CN108276280B - Method for preparing formate compounds - Google Patents

Method for preparing formate compounds Download PDF

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CN108276280B
CN108276280B CN201810124892.4A CN201810124892A CN108276280B CN 108276280 B CN108276280 B CN 108276280B CN 201810124892 A CN201810124892 A CN 201810124892A CN 108276280 B CN108276280 B CN 108276280B
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carrier
catalyst
reaction
composite catalyst
activated carbon
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CN108276280A (en
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石峰
魏瑞平
代兴超
王红利
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/04—Formic acid esters
    • C07C69/06—Formic acid esters of monohydroxylic compounds
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/04—Formic acid esters
    • C07C69/06—Formic acid esters of monohydroxylic compounds
    • C07C69/07—Formic acid esters of monohydroxylic compounds of unsaturated alcohols
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/04—Formic acid esters
    • C07C69/08—Formic acid esters of dihydroxylic compounds
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

The method takes an alcohol compound and 1, 3-dihydroxyacetone as reaction raw materials, and the alcohol compound and the 1, 3-dihydroxyacetone react in a reaction medium for 2 to 48 hours at a reaction temperature of between 25 and 100 ℃ in the presence of a composite catalyst and an oxidant so as to obtain the formate compound. The method is simple, the reaction conditions are mild, the target product can be obtained at low cost and high yield by the method, the used catalyst has high catalytic activity and is easy to separate and reuse from a reaction system, the whole process of the method is environment-friendly, the reaction raw material 1, 3-dihydroxyacetone is easy to convert from the biodiesel byproduct glycerol, and the utilization of the glycerol is promoted.

Description

Method for preparing formate compounds
Technical Field
The invention relates to a method for preparing a formate compound, in particular to a method for preparing the formate compound by taking 1, 3-dihydroxyacetone as a carbonyl source, selectively breaking a C-C bond and reacting the C-C bond with an alcohol compound to realize esterification.
Background
The formate compounds have wide application in the fields of chemistry and chemical engineering, pesticides and drug production. For example, methyl formate has higher reactivity because of containing ester groups, aldehyde groups and relatively active aldehyde hydrogen atoms, can be used as a formylation reagent in organic synthesis, can synthesize a plurality of compounds such as formic acid, formamide, dimethylformamide, glycol, trichloromethyl chloroformate, oxalate, acetic anhydride, acetic acid and the like, and is an important carbon-one chemical intermediate and an organic synthesis raw material; methyl formate can also be used as an insecticide, a bactericide, a tobacco treatment agent, a cellulose acetate solvent, and the like. In addition, methyl formate can also be used as a raw material for synthesizing medicaments such as sulfonic acid methyl pyrimidine, sulfonic acid methoxypyrimidine, cough-relieving agent methaphen and the like. It is well known that the reaction of alcohols with formic acid is the primary method for the synthesis of formate compounds. However, formic acid is very corrosive to the equipment and apparatus, and thus efforts are being made to develop cleaner reaction routes.
Glycerin is a main byproduct of biodiesel, and with the continuous development of the biodiesel industry, how to more efficiently and cleanly utilize the glycerin which is a biodiesel byproduct is an important research field. For the purpose of industrial application, there is a strong demand for the development of a method for producing a high value-added compound from glycerin as a raw material. And through microbial activity enzyme and direct catalytic oxidation, the method converts the cheap and easily obtained glycerol into the 1, 3-dihydroxyacetone with high added value, which is an important way in the conversion and utilization of the glycerol. As an important chemical production raw material, 1, 3-dihydroxyacetone has wide application in the industries of fine chemicals, foods, pharmacy and cosmetics.
Disclosure of Invention
The invention aims to provide a method for preparing a formate compound.
The method takes alcohol and 1, 3-dihydroxyacetone as raw materials to synthesize the formate compounds under the catalysis of the composite catalyst under the mild condition.
A method for preparing formate compounds, characterized by taking alcohol compound and 1, 3-dihydroxy acetone as reaction raw materials, in the presence of composite catalyst and oxidizing agent, react in reaction medium, at the reaction temperature of 25-100 duC for 2-48 hours, thus obtain said formate compounds; the composite catalyst consists of oxides of at least two of the following metals, or oxides of at least one of the following metals and at least one simple metal, or at least one simple metal selected from the following metals and activated carbon: aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium; the oxidising agent is a peroxide of the general formula R-O-R ', wherein R and R' are independently selected from H, C1-C5 alkyl or a metal ion.
The alcohol compound is selected from
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、
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、
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、
Figure 671490DEST_PATH_IMAGE004
Or
Figure 423545DEST_PATH_IMAGE005
Wherein R is1And R2Each independently selected from hydrogen and C1-18Alkyl, m is an integer from 1 to 6, n is an integer from 2 to 12; or is selected from
Figure 183691DEST_PATH_IMAGE006
、
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、
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、
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、
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、
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Or
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Wherein R is1、R2、R3And R4Each independently selected from hydrogen and C1-18Alkyl, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine, and n is an integer of 1 to 12.
The molar ratio of the alcohol compound to the 1, 3-dihydroxyacetone is 1: 1-10: 1.
The mass ratio of the composite catalyst to the oxidant to the alcohol compound is 1:5: 5-1: 50: 50.
The composite catalyst consists of oxides of at least two of the following metals, or oxides of at least one of the following metals and at least one simple metal, or at least one simple metal selected from the following metals and activated carbon: aluminum, zinc, silver, copper, palladium, platinum, rhodium, cobalt, iron, ruthenium, manganese, zirconium, and cerium.
The reaction medium is at least one of water, toluene, xylene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile, n-octane and chloroform.
The preparation method of the composite catalyst comprises the following steps: adding at least one oxide selected from the group consisting of aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium to an acetone solution of a soluble salt of at least one metal selected from the group consisting of aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium or at least one activated carbon selected from the group consisting of macroporous activated carbon, transition pore activated carbon, and microporous activated carbon as a carrier, and subjecting the mixture to a simple treatment to obtain a solid support; calcining the solid support to obtain the composite catalyst.
The solid support is carried out at room temperature to 100 ℃ for 2-48 hours; the temperature of the roasting is 200-1000 ℃ and the time is 2-10 hours.
The soluble salt is a nitrate or chloride of the metal; the carrier is selected from at least one oxide of aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium and barium oxides or at least one selected from macroporous activated carbon, transition pore activated carbon and microporous activated carbon.
The composite catalyst is composed of at least two oxides selected from aluminum oxide, zinc oxide, silver, copper oxide, cuprous oxide, copper, palladium, platinum, rhodium, ruthenium, cobalt, cobaltous oxide, ferric oxide, zirconium dioxide, cerium dioxide and cerium oxide, or at least one oxide and at least one metal simple substance or at least one metal simple substance and active carbon.
Compared with the prior art, the method for preparing the formate compound adopts 1, 3-dihydroxyacetone as a carbonyl source, and is economical, cheap and environment-friendly; the catalyst used by the method is simple to prepare and high in catalytic efficiency; the preparation method has mild reaction conditions, and the catalyst has no corrosiveness and is easy to separate and reuse.
Detailed Description
In the method for preparing the formate compound, an alcohol compound and 1, 3-dihydroxyacetone are used as reaction raw materials, and the alcohol compound and the 1, 3-dihydroxyacetone are subjected to catalytic reaction in a reactor for 2 to 48 hours in the presence of a composite catalyst and an oxidant in a reaction medium at the reaction temperature of 25 to 100 ℃, so that the formate compound is obtained.
In the present invention, the term "composite catalyst" refers to a catalyst formed by compounding two or more metal oxides, or at least one metal oxide and at least another metal element, or a catalyst formed by compounding at least one metal element and activated carbon. Preferably, the composite catalyst used consists of oxides of at least two metals selected from the following metals, or consists of an oxide of at least one metal selected from the following metals and at least another elemental metal, or consists of at least one elemental metal selected from the following metals and activated carbon: aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium. Particularly preferred composite catalysts are composed of oxides of at least two metals selected from the following group, or of an oxide of at least one metal selected from the following group and at least another elemental metal, or of at least one elemental metal selected from the following group and activated carbon: aluminum, zinc, silver, copper, palladium, platinum, rhodium, cobalt, iron, ruthenium, manganese, zirconium, and cerium.
In the present invention, the composite catalyst used is preferably prepared by the following method: adding at least one oxide selected from the group consisting of aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium to an acetone solution of a soluble salt of at least one metal selected from the group consisting of aluminum, bismuth, zinc, tin, gold, silver, copper, nickel, palladium, platinum, iridium, rhodium, cobalt, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, lanthanum, yttrium, cerium, magnesium, calcium, and barium or at least one activated carbon selected from the group consisting of macroporous activated carbon, transition-porous activated carbon, and microporous activated carbon as a carrier, and subjecting the carrier to a simple treatment to obtain a solid support; calcining the solid support to obtain the composite catalyst.
For example, in one embodiment, a method of making a composite catalyst comprises the steps of: adding an aqueous solution of any one or two of aluminum nitrate, zinc nitrate, silver nitrate, copper nitrate, cobalt nitrate, ferric nitrate, chloropalladic acid, potassium chloropalladate, chloroplatinic acid, rhodium chloride, ruthenium chloride, zirconium chloride, copper chloride, zirconium nitrate, cerium nitrate, ammonium ceric nitrate and cerium chloride as a carrier into the aqueous solution, impregnating and simply treating the aqueous solution by using aluminum oxide, magnesium oxide, zinc oxide, zirconium oxide, ferric oxide, nickel oxide, copper oxide, cobalt oxide or activated carbon as a carrier, and roasting the obtained solid load to obtain the composite catalyst.
Preferably, the solid support is from room temperature to 100 deg.CoC, performing the reaction for 2 to 48 hours; the temperature of the roasting is 200-800 ℃ and the time is 2-12 hours.
Preferably, the composite catalyst obtained by the above method: the composite material is composed of at least two oxides selected from aluminum oxide, zinc oxide, silver, copper oxide, cuprous oxide, copper, palladium, platinum, rhodium, ruthenium, cobalt, cobaltous oxide, ferric oxide, ferroferric oxide, zirconium dioxide, cerium dioxide and cerium oxide, or at least one oxide and at least one elementary metal, or at least one elementary metal and activated carbon.
In the present invention, it is preferable that the molar ratio of 1, 3-dihydroxyacetone as a carbonyl source to the alcohol compound as the reaction raw material is 1:1 to 1: 10. The 1, 3-dihydroxyacetone and alcohol used in the present invention are directly commercially available from the market.
In the present invention, it is preferable that the alcohol compound as a reaction raw material is selected from
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、
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、
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、
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Or
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Wherein R is1And R2Each independently selected from hydrogen and C1-18Alkyl, m is an integer from 1 to 6, n is an integer from 2 to 12; or is selected from
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、
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、
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、
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、
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、
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Or
Figure 91222DEST_PATH_IMAGE012
Wherein R is1、R2、R3And R4Each independently selected from hydrogen and C1-18Alkyl, methoxy, phenyl, phenoxy, fluorine, chlorine, bromineOr iodine, and n is an integer from 1 to 12;
in the present invention, the reaction medium used is preferably at least one of water, toluene, xylene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile, n-octane and chloroform.
In the present invention, the closed reaction vessel used may be a vessel known in the art which can be sealed to maintain a certain pressure therein, such as a pressure pipe commonly used in chemical reactions, which is generally equipped with a warming or cooling device, such as a water bath, an oil bath, or an ice bath, etc., commonly used in the art, and a venting or emptying supporting facility, such as a gas cylinder, a pressure gauge, etc., which are known to those skilled in the art.
Preparation of composite catalyst
Example 1
Commercially available copper chloride dihydrate 2.2mg (0.013 mmol) was weighed into 4 mL of acetone and magnetically stirred in a 50 mL round bottom flask at room temperature. After complete dissolution, e.g. 400mg of gamma-Al are added with stirring2O3As a carrier, stirring was continued at room temperature for 24 h to obtain a solid powder. Calcination at 450 ℃ for 4 hours in a muffle furnace gave the catalyst as a grey powder, which was shown to be Cu/Al by XRD, XPS, TEM and EXAFS analysis (spectra not shown)2O3The composite, designated catalyst A.
Example 2
Commercially available copper nitrate trihydrate 3.1mg (0.013 mmol) was weighed into 4 mL of acetone and magnetically stirred in a 50 mL round bottom flask at room temperature. After complete dissolution, for example 400mg of Al are added with stirring2O3As a carrier, stirring was continued at room temperature for 24 h to obtain a solid powder. Calcination at 450 ℃ for 4 hours in a muffle furnace gave the catalyst as a grey powder, which was shown to be Cu/Al by XRD, XPS, TEM and EXAFS analysis (spectra not shown)2O3The composite, designated catalyst B.
Example 3
The procedure is as in example 1, except that 400mg of Fe2O3Substituted for gamma-Al2O3To obtain the catalyst Cu/Fe2O3And is designated as catalyst C.
Example 4
The procedure is as in example 1 except that 400mg of Co2O3Substituted for gamma-Al2O3To obtain the catalyst Cu/Co2O3And is designated as catalyst D.
Example 5
The procedure is as in example 1, except that 400mg of Ni2O3Substituted for gamma-Al2O3To obtain the catalyst Cu/Ni2O3And is designated as catalyst E.
Example 6
The procedure is as in example 1, except that 400mg of ZnO is used instead of gamma-Al2O3The catalyst Cu/ZnO was obtained and is denoted as catalyst F.
Example 7
The procedure is as in example 1, except that 400mg of MgO is used instead of gamma-Al2O3The catalyst Cu/MgO, designated catalyst G, was obtained.
Example 8
The procedure is as in example 1, except that 400mg of activated carbon is used instead of gamma-Al2O3Catalyst Cu/C was obtained and was designated catalyst H.
Example 9
The operation is as in example 1, except that 0.013 mmol of zinc nitrate is used instead of copper chloride to obtain the catalyst Zn/Al2O3And is denoted as catalyst I.
Example 10
The same procedure as in example 1 was followed, except that 0.014 mmol of ferric nitrate was used in place of cupric chloride to obtain the catalyst Fe/Al2O3And is designated as catalyst J.
Example 11
The operation was carried out as in example 1 except that 0.006 mmol of cerium nitrate was used in place of copper nitrate to obtain a Ce/ZrO catalyst2And is denoted as catalyst K.
Example 12
The operation is as in example 1, except that 0.008 mmol of potassium hexachloropalladate (IV) aqueous solution is used instead of copper nitrate to obtain the catalyst Pd/Al2O3And is denoted as catalyst L.
Example 13
The operation was carried out as in example 1 except that 0.008 mmol of aqueous ruthenium trichloride solution was used instead of copper nitrate to obtain Ru/Al catalyst2O3And is denoted as catalyst M.
Preparation of formate compounds
Example 14
25 mg of the catalyst A prepared in example 1 was weighed into 38 mL of a pressure tube with magnetic stirring, and then 160 mg (5 mmol) of methanol, 90 mg (1 mmol) of 1, 3-dihydroxyacetone, 0.5 mL (6 mmol) of 35% hydrogen peroxide and 5 mL of chloroform were added. Thereafter, the temperature was raised to 50 ℃ by heating using an electric heating furnace and held for 24 hours. The reaction tube was then cooled to room temperature by water cooling, centrifuged at 8000 rpm for 5 minutes using a centrifuge (Shanghai Anning scientific Instrument Co., Ltd.) and separated to recover catalyst A from the reaction mixture. Using HP 6890/5973GC-MS gas phase mass spectrometer and Agilent 7890A (30 m.times.0.25 mm. times.0.33 μm capillary column, hydrogen flame ionization detector), qualitative and quantitative analysis were performed using a methyl formate standard product as a comparison to obtain the target product methyl formate by methods well known in the art, such as industrial rectification process, with the yield results shown in Table 1 below.
Examples 15 to 26
The same procedure as in example 14 was followed, except that catalyst B, C, D, E, F, G, H, I, J, K, L and M were used in place of catalyst A, respectively, to obtain the results set forth in Table 1 below.
Examples 27 to 34
The same procedure as in example 14 was conducted except that water, toluene, xylene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile and n-octane were used in place of chloroform, respectively, to obtain the results shown in Table 1 below.
TABLE 1
Figure 381389DEST_PATH_IMAGE013
The results in table 1 show that the target formate compound is obtained in a yield of 84% or more by reacting an alcohol compound as a reaction raw material, 1, 3-dihydroxyacetone as a carbonylation reagent, and hydrogen peroxide as an oxidizing agent in a reaction medium in the presence of the prepared composite catalyst. In addition, all the composite catalysts prepared by the invention have higher catalytic activity in the reaction. Furthermore, the results in table 1 also show that the reaction of the invention can be achieved in different reaction media.
Catalyst recycling
Example 35
The catalyst a recovered in example 14 was subjected to centrifugation using a centrifuge (shanghai anstin scientific instrument factory) at 8000 rpm for 5 minutes, followed by separation, washing with chloroform at room temperature and centrifugation, and repeated 3 times. The procedure of example 14 was repeated again using the catalyst A thus recovered. Using HP 6890/5973GC-MS gas phase mass spectrometer and Agilent 7890A (30 m.times.0.25 mm.times.0.33 μm capillary column, hydrogen flame ionization detector) for qualitative and quantitative analysis, a yield of 85% of methyl formate was obtained, using a methyl formate standard product as a comparison.
In addition, the procedure of example 14 was repeated again using the catalyst a recovered after the above-mentioned reuse as the recovery treatment. Using HP 6890/5973GC-MS gas phase mass spectrometer and Agilent 7890A (30 m.times.0.25 mm.times.0.33 μm capillary column, hydrogen flame ionization detector) for qualitative and quantitative analysis, a methyl formate standard product was obtained in 82% yield.
From the above results, it can be seen that the composite catalyst prepared by the present invention can be recycled and still have catalytic activity equivalent to that when initially used, in repeated use.
Further, the other catalysts B, C, D, E, F, G, H, I, J, K, L and M prepared above were also investigated for reuse, and the results obtained were similar to those of catalyst A, i.e., these catalysts still had catalytic activity comparable to that of the catalysts when they were used repeatedly for many times.
Use of different reaction raw materials
Examples 36 to 72
In the same manner as in example 14, 5 mmol of a reaction raw material alcohol, 1 mmol of 1, 3-dihydroxyacetone, 6 mmol of 35% hydrogen peroxide and 5 mL of chloroform were added to a 38 mL reaction tube equipped with magnetic stirring using 25 mg of catalyst A, respectively. The reaction time, temperature and the objective product are shown in tables 2 to 3 below, respectively. After stopping the reaction and cooling to room temperature, the reaction mixture was quantitatively analyzed using an HP 6890/5973GC-MS gas phase mass spectrometer and Agilent 7890A (30 m.times.0.25 mm.times.0.33 μm capillary column, hydrogen flame ionization detector), and the desired product was obtained by conventional means of separation and purification such as distillation, with yields of the desired product being shown in tables 2-3 below.
TABLE 2
Figure 261621DEST_PATH_IMAGE014
TABLE 3
Figure 637238DEST_PATH_IMAGE016
The results in tables 2-3 show that the corresponding formate compounds can be obtained by the method of the present invention in yields of even more than 99% by reacting various alcohol compounds as reaction raw materials with 1, 3-dihydroxyacetone as a carbonylation agent in the presence of the prepared composite catalyst and an oxidizing agent in a reaction medium.
In addition, the present invention also uses the other catalysts B, C, D, E, F, G, H, I, J, K, L and M prepared above to react under different alcohol compound reaction raw materials, temperature, pressure and time, respectively, and also obtains the corresponding target product formate compound, which has similar result (not shown) to the catalyst A.
The method adopts 1, 3-dihydroxyacetone as a formylation source, can use different alcohol compounds as substrates, simply and conveniently prepare the target product formate compound, and has the advantages of economic whole process, low cost and environmental protection; the catalysts used can be prepared simply and inexpensively and have high catalytic activity; the reaction condition is mild, the catalyst is non-corrosive and easy to separate and can be reused, and the method has a wide prospect of industrial production.
It should be noted that various modifications to these embodiments can be made by those skilled in the art without departing from the principles of the present invention, and these modifications should also be construed as being within the scope of the present invention.

Claims (7)

1. A method for preparing formate compounds, characterized by taking alcohol compound and 1, 3-dihydroxy acetone as reaction raw materials, in the presence of composite catalyst and oxidizing agent, react in reaction medium, at the reaction temperature of 25-100 duC for 2-48 hours, thus obtain said formate compounds; the composite catalyst consists of Cu/Al2O3、Cu/Fe2O3、Cu/Co2O3、Cu/Ni2O3、Cu/ZnO、Cu/MgO、Cu/C、Zn/Al2O3、Fe/Al2O3、Ce/ZrO2、Pd/Al2O3And Ru/Al2O3One of (1); the oxidant is H2O2(ii) a The alcohol compound is selected from
Figure DEST_PATH_IMAGE001
、
Figure 548229DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
Or
Figure 465370DEST_PATH_IMAGE004
Wherein R is1And R2Each independently selected from hydrogen and C1-18Alkyl, m is an integer from 1 to 6, n is an integer from 2 to 12; or is selected from
Figure DEST_PATH_IMAGE005
、
Figure 432058DEST_PATH_IMAGE006
、
Figure DEST_PATH_IMAGE007
、
Figure 764950DEST_PATH_IMAGE008
、
Figure DEST_PATH_IMAGE009
、
Figure 264808DEST_PATH_IMAGE010
Or
Figure DEST_PATH_IMAGE011
Wherein R is1、R2、R3And R4Each independently selected from hydrogen and C1-18Alkyl, methoxy, phenyl, phenoxy, fluorine, chlorine, bromine or iodine, and n is an integer of 1 to 12.
2. The method according to claim 1, wherein the molar ratio of the alcohol compound to 1, 3-dihydroxyacetone is 1:1 to 10: 1.
3. The method according to claim 1, wherein the mass ratio of the composite catalyst to the oxidant to the alcohol compound is 1:5:5 to 1:50: 50.
4. The process of claim 1 wherein the reaction medium is at least one of water, toluene, xylene, trimethylbenzene, dioxane, tetrahydrofuran, acetonitrile, n-octane, and chloroform.
5. The method according to claim 1, wherein the composite catalyst is prepared by a method comprising: adding Al to an acetone solution of a soluble salt of copper2O3、Fe2O3、Co2O3、Ni2O3、ZnO、One of MgO or at least one activated carbon selected from macroporous activated carbon, transition pore activated carbon and microporous activated carbon is used as a carrier; or adding Al to acetone solution of soluble salt of zinc2O3As a carrier; or adding Al to acetone solution of soluble salt of iron2O3As a carrier; or adding ZrO to an acetone solution of a soluble salt of cerium2As a carrier; or adding Al to an acetone solution of a soluble salt of palladium2O3As a carrier; or adding Al to acetone solution of soluble ruthenium salt2O3As a carrier; the carrier is simply processed to obtain a solid load; subjecting the solid support to calcination and optionally reduction to obtain the composite catalyst.
6. The method of claim 5, wherein the solid support is carried out at room temperature to 100 ℃ for 2 to 48 hours; the temperature of the roasting is 200-1000 ℃ and the time is 2-10 hours.
7. The method of claim 5, wherein said soluble salt is a nitrate or chloride of said metal.
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