CN112094214A - Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with nickel (II) porphyrin - Google Patents
Method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene with nickel (II) porphyrin Download PDFInfo
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- cumene
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 286
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 24
- BOTFKXVKNMDNDU-UHFFFAOYSA-N [Ni+2].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni+2].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 BOTFKXVKNMDNDU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 243
- 238000003756 stirring Methods 0.000 claims abstract description 109
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 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 110
- 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 23
- -1 methoxy, ethoxy, methyl Chemical group 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- CPJYUIYADJEPIO-UHFFFAOYSA-N C1=CC(Cl)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(Cl)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 CPJYUIYADJEPIO-UHFFFAOYSA-N 0.000 claims description 2
- XOZLUUILAFJRBF-UHFFFAOYSA-N ClC1=C(C=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound ClC1=C(C=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 XOZLUUILAFJRBF-UHFFFAOYSA-N 0.000 claims description 2
- VURVIMUXEPAEQH-UHFFFAOYSA-N ClC=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound ClC=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 VURVIMUXEPAEQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- NVCZKUSRWBBGAH-UHFFFAOYSA-N methyl 4-[10,15,20-tris(4-methoxycarbonylphenyl)-21,23-dihydroporphyrin-5-yl]benzoate Chemical compound COC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(=O)OC)c2ccc([nH]2)c(-c2ccc(cc2)C(=O)OC)c2ccc(n2)c(-c2ccc(cc2)C(=O)OC)c2ccc1[nH]2 NVCZKUSRWBBGAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 110
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 106
- 239000011541 reaction mixture Substances 0.000 description 102
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 100
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 100
- 239000000243 solution Substances 0.000 description 55
- 239000002904 solvent Substances 0.000 description 54
- 238000004817 gas chromatography Methods 0.000 description 53
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 50
- 239000005711 Benzoic acid Substances 0.000 description 50
- 235000010233 benzoic acid Nutrition 0.000 description 50
- XGSJPOKDEMPNAI-UHFFFAOYSA-N [Ni+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Ni+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 XGSJPOKDEMPNAI-UHFFFAOYSA-N 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- FNZPTIBLKWIZMS-UHFFFAOYSA-N ClC(C(C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1)=C1Cl)=CC=C1Cl Chemical compound ClC(C(C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1)=C1Cl)=CC=C1Cl FNZPTIBLKWIZMS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000004032 porphyrins Chemical class 0.000 description 4
- 241000510672 Cuminum Species 0.000 description 3
- 235000007129 Cuminum cyminum Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- SGJUFIMCHSLMRJ-UHFFFAOYSA-N 2-hydroperoxypropane Chemical compound CC(C)OO SGJUFIMCHSLMRJ-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- AQIFPEIUSQBFJF-UHFFFAOYSA-N 4-[10,15,20-tris(4-cyanophenyl)-21,23-dihydroporphyrin-5-yl]benzonitrile Chemical compound N#Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc([nH]2)c(-c2ccc(cc2)C#N)c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc1[nH]2 AQIFPEIUSQBFJF-UHFFFAOYSA-N 0.000 description 1
- SFQNUQLWBBZIOZ-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-methylphenyl)-21,23-dihydroporphyrin Chemical compound Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(C)cc2)c2ccc([nH]2)c(-c2ccc(C)cc2)c2ccc(n2)c(-c2ccc(C)cc2)c2ccc1[nH]2 SFQNUQLWBBZIOZ-UHFFFAOYSA-N 0.000 description 1
- VJMPWQBRZOFZNL-UHFFFAOYSA-N C(=O)(O)C=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound C(=O)(O)C=1C=C(C=CC=1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 VJMPWQBRZOFZNL-UHFFFAOYSA-N 0.000 description 1
- XOOCFDBOVZWCBC-UHFFFAOYSA-N ClC(C=C1)=CC(C2=C(C=C(C=C3)N=C3C=C(C=C3)NC3=CC(C=C3)=NC3=C3)NC3=C2)=C1Cl Chemical compound ClC(C=C1)=CC(C2=C(C=C(C=C3)N=C3C=C(C=C3)NC3=CC(C=C3)=NC3=C3)NC3=C2)=C1Cl XOOCFDBOVZWCBC-UHFFFAOYSA-N 0.000 description 1
- 102000002004 Cytochrome P-450 Enzyme System Human genes 0.000 description 1
- 108010015742 Cytochrome P-450 Enzyme System Proteins 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SATIABMUOHRMKS-UHFFFAOYSA-N OC(=O)C1=CC=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound OC(=O)C1=CC=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 SATIABMUOHRMKS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AAHWXBAEVBLHMN-UHFFFAOYSA-N [Fe+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Fe+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 AAHWXBAEVBLHMN-UHFFFAOYSA-N 0.000 description 1
- FFLULBDXPQSSFB-UHFFFAOYSA-N [Zn+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Zn+2].ClC1=C(C(=CC=C1Cl)Cl)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 FFLULBDXPQSSFB-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin, wherein the nickel (II) porphyrin is dispersed in the cumene, and the mass amount of the nickel (II) porphyrin is 1 x 10 of the mass amount of the cumene‑4Percent to 1 percent and mol/mol, sealing a reaction system, introducing an oxidant, heating to 40-100 ℃ under stirring, keeping the set temperature and pressure, and stirring for reaction for 3.0-24.0 hours to obtain a cumene solution of cumene hydroperoxide, wherein the solution can be directly used for subsequent reaction. And (4) carrying out post-treatment on the reaction liquid, and calculating the conversion rate of the cumene and the selectivity of the cumene hydroperoxide. The method has the advantages of low reaction temperature, higher cumene conversion rate, high cumene hydroperoxide selectivity, less by-products, small environmental influence and the like, and has low reaction temperature and high safety coefficient. The invention provides a heightThe method for synthesizing the cumene hydroperoxide by the catalytic oxidation of the cumene is efficient, feasible and safe.
Description
Technical Field
The invention relates to a method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin, belonging to the field of organic catalysis and fine organic synthesis.
Background
The preparation of cumene hydroperoxide by cumene oxidation is an important conversion process in chemical industry, and the cumene hydroperoxide as an oxidation product is not only a basic raw material for industrially producing phenol and acetone,is also an important oxidant for preparing propylene oxide by propylene oxidation in industry. Globally, 90% of phenol is produced by decomposition of cumene hydroperoxide, from which the importance of cumene hydroperoxide synthesis in the chemical industry (ACS Sustainable Chemistry) can also be seen&Engineering 2019, 7: 7708-; chemical Engineering Science 2018, 177: 391-398). Currently, the industrial production of cumene hydroperoxide is mainly O2Or air as oxidant, cumene hydroperoxide as initiator, in the range of 100-140%○C, realized under the pressure of 0.60-0.70 MPa, the conversion rate of the cumene is about 20 percent, and the selectivity of the cumene hydroperoxide is 90-92 percent (ACS Sustainable Chemistry)&Engineering 2019, 7: 7708-; applied Catalysis a, General 2018, 561: 59-67). The main problems are that the conversion rate of the cumene is not ideal, the selectivity of the cumene hydroperoxide is not high enough, the reaction temperature is high, and the safety coefficient is low. Thus, under mild conditions, especially at lower reaction temperatures, with O2The oxidation of cumene to cumene hydroperoxide with high selectivity by an oxidizing agent is still a very urgent practical need in the chemical industry.
Metalloporphyrin is used as a model compound of cytochrome P-450 and widely applied to biomimetic Catalysis of various organic synthesis reactions, in particular to oxidation reactions (ChemSusChem 2019, 12: 684-one 691; Polydron 2019, 163: 144-152; Journal of Catalysis 2019, 369: 133-142). The metalloporphyrin has an approximately planar molecular structure, so that a metal center with catalytic activity can be exposed in a catalytic system to the maximum extent to play a role, excellent catalytic activity can be shown in 1/1000000-1/100000 of the molar weight of a substrate, the cost of catalytic reaction can be obviously reduced, and the metalloporphyrin is one of the preferable catalysts for various catalytic reactions. Meanwhile, the metalloporphyrin is used as a catalyst, so that not only the central metal has a wide selection object, but also the substituent groups around the metalloporphyrin ring have a wide regulation space.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nickel (II) porphyrin-catalyzed cumene oxidation catalyst with high efficiency and high selectivityMethod for sexual synthesis of cumene hydroperoxide by using metalloporphyrin as catalyst to catalyze O2The method for synthesizing the cumene hydroperoxide by oxidizing the cumene has the advantages of less catalyst consumption, high catalytic efficiency, easy structure adjustment, good biocompatibility, environmental protection and the like, and is favorable for realizing the high-efficiency and high-selectivity oxidation synthesis of the cumene hydroperoxide.
The technical scheme of the invention is as follows:
a method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin, which comprises the following processes:
dispersing nickel (II) porphyrin in cumene, wherein the amount of substance of nickel (II) porphyrin is 1 × 10 of that of cumene-4Percent to 1 percent, mol/mol, sealing the reaction system, introducing an oxidant, heating to 40-100 ℃ under stirring○C, keeping the set temperature and pressure, stirring and reacting for 3.0-24.0 h to obtain a cumene solution of cumene hydroperoxide, and directly carrying out subsequent reaction for use; after the reaction liquid is subjected to post-treatment, calculating the conversion rate of the cumene and the selectivity of the cumene hydroperoxide;
the nickel (II) porphyrin is at least one of the compounds shown in the formula (I):
wherein R is1，R2，R3，R4，R5Each independently is: hydrogen, methoxy, ethoxy, methyl, ethyl, phenyl, fluoro, chloro, bromo, carboxy, methoxycarbonyl, acetyl, formyl, hydroxy, amino, hydroxymethyl, cyano or nitro;
the nickel (II) porphyrin is 5,10,15, 20-tetra (2-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (3-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (2, 4-dicarboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetrakis (2, 4, 6-tricarboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetrakis (2-chlorophenyl) porphyrin nickel (II), 5,10,15, 20-tetrakis (3-chlorophenyl) porphyrin nickel (II), 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin nickel (II) or 5,10,15, 20-tetrakis (4-methoxycarbonylphenyl) porphyrin nickel (II);
the ratio of the amount of nickel (II) porphyrin to cumene is 1:1000000 to 1:100, preferably 1:100000 to 1: 1000.
Further, the reaction temperature is 40-100 DEG C○C, preferably 60 to 90○C; the reaction pressure is 0.10-0.50 MPa, preferably 0.10-0.20 MPa; the reaction time is 3.0-24.0 h, preferably 6.0-12.0 h; 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 cumin compound is 30-60% of the cumene substance, and the cumin compound is used at room temperature (20-30%)○C) The peroxide formed by the reduction was stirred for 40min, and the conversion of cumene and the selectivity of cumene hydroperoxide were analyzed and calculated.
The method for analyzing the reaction result comprises the following steps: after the reaction, triphenylphosphine (PPh) was added to the reaction solution3The dosage of the cumin compound is 30-60 percent of the cumene substance, and the temperature is 20-30 percent of room temperature○C) The peroxide formed by the reduction was stirred for 40min, and the conversion of cumene and the selectivity of cumene hydroperoxide were analyzed and calculated. Acetone is used as a solvent for dilution, naphthalene is used as an internal standard, gas chromatography analysis is carried out, and the conversion rate of the cumene and the selectivity of the cumene hydroperoxide are calculated.
The method takes metalloporphyrin as a catalyst, and catalyzes molecular oxygen to oxidize cumene to selectively synthesize the isopropyl hydroperoxide under mild conditions, so that the reaction temperature is greatly reduced, the selectivity of the cumene hydroperoxide is obviously improved, the atom economy of the process is improved, the emission of environmental pollutants is reduced, the practical requirements of the chemical industry on energy conservation and emission reduction at present are met, and the urgent requirements of the chemical industry on selectively synthesizing the cumene hydroperoxide under mild conditions by catalytic oxidation of the cumene are also met.
The invention has the following beneficial effects: the method for efficiently and selectively synthesizing the cumene hydroperoxide by catalyzing and oxidizing the cumene by the nickel (II) porphyrin has the advantages of low reaction temperature, higher cumene conversion rate, high cumene hydroperoxide selectivity, less byproducts, small environmental influence and the like, and has low reaction temperature and high safety coefficient. Therefore, the invention provides a novel method for synthesizing cumene hydroperoxide by catalytic oxidation of cumene with high efficiency, feasibility and safety.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrin used in the invention is referred to Journal of Materials Chemistry A2018, 6: 17698-; journal of the American Chemical Society 2018, 140: 6383 and 6390. All reagents used were commercially available analytical grade.
Examples 1 to 47 are examples of catalytic oxidation of cumene.
Examples 48 to 51 are comparative experiments.
Example 52 is a magnified experimental case.
Example 1
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 15.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 2.2 percent, the selectivity of cumene hydroperoxide is 97.8 percent, and the generation of benzoic acid is not detected.
Example 2
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (3-carboxyphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene,the temperature is raised to 80 ℃ by stirring, and oxygen (0.20MPa) is introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 9.8%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 3.5%, the selectivity of cumene hydroperoxide is 96.5%, and the generation of benzoic acid is not detected.
Example 3
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (2-carboxyphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 10.2%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 1.8%, the selectivity of cumene hydroperoxide is 98.2%, and the generation of benzoic acid is not detected.
Example 4
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 9.2%, the selectivity of 2-phenyl-2-propanol was 0.0%, the selectivity of acetophenone was 5.3%, and the selectivity of cumene hydroperoxide was 94.7%, and no formation of benzoic acid was detected.
Example 5
In a 25mL pressure-resistant reaction tube, 0.0010g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (2, 5-dichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 10.5%, the selectivity of 2-phenyl-2-propanol is 2.2%, the selectivity of acetophenone is 4.1%, the selectivity of cumene hydroperoxide is 93.7%, and the generation of benzoic acid is not detected.
Example 6
In a 25mL pressure-resistant reaction tube, 0.0010g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (2, 6-trichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.3 percent, the selectivity of 2-phenyl-2-propanol is 4.6 percent, the selectivity of acetophenone is 8.0 percent, the selectivity of cumene hydroperoxide is 87.4 percent, and the generation of benzoic acid is not detected.
Example 7
In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. Removing 10mL of the obtained solution, using naphthalene as a solventInternal standard, gas chromatography analysis was performed. The conversion rate of cumene is 17.4%, the selectivity of 2-phenyl-2-propanol is 2.1%, the selectivity of acetophenone is 12.5%, the selectivity of cumene hydroperoxide is 85.4%, and the generation of benzoic acid is not detected.
Example 8
In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (3-chlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.4%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 7.4%, the selectivity of cumene hydroperoxide is 92.6%, and the generation of benzoic acid is not detected.
Example 9
In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (2-chlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.3 percent, the selectivity of 2-phenyl-2-propanol is 7.5 percent, the selectivity of acetophenone is 12.3 percent, the selectivity of cumene hydroperoxide is 80.2 percent, and the generation of benzoic acid is not detected.
Example 10
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (4-esterylphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was added1.3115g (5.00mmol) of triphenylphosphine (PPh) were added3) The resulting peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made to 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 4.8%, the selectivity of cumene hydroperoxide is 95.2%, and the generation of benzoic acid is not detected.
Example 11
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (3-esterylphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 7.9%, the selectivity of 2-phenyl-2-propanol was 0.0%, the selectivity of acetophenone was 3.7%, and the selectivity of cumene hydroperoxide was 96.3%, and no formation of benzoic acid was detected.
Example 12
In a 25mL pressure-resistant reaction tube, 0.0009g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (2-esterylphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.3%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 4.3%, the selectivity of cumene hydroperoxide is 95.7%, and the generation of benzoic acid is not detected.
Example 13
In a 25mL pressure-resistant reaction tube, 0.0007g (0.001mmol) of 5,10,15,20-Nickel (II) tetrakis (4-methylphenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, stirred and heated to 80 ℃ and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 5.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 14.3%, the selectivity of 2-phenyl-2-propanol is 5.2%, the selectivity of acetophenone is 7.3%, the selectivity of cumene hydroperoxide is 87.5%, and the generation of benzoic acid is not detected.
Example 14
In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of nickel (II) 5,10,15, 20-tetrakis (4-cyanophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 5.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 12.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 6.3%, the selectivity of cumene hydroperoxide is 93.7%, and the generation of benzoic acid is not detected.
Example 15
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 40 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 40 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. No formation of a significant product was detected.
Example 16
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 50 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 50 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. No formation of a significant product was detected.
Example 17
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 60 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 60 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 6.3 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 0.0 percent, the selectivity of cumene hydroperoxide is 100 percent, and the generation of benzoic acid is not detected.
Example 18
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 70 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 70 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 11.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 0.0 percent, and the selectivity of cumene hydroperoxide is 100 percentNo formation of benzoic acid was detected.
Example 19
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 90 ℃ with stirring, and oxygen (0.20MPa) 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 28.4%, the selectivity of 2-phenyl-2-propanol is 12.8%, the selectivity of acetophenone is 3.1%, the selectivity of cumene hydroperoxide is 84.1%, and the generation of benzoic acid is not detected.
Example 20
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 100 ℃ with stirring, and oxygen (0.20MPa) 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 38.6 percent, the selectivity of 2-phenyl-2-propanol is 18.2 percent, the selectivity of acetophenone is 3.2 percent, the selectivity of cumene hydroperoxide is 78.6 percent, and the generation of benzoic acid is not detected.
Example 21
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.10MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 reactingThe mixture was brought to 50 mL. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 13.3%, the selectivity of 2-phenyl-2-propanol was 0.0%, the selectivity of acetophenone was 2.2%, and the selectivity of cumene hydroperoxide was 97.8%, and no formation of benzoic acid was detected.
Example 22
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.30MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 16.2%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 3.2%, the selectivity of cumene hydroperoxide is 96.8%, and the generation of benzoic acid is not detected.
Example 23
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.40MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 17.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 3.5 percent, the selectivity of cumene hydroperoxide is 96.5 percent, and the generation of benzoic acid is not detected.
Example 24
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.50MPa) was introduced. At 80 deg.CNext, the 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 19.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 3.6 percent, the selectivity of cumene hydroperoxide is 96.4 percent, and the generation of benzoic acid is not detected.
Example 25
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 4.5%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 0.0%, the selectivity of cumene hydroperoxide is 100.0%, and the generation of benzoic acid is not detected.
Example 26
In a 25mL pressure-resistant reaction tube, 0.00001g (0.00001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 8.9%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 1.0%, the selectivity of cumene hydroperoxide is 99.0%, and the generation of benzoic acid is not detected.
Example 27
In a 25mL pressure-resistant reaction tube, 0.00011g (0.0001mmol) of nickel (II) 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 18.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 2.1%, the selectivity of cumene hydroperoxide is 97.9%, and the generation of benzoic acid is not detected.
Example 28
In a 25mL pressure-resistant reaction tube, 0.0022g (0.002mmol) of nickel (II) 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 21.8%, the selectivity of 2-phenyl-2-propanol is 1.2%, the selectivity of acetophenone is 2.5%, the selectivity of cumene hydroperoxide is 96.3%, and the generation of benzoic acid is not detected.
Example 29
In a 25mL pressure-resistant reaction tube, 0.0108g (0.01mmol) of nickel (II) 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the obtained solution was removed, and gas chromatography was performed using naphthalene as an internal standardAnd (4) performing spectrum analysis. The conversion rate of cumene is 24.9%, the selectivity of 2-phenyl-2-propanol is 2.4%, the selectivity of acetophenone is 4.1%, the selectivity of cumene hydroperoxide is 93.5%, and the generation of benzoic acid is not detected.
Example 30
In a 25mL pressure-resistant reaction tube, 0.0217g (0.02mmol) of nickel (II) 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 30.1 percent, the selectivity of 2-phenyl-2-propanol is 3.1 percent, the selectivity of acetophenone is 4.2 percent, the selectivity of cumene hydroperoxide is 92.7 percent, and the generation of benzoic acid is not detected.
Example 31
In a 25mL pressure-resistant reaction tube, 0.0542g (0.05mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 31.8%, the selectivity for 2-phenyl-2-propanol was 3.3%, the selectivity for acetophenone was 5.0%, and the selectivity for cumene hydroperoxide was 91.7%, and no formation of benzoic acid was detected.
Example 32
In a 25mL pressure-resistant reaction tube, 0.1084g (0.1mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. After the reaction was completed, it was cooled to room temperature, and added to the reaction mixture1.3115g (5.00mmol) of triphenylphosphine (PPh)3) The resulting peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made to 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 31.9%, the selectivity of 2-phenyl-2-propanol was 5.9%, the selectivity of acetophenone was 3.9%, and the selectivity of cumene hydroperoxide was 90.2%, and no formation of benzoic acid was detected.
Example 33
0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, stirred and heated to 80 ℃ and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 3.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 6.8%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 0.0%, the selectivity of cumene hydroperoxide is 100%, and the generation of benzoic acid is not detected.
Example 34
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 4.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 7.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 0.9%, the selectivity of cumene hydroperoxide is 99.1%, and the generation of benzoic acid is not detected.
Example 35
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin was addedNickel (II) was dispersed in 1.2019g (10mmol) of cumene, stirred and heated to 80 ℃ and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 5.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 10.2 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 1.5 percent, the selectivity of cumene hydroperoxide is 98.5 percent, and the generation of benzoic acid is not detected.
Example 36
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 6.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 12.2 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 1.7 percent, the selectivity of cumene hydroperoxide is 98.3 percent, and the generation of benzoic acid is not detected.
Example 37
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 7.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 13.6 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 1.8 percent, and cumene hydroperoxide is selectedThe selectivity is 98.2 percent, and the generation of benzoic acid is not detected.
Example 38
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 9.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of the cumene is 16.8 percent, the selectivity of the 2-phenyl-2-propanol is 0.0 percent, the selectivity of the acetophenone is 2.6 percent, the selectivity of the cumene hydroperoxide is 97.4 percent, and the generation of the benzoic acid is not detected.
Example 39
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 10.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 18.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 2.8 percent, the selectivity of cumene hydroperoxide is 97.2 percent, and the generation of benzoic acid is not detected.
Example 40
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 11.0h at 80 ℃. 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 acetone is used as a solvent, and the acetone is used as a solvent,the resulting reaction mixture was taken to a volume of 50 mL. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 20.2%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 3.1%, the selectivity of cumene hydroperoxide is 96.9%, and the generation of benzoic acid is not detected.
EXAMPLE 41
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 12.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 24.3%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 4.2%, the selectivity of cumene hydroperoxide is 95.8%, and the generation of benzoic acid is not detected.
Example 42
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 15.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 25.8 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 4.5 percent, the selectivity of cumene hydroperoxide is 95.5 percent, and the generation of benzoic acid is not detected.
Example 43
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, the temperature was raised to 80 ℃ with stirring, and oxygen (0.20M) was introduced thereintoPa) is added. The reaction was stirred at 800rpm for 20.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 26.9 percent, the selectivity of 2-phenyl-2-propanol is 0.2 percent, the selectivity of acetophenone is 4.8 percent, the selectivity of cumene hydroperoxide is 95.0 percent, and the generation of benzoic acid is not detected.
Example 44
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 24.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 30.8%, the selectivity of 2-phenyl-2-propanol is 1.1%, the selectivity of acetophenone is 5.4%, the selectivity of cumene hydroperoxide is 93.5%, and the generation of benzoic acid is not detected.
Example 45
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 600rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 13.5%, the selectivity of 2-phenyl-2-propanol was 0.0%, the selectivity of acetophenone was 1.2%, and the selectivity of cumene hydroperoxide was 98.8%, and no formation of benzoic acid was detected.
Example 46
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 1000rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 17.2 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 2.6 percent, the selectivity of cumene hydroperoxide is 97.4 percent, and the generation of benzoic acid is not detected.
Example 47
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 1200rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 17.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 3.0%, the selectivity of cumene hydroperoxide is 97.0%, and the generation of benzoic acid is not detected.
Example 48 (comparative experiment)
In a 25mL pressure-resistant reaction tube, 0.0001g (0.001mmol) of nickel (II) acetate was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the obtained solution was removed and subjected to gas chromatography using naphthalene as an internal standardAnd (6) analyzing. The conversion rate of cumene was 10.3%, the selectivity for 2-phenyl-2-propanol was 4.8%, the selectivity for acetophenone was 17.3%, and the selectivity for cumene hydroperoxide was 77.9%, and no formation of benzoic acid was detected.
Example 49 (comparative experiment)
In a 25mL pressure-resistant reaction tube, 0.00016g (0.001mmol) of nickel (II) sulfate was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 7.9%, the selectivity of 2-phenyl-2-propanol is 4.2%, the selectivity of acetophenone is 19.2%, the selectivity of cumene hydroperoxide is 76.6%, and the generation of benzoic acid is not detected.
Example 50 (comparative experiment)
In a 25mL pressure-resistant reaction tube, 0.0011g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin iron (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. 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 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 6.6%, the selectivity of 2-phenyl-2-propanol is 0.0%, the selectivity of acetophenone is 0.0%, the selectivity of cumene hydroperoxide is 100.0%, and the generation of benzoic acid is not detected.
Example 51 (comparative experiment)
In a 25mL pressure-resistant reaction tube, 0.0008g (0.001mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin zinc (II) was dispersed in 1.2019g (10mmol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was added1.3115g (5.00mmol) of triphenylphosphine (PPh) were added3) The resulting peroxide was reduced by stirring at room temperature for 40 min. The resulting reaction mixture was made to 50mL with acetone as the solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene was 13.3%, the selectivity of 2-phenyl-2-propanol was 0.0%, the selectivity of acetophenone was 4.5%, and the selectivity of cumene hydroperoxide was 95.5%, and no formation of benzoic acid was detected.
Example 52 (amplification experiment)
In a 500mL pressure-resistant reaction tube, 0.108g (0.1mmol) of 5,10,15, 20-tetrakis (2,3, 6-trichlorophenyl) porphyrin nickel (II) was dispersed in 120.19g (1mol) of cumene, and the temperature was raised to 80 ℃ with stirring, and oxygen (0.20MPa) was introduced. The reaction was stirred at 800rpm for 8.0h at 80 ℃. After the reaction was completed, it was cooled to room temperature, and 131.15g (500mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 40 min. The obtained reaction mixture was made to a volume of 5000mL using acetone as a solvent. 10mL of the resulting solution was removed and analyzed by gas chromatography using naphthalene as an internal standard. The conversion rate of cumene is 15.1 percent, the selectivity of 2-phenyl-2-propanol is 0.0 percent, the selectivity of acetophenone is 2.7 percent, the selectivity of cumene hydroperoxide is 97.3 percent, and the generation of benzoic acid is not detected.
Claims (6)
1. A method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin, which is characterized by comprising the following processes:
dispersing nickel (II) porphyrin in cumene, wherein the amount of substance of nickel (II) porphyrin is 1 × 10 of that of cumene-4Percent to 1 percent and mol/mol, sealing a reaction system, introducing an oxidant, heating to 40-100 ℃ under stirring, keeping the set temperature and pressure, stirring for reaction for 3.0-24.0 hours to obtain a cumene solution of cumene hydroperoxide, and directly carrying out subsequent reaction for use; after the reaction liquid is subjected to post-treatment, calculating the conversion rate of the cumene and the selectivity of the cumene hydroperoxide;
the nickel (II) porphyrin is at least one of the compounds shown in the formula (I):
wherein R is1，R2，R3，R4，R5Each independently is: hydrogen, methoxy, ethoxy, methyl, ethyl, phenyl, fluoro, chloro, bromo, carboxy, methoxycarbonyl, acetyl, formyl, hydroxy, amino, hydroxymethyl, cyano or nitro;
the nickel (II) porphyrin is 5,10,15, 20-tetra (2-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (3-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin nickel (II), 5,10,15, 20-tetra (2, 4-dicarboxyphenyl) porphyrin nickel (II), nickel (II) 5,10,15, 20-tetrakis (2, 4, 6-tricarboxyphenyl) porphyrin, nickel (II) 5,10,15, 20-tetrakis (2-chlorophenyl) porphyrin, nickel (II) 5,10,15, 20-tetrakis (3-chlorophenyl) porphyrin, nickel (II) 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin, or nickel (II) 5,10,15, 20-tetrakis (4-methoxycarbonylphenyl) porphyrin.
2. The method for synthesizing cumene hydroperoxide by catalytic oxidation of cumene with nickel (II) porphyrin according to claim 1, wherein the ratio of the amount of the nickel (II) porphyrin to the amount of cumene hydroperoxide is 1:100000 to 1: 1000.
3. The method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin according to claim 1 or 2, wherein the reaction pressure is 0.10-0.50 MPa.
4. The method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin according to claim 1 or 2, wherein the stirring speed is 600-1200 rpm.
5. The method of claim 1 or 2, wherein the oxidizing agent is oxygen, air, or a mixture thereof in any proportion.
6. As claimed in claim 1Or 2, the method for synthesizing cumene hydroperoxide by catalyzing and oxidizing cumene by nickel (II) porphyrin is characterized in that the post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the dosage is 30-60% of the cumene substance, peroxide generated by reduction is stirred for 40min at room temperature (20-30 ℃), and then the conversion rate of the cumene and the selectivity of the cumene hydroperoxide are analyzed and calculated.
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| CN101235007A (en) * | 2007-01-29 | 2008-08-06 | 湖南大学 | Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene |
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|---|---|---|---|---|
| CN101235007A (en) * | 2007-01-29 | 2008-08-06 | 湖南大学 | Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene |
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Application publication date: 20201218 |