CN110423185B - Method for selectively oxidizing cumene compound - Google Patents
Method for selectively oxidizing cumene compound Download PDFInfo
- Publication number
- CN110423185B CN110423185B CN201910801132.7A CN201910801132A CN110423185B CN 110423185 B CN110423185 B CN 110423185B CN 201910801132 A CN201910801132 A CN 201910801132A CN 110423185 B CN110423185 B CN 110423185B
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- China
- Prior art keywords
- ball milling
- selectivity
- formula
- phenyl
- cumene
- Prior art date
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 172
- -1 cumene compound Chemical class 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 178
- 238000006243 chemical reaction Methods 0.000 claims abstract description 168
- 239000011541 reaction mixture Substances 0.000 claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007599 discharging Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 241000510672 Cuminum Species 0.000 claims abstract description 13
- 235000007129 Cuminum cyminum Nutrition 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 150000001908 cumenes Chemical class 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 50
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 49
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 7
- 229960002218 sodium chlorite Drugs 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002346 iodo group Chemical group I* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 claims description 2
- MIMAPGJIEGEIGQ-UHFFFAOYSA-N 5,10,15,20-tetrakis(2,4-dichlorophenyl)-21,23-dihydroporphyrin Chemical compound ClC1=C(C=CC(=C1)Cl)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=C(C=C(C=C5)Cl)Cl)N4)C4=C(C=C(C=C4)Cl)Cl)N3)C3=C(C=C(C=C3)Cl)Cl)=N2 MIMAPGJIEGEIGQ-UHFFFAOYSA-N 0.000 claims 1
- UQASJTNIEXIESH-UHFFFAOYSA-N 5,10,15,20-tetrakis(2,6-dichlorophenyl)-21,23-dihydroporphyrin Chemical compound Clc1cccc(Cl)c1-c1c2ccc(n2)c(-c2c(Cl)cccc2Cl)c2ccc([nH]2)c(-c2c(Cl)cccc2Cl)c2ccc(n2)c(-c2c(Cl)cccc2Cl)c2ccc1[nH]2 UQASJTNIEXIESH-UHFFFAOYSA-N 0.000 claims 1
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 abstract description 43
- 238000001311 chemical methods and process Methods 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 7
- 231100000331 toxic Toxicity 0.000 abstract description 6
- 230000002588 toxic effect Effects 0.000 abstract description 6
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 382
- 239000000243 solution Substances 0.000 description 151
- 235000019441 ethanol Nutrition 0.000 description 94
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 67
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 64
- 239000012065 filter cake Substances 0.000 description 50
- 238000005406 washing Methods 0.000 description 49
- 238000001914 filtration Methods 0.000 description 48
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 34
- 238000004458 analytical method Methods 0.000 description 34
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 34
- 238000004811 liquid chromatography Methods 0.000 description 34
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- 239000005711 Benzoic acid Substances 0.000 description 32
- 235000010233 benzoic acid Nutrition 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- LFMLJRGWYGERGJ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=CC=C(C=C2)[Fe+] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=CC=C(C=C2)[Fe+] LFMLJRGWYGERGJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QMDIKTAULVBEJN-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=CC=C(C=C2)[Fe] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=CC=C(C=C2)[Fe] QMDIKTAULVBEJN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MOZHUOIQYVYEPN-UHFFFAOYSA-N 1-bromo-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Br)C=C1 MOZHUOIQYVYEPN-UHFFFAOYSA-N 0.000 description 2
- NNZRVXTXKISCGS-UHFFFAOYSA-N 1-methoxy-2-propan-2-ylbenzene Chemical compound COC1=CC=CC=C1C(C)C NNZRVXTXKISCGS-UHFFFAOYSA-N 0.000 description 2
- JULZQKLZSNOEEJ-UHFFFAOYSA-N 1-methoxy-4-propan-2-ylbenzene Chemical compound COC1=CC=C(C(C)C)C=C1 JULZQKLZSNOEEJ-UHFFFAOYSA-N 0.000 description 2
- JXMYUMNAEKRMIP-UHFFFAOYSA-N 1-nitro-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C([N+]([O-])=O)C=C1 JXMYUMNAEKRMIP-UHFFFAOYSA-N 0.000 description 2
- KWSHGRJUSUJPQD-UHFFFAOYSA-N 1-phenyl-4-propan-2-ylbenzene Chemical compound C1=CC(C(C)C)=CC=C1C1=CC=CC=C1 KWSHGRJUSUJPQD-UHFFFAOYSA-N 0.000 description 2
- LUJMEECXHPYQOF-UHFFFAOYSA-N 3-hydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1 LUJMEECXHPYQOF-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- XCCNRBCNYGWTQX-UHFFFAOYSA-N 3-propan-2-ylaniline Chemical compound CC(C)C1=CC=CC(N)=C1 XCCNRBCNYGWTQX-UHFFFAOYSA-N 0.000 description 2
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- RHBNKTONOWLWEO-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=C(C(=CC=C2)Cl)[Fe] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.ClC2=C(C(=CC=C2)Cl)[Fe] RHBNKTONOWLWEO-UHFFFAOYSA-N 0.000 description 2
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RQZGOIJRSJWNRB-UHFFFAOYSA-N n-methyl-4-propan-2-ylaniline Chemical compound CNC1=CC=C(C(C)C)C=C1 RQZGOIJRSJWNRB-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- XLPDVYGDNRIQFV-UHFFFAOYSA-N p-Cymen-8-ol Chemical compound CC1=CC=C(C(C)(C)O)C=C1 XLPDVYGDNRIQFV-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- QMWWLVOSZVWOMR-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-2-methoxybenzene Chemical compound COC1=C(C=CC=C1)C(C)(C)OO QMWWLVOSZVWOMR-UHFFFAOYSA-N 0.000 description 1
- UZXWWJQFCYHPIW-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methoxybenzene Chemical compound COC1=CC=C(C(C)(C)OO)C=C1 UZXWWJQFCYHPIW-UHFFFAOYSA-N 0.000 description 1
- YCCHNFGPIFYNTF-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)OO)C=C1 YCCHNFGPIFYNTF-UHFFFAOYSA-N 0.000 description 1
- QMGHWVFGQGKFAG-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-nitrobenzene Chemical compound OOC(C)(C)C1=CC=C([N+]([O-])=O)C=C1 QMGHWVFGQGKFAG-UHFFFAOYSA-N 0.000 description 1
- CVIWTMIBFCBFLR-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-phenylbenzene Chemical compound C1=CC(C(C)(OO)C)=CC=C1C1=CC=CC=C1 CVIWTMIBFCBFLR-UHFFFAOYSA-N 0.000 description 1
- HWCBEGMIBCYKST-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C(C)(C)OO)C=C1 HWCBEGMIBCYKST-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical compound C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 1
- PDLCCNYKIIUWHA-UHFFFAOYSA-N 1-(4-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=C(C(C)=O)C=C1 PDLCCNYKIIUWHA-UHFFFAOYSA-N 0.000 description 1
- TXYDPMWCZNWFGP-UHFFFAOYSA-N 1-bromo-4-(2-hydroperoxypropan-2-yl)benzene Chemical compound OOC(C)(C)C1=CC=C(Br)C=C1 TXYDPMWCZNWFGP-UHFFFAOYSA-N 0.000 description 1
- JXFVMNFKABWTHD-UHFFFAOYSA-N 1-methyl-4-propylbenzene Chemical compound CCCC1=CC=C(C)C=C1 JXFVMNFKABWTHD-UHFFFAOYSA-N 0.000 description 1
- YFCPNGWWGKAUHJ-UHFFFAOYSA-N 2-(2-methoxyphenyl)propan-2-ol Chemical compound COC1=CC=CC=C1C(C)(C)O YFCPNGWWGKAUHJ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- IYRJPNNPDGGYSU-UHFFFAOYSA-N 2-(3-aminophenyl)propan-2-ol Chemical compound CC(C)(O)C1=CC=CC(N)=C1 IYRJPNNPDGGYSU-UHFFFAOYSA-N 0.000 description 1
- IXQSZFHLLQMBAG-UHFFFAOYSA-N 2-(4-aminophenyl)propan-2-ol Chemical compound CC(C)(O)C1=CC=C(N)C=C1 IXQSZFHLLQMBAG-UHFFFAOYSA-N 0.000 description 1
- AOGYBHJTXLXRSM-UHFFFAOYSA-N 2-(4-bromophenyl)propan-2-ol Chemical compound CC(C)(O)C1=CC=C(Br)C=C1 AOGYBHJTXLXRSM-UHFFFAOYSA-N 0.000 description 1
- BFXOWZOXTDBCHP-UHFFFAOYSA-N 2-(4-methoxyphenyl)propan-2-ol Chemical compound COC1=CC=C(C(C)(C)O)C=C1 BFXOWZOXTDBCHP-UHFFFAOYSA-N 0.000 description 1
- BCERWYLBCDENFU-UHFFFAOYSA-N 2-(4-nitrophenyl)propan-2-ol Chemical compound CC(C)(O)C1=CC=C([N+]([O-])=O)C=C1 BCERWYLBCDENFU-UHFFFAOYSA-N 0.000 description 1
- GOKGIYHIVSGXDM-UHFFFAOYSA-N 2-(4-phenylphenyl)propan-2-ol Chemical compound C1=CC(C(C)(O)C)=CC=C1C1=CC=CC=C1 GOKGIYHIVSGXDM-UHFFFAOYSA-N 0.000 description 1
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CKQHAYFOPRIUOM-UHFFFAOYSA-N 3'-Aminoacetophenone Chemical compound CC(=O)C1=CC=CC(N)=C1 CKQHAYFOPRIUOM-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- UNMOIIPWKJPWJA-UHFFFAOYSA-N 3-(2-hydroperoxypropan-2-yl)aniline Chemical compound NC=1C=C(C=CC1)C(C)(C)OO UNMOIIPWKJPWJA-UHFFFAOYSA-N 0.000 description 1
- KSZYLMVLWCUBOA-UHFFFAOYSA-N 3-(2-hydroperoxypropan-2-yl)phenol Chemical compound OOC(C)(C)C1=CC=CC(O)=C1 KSZYLMVLWCUBOA-UHFFFAOYSA-N 0.000 description 1
- KNCICOZTHWGRMY-UHFFFAOYSA-N 3-(2-hydroxypropan-2-yl)phenol Chemical compound CC(C)(O)C1=CC=CC(O)=C1 KNCICOZTHWGRMY-UHFFFAOYSA-N 0.000 description 1
- QSBUOPMUAWKIQT-UHFFFAOYSA-N 4-(2-hydroperoxypropan-2-yl)-N-methylaniline Chemical compound CNC1=CC=C(C=C1)C(C)(C)OO QSBUOPMUAWKIQT-UHFFFAOYSA-N 0.000 description 1
- BCIJYOJSVDXJIJ-UHFFFAOYSA-N 4-(2-hydroperoxypropan-2-yl)aniline Chemical compound NC1=CC=C(C=C1)C(C)(C)OO BCIJYOJSVDXJIJ-UHFFFAOYSA-N 0.000 description 1
- RKYBQSMXIAGHIG-UHFFFAOYSA-N 4-(2-hydroperoxypropan-2-yl)benzoic acid Chemical compound OOC(C)(C)C1=CC=C(C(O)=O)C=C1 RKYBQSMXIAGHIG-UHFFFAOYSA-N 0.000 description 1
- UQMTZPVNEBHIEU-UHFFFAOYSA-N 4-(2-hydroperoxypropan-2-yl)phenol Chemical compound OOC(C)(C)C1=CC=C(O)C=C1 UQMTZPVNEBHIEU-UHFFFAOYSA-N 0.000 description 1
- SLFZJKUFAVHARP-UHFFFAOYSA-N 4-(2-hydroxypropan-2-yl)benzoic acid Chemical compound CC(C)(O)C1=CC=C(C(O)=O)C=C1 SLFZJKUFAVHARP-UHFFFAOYSA-N 0.000 description 1
- PMZXHWXCHFTBFZ-UHFFFAOYSA-N 4-(2-hydroxypropan-2-yl)phenol Chemical compound CC(C)(O)C1=CC=C(O)C=C1 PMZXHWXCHFTBFZ-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- QBHDSQZASIBAAI-UHFFFAOYSA-N 4-acetylbenzoic acid Chemical compound CC(=O)C1=CC=C(C(O)=O)C=C1 QBHDSQZASIBAAI-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 1
- JWQCBAQDIFIZEE-UHFFFAOYSA-N FC1=C(C(=C(C(=C1[Fe])F)F)F)F Chemical compound FC1=C(C(=C(C(=C1[Fe])F)F)F)F JWQCBAQDIFIZEE-UHFFFAOYSA-N 0.000 description 1
- ZVIDMSBTYRSMAR-UHFFFAOYSA-N N-Methyl-4-aminobenzoate Chemical compound CNC1=CC=C(C(O)=O)C=C1 ZVIDMSBTYRSMAR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- SUIWQPJXZIBYIS-UHFFFAOYSA-N [Fe].ClC1=C(C=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Fe].ClC1=C(C=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 SUIWQPJXZIBYIS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VBSMBCNJCBKQFP-UHFFFAOYSA-N p-Hydroxydiisopropylbenzene Chemical compound CC(C)C1=CC=C(C(C)(C)O)C=C1 VBSMBCNJCBKQFP-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/002—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by transformation of a functional group, e.g. oxo, carboxyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for the selective oxidation of cumene compounds, the process comprising: placing a cumin compound shown as a formula (I), a ferriporphyrin catalyst, an oxidant and a dispersing agent into a ball milling tank, sealing the ball milling tank, ball milling for 3-24 hours at room temperature at a rotating speed of 100-800 rpm, stopping ball milling once every 1-3 hours in the ball milling process, discharging gas in the ball milling tank, and after the reaction is finished, carrying out post-treatment on a reaction mixture to obtain a product 2-phenyl-2-propanol compound shown as a formula (II); the invention realizes the oxidation conversion of the isopropylbenzene and the derivatives thereof by solid-phase ball milling, and has novel reaction mode, convenient operation and low energy consumption; organic solvent is not needed, so that the use of toxic and harmful organic solvent is effectively avoided, and the environment is protected; the peroxide content is low, and the safety coefficient is high; the 2-phenyl-2-propanol and the derivatives thereof have high selectivity and meet the social requirements of the current green chemical process, the environmental compatibility chemical process and the biological compatibility chemical process.
Description
(I) technical field
The invention relates to a novel method for preparing a 2-phenyl-2-propanol compound by selectively oxidizing a cumene compound, belonging to the field of organic chemical industry and fine organic synthesis.
(II) background of the invention
2-phenyl-2-propanol and derivatives thereof are important fine Chemical intermediates and widely applied to the synthesis of fine Chemical products such as medicines, pesticides, dyes, perfumes and the like (WO 2017068412; WO 2015135094; Chemical Engineering Science 2018,177: 391-398; ChemCatchem 2014,6: 555-560). Currently, cumene and its derivatives are mainly used as raw materials for synthesizing 2-phenyl-2-propanol and its derivatives, and oxygen is used as oxidant to prepare the product through oxidation reaction (ACS Sustainable Chemistry & Engineering 2019,7: 7708-. In the oxidation process, the intermediate product 2-phenyl-2-propyl hydroperoxide and the derivatives thereof have good stability and are not easy to convert, so that the target product 2-phenyl-2-propanol and the derivatives thereof have low selectivity. Meanwhile, the safety of the oxidation system is also reduced due to the existence of peroxide with higher concentration in the reaction system. In addition, a large amount of organic solvents and transition metal catalysts which are toxic and harmful to the environment and organisms are also used in the oxidation process of part of the cumene and the derivatives thereof at present, so that the environmental compatibility and the biological compatibility of the reaction process are reduced, and the product transition metal pollution to a certain degree is also caused (Inorganica Chimica Acta 2019,486: 425-. Therefore, under mild conditions, the high-selectivity oxidation of the isopropyl benzene and the derivative thereof is realized by using a reagent and a catalyst with good environmental compatibility and biocompatibility to prepare the 2-phenyl-2-propanol, which has important significance in industrial production and theoretical research and also meets the urgent requirements of the whole society on green, safe and environment-friendly chemical industry at present.
The solid phase ball milling reaction is characterized in that the interaction between interface materials is promoted by the actions of shearing, rubbing, impacting, extruding and the like between two interfaces which move relatively, so as to realize chemical reaction (Green Chemistry 2018,20: 1435-. The solid-phase ball-milling reaction does not need a solvent, the reaction can be carried out at room temperature, the use of toxic and harmful organic solvents is effectively avoided, the materials do not need to be subjected to heat treatment, the energy consumption is low, and the safety coefficient is high. Meanwhile, due to the solid phase ball milling process, mechanical force is directly applied to the reaction mass, often resulting in a product distribution different from that of the liquid phase reaction. Under the urgent social requirements of development environment, society and human body compatibility chemical process, the solid phase ball milling is used for the catalytic oxidation of the cumene and the derivatives thereof, so that the catalytic oxidation of the cumene and the derivatives thereof can be realized at room temperature, the use of toxic and harmful organic solvents can be reduced, and the distribution of oxidation products can be even changed.
In the field of environmental and biocompatible catalysts, the model compound metalloporphyrin of cytochrome P450 is widely Applied to catalytic oxidation of hydrocarbons (ChemSusChem 2019,12: 684-691; Applied Surface Science 2017,402:436-443), especially ferriporphyrin, has good biocompatibility, effectively prevents the oxidation products and downstream products thereof from being polluted by the metal catalyst, and has high catalytic activity and reaction substrates 1/106～1/105The (mol/mol) amount can complete the catalytic conversion, and can also effectively avoid the pollution of the metal catalyst to the oxidation products. Therefore, the invention carries out the catalytic oxidation of the isopropylbenzene and the derivatives thereof by using the metal ferriporphyrin as the catalyst and the t-butyl hydroperoxide, the hydrogen peroxide, the sodium chlorite or the sodium hypochlorite with better environmental compatibility as the oxidant by a solid phase ball milling method, thereby not only realizing the oxidation conversion of the isopropylbenzene and the derivatives thereof under the mild condition, effectively avoiding the use of toxic and harmful organic solvents, but also obviously improving the selectivity of the 2-phenyl-2-propanol and the derivatives thereof, meeting the social requirements of the current green chemical process, the environmental compatibility chemical process and the biological compatibility chemical process, having important application value and theoretical research, and having important application valueMeaning.
Disclosure of the invention
The invention aims to provide a novel method for preparing a 2-phenyl-2-propanol compound by selectively oxidizing a cumene compound.
The technical scheme of the invention is as follows:
a process for the selective oxidation of cumene compounds, the process comprising:
placing a cumin compound shown as a formula (I), a ferriporphyrin catalyst, an oxidant and a dispersing agent into a ball milling tank, sealing the ball milling tank, ball milling at the room temperature (20-30 ℃) for 3-24 h (preferably 8-16 h) at the rotation speed of 100-800 rpm (preferably 500-800 rpm), stopping ball milling once every 1-3 h (preferably 1h) in the ball milling process, discharging gas in the ball milling tank, and after the reaction is finished, performing post-treatment on the reaction mixture to obtain a product 2-phenyl-2-propanol compound shown as a formula (II);
the material of ball-milling jar is agate, is furnished with the ball-milling pearl that the material is agate equally, and ball-milling pearl diameter is 8.0mm usually, and the total mass of ball-milling pearl is about 3 with the total mass of reaction material ratio: 1;
the quantity ratio of the ferriporphyrin catalyst to the substance of the cumin compound shown in the formula (I) is 1: 200000 to 1000, preferably 1: 20000 to 4000;
the mass ratio of the cumin compound shown in the formula (I) to the oxidant is 1: 1-50, preferably 1: 2-5;
the mass ratio of the cumin compound shown in the formula (I) to the dispersant is 1: 0.1 to 10, preferably 1: 3-5;
the post-treatment method comprises the following steps: after the reaction is finished, dissolving the reaction mixture in absolute ethyl alcohol, stirring for 30min at room temperature, filtering, washing a filter cake with the absolute ethyl alcohol, combining filtrate and washing liquid, recovering the absolute ethyl alcohol through atmospheric distillation, recovering unreacted raw materials through reduced pressure rectification, and separating a target oxidation product 2-phenyl-2-propanol compound;
the oxidation reaction of the invention not only obtains the product 2-phenyl-2-propanol compound shown in the formula (II), but also can oxidize and generate acetophenone compounds shown in the formula (III) and isopropyl benzene shown in the formula (IV) in the systemA peroxide compound; the method for analyzing the reaction result comprises the following steps: after the reaction is finished, dissolving the reaction mixture in absolute ethyl alcohol, stirring for 30min at room temperature, filtering, washing a filter cake by using the absolute ethyl alcohol, combining filtrate and washing liquid, sampling for analysis, performing liquid chromatography analysis by using 2-naphthoic acid as an internal standard, calculating the conversion rate of the raw material namely the cumin compound shown in the formula (I), and the selectivity of the products namely the 2-phenyl-2-propanol compound shown in the formula (II) and the acetophenone compound shown in the formula (III), wherein the selectivity of the cumin peroxide shown in the formula (IV) is determined by the method1H NMR analysis is carried out;
in the invention, the oxidant is t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite, preferably t-butyl hydroperoxide or hydrogen peroxide;
the dispersing agent is one or a mixture of more than two of silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate in any proportion, and preferably, the anhydrous sodium sulfate or the anhydrous magnesium sulfate;
the iron porphyrin catalyst is at least one of compounds shown in a formula (V), preferably 5,10,15, 20-tetra (4-chlorophenyl) iron porphyrin (II), 5,10,15, 20-tetra (2, 6-dichlorophenyl) iron porphyrin (II), 5,10,15, 20-tetra (2, 4-dichlorophenyl) iron porphyrin (II) or 5,10,15, 20-tetra (2,3,4,5, 6-pentafluorophenyl) iron porphyrin (II));
in the formula (V), Ra、Rb、Rc、Rd、ReEach independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo;
the structural formula of the cumene compound is shown as a formula (I), the structural formula of a corresponding obtained product 2-phenyl-2-propanol compound is shown as a formula (II), and the structural formulas of by-products, namely acetophenone compounds and cumene peroxide generated in the oxidation reaction are respectively shown as formulas (III) and (IV):
in the formula (I), (II), (III) or (IV), R1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo.
The invention has the following beneficial effects:
the method for preparing the 2-phenyl-2-propanol and the derivatives thereof by selectively oxidizing the cumene and the derivatives thereof realizes the oxidation conversion of the cumene and the derivatives thereof by solid-phase ball milling, and has novel reaction mode and convenient operation; the reaction is carried out at room temperature, and the energy consumption is low; organic solvent is not needed, so that the use of toxic and harmful organic solvent is effectively avoided, and the environment is protected; the peroxide content is low, and the safety coefficient is high; the 2-phenyl-2-propanol and the derivatives thereof have high selectivity, and meet the social requirements of the current green chemical process, the environmental compatibility chemical process and the biological compatibility chemical process. The invention is a high-efficiency, green, environment-friendly and safe oxidation method of cumene and derivatives thereof.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrins used in the present invention are all referred to Journal of the American Chemical Society 2017,139: 18590-18597; journal of the American Chemical Society 2018,140:6383-6390 synthesis.
All reagents used were commercially available analytical grade.
The 100mL agate ball-milling jar is provided with 50 agate ball-milling beads, each ball-milling bead has a diameter of 0.80mm and a mass of 0.9 g.
Example 1
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0004g (0.0005mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 2.57g (20mmol) of 70% aqueous t-butyl hydroperoxide and 3.60g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 33%, 2-phenyl-2-propanol selectivity 89%, acetophenone selectivity 5%, 2-phenyl-2-propyl hydroperoxide selectivity 6%, (1H NMR analysis) no significant benzoic acid was detected.
Example 2
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0020g (0.0025mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron porphyrin (II), 2.57g (20mmol) of 70% aqueous t-butyl hydroperoxide and 3.60g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 41 percent, the selectivity of 2-phenyl-2-propanol is 90 percent, the selectivity of acetophenone is 5 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 5 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 3
In a 100mL agate jar mill, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 2.57g (20mmol) of 70% aqueous t-butyl hydroperoxide, and 3.60g of anhydrous hydrogen peroxide were placedThe sodium sulfate is mixed evenly and the ball milling tank is sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 38 percent, the selectivity of 2-phenyl-2-propanol is 91 percent, the selectivity of acetophenone is 5 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 4 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 4
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 1.29g (10mmol) of 70% aqueous t-butyl hydroperoxide, and 3.60g of anhydrous sodium sulfate were mixed well and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 18 percent, the selectivity of 2-phenyl-2-propanol is 88 percent, the selectivity of acetophenone is 3 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 9 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 5
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtration, washing of the resulting filter cake with 2X 10mL of absolute ethanol, and combinationAnd mixing with ethanol solution, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion of 51%, 2-phenyl-2-propanol selectivity of 92%, acetophenone selectivity of 3%, 2-phenyl-2-propyl hydroperoxide selectivity of 5%, (1H NMR analysis) no significant benzoic acid was detected.
Example 6
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide and 4.80g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 48 percent, the selectivity of 2-phenyl-2-propanol is 90 percent, the selectivity of acetophenone is 4 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 6 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 7
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 7.20g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 50%, 2-phenyl-2-propanol selectivity 92%, acetophenone selectivity 5%, 2-phenyl-2-propyl hydroperoxide selectivity 3%, (1H NMR analysisObtained), no significant benzoic acid was detected.
Example 8
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 12.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 600rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropylbenzene is 29 percent, the selectivity of 2-phenyl-2-propanol is 86 percent, the selectivity of acetophenone is 6 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 8 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 9
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And performing ball milling reaction at the rotation speed of 500rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropylbenzene is 26 percent, the selectivity of 2-phenyl-2-propanol is 81 percent, the selectivity of acetophenone is 5 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 14 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 10
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 6.44g (50mmol) of 70% t-butylhydroperoxide waterThe solution was mixed with 6.00g of anhydrous sodium sulfate, and the ball mill jar was sealed. And (3) performing ball milling reaction for 12.0h at the rotating speed of 100rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 12%, 2-phenyl-2-propanol selectivity 16%, acetophenone selectivity 1%, 2-phenyl-2-propyl hydroperoxide selectivity 83%, (1H NMR analysis) no significant benzoic acid was detected.
Example 11
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 54 percent of cumene conversion rate, 90 percent of 2-phenyl-2-propanol selectivity, 4 percent of acetophenone selectivity and 6 percent of 2-phenyl-2-propyl hydroperoxide selectivity (1H NMR analysis) no significant benzoic acid was detected.
Example 12
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction for 8.0h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtration, 2X 10mL of absolute ethanolAnd washing the obtained filter cake, combining ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 42%, 2-phenyl-2-propanol selectivity 88%, acetophenone selectivity 7%, 2-phenyl-2-propyl hydroperoxide selectivity 5%, (1H NMR analysis) no significant benzoic acid was detected.
Example 13
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropylbenzene is 56 percent, the selectivity of 2-phenyl-2-propanol is 92 percent, the selectivity of acetophenone is 4 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 4 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 14
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 3.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 11 percent, the selectivity of 2-phenyl-2-propanol is 64 percent, the selectivity of acetophenone is 2 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 3 percent4％(1H NMR analysis) no significant benzoic acid was detected.
Example 15
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 24.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 53% conversion of cumene, 87% selectivity for 2-phenyl-2-propanol, 7% selectivity for acetophenone and 6% selectivity for 2-phenyl-2-propyl hydroperoxide (1H NMR analysis) no significant benzoic acid was detected.
Example 16
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 7.20g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 46% of cumene conversion, 89% of 2-phenyl-2-propanol selectivity, 3% of acetophenone selectivity and 8% of 2-phenyl-2-propyl hydroperoxide selectivity (1H NMR analysis) no significant benzoic acid was detected.
Example 17
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 5.67g (50mmol) of 30% peroxy compoundThe aqueous hydrogen oxide solution and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the ball mill jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion of 51%, 2-phenyl-2-propanol selectivity of 89%, acetophenone selectivity of 3%, 2-phenyl-2-propyl hydroperoxide selectivity of 8%, (1H NMR analysis) no significant benzoic acid was detected.
Example 18
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 12.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 23 percent, the selectivity of 2-phenyl-2-propanol is 72 percent, the selectivity of acetophenone is 4 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 24 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 19
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 5.67g (50mmol) of 30% aqueous hydrogen peroxide and 7.20g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction for 8.0h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtered and washed with 2X 10mL of absolute ethanolWashing the obtained filter cake, combining ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 33%, 2-phenyl-2-propanol selectivity 68%, acetophenone selectivity 6%, 2-phenyl-2-propyl hydroperoxide selectivity 26%, (1H NMR analysis) no significant benzoic acid was detected.
Example 20
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 0.90g (10mmol) of sodium chlorite and 2.40g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 14%, 2-phenyl-2-propanol selectivity 91%, acetophenone selectivity 3%, 2-phenyl-2-propyl hydroperoxide selectivity 6%, (1H NMR analysis) no significant benzoic acid was detected.
Example 21
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 4.51g (50mmol) of sodium chlorite and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction at the rotation speed of 800rpm for 12.0h at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 49% of cumene conversion, 86% of 2-phenyl-2-propanol selectivity, 9% of acetophenone selectivity and 5% of 2-phenyl-2-propyl hydroperoxide (i.e., (II))1Obtained by H NMR analysis), not detectedTo give significant benzoic acid.
Example 22
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 4.51g (50mmol) of sodium chlorite and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. And (3) performing ball milling reaction for 8.0h at the rotating speed of 800rpm at room temperature, stopping ball milling once every 1.0h, and discharging gas in the ball milling tank. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 39 percent, the selectivity of 2-phenyl-2-propanol is 90 percent, the selectivity of acetophenone is 6 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 4 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 23
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 4.51g (50mmol) of sodium chlorite and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion of 51%, 2-phenyl-2-propanol selectivity of 90%, acetophenone selectivity of 5%, 2-phenyl-2-propyl hydroperoxide selectivity of 5%, (1H NMR analysis) no significant benzoic acid was detected.
Example 24
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetra (4-chlorophenyl) iron porphyrin (II), 6.44g (50mmol) of 70% t-butyl hydrogen peroxide aqueous solution and 6.00g of neutral aluminum oxide were mixed uniformly, and the mixture was ball-milled in a sealed mannerAnd (7) a tank. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion 42%, 2-phenyl-2-propanol selectivity 91%, acetophenone selectivity 5%, 2-phenyl-2-propyl hydroperoxide selectivity 4%, (1H NMR analysis) no significant benzoic acid was detected.
Example 25
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous magnesium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion of 51%, 2-phenyl-2-propanol selectivity of 89%, acetophenone selectivity of 5%, 2-phenyl-2-propyl hydroperoxide selectivity of 6%, (1H NMR analysis) no significant benzoic acid was detected.
Example 26
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide, and 6.00g of silica gel were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake with 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and mixing the obtained ethanol solutionsThe volume is 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. Cumene conversion of 51%, 2-phenyl-2-propanol selectivity of 92%, acetophenone selectivity of 2%, 2-phenyl-2-propyl hydroperoxide selectivity of 6%, (1H NMR analysis) no significant benzoic acid was detected.
Example 27
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (2-chlorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide, and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. 58 percent of cumene conversion, 94 percent of 2-phenyl-2-propanol selectivity, 2 percent of acetophenone selectivity and 4 percent of 2-phenyl-2-propyl hydroperoxide selectivity (1H NMR analysis) no significant benzoic acid was detected.
Example 28
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0009g (0.0010mmol) of 5,10,15, 20-tetrakis (2, 6-dichlorophenyl) iron porphyrin (II), 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 61 percent, the selectivity of 2-phenyl-2-propanol is 90 percent, the selectivity of acetophenone is 5 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 5 percent (1H NMR analysis) no significant benzene was detectedFormic acid.
Example 29
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide and 6.00g of anhydrous sodium sulfate were mixed well, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 66 percent, the selectivity of 2-phenyl-2-propanol is 95 percent, the selectivity of acetophenone is 3 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 2 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 30
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0007g (0.0010mmol) of 5,10,15, 20-tetrakis (4-methylphenyl) iron porphyrin (II), 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 18 percent, the selectivity of 2-phenyl-2-propanol is 69 percent, the selectivity of acetophenone is 5 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 26 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 31
In a 100mL agate jar mill, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin iron (II), 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide, and 6.00gThe anhydrous sodium sulfate is mixed evenly and the ball milling tank is sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 56 percent, the selectivity of 2-phenyl-2-propanol is 89 percent, the selectivity of acetophenone is 7 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 4 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 32
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-fluorophenyl) iron porphyrin (II), 6.44g (50mmol) of 70% aqueous t-butyl hydroperoxide and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 55 percent, the selectivity of 2-phenyl-2-propanol is 92 percent, the selectivity of acetophenone is 3 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 5 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 33
In a 100mL agate jar, 1.20g (10mmol) of cumene, 0.0008g (0.0010mmol) of 5,10,15, 20-tetrakis (4-cyanophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide and 6.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing with 2X 10mL of absolute ethanolAnd (4) filtering a filter cake, combining ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. 10mL of the resulting solution was removed, and an internal standard 2-naphthoic acid was added to conduct liquid chromatography. The conversion rate of isopropyl benzene is 12 percent, the selectivity of 2-phenyl-2-propanol is 64 percent, the selectivity of acetophenone is 2 percent, and the selectivity of 2-phenyl-2-propyl hydroperoxide is 34 percent (1H NMR analysis) no significant benzoic acid was detected.
Example 34
In a 100mL agate jar, 1.34g (10mmol) of 4-methylisopropylbenzene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). 4-Methylpropylbenzene conversion 57%, 2- (4-methylphenyl) -2-propanol selectivity 87%, 4-methylacetophenone selectivity 8%, 2- (4-methylphenyl) -2-propylhydroperoxide selectivity 5%, no significant 4-methylbenzoic acid was detected.
Example 35
In a 100mL agate jar, 1.50g (10mmol) of 4-methoxycumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion rate of 4-methoxycumene is 49%, the selectivity of 2- (4-methoxyphenyl) -2-propanol is 85%, the selectivity of 4-methoxyacetophenone is 6%, the selectivity of 2- (4-methoxyphenyl) -2-propyl hydroperoxide is 9%, and no obvious 4-methoxybenzoic acid is detected.
Example 36
In a 100mL agate jar, 1.50g (10mmol) of 2-methoxycumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion rate of 2-methoxycumene is 38 percent, the selectivity of 2- (2-methoxyphenyl) -2-propanol is 89 percent, the selectivity of 2-methoxyacetophenone is 6 percent, the selectivity of 2- (2-methoxyphenyl) -2-propyl hydroperoxide is 5 percent, and no obvious 2-methoxybenzoic acid is detected.
Example 37
In a 100mL agate jar, 1.65g (10mmol) of 4-nitrocumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate＝4︰1～1︰4)。The conversion of 4-nitrocumene was 66%, the selectivity for 2- (4-nitrophenyl) -2-propanol was 86%, the selectivity for 4-nitroacetophenone was 4%, the selectivity for 2- (4-nitrophenyl) -2-propyl hydroperoxide was 10%, and no significant 4-nitrobenzoic acid was detected.
Example 38
In a 100mL agate jar, 1.64g (10mmol) of 4-carboxycumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion of 4-carboxycumene was 57%, the selectivity for 2- (4-carboxyphenyl) -2-propanol was 92%, the selectivity for 4-carboxyacetophenone was 5%, the selectivity for 2- (4-carboxyphenyl) -2-propylhydroperoxide was 3%, and no significant 4-carboxybenzoic acid was detected.
Example 39
In a 100mL agate jar, 1.96g (10mmol) of 4-phenylisopropylbenzene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed well, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). Conversion of 4-phenylisopropylbenzene 21%, selectivity of 2- (4-phenylphenyl) -2-propanol 92%, 4-phenylAcetophenone selectivity was 3% and 2- (4-phenylphenyl) -2-propylhydroperoxide selectivity was 5%, no significant 4-phenylbenzoic acid was detected.
Example 40
In a 100mL agate jar, 1.49g (10mmol) of 4-methylaminocumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% t-butylhydroperoxide aqueous solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion rate of 4-methylaminocumene is 71%, the selectivity of 2- (4-methylaminophenyl) -2-propanol is 32%, the selectivity of 4-methylaminoacetophenone is 5%, the selectivity of 2- (4-methylaminophenyl) -2-propyl hydroperoxide is 12%, and no obvious 4-methylaminobenzoic acid is detected.
EXAMPLE 41
In a 100mL agate jar, 1.99g (10mmol) of 4-bromocumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 10.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). 58% conversion of 4-bromocumene, 90% selectivity to 2- (4-bromophenyl) -2-propanol, 5% selectivity to 4-bromoacetophenone, 5% selectivity to 2- (4-bromophenyl) -2-propyl hydroperoxide, notSignificant 4-bromobenzoic acid was detected.
Example 42
In a 100mL agate jar, 1.36g (10mmol) of 4-hydroxycumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 10.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion of 4-hydroxycumene was 95%, the selectivity for 2- (4-hydroxyphenyl) -2-propanol was 16%, the selectivity for 4-hydroxyacetophenone was 0%, and the selectivity for 2- (4-hydroxyphenyl) -2-propylhydroperoxide was 0%, and no significant 4-hydroxybenzoic acid was detected.
Example 43
In a 100mL agate jar, 1.36g (10mmol) of 3-hydroxycumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 10.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion of 3-hydroxycumene was 93%, the selectivity for 2- (3-hydroxyphenyl) -2-propanol was 11%, the selectivity for 3-hydroxyacetophenone was 0%, and the selectivity for 2- (3-hydroxyphenyl) -2-propylhydroperoxide was 0%, and no significant 3-hydroxybenzoic acid was detected.
Example 44
In a 100mL agate jar, 1.35g (10mmol) of 4-aminocumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). 4-aminocumene conversion 90%, 2- (4-aminophenyl) -2-propanol selectivity 25%, 4-aminoacetophenone selectivity 2%, 2- (4-aminophenyl) -2-propyl hydroperoxide selectivity 0%, no significant 4-aminobenzoic acid was detected.
Example 45
In a 100mL agate jar, 1.35g (10mmol) of 3-aminocumene, 0.0010g (0.0010mmol) of 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II) porphyrin, 6.44g (50mmol) of 70% aqueous t-butylhydroperoxide solution and 8.00g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). The conversion of 3-aminocumene was 92%, the selectivity for 2- (3-aminophenyl) -2-propanol was 28%, the selectivity for 3-aminoacetophenone was 6%, and the selectivity for 2- (3-aminophenyl) -2-propylhydroperoxide was 0%, and no significant 3-aminobenzoic acid was detected.
Example 46
In a 100mL agate jar, 1.62g (10mmol) of 4-isopropyl alcohol was chargedCumene, 0.0010g (0.0010mmol)5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) iron (II), 6.44g (50mmol) 70% t-butylhydroperoxide aqueous solution and 8.00g anhydrous sodium sulfate were mixed well and the ball mill jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 30mL of anhydrous ethanol and stirred at room temperature for 30.0 min. Filtering, washing the obtained filter cake by 2X 10mL of absolute ethyl alcohol, combining the ethanol solutions, and fixing the volume of the obtained ethanol solution to 100 mL. Transferring 20mL of the resulting solution, desolventizing under reduced pressure, and separating the resulting reaction mixture by column chromatography (V)Cyclohexane︰VEthyl acetate4: 1-1: 4). 4-isopropylcumene conversion 62%, 2- (4-isopropylphenyl) -2-propanol selectivity 61%, 4-isopropylacetophenone selectivity 3%, 2- (4-isopropylphenyl) -2-propylhydroperoxide selectivity 0%, no significant 4-isopropylbenzoic acid was detected.
Example 47 (amplification experiment)
In a 500mL agate jar, 6.01g (50mmol) of cumene, 0.0040g (0.0050mmol) of 5,10,15, 20-tetrakis (2-chlorophenyl) porphyrin iron (II), 32.19g (250mmol) of 70% aqueous t-butyl hydroperoxide and 30.05g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 150mL of anhydrous ethanol and stirred at room temperature for 30.0 min. The filter cake was washed with 2X 50mL of absolute ethanol and the ethanol solutions were combined. The absolute ethyl alcohol is recovered by atmospheric distillation, the vacuum rectification is carried out, 2.26g of isopropyl benzene is recovered, the conversion rate is 62%, 3.88g of 2-phenyl-2-propanol is obtained by vacuum rectification separation, and the selectivity is 92%.
Example 48 (amplification experiment)
In a 500mL agate jar, 6.01g (50mmol) of cumene, 0.0040g (0.0050mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 32.19g (250mmol) of 70% aqueous t-butyl hydroperoxide and 30.05g of anhydrous sodium sulfate were mixed uniformly, and the jar was sealed. Ball milling reaction is carried out for 16.0h at the rotating speed of 800rpm at room temperature, ball milling is stopped once every 1.0h, and gas in a ball milling tank is discharged. After completion of the reaction, the resulting reaction mixture was dissolved in 150mL of anhydrous ethanol and stirred at room temperature for 30.0 min. The filter cake was washed with 2X 50mL of absolute ethanol and the ethanol solutions were combined. The absolute ethyl alcohol is recovered by atmospheric distillation, the vacuum rectification is carried out, 2.85g of isopropyl benzene is recovered, the conversion rate is 53 percent, 3.18g of 2-phenyl-2-propanol is obtained by vacuum rectification separation, and the selectivity is 88 percent.
Claims (7)
1. A method for selectively oxidizing cumene compounds, which is characterized by comprising the following steps:
placing a cumin compound shown as a formula (I), a ferriporphyrin catalyst, an oxidant and a dispersing agent into a ball milling tank, sealing the ball milling tank, ball milling for 3-24 hours at room temperature at a rotating speed of 100-800 rpm, stopping ball milling once every 1-3 hours in the ball milling process, discharging gas in the ball milling tank, and after the reaction is finished, carrying out post-treatment on a reaction mixture to obtain a product 2-phenyl-2-propanol compound shown as a formula (II);
the quantity ratio of the ferriporphyrin catalyst to the substance of the cumin compound shown in the formula (I) is 1: 200000 to 1000;
the mass ratio of the cumin compound shown in the formula (I) to the oxidant is 1: 1-50;
the mass ratio of the cumin compound shown in the formula (I) to the dispersant is 1: 0.1 to 10;
the oxidant is t-butyl hydroperoxide, hydrogen peroxide, sodium chlorite or sodium hypochlorite;
the dispersing agent is one or a mixture of more than two of silica gel, neutral aluminum oxide, anhydrous sodium sulfate or anhydrous magnesium sulfate in any proportion;
the ferriporphyrin catalyst is at least one of compounds shown as a formula (V):
in the formula (V), Ra、Rb、Rc、Rd、ReEach independently is: hydrogen, methyl, cyano, carboxyl, fluoro or chloro;
the structural formula of the isopropylbenzene compound is shown as the formula (I), and the structural formula of the corresponding obtained product 2-phenyl-2-propanol compound is shown as the formula (II):
in the formula (I) or (II), R1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo.
2. The method for the selective oxidation of cumene compounds according to claim 1 wherein the ratio of the amount of ferriporphyrin catalyst to the amount of substance of cumene compound of formula (I) is 1: 20000 to 4000.
3. The process for the selective oxidation of cumenes according to claim 1 wherein the mass ratio of cumenes of formula (I) to oxidant is 1: 2 to 5.
4. The process for the selective oxidation of cumene compounds according to claim 1 wherein the mass ratio of the cumene compound of formula (I) to the dispersant is 1: 3 to 5.
5. The process for the selective oxidation of cumins according to claim 1, wherein the oxidizing agent is t-butyl hydroperoxide or hydrogen peroxide.
6. The process for the selective oxidation of cumene compounds according to claim 1 wherein said dispersing agent is anhydrous sodium sulfate or anhydrous magnesium sulfate.
7. The method for selective oxidation of cumin compounds according to claim 1, wherein the iron porphyrin catalyst is 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin iron (II), 5,10,15, 20-tetrakis (2, 6-dichlorophenyl) porphyrin iron (II), 5,10,15, 20-tetrakis (2, 4-dichlorophenyl) porphyrin iron (II), or 5,10,15, 20-tetrakis (2,3,4,5, 6-pentafluorophenyl) porphyrin iron (II).
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| CN103058821A (en) * | 2012-12-20 | 2013-04-24 | 华南理工大学 | Synthesis method of 2-phenyl-2-propanol and acetophenone through catalytic oxidation of cumene |
| CN107879907A (en) * | 2017-09-26 | 2018-04-06 | 湖南大学 | A kind of high selectivity Oxidation Ethylbenzene acetophenone technique |
| CN109503328A (en) * | 2018-12-21 | 2019-03-22 | 大连理工大学 | The method of 2- phenyl -2- propyl alcohol is prepared at normal temperature |
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| CN103058821A (en) * | 2012-12-20 | 2013-04-24 | 华南理工大学 | Synthesis method of 2-phenyl-2-propanol and acetophenone through catalytic oxidation of cumene |
| CN107879907A (en) * | 2017-09-26 | 2018-04-06 | 湖南大学 | A kind of high selectivity Oxidation Ethylbenzene acetophenone technique |
| CN109503328A (en) * | 2018-12-21 | 2019-03-22 | 大连理工大学 | The method of 2- phenyl -2- propyl alcohol is prepared at normal temperature |
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| Selective Aerobic Oxidation of 4‑Ethylnitrobenzene to 4‑Nitroacetophenone Promoted by Metalloporphyrins;Yuning Yang等;《Org. Process Res. Dev.》;20190308;第23卷;1078-1086 * |
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