CN111943808A - Method for oxidizing cycloalkane under concerted catalysis of metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt - Google Patents
Method for oxidizing cycloalkane under concerted catalysis of metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt Download PDFInfo
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- CN111943808A CN111943808A CN202010877116.9A CN202010877116A CN111943808A CN 111943808 A CN111943808 A CN 111943808A CN 202010877116 A CN202010877116 A CN 202010877116A CN 111943808 A CN111943808 A CN 111943808A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 72
- 150000001924 cycloalkanes Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 17
- 230000002153 concerted effect Effects 0.000 title claims description 11
- 238000006555 catalytic reaction Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 190
- 238000003756 stirring Methods 0.000 claims abstract description 64
- -1 cycloalkyl alcohol Chemical compound 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 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 104
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 90
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 55
- 239000001301 oxygen Substances 0.000 claims description 55
- 229910052760 oxygen Inorganic materials 0.000 claims description 55
- 150000002978 peroxides Chemical class 0.000 claims description 55
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 5
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 4
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 4
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-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
- 239000003054 catalyst Substances 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 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 15
- 150000002576 ketones Chemical class 0.000 abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 141
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 106
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 96
- 239000011541 reaction mixture Substances 0.000 description 94
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 90
- 239000011572 manganese Substances 0.000 description 59
- 239000005711 Benzoic acid Substances 0.000 description 48
- 235000010233 benzoic acid Nutrition 0.000 description 48
- 238000004817 gas chromatography Methods 0.000 description 48
- 238000004811 liquid chromatography Methods 0.000 description 47
- 239000002904 solvent Substances 0.000 description 47
- 229910001220 stainless steel Inorganic materials 0.000 description 46
- 239000010935 stainless steel Substances 0.000 description 46
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 45
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 44
- 239000004810 polytetrafluoroethylene Substances 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 40
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 40
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 39
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 38
- 230000015572 biosynthetic process Effects 0.000 description 32
- 239000001361 adipic acid Substances 0.000 description 19
- 235000011037 adipic acid Nutrition 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BAUZLFKYYIVGPM-UHFFFAOYSA-N cyclononanone Chemical compound O=C1CCCCCCCC1 BAUZLFKYYIVGPM-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 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
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WFRBMXFCEAHLGH-UHFFFAOYSA-N cyclodecanol Chemical compound OC1CCCCCCCCC1 WFRBMXFCEAHLGH-UHFFFAOYSA-N 0.000 description 1
- SXOZDDAFVJANJP-UHFFFAOYSA-N cyclodecanone Chemical compound O=C1CCCCCCCCC1 SXOZDDAFVJANJP-UHFFFAOYSA-N 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- UDEKCKABZJKCKG-UHFFFAOYSA-N cyclononanol Chemical compound OC1CCCCCCCC1 UDEKCKABZJKCKG-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
- 230000006837 decompression Effects 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
- DHNWIBRXEZWDHT-UHFFFAOYSA-N hydroperoxycyclodecane Chemical compound OOC1CCCCCCCCC1 DHNWIBRXEZWDHT-UHFFFAOYSA-N 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
- UGQNEIXDQOBBHB-UHFFFAOYSA-N hydroperoxycyclononane Chemical compound OOC1CCCCCCCC1 UGQNEIXDQOBBHB-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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing 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
- 239000011148 porous material Substances 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
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
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- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt comprises the steps of dispersing PCN-224(Mn) (0.001% -5%, g/mol) and Zn (II) salt (0.01% -10%, mol/mol) in cycloalkane, sealing a 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 then carrying out aftertreatment on reaction liquid to obtain a product, namely cycloalkyl alcohol and 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 synergistically catalyzing and oxidizing cycloalkane with metalloporphyrin MOFs PCN-224(Mn)/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 in industry is predominantly homogeneous Mn2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, there are major problems of high reaction temperature, low substrate conversion, poor selectivity of the target product, and in particular, difficulty in inhibiting the formation of aliphatic diacids (Applied Catalysis a, General 2019,575: 120-; catalysis Communications 2019,132: 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 a novel process improvement with great application significance in the field of catalytic oxidation of the cycloalkane in industry.
The metal-organic framework material PCN-224 is a series of porous materials with better Chemical stability and thermal stability, which is applied to the field of organic catalysis, not only can realize the high-efficiency dispersion of catalytic active centers, but also can provide a certain micro-domain environment for Chemical reactions, 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 naphthenic hydrocarbon oxidation, 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 Communications 2019,132: 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 metalloporphyrin MOFs PCN-224(Mn) and Zn (II) salts, wherein the metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salts are 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 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, and the method provided by the invention has low content of naphthenic hydroperoxide and high safety factor, and is an efficient, feasible and safe method for selectively catalytically oxidizing the naphthenic hydrocarbon to synthesize the naphthenic alcohol and the naphthenic ketone.
The technical scheme of the invention is as follows:
a method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt, said method comprising the following steps:
dispersing metalloporphyrin MOFs PCN-224(Mn) and Zn (II) salt in cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-224(Mn) is 0.001% -5% of the mass of the cycloalkane, and g/mol; the amount of Zn (II) salt is 0.01-10% of that of naphthenic hydrocarbon, mol/mol, sealing the reaction system, heating to 90-150 ℃ under stirring, introducing an oxidant, keeping the set temperature and pressure, stirring for 2.0-24.0 h, and performing post-treatment on the reaction liquid to obtain the product naphthenic alcohol and naphthenic ketone;
the metalloporphyrin MOFs PCN-224(Mn) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
the Zn (II) salt is Zn (OAc)2,Zn(NO3)2,ZnSO4,ZnCl2And hydrates thereof, preferably anhydrous Zn (OAc)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 mass of the metalloporphyrin MOFs PCN-224(Mn) to the mass of the naphthenic hydrocarbon substance is 1: 100000-1: 20, preferably 1: 10000-1: 100.
The mass ratio of Zn (II) salt to cycloalkane is 1: 10000-1: 10, preferably 1: 1000-1: 100.
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 600-1200 rpm, preferably 800-1000 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 under reduced 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) carrying out liquid chromatography analysis by taking glutaric acid as an internal standard, and calculating the selectivity of the aliphatic diacid.
The invention constructs a binary catalytic system by using metalloporphyrin MOFs PCN-224(Mn)/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 metalloporphyrin of the invention MOFs PCN-224(Mn)/Zn (OAc)2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by synergistically catalyzing and oxidizing the cycloalkane 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.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrins MOFs PCN-224(Mn) used in the present invention are referred to Journal of the American Chemical Society 2017,139: 18590-18597; journal of the American Chemical Society 2013,135: 17105-17110; inorganic Chemistry 2019,58: 5145-. All reagents used were commercially available analytical grade.
Examples 1 to 3 are syntheses of the metalloporphyrins MOFs PCN-224 (Mn).
Examples 4 to 40 are examples of catalytic oxidation of cycloalkanes.
Examples 41 to 49 are comparative experimental cases.
Examples 50 to 53 are scale-up experimental cases.
Example 1
Synthesis of PCN-224(Mn) -m: t (3-COOH) PPMn (II) (0.0847g,0.1mmol), ZrCl were placed in a 35mL pressure resistant reaction tube4(0.1400g,0.6mmol), benzoic acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min until all dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, washed by DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, centrifuged by a low-speed centrifuge for 5.0min (3000rpm), the upper layer liquid is poured out, dried DMF (3 × 8.0mL) is leached to clarify the upper layer liquid, dried acetone (3 × 8.0mL) is leached to clarify the upper layer liquid, the lower layer solid is taken off, and dried at 90 ℃ for 8.0h, so that brick red powder (0.0680g, 44.7% yield) is obtained.
Example 2
Synthesis of PCN-224(Mn) -p: t (4-COOH) PPMn (II) (0.0847g,0.1mmol), ZrCl were placed in a 35mL pressure resistant reaction tube4(0.1400g,0.6mmol), benzoic acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min until all dissolved. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, washed by DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, the centrifugation is carried out by a low-speed centrifuge for 5.0min (3000rpm), the upper liquid is poured out, the DMF (3 × 8.0mL) is dried and extracted until the upper liquid is clear, the acetone (3 × 8.0mL) is dried and extracted until the upper liquid is clear, the lower solid is taken down, and the drying is carried out for 8.0h at 90 ℃ to obtain brick red powder (0.0690g, yield of 45.3%).
Example 3
Synthesis of PCN-224(Mn) -d: in a 35mL pressure-resistant reaction tube, [ T (4- (4-COOH) P) PPMn (II) ]](0.1152g,0.1mmol),ZrCl4(0.1400g,0.6mmol), benzylThe acid (5.4000g,44.3mmol) was dissolved in 16.0mL DMF and sonicated for 30min to dissolve completely. The mixture is put into an electric heating constant temperature air blast drying oven to be kept still for reaction for 48.0h at the temperature of 120 ℃. After the reaction is finished, the heating is closed, the reaction product is naturally cooled to room temperature, the crude product is filtered, washed by DMF and acetone sequentially and then transferred to a 10.0mL centrifuge tube, a low-speed centrifuge is used for centrifuging for 5.0m (3000.0rpm), the upper layer liquid is poured out, the DMF (3 × 8.0mL) is dried and extracted until the upper layer liquid is clear, the acetone (3 × 8.0mL) is dried and extracted until the upper layer liquid is clear, the lower layer solid is taken down, and the brick red powder (0.0670g, 43.3% yield) is obtained after drying for 8.0h at 90 ℃.
Example 4
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 7.54%, the cyclohexanol selectivity was 70%, the cyclohexanone selectivity was 26%, the cyclohexyl hydroperoxide selectivity was 2%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 5
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 600rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Transferring 10mL of the obtained solution, performing gas chromatography with toluene as an internal standard, and transferring 10mL of the obtained solutionThe liquid was analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.58%, cyclohexanol selectivity 82%, cyclohexanone selectivity 7%, cyclohexyl hydroperoxide selectivity 11%, no formation of glutaric acid was detected.
Example 6
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 1000rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 5.56%, the cyclohexanol selectivity was 83%, the cyclohexanone selectivity was 7%, the cyclohexyl hydroperoxide selectivity was 10%, and the formation of glutaric acid was not detected.
Example 7
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 1200rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion was 5.21%, cyclohexanol selectivity was 81%, cyclohexanone selectivity was 7%, cyclohexyl hydroperoxide selectivity was 12%, and no formation of glutaric acid was detected.
Example 8
Stainless steel with polytetrafluoroethylene inner container in 100mLIn an autoclave, 0.0020g of MOFs PCN-224(Mn) and 0.0020g of Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 90 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 90 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 1.08%, cyclohexanol selectivity 68%, cyclohexanone selectivity 17%, cyclohexyl hydroperoxide selectivity 15%, no formation of glutaric acid was detected.
Example 9
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 100 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 100 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 2.56%, the cyclohexanol selectivity was 76%, the cyclohexanone selectivity was 15%, the cyclohexyl hydroperoxide selectivity was 9%, and the formation of glutaric acid was not detected.
Example 10
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 110 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 110 ℃. After completion of the reaction, it was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) Stirring at room temperature for 40minThe peroxide originally produced. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 2.96%, the cyclohexanol selectivity was 78%, the cyclohexanone selectivity was 16%, the cyclohexyl hydroperoxide selectivity was 6%, and no glutaric acid formation was detected.
Example 11
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 130 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 130 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.20%, the cyclohexanol selectivity is 29%, the cyclohexanone selectivity is 56.0%, the cyclohexyl hydroperoxide selectivity is 11.0%, and the adipic acid selectivity is 4%.
Example 12
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 140 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 140 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 5.80%, cyclohexanol selectivity 24%, cyclohexanone selectivity 58.0%, cyclohexyl hydroperoxideThe selectivity is 13.0 percent, and the selectivity of adipic acid is 5 percent.
Example 13
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 150 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 150 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.0%, the cyclohexanol selectivity is 15%, the cyclohexanone selectivity is 15%, the cyclohexyl hydroperoxide selectivity is 60%, the glutaric acid selectivity is 2.2%, and the adipic acid selectivity is 7.8%.
Example 14
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 3.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.21%, the cyclohexanol selectivity is 23.5%, the cyclohexanone selectivity is 59.4%, the cyclohexyl hydroperoxide selectivity is 3.4%, the glutaric acid selectivity is 2.0%, and the adipic acid selectivity is 11.7%.
Example 15
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) cyclohexaneWhile stirring, the temperature was raised to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 5.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.73%, the cyclohexanol selectivity is 18.3%, the cyclohexanone selectivity is 7.7%, the cyclohexyl hydroperoxide selectivity is 64%, the glutaric acid selectivity is 4%, and the adipic acid selectivity is 6%.
Example 16
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 16.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.81%, the cyclohexanol selectivity is 8%, the cyclohexanone selectivity is 5%, the cyclohexyl hydroperoxide selectivity is 70%, the glutaric acid selectivity is 7%, and the adipic acid selectivity is 10%.
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 24.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. Using acetone as solvent, and mixing the obtained reaction mixtureThe volume is 100 mL. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.04%, the cyclohexanol selectivity is 6%, the cyclohexanone selectivity is 4%, the cyclohexyl hydroperoxide selectivity is 71%, the glutaric acid selectivity is 6%, and the adipic acid selectivity is 13%.
Example 18
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (0.10MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 1.91%, cyclohexanol selectivity 22%, cyclohexanone selectivity 10%, cyclohexyl hydroperoxide selectivity 63%, glutaric acid selectivity 5%.
Example 19
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (0.30MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.28%, the cyclohexanol selectivity is 30%, the cyclohexanone selectivity is 22%, the cyclohexyl hydroperoxide selectivity is 42%, and the glutaric acid selectivity is 6%.
Example 20
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (0.90MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 4.84%, the cyclohexanol selectivity is 32%, the cyclohexanone selectivity is 11%, the cyclohexyl hydroperoxide selectivity is 50%, and the glutaric acid selectivity is 7%.
Example 21
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.50MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 4.77%, the cyclohexanol selectivity is 27%, the cyclohexanone selectivity is 5%, the cyclohexyl hydroperoxide selectivity is 59%, and the glutaric acid selectivity is 9%.
Example 22
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (2.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After the reaction is finished, cooling to the roomTo the reaction mixture was added 1.3115g (5.00mmol) of triphenylphosphine (PPh) warm3) The resulting peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.48%, the cyclohexanol selectivity is 27%, the cyclohexanone selectivity is 5%, the cyclohexyl hydroperoxide selectivity is 55%, the glutaric acid selectivity is 5%, and the adipic acid selectivity is 8%.
Example 23
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0002g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 2.7%, cyclohexanol selectivity 70%, cyclohexanone selectivity 14%, cyclohexyl hydroperoxide selectivity 16%, no formation of glutaric acid was detected.
Example 24
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.00002g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Transferring 10mL of the obtained solution, performing gas chromatography with toluene as an internal standard, transferring 10mL of the obtained solution, performing gas chromatography with benzoic acid as an internal standard, and addingAnd (5) performing liquid chromatography analysis. Cyclohexane conversion 1.8%, cyclohexanol selectivity 73%, cyclohexanone selectivity 16%, cyclohexyl hydroperoxide selectivity 11%, no formation of glutaric acid was detected.
Example 25
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0200g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 6.68%, the cyclohexanol selectivity was 73%, the cyclohexanone selectivity was 10%, the cyclohexyl hydroperoxide selectivity was 17%, and the formation of glutaric acid was not detected.
Example 26
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0100g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 6.94%, the cyclohexanol selectivity was 69%, the cyclohexanone selectivity was 12%, the cyclohexyl hydroperoxide selectivity was 19%, and the formation of glutaric acid was not detected.
Example 27
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0020g MOFs PCN-224(Mn) and 0.0002g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 3.58%, the cyclohexanol selectivity was 64%, the cyclohexanone selectivity was 16%, the cyclohexyl hydroperoxide selectivity was 20%, and no glutaric acid formation was detected.
Example 28
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.00002g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 2.9%, cyclohexanol selectivity 61%, cyclohexanone selectivity 20%, cyclohexyl hydroperoxide selectivity 19%, no formation of glutaric acid was detected.
Example 29
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0020g MOFs PCN-224(Mn) and 0.0200g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min.The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 6.86%, the cyclohexanol selectivity was 69%, the cyclohexanone selectivity was 23%, the cyclohexyl hydroperoxide selectivity was 8%, and the formation of glutaric acid was not detected.
Example 30
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0100g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion was 6.83%, the cyclohexanol selectivity was 77%, the cyclohexanone selectivity was 12%, the cyclohexyl hydroperoxide selectivity was 11%, and the formation of glutaric acid was not detected.
Example 31
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and air (1.0MPa) was blown in. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion rate of 0.9%, cyclohexanol selectivity of 44%, cyclohexanone selectivity of 36%, cyclohexyl hydroperoxide selectivity of 20%, undetectedTo glutaric acid formation.
Example 32
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (NO)3)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 4.8%, cyclohexanol selectivity 51%, cyclohexanone selectivity 33%, cyclohexyl hydroperoxide selectivity 16%, no formation of glutaric acid was detected.
Example 33
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g ZnSO4Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 4.3%, cyclohexanol selectivity 67%, cyclohexanone selectivity 18%, cyclohexyl hydroperoxide selectivity 15%, no formation of glutaric acid was detected.
Example 34
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g ZnCl2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. At 120 deg.CThe reaction was stirred at 800rpm for 8.0 h. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 4.6%, cyclohexanol selectivity 64%, cyclohexanone selectivity 17%, cyclohexyl hydroperoxide selectivity 19%, no formation of glutaric acid was detected.
Example 35
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 14.0260g (200mmol) of cyclopentane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The conversion rate of cyclopentane was 2.60%, the selectivity for cyclopentanol was 36.5%, the selectivity for cyclopentanone was 38.1%, the selectivity for cyclopentyl hydroperoxide was 22.3%, the selectivity for glutaric acid was 2.5%, and the selectivity for succinic acid was 0.6%.
Example 36
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 19.6380g (200mmol) of cycloheptane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution was removed, and gas chromatography was performed using toluene as an internal standardAnd (4) performing spectrum analysis, namely transferring 10mL of the obtained solution, and performing liquid chromatography analysis by using benzoic acid as an internal standard. The conversion rate of cycloheptane is 13.5 percent, the selectivity of cycloheptanol is 11.9 percent, the selectivity of cycloheptanone is 56.1 percent, the selectivity of cycloheptyl hydroperoxide is 28.1 percent, the selectivity of pimelic acid is 3.1 percent, and the selectivity of adipic acid is 0.8 percent.
Example 37
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 22.4340g (200mmol) of cyclooctane, stirred and heated to 120 ℃, and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The conversion rate of cyclooctane is 16.8 percent, the selectivity of cyclooctanol is 32.1 percent, the selectivity of cyclooctanone is 45.2 percent, the selectivity of cyclooctyl hydrogen peroxide is 19.9 percent, the selectivity of suberic acid is 2.20 percent, and the selectivity of pimelic acid is 0.60 percent.
Example 38
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 25.2340g (200mmol) of cyclononane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The conversion rate of cyclononane is 20.7 percent, the selectivity of cyclononanol is 19.4 percent, the selectivity of cyclononanone is 58.5 percent, the selectivity of cyclononyl hydrogen peroxide is 22.1 percent, and the generation of azelaic acid and suberic acid is not detected.
Example 39
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 28.034g (200mmol) of cyclodecane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclodecane conversion rate was 22.4%, the cyclodecanol selectivity was 19.2%, the cyclodecanone selectivity was 57.6%, and the cyclodecyl hydrogen peroxide selectivity was 23.2%, and the formation of sebacic acid and azelaic acid was not detected.
Example 40
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0020g MOFs PCN-224(Mn) and 0.0020g Zn (OAc)2Dispersed in 33.6640g (200mmol) of cyclododecane, stirred and warmed to 120 ℃ and oxygen (1.0MPa) was passed in. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The conversion rate of cyclododecane was 25.3%, the selectivity for cyclododecanol was 18.1%, the selectivity for cyclododecanone was 58.2%, and the selectivity for cyclododecyl hydroperoxide was 23.7%, and the formation of undecanedioic acid and dodecanedioic acid was not detected.
Example 41 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner liner, 0.0020g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. At 120 deg.CThe reaction was stirred at 800rpm for 8.0 h. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate was 2.8%, the cyclohexanol selectivity was 28.6%, the cyclohexanone selectivity was 21.7%, and the cyclohexyl hydroperoxide selectivity was 49.7%, and formation of glutaric acid and adipic acid was not detected.
Example 42 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0002g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate was 1.4%, the cyclohexanol selectivity was 24.7%, the cyclohexanone selectivity was 23.6%, and the cyclohexyl hydroperoxide selectivity was 51.7%, and formation of glutaric acid and adipic acid was not detected.
Example 43 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.00002g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Transferring 10mL of the obtained solution, performing gas chromatography with toluene as an internal standard, and transferring10mL of the resulting solution was analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 0.7%, the cyclohexanol selectivity was 20.4%, the cyclohexanone selectivity was 28.4%, and the cyclohexyl hydroperoxide selectivity was 51.2%, and formation of glutaric acid and adipic acid was not detected.
Example 44 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.0200g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate was 3.4%, the cyclohexanol selectivity was 20.4%, the cyclohexanone selectivity was 31.2%, and the cyclohexyl hydroperoxide selectivity was 48.4%, and formation of glutaric acid and adipic acid was not detected.
Example 45 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner liner, 0.0100g Zn (OAc)2Dispersed in 16.8320g (200mmol) of cyclohexane, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate was 4.5%, the cyclohexanol selectivity was 18%, the cyclohexanone selectivity was 36%, the cyclohexyl hydroperoxide selectivity was 46%, and the formation of glutaric acid and adipic acid was not detected.
Example 46 (comparative experiment)
0.0020g of MOFs PCN-224(Mn) was dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a Teflon liner, the temperature was raised to 120 ℃ with stirring, and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. Cyclohexane conversion 4.01%, cyclohexanol selectivity 40.9%, cyclohexanone selectivity 39.9%, cyclohexyl hydroperoxide selectivity 9.6%, glutaric acid selectivity 1.7%, adipic acid selectivity 7.9%.
Example 47 (comparative experiment)
0.0002g of MOFs PCN-224(Mn) was dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, the temperature was raised to 120 ℃ with stirring, and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate was 1.5%, the cyclohexanol selectivity was 43.4%, the cyclohexanone selectivity was 38.9%, and the cyclohexyl hydroperoxide selectivity was 17.7%, and formation of glutaric acid and adipic acid was not detected.
Example 48 (comparative experiment)
0.0100g of MOFs PCN-224(Mn) is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, the temperature is raised to 120 ℃ by stirring, and oxygen (1.0MPa) is introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.19%, the cyclohexanol selectivity is 41.3%, the cyclohexanone selectivity is 41.0%, the cyclohexyl hydroperoxide selectivity is 12.9%, the glutaric acid selectivity is 0.5%, and the adipic acid selectivity is 4.3%.
Example 49 (comparative experiment)
0.0020g of 5,10,15, 20-tetracarboxyphenylporphyrin manganese (II) was dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave with a Teflon liner, stirred and heated to 120 ℃ and oxygen (1.0MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 120 ℃. After completion of the reaction, it was cooled to room temperature, 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 40 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed, and gas chromatography was performed using toluene as an internal standard, and 10mL of the resulting solution was removed, and liquid chromatography was performed using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.19%, the cyclohexanol selectivity is 36.3%, the cyclohexanone selectivity is 45.2%, the cyclohexyl hydroperoxide selectivity is 13.3%, the glutaric acid selectivity is 0.8%, and the adipic acid selectivity is 4.4%.
Example 50 (amplification experiment)
In a 500mL reactor, 0.0020g of MOF PCN-224(Mn) -m and 0.0020g of Zn (OAc)2Dispersing in 168.320g (2000mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.115g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. 155.78g of cyclohexane was recovered by distillation. The cyclohexane conversion rate is 7.45 percent, and the selectivity of 9.28g of cyclohexanol is 74 percent by decompression and rectification, and the selectivity of 2.30g of cyclohexanone is 18.34 percent.
Example 51 (amplification experiment)
In a 500mL reactor, 0.0020g MOF PCN-224(Mn) -p and 0.0020g Zn (OAc)2Dispersing in 168.320g (2000mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.115g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. 154.78g of cyclohexane was recovered by distillation. The cyclohexane conversion rate is 7.54 percent, and the pressure reduction and rectification are carried out to obtain 10.03g of cyclohexanol with the cyclohexanol selectivity of 74.08 percent and obtain 3.36g of cyclohexanone with the cyclohexanone selectivity of 24.82 percent.
Example 52 (amplification experiment)
In a 500mL reactor, 0.0020g of MOF PCN-224(Mn) -d and 0.0020g of Zn (OAc)2Dispersing in 168.320g (2000mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.115g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. 156.55g of cyclohexane was recovered by distillation. The cyclohexane conversion rate is 7.00 percent, and the pressure reduction and rectification are carried out to obtain 8.83g of cyclohexanol with the cyclohexanol selectivity of 75.58 percent and obtain 2.06g of cyclohexanone with the cyclohexanone selectivity of 17.49 percent.
Claims (8)
1. A method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt, characterized in that it comprises the following steps:
dispersing metalloporphyrin MOFs PCN-224(Mn) and Zn (II) salt in cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-224(Mn) is 0.001% -5% of the mass of the cycloalkane, and g/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 metalloporphyrin MOFs PCN-224(Mn) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
the Zn (II) salt is Zn (OAc)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 process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Mn)/zn (ii) salts according to claim 1, wherein the catalyst is a binary combination of metalloporphyrin MOFs PCN-224(Mn) and zn (ii) salts.
3. The method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt according to claim 1 or 2, wherein the ratio of the mass of the metalloporphyrin MOFs PCN-224(Mn) to the mass of cycloalkanes is 1: 10000 to 1: 100.
4. The method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt according to claim 1 or 2, wherein the mass ratio of Zn (II) salt to cycloalkanes is 1: 1000 to 1: 100.
5. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salts according to claim 1 or 2, wherein the reaction pressure is 0.10-2.0 MPa.
6. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salts according to claim 1 or 2, wherein the stirring speed is 600-1200 rpm.
7. The process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts MOFs PCN-224(Mn)/zn (ii) according to claim 1 or 2, wherein the oxidant is oxygen, air or a mixture thereof in any proportion.
8. The process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts MOFs PCN-224(Mn)/zn (ii) 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 under reduced pressure and recrystallized to obtain an oxidation product.
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