is (1-2): 1, for example, 1.1:1 or 1.3:1.
In the preparation of the compound represented by the formula (VIII), the ratio of the compound represented by the formula (VIII-A) to the compound represented by the formula (VIII-C) may be a ratio of the amounts 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), e.g., 1:1.3, 1:1.8, or 1:2.
In the preparation of the compound represented by the formula (VIII), the reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, 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 of formula (VIII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example, room temperature to 50 ℃, for example, room temperature.
In the preparation of the compound of formula (VIII), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally taken as the disappearance of the compound of formula (VIII-B). The reaction time is preferably 2 to 12 hours.
The invention also provides an application of the difluoro sulfimide as a catalyst in a rearrangement reaction of a compound shown as a formula (IX), which comprises the following steps:
In a solvent, under the action of bisfluorosulfonyl imide, carrying out rearrangement reaction on a compound shown as a formula (IX) to obtain a compound shown as a formula (IX-A) and/or a compound shown as a formula (IX-B);
Wherein R 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, in R 21, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 21, the C6-C10 aryl group and the C6-C10 aryl group of the R I substituted C6-C10 aryl group are independently phenyl.
Preferably, in R I, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.
Preferably, in R I, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R I, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 21, the number of substitution of R I in the C6-C10 aryl substituted by R I is 1-3 (for example, 1), and each R I is the same or different.
Preferably, R 21 is C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl, or isopropyl).
In the rearrangement reaction of the compound represented by the formula (IX), the amount of the bisfluorosulfonyl imide is preferably 20% to 150%, for example, 100% to 150%, still more 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 carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, for example, sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, 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 a reaction in the art, for example, 20℃to 150℃such as room temperature, 60 ℃.
In the rearrangement reaction of the compound of formula (IX), the progress of the rearrangement reaction can be generally monitored by a detection method conventional in the art (for example, TLC, HPLC or GC), and the end point of the reaction is generally the point when the compound of formula (IX) disappears. The time of the rearrangement reaction is preferably 2 to 12 hours, for example 3 hours.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (X) as a catalyst, which comprises the following steps:
Under the action of bisfluorosulfonyl imide, a compound shown as a formula (X-A) reacts with a compound shown as a formula (X-B) to obtain a compound shown as a formula (X);
Wherein R 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 are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, in R 22 or R 23, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 22 or R 23, the C6-C10 aryl, the R J substituted C6-C10 aryl, and the C6-C10 aryl in the R K substituted C6-C10 aryl are independently phenyl.
Preferably, in R J or R K, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, in R J or R K, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R J or R K, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 22, the number of substitution of R J in the C6-C10 aryl substituted by R J is 1-3 (for example, 1), and each R J is the same or different.
Preferably, in R 23, the number of substitution of R K in the C6-C10 aryl substituted by R K is 1-3 (for example, 1), and each R K is the same or different.
Preferably, R 22 is phenyl or R J substituted phenyl.
Preferably, R 23 is 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).
In the preparation of the compound represented by the formula (X), the amount of the bisfluorosulfonyl imide is preferably 0.1% to 10%, for example, 10% of the molar amount of the compound represented by the formula (X-A).
In the preparation of the compound represented by the formula (X), the ratio of the compound represented by the formula (X-A) to the compound represented by the formula (X-B) may be a ratio of the amounts commonly used in such reactions in the art, 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, 1:5.5.
In the preparation of the compound represented by the formula (X), the reaction may be carried out in a solvent-free or solvent-free solvent, and the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, toluene, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., and for example, toluene. Preferably, the reaction is carried out in the absence of a solvent.
In the preparation of the compound of formula (X), the temperature of the reaction may be a temperature commonly used in the art for such reactions, e.g., room temperature-the reflux temperature of the solvent used, e.g., 85 ℃.
In the preparation of the compound of formula (X), the progress of the reaction is generally monitored by detection methods conventional in the art (e.g., TLC, HPLC or GC), and the endpoint of the reaction is generally determined by the disappearance of the compound of formula (X-A). The reaction time is preferably 2 to 12 hours, for example 12 hours.
The invention also provides an application of the difluoro sulfimide as a catalyst in the reduction etherification reaction of a carbonyl compound shown in a formula (XI-A), which comprises the following steps:
In a solvent, under the action of difluoro sulfimide and silane compounds shown as a formula (XI-B), carbonyl compounds shown as a formula (XI-A) undergo a reduction etherification reaction to prepare compounds shown as a formula (XI);
Wherein R 24 and R 25 are independently H, C C16 alkyl, C6C 10 aryl or R L substituted C6C 10 aryl, R L is halogen, C1C 6 alkyl or C1C 6 alkoxy; r 24-1 is C1-C3 alkyl.
Preferably, in R 24 or R 25, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 24 or R 25, the C6-C10 aryl group and the C6-C10 aryl group of the R L substituted C6-C10 aryl group are independently phenyl.
Preferably, in R L, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.
Preferably, in R L, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R L, the C1-C6 alkoxy group is a C1-C3 alkoxy group, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 24 or R 25, the number of the substitutions of R L in the C6-C10 aryl substituted by R L is 1-3 (for example, 1), and each R L is the same or different.
Preferably, R 24 and R 25 are independently H, phenyl or R L substituted phenyl.
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 bisfluorosulfonyl imide is preferably 0.1% to 10%, for example, 0.1% to 5%, still for example, 1% of the molar amount of the carbonyl compound represented by the formula (XI-A).
In the reduction etherification reaction of the carbonyl compound shown in the formula (XI-A), the silane compound shown in the formula (XI-B) can be used in the common use amount in the field of such reactions, 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, 1:1.12 and 1:1.10.
In the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the solvent may be one or more solvents commonly used in such a reaction in the art, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, haloalkane solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, methylene chloride.
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 a reaction 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 may be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC), and the end point of the reaction is generally the point 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 hours, 1 hour.
The invention also provides a preparation method of the silicon bis (fluorosulfonyl) imide shown in the formula (XII), which comprises the following steps:
reacting a compound shown as a formula (XII-A) with bis (fluorosulfonyl) imide to obtain bis (fluorosulfonyl) imide silicon ester shown as a formula (XII);
Wherein Z is H, halogen, C1-C16 alkyl, C6-C10 aryl or R N -substituted C6-C10 aryl, R 26、R27 and R 28 are independently C1-C16 alkyl, C6-C10 aryl, R M -substituted C6-C10 aryl or R 29、R30 and R 31 are independently C1-C6 alkyl, R M and R N are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
Preferably, Z, R 26、R27 or R 28, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in Z, R 26、R27 or R 28, the C6-C10 aryl, the R N substituted C6-C10 aryl and the C6-C10 aryl of the R M substituted C6-C10 aryl are independently phenyl.
Preferably, Z, R M or R N, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, in R M or R N, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R M or R N, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 26、R27 or R 28, the number of the substitutions of R M in the C6-C10 aryl substituted by R M is 1-3 (for example, 1), and each R M is the same or different.
Preferably, in R 29、R30 or R 31, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in Z, the number of R N substituted in the C6-C10 aryl substituted by R N is 1-3 (for example 1), and each R N is the same or different.
Preferably, R 26、R27 and R 28 are independentlyR 29、R30 and R 31 are independently C1-C3 alkyl (e.g., methyl, ethyl, n-propyl or isopropyl).
Preferably, Z is H or halogen, more preferably Z is H.
Preferably, the compound represented by the formula (XII-A) is
In the method for preparing the silicon difluorosulfinate represented by the formula (XII), the ratio of the compound represented by the formula (XII-A) to the amount of the difluorosulfimide may be a ratio commonly used in the art for such reactions, for example, the molar ratio of the compound represented by the formula (XII-A) to the amount of the difluorosulfimide is (1-10): 1, e.g., 1:1.
In the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the reaction can be carried out in a solvent or in a solvent, wherein the solvent can be one or more solvents commonly used in the field of such reactions, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, acetonitrile or methylene chloride. Preferably, the reaction is carried out in the absence of a solvent.
In the method for preparing the silicon bisfluorosulfonyl imide represented by the formula (XII), the temperature of the reaction 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 bisfluorosulfonyl imide shown in the formula (XII), the progress of the reaction can be generally monitored by a detection method conventional in the art (such as TLC, HPLC or GC or NMR), and the endpoint of the reaction is generally the point when bisfluorosulfonyl imide disappears. The reaction time is preferably 30 minutes to 2 hours, for example 1 hour.
The invention also provides an application of the difluoro sulfimide in preparing a compound shown as a formula (XIII) as a catalyst, which comprises the following steps:
under the action of bisfluorosulfonyl imide, a compound shown in a formula (XIII-A), a compound shown in a formula (XIII-B) and a compound shown in a formula (XIII-C) react to obtain a compound shown in 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 are 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, in R 32, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine.
Preferably, in R 32 or R 33, the C1-C16 alkyl is, for example, C1-C10 alkyl, and more preferably C1-C6 alkyl (e.g., C1-C3 alkyl, and more preferably methyl, ethyl, n-propyl or isopropyl).
Preferably, in R 32 or R 33, the C6-C10 aryl, the R O substituted C6-C10 aryl, and the C6-C10 aryl in the R P substituted C6-C10 aryl are independently phenyl.
Preferably, in R O or R P, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine.
Preferably, in R O or R P, the C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl.
Preferably, in R O or R P, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy.
Preferably, in R 32, the number of substitution of R O in the C6-C10 aryl substituted by R O is 1-3 (for example, 1), and each R O is the same or different.
Preferably, in R 33, the number of substitution of R P in the C6-C10 aryl substituted by R P is 1-3 (for example, 1), and each R P is the same or different.
Preferably, R 33 is C1-C6 alkyl, such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl.
In the preparation of the compound of formula (XIII), the amount of the bis-fluorosulfonyl imide is preferably 5% to 20%, for example 10%, of the molar amount of the compound of formula (XIII-B).
In the preparation of the compound represented by the formula (XIII), the ratio of the compound represented by the formula (XIII-A) to the compound represented by the formula (XIII-B) may be a ratio of the amounts 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, 1:5.1.
In the preparation of the compound represented by the formula (XIII), the ratio of the compound represented by the formula (XIII-C) to the compound represented by the formula (XIII-B) may be a 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 shown in the formula (XIII), the reaction can be carried out in a solvent-free state or in a solvent, and the solvent can be one or more solvents commonly used in the field of such reactions, such as sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; for example, tetrahydrofuran, methylene chloride, ethyl acetate, dimethyl sulfoxide, N, N-dimethylformamide, 1, 4-dioxane, etc., for example, acetonitrile or methylene chloride. Preferably, the reaction is carried out in the absence of a solvent.
In the preparation of the compound of formula (XIII), the temperature of the reaction may be a temperature commonly used in such reactions in the art, for example 50℃to 120℃and still more 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 endpoint of the reaction is generally taken as the disappearance of the compound of formula (XIII-B). 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 indicated, 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, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like.
Examples of the term "sulfoxide solvents" include, but are not limited to, dimethyl sulfoxide.
Examples of the term "ketone solvent" include, but are not limited to, acetone or N-methylpyrrolidone, etc.
Examples of the term "alcoholic solvent" include, but are not limited to, methanol, ethanol, glycerol, t-butanol, and the like.
Examples of the term "ethereal solvent" include, but are not limited to, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, 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 solvent" include, but are not limited to, acetonitrile and the like.
Examples of the term "aromatic solvent" include, but are not limited to, benzene, toluene, xylene, benzotrifluoride, fluorobenzene, and 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 "halogenated hydrocarbon solvent" include, but are not limited to, methylene chloride, chloroform, 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 on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the invention creatively applies the difluoro sulfimide to the organic synthesis reaction, can efficiently catalyze various types of 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 mild reaction conditions, strong substrate adaptability and high atom economy.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Preparation example 1
10G of potassium difluorosulfimide (45.6 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) were charged into an autoclave, 60 g of sulfur dioxide was introduced at-70℃and slowly warmed to room temperature, a white solid was formed after the reaction for half an hour, then sulfur dioxide gas was slowly released, 50ml of methylene chloride was added, filtration was carried out, the solid was washed with 50ml of methylene chloride, the filtrate was dried by spinning, distillation under reduced pressure was carried out, and 85℃20mm Hg fractions were collected to give 7.7g (42.5 mmol) of difluorosulfimide as a colorless liquid in 93% yield.
19 F NMR (dichloromethane as solvent, monofluorotrichloromethane as internal standard): 57.3.
Preparation example 2
10G of sodium difluorosulfimide (49.26 mmol) and 10g of 98% concentrated sulfuric acid (100 mmol) were charged into an autoclave, 60 g of sulfur dioxide was introduced at-70℃and slowly warmed to room temperature, a white solid was formed after the reaction for half an hour, then sulfur dioxide gas was slowly released, 50ml of methylene chloride was added, filtration was carried out, the solid was washed with 50ml of methylene chloride, the filtrate was dried by spinning, distillation under reduced pressure was carried out, and 85℃20mm Hg fractions were collected to give 8.1g (44.75 mmol) of difluorosulfimide as a colorless liquid in a yield of 91%.
19 F NMR (dichloromethane as solvent, monofluorotrichloromethane as internal standard): 57.3.
Example 1
1.9998G (17.54 mmol,1 eq) of caprolactone, 5ml of methylene chloride, 175ul of a 1mol/L solution of phenylpropanol methylene chloride (1% eq) were charged into a 25ml three-necked flask, 35ul of a 0.5mol/L solution of difluoro sulfinamide acid methylene chloride (0.1% eq) was added under nitrogen protection, the reaction was allowed to react overnight at room temperature, the reaction solution was poured into 50ml of cold n-hexane, the solid was precipitated, filtered and dried to give 1.86g (yield 93%) of white polycaprolactone solid, which was checked by GPC, mn PS =25267, pdi=1.03.
Example 2
5.01G (16.92 mmol) of octamethyl cyclotetrasiloxane, 0.0687g (0.424 mmol) of hexamethyl silyl ether, and 0.12g of bis-fluorosulfonyl imide (0.66 mmol,4 mol% relative to octamethyl cyclotetrasiloxane) were charged into a 25ml single-neck flask, stirred magnetically, and reacted overnight at room temperature to give a colorless viscous liquid as simethicone. Mn PS =9820, pdi=1.0 as measured by GPC.
Example 3
To a 20ml single port flask was added 3-ethynylaniline (0.1068 g,0.912 mmol), sodium azide (0.065 g,1 mmol), triethyl orthoformate (0.162 g,1.1 mmol), glycerol (4 ml), bis-fluorosulfonyl imide (91ul,0.5M in DCM,5 mol% relative to 3-ethynylaniline) were added, the reaction was carried out overnight at room temperature, and after completion of the reaction of the starting material (3-ethynylaniline) for TLC (petroleum ether: ethyl acetate=10:1), 15ml of water was added, and a solid was precipitated, filtered, washed with water, and dried to give 0.13g (0.76 mmol) of a pale yellow solid in 84% yield. Melting point 98.6-100 deg.c.
1H NMR(400MHz,CD3CN):3.38(s,1H),7.17-7.32(m,4H),8.10(s,1H).
Example 4
To a 20ml single flask was added 3-bromoaniline (0.1 g,0.58 mmol), sodium azide (0.038 g,0.58 mmol), triethyl orthoformate (0.104 g,0.7 mmol), glycerol (4 ml), bis-fluorosulfonyl imide (58ul,0.5M in DCM,5% mol relative to 3-bromoaniline) and reacted overnight at room temperature, and TLC (petroleum ether: ethyl acetate=10:1) was used to detect the completion of the reaction of the starting material (3-bromoaniline), 15ml of water was added, and solids were 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 ℃.
1H NMR(400MHz,CDCl3):6.91-6.93(d,2H),7.4-7.42(d,2H),8.08(s,1H)。
Example 5
To a 20ml single vial was added 4-hexen-3-one (0.3095 g,3.15 mmol), benzyl carbamate (0.476 g,3.15 mmol), acetonitrile (6 ml), bis-fluorosulfonyl imide (315 ul,0.5m in CH 3 CN,5% mole relative to 4-hexen-3-one), and the reaction was continued for half an hour at room temperature, TLC (petroleum ether: ethyl acetate=10:3), rf=0.4, disappearance of the detection starting material (4-hexen-3-one), purification by column chromatography gave 0.74g of white solid in 95% yield.
1H NMR(400MHz,CDCl3):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 flask was added benzyl p-methoxyacetate (0.792 g,4.4 mmol), methoxybenzene (0.476 g,4.4 mmol), methylene chloride (6 ml), bis-fluorosulfonyl imide (440 ul,0.5m in CH 3 CN,5% mol relative to benzyl p-methoxyacetate), and reacted at room temperature for half an hour, TLC (petroleum ether: ethyl acetate=10:3), rf=0.4, disappearance of the starting material (benzyl p-methoxyacetate) was detected, and spin-drying gave 0.95g (4.17 mmol) as a yellow oil in 95% yield.
1H NMR(400MHz,CDCl3):3.80(s,6H),3.89(s,2H),6.83-7.13(m,8H)。
Example 7
In a 20ml single vial was added p-aminophenylacetylene (0.2265 g,1.935 mmol), water (0.1 g,5.56 mmol), 1, 4-dioxane (2.5 ml), bis-fluorosulfonimide (35 mg,0.193mmol,10% mol relative to p-aminophenylacetylene), reacted at 100℃for 8 hours, TLC (petroleum ether: ethyl acetate=5:2, rf=0.3), the disappearance of the starting material (p-aminophenylacetylene) was detected, extraction with ethyl acetate (20 ml) was added, washing with water (20 ml. Times.3), washing with saturated sodium chloride, drying with 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)。
1H NMR(400MHz,CD3CN):2.42(s,3H),4.79(s,2H),6.58-6.69(d,2H),7.68-7.79(d,2H)。
Example 8
In a20 ml single vial was added 4' -methoxychalcone (0.1157 g, 0.481 mmol), dichloromethane (3 ml), allyltrimethylsilane (66.4 mg,0.58mmol,1.2 eq), bis-fluorosulfonimide (9 mg,0.0497mmol,10% mol relative to 4' -methoxychalcone) was added under ice bath conditions, the reaction was slowly restored to room temperature for two hours, TLC (petroleum ether: ethyl acetate=10:1), the starting material (4 ' -methoxychalcone) was detected to disappear, washed with water (20 ml×3), washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and purified by column chromatography (petroleum ether: ethyl acetate=10:1, rf=0.4) to give 0.11g (0.393 mmol) as a pale yellow solid in 81% yield.
1H NMR(400MHz,CDCl3):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
To a 20ml single flask was added aniline (213 mg,2.29 mmol), benzaldehyde (192 mg,1.81 mmol) and bis-fluorosulfonyl imide (98 mg,0.54mmol,30% mole relative to benzaldehyde) and stirred for 5 minutes, then acetophenone (360 mg,3 mmol) was added and stirred overnight at room temperature. Column chromatography purification (n-hexane: ethyl acetate=10:1, rf=0.4) afforded 210mg (0.69 mmol) of the product as a white solid in 38% yield.
1H NMR(400HMz,CDCl3):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
To a 20ml single flask was added aniline (106 mg,1.14 mmol), p-chlorobenzaldehyde (140 mg,1 mmol) and acetophenone (240 mg,2 mmol), stirred well and bis-fluorosulfonyl imide (54 mg,0.298mmol,30% mol relative to p-chlorobenzaldehyde) was added and reacted overnight at room temperature. TLC (n-hexane: ethyl acetate=10:1) checked for aniline and formaldehyde disappearance and column chromatography purification (n-hexane: ethyl acetate=10:1, rf=0.4) gave 100mg (0.298 mmol) of the product as a white solid in 30% yield.
1H 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 (220 mg,1.62 mmol) and bis-fluorosulfonyl imide (360 mg,1.99 mmol) were added to a 10ml single-port flask, the reaction was stirred at room temperature overnight, the disappearance of phenyl acetate was detected by TLC (petroleum ether: ethyl acetate=3:1), and purification by column chromatography (petroleum ether: ethyl acetate=3:1, rf=0.3) afforded 50mg (0.367 mmol) as a yellow solid in 23% yield.
1H 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 (330 mg,2.4 mmol) and bis-fluorosulfonyl imide (540 mg,2.98 mmol) were added to a 10ml single-port flask, stirred at 60℃for 3h, disappearance of phenyl acetate was detected by TLC (petroleum ether: ethyl acetate=3:1), and purification by column chromatography (petroleum ether: ethyl acetate=3:1, rf=0.3) gave 100mg (0.735 mmol) as a yellow solid in 30% yield.
1H 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
Benzoic acid (0.21 g,1.72 mmol), anhydrous methanol (0.3 g,9.375 mmol) and toluene (1 ml) were added under nitrogen protection to a 25ml three-port flask, bis-fluorosulfonyl imide (31 mg,0.171mol,10% mol relative to benzoic acid) was added and reacted under stirring at 85℃for 12h, disappearance of benzoic acid was detected by TLC (petroleum ether: ethyl acetate=30:1), and purification by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) gave 160mg (1.18 mmol) as a colorless oily liquid in 68.6% yield.
1H NMR(400MHz,CDCl3):3.92(s,3H),7.42-7.45(t,2H),7.53-7.55(t,2H),8.03-8.05(d,2H)。
Example 14
To a 25ml single flask was added benzaldehyde (0.2198 g,2.07 mmol), triethylsilane (0.27 g,2.327 mmol) and dichloromethane (1 ml) under nitrogen protection, and bis-fluorosulfonyl imide (42 ul,0.5m dichloromethane solution, 1% mol relative to benzaldehyde) was added and reacted at room temperature with stirring for 30 minutes, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and the purification by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) gave 160mg (0.808 mmol) of colorless oily liquid in 78% yield.
1H NMR(400MHz,CDCl3):4.59(s,4H),7.38-7.40(m,10H)。
Example 15
4-Chlorobenzaldehyde (0.32 g, 2.284 mmol), triethylsilane (0.2927 g,2.52 mmol) and dichloromethane (1 ml) were added to a 25ml single port flask under nitrogen protection, and bis-fluorosulfonyl imide (45 ul,0.5M in dichloromethane, 1% mol relative to 4-chlorobenzaldehyde) was reacted at room temperature with stirring for 30 minutes, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.4) to give 260mg (0.974 mmol) of a white solid in 86% yield.
1H NMR(400MHz,CDCl3):4.52(s,4H),7.28-7.35(m,8H)。
Example 16
3-Methylbenzaldehyde (0.1387 g,1.156 mmol) was added to a 25ml single-port flask, triethylsilane (0.151 g,1.3 mmol) and methylene chloride (1 ml) were added under nitrogen protection, and bisfluorosulfonyl imide (23 ul,0.5M methylene chloride solution, 1 mol% relative to 3-methylbenzaldehyde) was added to react for 30 minutes under stirring at room temperature, and the disappearance of benzaldehyde was detected by TLC (petroleum ether: ethyl acetate=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.6) to give 130mg (0.575 mmol) of a white solid in 99% yield.
1H NMR(400MHz,CDCl3):2.35(s,6H),4.52(s,4H),7.09-7.26(m,8H)。
Example 17
4-Methylbenzaldehyde (0.1507 g,1.256 mmol), triethylsilane (0.16 g,1.38 mmol) and dichloromethane (1 ml) were added to a 25ml single-port flask under nitrogen protection, bis-fluorosulfonyl imide (25 ul,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=30:1), and column chromatography purification (petroleum ether: ethyl acetate=30:1, rf=0.5) gave 131mg (0.58 mmol) as a white solid in 92% yield.
1H NMR(400MHz,CDCl3):2.35(s,6H),4.5(s,4H),7.14-7.17(d,4H),7.24-7.26(d,4H)。
Example 19
To a 10ml single port flask was added 250ul of a solution of tris (trimethylsilyl) silane in deuterated acetonitrile (0.5M), followed by a slow addition of 250ul of bis-fluorosulfonyl imide in deuterated acetonitrile (0.5M) in ice bath and a slow return to room temperature followed by a 1 hour reaction. Thus obtaining the target product solution.
19 F NMR (deuterated acetonitrile as solvent, fluorotrichloromethane as internal standard): +54
1H NMR(400MHz,d-CD3CN):0.17(S)。
Example 19
In a 20ml single flask was charged benzotriazole (0.111 g,0.933 mmol), 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring (0.2 g,0.6 mmol), acetonitrile (6 ml), bis-fluorosulfonimide (12 mg,0.066mmol,10% mol relative to 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring) and reacted at 60℃for 3.5 hours, TLC (petroleum ether: ethyl acetate=5:2), 1- (trifluoromethyl) -3, 3-dimethyl-1, 2-benziodooxavaleric ring was detected to disappear, the quantitative yield of the product via fluorine spectrum was 83% (based on benzotrifluoride as internal standard).
19 F NMR (acetonitrile as solvent, fluorotrichloromethane as internal standard): -53;
LC-MS:229(M+1)。
Comparative example 1
This comparative example is selected from the document org.
4-Hexen-3-one (0.5 mmol,1.0 eq) with benzyl carbamate (0.75 mmol,1.5 eq), acetonitrile (1 ml), bis (trifluoromethanesulfonyl) imide (0.05 mmol,10% eq) was added and reacted at 20℃for 10min to give 117mg of product in 95% yield. The use amount of the bis (trifluoromethanesulfonyl) imide is large, and the reaction condition is severe, and the bis (trifluoromethanesulfonyl) imide needs to be carried out at the temperature of minus 20 ℃.
Comparative example 2
This comparative example is selected from J.org.chem.1987,52,4314-4319.
In reductive etherification of carbonyl compounds, as described in this document 4318, page experiment method a, trimethylsilyl triflate (TRIMETHYLSILYL TRIFLATE,44.45mg,0.20mmol,10% eq) and triethylsilyl hydrogen (0.460 g,4mmol,2 eq) were dissolved in 4ml dichloromethane, benzaldehyde (0.212 g,2mmol,1 eq) was added under ice bath and reacted at room temperature for 2 hours and purified by column chromatography (petroleum ether: ethyl acetate=30:1, rf=0.4) to give 0.1299g colorless oily liquid in 65.6% yield.
1H NMR(400MHz,CDCl3):4.59(s,4H),7.38-7.40(m,10H)。
Claims (24)
1. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (IV), comprising the steps of:
in Sup>A solvent, under the action of bisfluorosulfonyl imide, performing an addition reaction between Sup>A compound shown in formulSup>A (IV-A) and Sup>A compound shown in formulSup>A (IV-B) to obtain Sup>A compound shown in formulSup>A (IV);
Wherein,
X is NH, S or O;
R 7、R8 and R 9 are independently C1-C16 alkyl, C6-C10 aryl, R C substituted C6-C10 aryl or R C is halogen, C1-C6 alkyl or C1-C6 alkoxy.
2. Use according to claim 1, wherein in R 7、R8 or R 9, said C1-C16 alkyl is a C1-C10 alkyl, preferably a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 7、R8 or R 9, the C6-C10 aryl and the C6-C10 aryl of the R C substituted C6-C10 aryl are independently phenyl;
And/or, in R 7、R8 or R 9, the number of substitutions of R C in the benzyl group substituted by R C is 1 to 3 (for example, 1), and each R C is the same or different;
And/or, in R C, the halogen is fluorine, chlorine, bromine or iodine;
And/or, in R C, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R C, the C1-C6 alkoxy is C1-C3 alkoxy, 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 use amount of the bisfluorosulfonyl imide is 1-10% (such as 5%) of the molar amount of the compound shown in the formulSup>A (IV-A);
And/or, in the preparation of the compound shown in the formulSup>A (IV), the molar ratio of the compound shown in the formulSup>A (IV-A) to the compound shown in the formulSup>A (IV-B) is 1 (1-10), for example, 1:1;
And/or in the preparation of the compound shown in the formula (IV), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as acetonitrile;
and/or, in the preparation of the compound represented by the formula (IV), the temperature of the addition reaction is 20 ℃ to the reflux temperature of the solvent, for example, room temperature;
and/or, in the preparation of the compound represented by the formula (IV), the time of the addition reaction is 10 minutes to 12 hours, for example, 0.5 hours.
3. Use according to claim 2, wherein R 7 and R 8 are independently C1-C16 alkyl, such as C1-C10 alkyl, further such as C1-C6 alkyl (such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl); preferably, the compound represented by the formulSup>A (IV-A) is
And/or R 9 isPreferably, the compound represented by the formula (IV-B) is
4. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (V), comprising the steps of:
performing 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) in Sup>A solvent under the action of difluoro sulfimide to obtain the compound shown as the 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 are independently halogen, C1-C6 alkyl or C1-C6 alkoxy;
r 11 is C1-C6 alkyl or C1-C6 alkoxy.
5. The use according to claim 4, wherein in Y, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine, bromine or iodine;
And/or, in R 10, said C1-C16 alkyl is C1-C10 alkyl, for example C1-C6 alkyl (for example C1-C3 alkyl, for example methyl, ethyl, n-propyl or isopropyl);
And/or, in R 10, the C6-C10 aryl and the C6-C10 aryl of the R D substituted C6-C10 aryl are independently phenyl;
and/or, in R 10, the number of substitutions of R D in the C6-C10 aryl substituted by R D is 1-3 (for example, 1), and each R D is the same or different;
And/or, in R 10, the number of substitutions of R E in the benzyl group substituted by R E is 1 to 3 (for example, 1), and each R E is the same or different;
and/or, in R D or R E, the halogen is fluorine, chlorine, bromine or iodine;
And/or, in R D、RE or R 11, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
and/or, in R D、RE or R 11, said C1-C6 alkoxy is C1-C3 alkoxy, 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 use amount of the bisfluorosulfonyl 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, for example, 1:1;
and/or in the preparation of the compound shown in the formula (V), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as dichloromethane;
And/or, in the preparation of the compound represented by formula (V), the temperature of the friedel-crafts reaction is 20 ℃ to the reflux temperature of the solvent, for example, room temperature;
And/or, in the preparation of the compound shown as the formula (V), the Friedel-crafts reaction time is 5 minutes to 12 hours, for example, 0.5 hour.
6. The use according to claim 5, wherein R D and R E are independently C1-C6 alkoxy; preferably, R 10 is benzyl, phenyl, R D -substituted phenyl, or R E -substituted benzyl; 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
7. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (VI), comprising the steps of:
in a solvent, under the action of bisfluorosulfonyl imide, a compound shown in a formula (VI-A) and water are subjected to hydrolysis reaction to obtain the compound shown in the formula (VI);
Wherein R 12 is C1-C16 alkyl, C6-C10 aryl or R F substituted C6-C10 aryl, R F is amino.
8. Use according to claim 7, wherein in R 12, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 12, the C6-C10 aryl and the C6-C10 aryl of the R F substituted C6-C10 aryl are independently phenyl;
And/or, in R 12, the number of substitutions of R F in the C6-C10 aryl substituted by R F is 1-3 (for example, 1), and each R F is the same or different;
And/or, in the preparation of the compound shown in the formula (VI), the use amount of the bisfluorosulfonyl 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 1:2.9;
And/or in the preparation of the compound shown in the formula (VI), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, 1, 4-dioxane;
And/or, in the preparation of the compound represented by formula (VI), the temperature of the hydrolysis reaction is 20 ℃ to the reflux temperature of the solvent, for example 100 ℃;
And/or, in the preparation of the compound represented by the formula (VI), the hydrolysis reaction time is 2 to 12 hours, for example 8 hours.
9. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (VII), comprising the steps of:
In a solvent, under the action of difluoro-sulfonyl imide, a compound shown as a formula (VII-A) reacts with allyl trimethyl silane to obtain the compound shown as the formula (VII);
Wherein R 13 and R 14 are independently C1-C16 alkyl, C6-C10 aryl or R G substituted C6-C10 aryl, R G is halogen, C1-C6 alkyl or C1-C6 alkoxy.
10. Use according to claim 9, wherein in R 13 or R 14, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 13 or R 14, the C6-C10 aryl and the C6-C10 aryl of the R G substituted C6-C10 aryl are independently phenyl;
and/or, in R G, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;
And/or, in R G, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R G, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
And/or, in R 13 or R 14, the number of substitutions of R G in the C6-C10 aryl substituted by R G is 1 to 3 (for example, 1), and each R G is the same or different;
and/or, in the preparation of the compound shown in the formula (VII), the use amount of the bisfluorosulfonyl imide is 5-30%, such as 10%, of the molar amount of the compound shown in the formula (VII-A);
And/or, in the preparation of the compound shown as the formula (VII), the molar ratio of the compound shown as the formula (VII-A) to the allyltrimethylsilane is 1 (1-10), such as 1:1.2;
And/or in the preparation of the compound shown in the formula (VII), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, and further such as dichloromethane;
And/or, in the preparation of the compound represented by the formula (VII), the temperature of the reaction is-20 ℃ to room temperature, for example, room temperature;
and/or, in the preparation of the compound represented by the formula (VII), the reaction time is 2 to 12 hours, for example, 2 hours.
11. The use according to claim 10, wherein R 13 and R 14 are independently phenyl or R G substituted phenyl, R G is C1-C3 alkoxy; preferably, the compound represented by the formula (VII-A) is
12. Use of a bis-fluorosulfonyl imide as a catalyst in the preparation of a compound of formula (X), comprising the steps of:
Under the action of bisfluorosulfonyl imide, a compound shown as a formula (X-A) reacts with a compound shown as a formula (X-B) to obtain a compound shown as a formula (X);
Wherein R 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 are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
13. Use according to claim 12, wherein in R 22 or R 23, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 22 or R 23, C6-C10 aryl of the C6-C10 aryl, the R J substituted C6-C10 aryl, and the R K substituted C6-C10 aryl are independently phenyl;
And/or, in R J or R K, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
And/or, in R J or R K, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R J or R K, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
And/or, in R 22, the number of substitutions of R J in the C6-C10 aryl substituted by R J is 1-3 (for example, 1), and each R J is the same or different;
And/or, in R 23, the number of substitutions of R K in the C6-C10 aryl substituted by R K is 1-3 (for example, 1), and each R K is the same or different;
And/or, in the preparation of the compound shown in the formula (X), the use amount of the bisfluorosulfonyl imide is 0.1% -10%, such as 10%, of the molar amount of the compound shown in the formula (X-A);
and/or, in the preparation of the compound shown as the formula (X), the molar ratio of the compound shown as the formula (X-A) to the compound shown as the formula (X-B) is 1 (1-10), such as 1:5.5;
And/or, in the preparation of the compound represented by the formula (X), the reaction is carried out in a solvent or in a solvent-free state, 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 haloalkane solvent and an alkane solvent, for example, one or more of tetrahydrofuran, methylene chloride, ethyl acetate, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, toluene; preferably, the reaction is carried out in the absence of a solvent;
And/or, in the preparation of the compound represented by the 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 represented by the formula (X), the reaction time is 2 to 12 hours, for example, 12 hours.
14. Use of a bis-fluorosulfonyl imide as a catalyst in the reductive etherification of carbonyl compounds of formula (XI-a), comprising the steps of:
In a solvent, under the action of difluoro sulfimide and silane compounds shown as a formula (XI-B), carbonyl compounds shown as a formula (XI-A) undergo a reduction etherification reaction to prepare compounds shown as a formula (XI);
Wherein R 24 and R 25 are independently H, C C16 alkyl, C6C 10 aryl or R L substituted C6C 10 aryl, R L is halogen, C1C 6 alkyl or C1C 6 alkoxy; r 24-1 is C1-C3 alkyl.
15. Use according to claim 14, wherein in R 24 or R 25, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 24 or R 25, the C6-C10 aryl and the C6-C10 aryl of the R L substituted C6-C10 aryl are independently phenyl;
And/or, in R L, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;
And/or, in R L, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R L, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
And/or, in R 24 or R 25, the number of substitutions of R L in the C6-C10 aryl substituted by R L is 1 to 3 (for example, 1), and each R L is 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 use amount of the bisfluorosulfonyl imide is 0.1-10%, such as 0.1-5%, and still more such as 1% of the molar amount 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), for example, 1:1.12 or 1:1.10;
And/or in the reductive etherification reaction of the carbonyl compound shown in the formula (XI-A), the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, such as dichloromethane;
and/or, in the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the temperature of the reductive etherification reaction is 0 ℃ to room temperature, for example, room temperature;
and/or, in the reductive etherification reaction of the carbonyl compound represented by the formula (XI-A), the time of the reductive etherification reaction is 5 minutes to 12 hours, for example, 0.5 hours or 1 hour.
16. The use according to claim 15, wherein R 24 and R 25 are independently H, phenyl or R L substituted phenyl, preferably the carbonyl compound of formula (XI-a)
17. A method for preparing silicon bis-fluorosulfonyl imide represented by the formula (XII), comprising the steps of:
reacting a compound shown as a formula (XII-A) with bis (fluorosulfonyl) imide to obtain bis (fluorosulfonyl) imide silicon ester shown as a formula (XII);
Wherein Z is H, halogen, C1-C16 alkyl, C6-C10 aryl or R N -substituted C6-C10 aryl, R 26、R27 and R 28 are independently C1-C16 alkyl, C6-C10 aryl, R M -substituted C6-C10 aryl or R 29、R30 and R 31 are independently C1-C6 alkyl, R M and R N are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
18. The method of claim 17, wherein in Z, R 26、R27 or R 28, the C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g., a C1-C3 alkyl, such as methyl, ethyl, n-propyl, or isopropyl);
And/or, Z, R 26、R27 or R 28, C6-C10 aryl of the C6-C10 aryl, the R N substituted C6-C10 aryl, and the R M substituted C6-C10 aryl are independently phenyl;
And/or Z, R M or R N, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;
and/or, in R M or R N, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R M or R N, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
And/or, in R 26、R27 or R 28, the number of substitutions of R M in the C6-C10 aryl substituted by R M is 1 to 3 (for example, 1), and each R M is the same or different;
And/or, in Z, the number of substitutions of R N in the C6-C10 aryl substituted by R N is 1-3 (for example, 1), and each R N is the same or different;
And/or, in R 29、R30 or R 31, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in the preparation method of the silicon bis (fluorosulfonyl) imide represented by the formula (XII), the molar ratio of the compound represented by the formula (XII-A) to the bis (fluorosulfonyl) imide is (1-10): 1, e.g., 1:1;
And/or, in the preparation method of the silicon bisfluorosulfonyl imide shown in the formula (XII), the reaction is carried out in a solvent or in a solvent-free state, wherein the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, 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 silicon bisfluorosulfonyl imide shown in the formula (XII), the temperature of the reaction is 0-room temperature, such as room temperature;
and/or, in the method for producing silicon bisfluorosulfonyl imide represented by the formula (XII), the reaction time is 30 minutes to 2 hours, for example, 1 hour.
19. The method of claim 18, wherein R 26、R27 and R 28 are independentlyR 29、R30 and R 31 are independently C1-C3 alkyl (e.g., methyl, ethyl, n-propyl, or isopropyl);
and/or Z is H or halogen, preferably Z is H.
20. 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, under the action of bisfluorosulfonyl imide, carrying out rearrangement reaction on a compound shown as a formula (IX) to obtain a compound shown as a formula (IX-A) and/or a compound shown as a formula (IX-B);
Wherein R 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.
21. Use according to claim 20, wherein in R 21, said C1-C16 alkyl is a C1-C10 alkyl, such as a C1-C6 alkyl (e.g. a C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl);
And/or, in R 21, the C6-C10 aryl and the C6-C10 aryl of the R I substituted C6-C10 aryl are independently phenyl;
And/or, in R I, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;
And/or, in R I, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R I, the C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
And/or, in R 21, the number of substitutions of R I in the C6-C10 aryl substituted by R I is 1-3 (for example, 1), and each R I is the same or different;
And/or, in the rearrangement reaction of the compound shown in the formula (IX), the amount of the bisfluorosulfonyl imide is 20% -150%, for example 100% -150%, still more for example 123% or 124% of the molar amount of the compound shown in the formula (IX);
And/or in the rearrangement reaction of the compound shown as the formula (IX), the rearrangement reaction is carried out in a solvent or in a solvent-free state, and the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, nitrile solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, acetonitrile, dimethylsulfoxide, 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 represented by the formula (IX), the temperature of the rearrangement reaction is 20 ℃ to 150 ℃, for example, room temperature, 60 ℃;
and/or, in the rearrangement reaction of the compound represented by the formula (IX), the time of the rearrangement reaction is 2 to 12 hours, for example, 3 hours.
22. 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 bisfluorosulfonyl imide, a compound shown in a formula (XIII-A), a compound shown in a formula (XIII-B) and a compound shown in a formula (XIII-C) react to obtain a compound shown in 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 are independently halogen, C1-C6 alkyl or C1-C6 alkoxy.
23. The use according to claim 22, wherein in R 32, the halogen is fluorine, chlorine, bromine or iodine, such as chlorine;
and/or R 32 or R 33, said C1-C16 alkyl is, for example, C1-C10 alkyl, further for example, C1-C6 alkyl (e.g., C1-C3 alkyl, further for example, methyl, ethyl, n-propyl or isopropyl);
And/or, in R 32 or R 33, C6-C10 aryl of the C6-C10 aryl, the R O substituted C6-C10 aryl, and the R P substituted C6-C10 aryl are independently phenyl;
And/or, in R O or R P, the halogen is fluorine, chlorine, bromine or iodine, for example chlorine;
And/or, in R O or R P, said C1-C6 alkyl is C1-C3 alkyl, such as methyl, ethyl, n-propyl or isopropyl;
And/or, in R O or R P, said C1-C6 alkoxy is C1-C3 alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy;
and/or, in R 32, the number of substitutions for R O in the R O substituted C6-C10 aryl group may be 1 to 3 (e.g., 1), each R O being the same or different;
And/or, in R 33, the number of substitutions for R P in the R P substituted C6-C10 aryl group may be 1 to 3 (e.g., 1), each R P being the same or different;
And/or, in the preparation of the compound represented by the formula (XIII), the amount of the bisfluorosulfonyl imide is preferably 5% to 20%, for example 10%, of the molar amount of the compound represented by 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, 1:5.1;
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 in the formula (XIII), the reaction is carried out in a solvent or in a solvent-free state, wherein the solvent is one or more of sulfoxide solvents, ketone solvents, alcohol solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, halogenated hydrocarbon solvents and alkane solvents; such as one or more of tetrahydrofuran, dichloromethane, ethyl acetate, dimethylsulfoxide, N-dimethylformamide and 1, 4-dioxane, for example, acetonitrile or dichloromethane; preferably, the reaction is carried out in the absence of a solvent;
And/or, in the preparation of the compound represented by formula (XIII), the temperature of the reaction is 50-120 ℃, for example 60 ℃;
And/or, in the preparation of the compound represented by the formula (XIII), the reaction time is 1 to 5 hours, for example, 3.5 hours.
24. Use according to claim 23, wherein m 3 is 0 or 1, preferably m 3 is 0;
And/or, Q is N;
and/or R 33 is C1-C6 alkyl, such as C1-C3 alkyl, further such as methyl, ethyl, n-propyl or isopropyl.
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