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CN119264188A - Chromium compounds and preparation methods and applications thereof, and catalytic oxidation methods for benzyl alcohol compounds - Google Patents

Chromium compounds and preparation methods and applications thereof, and catalytic oxidation methods for benzyl alcohol compounds Download PDF

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Publication number
CN119264188A
CN119264188A CN202310813731.7A CN202310813731A CN119264188A CN 119264188 A CN119264188 A CN 119264188A CN 202310813731 A CN202310813731 A CN 202310813731A CN 119264188 A CN119264188 A CN 119264188A
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Prior art keywords
formula
hydrogen
compound
solvent
reaction
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Inventor
冯思涵
高珊
祖钰
赵臣康
代曼
郭鸿宇
姜伟
王伟众
王东军
葛腾杰
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to CN202310813731.7A priority Critical patent/CN119264188A/en
Priority to PCT/CN2023/123737 priority patent/WO2025007440A1/en
Publication of CN119264188A publication Critical patent/CN119264188A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C07C33/22—Benzylalcohol; phenethyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C07C63/06—Benzoic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及有机合成领域技术领域，具体涉及一种铬系化合物及其制备方法与应用、苄醇类化合物催化氧化的方法。该化合物具有式(1)所示的结构：其中，式(1)中，Ar为*表示Ar与Si的连接位点；R1、R2和R3各自独立地选自氰基、烷基、卤素或氢，且不全为氢。将本发明的铬系化合物用于催化氧化反应中，例如苄醇类化合物催化氧化中的应用中具有好的催化氧化效果。

The present invention relates to the technical field of organic synthesis, and in particular to a chromium compound and a preparation method and application thereof, and a method for catalytic oxidation of benzyl alcohol compounds. The compound has a structure shown in formula (1): Wherein, in formula (1), Ar is * represents the connection site between Ar and Si; R 1 , R 2 and R 3 are independently selected from cyano, alkyl, halogen or hydrogen, and not all are hydrogen. The chromium compound of the present invention has a good catalytic oxidation effect when used in catalytic oxidation reactions, such as catalytic oxidation of benzyl alcohol compounds.

Description

Chromium compound, preparation method and application thereof, and benzyl alcohol compound catalytic oxidation method
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a chromium compound, a preparation method and application thereof, and a benzyl alcohol compound catalytic oxidation method.
Background
Benzoic acid compounds are an important class of organic compounds that are widely used in the fields of medicine, pesticides and macromolecules.
The organic pyridinium dichromate can oxidize primary and secondary alcohols into aldehydes and ketones in an organic solvent, but generally does not oxidize alcohols to carboxylic acids, but when the reaction system contains water, the aldehyde ketone formed further forms hydrated aldehyde or hydrated ketone and further oxidizes to give carboxylic acids, but the organic pyridinium dichromate has the disadvantages that (1) the organic pyridinium dichromate is weakly acidic in the reaction system and is not suitable for certain acid-sensitive compounds, although the acidity thereof can be reduced by adding NaOAC powder as a buffer, the effect is not very good, (2) the organic pyridinium dichromate has stronger oxidizing ability than the organic pyridinium dichromate for (Suggs E.Pyridiniumchlorochromate.An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds[J].Tetrahedron Letters,1975.); chloropyridinium chromate which has serious environmental pollution, the oxidizing effect is generally carried out under neutral conditions, but no matter whether the organic pyridinium dichromate or the pyridinium chlorochromate is used for oxidation, black brown oily residues are generated with the progress of the reaction, the products are wrapped by the residues, and the yield is reduced (E.J,Corey,and,et al.Useful procedures for the oxidation of alcohols involving pyridinium dichromate in approtic media[J].Tetrahedron Letters,1979,20(5):399-402.).
The Jones oxidation reaction (Jones reagent oxidation) is a reaction (Ley S V,Madin A.Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents[J].Comprehensive Organic Synthesis,1991.), in which chromic acid oxidizes primary and secondary alcohols to carboxylic acids and ketones, respectively, in acetone, and when it oxidizes a secondary benzyl alcohol raw material, it does not give a benzoic acid-based compound in high yield, it does not give a high yield, and the Jones reagent (Jones reagent) is an aqueous solution composed of chromium trioxide, sulfuric acid and water, and is not suitable for an acid-intolerant secondary benzyl alcohol raw material.
To sum up, benzyl alcohol is a stable and readily available starting material, but it is currently difficult to prepare benzoic acid from benzyl alcohol.
Disclosure of Invention
The invention aims to provide a chromium compound and a preparation method thereof, wherein the chromium compound is used in catalytic oxidation reaction, for example, the application of catalytic oxidation of benzyl alcohol compound has good catalytic oxidation effect, the prepared chromium compound can be dissolved in organic solvent to form homogeneous reaction with benzyl alcohol compound, so that the reaction is more favorable to be carried out, the reaction condition is mild, and the reaction toxicity of trivalent chromium is low after oxidation is completed.
The first aspect of the present invention provides a chromium-based compound having a structure represented by formula (1):
wherein Ar in formula (1) is * R 1、R2 and R 3 are each independently selected from cyano, alkyl, halogen or hydrogen, and are not all hydrogen.
The second aspect of the present invention provides a process for producing a chromium-based compound having a structure represented by formula (1), which comprises subjecting a compound represented by formula (2-1) to an esterification reaction with CrO 3 in the presence of a solvent and optionally a water scavenger;
Wherein Ar, R 1、R2 and R 3 are as defined above.
In a third aspect, the present invention provides the use of a chromium-based compound according to the present invention in a catalytic oxidation reaction.
In a fourth aspect, the present invention provides a method for catalytic oxidation of benzyl alcohol compounds, the method comprising:
In the presence of an organic solvent, adding the chromium compound into the benzyl alcohol compound shown in the formula (I) for catalytic oxidation reaction;
Wherein R a in formula (I) is selected from H, CH 3, cl or F.
Through the technical scheme, the novel chromium compound is provided, and has a good catalytic oxidation effect when being used in catalytic oxidation reaction, such as application in catalytic oxidation of benzyl alcohol compounds, the benzyl alcohol compounds have high conversion rate and target product benzoic acid compounds have high selectivity, the catalytic oxidation reaction condition is mild, and the reaction toxicity of forming trivalent chromium after oxidation is low.
Drawings
FIG. 1 is a hydrogen spectrum of the product obtained in the first step in example 1;
FIG. 2 is a carbon spectrum of the product obtained in the first step in example 1;
FIG. 3 is an infrared spectrum of the product obtained in the first step of example 1;
FIG. 4 is a hydrogen spectrum of the product obtained in the second step in example 1;
FIG. 5 is a carbon spectrum of the product obtained in the second step of example 1;
FIG. 6 is an infrared spectrum of the product obtained in the second step of example 1;
FIG. 7 is a hydrogen spectrum of the product obtained in the third step in example 1;
FIG. 8 is a carbon spectrum of the product obtained in the third step in example 1;
FIG. 9 is an infrared spectrum of the product obtained in the third step of example 1;
FIG. 10 is a xrd crystal diffraction structure of the product obtained in the third step in example 1;
FIG. 11 is a hydrogen spectrum of the product obtained in the first step in example 2;
FIG. 12 is a carbon spectrum of the product obtained in the first step in example 2;
FIG. 13 is an infrared spectrum of the product obtained in the first step of example 2;
FIG. 14 is a hydrogen spectrum of the product obtained in the second step in example 2;
FIG. 15 is a carbon spectrum of the product obtained in the second step in example 2;
FIG. 16 is an infrared spectrum of the product obtained in the second step of example 2;
FIG. 17 is a hydrogen spectrum of the product obtained in the first step in example 3;
FIG. 18 is a carbon spectrum of the product obtained in the first step in example 3;
FIG. 19 is an infrared spectrum of the product obtained in the first step in example 3;
FIG. 20 is a hydrogen spectrum of the product obtained in the second step in example 3;
FIG. 21 is a carbon spectrum of the product obtained in the second step in example 3;
FIG. 22 is an infrared spectrum of the product obtained in the second step in example 3;
FIG. 23 is a hydrogen spectrum of the product obtained in the third step in example 3;
FIG. 24 is a carbon spectrum of the product obtained in the third step in example 3;
FIG. 25 is an infrared spectrum of the product obtained in the third step in example 3;
FIG. 26 is a xrd crystal diffraction structure of the product obtained in the third step in example 3;
FIG. 27 is a hydrogen spectrum of the product obtained in the first step in example 4;
FIG. 28 is a carbon spectrum of the product obtained in the first step in example 4;
FIG. 29 is an infrared spectrum of the product obtained in the first step in example 4;
FIG. 30 is a hydrogen spectrum of the product obtained in the second step in example 4;
FIG. 31 is a carbon spectrum of the product obtained in the second step in example 4;
FIG. 32 is an infrared spectrum of the product obtained in the second step in example 4;
FIG. 33 is a hydrogen spectrum of the product obtained in the first step in example 5;
FIG. 34 is a carbon spectrum of the product obtained in the first step in example 5;
FIG. 35 is an infrared spectrum of the product obtained in the first step of example 5;
FIG. 36 is a hydrogen spectrum of the product obtained in the second step in example 5;
FIG. 37 is a carbon spectrum of the product obtained in the second step in example 5;
FIG. 38 is an infrared spectrum of the product obtained in the second step of example 5.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The halogen in the present invention represents at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine.
The alkyl group in the present invention may be a branched alkyl group, a linear alkyl group, or a linear cycloalkyl group, and the present invention is not particularly limited thereto.
The alkyl group C 1-C10 alkyl group in the present invention means an alkyl group having 1 to 10 carbon atoms, and may be, for example, a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, which may be, for example, a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, methylcyclopropyl, cyclohexyl or the like, and the "C 1-C4 alkyl group" has a similar explanation thereto except that the number of carbon atoms is different.
As described above, the first aspect of the present invention provides a chromium-based compound having a structure represented by formula (1):
wherein Ar in formula (1) is * R 1、R2 and R 3 are each independently selected from cyano, alkyl, halogen or hydrogen, and are not all hydrogen.
According to one embodiment of the invention, in formula (1), R 1、R2 and R 3 are each independently selected from cyano, C 1-C10 alkyl, halogen or hydrogen, and are not all hydrogen.
According to a preferred embodiment of the present invention, in formula (1), R 1、R2 and R 3 are each independently selected from C 1-C4 alkyl, halogen or hydrogen, and are not all hydrogen.
According to a particularly preferred embodiment of the invention, in formula (1), R 1 and R 3 are each independently selected from C 1-C4 alkyl, halogen or hydrogen, R 2 is hydrogen and not all hydrogen.
According to a particularly preferred embodiment of the present invention, the compound having the structure represented by formula (1) is selected from compounds having the structures represented by formulae (1-1) -formula (1-5):
R 1、R2 is hydrogen, R 3 is CH 3;
R 1、R2 is hydrogen, R 3 is F;
R 1、R2 is hydrogen, R 3 is Cl;
R 1、R2 is hydrogen, R 3 is C (CH 3);
R 2、R3 is hydrogen, and R 1 is CH 3.
The second aspect of the present invention provides a process for producing a chromium-based compound having a structure represented by formula (1), which comprises subjecting a compound represented by formula (2-1) to an esterification reaction with CrO 3 in the presence of a solvent and optionally a water scavenger;
Wherein Ar, R 1、R2 and R 3 are as defined above.
The chromium-based compound of the structure represented by the formula (1) according to the second aspect of the present invention and the following description are the same as the substituents of the chromium-based compound described in the first aspect of the present invention, and the present invention is not repeated, and those skilled in the art should not understand the limitation of the present invention, and the substituents R 1、R2 and R 3 in the compound of the formula (2-1) according to the present invention are the same as the substituents in the chromium-based compound of the structure represented by the formula (1).
According to the present invention, the kind of the solvent is not particularly limited as long as the object of the present invention can be achieved, and in some embodiments, the solvent is selected from a nonpolar solvent, preferably at least one of carbon tetrachloride, methylene chloride, benzene and hexane.
According to the present invention, the molar ratio of the compound represented by the formula (2-1) to CrO 3 may be 1 (2-4).
According to the present invention, the amount of the solvent is not particularly limited, and may be an amount conventional in the art, for example, an amount of the solvent such that the content of the compound represented by the formula (2-1) in the solvent is 10 to 50mg/mL.
According to the present invention, the water scavenger may be optionally present or absent when the esterification reaction is carried out, water may be generated when the esterification reaction is carried out, and it is preferable to carry out the esterification reaction in the presence of the water scavenger in order to avoid the influence of water on the esterification reaction, and the water scavenger may be a conventional water scavenger in the art, for example, at least one of anhydrous calcium chloride, anhydrous magnesium sulfate, sodium polyacrylate, anhydrous magnesium chloride, molecular sieve and anhydrous sodium sulfate, and the amount of the water scavenger is not particularly required, and may be an amount conventionally used in the art, for example, the water scavenger may be 30 to 110% by weight based on the mass of the compound represented by the formula (2-1).
According to the present invention, the conditions for the esterification reaction are not particularly limited as long as the objects of the present invention can be achieved, and in some embodiments, the conditions for the esterification reaction include a reaction temperature of room temperature (refer to 25.+ -. 5 ℃ C.).
According to a particularly preferred embodiment of the present invention, the esterification reaction conditions include a reaction time of 12 to 36 hours.
According to the invention, the compound shown in the formula (1) obtained after the esterification reaction is firstly obtained by post-treatment means conventionally adopted in the art, for example, the compound is obtained by filtering, drying and recrystallization after the esterification reaction, the drying can be selected to be normal-pressure drying or vacuum drying, and the method is not particularly limited in the technical means conventional in the art, so that excessive details are not needed, and the recrystallization can be carried out in a solvent favorable for crystal precipitation, preferably in dichloromethane and/or n-hexane.
According to a preferred embodiment of the present invention, the method for producing a chromium-based compound according to the present invention further comprises the step of producing a compound represented by the formula (2-1):
(1) Coupling the compound shown in the formula (2-2) with HSiCl 3 in the presence of an inert atmosphere and a first solvent to obtain a compound shown in the formula (2-3);
(2) Oxidizing the compound represented by the formula (2-3) with an oxidizing agent in the presence of a second solvent;
The R 1、R2 and R 3 substituents in the compounds represented by the formulas (2-2) and (2-3) are the same as the substituents in the chromium compound having the structure represented by the formula (1).
The inert atmosphere described in the present invention is nitrogen and/or argon, and nitrogen is preferred for cost reasons.
According to a preferred embodiment of the present invention, the first solvent is selected from ether solvents, preferably at least one of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether and 1, 2-dimethoxypropane, more preferably diethyl ether and/or tetrahydrofuran.
According to the present invention, in preparing the compound represented by the formula (2-3), as long as the compound represented by the formula (2-2) is brought into contact with HSiCl 3 to perform the coupling reaction to obtain the compound represented by the formula (2-3), a person skilled in the art may select the order of addition according to the need, for example, a material containing the first solvent and HSiCl 3 is added dropwise to a material containing the first solvent and the compound represented by the formula (2-2) to perform the coupling reaction, and preferably the time of addition is controlled to be 0.5 to 2 hours.
The amount of the first solvent used in the present invention is not particularly limited and may be an amount conventionally used in the art, for example, the amount of the first solvent used is such that the concentration of the compound of formula (2-2) in the material containing the first solvent and the compound of formula (2-2) is 0.5 to 1.5M and the concentration of HSiCl 3 in the material containing the first solvent and HSiCl 3 is 0.1 to 0.5M.
According to the present invention, the molar ratio of the compound of formula (2-2) to HSiCl 3 may be 3:1 or more, preferably (3.1-3.5): 1.
According to a preferred embodiment of the present invention, the conditions of the coupling reaction include a reaction temperature of 0-100 ℃, preferably 0-50 ℃.
According to a preferred embodiment of the present invention, the conditions for the coupling reaction include a reaction time of 2 to 24 hours, which is a time from the start of the contact of the compound of formula (2-2) with HSiCl 3 to the end of the reaction.
In the invention, the compound shown in the formula (2-2) and HSiCl 3 are subjected to coupling reaction to obtain the compound shown in the formula (2-3), the compound is subjected to aftertreatment by a aftertreatment means conventionally adopted in the field, then is introduced into the next step to perform oxidation reaction with o-chloroperoxybenzoic acid, for example, the compound is subjected to aftertreatment by means of separation, organic phase concentration, drying, recrystallization, washing and drying, the product is extracted by the aid of an analysis solution, the aftertreatment further comprises an acidification step, hydrochloric acid or acetic acid is more preferably used for acidification, the water in a plurality of layers is preferably used for drying the analysis solution, ethanol and isopropyl ether are preferably used for recrystallization, the material obtained after coupling reaction is subjected to acidification and neutralization by means of a solution of 0.5-2M hydrochloric acid, the isopropyl ether is added into the material, the analysis solution is subjected to crystallization, the solution is subjected to evaporation by a solution of 0.5-2M, the solution is dried by a rotary evaporator, the solution is concentrated by a solution of the solution is obtained after the solution is dried by a solution of the solution of 0.5-2M and the solution is dried by a rotary evaporator, and the solution is dried by the solution of the solution under the conditions shown in a vacuum condition shown in the vacuum condition of the condition of 2-3.
According to a preferred embodiment of the present invention, the second solvent is selected from at least one of dichloromethane, carbon tetrachloride, chloroform and 1, 2-dichloroethane.
According to a preferred embodiment of the present invention, the oxidizing agent is selected from at least one of hydrogen peroxide, m-chloroperoxybenzoic acid, t-butyl peroxide and peracetic acid, preferably m-chloroperoxybenzoic acid.
According to the present invention, the amount of the second solvent is not particularly limited, and may be an amount conventional in the art, for example, an amount of the second solvent such that the content of the compound represented by the formula (2-3) in the second solvent is 0.02 to 0.15mg/mL.
According to a preferred embodiment of the present invention, the molar ratio of the compound represented by the formula (2-3) to the oxidizing agent is 1 (1.5-3).
In a preferred embodiment according to the present invention, the conditions of the oxidation reaction include a reaction temperature of 0 to 80 ℃.
In a preferred embodiment according to the present invention, the conditions of the oxidation reaction include a reaction time of 5 to 100 hours.
In the invention, the compound shown in the formula (2-3) and the o-chloroperoxybenzoic acid are subjected to oxidation reaction and then subjected to post-treatment by post-treatment means which are conventionally adopted in the field, for example, the material obtained by the oxidation reaction is washed by saturated sodium bicarbonate solution and saturated saline water, the organic phase is concentrated and dried, and then the compound shown in the formula (2-1) is obtained by column chromatography, and preferably, the eluent in the column chromatography is a mixed solution of Petroleum Ether (PE) and Ethyl Acetate (EA) with the volume ratio of (8-12): 1.
In a third aspect, the present invention provides the use of a chromium-based compound according to the present invention in a catalytic oxidation reaction.
The chromium-based compound of the present invention has excellent catalytic oxidation properties.
According to a preferred embodiment of the present invention, the chromium-based compound is used in catalytic oxidation of benzyl alcohol-based compounds.
In the invention, when the chromium compound is used in the catalytic oxidation of the benzyl alcohol compound, the purpose of obtaining the benzoic acid compound by directly catalyzing and oxidizing the benzyl alcohol compound can be better realized, the raw material has high conversion rate, and the target product has high selectivity.
In a fourth aspect, the present invention provides a method for catalytic oxidation of benzyl alcohol compounds, the method comprising:
In the presence of an organic solvent, adding the chromium compound into the benzyl alcohol compound shown in the formula (I) for catalytic oxidation reaction;
Wherein R a in formula (I) is selected from H, CH 3, cl or F.
In the invention, the chromium compound is used in the catalytic oxidation reaction of the benzyl alcohol compound, so that the benzoic acid compound can be obtained under the conditions of no water and no additional acidic additive, and the method can be applied to the catalytic oxidation of different types of benzyl alcohol compounds to obtain the benzoic acid compound with high selectivity.
According to a preferred embodiment of the present invention, the molar ratio of the chromium-based compound to the benzyl alcohol-based compound is 0.5 to 3.0.
In a preferred embodiment according to the present invention, the conditions for the catalytic oxidation reaction include a reaction temperature of 10 to 80 ℃.
In a preferred embodiment according to the present invention, the conditions for the catalytic oxidation reaction include a reaction time of 3 to 24 hours.
The present invention will be described in detail by examples. In the following examples, the sources of the raw materials are shown in Table 1, and other raw materials are commercially available unless otherwise specified:
TABLE 1 sources of raw materials
Characterization analysis such as FTIR, 1 H NMR, XRD and the like is carried out on the prepared compound, the elemental analyzer is adopted for quantification, the melting point is measured by the melting point meter, and the related characterization and analysis methods are shown in table 2:
Table 2 evaluation and analysis method
Example 1
Synthesis of bis (tri-p-tolylsilyl) chromate:
The first step:
100mL of a 1.0M solution of p-tolylmagnesium bromide was forced into a 500mL three-necked flask in which the internal gas was replaced with nitrogen gas in advance by using a double-ended needle, then 100mL of a solution of 4.20g of trichlorosilane (31 mmol) in tetrahydrofuran was slowly dropped over 1 hour, the temperature was controlled to be below 35℃and stirring was continued at room temperature for 3 hours after the completion of the dropping, 25mL of 1.0M hydrochloric acid was used for neutralization after the completion of the reaction, 200mL of isopropyl ether was used for the separation, 25mL of 1.0M hydrochloric acid was used for the organic layer was used for the separation, the organic layer was dried over 20g of anhydrous magnesium sulfate, filtered, and rotary evaporated at 35℃to obtain a crude product, then the crude product was dissolved in 15mL of ethanol and 15mL of isopropyl ether, concentrated under reduced pressure, crystallized by cooling, and finally the crystallized crystals were washed with 20mL of absolute ethanol and then vacuum-dried to obtain a product, 5.60g of which was obtained in a yield of 60.3% and a melting point of 75-76 ℃.
FIG. 1 is a hydrogen spectrum of the product obtained in the first step, FIG. 2 is a carbon spectrum of the product obtained in the first step, FIG. 3 is an infrared spectrum of the product obtained in the first step, and the product obtained in the first step is tris (p-tolyl) silane as obtained in FIGS. 1 to 3.
And a second step of:
2.50g of tris (p-tolyl) silane (8.25 mmol) was dissolved in 30mL of methylene chloride and placed in a 50mL three-necked flask, 2.84g (16.50 mmol) of mCPBA was added after cooling to 0℃and then diluted with 370mL of methylene chloride after removing the ice bath and stirring at room temperature for 48 hours, the liquid was transferred to a 1000mL separating funnel and washed 3 times with 150mL of saturated sodium bicarbonate solution and 100mL of saturated sodium chloride solution in this order, the organic phase was dried over 20g of anhydrous magnesium sulfate and dried under spin-drying at 35℃to give the crude product which was eluted by column chromatography (PE: EA=9:1 in eluent) to give 700mg of product, 26.6% yield, melting point 108-109 ℃.
FIG. 4 is a hydrogen spectrum of the product obtained in the second step, FIG. 5 is a carbon spectrum of the product obtained in the second step, FIG. 6 is an infrared spectrum of the product obtained in the second step, and the product obtained in the second step is tris (p-tolyl) silanol, which can be obtained by FIGS. 4 to 6.
And a third step of:
500mg of tris (p-tolyl) silanol (1.57 mmol), 450mg of chromium trioxide (4.50 mmol) and 0.5g of anhydrous magnesium sulfate were placed in a 100mL round bottom flask, stirred at room temperature for 24 hours with 30mL of carbon tetrachloride as a solvent, followed by filtration, drying under vacuum to give a crude orange-red product, recrystallization from n-hexane at room temperature to give a product, and X-ray crystallography testing of the obtained product.
FIG. 7 is a hydrogen spectrum of the product obtained in the third step, FIG. 8 is a carbon spectrum of the product obtained in the third step, FIG. 9 is an infrared spectrum of the product obtained in the third step, FIG. 10 is a xrd crystal diffraction structure of the product obtained in the third step, and the product obtained in the third step is bis (tri-p-tolylsilyl) chromate obtained by FIGS. 7 to 10.
Example 2:
synthesis of bis (trifluorophenylsilyl) chromate:
The first step:
100mL of 1.0M para-fluorophenylmagnesium bromide was added to a 500mL three-necked flask in which the internal gas was replaced with nitrogen gas in advance, followed by dropwise addition of 100mL of a solution of 4.20g of trichlorosilane (31 mmol) in tetrahydrofuran slowly over 1 hour, the temperature was controlled to be not higher than 35℃and stirring was continued at room temperature for 3 hours after completion of the dropwise addition, 25mL of 1.0M hydrochloric acid was used for neutralization after completion of the reaction, 200mL of isopropyl ether was used for separation, 25mL of 1.0M hydrochloric acid was used for washing the organic layer, the organic layer was dried over 20g of anhydrous magnesium sulfate, filtered, rotary evaporated at 35℃to give a crude product, followed by dissolution of the crude product in 15mL of n-pentane, removal of the precipitated colored product by filtration with a slow filter paper at normal pressure, recrystallization of the filtrate with 10mL of methanol after completion of the dropwise evaporation at 35℃to give 4.50g of the product, yield 46.2%, melting point 44-45 ℃.
FIG. 11 is a hydrogen spectrum of the product obtained in the first step, FIG. 12 is a carbon spectrum of the product obtained in the first step, FIG. 13 is an infrared spectrum of the product obtained in the first step, and the product obtained in the first step is tris (p-fluorophenyl) silane, which can be obtained by FIGS. 11 to 13.
And a second step of:
2.59g of tris (p-fluorophenyl) silane (8.25 mmol) was dissolved in 30mL of methylene chloride and placed in a 50mL three-necked flask, 2.84g (16.50 mmol) of mCPBA was added after cooling to 0℃and then diluted with 370mL of methylene chloride after removing the ice bath and stirring at room temperature for 96 hours, the liquid was transferred to a 1000mL separating funnel and washed 3 times with 150mL of saturated sodium bicarbonate solution and 100mL of saturated sodium chloride solution in this order, the organic phase was dried over 20g of anhydrous magnesium sulfate and dried under a spin-dry condition at 35℃to give a crude product which was eluted by column chromatography (PE: EA=19:1 in eluent) to give 1.80g of the product in 66.2% yield with a melting point of 81-82 ℃.
Fig. 14 is a hydrogen spectrum of the product obtained in the second step, fig. 15 is a carbon spectrum of the product obtained in the second step, fig. 16 is an infrared spectrum of the product obtained in the second step, and the product obtained in the second step is tris (p-fluorophenyl) silanol obtained in fig. 14 to 16.
And a third step of:
517mg of tris (p-fluorophenyl) silanol (1.57 mmol), 450mg of chromium trioxide (4.50 mmol) and 0.5g of anhydrous magnesium sulfate were placed in a 100mL round bottom flask, stirred at room temperature for 24 hours with 30mL of carbon tetrachloride as a solvent, followed by filtration, drying under vacuum to give an orange-red crude product, which was recrystallized from n-hexane at room temperature to give the product as bis (tri-p-fluorophenyl silyl) chromate.
Example 3:
synthesis of bis (tri-p-chlorophenyl silyl) chromate:
The first step:
100mL of 1.0M p-chlorophenyl magnesium bromide solution was added to a 500mL three-necked flask in which the internal gas was replaced with nitrogen gas in advance, then 100mL of a tetrahydrofuran solution of 4.20g of trichlorosilane (31 mmol) was slowly dropped over 1 hour, the temperature was controlled to be below 35℃and stirring was continued at room temperature for 3 hours after the completion of the dropping, 25mL of 1.0M hydrochloric acid was used for neutralization after the completion of the reaction, 200mL of isopropyl ether was used for separation, 25mL of 1.0M hydrochloric acid was used for washing the organic layer, the organic layer was dried over 20g of anhydrous magnesium sulfate, filtered, rotary evaporation was performed at 35℃to obtain a crude product, and then the crude product was recrystallized in 15mL of anhydrous ethanol, filtered and dried under vacuum to obtain a white solid, 9.00g of the product was obtained, 79.8% yield, and melting point was 75-77 ℃.
FIG. 17 is a hydrogen spectrum of the product obtained in the first step, FIG. 18 is a carbon spectrum of the product obtained in the first step, FIG. 19 is an infrared spectrum of the product obtained in the first step, and the product obtained in the first step is tris (p-chlorophenyl) silanol obtained in the first step through FIGS. 17 to 19.
And a second step of:
3.00g of tris (p-chlorophenyl) silane (8.25 mmol) was dissolved in 30mL of methylene chloride and placed in a 50mL three-necked flask, 2.84g (16.50 mmol) of mCPBA was added after cooling to 0℃and then after removing the ice bath and stirring at room temperature for 48 hours, diluted with 370mL of methylene chloride, the liquid was transferred to a 1000mL separating funnel and washed 3 times with 150mL of saturated sodium bicarbonate solution and 100mL of saturated sodium chloride solution in sequence, the organic phase was dried over 20g of anhydrous magnesium sulfate and dried under a spin-dry condition at 35℃to give the crude product, which was washed with 50mL of n-hexane to give 2.30g of pure product in 73.5% yield and 115-116℃melting point.
FIG. 20 is a hydrogen spectrum of the product obtained in the second step, FIG. 21 is a carbon spectrum of the product obtained in the second step, FIG. 22 is an infrared spectrum of the product obtained in the second step, and the product obtained in the second step is tris (p-chlorophenyl) silanol obtained in the second step through FIGS. 20 to 22.
And a third step of:
1g of tris (p-chlorophenyl) silanol (2.70 mmol), 720mg of chromium trioxide (7.20 mmol) and 0.5g of anhydrous magnesium sulfate were placed in a 100mL round bottom flask, 30mL of carbon tetrachloride was used as a solvent, stirred at room temperature for 24 hours, followed by filtration, drying under vacuum to obtain an orange-red crude product, recrystallization at room temperature from a mixed solvent of methylene chloride/n-hexane in a volume ratio of 1:1 was carried out to obtain a product, and X-ray crystallography test was carried out on the obtained product.
FIG. 23 is a hydrogen spectrum of the product obtained in the third step, FIG. 24 is a carbon spectrum of the product obtained in the third step, FIG. 25 is an infrared spectrum of the product obtained in the third step, FIG. 26 is a xrd crystal diffraction structure of the product obtained in the third step, and the product obtained in the third step is bis (tri-p-chlorophenyl silyl) chromate which can be obtained by FIGS. 23 to 26.
Example 4:
synthesis of bis (tri-p-tert-butylphenylsilyl) chromate:
The first step:
100mL of 1.0M p-tert-butylphenyl magnesium bromide solution was added to a three-necked flask in which the internal gas was replaced with nitrogen gas in advance, then 100mL of a tetrahydrofuran solution of 4.20g of trichlorosilane (31 mmol) was slowly dropped over 1 hour, the temperature was controlled to be less than 35℃and stirring was continued at room temperature for 3 hours after the completion of the dropping, 25mL of 1.0M hydrochloric acid was used for neutralization after the completion of the reaction, 200mL of isopropyl ether was used for separation, 25mL of 1.0M hydrochloric acid was used for washing the organic layer, the organic layer was dried over 20g of anhydrous magnesium sulfate, filtration was carried out, rotary evaporation was carried out at 35℃to obtain a crude product, and then the crude product was recrystallized in absolute ethanol, filtered and dried under vacuum to obtain a white solid, 10.80g of the product was obtained, the yield was 81.2%, and the melting point was 109-112 ℃.
FIG. 27 is a hydrogen spectrum of the product obtained in the first step, FIG. 28 is a carbon spectrum of the product obtained in the first step, FIG. 29 is an infrared spectrum of the product obtained in the first step, and the product obtained in the first step can be obtained as tris (p-t-butylphenyl) silane by FIGS. 27 to 29.
And a second step of:
3.54g of tris (p-tert-butylphenyl) silane (8.16 mmol) were dissolved in 30mL of methylene chloride and placed in a 50mL three-necked flask, 2.81g (16.32 mmol) of mCPBA was added after cooling to 0℃and then, after removing the ice bath and stirring at room temperature for 24 hours, diluted with 370mL of methylene chloride, the liquid was transferred to a 1000mL separating funnel and washed 3 times with 150mL of saturated sodium hydrogencarbonate solution and 100mL of saturated sodium chloride solution in this order, the organic phase was dried over 20g of anhydrous magnesium sulfate and dried by spinning at 35℃to give the crude product, which was washed with 50mL of n-hexane to give 1.90g of the product, yield 52.3% and melting point 192-194 ℃.
FIG. 30 is a hydrogen spectrum of the product obtained in the second step, FIG. 31 is a carbon spectrum of the product obtained in the second step, FIG. 32 is an infrared spectrum of the product obtained in the second step, and the product obtained in the second step can be obtained as tris (p-t-butylphenyl) silanol by FIGS. 30 to 32.
And a third step of:
1.20g of tris (p-tert-butylphenyl) silanol (2.70 mmol), 720mg of chromium trioxide (7.20 mmol) and 0.5g of anhydrous magnesium sulfate were placed in a 100mL round bottom flask, 30mL of carbon tetrachloride was used as a solvent, stirred at room temperature for 24 hours, followed by filtration, drying under vacuum to give an orange-red crude product, which was recrystallized at room temperature from a mixed solvent of methylene chloride/n-hexane in a volume ratio of 1:1 to give the product as bis (tri-p-tert-butylphenylsilyl) chromate.
Example 5:
Synthesis of bis (tri-o-tolylsilyl) chromate:
The first step:
100mL of 1.0M o-tolylmagnesium bromide was added to a three-necked flask in which the internal gas was replaced with nitrogen gas in advance, followed by dropwise addition of 100mL of a solution of 4.20g of trichlorosilane (31 mmol) in tetrahydrofuran slowly over 1 hour, the temperature was controlled to be not higher than 35℃and stirring was continued at room temperature for 3 hours after completion of the dropwise addition, 25mL of 1.0M hydrochloric acid was used for neutralization after completion of the reaction, 200mL of isopropyl ether was used for liquid separation, 25mL of 1.0M hydrochloric acid was used for washing the organic layer, then 20g of anhydrous magnesium sulfate was used for drying the organic layer, filtration was carried out, rotary evaporation was carried out at 35℃to obtain a crude product, removal of dark impurities by column chromatography with petroleum ether was carried out, and finally 15mL of methanol was used for washing and drying to obtain a white solid, to obtain 3.95g of the product, 42.0% in yield, melting point 71-72 ℃.
FIG. 33 is a hydrogen spectrum of the product obtained in the first step, FIG. 34 is a carbon spectrum of the product obtained in the first step, FIG. 35 is an infrared spectrum of the product obtained in the first step, and the product obtained in the first step is tris (o-tolyl) silane as obtained in FIGS. 33 to 35.
And a second step of:
1.25g of tris (o-tolyl) silane (4.13 mmol) was dissolved in 30mL of methylene chloride and placed in a 50mL three-necked flask, 1.42g (8.25 mmol) of mCPBA was added after cooling to 0℃and then diluted with 200mL of methylene chloride after removing the ice bath and stirring at room temperature for 5 hours, the liquid was transferred to a 1000mL separating funnel and washed 3 times with 100mL of saturated sodium bicarbonate solution and 50mL of saturated sodium chloride solution in this order, the organic phase was dried over 10g of anhydrous magnesium sulfate and dried under a spin-dry condition at 35℃to give the crude product which was washed with 50mL of n-hexane to give the product as a white solid in yield 860mg, yield 45.5% and melting point 87-88 ℃.
FIG. 36 is a hydrogen spectrum of the product obtained in the second step, FIG. 37 is a carbon spectrum of the product obtained in the second step, FIG. 38 is an infrared spectrum of the product obtained in the second step, and the product obtained in the second step can be obtained as tris (o-tolyl) silanol by FIGS. 36 to 38.
And a third step of:
8.6g of tris (o-tolyl) silane (2.70 mmol), 720mg of chromium trioxide (7.20 mmol) and 0.5g of anhydrous magnesium sulfate were placed in a 100mL round bottom flask with 30mL of carbon tetrachloride as a solvent, stirred at room temperature for 24 hours, followed by filtration, drying under vacuum to give a crude orange-red product, and recrystallization from a mixed solvent of methylene chloride/n-hexane at room temperature to give the product as bis (tri-p-o-tolylsilyl) chromate.
Application example
After 1-fold molar amount of benzyl alcohol was dissolved in methylene chloride and the chromium-based compounds prepared in examples 1 to 5 were added at 0℃respectively, the mixture was stirred for 3 hours, and then the reaction was continued at room temperature for 3 hours, and the conversion of benzyl alcohol and the selectivity of benzoic acid were evaluated by liquid chromatography, as shown in Table 3.
TABLE 3 conversion of benzyl alcohol and selectivity to benzoic acid
Chromium-based compound Conversion of benzyl alcohol (%) Selectivity of benzoic acid (%)
Example 1 98% 92%
Example 2 99% 93%
Example 3 99% 96%
Example 4 97% 95%
Example 5 98% 96%
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1.一种铬系化合物，其特征在于，该化合物具有式(1)所示的结构：1. A chromium compound, characterized in that the compound has a structure shown in formula (1): 其中，式(1)中，Ar为*表示Ar与Si的连接位点；Wherein, in formula (1), Ar is * indicates the bonding site between Ar and Si; R1、R2和R3各自独立地选自氰基、烷基、卤素或氢，且不全为氢。R 1 , R 2 and R 3 are each independently selected from cyano, alkyl, halogen or hydrogen, and not all are hydrogen. 2.根据权利要求1所述的化合物，其中，2. The compound according to claim 1, wherein 式(1)中，R1、R2和R3各自独立地选自氰基、C1-C10烷基、卤素或氢，且不全为氢；In formula (1), R 1 , R 2 and R 3 are each independently selected from cyano, C 1 -C 10 alkyl, halogen or hydrogen, and not all are hydrogen; 优选地，R1、R2和R3各自独立地选自C1-C4烷基、卤素或氢，且不全为氢；Preferably, R 1 , R 2 and R 3 are each independently selected from C 1 -C 4 alkyl, halogen or hydrogen, and not all are hydrogen; 更优选地，R1和R3各自独立地选自C1-C4烷基、卤素或氢，R2为氢，且不全为氢。More preferably, R 1 and R 3 are each independently selected from C 1 -C 4 alkyl, halogen or hydrogen, and R 2 is hydrogen, and not all of them are hydrogen. 3.根据权利要求1或2所述的化合物，其中，具有式(1)所示的结构的化合物选自如式(1-1)-式(1-5)中所述结构的化合物：3. The compound according to claim 1 or 2, wherein the compound having the structure represented by formula (1) is selected from the compounds having the structures represented by formula (1-1) to formula (1-5): 式(1-1)：R1、R2为氢，R3为CH3；Formula (1-1): R 1 and R 2 are hydrogen, and R 3 is CH 3 ; 式(1-2)：R1、R2为氢，R3为F；Formula (1-2): R 1 and R 2 are hydrogen, and R 3 is F; 式(1-3)：R1、R2为氢，R3为Cl；Formula (1-3): R 1 and R 2 are hydrogen, and R 3 is Cl; 式(1-4)：R1、R2为氢，R3为C(CH3)；Formula (1-4): R 1 and R 2 are hydrogen, and R 3 is C(CH 3 ); 式(1-5)：R2、R3为氢，R1为CH3。Formula (1-5): R 2 and R 3 are hydrogen, and R 1 is CH 3 . 4.一种铬系化合物的制备方法，其特征在于，该铬系化合物具有式(1)所示结构，该制备方法包括：将在溶剂和任选地除水剂存在下，将式(2-1)所示的化合物与CrO3进行酯化反应；4. A method for preparing a chromium compound, characterized in that the chromium compound has a structure shown in formula (1), and the preparation method comprises: esterifying the compound shown in formula (2-1) with CrO 3 in the presence of a solvent and optionally a dehydrating agent; 其中，Ar、R1、R2和R3的定义如权利要求1-3中任意一项所述。wherein Ar, R 1 , R 2 and R 3 are as defined in any one of claims 1-3. 5.根据权利要求4所述的制备方法，其中，5. The preparation method according to claim 4, wherein 所述溶剂选自四氯化碳、二氯甲烷、苯和己烷中的至少一种；和/或The solvent is selected from at least one of carbon tetrachloride, dichloromethane, benzene and hexane; and/or 所述除水剂包括无水氯化钙、无水硫酸镁、聚丙烯酸钠、无水氯化镁、分子筛和无水硫酸钠中的至少一种；和/或The dehydrating agent comprises at least one of anhydrous calcium chloride, anhydrous magnesium sulfate, sodium polyacrylate, anhydrous magnesium chloride, molecular sieves and anhydrous sodium sulfate; and/or 所述酯化反应的条件包括：反应温度为室温；和/或反应时间为12-36h小时。The conditions of the esterification reaction include: the reaction temperature is room temperature; and/or the reaction time is 12-36 hours. 6.根据权利要求4或5所述的制备方法，其中，6. The preparation method according to claim 4 or 5, wherein: 该制备方法还包括按照以下步骤制备式(2-1)所述的化合物：The preparation method also includes preparing the compound described in formula (2-1) according to the following steps: (1)在惰性气氛和第一溶剂存在下，将式(2-2)所述的化合物与HSiCl3进行偶联反应，得到式(2-3)所示的化合物；(1) In the presence of an inert atmosphere and a first solvent, coupling the compound of formula (2-2) with HSiCl 3 to obtain a compound of formula (2-3); (2)在第二溶剂存在下，将式(2-3)所示的化合物与氧化剂进行氧化反应；(2) in the presence of a second solvent, subjecting the compound represented by formula (2-3) to an oxidation reaction with an oxidizing agent; 其中，R1、R2和R3的定义如权利要求1-3中任意一项所述，X为卤素。wherein R 1 , R 2 and R 3 are as defined in any one of claims 1 to 3, and X is a halogen. 7.根据权利要求6所述的制备方法，其中，7. The preparation method according to claim 6, wherein: 所述第一溶剂选自醚类溶剂，优选为乙醚、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚和1,2-二甲氧丙烷中的至少一种，进一步优选为乙醚和/或四氢呋喃；和/或The first solvent is selected from ether solvents, preferably at least one of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether and 1,2-dimethoxypropane, more preferably diethyl ether and/or tetrahydrofuran; and/or 所述偶联反应的条件包括：反应温度为0-100℃；和/或反应时间为2-24小时；和/或The conditions of the coupling reaction include: a reaction temperature of 0-100° C.; and/or a reaction time of 2-24 hours; and/or 所述第二溶剂选自二氯甲烷、四氯化碳、氯仿和1，2-二氯乙烷中的至少一种；和/或The second solvent is selected from at least one of dichloromethane, carbon tetrachloride, chloroform and 1,2-dichloroethane; and/or 所述氧化剂选自双氧水、间氯过氧苯甲酸、过氧叔丁醇和过氧乙酸中的至少一种，优选为间氯过氧苯甲酸；和/或The oxidant is selected from at least one of hydrogen peroxide, meta-chloroperbenzoic acid, tert-butyl peroxide and peracetic acid, preferably meta-chloroperbenzoic acid; and/or 式(2-3)所示的化合物与氧化剂的摩尔比为1：(1.5-3)；和/或The molar ratio of the compound represented by formula (2-3) to the oxidant is 1:(1.5-3); and/or 所述氧化反应的条件包括：反应温度为0-80℃；和/或反应时间为5-100小时。The conditions of the oxidation reaction include: a reaction temperature of 0-80° C.; and/or a reaction time of 5-100 hours. 8.权利要求1-3中任意一项所述铬系化合物在催化氧化反应中的应用，优选在苄醇类化合物催化氧化中的应用。8. Use of the chromium compound according to any one of claims 1 to 3 in a catalytic oxidation reaction, preferably in the catalytic oxidation of benzyl alcohol compounds. 9.一种苄醇类化合物催化氧化的方法，其特征在于，该方法包括：9. A method for catalytic oxidation of benzyl alcohol compounds, characterized in that the method comprises: 在有机溶剂存在下，将权利要求1-3中任意一项所述铬系化合物加入式(I)所述的苄醇类化合物中进行催化氧化反应；In the presence of an organic solvent, adding the chromium compound described in any one of claims 1 to 3 to the benzyl alcohol compound described in formula (I) to carry out a catalytic oxidation reaction; 其中，式(I)中Ra选自H、CH3、Cl或F。Wherein, in formula (I), Ra is selected from H, CH3 , Cl or F. 10.根据权利要求9所述的方法，其中，10. The method according to claim 9, wherein: 所述铬系化合物与苄醇类化合物的摩尔比为0.5-3.0；和/或The molar ratio of the chromium compound to the benzyl alcohol compound is 0.5-3.0; and/or 所述催化氧化反应的条件包括：反应温度为10-80℃；和/或反应时间为3-24小时。The conditions of the catalytic oxidation reaction include: a reaction temperature of 10-80° C.; and/or a reaction time of 3-24 hours.
CN202310813731.7A 2023-07-04 2023-07-04 Chromium compounds and preparation methods and applications thereof, and catalytic oxidation methods for benzyl alcohol compounds Pending CN119264188A (en)

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