CN114292247A - Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound - Google Patents
Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound Download PDFInfo
- Publication number
- CN114292247A CN114292247A CN202210061469.0A CN202210061469A CN114292247A CN 114292247 A CN114292247 A CN 114292247A CN 202210061469 A CN202210061469 A CN 202210061469A CN 114292247 A CN114292247 A CN 114292247A
- Authority
- CN
- China
- Prior art keywords
- disulfide
- compound
- compounds
- alkyl
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Disulfide compound Chemical class 0.000 title claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 title claims abstract description 8
- 150000002019 disulfides Chemical class 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 123
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 21
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000001743 benzylic group Chemical group 0.000 claims description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 229940102396 methyl bromide Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 150000008365 aromatic ketones Chemical class 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- DQGBSPYYYCIELK-UHFFFAOYSA-N 1,1-bis(sulfanylidene)-1,3-benzothiazole Chemical class C1=CC=C2S(=S)(=S)C=NC2=C1 DQGBSPYYYCIELK-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 32
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 20
- 238000004440 column chromatography Methods 0.000 description 19
- 239000003480 eluent Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 238000000926 separation method Methods 0.000 description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 230000006837 decompression Effects 0.000 description 17
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 15
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 4
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical class C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 2
- PIMNFNXBTGPCIL-UHFFFAOYSA-N 1-(2-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Br PIMNFNXBTGPCIL-UHFFFAOYSA-N 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 2
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- ZNQNZGIVOOEJHQ-UHFFFAOYSA-N 2-acetylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)C)=CC=C3C(=O)C2=C1 ZNQNZGIVOOEJHQ-UHFFFAOYSA-N 0.000 description 2
- MNDZHERKKXUTOE-UHFFFAOYSA-N 2-butylthiophene Chemical compound CCCCC1=CC=CS1 MNDZHERKKXUTOE-UHFFFAOYSA-N 0.000 description 2
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 description 2
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 2
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- SXJIZQPZESTWLD-UHFFFAOYSA-N N-[6-(propan-2-ylthio)-1H-benzimidazol-2-yl]carbamic acid methyl ester Chemical compound C1=C(SC(C)C)C=C2NC(NC(=O)OC)=NC2=C1 SXJIZQPZESTWLD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical class C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 150000008427 organic disulfides Chemical class 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- LRFWYBZWRQWZIM-UHFFFAOYSA-N (2-fluorophenyl)methanamine Chemical compound NCC1=CC=CC=C1F LRFWYBZWRQWZIM-UHFFFAOYSA-N 0.000 description 1
- PXJACNDVRNAFHD-UHFFFAOYSA-N (2-methoxyphenyl)methanamine Chemical compound COC1=CC=CC=C1CN PXJACNDVRNAFHD-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- MPWSRGAWRAYBJK-UHFFFAOYSA-N (4-tert-butylphenyl)methanamine Chemical compound CC(C)(C)C1=CC=C(CN)C=C1 MPWSRGAWRAYBJK-UHFFFAOYSA-N 0.000 description 1
- WNIZAVGUKSWHED-UHFFFAOYSA-N 1,1-bis(sulfanylidene)thiophene Chemical compound S=S1(=S)C=CC=C1 WNIZAVGUKSWHED-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- YXHIINNJOGKPLF-UHFFFAOYSA-N 1-(2-Thienyl)-1-butanone Chemical compound CCCC(=O)C1=CC=CS1 YXHIINNJOGKPLF-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- HVRUGFJYCAFAAN-UHFFFAOYSA-N 1-bromo-2-ethylbenzene Chemical compound CCC1=CC=CC=C1Br HVRUGFJYCAFAAN-UHFFFAOYSA-N 0.000 description 1
- HDNRAPAFJLXKBV-UHFFFAOYSA-N 1-ethyl-4-methoxybenzene Chemical compound CCC1=CC=C(OC)C=C1 HDNRAPAFJLXKBV-UHFFFAOYSA-N 0.000 description 1
- SRQOBNUBCLPPPH-UHFFFAOYSA-N 1-ethyl-4-phenylbenzene Chemical group C1=CC(CC)=CC=C1C1=CC=CC=C1 SRQOBNUBCLPPPH-UHFFFAOYSA-N 0.000 description 1
- TVCLHSCUNDIOEP-UHFFFAOYSA-N 1-fluoro-4-[[(4-fluorophenyl)methyldisulfanyl]methyl]benzene Chemical compound C1=CC(F)=CC=C1CSSCC1=CC=C(F)C=C1 TVCLHSCUNDIOEP-UHFFFAOYSA-N 0.000 description 1
- DYQAZJQDLPPHNB-UHFFFAOYSA-N 1-phenyl-2-hexanone Chemical compound CCCCC(=O)CC1=CC=CC=C1 DYQAZJQDLPPHNB-UHFFFAOYSA-N 0.000 description 1
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 1
- MNNZINNZIQVULG-UHFFFAOYSA-N 2-chloroethylbenzene Chemical compound ClCCC1=CC=CC=C1 MNNZINNZIQVULG-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- QFNABHBYVSJWLO-UHFFFAOYSA-N 3,4,4a,5-tetrahydro-2h-naphthalen-1-one Chemical compound C1C=CC=C2C(=O)CCCC21 QFNABHBYVSJWLO-UHFFFAOYSA-N 0.000 description 1
- GUCPYIYFQVTFSI-UHFFFAOYSA-N 4-methoxybenzamide Chemical compound COC1=CC=C(C(N)=O)C=C1 GUCPYIYFQVTFSI-UHFFFAOYSA-N 0.000 description 1
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- AHHIZGRCBJEBIX-UHFFFAOYSA-N cyclohexylmethylbenzene Chemical compound C=1C=CC=CC=1CC1CCCCC1 AHHIZGRCBJEBIX-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- FPRGYYWYHOYPOK-UHFFFAOYSA-N n-[(4-methoxyphenyl)methyl]benzamide Chemical compound C1=CC(OC)=CC=C1CNC(=O)C1=CC=CC=C1 FPRGYYWYHOYPOK-UHFFFAOYSA-N 0.000 description 1
- LKQUCICFTHBFAL-UHFFFAOYSA-N n-benzylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NCC1=CC=CC=C1 LKQUCICFTHBFAL-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a disulfide compound and a method for catalyzing benzyl oxidation of an alkyl aromatic compound by using the disulfide compound; is a method for preparing aromatic ketone (aromatic aldehyde) compounds by catalyzing the oxidation of a benzylic C-H bond of alkyl aromatic hydrocarbon compounds by visible light excited disulfide compounds. The invention uses commercial, cheap and stable benzothiazole disulfide compounds as catalysts, and realizes the oxidation of the benzylic C-H bond of alkyl aromatic compounds under the irradiation of visible light without adding metal, alkali, reducing agent and the like at room temperature to efficiently prepare aromatic ketone and aromatic aldehyde compounds. The process has the advantages of simple operation, wide substrate applicability, low carbon and low cost, and is suitable for industrial scale production.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a disulfide photocatalyst and a method for preparing ketone by oxidizing benzyl of an alkyl aromatic compound.
Technical Field
Due to the strong electron transfer and free radical generation capacity of the organic disulfide, the organic disulfide has good heat in the field of visible light catalytic molecular oxygen oxidation: in 2008, Tsuboi project group reported the light-induced oxidation of allyl alcohol to acrolein catalyzed by diphenyl disulfide derivatives at room temperature (ball. chem. soc. jpn.2008,81, 361-; in 2016, the Wang Lei project group reports that a sulfhydryl radical formed by visible light excitation is used for catalyzing molecular oxygen to oxidize an internal acetylene compound to prepare a 1, 2-diketone compound (Green chem.2016,18, 6373-6379.); the subject group found in 2017 realizes the conversion of mono-or poly-substituted aromatic olefins into aldehydes or ketones at normal temperature under visible light conditions by combining experiments and calculations, using electron-rich aromatic disulfide as a catalyst and oxygen as an oxidant (Angew. chem., int. Ed.2017,56, 832-836.); in 2019, the Bombay project group reported that disulfide was used as a photocatalyst to respectively realize ketonic acid hydroxylation and hydroxymethylation reactions (Chemical Communications,2019,55: 13008-13011; 108558665A; 108752213A). In conclusion, disulfide-mediated visible-light-catalyzed molecular oxygen oxidation is only reported in small quantities in the oxidation of alkenes, alkynes and allylic alcohols, while sp is3The molecular oxygen oxidation reaction of C-H bond has not been reported in public, because sp3C-H bond compared to sp2And sp C-H bonds, with higher bond energies that are difficult to activate.
C-H bond activation is one of the powerful tools for the construction of complex organic molecules, sp and sp2The activation of C-H bonds usually requires a transition metal for catalysis, while the radical C-H bond activation is in sp3The activation of the C-H bond shows great application value. To realize a free radical C-H bondActivation should be selected with a suitable free radical initiation system. Generally, diazo compounds or peroxides are capable of inducing C-H bonds to form free radicals under high temperature or photoinitiated conditions. The most commonly used free radical initiator at present is peroxide (such as TBHP \ DTBP, etc.), because peroxide can generate homolytic cracking to generate alkoxy radical, and high temperature is usually required or low-valence metal is added into reactants to promote generation of alkoxy radical, so that H is extracted from reaction substrate to generate free radical intermediate, and finally C-H bond free radical activation is realized. However, the peroxide is unstable and explosive, the use of a large amount of peroxide has limitations in industrial production, and the use of high temperature and metal catalysts causes a large amount of energy waste. Therefore, there is a need to develop a new technology for realizing a series of benzyl sp under mild conditions3C-H bond oxidation.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention uses a disulfide compound which is cheap and easy to obtain and has a simple structure as a novel free radical initiator, does not contain additional metal, alkali, free radical initiator and reducing agent, and realizes the substrate benzylic sp under the action of visible light3C-H bond activation and a series of aerobic oxidation reactions.
In a first aspect of the present invention, there is provided a class of disulfide compounds for catalyzing the benzylic oxidation of alkylaromatic compounds; the disulfide compound is shown as a formula I:
wherein R is1And R2Each independently selected from phenyl, five-membered aromatic heterocycle or six-membered aromatic heterocycle;
in the above-mentioned technical solutions, it is further preferable that R is1，R2When it is a benzene ring group, it has the following formula:
wherein each benzene ring has a substituent R adjacent to, spaced from or para to the disulfide bond9、R10(ii) a And said R is9And R10Each independently selected from halogen and NO2One of cyano, C1-C8 alkyl or C1-C8 alkoxy.
In the above-mentioned technical solutions, it is further preferable that R is1、R2Each is independently selected from one of pyridyl, pyrimidyl, thienyl and benzothiazolyl;
in the above-mentioned embodiments, it is further preferred that the disulfide compound (formula I) is benzothiazole disulfide, and has the formula Ia:
the second aspect of the invention is to disclose a method for catalyzing benzyl oxidation of alkyl aromatic compounds by visible light excited disulfide compounds, which can prepare aromatic ketone or aromatic aldehyde; which comprises the following steps: in a solvent, a disulfide compound with a structural formula shown as I is used as a photosensitive catalyst, molecular oxygen is used as an oxidant, visible light is used as an excitation light source, and a benzylic C-H bond of an alkyl aromatic hydrocarbon compound is directly oxidized to generate an aromatic ketone compound or an aromatic benzylamine compound is oxidized to aldehyde.
In the above technical solution, it is further preferred that the alkyl aromatic hydrocarbon compound is represented by formula II:
wherein R is3One selected from hydrogen atom, halogen, alkyl and alkoxy; r4And R5Each independently selected from one of hydrogen atom, alkyl and acyl chloride;
in the above technical solutions, it is further preferable that the aromatic benzylamine compound is represented by formula III:
wherein R is6One selected from hydrogen atom, halogen, alkyl and alkoxy; r7And R8Each independently selected from one of hydrogen atom, alkyl, benzoyl and acyl chloride;
in the above technical solutions, it is further preferred that when the disulfide compound (formula I) is benzothiazole disulfide, the corresponding photocatalytic reaction formula is represented by formulas (1) and (2):
in the above technical solution, it is further preferable that the temperature of the photocatalytic reaction is-30 to 100 ℃; the molar ratio of the disulfide compound with the structural formula shown as I to the substrate is 0.001-0.5: 1, and the wavelength of visible light is 365nm-700 nm.
In the above technical solution, it is further preferable that the temperature of the photocatalytic reaction is 10 ℃ to 50 ℃; the molar ratio of the disulfide compound to the substrate is 0.005-0.5: 1.
In the above-mentioned technical solution, it is further preferable that the solvent is at least one selected from the group consisting of water, toluene, p-xylene, o-xylene, mesitylene, n-hexane, tetrahydrofuran, ethyl acetate, acetonitrile, DMF, DMAP, DMSO, chloroform, carbon tetrachloride, dichloromethane, bromomethane, dibromomethane, 1, 2-dichloroethane, 1, 3-dibromopropane, carbon disulfide, dioxane, petroleum ether, methanol, ethanol, tetrahydronaphthalene, and morpholine.
In the above technical solution, it is further preferable that the molecular oxygen is pure oxygen, air or a mixture containing oxygen molecules.
The invention has the beneficial effects that: the invention uses the disulfide compound which is easy to obtain, cheap and stable in commerce as a catalyst to realize the oxidation of the benzylic C-H bond under the irradiation of visible light. The method has the advantages of mild reaction conditions, simple operation, good substrate applicability, environment friendliness, low cost and suitability for industrial scale production, and can effectively prepare carbonyl and aldehyde compounds without adding metal, alkali, reducing agent and the like.
Detailed Description
The following detailed description of the embodiments of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the embodiments.
EXAMPLE 1 preparation of 1-Tetrahydronaphthalenone
To a 2mL acetonitrile solution were added tetralin (66.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 64.3mg of 1-tetralone is obtained with the yield of 88%.
1H NMR(400MHz,Chloroform-d)δ8.03(dd,J＝7.8,1.4Hz,1H),7.46(td,J＝7.8,1.4Hz,1H),7.36–7.10(m,2H),2.96(t,J＝6.1Hz,2H),2.65(t,J＝7.3,6.1Hz,2H),2.27–1.97(m,2H).
EXAMPLE 2 preparation of 1-Indanone
To a 2mL solution of acetonitrile were added indane (59.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 49.5mg of 1-indanone is obtained with the yield of 75%.
1H NMR(400MHz,Chloroform-d)δ8.29–6.82(m,4H),4.99–2.91(m,2H),2.62(q,J＝8.8,5.4Hz,2H).
EXAMPLE 3 preparation of 9-fluorenone
To a 2mL acetonitrile solution were added fluorene (83.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so as to obtain 81.1mg of 9-fluorenone with the yield of 90 percent.
1H NMR(400MHz,Chloroform-d)δ7.57(d,J＝7.3Hz,2H),7.47–7.33(m,4H),7.20(td,J＝7.3,1.5Hz,2H).
EXAMPLE 4 preparation of Diphenyl methanones
To a 2mL acetonitrile solution were added diphenylmethane (84.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and eluent is petroleum ether/ethyl acetate, so that 84.7mg of diphenyl ketone is obtained with the yield of 93 percent.
Example 5 preparation of acetophenone
To a 2mL acetonitrile solution were added ethylbenzene (53.08mg,0.5mmol) and benzothiazole disulfide (33.2mg,0.1mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 36 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 43.8mg of acetophenone is obtained with the yield of 73%.
1H NMR(400MHz,Chloroform-d)δ7.99–7.88(m,2H),7.58–7.49(m,1H),7.44(tt,J＝6.7,1.4Hz,2H),2.58(s,3H).
EXAMPLE 6 preparation of p-methoxyacetophenone
To a 2mL acetonitrile solution were added p-methoxyethylbenzene (68.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 66.1mg of p-methoxyacetophenone is obtained with the yield of 88%.
1H NMR(400MHz,Chloroform-d)δ7.94(d,J＝8.9Hz,2H),6.94(d,J＝8.9Hz,2H),3.87(s,3H),2.56(s,3H).
EXAMPLE 7 preparation of p-bromoacetophenone
To 2mL of the acetonitrile solution were added p-bromoethylbenzene (92.53mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 67.7mg of p-bromoacetophenone is obtained with the yield of 68%.
1H NMR(400MHz,Chloroform-d)δ7.81(d,J＝8.5Hz,2H),7.59(d,J＝8.5Hz,2H),2.58(s,3H).
EXAMPLE 8 preparation of o-bromoacetophenone
O-bromoethylbenzene (92.5mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) were added to 2mL of the acetonitrile solution, and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 40.8mg of o-bromoacetophenone is obtained with the yield of 41%.
1H NMR(400MHz,Chloroform-d)δ7.61(dd,J＝8.0,1.3Hz,1H),7.46(dd,J＝7.6,1.8Hz,1H),7.37(td,J＝7.6,1.3Hz,1H),2.63(s,3H).
EXAMPLE 9 preparation of 2-methyl-1-phenylpropanone
To a 2mL acetonitrile solution were added isobutylbenzene (67.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, thereby obtaining 25.2mg of 2-methyl-1-phenyl acetone with the yield of 34 percent.
1H NMR(400MHz,Chloroform-d)δ8.02–7.92(m,2H),7.62–7.51(m,1H),7.46(dd,J＝8.2,6.8Hz,2H),3.57(h,J＝6.8Hz,1H),1.22(d,J＝6.8Hz,6H).
EXAMPLE 10 preparation of Benzocaproketone
To a 2mL acetonitrile solution were added phenylhexane (81.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 49.3mg of the phenylhexanone is obtained, and the yield is 56%.
1H NMR(400MHz,Chloroform-d)δ8.43–7.92(m,2H),7.61–7.50(m,1H),7.46(t,J＝7.6Hz,2H),2.96(t,J＝7.4Hz,2H),1.74(dd,J＝9.1,5.7Hz,2H),1.37(q,J＝3.8Hz,4H),1.13–0.77(m,3H).
EXAMPLE 11 preparation of 2-Chloroacylbenzene
To a 2mL acetonitrile solution were added 2- (chloroethyl) benzene (70.3mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 27.0mg of 2-chloracetyl benzene is obtained with the yield of 35%.
1H NMR(400MHz,Chloroform-d)δ7.89(d,J＝7.6Hz,2H),7.58–7.52(m,1H),7.43(t,J＝7.6Hz,2H),4.65(s,2H).
EXAMPLE 12 preparation of methyl benzoate
Benzyl methyl ether (61.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) were added to a 2mL acetonitrile solution and subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 31.3mg of methyl benzoate is obtained with the yield of 46%.
1H NMR(400MHz,Chloroform-d)δ8.13–7.92(m,2H),7.68–7.49(m,1H),7.50–7.35(m,2H),3.91(s,3H).
EXAMPLE 13 preparation of 2-n-Butanoylthiophene
2-n-butylthiophene (70.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) were added to 2mL of the acetonitrile solution, and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so as to obtain 32.4mg of 2-n-butyl thiophene with the yield of 42 percent.
1H NMR(400MHz,Chloroform-d)δ7.85–6.83(m,1H),6.59(t,J＝7.3Hz,1H),6.45(d,J＝7.3Hz,1H),3.68–3.08(m,2H),2.75(t,J＝6.4Hz,2H),1.92(p,J＝6.4Hz,2H).
EXAMPLE 14 preparation of 2-acetylpyridine
To a 2mL acetonitrile solution were added 2-ethylpyridine (53.8mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and the eluent is petroleum ether/ethyl acetate, so that 8.5mg of 2-acetylpyridine is obtained with the yield of 14%.
1H NMR(400MHz,CDCl3)δ8.62(d,J＝4.0Hz,1H),7.98(d,J＝8.0,8.0Hz,1H),7.81-7.74(m,1H),7.44-7.39(m,1H),2.65(s,3H).
EXAMPLE 15 preparation of 2-Acetylanthraquinone
To a 2mL acetonitrile solution were added 2-ethylanthraquinone (118.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to violet irradiation under an oxygen atmosphere for 16 hours. After the reaction, the solvent acetonitrile was removed by concentration under reduced pressure, and column chromatography separation was carried out with petroleum ether/ethyl acetate as eluent to obtain 111.4mg of 2-acetylanthraquinone with a yield of 89%.
1H NMR(400MHz,Chloroform-d)δ8.74(d,J＝1.6Hz,1H),8.56–8.13(m,4H),7.82(dd,J＝5.9,3.3Hz,2H),2.74(s,3H).
EXAMPLE 16 preparation of 4-acetylbiphenyl
To a 2mL acetonitrile solution were added 4-ethylbiphenyl (91.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and eluent is petroleum ether/ethyl acetate, so that 88.3mg of 4-acetylbiphenyl is obtained with the yield of 90%.
1H NMR(400MHz,Chloroform-d)δ8.09–7.99(m,2H),7.77–7.65(m,2H),7.66–7.60(m,2H),7.55–7.44(m,2H),7.43–7.36(m,1H),2.64(s,3H).
Example 17 preparation of cyclohexyl phenyl methanones
To a 2mL acetonitrile solution were added (cyclohexylmethyl) benzene (87.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol), and the mixture was subjected to violet irradiation under an oxygen atmosphere for 16 hours. After the reaction, the solvent acetonitrile was removed by concentration under reduced pressure, and column chromatography separation was carried out with petroleum ether/ethyl acetate as eluent to obtain 69.6mg of cyclohexylphenyl methanone with a yield of 74%.
1H NMR(400MHz,Chloroform-d)δ8.02–7.86(m,2H),7.57–7.49(m,1H),7.45(dd,J＝8.3,6.7Hz,2H),3.26(tt,J＝11.5,3.3Hz,1H),1.98–1.76(m,4H),1.73(dtt,J＝12.7,3.4,1.6Hz,1H),1.57–1.13(m,5H).
Example 18 preparation of diphenylethanone
To a 2mL acetonitrile solution were added 1, 2-diphenylethane (91.1mg,0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) and the mixture was subjected to violet irradiation under an oxygen atmosphere for 16 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, and eluent is petroleum ether/ethyl acetate, so that 88.3mg of diphenylethanone is obtained with the yield of 61%.
1H NMR(400MHz,Chloroform-d)δ8.10–7.97(m,2H),7.77–7.66(m,2H),7.65–7.60(m,2H),7.54–7.44(m,2H),7.43–7.34(m,1H),2.64(d,J＝1.0Hz,3H).
EXAMPLE 19 preparation of benzaldehyde (formula III, wherein R1Is H)
To 3mL CHCl3Benzylamine (formula II, wherein R is10.0536g, 0.5mmol) and benzothiazyl disulfide (16.6mg,0.05mmol),10W violet light for 8 hours, benzylamine>99% conversion, benzaldehyde formation, yield 74%.
EXAMPLE 20 preparation of benzaldehyde (formula III, wherein R1Is H)
To 3mL CHCl3Benzylamine (formula II, wherein R is1H, 0.0536g, 0.5mmol) and thiophene disulfide (16.6mg,0.05mmol),10W violet irradiation for 8 hours, produced benzaldehyde in 60% yield.
EXAMPLE 21 preparation of p-tolualdehyde (formula III, wherein R1Is 4-Me)
To 3mL CHCl3Adding p-methylbenzylamine (formula II, wherein R is1As 4-Me, 0.0605g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light was irradiated for 8 hours to give p-tolualdehyde in a yield of 72%.
Example 22 preparation of 3-methylbenzaldehyde (formula III, wherein R1Is 3-Me)
To 3mL CHCl3To the solution was added 3-methylbenzylamine (formula II, wherein R is13-Me, 0.0605g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) in 10W violet light for 8 hours gave 3-methylbenzaldehyde in 51% nuclear magnetic yield.
EXAMPLE 23 preparation of 4-methoxybenzaldehyde (formula III, wherein R1Is 4-OMe)
To 3mL CHCl3Adding 4-methoxybenzylamine (formula II, wherein R is14-OMe, 0.0605g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) in 10W violet light for 8 hours to form 4-methoxybenzeneAldehyde, nuclear magnetic yield 77%.
EXAMPLE 24 preparation of 2-methoxybenzaldehyde (formula III, wherein R1Is 2-OMe)
To 3mL CHCl3Adding 2-methoxybenzylamine (formula II, wherein R is12-OMe, 0.0605g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light irradiation 8 hours, 2-methoxybenzaldehyde was formed with a nuclear magnetic yield of 61%.
EXAMPLE 25 preparation of 4-tert-butylbenzaldehyde (formula III, wherein R1Is 4-t-Bu)
To 3mL CHCl3To the solution was added 4-tert-butylbenzylamine (formula II, wherein R is14-t-Bu, 0.0816g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) were irradiated with 10W violet light for 8 hours to give 4-tert-butylbenzaldehyde in 83% nuclear magnetic yield.
EXAMPLE 26 preparation of 2-fluorobenzaldehyde (formula III, wherein R1Is 2-F)
To 3mL CHCl3Adding 2-fluorobenzylamine (formula II, wherein R is10.0626g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) in 10W violet light for 8 hours to yield 2-fluorobenzaldehyde in 68% yield.
EXAMPLE 27 preparation of benzaldehyde (formula III, wherein R1Is H)
To 3mL CHCl3Adding N-methylbenzylamine (formula II, wherein R is1，R3Is H, wherein R210W violet irradiation for 8 hours with 0.0606g, 0.5mmol) of Me and benzothiazole disulfide (16.6mg,0.05mmol) produced benzaldehyde in 62% nuclear magnetic yield.
EXAMPLE 28 preparation of benzaldehyde
To 3mL CHCl3Adding N, N-dimethylbenzylamine (formula III, wherein R is6Is H, R7，R80.0726g, 0.5mmol) of Me and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light irradiation for 8 h gave benzaldehyde in 49% yield.
EXAMPLE 29 preparation of benzaldehyde
To 3mL CHCl3Benzylamine (formula III, wherein R is6，R8Is a compound of formula (I) in the formula (H),wherein R is7i-Pr, 0.0746g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light irradiation for 8 hours produced benzaldehyde in nuclear magnetic yield of 43%.
Example 30
To 3mL CHCl3Benzylamine (formula III, wherein R is6，R8Is H, wherein R7Ph, 0.1556g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light for 8 hours gave benzaldehyde in 44% nuclear magnetic yield.
Example 31
To 3mL CHCl3To the solution was added N-benzoylbenzylamine (formula III, wherein R6，R8Is H, wherein R70.0916g, 0.5mmol) of benzoyl and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light was irradiated for 8 hours to generate benzaldehyde with a nuclear magnetic yield of 70%; benzamide was formed in a nuclear magnetic yield of 81%.
Example 32
To 3mL CHCl3Adding N-benzoyl p-methoxybenzylamine (formula III, wherein R is6Is 4-OMe, R8Is H, wherein R70.1206g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol) in a nuclear magnetic yield of 66% with 10W violet irradiation for 8 hours to form p-methoxybenzaldehyde; benzamide was formed with a nuclear magnetic yield of 68%.
Example 33
To 3mL CHCl3Adding N- (p-methoxy) benzoyl benzylamine (formula III, wherein R is6Is H, R8Is H, wherein R70.1206g, 0.5mmol of p-methoxybenzoyl) and benzothiazole disulfide (16.6mg,0.05mmol),10W of violet light was irradiated for 8 hours to produce p-methoxybenzaldehyde with a nuclear magnetic yield of 83%; p-methoxybenzamide was produced with a nuclear magnetic yield of 77%.
Example 34
To 3mL CHCl3Adding N-formyl chloride benzylamine (formula III in which R is6Is represented by8Is H, wherein R7As formyl chloride, 0.0918g, 0.5mmol) and benzothiazole disulfide (16.6mg,0.05mmol),10W violet light irradiationAfter 8 hours, benzaldehyde is generated, and the nuclear magnetic yield is 42%.
EXAMPLE 35 preparation of benzaldehyde
To 3mL CHCl3Benzylamine (formula III, wherein R is6H, 0.0536g, 0.5mmol) and benzothiazole disulfide (0.0830g,0.25mmol),10W violet light for 8 hours to yield benzaldehyde in 80% yield.
Comparative example 1 preparation of acetophenone
Ethylbenzene (53.08mg,0.5mmol) and diphenyldisulfide (21.8mg,0.1mmol) were added to 2mL of the acetonitrile solution, and subjected to ultraviolet irradiation under an oxygen atmosphere for 36 hours. Almost no product was obtained.
Comparative example 2 preparation of acetophenone
To a 2mL acetonitrile solution were added ethylbenzene (53.08mg,0.5mmol) and 4-fluorobenzyldisulfide (21.8mg,0.1mmol), and the mixture was subjected to ultraviolet irradiation under an oxygen atmosphere for 36 hours. After the reaction is finished, the solvent acetonitrile is removed by decompression and concentration, column chromatography separation is carried out, the eluent is petroleum ether/ethyl acetate, 4.2mg of acetophenone is obtained, and the yield is only 7%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and those skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A disulfide compound for catalyzing benzyl oxidation of alkyl aromatic compounds is characterized in that: the structural formula of the disulfide compound is shown as the formula I:
wherein R is1And R2Each independently selected from one of phenyl, five-membered aromatic heterocycle or six-membered aromatic heterocycle.
2. According toThe disulfide compounds of claim 1 for catalyzing the benzylic oxidation of alkylaromatic compounds, wherein: the R is1，R2When it is a benzene ring group, it has the following formula:
wherein each benzene ring has a substituent R adjacent to, spaced from or para to the disulfide bond9、R10(ii) a And said R is9And R10Each independently selected from halogen and NO2One of cyano, C1-C8 alkyl or C1-C8 alkoxy.
3. The disulfide compounds of claim 1, wherein said disulfide compounds are selected from the group consisting of: the R is1、R2Each independently selected from one of pyridyl, pyrimidyl, thienyl and benzothiazolyl.
4. The disulfide compounds of claim 1, wherein said disulfide compounds are selected from the group consisting of: the disulfide compound is benzothiazole disulfide, and the structural formula of the disulfide compound is shown in a formula Ia:
5. a method for catalyzing benzyl oxidation of alkyl aromatic compounds by visible light excited disulfide compounds is characterized by comprising the following steps: in a solvent, a disulfide compound with a structural formula shown as I is used as a photosensitive catalyst, molecular oxygen is used as an oxidant, visible light is used as an excitation light source, and a benzylic C-H bond of an alkyl aromatic hydrocarbon compound is directly oxidized to generate an aromatic ketone compound or an aromatic benzylamine compound is oxidized to aldehyde.
6. The method of claim 5, wherein the alkylaromatic hydrocarbon is of formula II:
wherein R is3One selected from hydrogen atom, halogen, alkyl and alkoxy; r4And R5Each independently selected from one of hydrogen atom, alkyl and acyl chloride.
7. The method of claim 5, wherein the aromatic benzylamine compound is represented by formula III:
wherein R is6One selected from hydrogen atom, halogen, alkyl and alkoxy; r7And R8Each independently selected from one of hydrogen atom, alkyl, benzoyl and acyl chloride.
8. The method of claim 5, wherein when the disulfide compound is benzothiazole disulfide, the corresponding photocatalytic reaction formulas are as shown in formulas (1) and (2):
9. the method according to claim 5, wherein the temperature of the photocatalytic reaction is-30 to 100 ℃; the molar ratio of the disulfide compound with the structural formula shown as I to the substrate is 0.001-0.5: 1, and the wavelength of visible light is 365nm-700 nm; the molecular oxygen comprises pure oxygen, air or mixed gas containing oxygen molecules.
10. The method according to claim 5, wherein the solvent is at least one selected from the group consisting of water, toluene, p-xylene, o-xylene, mesitylene, n-hexane, tetrahydrofuran, ethyl acetate, acetonitrile, DMF, DMAP, DMSO, chloroform, carbon tetrachloride, dichloromethane, methyl bromide, methylene bromide, 1, 2-dichloroethane, 1, 3-dibromopropane, carbon disulfide, dioxane, petroleum ether, methanol, ethanol, tetrahydronaphthalene, and morpholine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210061469.0A CN114292247A (en) | 2022-01-19 | 2022-01-19 | Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210061469.0A CN114292247A (en) | 2022-01-19 | 2022-01-19 | Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114292247A true CN114292247A (en) | 2022-04-08 |
Family
ID=80978184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210061469.0A Pending CN114292247A (en) | 2022-01-19 | 2022-01-19 | Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114292247A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073275A (en) * | 2022-08-22 | 2022-09-20 | 天津深蓝化工技术有限公司 | Preparation method of photoinitiator 1-hydroxycyclohexyl phenyl ketone |
| CN115433072A (en) * | 2022-08-22 | 2022-12-06 | 浙江工业大学 | Method for preparing aryl ketone by photocatalytic oxidation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011133A (en) * | 2017-05-25 | 2017-08-04 | 中国科学技术大学 | The method that a kind of benzyl position C H keys are direct oxidation into ketone |
| CN108752213A (en) * | 2018-05-09 | 2018-11-06 | 大连理工大学 | A kind of method that the catalysis of excited by visible light disulfide prepares alpha-hydroxymethyl-beta-dicarbonyl compound |
| CN111978163A (en) * | 2020-07-24 | 2020-11-24 | 华东理工大学 | Method for synthesizing aromatic aldehyde ketone by catalyzing alkyl aromatic hydrocarbon with water as oxygen source |
-
2022
- 2022-01-19 CN CN202210061469.0A patent/CN114292247A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011133A (en) * | 2017-05-25 | 2017-08-04 | 中国科学技术大学 | The method that a kind of benzyl position C H keys are direct oxidation into ketone |
| CN108752213A (en) * | 2018-05-09 | 2018-11-06 | 大连理工大学 | A kind of method that the catalysis of excited by visible light disulfide prepares alpha-hydroxymethyl-beta-dicarbonyl compound |
| CN111978163A (en) * | 2020-07-24 | 2020-11-24 | 华东理工大学 | Method for synthesizing aromatic aldehyde ketone by catalyzing alkyl aromatic hydrocarbon with water as oxygen source |
Non-Patent Citations (3)
| Title |
|---|
| H. FIROUZABADI ET AL.: "DINITRATOCERIUM (IV) CHROMATE DIHYDRATE, [Ce(N03)2] Cr04.2H20，A MILD REAGENT FOR THE OXIDATION OF ORGANIC COMPOUNDS IN ORGANIC MEDIA", 《SYNTHETIC COMMUNICATIONS》 * |
| MOSLEM MANSOUR LAKOURAJ ET AL.: "2, 4-Ionene Supported Permanganate: A Novel, Efficient and Selective Solid Phase Oxidizing Agent for Oxidation of Organic Compounds", 《J. ADV. OXID. TECHNOL.》 * |
| YONG DING ET AL.: "Novel Synthesis of Poly(thioarylene)s via Reaction between Arenethiols and Bromo Compounds with a Free Radical Initiator", 《MACROMOLECULES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073275A (en) * | 2022-08-22 | 2022-09-20 | 天津深蓝化工技术有限公司 | Preparation method of photoinitiator 1-hydroxycyclohexyl phenyl ketone |
| CN115433072A (en) * | 2022-08-22 | 2022-12-06 | 浙江工业大学 | Method for preparing aryl ketone by photocatalytic oxidation |
| CN115433072B (en) * | 2022-08-22 | 2023-08-08 | 浙江工业大学 | Method for preparing aryl ketone by photocatalytic oxidation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114292247A (en) | Disulfide compound and method for catalyzing benzyl oxidation of alkyl aromatic compound by using disulfide compound | |
| Plevyak et al. | Palladium-catalyzed arylation of ethylene | |
| Pillai et al. | Selective oxidation of alcohols by molecular oxygen over a Pd/MgO catalyst in the absence of any additives | |
| Xu et al. | Selective oxidation of alkenes to carbonyls under mild conditions | |
| Li et al. | Cercosporin-bioinspired selective photooxidation reactions under mild conditions | |
| Gazi et al. | Bromodimethylsulfonium bromide as a potential candidate for photocatalytic selective oxidation of benzylic alcohols using oxygen and visible light | |
| Lu et al. | [3+ 2] Photooxygenation of aryl cyclopropanes via visible light photocatalysis | |
| Wang et al. | Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI) | |
| Shen et al. | Efficient and selective oxidation of secondary benzylic CH bonds to ketones with O2 catalyzed by metalloporphyrins under solvent-free and additive-free conditions | |
| Lounis et al. | Chromium-exchanged zeolite (CrE-ZSM-5) as catalyst for alcohol oxidation and benzylic oxidation with t-BuOOH | |
| Nechab et al. | New aerobic oxidation of benzylic compounds: efficient catalysis by N-hydroxy-3, 4, 5, 6-tetraphenylphthalimide (NHTPPI)/CuCl under mild conditions and low catalyst loading | |
| Zhang et al. | Efficient metal‐free aerobic oxidation of aromatic hydrocarbons utilizing aryl‐tetrahalogenated N‐hydroxyphthalimides and 1, 4‐diamino‐2, 3‐dichloroanthraquinone | |
| Bindu et al. | Iodosobenzoic acid (IBA) catalysed benzylic and aromatic C–H oxidations | |
| CN112159314A (en) | Method for generating benzaldehyde by oxidizing alpha-monosubstituted styrene under catalysis of N-hydroxyphthalimide | |
| Shaikh et al. | Benzils: A Review on their Synthesis | |
| Han et al. | Efficient selective oxidation of alcohols to carbonyl compounds catalyzed by Ru-terpyridine complexes with molecular oxygen | |
| Akane et al. | Generation and reaction of samarium (II) Iodide Equivalent from Samarium and Chlorotrimethylsilane/Sodium Iodide System in Acetonitrile. | |
| Luo et al. | H 2 O 2-mediated room temperature synthesis of 2-arylacetophenones from arylhydrazines and vinyl azides in water | |
| Farhadi et al. | Aerobic photocatalytic oxidation of activated benzylic and allylic alcohols to carbonyl compounds catalyzed by molecular iodine | |
| Moore et al. | Cyanoketenes. Cycloadditions of halocyanoketenes to benzaldehydes | |
| CN113816899B (en) | Method for generating ketone or ester by catalytic oxidation of substituted aromatic compound with carbon material | |
| Wang et al. | Microwave-assisted cross-coupling reaction of sodium tetraphenylborate with aroyl chlorides on palladium-doped KF/Al2O3 | |
| CN108558665B (en) | Method for preparing alpha-hydroxy-beta-dicarbonyl compound by visible light excited disulfide catalysis | |
| CN108752213B (en) | Method for preparing alpha-hydroxymethyl-beta-dicarbonyl compound by visible light excited disulfide catalysis | |
| Alizadeh et al. | Green and diasteroselective oxidative cyclization of bisnaphthols to spirans |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220408 |