WO2025007440A1 - 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 - Google Patents

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 Download PDF

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WO2025007440A1
WO2025007440A1 PCT/CN2023/123737 CN2023123737W WO2025007440A1 WO 2025007440 A1 WO2025007440 A1 WO 2025007440A1 CN 2023123737 W CN2023123737 W CN 2023123737W WO 2025007440 A1 WO2025007440 A1 WO 2025007440A1
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formula
preparation
compound
solvent
hydrogen
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French (fr)
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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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    • 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
    • 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
    • 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
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • 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
    • 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
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues

Definitions

  • the 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 a benzyl alcohol compound.
  • Benzoic acid compounds are an important class of organic compounds that are widely used in medicine, pesticides and polymers.
  • Organic pyridinium dichromate can oxidize primary and secondary alcohols into aldehydes and ketones in organic solvents, but generally will not oxidize alcohols to carboxylic acids. However, when the reaction system contains water, the generated aldehydes and ketones will further form hydrated aldehydes or hydrated ketones, and then continue to oxidize to obtain carboxylic acids.
  • organic pyridinium dichromate has the following disadvantages: (1) Organic pyridinium dichromate is weakly acidic in the reaction system and is not suitable for certain acid-sensitive compounds. Although its acidity can be weakened by adding NaOAC powder as a buffer, the effect is not very good; (2) Organic pyridinium dichromate has serious environmental pollution (Suggs E.
  • Pyridinium chlorochromate An efficient reagent for oxidation of primary and secondary alcohols to carbonyl com pounds[J].Tetrahedron Letters,1975.); The oxidizing ability of pyridinium chlorochromate is stronger than that of organic pyridinium dichromate, and its oxidation is generally carried out under neutral conditions. However, whether organic pyridinium dichromate or pyridinium chlorochromate is used for oxidation reaction, dark brown oily residue will be generated as the reaction proceeds.
  • Jones oxidation reaction (Jones reagent oxidation) is a reaction in which chromic acid in acetone oxidizes primary and secondary alcohols to carboxylic acids and ketones, respectively (Ley S V, Madin A. Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents [J]. Comprehensive Organic Synthesis, 1991.). When it oxidizes secondary benzyl alcohol raw materials, it cannot obtain benzoic acid compounds in high yield.
  • Jones reagent is an aqueous solution composed of chromium trioxide, sulfuric acid and water, and is not suitable for secondary benzyl alcohol raw materials that are not acid-resistant.
  • benzyl alcohol is a stable and readily available raw material, but it is currently difficult to prepare benzoic acid from benzyl alcohol.
  • the object of the present invention is to provide a chromium compound and a preparation method thereof.
  • the chromium compound is used in a catalytic oxidation reaction, for example, in the catalytic oxidation of benzyl alcohol compounds, and has a good catalytic oxidation effect.
  • the prepared chromium compound can be dissolved in an organic solvent to form a homogeneous reaction with the benzyl alcohol compound, so that the reaction is more favorable, the reaction conditions are mild, and the trivalent chromium formed after the oxidation is completed has low toxicity.
  • the first aspect of the present invention provides a chromium compound having a structure shown in formula (1):
  • Ar is * represents the bonding site of Ar and Si; R 1 , R 2 and R 3 are each independently selected from cyano, alkyl, halogen or hydrogen, and not all are hydrogen.
  • the second aspect of the present invention provides a method for preparing a chromium compound having a structure shown in formula (1), the preparation method comprising: subjecting the compound shown in formula (2-1) to an esterification reaction with CrO 3 in the presence of a solvent and an optional dehydrating agent;
  • Ar, R 1 , R 2 and R 3 are as defined above in the present invention.
  • the third aspect of the present invention provides the use of the chromium compound of the present invention in catalytic oxidation reaction.
  • a fourth aspect of the present invention provides a method for catalytic oxidation of benzyl alcohol compounds, the method comprising:
  • the chromium compound of the present invention is added to the benzyl alcohol compound of formula (I) to carry out a catalytic oxidation reaction;
  • Ra is selected from H, CH3 , Cl or F.
  • the present invention provides a new chromium-based compound, and uses it in a catalytic oxidation reaction, for example, in the application of catalytic oxidation of benzyl alcohol compounds, it has a good catalytic oxidation effect, the benzyl alcohol compound has a high conversion rate, and the target product benzoic acid compound has a high selectivity, and the reaction conditions of the catalytic oxidation are mild, and the trivalent chromium formed after the oxidation is completed has low toxicity.
  • FIG1 is a hydrogen spectrum of the product obtained in the first step of Example 1;
  • FIG2 is a carbon spectrum of the product obtained in the first step of Example 1;
  • FIG3 is an infrared spectrum of the product obtained in the first step in Example 1;
  • FIG4 is a hydrogen spectrum of the product obtained in the second step of Example 1;
  • FIG5 is a carbon spectrum of the product obtained in the second step of Example 1;
  • FIG6 is an infrared spectrum of the product obtained in the second step of Example 1;
  • FIG7 is a hydrogen spectrum of the product obtained in the third step of Example 1;
  • FIG8 is a carbon spectrum of the product obtained in the third step of Example 1;
  • FIG9 is an infrared spectrum of the product obtained in the third step of Example 1;
  • FIG10 is an XRD crystal diffraction structure of the product obtained in the third step of Example 1;
  • FIG11 is a hydrogen spectrum of the product obtained in the first step of Example 2.
  • FIG12 is a carbon spectrum of the product obtained in the first step of Example 2.
  • FIG13 is an infrared spectrum of the product obtained in the first step of Example 2;
  • FIG14 is a hydrogen spectrum of the product obtained in the second step of Example 2.
  • FIG15 is a carbon spectrum of the product obtained in the second step of Example 2.
  • FIG16 is an infrared spectrum of the product obtained in the second step of Example 2.
  • FIG17 is a hydrogen spectrum of the product obtained in the first step of Example 3.
  • FIG18 is a carbon spectrum of the product obtained in the first step of Example 3.
  • FIG19 is an infrared spectrum of the product obtained in the first step of Example 3.
  • FIG20 is a hydrogen spectrum of the product obtained in the second step of Example 3.
  • FIG21 is a carbon spectrum of the product obtained in the second step of Example 3.
  • FIG22 is an infrared spectrum of the product obtained in the second step of Example 3.
  • FIG23 is a hydrogen spectrum of the product obtained in the third step of Example 3.
  • FIG24 is a carbon spectrum of the product obtained in the third step of Example 3.
  • FIG25 is an infrared spectrum of the product obtained in the third step of Example 3.
  • FIG26 is the XRD crystal diffraction structure of the product obtained in the third step of Example 3.
  • FIG27 is a hydrogen spectrum of the product obtained in the first step of Example 4.
  • FIG28 is a carbon spectrum of the product obtained in the first step of Example 4.
  • FIG29 is an infrared spectrum of the product obtained in the first step in Example 4.
  • FIG30 is a hydrogen spectrum of the product obtained in the second step of Example 4.
  • FIG31 is a carbon spectrum of the product obtained in the second step of Example 4.
  • FIG32 is an infrared spectrum of the product obtained in the second step of Example 4.
  • FIG33 is a hydrogen spectrum of the product obtained in the first step of Example 5.
  • FIG34 is a carbon spectrum of the product obtained in the first step of Example 5.
  • FIG35 is an infrared spectrum of the product obtained in the first step in Example 5;
  • FIG36 is a hydrogen spectrum of the product obtained in the second step of Example 5.
  • FIG37 is a carbon spectrum of the product obtained in the second step of Example 5.
  • Figure 38 is the infrared spectrum of the product obtained in the second step in Example 5.
  • the halogen mentioned in the present invention means at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • the alkyl group described in the present invention may be a branched alkyl group, a straight chain alkyl group, or a straight cyclic alkyl group, and the present invention has no particular limitation on this.
  • the alkyl C1 - C10alkyl mentioned in the present invention means an alkyl group having 1-10 carbon atoms, for example, a straight chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, a branched chain alkyl group or a cycloalkyl group having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopropyl group, a methylcyclopropyl group, a cyclohexyl group, etc.; a similar explanation shall apply to " C1 -
  • the first aspect of the present invention provides a chromium compound having a structure shown in formula (1):
  • Ar is * represents the bonding site of Ar and Si; R 1 , R 2 and R 3 are each independently selected from cyano, alkyl, halogen or hydrogen, and not all are hydrogen.
  • 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.
  • 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.
  • 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.
  • the compound having the structure shown in formula (1) is selected from the compounds having the structures described in formula (1-1) to formula (1-5):
  • R 1 and R 2 are hydrogen, and R 3 is F;
  • R 1 and R 2 are hydrogen, and R 3 is C(CH 3 ) 3 ;
  • R 2 and R 3 are hydrogen, and R 1 is CH 3 ;
  • R 1 and R 2 are hydrogen, and R 3 is CH 3 ;
  • R 1 and R 2 are hydrogen, and R 3 is Cl.
  • the second aspect of the present invention provides a method for preparing a chromium compound having a structure shown in formula (1), the preparation method comprising: subjecting the compound shown in formula (2-1) to an esterification reaction with CrO 3 in the presence of a solvent and an optional dehydrating agent;
  • Ar, R 1 , R 2 and R 3 are as defined above in the present invention.
  • the chromium compounds of the structure represented by formula (1) involved in the second aspect and thereafter of the present invention have the same substituents as those of the chromium compounds described in the first aspect of the present invention.
  • the present invention will not elaborate on the chromium compounds, and those skilled in the art should not understand this as a limitation of the present invention.
  • the substituents R1 , R2 and R3 in the compounds represented by formula (2-1) of the present invention are the same as the substituents in the chromium compounds of the structure represented by formula (1).
  • the type of the solvent is not particularly limited.
  • the solvent is selected from non-polar solvents, preferably at least one of carbon tetrachloride, dichloromethane, benzene and hexane.
  • the molar ratio of the compound represented by formula (2-1) to CrO 3 can be 1:(2-4).
  • the amount of solvent used there is no particular limitation on the amount of solvent used, and the amount can be any conventional amount in the art, for example, The amount of the compound represented by formula (2-1) in the solvent is 10-50 mg/mL.
  • the optional dehydrating agent means that the dehydrating agent may be present or absent during the esterification reaction.
  • water will be generated.
  • the type of dehydrating agent may be a conventional dehydrating agent in the art, for example, the dehydrating agent includes at least one of anhydrous calcium chloride, anhydrous magnesium sulfate, sodium polyacrylate, anhydrous magnesium chloride, molecular sieves and anhydrous sodium sulfate.
  • the amount of the dehydrating agent which may be the amount conventionally used in the art, for example, the mass of the dehydrating agent is 30-110wt% of the mass of the compound represented by formula (2-1).
  • the conditions of the esterification reaction are not particularly limited.
  • the conditions of the esterification reaction include: the reaction temperature is room temperature (referring to 25 ⁇ 5°C).
  • the conditions of the esterification reaction include: the reaction time is 12-36 hours.
  • the compound represented by formula (1) obtained after the esterification reaction is first post-treated by post-treatment means conventionally used in the art, for example, filtering, drying, and recrystallization after the esterification reaction;
  • the drying can be selected to be drying at normal pressure or vacuum drying, which is a conventional technical means in the art, and the present invention has no special limitation on this, so no further details are given;
  • the recrystallization can be selected to be carried out in a solvent that is conducive to crystal precipitation, preferably in dichloromethane and/or n-hexane.
  • the method for preparing the chromium compound of the present invention further comprises: preparing the compound represented by formula (2-1) according to the following steps:
  • the inert atmosphere described in the present invention is nitrogen and/or argon. Based on cost considerations, nitrogen is preferred.
  • 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, and more preferably diethyl ether and/or tetrahydrofuran.
  • the order of adding materials for example, adding the material containing the first solvent and HSiCl3 dropwise to the material containing the first solvent and the compound represented by formula (2-2) to carry out coupling reaction; preferably, the dropping time is controlled to be 0.5-2 hours.
  • the present invention has no particular limitation on the amount of the first solvent, which can be a conventional amount in the art.
  • the first solvent is used in an amount 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 0.5-1.5 M, and the concentration of HSiCl 3 in the material containing the first solvent and HSiCl 3 is 0.1-0.5 M.
  • the molar ratio of the compound described in formula (2-2) to HSiCl 3 can be greater than or equal to 3:1, preferably (3.1-3.5):1.
  • the conditions of the coupling reaction include: the reaction temperature is 0-100°C, preferably 0-50°C.
  • the conditions of the coupling reaction include: the reaction time is 2-24 hours; the reaction time refers to the time from the beginning of contact between the compound described in formula (2-2) and HSiCl 3 to the end of the reaction.
  • the compound represented by the formula (2-3) is obtained by coupling reaction of the compound represented by the formula (2-2) with HSiCl 3 , and then the compound is subjected to post-treatment by post-treatment means conventionally used in the art, and then introduced into the next step for oxidation reaction with o-chloroperoxybenzoic acid; for example, post-treatment is carried out by separation, organic phase concentration, drying, recrystallization, washing and drying, etc.; in order to neutralize the base that has not been completely reacted, which is the base of the reaction alkane, and at the same time, it is more conducive to separation and extraction of the product, preferably, the post-treatment also includes an acidification step, and more preferably, hydrochloric acid or acetic acid is used for acidification; in order to remove water in the layers obtained after separation, preferably, a water absorbent (such as anhydrous magnesium sulfate) is used after separation.
  • post-treatment also includes an acidification step, and more preferably, hydrochloric
  • the organic layer is dried; preferably ethanol and isopropyl ether are used for recrystallization; preferably anhydrous ethanol is used for washing; specifically, 0.5-2M hydrochloric acid is used to acidify and neutralize the material obtained after the coupling reaction, and then isopropyl ether is added for liquid separation, the organic layer is washed with 25mL of 0.5-2M hydrochloric acid and then separated, and the organic layer is dried over anhydrous magnesium sulfate, and then filtered, and rotary evaporated at 30-40°C to obtain a crude product, and then the crude product is dissolved in a mixed solution of ethanol and isopropyl ether, concentrated under reduced pressure, cooled for crystallization, and finally the precipitated crystals are washed with anhydrous ethanol and vacuum dried to obtain the compound shown in formula (2-3).
  • the second solvent is selected from at least one of dichloromethane, carbon tetrachloride, chloroform and 1,2-dichloroethane.
  • the oxidant is selected from at least one of hydrogen peroxide, meta-chloroperbenzoic acid, tert-butyl peroxide and peracetic acid, preferably meta-chloroperbenzoic acid.
  • the amount of the second solvent which can be a conventional amount in the art.
  • the amount of the second solvent is such that the content of the compound represented by formula (2-3) in the second solvent is 0.02-0.15 mg/mL.
  • the molar ratio of the compound represented by formula (2-3) to the oxidant is 1:(1.5-3).
  • the conditions of the oxidation reaction include: the reaction temperature is 0-80°C.
  • the conditions of the oxidation reaction include: the reaction time is 5-100 hours.
  • the compound represented by formula (2-3) is subjected to an oxidation reaction with o-chloroperoxybenzoic acid and then subjected to post-treatment by post-treatment means conventionally used in the art to obtain the compound represented by formula (2-1).
  • the material obtained by the oxidation reaction is washed with a saturated sodium bicarbonate solution and a saturated saline solution in sequence, and the organic phase is concentrated and dried, and then separated by column chromatography to obtain the compound represented by formula (2-1);
  • the eluent for column chromatography separation is a mixture of petroleum ether (PE) and ethyl acetate (EA) in a volume ratio of (8-12):1.
  • the third aspect of the present invention provides the use of the chromium compound of the present invention in catalytic oxidation reaction.
  • the chromium compound in the present invention has excellent catalytic oxidation performance.
  • the chromium compound is used in the catalytic oxidation of benzyl alcohol compounds.
  • the chromium compound of the present invention when used in the catalytic oxidation of benzyl alcohol compounds, the purpose of directly catalytically oxidizing benzyl alcohol compounds to obtain benzoic acid compounds can be well achieved, and the raw materials have a high conversion rate and the target product has a high selectivity.
  • a fourth aspect of the present invention provides a method for catalytic oxidation of benzyl alcohol compounds, the method comprising:
  • the chromium compound of the present invention is added to the benzyl alcohol compound of formula (I) to carry out a catalytic oxidation reaction;
  • Ra is selected from H, CH3 , Cl or F.
  • the chromium-based compounds of the present invention are used in the catalytic oxidation reaction of benzyl alcohol compounds, so that benzoic acid compounds can be obtained in the absence of water and additional acidic additives, and can be applied to the catalytic oxidation of different types of benzyl alcohol compounds to obtain benzoic acid compounds with high selectivity.
  • the molar ratio of the chromium compound to the benzyl alcohol compound is 0.5-3.0.
  • the conditions of the catalytic oxidation reaction include: the reaction temperature is 10-80°C.
  • the conditions of the catalytic oxidation reaction include: the reaction time is 3-24 hours.
  • the prepared compounds were subjected to characterization and analysis such as FTIR, 1 H NMR, and XRD. Quantification was performed using an element analyzer, and the melting point was measured using a melting point instrument. The characterization and analysis methods involved are shown in Table 2:
  • Figure 1 is a hydrogen spectrum of the product obtained in the first step
  • Figure 2 is a carbon spectrum of the product obtained in the first step
  • Figure 3 is an infrared spectrum of the product obtained in the first step. From Figures 1-3, it can be concluded that the product obtained in the first step is tri(p-tolyl)silane.
  • the organic phase was dried over 20 g of anhydrous magnesium sulfate, and the crude product was obtained by spin drying at 35°C.
  • Figure 4 is a hydrogen spectrum of the product obtained in the second step
  • Figure 5 is a carbon spectrum of the product obtained in the second step
  • Figure 6 is an infrared spectrum of the product obtained in the second step. From Figures 4-6, it can be concluded that the product obtained in the second step is tri(p-tolyl)silanol.
  • Figure 7 is a hydrogen spectrum of the product obtained in the third step
  • Figure 8 is a carbon spectrum of the product obtained in the third step
  • Figure 9 is an infrared spectrum of the product obtained in the third step
  • Figure 10 is an XRD crystal diffraction structure of the product obtained in the third step. From Figures 7-10, it can be concluded that the product obtained in the third step is bis(tri-p-tolylsilyl) chromate.
  • the organic layer was dried over 20 g of anhydrous magnesium sulfate, filtered, and rotary evaporated at 35 ° C to obtain a crude product.
  • the crude product was then dissolved in 15 mL of n-pentane and filtered with slow filter paper at normal pressure to remove the precipitated colored product.
  • the filtrate was rotary evaporated at 35 ° C and recrystallized with 10 mL of methanol to obtain 4.50 g of the product with a yield of 46.2% and a melting point of 44-45 ° C.
  • Figure 11 is a hydrogen spectrum of the product obtained in the first step
  • Figure 12 is a carbon spectrum of the product obtained in the first step
  • Figure 13 is an infrared spectrum of the product obtained in the first step. From Figures 11-13, it can be concluded that the product obtained in the first step is tri(p-fluorophenyl)silane.
  • the organic phase was dried over 20 g of anhydrous magnesium sulfate, and the crude product was obtained by spin drying at 35°C.
  • Figure 14 is a hydrogen spectrum of the product obtained in the second step
  • Figure 15 is a carbon spectrum of the product obtained in the second step
  • Figure 16 is an infrared spectrum of the product obtained in the second step. From Figures 14-16, it can be concluded that the product obtained in the second step is tri(p-fluorophenyl)silanol.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Figure 17 is the hydrogen spectrum of the product obtained in the first step
  • Figure 18 is the carbon spectrum of the product obtained in the first step
  • Figure 19 is the infrared spectrum of the product obtained in the first step. From Figures 17-19, it can be concluded that the product obtained in the first step is tri(p-chlorophenyl)silanol.
  • the organic phase was dried over 20 g of anhydrous magnesium sulfate, and the crude product was dried at 35°C and washed with 50 mL of n-hexane to obtain 2.30 g of pure product with a yield of 73.5% and a melting point of 115-116°C.
  • Figure 20 is the hydrogen spectrum of the product obtained in the second step
  • Figure 21 is the carbon spectrum of the product obtained in the second step
  • Figure 22 is the infrared spectrum of the product obtained in the second step. From Figures 20-22, it can be concluded that the product obtained in the second step is tri(p-chlorophenyl)silanol.
  • Figure 23 is the hydrogen spectrum of the product obtained in the third step
  • Figure 24 is the carbon spectrum of the product obtained in the third step
  • Figure 25 is the infrared spectrum of the product obtained in the third step
  • Figure 26 is the XRD crystal diffraction structure of the product obtained in the third step. From Figures 23-26, it can be concluded that the product obtained in the third step is bis(tri-p-chlorophenylsilyl) chromate.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Figure 27 is the hydrogen spectrum of the product obtained in the first step
  • Figure 28 is the carbon spectrum of the product obtained in the first step
  • Figure 29 is the infrared spectrum of the product obtained in the first step. From Figures 27-29, it can be concluded that the product obtained in the first step is tri(p-tert-butylphenyl)silane.
  • the organic phase was dried over 20 g of anhydrous magnesium sulfate, and the crude product was dried at 35°C and washed with 50 mL of n-hexane to obtain 1.90 g of product with a yield of 52.3% and a melting point of 192-194°C.
  • Figure 30 is the hydrogen spectrum of the product obtained in the second step
  • Figure 31 is the carbon spectrum of the product obtained in the second step
  • Figure 32 is the infrared spectrum of the product obtained in the second step. From Figures 30-32, it can be concluded that the product obtained in the second step is tri(p-tert-butylphenyl)silanol.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • Figure 33 is the hydrogen spectrum of the product obtained in the first step
  • Figure 34 is the carbon spectrum of the product obtained in the first step
  • Figure 35 is the infrared spectrum of the product obtained in the first step. From Figures 33-35, it can be concluded that the product obtained in the first step is tri(o-tolyl)silane.
  • the organic phase was dried over 10 g of anhydrous magnesium sulfate, and the crude product was dried at 35°C and washed with 50 mL of n-hexane to obtain a white solid product with a yield of 860 mg and a yield of 45.5%.
  • the melting point was 87-88°C.
  • Figure 36 is the hydrogen spectrum of the product obtained in the second step
  • Figure 37 is the carbon spectrum of the product obtained in the second step
  • Figure 38 is the infrared spectrum of the product obtained in the second step. From Figures 36-38, it can be concluded that the product obtained in the second step is tri(o-tolyl)silanol.

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Abstract

提供了一种铬系化合物、其制备方法和应用，以及苄醇类化合物催化氧化的方法。所述铬系化合物具有如式(1)所示的结构：，其中，Ar为 (II)，*表示Ar与Si的连接位点；R 1、R 2和R 3各自独立地选自氰基、烷基、卤素或氢，且不全为氢。所述铬系化合物可用于催化氧化反应，例如，催化氧化苄醇类化合物时，具有好的催化氧化效果。

Description

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
相关申请的交叉引用
本申请要求2023年07月04日提交的中国专利申请202310813731.7的权益，该申请的内容通过引用被合并于本文。
技术领域
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。
背景技术
苯甲酸类化合物是一类重要的有机化合物，其被广泛用于医药、农药和高分子领域。
有机重铬酸吡啶盐在有机溶剂中可以将伯醇和仲醇氧化成醛和酮，一般不会将醇氧化到羧酸，但当反应体系中含有水时，生成的醛酮会进一步形成水合醛或水合酮，进而继续氧化得到羧酸，但是有机重铬酸吡啶盐存在以下缺点：(1)有机重铬酸吡啶盐在反应体系中呈弱酸性，不适用于某些酸敏感化合物，虽可通过加NaOAC粉末作为缓冲剂来减弱其酸性，但效果也不是太好；(2)有机重铬酸吡啶盐对环境污染较严重(Suggs E.Pyridinium chlorochromate.An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds[J].Tetrahedron Letters,1975.)；氯铬酸吡啶盐的氧化能力较有机重铬酸吡啶盐强，其氧化作用一般在中性条件下进行，但是无论是使用有机重铬酸吡啶盐或氯铬酸吡啶盐进行氧化反应，伴随着反应的进行，会生成出黑褐色油状残渣，生成物被这些残渣所包裹，导致产率降低(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.)。
Jones氧化反应(琼斯试剂氧化)是铬酸在丙酮中将一级和二级醇分别氧化为羧酸和酮的反应(Ley S V,Madin A.Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents[J].Comprehensive Organic Synthesis,1991.)，当其氧化二级苄醇原料时，并不能够得到高收率的苯甲酸类化合物，其并不能够得到高收率的，并且Jones试剂(琼斯试剂)是由三氧化铬、硫酸与水配成的水溶液，对于不耐酸性的二级苄醇原料并不适用。
综上，苄醇是一种稳定且易得的原料，但是目前通过苄醇制备苯甲酸较为困难。
发明内容
本发明的目的是为了提供一种铬系化合物及其制备方法，将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，所制的铬系化合物可以溶于有机溶剂中与苄醇类化合物形成均相反应，使反应更有利进行，反应条件温和，氧化完成后形成三价铬反应毒性小。
本发明第一方面提供一种铬系化合物，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。
本发明的第二方面提供了一种铬系化合物的制备方法，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；
其中，Ar、R1、R2和R3的定义其的定义如本发明前述所述。
本发明第三方面提供了本发明所述铬系化合物在催化氧化反应中的应用。
本发明第四方面提供了一种苄醇类化合物催化氧化的方法，该方法包括：
在有机溶剂存在下，将本发明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；
其中，式(I)中Ra选自H、CH3、Cl或F。
通过上述技术方案，本发明提供了一种新的铬系化合物，并且将其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，苄醇类化合物具有高的转化率以及目标产物苯甲酸类化合物具有高的选择性，且催化氧化的反应条件温和，氧化完成后形成三价铬反应毒性小。
附图说明
图1是实施例1中第一步所得产物的氢谱图；
图2是实施例1中第一步所得产物的碳谱图；
图3是实施例1中第一步所得产物的红外谱图；
图4是实施例1中第二步所得产物的氢谱图；
图5是实施例1中第二步所得产物的碳谱图；
图6是实施例1中第二步所得产物的红外谱图；
图7是实施例1中第三步所得产物的氢谱图；
图8是实施例1中第三步所得产物的碳谱图；
图9是实施例1中第三步所得产物的红外谱图；
图10是实施例1中第三步所得产物的xrd晶体衍射结构；
图11是实施例2中第一步所得产物的氢谱图；
图12是实施例2中第一步所得产物的碳谱图；
图13是实施例2中第一步所得产物的红外谱图；
图14是实施例2中第二步所得产物的氢谱图；
图15是实施例2中第二步所得产物的碳谱图；
图16是实施例2中第二步所得产物的红外谱图；
图17是实施例3中第一步所得产物的氢谱图；
图18是实施例3中第一步所得产物的碳谱图；
图19是实施例3中第一步所得产物的红外谱图；
图20是实施例3中第二步所得产物的氢谱图；
图21是实施例3中第二步所得产物的碳谱图；
图22是实施例3中第二步所得产物的红外谱图；
图23是实施例3中第三步所得产物的氢谱图；
图24是实施例3中第三步所得产物的碳谱图；
图25是实施例3中第三步所得产物的红外谱图；
图26是实施例3中第三步所得产物的xrd晶体衍射结构；
图27是实施例4中第一步所得产物的氢谱图；
图28是实施例4中第一步所得产物的碳谱图；
图29是实施例4中第一步所得产物的红外谱图；
图30是实施例4中第二步所得产物的氢谱图；
图31是实施例4中第二步所得产物的碳谱图；
图32是实施例4中第二步所得产物的红外谱图；
图33是实施例5中第一步所得产物的氢谱图；
图34是实施例5中第一步所得产物的碳谱图；
图35是实施例5中第一步所得产物的红外谱图；
图36是实施例5中第二步所得产物的氢谱图；
图37是实施例5中第二步所得产物的碳谱图；
图38是实施例5中第二步所得产物的红外谱图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中所述的卤素表示选自氟元素、氯元素、溴元素和碘元素中的至少一种元素。
本发明中所述的烷基可以为支链烷基，也可以为直链烷基、还可以为直环烷基，本发明对此无特殊限定。
本发明中所述的烷基C1-C10烷基表示碳原子数为1-10的烷基，例如可以为例如可以为碳原子总数为1、2、3、4、5、6、7、8、9或10的直链烷基、支链烷基或者碳原子总数为3、4、5、6、7、8、9或10的环烷基，例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、环丙基、甲基环丙基、环己基等；针对“C1-C4烷基”具有与此相似的解释，所不同的是，碳原子数不同。
如前述，本发明第一方面提供一种铬系化合物，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。
根据本发明一种实施方式，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。
根据本发明一种优选的实施方式，式(1)中，R1、R2和R3各自独立地选自C1-C4烷基、卤素或氢，且不全为氢。
根据本发明一种特别优选的实施方式，式(1)中，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。
根据本发明一种特别优选的实施方式，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：
式(1-1)：R1、R2为氢，R3为F；
式(1-2)：R1、R2为氢，R3为C(CH3)3；
式(1-3)：R2、R3为氢，R1为CH3；
式(1-4)：R1、R2为氢，R3为CH3；
式(1-5)：R1、R2为氢，R3为Cl。
本发明的第二方面提供了一种铬系化合物的制备方法，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；
其中，Ar、R1、R2和R3的定义其的定义如本发明前述所述。
本发明第二方面及以后所涉及的式(1)所示结构的铬系化合物与本发明第一方面中所述的铬系化合物的取代基相同，为了避免重复，本发明不在对铬系化合物进行赘述，本领域技术人员不应理解为对本发明的限制；并且本发明式(2-1)所示的化合物中的R1、R2和R3取代基均与式(1)所示结构的铬系化合物中的取代基对应相同。
根据本发明，只要能实现本发明的目的，所述溶剂的种类没有特殊限制，在一些实施方式中，所述溶剂选自非极性溶剂，优选为四氯化碳、二氯甲烷、苯和己烷中的至少一种。
根据本发明，对于式(2-1)所示的化合物与CrO3的摩尔比可以为1：(2-4)。
根据本发明，对于溶剂的用量没有特殊限制，可为本领域常规的用量，例如溶剂的用 量使式(2-1)所示的化合物在溶剂中的含量为10-50mg/mL。
根据本发明，任选地除水剂指在进行酯化反应时可有除水剂的存在，也可没有除水剂的存在，在进行酯化反应时，会有水产生，为了避免水对酯化反应的影响，优选在有除水剂存在进行酯化反应，对于除水剂的种类，可为本领域常规的除水剂，例如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；对于除水剂的用量没有特别的要求，可以为本领域内常规使用的量，例如除水剂的质量为式(2-1)所示的化合物的质量的30-110wt％。
根据本发明，只要能实现本发明的目的，所述酯化反应的条件没有特殊限定，在一些实施方式中，所述酯化反应的条件包括：反应温度为室温(指25±5℃)。
根据本发明一种特别优选的实施方式，所述酯化反应的条件包括：反应时间为12-36小时。
根据本发明，酯化反应后得到的式(1)所示的化合物先经本领域内常规采用的后处理手段进行后处理得到，例如酯化反应后经过过滤、干燥、重结晶得到；对所述干燥可选择常压干燥，也可选择真空干燥，为本领域常规的技术手段，本发明对此无特殊限制，故不做过多赘述；所述重结晶可选择在有利于晶体析出的溶剂中进行，优选在二氯甲烷和/正己烷中进行重结晶。
根据本发明一种优选的实施方式，本发明所述的铬系化合物的制备方法还包括：按照以下步骤制备式(2-1)所示的化合物：
(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；
(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；
本发明式(2-2)、式(2-3)所示的化合物中的R1、R2和R3取代基均与式(1)所示结构的铬系化合物中的取代基对应相同。
本发明中所述的惰性气氛为氮气和/或氩气，基于成本考虑，优选为氮气。
根据本发明一种优选的实施方式，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。
根据本发明，在制备式(2-3)所示的化合物时，只要能实现式(2-2)所述的化合物与HSiCl3接触进行偶联反应得到式(2-3)所示的化合物即可，本领域技术人员可根据需要选择加料的顺序，例如将含第一溶剂和HSiCl3的物料以滴加的方式加入含第一溶剂和式(2-2)所述的化合物的物料中进行偶联反应；优选滴加的时间控制在0.5-2小时。
本发明对于第一溶剂的用量没有特殊限制，可为本领域常规的用量，例如第一溶剂用量使：含第一溶剂和式(2-2)所述的化合物的物料中式(2-2)所述的化合物的浓度为0.5-1.5M，含第一溶剂和HSiCl3的物料中HSiCl3的浓度为0.1-0.5M。
根据本发明，对于式(2-2)所述的化合物与HSiCl3的摩尔比可以大于等于3:1，优选为 (3.1-3.5):1。
根据本发明一种优选的实施方式，所述偶联反应的条件包括：反应温度为0-100℃，优选为0-50℃。
根据本发明一种优选的实施方式，所述偶联反应的条件包括：反应时间为2-24小时；该反应时间指式(2-2)所述的化合物与HSiCl3开始接触到结束反应的时间。
在本发明中，由式(2-2)所述的化合物与HSiCl3进行偶联反应后得到所述式(2-3)所示的化合物，先经过本领域内常规采用的后处理手段进行后处理，然后再引入至下一个步骤中与邻氯过氧化苯甲酸进行氧化反应；例如，通过分液、有机相浓缩、干燥、重结晶、洗涤后干燥等方式进行后处理；为了中和未完全反应的碱为反应烷的碱，同时更有利于分液提取产物，优选所述后处理还包括酸化步骤，更优选使用盐酸或醋酸进行酸化；为了除去分液后所得有几层中的水，优选所述分液后再使用吸水剂(例如无水硫酸镁)有机层进行干燥；优选使用乙醇与异丙醚进行重结晶；优选使用无水乙醇进行洗涤；具体地，使用0.5-2M的盐酸对偶联反应后得到的物料进行酸化中和，之后加入异丙醚进行分液，有有机层用0.5-2M盐酸25mL洗涤后分液，再无水硫酸镁干燥有机层、之后过滤，在30-40℃下旋转蒸发得到粗产物，随后将粗产物溶于乙醇和异丙醚的混合溶液中，减压浓缩，冷却析晶，最后将析出的晶体用无水乙醇洗涤后真空干燥得到得到式(2-3)所示的化合物。
根据本发明一种优选的实施方式中，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。
根据本发明一种优选的实施方式中，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。
根据本发明，对于第二溶剂的用量没有特殊限制，可为本领域常规的用量，例如第二溶剂的用量使式(2-3)所示的化合物在第二溶剂中的含量为0.02-0.15mg/mL。
根据本发明一种优选的实施方式中，式(2-3)所示的化合物与氧化剂的摩尔比为1：(1.5-3)。
根据本发明一种优选的实施方式中，所述氧化反应的条件包括：反应温度为0-80℃。
根据本发明一种优选的实施方式中，所述氧化反应的条件包括：反应时间为5-100小时。
在本发明中，式(2-3)所示的化合物与邻氯过氧化苯甲酸进行氧化反应经过本领域内常规采用的后处理手段进行后处理后能够得到式(2-1)所述的化合物，例如氧化反应得到的物料依次用饱和碳酸氢钠溶液、饱和食盐水洗涤，有机相经浓缩干燥后，用柱色谱分离得到式(2-1)所述的化合物；优选柱色谱分离时的洗脱液为体积比为(8-12)：1的石油醚(PE)与乙酸乙酯(EA)的混合液。
本发明第三方面提供了本发明所述铬系化合物在催化氧化反应中的应用。
本发明中的铬系化合物具有优异的催化氧化性。
根据本发明一种优选的实施方式中，所述铬系化合物在苄醇类化合物催化氧化中的应用。
在本发明中，将本发明的铬系化合物用于苄醇类化合物催化氧化中时，能够较好地实现苄醇类化合物直接催化氧化得到苯甲酸类化合物的目的，且原料具有高的转化率，目标产物具有高的选择性。
本发明第四方面提供了一种苄醇类化合物催化氧化的方法，该方法包括：
在有机溶剂存在下，将本发明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；
其中，式(I)中Ra选自H、CH3、Cl或F。
在本发明中，将本发明中的铬系化合物用于苄醇类化合物的催化氧化反应中，能够实现在无水、无额外酸性添加剂的情况下得到苯甲酸类化合物，能够适用于不同种类的苄醇类化合物催化氧化高选择性地得到苯甲酸类化合物。
根据本发明一种优选的实施方式中，所述铬系化合物与苄醇类化合物的摩尔比为0.5-3.0。
根据本发明一种优选的实施方式中，所述催化氧化反应的条件包括：反应温度为10-80℃。
根据本发明一种优选的实施方式中，所述催化氧化反应的条件包括：反应时间为3-24小时。
以下将通过实施例对本发明进行详细描述。以下实施例中，原料的来源如表1所示，如无特殊说明，其他原料均可市售得到：
表1原料的来源
对制备得到的化合物进行FTIR、1H NMR、XRD等表征分析，采用元素分析仪进行定量，熔点采用熔点仪进行测定，所涉及的表征、分析方法如表2所示：
表2评价分析方法
实施例1
铬酸双(三对甲苯基甲硅烷基)酯的合成：
第一步：
利用双头针将100mL 1.0M对甲苯基溴化镁溶液压入提前用氮气置换好内部气体的500mL三口瓶，随后用1小时缓慢滴加4.20g三氯硅烷(31mmol)的四氢呋喃溶液100mL，控制温度在35℃以下，滴加完成后在室温下继续搅拌3小时，反应结束后用1.0M盐酸25mL进行中和，用200mL异丙醚进行分液，有机层用1.0M盐酸25mL洗涤后分液，再用20g无水硫酸镁干燥有机层，过滤，在35℃下旋转蒸发得到粗产物，随后将粗产物溶于15mL乙醇和15mL异丙醚中，减压浓缩，冷却析晶，最后将析出的晶体用20mL无水乙醇洗涤后真空干燥得到产物，得到产物5.60g，产率60.3％，熔点75-76℃。
图1为第一步所得产物的氢谱图，图2为第一步所得产物的碳谱图，图3为第一步所得产物的红外谱图，通过图1-3可以得到第一步所得的产物为三(对甲苯基)硅烷。
第二步：
将2.50g三(对甲苯基)硅烷(8.25mmol)溶于30mL二氯甲烷置于50mL三口瓶中，冷却至0℃后加入2.84g(16.50mmol)mCPBA，随后撤去冰浴在室温下搅拌48小时后用370mL二氯甲烷稀释，将液体转移至1000mL分液漏斗中后依次用150mL饱和碳酸氢钠溶液和100mL饱和氯化钠溶液洗涤3次，用20g无水硫酸镁干燥有机相，35℃下旋干得到粗产物后用柱色谱法洗脱(洗脱液中PE:EA＝9:1)得到产物700mg，产率26.6％，熔点108-109℃。
图4为第二步所得产物的氢谱图，图5为第二步所得产物的碳谱图，图6为第二步所得产物的红外谱图，通过图4-6可以得到第二步所得的产物为三(对甲苯基)硅醇。
第三步：
将500mg三(对甲苯基)硅醇(1.57mmol)、450mg三氧化铬(4.50mmol)和0.5g无水硫酸镁置于100mL圆底烧瓶中，以30mL四氯化碳为溶剂，在室温下搅拌24h，随后过滤，在真空下进行干燥得到橙红色粗产物，在室温下从正己烷中重结晶得到产物，并对获得的产物进行X射线晶体衍射测试。
图7为第三步所得产物的氢谱图，图8为第三步所得产物的碳谱图，图9为第三步所得产物的红外谱图；图10为第三步所得产物的xrd晶体衍射结构，通过图7-10可以得到第三步所得的产物为铬酸双(三对甲苯基甲硅烷基)酯。
实施例2
铬酸双(三对氟苯基甲硅烷基)酯的合成：
第一步：
将100mL 1.0M对氟苯基溴化镁加入到提前用氮气置换好内部气体的500mL三口瓶，随后用1小时缓慢滴加4.20g三氯硅烷(31mmol)的四氢呋喃溶液100mL，控制温度在35℃以下，滴加完成后在室温下继续搅拌3小时，反应结束后用1.0M盐酸25mL进行中和，用 200mL异丙醚进行分液，有机层用1.0M盐酸25mL洗涤后分液，再用20g无水硫酸镁干燥有机层，过滤，在35℃下旋转蒸发得到粗产物，随后将粗产物溶于15mL正戊烷，常压下用慢速滤纸过滤脱去析出的有色产物，将滤液在35℃下旋蒸后用10mL甲醇重结晶得到产物4.50g，产率46.2％，熔点44-45℃。
图11为第一步所得产物的氢谱图，图12为第一步所得产物的碳谱图，图13为第一步所得产物的红外谱图，通过图11-13可以得到第一步所得的产物为三(对氟苯基)硅烷。
第二步：
将2.59g三(对氟苯基)硅烷(8.25mmol)溶于30mL二氯甲烷置于50mL三口瓶中，冷却至0℃后加入2.84g(16.50mmol)mCPBA，随后撤去冰浴在室温下搅拌96小时后用370mL二氯甲烷稀释，将液体转移至1000mL分液漏斗中后依次用150mL饱和碳酸氢钠溶液和100mL饱和氯化钠溶液洗涤3次，用20g无水硫酸镁干燥有机相，35℃下旋干得到粗产物后用柱色谱法洗脱(洗脱液中PE:EA＝19:1)得到产物1.80g，产率66.2％，熔点81-82℃。
图14为第二步所得产物的氢谱图，图15为第二步所得产物的碳谱图，图16为第二步所得产物的红外谱图，通过图14-16可以得到第二步所得的产物为三(对氟苯基)硅醇。
第三步：
将517mg三(对氟苯基)硅醇(1.57mmol)、450mg三氧化铬(4.50mmol)和0.5g无水硫酸镁置于100mL圆底烧瓶中，以30mL四氯化碳为溶剂，在室温下搅拌24h，随后过滤，在真空下进行干燥得到橙红色粗产物，在室温下从正己烷中重结晶得到产物，所得产物为铬酸双(三对氟苯基甲硅烷基)酯。
实施例3：
铬酸双(三对氯苯基甲硅烷基)酯的合成：
第一步：
将100mL 1.0M对氯苯基溴化镁溶液加入到提前用氮气置换好内部气体的500mL三口瓶，随后用1小时缓慢滴加4.20g三氯硅烷(31mmol)的四氢呋喃溶液100mL，控制温度在35℃以下，滴加完成后在室温下继续搅拌3小时，反应结束后用1.0M盐酸25mL进行中和，用200mL异丙醚进行分液，有机层用1.0M盐酸25mL洗涤后分液，再用20g无水硫酸镁干燥有机层，过滤，在35℃下旋转蒸发得到粗产物，随后将粗产物在15mL无水乙醇中进行重结晶，过滤后真空干燥得到白色固体，得到产物9.00g，产率79.8％，熔点75-77℃。
图17为第一步所得产物的氢谱图，图18为第一步所得产物的碳谱图，图19为第一步所得产物的红外谱图，通过图17-19可以得到第一步所得的产物为三(对氯苯基)硅醇。
第二步：
将3.00g三(对氯苯基)硅烷(8.25mmol)溶于30mL二氯甲烷置于50mL三口瓶中，冷却至0℃后加入2.84g(16.50mmol)mCPBA，随后撤去冰浴在室温下搅拌48小时后用370mL二氯甲烷稀释，将液体转移至1000mL分液漏斗中后依次用150mL饱和碳酸氢钠溶液和100mL饱和氯化钠溶液洗涤3次，用20g无水硫酸镁干燥有机相，35℃下旋干得到粗产物后用50mL正己烷洗涤得到纯净产物2.30g，产率73.5％，熔点115-116℃。
图20为第二步所得产物的氢谱图，图21为第二步所得产物的碳谱图，图22为第二步所得产物的红外谱图，通过图20-22可以得到第二步所得的产物为三(对氯苯基)硅醇。
第三步：
将1g三(对氯苯基)硅醇(2.70mmol)、720mg三氧化铬(7.20mmol)和0.5g无水硫酸镁置于100mL圆底烧瓶中，以30mL四氯化碳为溶剂，在室温下搅拌24h，随后过滤，在真空下进行干燥得到橙红色粗产物，在室温下从体积比为1:1的二氯甲烷/正己烷的混合溶剂中重结晶得到产物，并对获得的产物进行X射线晶体衍射测试。
图23为第三步所得产物的氢谱图，图24为第三步所得产物的碳谱图，图25为第三步所得产物的红外谱图；图26为第三步所得产物的xrd晶体衍射结构，通过图23-26可以得到第三步所得的产物为铬酸双(三对氯苯基甲硅烷基)酯。
实施例4：
铬酸双(三对叔丁基苯基甲硅烷基)酯的合成：
第一步：
将100mL 1.0M对叔丁基苯基溴化镁溶液加入到提前用氮气置换好内部气体的三口瓶，随后用1小时缓慢滴加4.20g三氯硅烷(31mmol)的四氢呋喃溶液100mL，控制温度在35℃以下，滴加完成后在室温下继续搅拌3小时，反应结束后用1.0M盐酸25mL进行中和，用200mL异丙醚进行分液，有机层用1.0M盐酸25mL洗涤后分液，再用20g无水硫酸镁干燥有机层，过滤，在35℃下旋转蒸发得到粗产物，随后将粗产物在无水乙醇中进行重结晶，过滤后真空干燥得到白色固体，得到产物10.80g，产率81.2％，熔点109-112℃。
图27为第一步所得产物的氢谱图，图28为第一步所得产物的碳谱图，图29为第一步所得产物的红外谱图，通过图27-29可以得到第一步所得的产物为三(对叔丁基苯基)硅烷。
第二步：
将3.54g三(对叔丁基苯基)硅烷(8.16mmol)溶于30mL二氯甲烷置于50mL三口瓶中，冷却至0℃后加入2.81g(16.32mmol)mCPBA，随后撤去冰浴在室温下搅拌24小时后用370mL二氯甲烷稀释，将液体转移至1000mL分液漏斗中后依次用150mL饱和碳酸氢钠溶液和100mL饱和氯化钠溶液洗涤3次，用20g无水硫酸镁干燥有机相，35℃下旋干得到粗产物后用50mL正己烷洗涤得到产物1.90g，产率52.3％，熔点192-194℃。
图30为第二步所得产物的氢谱图，图31为第二步所得产物的碳谱图，图32为第二步所得产物的红外谱图，通过图30-32可以得到第二步所得的产物为三(对叔丁基苯基)硅醇。
第三步：
将1.20g三(对叔丁基苯基)硅醇(2.70mmol)、720mg三氧化铬(7.20mmol)和0.5g无水硫酸镁置于100mL圆底烧瓶中，以30mL四氯化碳为溶剂，在室温下搅拌24h，随后过滤，在真空下进行干燥得到橙红色粗产物，在室温下从体积比为1:1的二氯甲烷/正己烷的混合溶剂中重结晶获得得到产物，所得产物为铬酸双(三对叔丁基苯基甲硅烷基)酯。
实施例5：
铬酸双(三邻甲苯基甲硅烷基)酯的合成：
第一步：
将100mL 1.0M邻甲苯基溴化镁加入到提前用氮气置换好内部气体的三口瓶，随后用1小时缓慢滴加4.20g三氯硅烷(31mmol)的四氢呋喃溶液100mL，控制温度在35℃以下，滴加完成后在室温下继续搅拌3小时，反应结束后用1.0M盐酸25mL进行中和，用200mL异丙醚进行分液，有机层用1.0M盐酸25mL洗涤后分液，再用20g无水硫酸镁干燥有机层，过滤，在35℃下旋转蒸发得到粗产物，通过柱色谱法用石油醚脱去深色的杂质，最后用15mL甲醇洗涤粗产物并干燥得到白色固体，得到产物3.95g，产率42.0％，熔点71-72℃。
图33为第一步所得产物的氢谱图，图34为第一步所得产物的碳谱图，图35为第一步所得产物的红外谱图，通过图33-35可以得到第一步所得的产物为三(邻甲苯基)硅烷。
第二步：
将1.25g三(邻甲苯基)硅烷(4.13mmol)溶于30mL二氯甲烷置于50mL三口瓶中，冷却至0℃后加入1.42g(8.25mmol)mCPBA，随后撤去冰浴在室温下搅拌5小时后用200mL二氯甲烷稀释，将液体转移至1000mL分液漏斗中后依次用100mL饱和碳酸氢钠溶液和50mL饱和氯化钠溶液洗涤3次，用10g无水硫酸镁干燥有机相，35℃下旋干得到粗产物后用50mL正己烷洗涤得到白色固体产物，产量860mg，产率45.5％，熔点87-88℃。
图36为第二步所得产物的氢谱图，图37为第二步所得产物的碳谱图，图38为第二步所得产物的红外谱图，通过图36-38可以得到第二步所得的产物为三(邻甲苯基)硅醇。
第三步：
将8.6g三(邻甲苯基)硅烷(2.70mmol)、720mg三氧化铬(7.20mmol)和0.5g无水硫酸镁置于100mL圆底烧瓶中，以30mL四氯化碳为溶剂，在室温下搅拌24h，随后过滤，在真空下进行干燥得到橙红色粗产物，在室温下从二氯甲烷/正己烷的混合溶剂中重结晶获得得到产物，所得产物为铬酸双(三对邻甲苯基甲硅烷基)酯。
应用例
将1倍摩尔量的苄醇溶于二氯甲烷中，分别于0℃下加入实施例1-5中制备得到铬系化合物后，搅拌3小时，然后升至室温继续反应3小时，经过液相色谱鉴定分析,苄醇的转化率、苯甲酸的选择性如表3所示。
表3苄醇的转化率、苯甲酸的选择性
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (28)

  1. 一种铬系化合物，其特征在于，该化合物具有式(1-1)、式(1-2)、式(1-3)所示的结构：
    其中，式(1)中，Ar为*表示Ar与Si的连接位点；
    式(1-1)：R1、R2为氢，R3为F；
    式(1-2)：R1、R2为氢，R3为C(CH3)3；
    式(1-3)：R2、R3为氢，R1为CH3。
  2. 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，
    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；
    其中，
    其中，式(1)、式(2-1)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。
  3. 根据权利要求2所述的制备方法，其中，
    所述溶剂选自四氯化碳、二氯甲烷、苯和己烷中的至少一种。
  4. 根据权利要求2所述的制备方法，其中，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。
  5. 根据权利要求2所述的制备方法，其中，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。
  6. 根据权利要求2所述的制备方法，其中，
    式(2-1)所示的化合物与CrO3的摩尔比为1：2-4。
  7. 根据权利要求2或3所述的制备方法，其中，
    溶剂的用量使式(2-1)所示的化合物在溶剂中的含量为10-50mg/mL。
  8. 根据权利要求2所述的制备方法，其中，
    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：
    (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；
    (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；
    其中，R1、R2和R3的定义如权利要求2所述，X为卤素。
  9. 根据权利要求8所述的制备方法，其中，所述第一溶剂选自醚类溶剂中的至少一种。
  10. 根据权利要求8或9所述的制备方法，其中，
    所述第一溶剂为乙醚、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。
  11. 根据权利要求8或9所述的制备方法，其中，
    所述第一溶剂为乙醚和/或四氢呋喃。
  12. 根据权利要求8或9所述的制备方法，其中，
    含第一溶剂和式(2-2)所述的化合物的物料中式(2-2)所述的化合物的浓度为0.5-1.5M，含第一溶剂和HSiCl3的物料中HSiCl3的浓度为0.1-0.5M。
  13. 根据权利要求8或9所述的制备方法，其中，
    式(2-2)所述的化合物与HSiCl3的摩尔比大于等于3:1。
  14. 根据权利要求13所述的制备方法，其中，
    式(2-2)所述的化合物与HSiCl3的摩尔比为(3.1-3.5):1。
  15. 根据权利要求8或9所述的制备方法，其中，
    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。
  16. 根据权利要求8所述的制备方法，其中，
    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。
  17. 根据权利要求8所述的制备方法，其中，
    第二溶剂的用量使式(2-3)所示的化合物在第二溶剂中的含量为0.02-0.15mg/mL。
  18. 根据权利要求8所述的制备方法，其中，
    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。
  19. 根据权利要求18所述的制备方法，其中，所述氧化剂为间氯过氧苯甲酸。
  20. 根据权利要求8所述的制备方法，其中，
    式(2-3)所示的化合物与氧化剂的摩尔比为1：1.5-3。
  21. 根据权利要求8所述的制备方法，其中，
    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。
  22. 根据权利要求8所述的制备方法，其中，
    制备式(2-1)所述的化合物还包括以下步骤：
    氧化反应得到的物料依次用饱和碳酸氢钠溶液、饱和食盐水洗涤，有机相经浓缩干燥后，用柱色谱分离得到式(2-1)所述的化合物。
  23. 根据权利要求22所述的制备方法，其中，
    柱色谱分离的洗脱液为石油醚与乙酸乙酯的混合液，石油醚与乙酸乙酯体积比为8-12：1。
  24. 铬系化合物在催化氧化反应中的应用，其特征在于，所述铬系化合物具有式(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。
  25. 铬系化合物在苄醇类化合物催化氧化中的应用，其特征在于，所述铬系化合物具有式(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。
  26. 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：
    在有机溶剂存在下，将铬系化合物加入式(I)所述的苄醇类化合物中进行催化氧化反应；
    其中，式(I)中Ra选自H、CH3、Cl或F；
    所述铬系化合物具有式(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。
  27. 根据权利要求26所述的方法，其中，
    所述铬系化合物与苄醇类化合物的摩尔比为0.5-3.0。
  28. 根据权利要求26所述的方法，其中，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。
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