CN117263946A - Metalloporphyrin containing hexafluoropropylene trimer group, and preparation method and application thereof - Google Patents

Metalloporphyrin containing hexafluoropropylene trimer group, and preparation method and application thereof Download PDF

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CN117263946A
CN117263946A CN202311200329.8A CN202311200329A CN117263946A CN 117263946 A CN117263946 A CN 117263946A CN 202311200329 A CN202311200329 A CN 202311200329A CN 117263946 A CN117263946 A CN 117263946A
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metalloporphyrin
hexafluoropropylene trimer
selectivity
mmol
reaction
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佘远斌
金文栋
沈海民
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • 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
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    • 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
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    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
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    • 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
    • B01J2531/842—Iron
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • 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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    • 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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    • C07C2601/14—The ring being saturated
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    • 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

The invention discloses metalloporphyrin containing hexafluoropropylene trimer groups, a preparation method and application thereof; dissolving benzaldehyde derivative containing hexafluoropropylene trimer group, newly distilled pyrrole, and metal acetate in mixed solvent of methanol and chloroform, and N 2 Stirring and reacting for 6.0-168.0 h at 0-80 ℃ under the atmosphere, and after the reaction is finished, obtaining metalloporphyrin containing hexafluoropropylene trimer groups through post-treatment; the metalloporphyrin containing hexafluoropropylene trimer group of the invention can be used for O 2 In the reaction of catalyzing and oxidizing cycloalkane, the cycloalkane oxidation method provided by the invention has the advantages of high selectivity of partial oxidation products (cycloalkyl alcohol and cycloalkyl ketone), low content of explosive peroxide and deep oxidation products aliphatic diacid, and is a safe, effective and low-energy-consumption cycloalkane oxidation method for separation.

Description

Metalloporphyrin containing hexafluoropropylene trimer group, and preparation method and application thereof
Technical Field
The invention relates to metalloporphyrin containing hexafluoropropylene trimer group and a preparation method thereof, and application of the metalloporphyrin serving as a catalyst in partial oxidation of cycloalkanes, belonging to the fields of organic catalysis and fine organic synthesis.
Background
The catalytic oxidation of cycloalkanes can convert hydrocarbons widely existing in fossil resources into alcohol compounds and ketone compounds with high added value, and has wide application in the chemical industry (ZL 202111006432.X;ZL 202010884408.5;ZL 201911161924.9). However, the chemical activity of the generated partial oxidation products (cycloalkyl alcohol and cycloalkyl ketone) is higher than that of substrate cycloalkane, so that the partial oxidation products are extremely easy to undergo deep oxidation to generate ring-opening product aliphatic diacid and derivatives thereof, the selectivity of the partial oxidation products is reduced, the energy consumption and equipment requirements for separation and purification are increased, and the generated aliphatic diacid and derivatives thereof are easy to crystallize, block production pipelines and cause great difficulty to industrial production. In order to ensure the better selectivity of partial oxidation products (cycloalkanol and cycloalkanone), the industrial catalytic oxidation of cyclohexane often controls the conversion rate of cyclohexane to about 5% so as to obtain the selectivity of partial oxidation products of about 85%. (Chemical Engineering Journal,2022,443:136126;Chemical Engineering Science,2022,260:117825;Molecular Catalysis,2023,535:112853). Further improving the substrate conversion, the selectivity of the partial oxidation products (cyclohexanol and cyclohexanone) is obviously reduced, and the simultaneous improvement of the substrate conversion and the selectivity of the partial oxidation products cannot be realized. The root of the above problems is that, in addition to the high reactivity of the oxidation products (cycloalkyl alcohols and cycloalkyl ketones), another important reason is the frequent contact of the partial oxidation products with the catalytically active sites. In the chemical industry, catalysts used for catalytic oxidation of cycloalkanes are currently mainly Salts, complexes and derivatives of cobalt (II) and manganese (II) are used. The catalyst not only can catalyze O 2 Oxidation of C-H bond of cycloalkane to partial oxidation products of alcohol, ketone, etc., and can catalyze O 2 Oxidizing the alcohol compounds and ketone compounds to deep oxidation products. Therefore, the frequent contact between partial oxidation products (cycloalkyl alcohol and cycloalkyl ketone) and the catalytic active center is effectively avoided, the deep oxidation of alcohol compounds and ketone compounds in the partial oxidation process of cycloalkane is avoided, and O is realized 2 High efficiency, selective oxidation of cycloalkanes to partial oxidation products cycloalkyl alcohols and cycloalkyl ketones. The high-selectivity preparation of the cycloalkyl alcohol and the cycloalkyl ketone is realized, so that the difficulty and equipment requirements for separating and purifying the industrial cycloalkane partial oxidation products are reduced, the separation energy consumption is reduced, the safety accidents caused by pipeline blockage can be effectively prevented, and the method has important significance for the safety, energy conservation and emission reduction production of industrial cycloalkanes.
The fluorine-containing compound has relatively low polarity, thus not only having relatively strong hydrophobic property, but also having relatively strong repellency to some oil compounds, especially to some organic compounds with relatively high polarity, and relatively strong oleophobicity (CN 115926069A;WO 2022059620A1). Oxidation of the cycloalkane moiety to the cycloalkanol and the cycloalkanone is a polarity-increasing process, and oxidation of the low polarity cycloalkane moiety to the polarity-increasing cycloalkanol and cycloalkanone. Therefore, the catalytic material for partial oxidation of cycloalkanes is modified by low-polarity fluorocarbon chains, which is favorable for realizing the separation of cycloalkyl alcohol and cycloalkyl ketone with larger polarity from the catalytic active center, and avoiding the contact between the disordered diffusion process and the catalytic active center and preventing the deep oxidation. In the process, the introduction of fluorocarbon chains has little influence on the contact of the cycloalkanes with the catalytic active center due to the low polarity of the cycloalkanes, so that the substrate cycloalkanes can smoothly contact the catalytic active center and be partially oxidized into cycloalkyl alcohol and cycloalkyl ketone. Therefore, the fluorocarbon chain modified cycloalkane partial oxidation catalyst is favorable for realizing the high efficiency of cycloalkane, and selective catalytic oxidation to generate cycloalkyl alcohol and cycloalkyl ketone, and has important significance for the safety, energy conservation and emission reduction production of industrial cycloalkane.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides metalloporphyrin containing hexafluoropropylene trimer group, a preparation method thereof and application thereof as a catalyst in partial oxidation of cycloalkanes.
According to the invention, hexafluoropropylene trimer is taken as a modification group, so that partial oxidation products, namely cycloalkyl alcohol and cycloalkyl ketone, are timely separated from a catalytic active center, contact between the partial oxidation products and the catalytic active center is prevented, deep oxidation is prevented, and the selectivity of the partial oxidation products is improved; the branched structure of hexafluoropropylene trimer group builds high bond energy C-F bond near the metal catalytic active center, prevents the oxidation degradation of metalloporphyrin catalyst, strengthens the catalytic conversion proportion of cycloalkane oxidation process, further improves the selectivity of cycloalkyl alcohol and cycloalkyl ketone, and prevents accidents possibly caused by peroxide accumulation.
The partial oxidation method of cycloalkane has high selectivity of cycloalkyl alcohol and cycloalkyl ketone, low content of cycloalkyl hydroperoxide and high safety coefficient, and is a method for synthesizing cycloalkyl alcohol and cycloalkyl ketone by catalytic oxidation of cycloalkane part with high efficiency, feasibility and safety.
The technical scheme of the invention is as follows:
metalloporphyrin containing hexafluoropropylene trimer group, its structure is shown in formula (I):
in the formula (I), the metal center M is Co (II), mn (II), fe (II), ni (II) or Cu (II), preferably Co (II).
The preparation method of metalloporphyrin containing hexafluoropropylene trimer group comprises the following steps:
dissolving benzaldehyde derivative containing hexafluoropropylene trimer group, pyrrole (redistilled), and metal acetate in reaction solvent, N 2 Stirring and reacting for 6.0-168.0 h at 0-80 ℃ under the atmosphere; after the reaction is finished, the reaction is mixedThe compound is decompressed and desolventized to obtain a metalloporphyrin crude product; sequentially washing the obtained metalloporphyrin crude product with water, washing with absolute ethyl alcohol, and separating by silica gel column chromatography to obtain metalloporphyrin containing hexafluoropropylene trimer group;
wherein,
the molar ratio of the benzaldehyde derivative containing hexafluoropropylene trimer group to pyrrole is 1:1 to 10;
the molar ratio of the metal acetate to the pyrrole is 1:0.20 to 20;
the molar ratio of the metal acetate to the benzaldehyde derivative containing hexafluoropropylene trimer group is 0.10-10: 1, preferably 0.40 to 10:1, a step of;
the reaction solvent is a mixture of methanol and chloroform, and the volume ratio of the methanol to the chloroform is 1:0.10 to 10.0, preferably 1:0.80 to 10.0;
Preferably, the reaction temperature is 20-50 ℃ and the reaction time is 72.0-168.0 h;
the eluent for silica gel column chromatography separation is dichloromethane;
in the preparation method, the structure of the benzaldehyde derivative containing hexafluoropropylene trimer group is shown as a formula (II):
the preparation method of the benzaldehyde derivative containing hexafluoropropylene trimer group comprises the following steps:
hexafluoropropylene trimer and 4-hydroxy benzaldehyde are added into halogenated methane solvent, N 2 Stirring and reacting for 6-10 h at a reflux state of 35-45 ℃ under the atmosphere; after the reaction is finished, cooling the reaction liquid to room temperature, then adding deionized water, extracting and separating liquid, drying an organic phase by using anhydrous sodium sulfate, concentrating, and separating and purifying by using a chromatographic column chromatography to obtain a benzaldehyde derivative (colorless liquid) containing hexafluoropropylene trimer groups;
wherein,
the molar ratio of hexafluoropropylene trimer to 4-hydroxybenzaldehyde is 1:0.5 to 2, preferably 1:1, a step of;
the volume ratio of the eluent for chromatographic separation of the chromatographic column is 4-6: 1, preferably the cyclohexane-dichloromethane mixed solvent has a cyclohexane-dichloromethane volume ratio of 5:1.
the metalloporphyrin containing hexafluoropropylene trimer group can be applied to cycloalkane partial oxidation reaction. The specific application method is as follows:
Dispersing metalloporphyrin containing hexafluoropropylene trimer group in cycloalkane, sealing the reaction system, heating to 100-150 ℃ under stirring, introducing oxygen to 0.40-2.0 MPa, maintaining the set temperature and oxygen pressure, and stirring for 3.0-15.0 h; then, the reaction solution is stirred and cooled to room temperature, and stirred and reacted for 3.0 to 12.0 hours at room temperature to obtain a reaction mixture containing partial oxidation products of cycloalkyl alcohol and cycloalkyl ketone;
wherein, the feeding ratio of metalloporphyrin containing hexafluoropropylene trimer group to cycloparaffin is 1mg:0.2 to 235mmol, preferably 1mg: 0.2-12 mmol;
preferably, the reaction temperature is 120-150 ℃, the oxygen pressure is 1.0-2.0 MPa, and the stirring reaction time is 6-12 h;
the cycloalkane is at least one selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclododecane, and the corresponding partial oxidation products are cycloalkyl alcohol and cycloalkyl ketone.
The technical conception of the invention is as follows:
the invention takes metalloporphyrin modified by branched hexafluoropropylene trimer as a catalyst to catalyze O 2 Partial oxidation of cycloalkanes to produce partial oxidation products cycloalkyl alcohols and cycloalkyl ketones. The branched hexafluoropropylene trimer is used as a modification group, so that partial oxidation products, namely cycloalkyl alcohol and cycloalkyl ketone, are timely separated from a catalytic active center, contact between the partial oxidation products and the catalytic active center is prevented, deep oxidation is prevented, and the selectivity of the partial oxidation products is improved; the branched structure of hexafluoropropylene trimer group builds high bond energy C-F bond near the metal catalytic active center, prevents the oxidation degradation of metalloporphyrin catalyst, strengthens the catalytic conversion proportion of cycloalkane oxidation process, further improves the selectivity of cycloalkyl alcohol and cycloalkyl ketone, and prevents accidents possibly caused by peroxide accumulation.
Therefore, the partial oxidation method of the cycloalkane has the advantages of high selectivity of the cycloalkyl alcohol and the cycloalkyl ketone, low content of cycloalkyl hydroperoxide and high safety coefficient, and has the potential of solving the problem that partial oxidation products of the cycloalkyl alcohol and the cycloalkyl ketone are easy to deeply oxidize to generate byproducts such as aliphatic diacid and the like in the industrial catalytic oxidation process of the cycloalkane and realizing the efficient synthesis of the partial oxidation products. Not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity of other catalytic oxidation systems.
The beneficial effects of the invention are mainly as follows:
the invention takes branched hexafluoropropylene trimer modified metalloporphyrin as a catalyst, has smart design, novel structure and wide application range. In the partial oxidation reaction of cycloalkanes, the selectivity of cycloalkyl alcohol and cycloalkyl ketone is high, and the deep oxidation of partial oxidation products and the generation of aliphatic diacid and derivatives thereof are effectively inhibited. The selectivity of the aliphatic diacid and the derivative thereof is low, and the method is also beneficial to the continuity of the partial oxidation process of the cycloalkane and the low-energy separation of products.
The invention solves the problem that partial oxidation products, namely cycloalkyl alcohol and cycloalkyl ketone, are easy to deeply oxidize to generate byproducts, such as aliphatic diacid, in the industrial cycloalkane catalytic oxidation process, and has the potential of realizing the efficient synthesis of partial oxidation products. Not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity of other catalytic oxidation systems. The invention is a novel efficient and feasible selective catalytic oxidation method for cycloalkanes.
Detailed Description
The present invention is further described below by way of specific examples, but the scope of the present invention is not limited thereto.
Example 1 is the synthesis of benzaldehyde derivatives containing hexafluoropropylene trimer groups.
Examples 2-25 are syntheses of metalloporphyrin catalysts containing hexafluoropropylene trimer groups.
Examples 26-63 are the use of metalloporphyrin catalysts containing hexafluoropropylene trimer groups in a cycloalkane partial oxidation reaction.
Examples 64-65 are comparative experiments in which metalloporphyrin catalysts containing hexafluoropropylene trimer groups were used in a cycloalkane partial oxidation reaction.
Example 66 is a scaled-up experiment using metalloporphyrin catalyst containing hexafluoropropylene trimer groups in a cycloalkane partial oxidation reaction.
The benzaldehyde derivative containing hexafluoropropylene trimer group used in the present invention has a branched structure as shown in formula (II), and is prepared by laboratory (university chemical engineering journal, 2009, 23 (4): 679-683; pesticide, 2007, 46 (8): 520-522.). The other reagents used were all commercially available.
Metalloporphyrin catalyst naming convention containing hexafluoropropylene trimer groups:
T(4-C 9 F 17 ) PPCo-2.00@2.40@1.20@60@80 represents porphyrin cobalt (II) containing hexafluoropropylene trimer groups, the molar ratio of the benzaldehyde derivative containing hexafluoropropylene trimer groups to the freshly steamed pyrrole in the synthesis reaction is 1:2.00, the molar ratio of the metal acetate to the freshly steamed pyrrole is 1:2.40, the volume ratio of methanol to chloroform is 1:1.20, the reaction temperature is 60 ℃, and the reaction time is 80.0h.
Example 1
Hexafluoropropylene trimer (C) 9 F 18 ) (4.5000 g,10.0 mmol), 4-hydroxybenzaldehyde (1.2212 g,10.00 mmol) was added to 30mL of dichloromethane. N (N) 2 Heating to 40 ℃ under the atmosphere, and stirring and reacting for 8.0h under the reflux state. After the reaction was completed, the reaction solution was cooled to room temperature, then 20mL of deionized water was added, the separated liquid was extracted (2×20mL of water was washed twice), and then the organic phase was dried over anhydrous sodium sulfate. Separating and purifying by chromatography column (silica gel of 200-300 mesh, eluting with V) Cyclohexane ：V Dichloromethane (dichloromethane) =5:1) the organic phase was collected, spin dried to give no2.1742g of a benzaldehyde derivative containing hexafluoropropylene trimer group as a coloring liquid was obtained in 39.3% yield.
Example 2
In a 25mL glass reaction tube, a benzaldehyde derivative (II) containing hexafluoropropylene trimer group (1.1044 g,2.0 mmol), freshly distilled pyrrole (0.2684 g,4.00 mmol), and anhydrous cobalt acetate (0.7081 g,4.00 mmol) were dissolved in a mixed solvent of 20mL of methanol and chloroform (volume ratio 1:1). N (N) 2 The reaction was stirred at 30℃for 84.0h under an atmosphere. After the reaction is finished, the reaction mixture is decompressed and desolventized to obtain a metalloporphyrin crude product. Washing the obtained metalloporphyrin crude product with water (5×20 mL), washing with absolute ethanol (5×20 mL), separating by silica gel column chromatography (eluting solvent is dichloromethane), to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@30@84, 0.1762g of purple solid powder and yield 14.3%. 1 H NMR(500MHz,CDCl 3 ):δ＝9.14(s,8H),8.36(d,8H),8.19(d,8H),-2.58(s,2H).
Example 3
Example 3 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "manganese acetate anhydrous (0.8981 g,4.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPMn-2.00@1.00@1.00@30@84, 0.2355g of purple black solid powder and yield 19.2%. 1 H NMR(500MHz,CDCl 3 ):δ＝9.10(s,8H),8.33(d,8H),8.14(d,8H),-2.59(s,2H).
Example 4
Example 4 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "iron acetate anhydrous (0.7758 g,4.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPFe-2.00@1.00@1.00@30@84, 0.2016g of purple black solid powder and yield 16.4%. 1 H NMR(500MHz,CDCl 3 ):δ＝9.11(s,8H),8.33(d,8H),8.16(d,8H),-2.61(s,2H).
Example 5
Example 5 preparation of catalyst example 2 was repeated except that "anhydrous cobalt acetate (0.7081 g,4.00 mmol)" was changed to "nickel acetate, tetrahydrate (0.9954 g,4.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPNi-2.00@1.00@1.00@30@84, 0.2335g of purple black solid powder and yield 19.0%. 1 HNMR(500MHz,CDCl 3 ):δ＝9.10(s,8H),8.34(d,8H),8.18(d,8H),-2.59(s,2H).
Example 6
Example 6 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "copper acetate anhydrous (0.7266 g,4.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPNi-2.00@1.00@1.00@30@84, 0.2861g of purple solid powder and yield 23.3%. 1 H NMR(500MHz,CDCl 3 ):δ＝9.18(s,8H),8.41(d,8H),8.23(d,8H),-2.62(s,2H).
Example 7
Example 7 the procedure for the preparation of the catalyst was repeated for example 2, except that "freshly distilled pyrrole (0.2684 g,4.00 mmol)" was changed to "freshly distilled pyrrole (0.1342 g,2.00 mmol)". The other conditions were the same as in example 1 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-1.00@1.00@1.00@30@84, 0.1312g of purple solid powder and yield 10.7%.
Example 8
Example 8 the procedure for the preparation of the catalyst was repeated for example 2, except that "freshly distilled pyrrole (0.2684 g,4.00 mmol)" was changed to "freshly distilled pyrrole (0.4025 g,6.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-3.00@1.00@1.00@30@84, 0.1791g of purple solid powder and yield 14.6%.
Example 9
Example 9 preparation of catalyst example 2 was repeated except that the catalyst was "freshSteamed pyrrole (0.2684 g,4.00 mmol) "was changed to" freshly steamed pyrrole (1.3148 g,20.00 mmol) ". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-10.00@1.00@1.00@30@84, 0.1815g of purple solid powder and yield 14.7%.
Example 10
Example 10 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "cobalt acetate anhydrous (3.5405 g,20.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@0.20@1.00@30@84, 0.1835g of purple solid powder and yield 14.9%.
Example 11
Example 11 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "cobalt acetate anhydrous (0.8851 g,5.00 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@0.80@1.00@30@84, 0.1124g of purplish red solid powder and 9.2% of yield.
Example 12
Example 12 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "cobalt acetate anhydrous (0.1416 g,0.80 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@5.00@1.00@30@84, 0.1582g of purple solid powder and yield 7.5%.
Example 13
Example 13 preparation of catalyst example 2 was repeated except that "cobalt acetate anhydrous (0.7081 g,4.00 mmol)" was changed to "cobalt acetate anhydrous (0.0354 g,0.20 mmol)". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@20.00@1.00@30@84, 0.0168g of purplish red solid powder and 3.4% of yield.
Example 14
Example 14 the procedure for preparing the catalyst was repeated in example 2 except that "in a mixed solvent of methanol and chloroform (volume ratio of 1:1)" was changed to "in a mixed solvent of methanol and chloroform (volume ratio of 1:0.1)" of 20 mL. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@0.10@30@84, 0.1171g of purple solid powder and 9.5% yield.
Example 15
Example 15 the procedure for preparing the catalyst was repeated in example 2 except that "in a mixed solvent of methanol and chloroform (volume ratio of 1:1)" was changed to "in a mixed solvent of methanol and chloroform (volume ratio of 1:0.8)" of 20 mL. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@0.80@30@84, 0.1254g of purple solid powder and yield 10.2%.
Example 16
Example 16 the procedure for preparing the catalyst was repeated in example 2 except that "in a mixed solvent of methanol and chloroform (volume ratio of 1:1)" was changed to "in a mixed solvent of methanol and chloroform (volume ratio of 1:2)" of 20 mL. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@2.00@30@84, 0.1138g of purple solid powder and 9.3% yield.
Example 17
Example 17 the procedure for preparing the catalyst was repeated in example 2 except that "in a mixed solvent of methanol and chloroform (volume ratio of 1:1)" was changed to "in a mixed solvent of methanol and chloroform (volume ratio of 1:10)" of 20 mL. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@10.00@30@84, 0.1345g of purple solid powder and yield 10.9%.
Example 18
Example 18 preparation of catalyst example 2 was repeated, except thatOnly in that "N" is to be taken 2 Under atmosphere, 30 ℃ is changed into N 2 Under the atmosphere, 0 ℃. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@0@84, 0.0341g of purplish red solid powder and 2.8% yield.
Example 19
Example 19 the procedure for the preparation of the catalyst was repeated for example 2, except that "N2 atmosphere" was changed to "30 c" and "N2 atmosphere, 20 c". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C9F 17) PPCo-2.00@1.00@1.00@20@84 containing hexafluoropropylene trimer group, 0.1019g of a purplish red solid powder, yield 8.3%.
Example 20
Example 20 preparation of catalyst example 2 was repeated except that "N" was used 2 Under atmosphere, 30 ℃ is changed into N 2 50 ℃ under the atmosphere. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@50@84, 0.1031g of purple solid powder and yield 8.4%.
Example 21
Example 21 preparation of catalyst example 2 was repeated except that "N" was used 2 Under atmosphere, 30 ℃ is changed into N 2 80 ℃ under the atmosphere. The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@80@84, 0.1125g of purplish red solid powder and 9.2% of yield.
Example 22
Example 22 catalyst preparation procedure example 2 was repeated except that the "stirred reaction 84.0h" was changed to "stirred reaction 6.0h". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@30@6, 0.0491g of purple solid powder and 4.0% yield.
Example 23
Example 23 preparation of catalystExample 2 was repeated except that the "stirring reaction for 84.0h" was changed to "stirring reaction for 72.0h". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@30@72, 0.1058g of purple solid powder and yield 8.2%.
Example 24
Example 24 preparation of catalyst example 2 was repeated except that the "stirred reaction for 84.0h" was changed to "stirred reaction for 96.0h". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C9F 17) PPCo-2.00@1.00@1.00@30@96 containing hexafluoropropylene trimer group, 0.1003g of purplish red solid powder, yield 8.3%.
Example 25
Example 25 catalyst preparation procedure example 2 was repeated except that the "stirred reaction 84.0h" was changed to "stirred reaction 168.0h". The other conditions were the same as in example 2 to obtain metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@30@168, 0.1278g of purple solid powder and yield 10.4%.
Example 26
Metalloporphyrin T (4-C) containing hexafluoropropylene trimer groups was treated in a 100mL stainless steel autoclave lined with polytetrafluoroethylene 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was dispersed in cyclohexane (16.8320 g,200 mmol), the reaction system was sealed and the temperature was raised to 125℃with stirring. When the temperature reaches the set temperature, oxygen is introduced to 1.00MPa, the set temperature and the oxygen pressure are kept, and the reaction is stirred for 8.0h. After the reaction is finished, the reaction solution is stirred and cooled to room temperature, and is stirred and reacted for 6.0 hours at room temperature, so that a small amount of residual cycloalkyl hydrogen peroxide is completely decomposed and converted. After the reaction is finished, slowly releasing residual gas, opening the reaction kettle, and fixing the volume of the anhydrous methanol to 100mL. Accurately transferring 10mL of constant volume solution, adding gas phase analysis internal standard toluene (0.1843 g,2.0 mmol) for GC analysis, and determining the conversion rate of cyclohexane as a substrate, and the yield and selectivity of cyclohexanol and cyclohexanone as partial oxidation products; accurately transferring 10mL of constant volume solution, adding liquid phase analysis internal standard benzoic acid (0.1221) g,1.0 mmol) was analyzed by HPLC to determine the yield and selectivity of the deeply oxidized products adipic acid and glutaric acid. Cyclohexane conversion was 11.5%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2% as analyzed by GC, HPLC, no glutaric acid and other by-products were detected.
Example 27
Example 27 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 3 9 F 17 ) PPMn-2.00@1.00@1.00@30@84 (9.7 mg, 0.04 mmol). The experimental results of example 27 are: cyclohexane conversion was 10.7%, cyclohexanol selectivity was 39%, cyclohexanone selectivity was 57%, adipic acid selectivity was 4%, and glutaric acid and other by-products were not detected.
Example 28
Example 28 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 4 9 F 17 ) PPFe-2.00@1.00@1.00@30@84 (9.7 mg, 0.04 mmol). The experimental results of example 28 were: cyclohexane conversion 10.1%, cyclohexanol selectivity 42%, cyclohexanone selectivity 56%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 29
Example 29 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 5 9 F 17 ) PPNi-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 29 were: cyclohexane conversion was 9.8%, cyclohexanol selectivity was 47%, cyclohexanone selectivity was 51%, adipic acid selectivity was 2%, and no pentane was detectedDiacid and other byproducts.
Example 30
Example 30 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 6 9 F 17 ) PPCu-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 30 were: cyclohexane conversion was 9.6%, cyclohexanol selectivity was 39%, cyclohexanone selectivity was 60%, adipic acid selectivity was 1%, and glutaric acid and other by-products were not detected.
Example 31
Example 31 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced by the amount (0.4912 g,0.2 mmol). The experimental results of example 31 are: cyclohexane conversion 11.9%, cyclohexanol selectivity 31%, cyclohexanone selectivity 63%, adipic acid selectivity 6%, no glutaric acid and other by-products were detected.
Example 32
Example 32 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced with an amount of 0.0491g,0.02 mmol). The experimental results of example 32 were: cyclohexane conversion 11.3%, cyclohexanol selectivity 47%, cyclohexanone selectivity 49%, adipic acid selectivity 4%, no glutaric acid and other by-products were detected.
Example 33
Example 33 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced by the amount (4.9 mg, 0.002mmol). The experimental results of example 33 were: cyclohexane conversion 10.6%, cyclohexanol selectivity 48%, cyclohexanone selectivity 49%, adipic acid selectivity3% by weight, no glutaric acid or other by-products were detected.
Example 34
Example 34 differs from example 26 only in that the reaction temperature was changed to 120 ℃. The experimental results of example 34 were: cyclohexane conversion was 9.7%, cyclohexanol selectivity 46%, cyclohexanone selectivity 53%, adipic acid selectivity 1%, no glutaric acid and other by-products were detected.
Example 35
Example 35 differs from example 26 only in that the reaction temperature was changed to 135 ℃. The experimental results of example 35 were: cyclohexane conversion 11.7%, cyclohexanol selectivity 42%, cyclohexanone selectivity 53%, adipic acid selectivity 5%, no glutaric acid and other by-products were detected.
Example 36
Example 36 differs from example 26 only in that the reaction temperature was changed to 150 ℃. The experimental results of example 36 were: cyclohexane conversion was 12.0%, cyclohexanol selectivity was 38%, cyclohexanone selectivity was 57%, adipic acid selectivity was 5%, and glutaric acid and other by-products were not detected.
Example 37
Example 37 differs from example 26 only in that the reaction oxygen pressure was changed to 0.40MPa. The experimental results of example 37 were: cyclohexane conversion was 10.0%, cyclohexanol selectivity was 42%, cyclohexanone selectivity was 56%, adipic acid selectivity was 2%, and glutaric acid and other by-products were not detected.
Example 38
Example 38 differs from example 26 only in that the reaction oxygen pressure was changed to 1.20MPa. The experimental results of example 38 are: cyclohexane conversion 11.1%, cyclohexanol selectivity 41%, cyclohexanone selectivity 55%, adipic acid selectivity 4%, no glutaric acid and other by-products were detected.
Example 39
Example 39 differs from example 26 only in that the set temperature and oxygen pressure were maintained and the stirring reaction time was changed to 6.0h. Cyclohexane conversion was 10.0%, cyclohexanol selectivity was 34%, cyclohexanone selectivity was 62%, adipic acid selectivity was 4%, and glutaric acid and other by-products were not detected.
Example 40
Example 40 differs from example 26 only in that the set temperature and oxygen pressure were maintained and the stirring reaction time was changed to 12.0h. Cyclohexane conversion was 10.4%, cyclohexanol selectivity 33%, cyclohexanone selectivity 65%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 41
Example 41 differs from example 26 only in that cyclohexane (16.8320 g,200 mmol) was replaced with cyclopentane (14.0260 g,200 mmol). The experimental results of example 41 were: the cyclopentane conversion was 11.4%, the cyclopentanol selectivity was 20%, the cyclopentanone selectivity was 65%, the glutaric acid selectivity was 15%, and no succinic acid and other by-products were detected.
Example 42
Example 42 differs from example 26 only in that cyclohexane (16.8320 g,200 mmol) was replaced with cycloheptane (19.6372 g,200 mmol). The experimental results of example 42 are: cycloheptane conversion 24.5%, cycloheptanol selectivity 26%, cycloheptanone selectivity 61%, pimelic acid selectivity 3%, no adipic acid and other by-products were detected. .
Example 43
Example 43 differs from example 26 only in that cyclohexane (16.8320 g,200 mmol) was replaced with cyclooctane (22.4426 g,200 mmol). The experimental results of example 43 are: cyclooctane conversion was 30.1%, cyclooctanone selectivity was 46%, cyclooctanone selectivity was 51%, suberic acid selectivity was 3%, and pimelic acid and other byproducts were not detected.
Example 44
Example 44 differs from example 26 only in that cyclohexane (16.8320 g,200 mmol) was replaced with cyclododecane (33.6640 g,200 mmol). Example 44 experimental results were: cyclododecane conversion 38.6%, cyclododecanol selectivity 46%, cyclododecanone selectivity 54%, and cyclododecanoic acid, cycloundecanoic acid, and other by-products were not detected.
Example 45
Example 45 differs from example 26 only in that example 2 was used to makeObtaining metalloporphyrin T (4-C) containing hexafluoropropylene trimer group 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 7 9 F 17 ) PPCo-1.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 45 were: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 46
Example 46 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 8 9 F 17 ) PPCo-3.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 46 are: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 47
Example 47 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 9 9 F 17 ) PPCo-10.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 47 were: cyclohexane conversion 11.5%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 48
Example 48 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 10 9 F 17 )PPCo-2.00@0.20@1.00@30@84 (9.8 mg, 0.004mmol). The experimental results of example 48 are: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 49
Example 49 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 11 9 F 17 ) PPCo-2.00@0.80@1.00@30@84 (9.8 mg, 0.04 mmol). Example 49 experimental results were: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 50
Example 50 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 12 9 F 17 ) PPCo-2.00@5.00@1.00@30@84 (9.8 mg, 0.04 mmol). Example 50 the experimental results were: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 51
Example 51 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 13 9 F 17 ) PPCo-2.00@20.00@1.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 51 are: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 52
Example 52 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 14 9 F 17 ) PPCo-2.00@1.00@0.10@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 52 were: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 53
Example 53 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 15 9 F 17 ) PPCo-2.00@1.00@0.80@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 53 are: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 54
Example 54 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 16 9 F 17 ) PPCo-2.00@1.00@2.00@30@84 (9.8 mg, 0.04 mmol). Example 54 experimental results were: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 55
Example 55 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 )PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.04 mmol) of metalloporphyrin T T containing hexafluoropropylene trimer group obtained in example 17 (4-C) 9 F 17 ) PPCo-2.00@1.00@10.00@30@84 (9.8 mg, 0.04 mmol). The experimental results of example 55 are: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 56
Example 56 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 18 9 F 17 ) PPCo-2.00@1.00@1.00@0@84 (9.8 mg, 0.04 mmol). The experimental results of example 56 are: cyclohexane conversion 11.3%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 57
Example 57 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 19 9 F 17 ) PPCo-2.00@1.00@1.00@20@84 (9.8 mg, 0.04 mmol). The experimental results of example 57 are: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 58
Example 58 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 20 9 F 17 ) PPCo-2.00@1.00@1.00@50@84 (9.8 mg, 0.04 mmol). The experimental results of example 58 were: cyclohexane conversion 11.3%, cycloHexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, glutaric acid and other byproducts were not detected.
Example 59
Example 59 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 21 9 F 17 ) PPCo-2.00@1.00@1.00@80@84 (9.8 mg, 0.04 mmol). The experimental results of example 59 were: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 60
Example 60 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 22 9 F 17 ) PPCo-2.00@1.00@1.00@30@6 (9.8 mg, 0.04 mmol). The experimental results of example 60 are: cyclohexane conversion 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 61
Example 61 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 23 9 F 17 ) PPCo-2.00@1.00@1.00@30@72 (9.8 mg, 0.04 mmol). The experimental results of example 61 are: cyclohexane conversion 11.5%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 62
Example 62 differs from example 26 only in thatThe metalloporphyrin T (4-C) containing hexafluoropropylene trimer group obtained in example 2 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 24 9 F 17 ) PPCo-2.00@1.00@1.00@30@96 (9.8 mg, 0.04 mmol). The experimental results of example 62 were: cyclohexane conversion 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, no glutaric acid and other by-products were detected.
Example 63
Example 63 differs from example 26 only in that the metalloporphyrin T (4-C) containing hexafluoropropylene trimer group obtained in example 2 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) replaced by metalloporphyrin T (4-C) containing hexafluoropropylene trimer group prepared in example 25 9 F 17 ) PPCo-2.00@1.00@1.00@30@168 (9.8 mg, 0.04 mmol). The experimental results of example 63 were: cyclohexane conversion was 11.4%, cyclohexanol selectivity was 47%, cyclohexanone selectivity was 51%, adipic acid selectivity was 2%, and glutaric acid and other by-products were not detected.
Example 64 (comparative experiment)
Preparation of TPPCo-2.00@1.00@1.00@30@84 and catalysis
Preparation in a 25mL glass reaction tube, benzaldehyde (0.2122 g,2.0 mmol), freshly distilled pyrrole (0.2684 g,4.00 mmol), and anhydrous cobalt acetate (0.7081 g,4.00 mmol) were dissolved in a mixed solvent of 20mL methanol and chloroform (volume ratio 1:1). N (N) 2 The reaction was stirred at 30℃for 84.0h under an atmosphere. After the reaction is finished, the reaction mixture is decompressed and desolventized to obtain a metalloporphyrin crude product. The obtained metalloporphyrin crude product is washed by water (5X 20 mL), washed by absolute ethyl alcohol (5X 20 mL), and separated by silica gel column chromatography (eluting agent is methylene dichloride), so that metalloporphyrin TPPCo-2.00@1.00@1.00@30@84 is obtained, 0.1238g of purple black solid powder is obtained, and the yield is 18.1%.
Catalysis: example 64 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 )PPCo-2.00@1.00@1.00@30@84(9.8mg，0.004mmol)，The metalloporphyrin TPPCo-2.00@1.00@1.00@30@84 prepared in example 64 is replaced. Cyclohexane conversion was 6.5%, cyclohexanol selectivity 29%, cyclohexanone selectivity 48%, adipic acid selectivity 17%, glutaric acid selectivity 6%.
Example 65 (comparative experiment)
Preparation and catalysis of T (4-Cl) PPCo-2.00@1.00@1.00@30@84
Preparation: example 65 differs from example 64 only in that the benzaldehyde of example 64 (0.2122 g,2.0 mmol) was replaced with 4-chlorobenzaldehyde (0.2811 g,2.0 mmol) to give metalloporphyrin T (4-Cl) PPCo-2.00@1.00@1.00@30@84, and a reddish solid powder 0.1457g in 15.4% yield.
Catalysis: example 65 differs from example 26 only in that the hexafluoropropylene trimer group-containing metalloporphyrin T (4-C) obtained in example 2 was used 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.04 mmol) was replaced with metalloporphyrin T (4-Cl) PPCo-2.00@1.00@1.00@30@84 prepared in example 65. Cyclohexane conversion was 6.8%, cyclohexanol selectivity 32%, cyclohexanone selectivity 50%, adipic acid selectivity 15%, glutaric acid selectivity 3%.
As is evident from the comparison of the catalysts and the comparison experiments, the catalysts prepared according to the invention catalyze O 2 The conversion rate of cycloalkane can be improved, the selectivity of partial oxidation products (cycloalkanol and cycloalkanone) is also greatly improved, the selectivity of by-product aliphatic diacid is obviously reduced, and the deep oxidation is effectively inhibited.
Example 66 (amplification experiment)
Metalloporphyrin T (4-C) containing hexafluoropropylene trimer groups was treated in a 1L stainless steel autoclave lined with polytetrafluoroethylene 9 F 17 ) PPCo-2.00@1.00@1.00@30@84 (0.0980 g, 0.04 mmol) was dispersed in cyclohexane (168.32 g,2 mol), the reaction system was sealed and the temperature was raised to 125℃with stirring. When the temperature reaches the set temperature, oxygen is introduced to 1.00MPa, the set temperature and the oxygen pressure are kept, and the reaction is stirred for 8.0h. After the reaction, the reaction solution is stirred and cooled to room temperature, and stirred and reacted for 6.0h at room temperature to make a small amount of residual cycloalkyl pass through The hydrogen oxide is completely decomposed and converted.
Repeating the experiment for three times, mixing the reaction mixtures after the reaction, distilling at normal pressure, separating cyclohexane to obtain 437.29g of cyclohexane, rectifying under reduced pressure, and taking 29.19g of fraction at 156 ℃ to obtain cyclohexanone; 43.48g of a 162℃fraction was taken as cyclohexanol. The remaining mixture was subjected to vacuum distillation and recrystallized from isopropanol/cyclohexane (1:1) to give 10.57g of white crystals. Calculated, the cyclohexane conversion was 13.4%, the cyclohexanol selectivity was 37%, the cyclohexanone selectivity was 54%, and the adipic acid selectivity was 9%.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.

Claims (10)

1. Metalloporphyrin containing hexafluoropropylene trimer group, its structure is shown in formula (I):
in the formula (I), the metal center M is Co (II), mn (II), fe (II), ni (II) or Cu (II).
2. A process for the preparation of metalloporphyrin containing hexafluoropropylene trimer groups as claimed in claim 1, said process comprising:
dissolving benzaldehyde derivative containing hexafluoropropylene trimer group, pyrrole and metal acetate in reaction solvent, N 2 Stirring and reacting for 6.0-168.0 h at 0-80 ℃ under the atmosphere; after the reaction is finished, the reaction mixture is decompressed and desolventized to obtain a metalloporphyrin crude product; sequentially washing the obtained metalloporphyrin crude product with water, washing with absolute ethyl alcohol, and separating by silica gel column chromatography to obtain metalloporphyrin containing hexafluoropropylene trimer group;
Wherein the structure of the benzaldehyde derivative containing hexafluoropropylene trimer group is shown as a formula (II):
3. the process according to claim 2, wherein the molar ratio of benzaldehyde derivative containing hexafluoropropylene trimer group to pyrrole is 1:1 to 10.
4. The method of claim 2, wherein the molar ratio of metal acetate to pyrrole is 1:0.20 to 20.
5. The process according to claim 2, wherein the molar ratio of the metal acetate to the benzaldehyde derivative containing hexafluoropropylene trimer groups is from 0.10 to 10:1.
6. the preparation method according to claim 2, wherein the reaction solvent is a mixture of methanol and chloroform, and the volume ratio of methanol to chloroform is 1:0.10 to 10.0.
7. The method according to claim 2, wherein the eluent for silica gel column chromatography separation is methylene chloride.
8. Use of a metalloporphyrin containing hexafluoropropylene trimer groups as defined in claim 1 in a cycloalkane partial oxidation reaction.
9. The application according to claim 8, wherein the method of application is as follows:
dispersing metalloporphyrin containing hexafluoropropylene trimer group in cycloalkane, sealing the reaction system, heating to 100-150 ℃ under stirring, introducing oxygen to 0.40-2.0 MPa, maintaining the set temperature and oxygen pressure, and stirring for 3.0-15.0 h; then, the reaction solution is stirred and cooled to room temperature, and stirred and reacted for 3.0 to 12.0 hours at room temperature to obtain a reaction mixture containing partial oxidation products of cycloalkyl alcohol and cycloalkyl ketone;
Wherein the cycloalkane is at least one selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclododecane.
10. Use according to claim 9, characterized in that the ratio of metalloporphyrin containing hexafluoropropylene trimer groups to cycloparaffin is 1mg:0.2 to 235mmol.
CN202311200329.8A 2023-09-18 2023-09-18 Metalloporphyrin containing hexafluoropropylene trimer group, and preparation method and application thereof Pending CN117263946A (en)

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