CN111995506A - Method for oxidizing cycloparaffin through synergistic catalysis of limited-domain metalloporphyrin manganese (II)/Zn (II) salt - Google Patents
Method for oxidizing cycloparaffin through synergistic catalysis of limited-domain metalloporphyrin manganese (II)/Zn (II) salt Download PDFInfo
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- CN111995506A CN111995506A CN202010893855.7A CN202010893855A CN111995506A CN 111995506 A CN111995506 A CN 111995506A CN 202010893855 A CN202010893855 A CN 202010893855A CN 111995506 A CN111995506 A CN 111995506A
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- selectivity
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- manganese
- metalloporphyrin
- reaction mixture
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- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title abstract description 9
- 230000002195 synergetic effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 198
- 238000003756 stirring Methods 0.000 claims abstract description 70
- -1 cycloalkyl alcohol Chemical compound 0.000 claims abstract description 64
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 98
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 97
- 239000001301 oxygen Substances 0.000 claims description 97
- 229910052760 oxygen Inorganic materials 0.000 claims description 97
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 88
- 150000002978 peroxides Chemical class 0.000 claims description 52
- 150000004032 porphyrins Chemical class 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 22
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000002153 concerted effect Effects 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004914 cyclooctane Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 11
- 150000002576 ketones Chemical class 0.000 abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 141
- 239000011541 reaction mixture Substances 0.000 description 135
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 94
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 94
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 88
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 86
- 239000005711 Benzoic acid Substances 0.000 description 47
- 235000010233 benzoic acid Nutrition 0.000 description 47
- 238000004811 liquid chromatography Methods 0.000 description 47
- 239000002904 solvent Substances 0.000 description 47
- 238000004458 analytical method Methods 0.000 description 46
- 238000004817 gas chromatography Methods 0.000 description 46
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 46
- 239000004810 polytetrafluoroethylene Substances 0.000 description 46
- 229910001220 stainless steel Inorganic materials 0.000 description 46
- 239000010935 stainless steel Substances 0.000 description 46
- 239000005457 ice water Substances 0.000 description 45
- 239000001361 adipic acid Substances 0.000 description 44
- 235000011037 adipic acid Nutrition 0.000 description 44
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 43
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 43
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 43
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 42
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 30
- 239000004246 zinc acetate Substances 0.000 description 30
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 25
- 238000002474 experimental method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 5
- FAVQKWLSCDXWNP-UHFFFAOYSA-N [Mn+2].C1=C(C=CC2=CC=CC=C12)N1C2=C(C(=C1C=C1C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=C2)N4)Br)Br)N3)Br)Br)=N1)Br)Br)Br)Br Chemical compound [Mn+2].C1=C(C=CC2=CC=CC=C12)N1C2=C(C(=C1C=C1C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=C2)N4)Br)Br)N3)Br)Br)=N1)Br)Br)Br)Br FAVQKWLSCDXWNP-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 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 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NADLSZOUVVCJJL-UHFFFAOYSA-N [Mn+2].C1(=CC=C2C=CC3=CC=CC4=CC=C1C2=C34)N3C4=C(C(=C3C=C3C(=C(C(C=C2C(=C(C(=CC=1C(=C(C(=C4)N1)Br)Br)N2)Br)Br)=N3)Br)Br)Br)Br Chemical compound [Mn+2].C1(=CC=C2C=CC3=CC=CC4=CC=C1C2=C34)N3C4=C(C(=C3C=C3C(=C(C(C=C2C(=C(C(=CC=1C(=C(C(=C4)N1)Br)Br)N2)Br)Br)=N3)Br)Br)Br)Br NADLSZOUVVCJJL-UHFFFAOYSA-N 0.000 description 2
- XEODALQQXYIGCG-UHFFFAOYSA-N [Mn+2].C1(=CC=CC2=CC=C3C=C4C=CC=CC4=CC3=C12)C1=C2C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C1N5)Br)Br)N4)Br)Br)N3)Br)Br)=N2)Br)Br Chemical compound [Mn+2].C1(=CC=CC2=CC=C3C=C4C=CC=CC4=CC3=C12)C1=C2C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=CC5=C(C(=C1N5)Br)Br)N4)Br)Br)N3)Br)Br)=N2)Br)Br XEODALQQXYIGCG-UHFFFAOYSA-N 0.000 description 2
- MIDZUHNOJZZLIG-UHFFFAOYSA-N [Mn+2].C1=CC=CC=2C3=CC=CC=C3C(=CC12)N1C2=C(C(=C1C=C1C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=C2)N4)Br)Br)N3)Br)Br)=N1)Br)Br)Br)Br Chemical compound [Mn+2].C1=CC=CC=2C3=CC=CC=C3C(=CC12)N1C2=C(C(=C1C=C1C(=C(C(C=C3C(=C(C(=CC=4C(=C(C(=C2)N4)Br)Br)N3)Br)Br)=N1)Br)Br)Br)Br MIDZUHNOJZZLIG-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- ALZIGBWJIBHLNN-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2=CC=CC=1C3=CC=CC=C3C(=CC21)[Mn] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C2=CC=CC=1C3=CC=CC=C3C(=CC21)[Mn] ALZIGBWJIBHLNN-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
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- JAECSTVQZDJAFD-UHFFFAOYSA-N [Mn].C1(=CC=C2C=CC3=CC=CC4=CC=C1C2=C34)C3=C4NC(=C3)C=C3C=CC(=N3)C=C3C=CC(N3)=CC=3C=CC(N3)=C4 Chemical compound [Mn].C1(=CC=C2C=CC3=CC=CC4=CC=C1C2=C34)C3=C4NC(=C3)C=C3C=CC(=N3)C=C3C=CC(N3)=CC=3C=CC(N3)=C4 JAECSTVQZDJAFD-UHFFFAOYSA-N 0.000 description 1
- YSECDAMZUAGIGK-UHFFFAOYSA-N [Mn].C1(=CC=CC2=CC=CC=C12)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Mn].C1(=CC=CC2=CC=CC=C12)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 YSECDAMZUAGIGK-UHFFFAOYSA-N 0.000 description 1
- FVIFLUULFXDIPR-UHFFFAOYSA-N [Mn].C1=C(C=CC2=CC=CC=C12)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Mn].C1=C(C=CC2=CC=CC=C12)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 FVIFLUULFXDIPR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPHZOCJETVZYTP-UHFFFAOYSA-N hydroperoxycyclododecane Chemical compound OOC1CCCCCCCCCCC1 GPHZOCJETVZYTP-UHFFFAOYSA-N 0.000 description 1
- GRLDKEKHXHSXQW-UHFFFAOYSA-N hydroperoxycycloheptane Chemical compound OOC1CCCCCC1 GRLDKEKHXHSXQW-UHFFFAOYSA-N 0.000 description 1
- DTMZBUVZQPKYDT-UHFFFAOYSA-N hydroperoxycyclooctane Chemical compound OOC1CCCCCCC1 DTMZBUVZQPKYDT-UHFFFAOYSA-N 0.000 description 1
- VGGFAUSJLGBJRZ-UHFFFAOYSA-N hydroperoxycyclopentane Chemical compound OOC1CCCC1 VGGFAUSJLGBJRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- C07C29/50—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 with molecular oxygen only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
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Abstract
A method for oxidizing cycloalkane by synergistic catalysis of limited-domain metalloporphyrin manganese (II)/Zn (II) salt is disclosed, wherein limited-domain metalloporphyrin manganese (II) (1 × 10)‑40.1 percent of (mol/mol) and 0.01 to 10 percent of Zn (II) salt (mol/mol) are dispersed in cycloalkane, a reaction system is sealed, the temperature is raised to 90 to 150 ℃ under stirring, an oxidant is introduced, the set temperature and pressure are kept, stirring reaction is carried out for 2.0 to 24.0 hours, and then the reaction solution is subjected to post-treatment to obtain the product, namely the cycloalkyl alcohol and the cycloalkyl ketone. The method has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Description
Technical Field
The invention relates to a method for synthesizing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane under the coordination of a limited metalloporphyrin manganese (II)/Zn (II) salt, and belongs to the field of industrial catalysis and fine organic synthesis.
Background
Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important intermediates in fine chemical industry, and are widely used in synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins, and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, has the main problems of high reaction temperature, low substrate conversion rate, poor selectivity of the target product, and in particular, difficulty in inhibiting the formation of aliphatic diacids (Applied Catalysis a, general2019,575: 120-; catalysis Communications2019,132: 105809). The main sources of the above problems are: (1) at present, O is industrially used2Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled2The free radical diffusion in the process of catalytically oxidizing the cycloalkane and the catalytic conversion of the intermediate product of the oxidation, namely the cycloalkyl hydrogen peroxide, are beneficial to the improvement of the catalytic oxidation selectivity of the cycloalkane, and are novel process improvement with great application significance in the field of catalytic oxidation of the cycloalkane in industry.
Metalloporphyrin is used as a model compound of cytochrome P-450 and widely applied to various organic synthesis reactions in the field of biomimetic Catalysis, in particular to oxidation reactions (ChemSusChem 2019,12(3): 684-152; Polydron 2019,163: 144-152; Journal of Catalysis 2019,369: 133-142). The metalloporphyrin has an approximately planar molecular structure, so that a metal center with catalytic activity can be exposed in a catalytic system to play a role to the maximum extent, excellent catalytic activity can be shown at 1/1000000-1/100000 of the amount of a substrate, the cost of catalytic oxidation of naphthenic hydrocarbon C-H bonds can be remarkably reduced, and the metalloporphyrin is one of the preferable catalysts for catalytic oxidation of naphthenic hydrocarbon C-H bonds. Meanwhile, the metalloporphyrin is used as a catalyst, so that not only the central metal has a wide selective object, but also the substituent groups around the metalloporphyrin ring have a wide regulation space. Therefore, the metalloporphyrin selected as the catalyst has the advantages of small catalyst dosage, high catalytic efficiency, easy structure adjustment, good biocompatibility, environmental protection and the like. By regulating the volume of the substituent group around the metalloporphyrin ring and brominating the pyrrole ring, the stability of the metalloporphyrin is improved, and a certain microscopic restricted environment is also constructed. The use of the limited-domain metalloporphyrin as a catalyst not only can realize the high-efficiency dispersion of the catalytic active center, but also can provide a certain microscopic limited-domain environment for Chemical reaction, effectively prevent the disordered diffusion of free radicals and improve the reaction selectivity (Journal of the American Chemical Society 2017,139: 18590-. In addition, Zn (II) can catalyze the decomposition and conversion of naphthenic base hydrogen peroxide which is an intermediate product of oxidation of naphthenic hydrocarbon, prevent the non-selective thermal decomposition and conversion of the naphthenic base hydrogen peroxide and improve the selectivity of catalytic oxidation of the naphthenic hydrocarbon (Catalysis communications2019,132: 105809).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by synergistically catalyzing and oxidizing cycloalkane with a limited-domain metalloporphyrin manganese (II)/Zn (II) salt, wherein the limited-domain metalloporphyrin manganese (II)/Zn (II) salt is combined as a binary catalyst to synergistically catalyze O2The method for selectively synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the naphthenic hydrocarbon not only has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less by-products, small environmental influence and the like, but also has the advantages ofThe method has low content of alkyl hydroperoxide and high safety coefficient, and is a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
The technical scheme of the invention is as follows:
a method for synthesizing cycloalkanol and cycloalkanone by the concerted catalytic oxidation of cycloalkane with a limited-domain metalloporphyrin manganese (II)/Zn (II) salt, the method comprises the following processes:
dispersing limited metalloporphyrin manganese (II) and Zn (II) salt in cycloparaffin, wherein the amount of substance of the limited metalloporphyrin manganese (II) is 1 x 10 of the amount of substance of the cycloparaffin-40.1 percent of the total weight of the mixture, mol/mol; the amount of Zn (II) salt substance is 0.01-10% of the amount of cycloalkane substance, mol/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the limited-domain metalloporphyrin manganese (II) comprises compounds shown as a formula (I), a formula (II), a formula (III), a formula (IV) and a formula (V):
the Zn (II) salt is Zn (CH)3COO)2,Zn(NO3)2,ZnSO4,ZnCl2And hydrates thereof, preferably anhydrous Zn (CH)3COO)2；
The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
Further, the ratio of the amount of the substance of the limited-domain metalloporphyrin manganese (II) to the amount of the substance of the cycloalkane is 1: 1000000 to 1: 1000, preferably 1: 100000 to 1: 10000.
The ratio of Zn (II) salt substance to cycloalkane substance is 1: 10000-1: 10, preferably 1: 1000-1: 50.
The reaction temperature is 90-150 ℃, and preferably 100-130 ℃; the reaction pressure is 0.10-2.0 MPa, preferably 0.60-1.20 MPa; the stirring speed is 400-800 rpm, preferably 500-700 rpm.
The oxidant is oxygen, air or a mixture of oxygen and air in any proportion.
The post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 3 percent of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified at normal pressure and recrystallized to obtain an oxidation product.
The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of the reaction liquid by triphenylphosphine is sampled and analyzed. Diluting with acetone as solvent, performing gas chromatography with toluene as internal standard, and calculating conversion rate of cycloalkane and selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; and (4) performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid.
The invention constructs a binary catalytic system by using a limited-domain metalloporphyrin manganese (II)/Zn (II) salt to synergistically catalyze O2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the cycloalkane not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product naphthenic hydrogen peroxide, greatly improves the selectivity of the target product naphthenic alcohol and naphthenic ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing naphthenic alcohol and naphthenic ketone by efficiently and selectively oxidizing naphthenic C-H bonds, but also has certain reference value for efficiently preparing alcohol and ketone compounds by selectively catalyzing and oxidizing other hydrocarbon C-H bonds.
The invention has the following beneficial effects: the method uses the limited-domain metalloporphyrin manganese (II)/Zn (II) salt to synergistically catalyze and oxidize cycloalkane to synthesize the cycloalkyl alcohol and the cycloalkyl ketone, and has the advantages of high selectivity of the cycloalkyl alcohol and the cycloalkyl ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The limited porphyrin ligand and limited metalloporphyrin manganese (II) used in the present invention are described in Journal of Organic Chemistry 1967,32(2): 476-; journal of the American Chemical Society 2017,139(51), 18590-18597; russian Journal of General Chemistry 2016,86(5): 1091-1094. All reagents used were commercially available analytical grade.
Examples 1 to 32 are examples of catalytic oxidation of cycloalkanes.
Examples 33 to 46 are comparative experimental cases of catalytic oxidation of cycloalkanes.
Example 47 is a scale-up experiment for catalytic oxidation of cycloalkanes.
Example 1
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.06%, cyclohexanol selectivity 41.19%, cyclohexanone selectivity 53.82%, cyclohexyl hydroperoxide selectivity 2.48%, adipic acid selectivity 2.16%, glutaric acidThe selectivity was 0.35%.
Example 2
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (1-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.88%, cyclohexanol selectivity 40.07%, cyclohexanone selectivity 51.39%, cyclohexyl hydroperoxide selectivity 6.24%, adipic acid selectivity 2.04%, glutaric acid selectivity 0.26%.
Example 3
0.0031g (0.0024mmol) of 5,10,15, 20-tetraphenyl-2, 3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, the autoclave is sealed, the temperature is raised to 120 ℃ with stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.18%, cyclohexanol selectivity 38.54%, cyclohexanone selectivity 52.41%, cyclohexyl hydroperoxide selectivity 5.85%, adipic acid selectivity 2.71%, glutaric acid selectivity 0.49%.
Example 4
0.0041g (0.0024mmol) of 5,10,15, 20-tetrakis (9-phenanthryl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.68%, the cyclohexanol selectivity is 43.78%, the cyclohexanone selectivity is 47.95%, the cyclohexyl hydroperoxide selectivity is 4.30%, the adipic acid selectivity is 3.53%, and the glutaric acid selectivity is 0.44%.
Example 5
0.0043g (0.0024mmol) of 5,10,15, 20-tetrakis (1-pyrenyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion was 6.41%, cyclohexanol selectivity was 45.02%, cyclohexanone selectivity was 47.35%, cyclohexyl hydroperoxide selectivity was 4.56%, adipic acid selectivity was 2.78%, and glutaric acid selectivity was 0.29%.
Example 6
100mL of the container with a polytetrafluoroethylene inner container0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4167g (2.200mmol) of zinc nitrate were dispersed in 16.8320g (200mmol) of cyclohexane in a steel autoclave, the autoclave was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.01 percent, the cyclohexanol selectivity is 38.71 percent, the cyclohexanone selectivity is 51.95 percent, the cyclohexyl hydroperoxide selectivity is 6.85 percent, the adipic acid selectivity is 2.03 percent, and the glutaric acid selectivity is 0.46 percent.
Example 7
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.2998g (2.200mmol) of zinc chloride are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.71%, the cyclohexanol selectivity is 37.22%, the cyclohexanone selectivity is 51.14%, the cyclohexyl hydroperoxide selectivity is 8.79%, the adipic acid selectivity is 2.18%, and the glutaric acid selectivity is 0.67%.
Example 8
In a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthalene)2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.3552g (2.200mmol) of zinc sulfate are dispersed in 16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.08%, cyclohexanol selectivity 38.54%, cyclohexanone selectivity 49.22%, cyclohexyl hydroperoxide selectivity 9.28%, adipic acid selectivity 2.41%, glutaric acid selectivity 0.55%.
Example 9
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 14.0280g (200mmol) of cyclopentane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 4.52%, the selectivity for cyclopentanol was 7.55%, the selectivity for cyclopentanone was 46.31%, the selectivity for cyclopentyl hydroperoxide was 15.21%, the selectivity for glutaric acid was 29.45%, and the selectivity for succinic acid was 1.48%.
Example 10
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of ethyl acetate were placedDispersing zinc salt in 19.6380g (200mmol) of cycloheptane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 21.48 percent, the selectivity of cycloheptanol is 10.11 percent, the selectivity of cycloheptanone is 66.91 percent, the selectivity of cycloheptyl hydroperoxide is 20.34 percent, the selectivity of pimelic acid is 2.23 percent, and the selectivity of adipic acid is 0.41 percent.
Example 11
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 22.4440g (200mmol) of cyclooctane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclooctane is 26.18%, the selectivity of cyclooctanol is 30.69%, the selectivity of cyclooctanone is 51.43%, the selectivity of cyclooctyl hydrogen peroxide is 16.09%, the selectivity of suberic acid is 1.79%, and the generation of pimelic acid is not detected.
Example 12
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate were dispersed in 33.6640g (200mmol) of cyclododecane and the reaction was sealed and reverse-reactedThe mixture is stirred in a kettle and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclododecane conversion 30.94%, cyclododecanol selectivity 18.67%, cyclododecanone selectivity 49.95%, cyclododecyl hydroperoxide selectivity 31.38%, and formation of dodecanoic acid and undecanoic acid was not detected.
Example 13
0.0003g (0.0002mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene inner vessel, the autoclave is sealed, stirred and heated to 120 ℃ and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.03%, cyclohexanol selectivity 27.77%, cyclohexanone selectivity 21.20%, cyclohexyl hydroperoxide selectivity 51.03%, no formation of adipic acid and glutaric acid was detected.
Example 14
0.0030g (0.0020mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. At 120 ℃ and 1.0The reaction is stirred at 600rpm for 8.0h under the oxygen pressure of MPa. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.84%, the cyclohexanol selectivity is 40.75%, the cyclohexanone selectivity is 52.80%, the cyclohexyl hydroperoxide selectivity is 3.78%, the adipic acid selectivity is 2.26%, and the glutaric acid selectivity is 0.41%.
Example 15
0.0300g (0.0200mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, the autoclave is sealed, stirred and heated to 120 ℃ and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.17%, cyclohexanol selectivity 40.62%, cyclohexanone selectivity 52.10%, cyclohexyl hydroperoxide selectivity 4.55%, adipic acid selectivity 2.31%, glutaric acid selectivity 0.42%.
Example 16
0.2998g (0.2000mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After the reaction is finished, cooling with ice waterCooled to room temperature, 1.3115g (5.00mmol) of triphenylphosphine (PPh) were added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.35%, cyclohexanol selectivity 38.46%, cyclohexanone selectivity 50.70%, cyclohexyl hydroperoxide selectivity 7.47%, adipic acid selectivity 2.65%, glutaric acid selectivity 0.72%.
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.0037g (0.020mmol) of zinc acetate were dispersed in 16.8320g (200mmol) of cyclohexane, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.34%, the cyclohexanol selectivity is 32.75%, the cyclohexanone selectivity is 36.79%, the cyclohexyl hydroperoxide selectivity is 20.90%, the adipic acid selectivity is 8.71%, and the glutaric acid selectivity is 0.85%.
Example 18
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.0367g (0.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenyl (phenyl) was added to the reaction mixturePhenylphosphine (PPh)3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.72%, the cyclohexanol selectivity is 35.83%, the cyclohexanone selectivity is 41.21%, the cyclohexyl hydroperoxide selectivity is 17.02%, the adipic acid selectivity is 5.28%, and the glutaric acid selectivity is 0.66%.
Example 19
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.7339g (4.000mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.73 percent, the cyclohexanol selectivity is 38.34 percent, the cyclohexanone selectivity is 45.20 percent, the cyclohexyl hydroperoxide selectivity is 11.37 percent, the adipic acid selectivity is 4.59 percent, and the glutaric acid selectivity is 0.50 percent.
Example 20
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 3.6694g (20.000mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) Stirring at room temperature for 30min to reduce the productAn oxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.30%, the cyclohexanol selectivity is 31.87%, the cyclohexanone selectivity is 37.52%, the cyclohexyl hydroperoxide selectivity is 20.78%, the adipic acid selectivity is 8.24%, and the glutaric acid selectivity is 1.59%.
Example 21
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 90 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 90 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.19%, no formation of cyclohexanol was detected, cyclohexanone selectivity 19.17%, cyclohexyl hydroperoxide selectivity 80.83%, and no formation of adipic acid and glutaric acid was detected.
Example 22
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 100 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 100 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent.10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.25%, no formation of cyclohexanol was detected, cyclohexanone selectivity 25.94%, cyclohexyl hydroperoxide selectivity 74.06%, and no formation of adipic acid and glutaric acid was detected.
Example 23
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 130 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 600rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.51%, cyclohexanol selectivity 37.30%, cyclohexanone selectivity 49.05%, cyclohexyl hydroperoxide selectivity 8.74%, adipic acid selectivity 4.14%, glutaric acid selectivity 0.77%.
Example 24
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 150 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 150 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard;10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 11.52%, the cyclohexanol selectivity is 30.22%, the cyclohexanone selectivity is 39.66%, the cyclohexyl hydroperoxide selectivity is 21.01%, the adipic acid selectivity is 6.84%, and the glutaric acid selectivity is 2.27%.
Example 25
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 0.10 MPa. The reaction was stirred at 120 ℃ under 0.1MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.18%, cyclohexanol selectivity 29.73%, cyclohexanone selectivity 42.22%, cyclohexyl hydroperoxide selectivity 18.84%, adipic acid selectivity 7.81%, glutaric acid selectivity 1.40%.
Example 26
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 0.60 MPa. The reaction was stirred at 120 ℃ under 0.6MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and liquid chromatography was performed using benzoic acid as an internal standardAnd (4) performing spectrum analysis. The cyclohexane conversion rate is 6.63%, the cyclohexanol selectivity is 39.80%, the cyclohexanone selectivity is 50.73%, the cyclohexyl hydroperoxide selectivity is 5.94%, the adipic acid selectivity is 2.47%, and the glutaric acid selectivity is 1.06%.
Example 27
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.20 MPa. The reaction was stirred at 600rpm for 8.0h at 120 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.76%, the cyclohexanol selectivity is 38.53%, the cyclohexanone selectivity is 50.38%, the cyclohexyl hydroperoxide selectivity is 7.05%, the adipic acid selectivity is 2.81%, and the glutaric acid selectivity is 1.23%.
Example 28
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 2.00 MPa. The reaction was stirred at 120 ℃ under 2.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate is 6.88 percent, and cyclohexanol selectivity is 41.90 percentThe selectivity for cyclohexanone was 49.73%, the selectivity for cyclohexyl hydroperoxide was 2.16%, the selectivity for adipic acid was 5.51%, and the selectivity for glutaric acid was 0.70%.
Example 29
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure at 400rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.30%, the cyclohexanol selectivity is 38.60%, the cyclohexanone selectivity is 51.89%, the cyclohexyl hydroperoxide selectivity is 7.24%, the adipic acid selectivity is 1.81%, and the glutaric acid selectivity is 0.46%.
Example 30
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 500rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.49%, cyclohexanol selectivity 39.77%, cyclohexanone selectivity 52.64%, cyclohexyl hydroperoxide selectivity 5.10Percent, adipic acid selectivity is 1.94 percent, and glutaric acid selectivity is 0.55 percent.
Example 31
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 700rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.09%, cyclohexanol selectivity 41.12%, cyclohexanone selectivity 52.73%, cyclohexyl hydroperoxide selectivity 3.28%, adipic acid selectivity 2.51%, glutaric acid selectivity 0.36%.
Example 32
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin and 0.4036g (2.200mmol) of zinc acetate are dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 7.17%, the cyclohexanol selectivity is 41.83%, the cyclohexanone selectivity is 53.95%, the cyclohexyl hydroperoxide selectivity is 2.14%, the adipic acid selectivity is 1.73%, and the glutaric acid selectivity is 0.35%.
Example 33 (comparative experiment)
0.0021g (0.0024mmol) of 5,10,15, 20-tetra (2-naphthyl) porphyrin manganese is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.39%, the cyclohexanol selectivity is 37.54%, the cyclohexanone selectivity is 42.35%, the cyclohexyl hydroperoxide selectivity is 10.22%, the adipic acid selectivity is 6.84%, and the glutaric acid selectivity is 3.05%.
Example 34 (comparative experiment)
0.0021g (0.0024mmol) of 5,10,15, 20-tetra (1-naphthyl) porphyrin manganese is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.20%, cyclohexanol selectivity 34.79%, cyclohexanone selectivity 44.70%, cyclohexyl hydroperoxide selectivity 11.16%, adipic acid selectivity 7.84%, glutaric acid selectivity 1.51%.
Example 35 (comparative experiment)
Stainless steel high-pressure reaction kettle with polytetrafluoroethylene inner container in 100mLIn the reaction, 0.0016g (0.0024mmol) of 5,10,15, 20-manganese tetraphenylporphyrin was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.05%, cyclohexanol selectivity 34.66%, cyclohexanone selectivity 45.80%, cyclohexyl hydroperoxide selectivity 8.49%, adipic acid selectivity 9.73%, glutaric acid selectivity 1.32%.
Example 36 (comparative experiment)
0.0026g (0.0024mmol) of 5,10,15, 20-tetra (9-phenanthryl) manganese porphyrin is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.16%, the cyclohexanol selectivity is 36.13%, the cyclohexanone selectivity is 45.38%, the cyclohexyl hydroperoxide selectivity is 7.24%, the adipic acid selectivity is 9.98%, and the glutaric acid selectivity is 1.27%.
Example 37 (comparative experiment)
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0028g (0.0024mmol) of 5,10,15, 20-tetra (1-pyrenyl) porphyrin manganese is dispersed in 16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.28%, cyclohexanol selectivity 37.13%, cyclohexanone selectivity 41.79%, cyclohexyl hydroperoxide selectivity 11.18%, adipic acid selectivity 8.72%, glutaric acid selectivity 1.18%.
Example 38 (comparative experiment)
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (1-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.93%, the cyclohexanol selectivity is 36.12%, the cyclohexanone selectivity is 39.03%, the cyclohexyl hydroperoxide selectivity is 13.40%, the adipic acid selectivity is 9.31%, and the glutaric acid selectivity is 2.14%.
Example 39 (comparative experiment)
0.0036g (0.0024mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromomanganese (II) porphyrin is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After the reaction is finished, cooling the reaction product to room with ice waterTo the reaction mixture was added 1.3115g (5.00mmol) of triphenylphosphine (PPh) warm3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.13%, the cyclohexanol selectivity is 40.85%, the cyclohexanone selectivity is 35.63%, the cyclohexyl hydroperoxide selectivity is 12.25%, the adipic acid selectivity is 9.17%, and the glutaric acid selectivity is 2.10%.
Example 40 (comparative experiment)
0.0031g (0.0024mmol) of 5,10,15, 20-tetraphenyl-2, 3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.02%, the cyclohexanol selectivity is 34.23%, the cyclohexanone selectivity is 44.06%, the cyclohexyl hydroperoxide selectivity is 10.26%, the adipic acid selectivity is 9.10%, and the glutaric acid selectivity is 2.35%.
Example 41 (comparative experiment)
0.0041g (0.0024mmol) of 5,10,15, 20-tetra (9-phenanthryl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) Stirring at room temperature for 30min reducing the generated peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.75%, the cyclohexanol selectivity is 40.35%, the cyclohexanone selectivity is 34.43%, the cyclohexyl hydroperoxide selectivity is 12.99%, the adipic acid selectivity is 9.85%, and the glutaric acid selectivity is 2.38%.
Example 42 (comparative experiment)
0.0043g (0.0024mmol) of 5,10,15, 20-tetra (1-pyrenyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.87%, the cyclohexanol selectivity is 42.66%, the cyclohexanone selectivity is 33.50%, the cyclohexyl hydroperoxide selectivity is 12.86%, the adipic acid selectivity is 9.03%, and the glutaric acid selectivity is 1.95%.
Example 43 (comparative experiment)
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.4036g (2.200mmol) of zinc acetate is dispersed in 16.8320g (200mmol) of cyclohexane, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed and subjected to gas phase chromatography using toluene as an internal standardCarrying out chromatographic analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.92%, cyclohexanol selectivity 28.60%, cyclohexanone selectivity 21.70%, cyclohexyl hydroperoxide selectivity 49.70%, no formation of adipic acid and glutaric acid was detected.
Example 44 (comparative experiment)
0.4167g (2.200mmol) of zinc nitrate was dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave having a Teflon liner, the autoclave was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.73%, cyclohexanol selectivity 24.72%, cyclohexanone selectivity 18.21%, cyclohexyl hydroperoxide selectivity 57.07%, no formation of adipic acid and glutaric acid was detected.
Example 45 (comparative experiment)
0.2998g (2.200mmol) of zinc chloride is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.99%, cyclohexanol selectivity 22.49%, cyclohexanone selectivity 17.11%, cyclohexyl hydroperoxide selectivity 60.40%, undetectedFormation of adipic acid and glutaric acid.
Example 46 (comparative experiment)
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.3552g (2.200mmol) of zinc sulfate is dispersed in 16.8320g (200mmol) of cyclohexane, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.72%, cyclohexanol selectivity 21.30%, cyclohexanone selectivity 17.27%, cyclohexyl hydroperoxide selectivity 61.43%, no formation of adipic acid and glutaric acid was detected.
Example 47 (amplification experiment)
0.0359g (0.0240mmol) of 5,10,15, 20-tetrakis (2-naphthyl) -2,3,7,8,12,13,17, 18-octabromoporphyrin manganese (II) and 4.0363g (22.000mmol) of zinc acetate are dispersed in 168.32g (2mol) of cyclohexane in a 1L stainless steel autoclave with a polytetrafluoroethylene inner vessel, the autoclave is sealed and stirred to 120 ℃ and oxygen is introduced to 1.00 MPa. The reaction was stirred at 600rpm for 8.0h at 120 ℃. After completion of the reaction, ice water was cooled to room temperature, and 131.15g (500.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 40 min. Distilling, recovering 156.51g of cyclohexane, and ensuring the conversion rate to be 7.02%; vacuum rectification is carried out to obtain 4.84g of cyclohexanol, the selectivity is 40.98 percent, the cyclohexanone is 6.31g, the selectivity is 53.43 percent, recrystallization is carried out to obtain 0.23g of adipic acid, the selectivity is 1.95 percent, the glutaric acid is 0.035g, and the selectivity is 0.30 percent.
Claims (8)
1. A method for the concerted catalytic oxidation of cycloalkanes by a limited-domain metalloporphyrin manganese (II)/Zn (II) salt, the method comprising the following steps:
will confine the metalManganese (II) porphyrin and Zn (II) salt are dispersed in cycloalkane, wherein the amount of substance of limited metalloporphyrin manganese (II) is 1 × 10 of the amount of substance of cycloalkane-40.1 percent of the total weight of the mixture, mol/mol; the amount of Zn (II) salt substance is 0.01-10% of the amount of cycloalkane substance, mol/mol; sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and performing aftertreatment on the reaction solution to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the limited-domain metalloporphyrin manganese (II) comprises compounds shown as a formula (I), a formula (II), a formula (III), a formula (IV) and a formula (V):
the Zn (II) salt is Zn (CH)3COO)2,Zn(NO3)2,ZnSO4,ZnCl2And hydrates thereof, or a mixture of at least two of the hydrates in any proportion;
the cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
2. The method for the concerted catalytic oxidation of cycloalkanes with a limited metalloporphyrin manganese (II)/zn (II) salt according to claim 1 wherein the catalyst is a binary combination of limited metalloporphyrin manganese (II) and zn (II) salts.
3. The method for the concerted catalytic oxidation of cycloalkane by a limited-domain metalloporphyrin manganese (II)/Zn (II) salt according to claim 1 or 2, wherein the ratio of the amount of substance of limited-domain metalloporphyrin manganese (II) to the amount of substance of cycloalkane is 1: 1000000 to 1: 1000.
4. The method for the concerted catalytic oxidation of cycloalkane by a limited-area metalloporphyrin manganese (II)/Zn (II) salt according to claim 1 or 2, wherein the ratio of the amount of substance of Zn (II) salt to the amount of substance of cycloalkane is 1: 10000 to 1: 10.
5. The method for the concerted catalytic oxidation of cycloalkanes by the limited-domain metalloporphyrin manganese (II)/Zn (II) salt according to claim 1 or 2, wherein the reaction pressure is 0.10-2.0 MPa.
6. The method for the co-catalytic oxidation of cycloalkanes with a limited metalloporphyrin manganese (II)/Zn (II) salt according to claim 1 or 2, wherein the stirring speed is 400-800 rpm.
7. The method for the co-catalytic oxidation of cycloalkanes with a limited metalloporphyrin manganese (II)/zn (II) salt according to claim 1 or 2, wherein the oxidant is oxygen, air or a mixture thereof in any ratio.
8. The method for the concerted catalytic oxidation of cycloalkanes by the limited metalloporphyrin manganese (II)/zn (II) salt according to claim 1 or 2, wherein the post-treatment is carried out by: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 3 percent of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and the crude product is distilled, rectified at normal pressure and recrystallized to obtain an oxidation product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405131A (en) * | 2002-10-29 | 2003-03-26 | 郭灿城 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN110563555A (en) * | 2019-08-28 | 2019-12-13 | 浙江工业大学 | Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405131A (en) * | 2002-10-29 | 2003-03-26 | 郭灿城 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN110563555A (en) * | 2019-08-28 | 2019-12-13 | 浙江工业大学 | Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt |
Non-Patent Citations (1)
| Title |
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| GILSON DE FREITAS SILVA等: "Cyclohexane hydroxylation by iodosylbenzene and iodobenzene diacetate catalyzed by a new β-octahalogenated Mn–porphyrin complex: The effect of meso-3-pyridyl substituents", 《JOURNAL OF MOLECULAR CATALYSIS A》 * |
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