CN112108186A - Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt - Google Patents
Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt Download PDFInfo
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- 150000001924 cycloalkanes Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 29
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title abstract description 9
- 230000002195 synergetic effect Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 185
- 238000003756 stirring Methods 0.000 claims abstract description 92
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000007789 sealing Methods 0.000 claims abstract description 41
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002576 ketones Chemical class 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 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 86
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 82
- 239000001301 oxygen Substances 0.000 claims description 82
- 229910052760 oxygen Inorganic materials 0.000 claims description 82
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 74
- 150000002978 peroxides Chemical class 0.000 claims description 44
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 12
- 230000002153 concerted effect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004914 cyclooctane Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 119
- 239000011541 reaction mixture Substances 0.000 description 116
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 86
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 86
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 72
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 72
- -1 cycloalkyl hydroperoxide Chemical compound 0.000 description 47
- 239000005711 Benzoic acid Substances 0.000 description 43
- 235000010233 benzoic acid Nutrition 0.000 description 43
- 238000004458 analytical method Methods 0.000 description 40
- 238000004817 gas chromatography Methods 0.000 description 40
- 239000002904 solvent Substances 0.000 description 40
- 229910001220 stainless steel Inorganic materials 0.000 description 40
- 239000010935 stainless steel Substances 0.000 description 40
- 239000005457 ice water Substances 0.000 description 39
- 238000004811 liquid chromatography Methods 0.000 description 39
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 description 39
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 36
- 239000001361 adipic acid Substances 0.000 description 36
- 235000011037 adipic acid Nutrition 0.000 description 36
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 36
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 35
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 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
- 238000004587 chromatography analysis Methods 0.000 description 2
- 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 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-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
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPHZOCJETVZYTP-UHFFFAOYSA-N hydroperoxycyclododecane Chemical compound OOC1CCCCCCCCCCC1 GPHZOCJETVZYTP-UHFFFAOYSA-N 0.000 description 1
- GRLDKEKHXHSXQW-UHFFFAOYSA-N hydroperoxycycloheptane Chemical compound OOC1CCCCCC1 GRLDKEKHXHSXQW-UHFFFAOYSA-N 0.000 description 1
- DTMZBUVZQPKYDT-UHFFFAOYSA-N hydroperoxycyclooctane Chemical compound OOC1CCCCCCC1 DTMZBUVZQPKYDT-UHFFFAOYSA-N 0.000 description 1
- VGGFAUSJLGBJRZ-UHFFFAOYSA-N hydroperoxycyclopentane Chemical compound OOC1CCCC1 VGGFAUSJLGBJRZ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 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
- 238000001953 recrystallisation Methods 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
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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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
- 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]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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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
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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
- C07C45/27—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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- 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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- 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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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Abstract
A method for oxidizing cycloalkane under the synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt comprises the steps of dispersing PCN-224(Co) (0.001% -10%, g/mol) and Cu (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 the product, namely, cycloalkanol and cycloalkanone. 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 oxidizing cycloalkane under the concerted catalysis of metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt, belonging to the field of industrial catalysis and fine organic synthesis.
Background
Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important intermediates in fine chemical industry, and are widely used in synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins, and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, 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 Communications2019,132: 105809). The main sources of the above problems are: (1) at present, O is industrially used2Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled2The free radical diffusion in the process of catalytically oxidizing cycloalkane and the catalytic conversion of the intermediate product cycloalkyl hydroperoxide are beneficial to the improvement of the catalytic oxidation selectivity of cycloalkane, and the method is one of the fields of catalytic oxidation of cycloalkane in industryIs novel and has great application significance.
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, Cu (II) can catalyze the decomposition and conversion of naphthenic base hydrogen peroxide which is an intermediate product of oxidation of naphthenic hydrocarbon, prevent the non-selective thermal decomposition and conversion of the naphthenic base hydrogen peroxide and improve the selectivity of catalytic oxidation of the naphthenic hydrocarbon (Catalysis communications2019,132: 105809).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by synergistically catalyzing and oxidizing cycloalkane with metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt, wherein the metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt is used 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(Co)/Cu (II) salt, said method comprising the following steps:
dispersing metalloporphyrin MOFs PCN-224(Co and Cu (II)) salt in cycloalkane, wherein the mass of the metalloporphyrin MOFs PCN-224(Co) is 0.001% -10% of that of the cycloalkane, and the mass of the Cu (II) salt is 0.01% -10% of that of the cycloalkane, sealing the reaction system, heating to 90-150 ℃ under stirring○C, introducing an oxidizing agent and protectingStirring and reacting for 2.0-24.0 h at a set temperature and pressure, and then carrying out post-treatment on reaction liquid to obtain a product, namely cycloalkyl alcohol and cycloalkyl ketone;
the metalloporphyrin MOFs PCN-224(Co) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
the Cu (II) salt is Cu (CH)3COO)2，Cu(NO3)2，CuSO4，CuCl2And hydrate thereof, preferably anhydrous Cu (CH)3COO)2；
The cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of at least two of the above materials in any proportion.
Further, the ratio of the mass of the metalloporphyrin MOFs PCN-224(Co) to the amount of substances of the cycloalkane is 1: 100000-1: 10, preferably 1: 10000-1: 10.
The mass ratio of the Cu (II) salt to the cycloalkane is 1: 10000-1: 10, preferably 1: 1000-1: 10.
The reaction temperature is 90-150 DEG C○C, preferably 100 to 130○C; 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 solution3The dosage of the catalyst is 3 percent of the amount of cyclane substances, and the catalyst is used at room temperature (20-30 percent)○C) Stirring for 40min to reduce the generated peroxide, distilling the crude product,and (4) carrying out reduced pressure rectification and recrystallization 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; performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid;
the invention constructs a binary catalytic system by using metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt to synergistically catalyze O2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the cycloalkane not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product naphthenic hydrogen peroxide, greatly improves the selectivity of the target product naphthenic alcohol and naphthenic ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing naphthenic alcohol and naphthenic ketone by efficiently and selectively oxidizing naphthenic C-H bonds, but also has certain reference value for efficiently preparing alcohol and ketone compounds by selectively catalyzing and oxidizing other hydrocarbon C-H bonds.
The invention has the following beneficial effects: the method for synthesizing the naphthenic alcohol and the naphthenic ketone by the synergistic catalytic oxidation of the metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt 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(Co) used in the present invention are all referred to Journal of the American Chemical Society 2017,139: 18590-18597; journal of the American Chemical Society 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 (Co).
Examples 4 to 36 are examples of catalytic oxidation of cycloalkanes.
Examples 37 to 42 are comparative experimental cases of catalytic oxidation of cycloalkanes.
Example 43 is a catalytic oxidation scale-up experimental case for cycloalkanes.
Example 1
(0.0847g,0.1mmol) T (4-COOH) PPCo (II), (0.1864g,0.8mmol) ZrCl was placed in a 35mL pressure tube42.4421g (20.0mmol) of benzoic acid is dissolved in 10mL of DMF, ultrasonic treatment is carried out for 10min to assist the dissolution, the temperature of a pressure-resistant tube is raised from room temperature to 120 ℃ in a constant-temperature oven, the reaction is carried out for 72.0h at the temperature, and brick-red solid is generated on the inner wall of the tube. And (3) turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower-layer solid, washing the solid by using N, N dimethylformamide (5X 6mL) and acetone (5X 6mL) respectively, taking the lower-layer brick-red solid, and drying the lower-layer brick-red solid at 60 ℃ for 8.0h to obtain 0.0312g of the target product PCN-224-p.
Example 2
(0.0847g,0.1mmol) T (3-COOH) PPCo (II), (0.1864g,0.8mmol) ZrCl was placed in a 35mL pressure tube42.4421g (20.0mmol) of benzoic acid is dissolved in 10mL of DMF, ultrasonic treatment is carried out for 10min to assist the dissolution, the temperature of a pressure-resistant tube is raised from room temperature to 120 ℃ in a constant-temperature oven, the reaction is carried out for 72.0h at the temperature, and brick-red solid is generated on the inner wall of the tube. And (3) turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower-layer solid, washing the solid by respectively using N, N dimethylformamide (5X 6mL) and acetone (5X 6mL), taking the lower-layer brick-red solid, and drying the lower-layer brick-red solid at 60 ℃ for 8.0h to obtain 0.0211g of a target product PCN-224-m.
Example 3
In a 35mL pressure tube, (0.1152g,0.1mmol) [ T (4- (4-COOH) P) PPCo (II) ]]，(0.1864g,0.8mmol)ZrCl42.4421g (20.0mmol) of benzoic acid is dissolved in 10.0mL of DMF, ultrasonic treatment is carried out for 10.0min to assist the dissolution, the temperature of a pressure-resistant pipe is raised from room temperature to 120 ℃ in a constant-temperature oven, the reaction is carried out for 72.0h at the temperature, and brick-red solid is generated on the inner wall of the pipe. Turning off heating, naturally cooling to room temperature, transferring the crude product to a 10mL centrifuge tube, centrifuging the crude product for 5min at 4000rpm of a centrifuge, taking the lower layer solid, washing the solid with N, N dimethylformamide (5X 6mL) and acetone (5X 6mL) respectively, taking the lower layer brick-red solid, and drying at 60 ℃ for 8.0h to obtain 0.0120g of the target product PCN-224-d.
Example 4
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.000002g PCN-224-d (Co) and 0.00399g (0.02mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.12%, cyclohexanol selectivity 35%, cyclohexanone selectivity 31%, cyclohexyl hydroperoxide selectivity 34%, no detectable formation of adipic acid and glutaric acid.
Example 5
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.00002g PCN-224-d (Co) and 0.00399g (0.02mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Move and get 10mPerforming gas chromatography analysis on the solution obtained by the step L by taking methylbenzene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.59%, cyclohexanol selectivity 33%, cyclohexanone selectivity 33%, cyclohexyl hydroperoxide selectivity 34%, no formation of adipic acid and glutaric acid was detected.
Example 6
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.00399g (0.02mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 5.45%, the cyclohexanol selectivity was 49%, the cyclohexanone selectivity was 42%, the cyclohexyl hydroperoxide selectivity was 7%, the adipic acid selectivity was 2%, and no formation of glutaric acid was detected.
Example 7
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0180g PCN-224-d (Co) and 0.00399g (0.02mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.67%, cyclohexaneThe alcohol selectivity was 52%, the cyclohexanone selectivity was 40%, the cyclohexyl hydroperoxide selectivity was 6%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 8
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0200g PCN-224-d (Co) and 0.00399g (0.02mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.83%, cyclohexanol selectivity 51%, cyclohexanone selectivity 40%, cyclohexyl hydroperoxide selectivity 7%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 9
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.0399g (0.20mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.55%, cyclohexanol selectivity 49%, cyclohexanone selectivity 40%, cyclohexyl hydroperoxide selectivity 7%, adipic acid selectivity 4%, and no formation of glutaric acid was detected.
Example 10
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.64%, the cyclohexanol selectivity was 49%, the cyclohexanone selectivity was 48%, the cyclohexyl hydroperoxide selectivity was 2%, the adipic acid selectivity was 1%, and the formation of glutaric acid was not detected.
Example 11
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 3.9930g (20.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 7.66%, the cyclohexanol selectivity was 48%, the cyclohexanone selectivity was 42%, the cyclohexyl hydroperoxide selectivity was 5%, the adipic acid selectivity was 5%, and the formation of glutaric acid was not detected.
Example 12
0.0140g of PCN-224-d (Co) and 0.3 g of PCN-224-d (Co) were placed in a 100mL stainless steel autoclave having a Teflon liner993g(2.0mmol)Cu(CH3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 100 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.09%, cyclohexanol selectivity 36%, cyclohexanone selectivity 29%, cyclohexyl hydroperoxide selectivity 33%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 13
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 110 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 110 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 2.21%, the cyclohexanol selectivity was 45%, the cyclohexanone selectivity was 30%, the cyclohexyl hydroperoxide selectivity was 22%, the adipic acid selectivity was 3%, and the formation of glutaric acid was not detected.
Example 14
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 90 ℃, and introducing oxygen to 1.0 MPa. At 120 deg.CStirring and reacting at 800rpm for 8.0h under the oxygen pressure of 1.0 MPa. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.56%, cyclohexanol selectivity 26%, cyclohexanone selectivity 22%, cyclohexyl hydroperoxide selectivity 52%, no detectable formation of adipic acid and glutaric acid.
Example 15
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 130 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 9.12%, the cyclohexanol selectivity is 36%, the cyclohexanone selectivity is 40%, the cyclohexyl hydroperoxide selectivity is 7%, the adipic acid selectivity is 11%, and the glutaric acid selectivity is 6%.
Example 16
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 150 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 150 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) Stirring at room temperatureThe generated peroxide was reduced for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 15.94%, the cyclohexanol selectivity is 24%, the cyclohexanone selectivity is 46%, the cyclohexyl hydroperoxide selectivity is 8%, the adipic acid selectivity is 15%, and the glutaric acid selectivity is 7%.
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 0.1 MPa. Stirring and reacting at 120 ℃ and 0.1MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.75%, cyclohexanol selectivity 27%, cyclohexanone selectivity 26%, cyclohexyl hydroperoxide selectivity 47%, no formation of adipic acid and glutaric acid was detected.
Example 18
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 0.6 MPa. Stirring and reacting at 120 ℃ and 0.6MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; moving and taking 10mL of the resulting solution was analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.81%, cyclohexanol selectivity 46%, cyclohexanone selectivity 47%, cyclohexyl hydroperoxide selectivity 5%, adipic acid selectivity 2%, and no formation of glutaric acid was detected.
Example 19
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 8.69%, the cyclohexanol selectivity was 44%, the cyclohexanone selectivity was 47%, the cyclohexyl hydroperoxide selectivity was 7%, the adipic acid selectivity was 2%, and no formation of glutaric acid was detected.
Example 20
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.4 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.4MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 8.72%, cyclohexanol selectivity 43%, cyclohexanone selectivity 49%, cyclohexyl peroxyThe hydrogen selectivity was 6% and the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 21
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.6 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.6MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 8.77%, the cyclohexanol selectivity was 41%, the cyclohexanone selectivity was 52%, the cyclohexyl hydroperoxide selectivity was 5%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 22
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 2.0 MPa. Stirring and reacting at 120 ℃ and 2.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.84%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 55%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 23
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 7.47%, the cyclohexanol selectivity was 47%, the cyclohexanone selectivity was 42%, the cyclohexyl hydroperoxide selectivity was 9%, the adipic acid selectivity was 2%, and no formation of glutaric acid was detected.
Example 24
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 900rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.66%, the cyclohexanol selectivity was 45%, the cyclohexanone selectivity was 49%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 25
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersed in 16.8320g(200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 1200rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 8.79%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 55%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 26
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 2.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.39%, cyclohexanol selectivity 29%, cyclohexanone selectivity 30%, cyclohexyl hydroperoxide selectivity 41%, no detectable formation of adipic acid and glutaric acid.
Example 27
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 6.0h at 800 rpm. After the reaction is finished, cooling with ice waterTo the reaction mixture was added 1.3115g (5.00mmol) of triphenylphosphine (PPh) to room temperature3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 5.31%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 45%, the cyclohexyl hydroperoxide selectivity was 15%, the adipic acid selectivity was 1%, and the formation of glutaric acid was not detected.
Example 28
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 10.94%, the cyclohexanol selectivity is 35%, the cyclohexanone selectivity is 49%, the cyclohexyl hydroperoxide selectivity is 5%, the adipic acid selectivity is 9%, and the glutaric acid selectivity is 2%.
Example 29
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) cyclohexane, sealing the reaction kettle, stirring and heating to 120 ℃, and introducing oxygen to 1.0 MPa. The reaction was stirred at 800rpm for 24.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Using acetone as solvent, and mixing the obtained productThe reaction mixture was brought to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 16.43%, the cyclohexanol selectivity is 31%, the cyclohexanone selectivity is 32%, the cyclohexyl hydroperoxide selectivity is 4%, the adipic acid selectivity is 23%, and the glutaric acid selectivity is 10%.
Example 30
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, stirred and heated to 120 ℃, and air is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa air pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 3.33%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 36%, the cyclohexyl hydroperoxide selectivity was 23%, the adipic acid selectivity was 2%, and no formation of glutaric acid was detected.
Example 31
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-p (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and subjected to liquid phase chromatography using benzoic acid as an internal standardAnd (4) performing chromatographic analysis. The cyclohexane conversion rate was 8.12%, the cyclohexanol selectivity was 49%, the cyclohexanone selectivity was 45%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 32
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-m (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion was 7.87%, the cyclohexanol selectivity was 50%, the cyclohexanone selectivity was 44%, the cyclohexyl hydroperoxide selectivity was 4%, the adipic acid selectivity was 2%, and the formation of glutaric acid was not detected.
Example 33
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 14.0260g (200mmol) of cyclopentane, 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. 4.57% of cyclopentane conversion, 49% of cyclopentanol selectivity, 47% of cyclopentanone selectivity, 3% of cyclopentyl hydroperoxide selectivity, 1% of glutaric acid selectivity, and no detectionThe formation of succinic acid was measured.
Example 34
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 19.6380g (200mmol) of cycloheptane, 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 25.32 percent, the selectivity of cycloheptanol is 49 percent, the selectivity of cycloheptanone is 47 percent, the selectivity of cycloheptyl hydroperoxide is 3 percent, the selectivity of pimelic acid is 1 percent, and the generation of adipic acid is not detected.
Example 35
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0140g PCN-224-d (Co) and 0.3993g (2.0mmol) Cu (CH)3COO)2Dispersing in 22.4440g (200mmol) of cyclooctane, sealing the reaction kettle, stirring, 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclooctane is 32.29 percent, the selectivity of cyclooctanol is 50 percent, the selectivity of cyclooctanone is 47 percent, the selectivity of cyclooctyl hydrogen peroxide is 2 percent, the selectivity of suberic acid is 1 percent, and the generation of pimelic acid is not detected.
Example 36
In 100mL stainless steel height with polytetrafluoroethylene inner containerIn a autoclave, 0.0140g of PCN-224-d (Co) and 0.3993g (2.0mmol) of Cu (CH)3COO)2Dispersing in 16.8451g (100.0mmol) of cyclododecane, 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 34.64%, the selectivity for cyclododecanol was 49%, the selectivity for cyclododecanone was 47%, and the selectivity for cyclododecyl hydroperoxide was 4%, and no formation of acid was detected.
Example 37
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0029g [ T (4- (4-COOMe) P) PPCo (II) ]]Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.54%, the cyclohexanol selectivity is 40%, the cyclohexanone selectivity is 39%, the cyclohexyl hydroperoxide selectivity is 5%, the adipic acid selectivity is 10%, and the glutaric acid selectivity is 6%.
Example 38
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0027g [ T (4- (4-COOH) P) PPCo (II) ]]Dispersing in 16.8320g (200mmol) 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. Reaction ofAfter completion, the ice water 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 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.61%, cyclohexanol selectivity 26%, cyclohexanone selectivity 19%, cyclohexyl hydroperoxide selectivity 49%, adipic acid selectivity 6%, no formation of glutaric acid was detected.
Example 39
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.3993g (2.0mmol) of Cu (CH)3COO)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.97%, the cyclohexanol selectivity is 31%, the cyclohexanone selectivity is 34%, the cyclohexyl hydroperoxide selectivity is 20%, the adipic acid selectivity is 11%, and the glutaric acid selectivity is 4%.
Example 40
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.3751g (2.0mmol) Cu (NO)3)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Taking acetone as a solvent, and fixing the volume of the obtained reaction mixture to 100mL.10 mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.83%, the cyclohexanol selectivity is 33%, the cyclohexanone selectivity is 34%, the cyclohexyl hydroperoxide selectivity is 18%, the adipic acid selectivity is 11%, and the glutaric acid selectivity is 4%.
EXAMPLE 41
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.2689g (2.0mmol) Cu (Cl)2Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.71%, the cyclohexanol selectivity is 34%, the cyclohexanone selectivity is 32%, the cyclohexyl hydroperoxide selectivity is 20%, the adipic acid selectivity is 11%, and the glutaric acid selectivity is 3%.
Example 42
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.3192g (2.0mmol) of CuSO was charged4Dispersing in 16.8320g (200mmol) 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, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 2.41%, cyclohexanol selectivity 29%, cyclohexanone selectivity 29%, cyclohexyl hydroperoxideThe selectivity is 25%, the selectivity for adipic acid is 12% and the selectivity for glutaric acid is 5%.
Example 43
In a 1.00L stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.1200g of PCN-224-d (Co) and 3.9930g (2.0mmol) of Cu (CH)3COO)2Dispersing in 168.32g (2.00mol) 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 13.1145g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Distilling, recovering 154.89g of cyclohexane, and obtaining a conversion rate of 7.98%; vacuum rectification is carried out to obtain 6.4473g of cyclohexanol with selectivity of 48 percent, 6.3130g of cyclohexanone with selectivity of 47 percent.
Claims (8)
1. A method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt, characterized in that it comprises the following steps:
dispersing metalloporphyrin MOFs PCN-224(Co) (0.001% -10%, g/mol) and Cu (II) salt (0.01% -10%, mol/mol) in cycloalkane, wherein the metalloporphyrin MOFs PCN-224(Co) is 0.001% -10%, g/mol, the Cu (II) salt is 0.01% -10%, mol/mol, sealing the reaction system, heating to 90-150% under stirring○C, introducing an oxidant, keeping the set temperature and pressure, stirring and reacting for 2.0-24.0 hours, and then carrying out post-treatment on the reaction liquid to obtain a product, namely the naphthenic alcohol and the naphthenic ketone;
the metalloporphyrin MOFs PCN-224(Co) contains at least one metalloporphyrin unit of compounds shown in a formula (I), a formula (II) and a formula (III):
the Cu (II) salt is Cu (CH)3COO)2，Cu(NO3)2，CuSO4，CuCl2And hydrate thereof in any ratio of one or at least twoThe mixtures of examples;
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(Co)/cu (ii) salts according to claim 1 or 2, wherein the catalyst is a binary combination of metalloporphyrin MOFs PCN-224(Co) and cu (ii) salts.
3. The method for the concerted catalytic oxidation of cycloalkanes by a metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt according to claim 1 or 2, wherein the ratio of the mass of the metalloporphyrin MOFs PCN-224(Co) to the amount of cycloalkanes is 1: 100000 to 1: 10.
4. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt according to claim 1 or 2, wherein the mass ratio of Cu (II) salt to cycloalkanes is 1: 10000 to 1: 10.
5. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/Cu (II) salts according to claim 1 or 2, wherein the reaction temperature is 90-150%○C。
6. The method for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin MOFs PCN-224(Co)/Cu (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(Co)/cu (ii), according to claim 1 or 2, wherein said oxidant is oxygen, air or a mixture thereof in any proportion.
8. A process for the concerted catalytic oxidation of cycloalkanes with metalloporphyrin salts, MOFs PCN-224(Co)/Cu (II) according to claim 1 or 2,the post-processing method is characterized by comprising the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3The dosage of the catalyst is 3 percent of the amount of cyclane substances, and the catalyst is used at room temperature (20-30 percent)○C) Stirring for 40min to reduce the generated peroxide, distilling the crude product, vacuum rectifying and recrystallizing to obtain the oxidation product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717394A (en) * | 2021-08-26 | 2021-11-30 | 浙江工业大学 | End-capped 3D cobalt (II) porphyrin POF material and preparation method and application thereof |
| CN113717394B (en) * | 2021-08-26 | 2022-06-03 | 浙江工业大学 | End-capped 3D cobalt (II) porphyrin POF material and preparation method and application thereof |
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