JP2023167909A - Method for producing vicinal diol derivative and catalyst - Google Patents

Abstract

To provide an oxidation catalyst that introduces oxygen into vicinal carbon atoms (vicinal carbon) of unsaturated bonds in unsaturated hydrocarbons with a high yield and selectivity and to provide a method for obtaining a desired diol derivative efficiently by using the catalyst for oxidation of unsaturated hydrocarbons.SOLUTION: The present invention provides a method for producing an oxygen-containing compound. In the presence of a catalyst and a carboxylic acid represented by a formula (1), molecular oxygen is used to oxidize vicinal carbon atoms of unsaturated bonds in unsaturated hydrocarbons represented by a formula (2) to obtain the compound, wherein the catalyst is at least one element selected from a group consisting of Group 11 elements, and metalloid elements such as S, Se, Te, P, As, Sb, Bi, Sn and Pb.SELECTED DRAWING: None

Description

The present invention relates to a method and a catalyst for producing oxygen-containing compounds by oxidizing unsaturated hydrocarbons. Specifically, a method of bonding oxygen to each adjacent carbon of one unsaturated bond of an unsaturated hydrocarbon by an oxidation reaction to obtain an oxygen-containing compound (hereinafter referred to as an adjacent diol derivative), and a catalyst used in the method. be. It has the characteristic of carrying out an oxidation reaction in the presence of a carboxylic acid using a catalyst containing two or more elements as active ingredients and using molecular oxygen as an oxygen source, and has one carboxy group and one OH group, two carboxy groups, or An oxygen-containing compound (hereinafter referred to as an adjacent diol derivative) in which two OH groups are introduced into adjacent carbons of an unsaturated bond is obtained.
A catalyst containing a Group 11 element represented by Au and a metalloid element represented by Te is used.
For example, if 1,3-butadiene is used as the unsaturated hydrocarbon and acetic acid is used as the carboxylic acid,
3,4-dihydroxy-1-butene, 3-hydroxy-4-acetoxy-1-butene, 3
-acetoxy-4-hydroxy-1-butene, 3,4-diacetoxy-1-butene, etc. are obtained.

Diol derivatives are useful compounds that serve as monomers for polymerization of polymer raw materials. Among them, 3,4-diacetoxy-1-butene is used industrially as a monomer for vinyl ester resins and the like. However, 3,4-diacetoxy-1-butene is not a compound that can be obtained by a simple manufacturing method. For example, when oxidative acetoxylation is performed from 1,3-butadiene using an oxidation catalyst such as a palladium telluride catalyst, 1,4-diacetoxy-2-butene is mainly produced, and 3,4-diacetoxy-1- Butene is obtained only in small amounts as a by-product. Although 3,4-diacetoxy-1-butene can also be obtained by isomerizing this 1,4-diacetoxy-2-butene, an additional step for isomerization is required.
As a method for directly producing 3,4-diacetoxy-1-butene, for example, 1,3
A method of acetoxylating -butadiene, acetic acid, and acetic anhydride in the presence of a catalyst such as lithium halide or tellurium oxide has been reported (Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3). However, the yield is low and it is not efficient as it requires additional reagents such as lithium halide.
On the other hand, the unsaturated bonds of unsaturated hydrocarbons are epoxidized by a method such as using a catalyst or peroxygen species such as hydrogen peroxide as described in Patent Document 1, and then the unsaturated bonds of unsaturated hydrocarbons are epoxidized via an epoxy compound (by opening the epoxy ring).
Methods of obtaining vicinal diol derivatives are also conceivable. For example, when using 1,3-butadiene as a raw material, 3,4-epoxy-1-butene is first obtained, and acetic anhydride is reacted with it to produce 3.
, 4-diacetoxy-1-butene (Patent Document 2). but,
There is a concern that the process will become complicated because a peroxygen species such as hydrogen peroxide may be required.
Under these circumstances, the adjacent carbons of the unsaturated bonds of unsaturated hydrocarbons are oxidized by oxidation using molecular oxygen, and a compound (adjacent diol derivative) in which oxygen is introduced into each adjacent carbon is created. A method for directly and selectively obtaining a compound represented by 3,4-diacetoxy-1-butene (for example, the oxidation reaction of 1,3-butadiene in the presence of acetic acid) is desired. It was getting worse.

US Patent No. 6455713 International publication 2000/024702

J.Chem.Soc.,Perkin Trans.1,1985,Pages 499-503 Tetrahedron Letters Volume 22, Issue 52, 1981, Pages 5331-5334 Tetrahedron,Volume 37,Issue 2,1981,Pages 291-295

The present invention has been made in view of the above circumstances. The purpose is to design an oxidation catalyst that introduces oxygen to carbons adjacent to unsaturated bonds (adjacent carbons) of unsaturated hydrocarbons with good yield and selectivity. The purpose is to oxidize unsaturated hydrocarbons using the catalyst to efficiently obtain the desired vicinal diol derivative, and to provide a method that can be applied not only to 1,3-butadiene but also to other unsaturated hydrocarbons. It is.

The present inventor discovered that Group 11 elements such as Au, which were conventionally considered to be catalytically inactive, can be used as catalysts for the oxidation reaction of unsaturated hydrocarbons with molecular oxygen in the presence of carboxylic acids such as acetic acid.
We focused on the combination with metalloids that change the electronic structural properties of group elements. As a result of extensive studies, we found that S, Se, Te, P, As, Sb, Bi
, Sn, and Pb, a catalyst with an appropriate combination of at least one element selected from the group consisting of at least one element selected from the group consisting of Pb, Sn, and Pb has been found to exhibit characteristic selectivity, and a compound in which oxygen is introduced into a carbon adjacent to an unsaturated bond can be selectively obtained. reached.
That is, the gist of the present invention is the following [1] to [6].

[式（１）において、
Ｒ¹は、水素原子、炭素数１又は２の脂肪族炭化水素基を表す。］

[式（２）において、
Ｒ²、Ｒ³、Ｒ⁵及びＲ⁶は、それぞれ独立に、水素原子又はメチル基を表し、
Ｒ⁴は、水素原子又は炭素数１～３の脂肪族炭化水素基を表し、
Ｒ²とＲ⁴は、結合して環を形成していてもよい。］

[式（３）～（６）において、
Ｒ¹～Ｒ⁶は、それぞれ独立であり、式（１）及び（２）のＲ¹～Ｒ⁶とそれぞれ同義であ
る。］
［２］前記式（１）Ｒ¹が、炭素数１又は２の脂肪族炭化水素基である、［１］に記載
の含酸素化合物の製造方法。
［３］前記不飽和結合の隣接炭素を酸化する反応温度が、２５℃以上２００℃以下であ
る、［１］又は［２］に記載の含酸素化合物の製造方法。
［４］不飽和炭化水素の不飽和結合の隣接炭素を酸化する触媒であって、
第１１族元素、半金属元素としてＳ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｎ及びＰｂ
からなる群より選ばれる元素の１種以上を含有するものである、触媒。
［５］前記第１１族元素がＡｕである、［４］に記載の触媒。
［６］前記半金属元素がＴｅである、［４］又は［５］に記載の触媒。 [1] In the presence of a catalyst and a carboxylic acid represented by formula (1),
The catalyst contains Group 11 elements and metalloid elements such as S, Se, Te, P, As, Sb,
Contains one or more elements selected from the group consisting of Bi, Sn and Pb,
Oxidizing the carbon adjacent to the unsaturated bond of the unsaturated hydrocarbon represented by formula (2) using molecular oxygen to obtain a compound represented by any one of formulas (3) to (6), Method for producing oxygen-containing compounds.

[In formula (1),
R ¹ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms. ]

[In formula (2),
R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ² and R ⁴ may be combined to form a ring. ]

[In formulas (3) to (6),
R ¹ to R ⁶ are each independent and have the same meaning as R ¹ to R ⁶ in formulas (1) and (2), respectively. ]
[2] The method for producing an oxygen-containing compound according to [1], wherein R ¹ in the formula (1) is an aliphatic hydrocarbon group having 1 or 2 carbon atoms.
[3] The method for producing an oxygen-containing compound according to [1] or [2], wherein the reaction temperature for oxidizing the carbon adjacent to the unsaturated bond is 25°C or more and 200°C or less.
[4] A catalyst that oxidizes carbon adjacent to an unsaturated bond of an unsaturated hydrocarbon,
Group 11 elements, S, Se, Te, P, As, Sb, Bi, Sn and Pb as metalloid elements
A catalyst containing one or more elements selected from the group consisting of:
[5] The catalyst according to [4], wherein the Group 11 element is Au.
[6] The catalyst according to [4] or [5], wherein the metalloid element is Te.

According to the present invention, the Group 11 elements and metalloid elements include S, Se, Te, P, As, Sb,
By using a catalyst containing one or more elements selected from the group consisting of Bi, Sn, and Pb, carbons adjacent to unsaturated bonds of unsaturated hydrocarbons can be oxidized using molecular oxygen in the presence of a carboxylic acid. Therefore, industrially useful diol derivatives can be efficiently produced in one step from unsaturated hydrocarbons.

Hereinafter, embodiments of the present invention will be described in detail, but the explanation of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents.

(unsaturated hydrocarbon)
In the present invention, a compound (vicinal diol derivative) is obtained by oxidizing an unsaturated hydrocarbon in the presence of a catalyst and a carboxylic acid. The unsaturated hydrocarbon having a double bond is given by the following formula (2).

[In formula (2),
R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ² and R ⁴ may be combined to form a ring. ]

R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and the hydrogen atom of the methyl group may be substituted. When R ³ and R ⁶ are methyl groups, the hydrogen atom of the methyl group may be substituted with a hydroxy group, formyl group, carboxy group, halogen, amino group, nitro group, sulfo group, etc.
Specific examples of formula (2) include diene compounds such as 1,3-butadiene, isoprene, pentadiene, hexadiene, cyclohexadiene, heptadiene, octadiene, and nonadiene.
Among the above, 1,3-butadiene, which is an unsaturated hydrocarbon whose oxidation reaction can be easily controlled, is particularly suitable.

(carboxylic acid)
The carboxylic acid used in the present invention is represented by formula (1).

[In formula (1),
R ¹ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms. ]

R ¹ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms, and among these, an aliphatic hydrocarbon group having 1 or 2 carbon atoms is preferable. Further, the aliphatic hydrocarbon group having 1 or 2 carbon atoms may have a substituent.
The carboxylic acid represented by formula (1) is not particularly limited, and a plurality of carboxylic acids may be used.
Carboxylic acids include saturated fatty acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, and isophthalic acid; acid, dicarboxylic acids such as malonic acid and succinic acid; and the like. From the viewpoint of obtaining high reactivity, saturated fatty acids are preferred, and among these, acetic acid and propionic acid are more preferred, and acetic acid is even more preferred.

Further, a carboxylic anhydride may be further coexisted in the reaction system, and reaction in the coexistence of carboxylic anhydrides such as acetic anhydride, propionic anhydride, benzoic anhydride, oxalic anhydride, and succinic anhydride is preferred. It will be held on. By using a carboxylic anhydride, the yield may be improved by taking advantage of the reaction between the carboxylic anhydride and the water produced during the oxidation reaction. Taking acetic anhydride as an example, the hydrolysis of the carboxy group can be improved. It becomes possible to suppress the hydroxyl group and convert the hydroxyl group to an acetoxy group, thereby improving the yield of the diacetoxy compound.

(Diol derivative)
Diol derivatives, which are the target products of the oxidation reaction of the present invention, are represented by the following formulas (3) to (6).

[In formulas (3) to (6),
R ¹ to R ⁶ are each independent and have the same meaning as R ¹ to R ⁶ in formulas (1) and (2), respectively. ]

For example, if 1,3-butadiene is selected as the raw material unsaturated hydrocarbon (2) and acetic acid is used as the coexisting carboxylic acid (1), the resulting products are expressed by formulas (3) to (6). Specifically, the diol compound is 3,4-dihydroxy-1-butene, 3-hydroxy-4
-acetoxy-1-butene, 3-acetoxy-4-hydroxy-1-butene, and 3,4-diacetoxy-1-butene.

(Non-adjacent diol derivative)
In the oxidation reaction of the present invention, non-adjacent diol derivatives (non-adjacent diol derivatives) may also be produced.
For example, if 1,3-butadiene is selected as the raw material unsaturated hydrocarbon and acetic acid is used as the coexisting carboxylic acid, the non-adjacent diol compound produced is specifically 1,4-butadiene.
-butene diol, 1,3-butene diol, 1,4-diacetoxybutene, 1,3-diacetoxybutene, 1-hydroxy 4-acetoxybutene, 1-acetoxy-4-hydroxybutene, and the like.

(monoalcohol derivative)
In the oxidation reaction of the present invention, a monoalcohol derivative having one oxygen bonded may also be produced. Specific examples include butanol, butenol, acetoxybutene, and acetoxybutane.

If the product obtained by oxidizing an unsaturated hydrocarbon in the presence of a carboxylic acid is a mixture of several types including diol derivatives, or a mixture with non-adjacent diol derivatives or monoalcohol derivatives, distillation etc. It is possible to separate and purify the desired diol derivative by operation. Furthermore, it is possible to provide an additional step, for example, a step of hydrolysis to convert the vicinal diol derivative into a vicinal diol, and a step of reacting (esterifying) with a carboxylic acid or carboxylic acid anhydride to form a hydroxyl diol. A group can be converted to a carboxy group. For example, vicinal diol derivatives obtained by oxidizing 1,3-butadiene in the presence of acetic acid include 3,4-butenediol, 3-hydroxy-4-acetoxybutene, and 4-hydroxy-3-acetoxybutene in the presence of acetic acid or By reacting with acetic anhydride, 3,4-diacetoxybutene can be obtained.

[catalyst]
The catalyst of the present invention is used in a reaction to produce an adjacent diol derivative by introducing oxygen into adjacent carbons of an unsaturated bond of an unsaturated hydrocarbon in the presence of a carboxylic acid, and includes a group 11 element,
and a metalloid element (at least one selected from the group consisting of S, Se, Te, P, As, Sb, Bi, Sn, and Pb) as an active ingredient.
By using the catalyst of the present invention, it is possible to easily produce the desired vicinal diol derivative in one step without the need for multi-step reaction steps or additional reagents such as lithium halide, thereby increasing the selectivity and yield of the desired vicinal diol derivative. will improve.
The respective roles of Group 11 elements and metalloid elements are not clear, but due to interactions such as alloying and intermetallic compounds, or adjacency of each element in the catalyst, the electronic structure characteristics of each other or the raw material It affects stereoelectronic effects with intermediates and products, and exhibits the effect of introducing oxygen to the carbon adjacent to the unsaturated bond in reactions with unsaturated hydrocarbons, carboxylic acids, and oxygen. Furthermore, each element plays an auxiliary role such as reoxidizing the catalytic active sites, thereby improving the catalytic activity. Such concerted action improves the selectivity of adjacent diol derivatives and promotes catalytic activity.

(Group 11 elements)
Group 11 elements include Au, Cu, Ag, etc. Among these, Au is more preferable because it has a high oxidation-reduction potential and is less likely to be eluted as a metal in a carboxylic acid solution.
Since Group 11 elements also play the role of active sites, it is preferable to maintain their metallic state during the oxidation reaction, but it is also preferable to control the reaction selectivity toward adjacent diol derivatives by forming them into alloys, etc. used.

The amount of the Group 11 element contained in the catalyst of the present invention is not particularly limited, and can be appropriately adjusted depending on other elements contained in the catalyst and the type of support described below. However, usually 0.
1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less,
The content is more preferably 40% by mass or less, and even more preferably 20% by mass or less. When it is at least the lower limit, a sufficient number of active sites are formed, and when it is at most the upper limit, aggregation of elements is suppressed, and adjacent diol derivatives can be efficiently produced.

(metalloid element)
By interacting with the Group 11 element or being adjacent to the Group 11 element, the metalloid element influences the electronic structure properties of the Group 11 element and improves the reaction selectivity toward adjacent diol derivatives, and also serves as a catalyst. It plays a role in maintaining or promoting activity. Stability that does not cause leaching even in the presence of a carboxylic acid is also required, and elements that have high electronegativity and are difficult to become cations are preferred. In terms of allene electronegativity, it is an element with an electronegativity of 1.8 or more and 2.6 or less, S, S
At least one kind is selected from the group consisting of e, Te, P, As, Sb, Bi, Sn, and Pb. Among these, Se, Te, Sb and Bi have excellent ability to improve selectivity and activity.
It is preferable to include Te, and Te is particularly preferable.

The amount of the metalloid element contained in the catalyst of the present invention is not particularly limited, but it is usually 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and usually 80% by mass. % or less, preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 20% by mass or less. Metalloid elements have a strong influence on catalytic activity and selectivity, so
It is preferable to adjust the supported amount depending on the number of moles of the Group 11 element.
The amount of metalloid element to Group 11 element expressed as a molar ratio is usually 0.001 to 100.
0, more preferably 0.05 to 500. By using an appropriate amount of metalloid element, the selectivity and yield of the vicinal diol derivative can be increased.

The catalyst of the present invention is not particularly limited as long as it contains one or more of Group 11 elements and metalloid elements as active ingredients, but it may contain two or more of each of them. It may be contained in the catalyst as an oxide and may also function as a carrier. The Group 11 element and the metalloid element may form an alloy or an intermetallic compound. In addition, active ingredients other than Group 11 elements and metalloid elements may be included. For example, when Rh or Ir is combined with a Group 11 element, the properties can be changed and the selectivity of adjacent diol derivatives can be increased.
Further, in order to obtain a large number of catalytic active sites, it is preferable that the particles of Group 11 elements, metalloid elements, alloys thereof, and intermetallic compounds are kept in nano size. The particle size can be estimated using the Scherrer equation from analysis using a transmission electron microscope or from the half-value width of a diffraction line peak in powder X-ray diffraction measurement. Usually, it is 0.1 nm or more and 100 nm or less, preferably 0.5 nm or more and 50 nm or less, particularly preferably 1 nm or more and 30 nm or less.

(Catalyst carrier)
The catalyst of the present invention is a complex catalyst having one or more of Group 11 elements and metalloid elements as active components, but in order to effectively utilize these elements and to promote their interaction and contact, A carrier can be used.
The type of carrier is not particularly limited, but it usually includes silica, alumina, zirconia, ceria, silica alumina, magnesia silica, titanosilicate, zeolite, titania, mesoporous silica, mesoporous titania, iron oxide, copper oxide, tungsten oxide, and oxide. Inorganic compounds such as niobium, manganese oxide, molybdenum oxide, carbon nitride, porous silica, activated carbon, carbon black, and Ketjen black are used.
When using these carriers, the total supported amount of Group 11 elements and metalloid elements is 0.05
% or more, more preferably 0.1% or more, even more preferably 0.5% or more, 1.
Particularly preferred is 0% or more. Also, preferably 50% or less, more preferably 30% or less, 2
It is more preferably 0% or less, particularly preferably 10% or less.

(Catalyst preparation method)
The method for preparing the catalyst is not particularly limited, and the following existing methods and combinations thereof can be used. When using a carrier, it is possible to use a coprecipitation method, a precipitation precipitation method, an ion exchange method, an impregnation support method, a pore filling method, an incipient-wetness method, a spray support method, and the like.
As raw materials used in the precipitation precipitation method, ion exchange method, impregnation support method, etc., water-soluble salts such as halogen compounds and nitrates, or acidic solutions thereof are usually used. In addition to carbonates, formates, acetates, oxalates, nitrates, and sulfates, halogen-free water-soluble raw materials such as ammine nitrates, ethylenediamine nitrates, and ammine nitro compounds are preferred. When a halogen substance is used, the halogen is preferably removed by washing with a basic aqueous solution or water before firing or hydrogen reduction.
In particular, in the catalyst of the present invention, selection of the raw material for the Group 11 element is important in obtaining a high-performance catalyst. Usually, acidic raw materials such as chloroauric acid are used, but as raw materials that do not contain halogen elements, catalysts prepared using nanometals modified with protective agents such as PVP (polyvinylpyrrolidone), ethylenediamine complexes, etc. Alanine complexes and oxalates may be used as raw materials. In particular, chloroauric acid and ethylenediamine complexes are preferred from the viewpoints of solubility in water, ease of preparation, and storage stability under air.
These raw materials are used as a solution, and the raw material concentration, pH, temperature, etc. are controlled during contact with the carrier. After an active metal component is supported on a carrier by a precipitation precipitation method, an ion exchange method, or an impregnation support method, water is removed by filtration, washing with water, or drying.
Using the existing methods described above, multiple types of elements may be simultaneously introduced into one carrier using raw material liquids containing multiple types of Group 11 elements and metalloid elements, or by using liquids containing each element. Multiple species may be introduced by multiple operations, such as sequentially introducing them. Furthermore, it is also preferable to interpose treatments such as drying, calcination, and hydrogen reduction between the sequential introductions. Furthermore, carriers carrying respective elements of Group 11 elements and metalloid elements may be mixed by physical mixing.
The obtained catalyst (precursor) is usually subjected to an oxidation reaction in the presence of a carboxylic acid after drying or calcination, but it is also effective to perform pretreatment before the reaction in order to efficiently develop active sites. It is carried out according to As the pretreatment, high-temperature treatment in an inert gas atmosphere or high-temperature treatment (hydrogen reduction) in a gas containing hydrogen is suitably performed.

[Oxidation reaction in the presence of carboxylic acid]
In the oxidation reaction of the present invention, an unsaturated hydrocarbon is brought into contact with the catalyst of the present invention in the presence of a carboxylic acid at normal or pressurized conditions to obtain a vicinal diol derivative. The oxidation reaction can be carried out by either a liquid phase reaction or a gas phase reaction, but it is possible to carry out the oxidation reaction by continuously supplying a mixed gas of a gaseous unsaturated hydrocarbon and molecular oxygen into a carboxylic acid solvent containing a catalyst. A liquid phase reaction in which an oxidation reaction is carried out by bringing an unsaturated hydrocarbon or molecular oxygen dissolved in a carboxylic acid into contact is preferred.

The reaction format is not particularly limited and can be carried out by any method such as a batch reaction method or a flow reaction method, but it is preferable to use a flow reaction method that can be carried out continuously industrially. . The flow reaction method using a fixed bed also has the advantage that the catalyst can be easily replaced and regenerated by devising the reactor and process.

There is no limit to the concentration of molecular oxygen for the oxidation reaction to proceed, but it is usually adjusted to maintain a concentration that avoids the explosive range of unsaturated hydrocarbons and carboxylic acids at the inlet and outlet of the reactor. be done. At the inlet of the reactor, the overall concentration is usually 1 mol.
The content is 1 mol% or more and 50 mol% or less, preferably 2 mol% or more and 20 mol% or less, and more preferably 4 mol% or more and 10 mol% or less. As the oxygen source, air may be used in addition to oxygen gas.
The reaction temperature is preferably 25°C or higher, more preferably 40°C or higher, and even more preferably 5°C or higher.
The temperature is 0°C or higher. Further, the temperature is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. By setting the reaction temperature to the above upper limit value or less, it is possible to suppress the sequential reactions of the raw material unsaturated hydrocarbon and the produced adjacent diol derivative. When the reaction temperature is equal to or higher than the above lower limit, the progress of the reaction is promoted and an industrially satisfactory reaction rate can be obtained.
The reaction pressure is preferably 0.1 MPa or higher, more preferably 1 MPa or higher, even more preferably 2 MPa or higher. Also, preferably 10 MPa or less, more preferably 5 MPa
The pressure is preferably 4 MPa or less. By the reaction pressure being below the above upper limit,
Oxidative decomposition of the raw material unsaturated hydrocarbon and the produced vicinal diol derivative can be prevented. When the reaction pressure is equal to or higher than the above lower limit, the progress of the reaction is promoted and an industrially satisfactory reaction rate can be obtained.

The generated vicinal diol derivative is usually separated from unreacted unsaturated hydrocarbons, carboxylic acids, by-products, etc., and further refined to increase its purity and become a product. Note that unreacted unsaturated hydrocarbons, carboxylic acids, and byproducts are recovered and used again as raw materials or products. In separation and purification, distillation that utilizes the difference in boiling points is preferably used.

As explained above, the catalyst of the present invention has a Group 11 element represented by Au and a metalloid element represented by Te, and the oxidation reaction of unsaturated hydrocarbons in the presence of a carboxylic acid using the catalyst. By this method, vicinal diol derivatives can be obtained in a very simple and one-step reaction with good yield and selectivity. For example, when 1,3-butadiene is selected as the unsaturated hydrocarbon and acetic acid is used as the carboxylic acid, 3,4-dihydroxy-1-butene, 3,4-diacetoxy-1-butene, 3-hydroxy- 4-acetoxy-1-butene, 3-acetoxy-4-
Hydroxy-1-butene can be obtained efficiently.
Furthermore, more dicarboxy compounds can be obtained by additionally providing a reaction (esterification) step with a carboxylic acid or carboxylic acid anhydride to convert a hydroxy group into a carboxy group. For example, vicinal diol derivatives obtained by oxidizing 1,3-butadiene in the presence of acetic acid include 3,4-butenediol, 3-hydroxy-4-acetoxybutene, and 4-hydroxy-3-acetoxybutene in the presence of acetic acid or By reacting with acetic anhydride,
More 3,4-diacetoxybutene can be obtained.

EXAMPLES The present invention will be described in more detail below with reference to Examples. However, the present invention is not limited to these Examples. Note that quantitative analysis of organic compounds such as products shown in Examples and Comparative Examples was performed by gas chromatography (GC). Details are shown below.

・Quantitative analysis method for organic compounds Accurately weigh 0.15 g of the reaction solution from which the catalyst has been separated by a method such as filtration, and 0.05 g of diethylene glycol dimethyl ether (internal standard), and add 1.5 mL of isopropyl alcohol.
The sample was used as an analytical sample and subjected to GC analysis under the following conditions.
Equipment: FID-GC Shimadzu GC2014
Column: Agilent DB-FFAP column, 60m
Temperature: Vaporization chamber temperature 240℃, detector temperature 240℃
Measurement conditions: Column section program temperature increase used
Hold at 60℃ for 10 minutes, raise temperature to 220℃ at 5℃/min, hold at 220℃ for 20 minutes

(Example 1)
A catalyst in which Au (group 11 element) and Te (group 16 element) were supported on silica was prepared as shown below.
First, Au ethylenediamine chloride was prepared as follows. Ethylenediamine 3.7
5 g of ethanol and 100 mL of ethanol were placed in a three-necked flask equipped with a Dimroth condenser and a stirrer, and 100 mL of diethyl ether in which 5.0 g of chloroauric acid was dissolved was slowly added while stirring. After stirring for 24 hours at 25°C, the precipitate was filtered off and washed with acetone. The resulting precipitate was dried under vacuum for 12 hours to obtain Au ethylenediamine chloride.
0.215 g of the obtained Au ethylenediamine chloride was dissolved in 10 mL of deionized water to form an aqueous solution. This solution was impregnated into 5.00 g of a silica carrier (Carryact Q15 75-500 μm, manufactured by Fuji Silysia) using a glass container without a lid. After mixing to a uniform state, the container was heated in a hot water bath to remove water from the mixture while stirring. Next, 10 mL of a 0.5M NaOH aqueous solution was impregnated into the silica carrier supporting the above Au complex. After mixing to a uniform state, the container was heated in a hot water bath to remove water from the mixture while stirring. Furthermore, after suspending the above dried product in 100 mL of 0.05M NaOH aqueous solution, the suspended solid was filtered off. After washing with water until Cl- was no longer detected in the washing solution, it was transferred to a glass container without a lid, and the container was heated in a hot water bath to remove moisture. The obtained dried product was loaded into a glass baking tube and heated at 100°C under air flow of 200mL/min.
After drying for 7 hours, the temperature was raised to 400°C over 2 hours. After maintaining the temperature at 400° C. for 4 hours, the temperature was raised to room temperature to obtain silica-supported Au.
Next, the above silica-supported Au was impregnated with an aqueous solution in which 0.180 g of telluric acid was dissolved in 10 mL of demineralized water using a glass container without a lid. After mixing to a homogeneous state,
The container was heated in a hot water bath to remove water from the mixture while mixing. The obtained dried product was loaded into a glass firing tube, and the temperature was raised to 300° C. over 2 hours under air circulation at 200 mL/min. After maintaining the temperature at 300° C. for 4 hours, the temperature was lowered to room temperature. Furthermore, the temperature of the obtained calcined product was raised to 400°C over 2 hours under a hydrogen flow of 75 mL/min, and the temperature was maintained at 400°C for 2 hours to perform a reduction treatment. 2wt
%, Te: 2wt%).
Using the prepared silica-supported Au⇒Te catalyst, the oxidation reaction of 1,3-butadiene in the presence of acetic acid was carried out as follows. 1.0 g of the above catalyst and 40 mL of acetic acid were loaded into a 50 mL Pyrex (registered trademark) three-necked flask equipped with a thermometer for measuring liquid temperature and a stirring bar, and the liquid was stirred using a magnetic stirrer to dissolve the catalyst in acetic acid. suspended in. Nitrogen (
50 Nml/min) and heated the flask using an oil bath under a nitrogen atmosphere. The temperature was raised at a rate of 5 to 10°C/min, and after the temperature of the liquid reached 90°C, the composition of the bubbling gas was changed to a mixed gas of 1,3-butadiene 6NmL/min and oxygen 4Nml/min, and the mixture was heated to normal pressure. The oxidation reaction was carried out under the following conditions: , 90° C., and a stirrer rotating at 500 rpm for catalyst suspension. Six hours after starting the introduction of the raw material 1,3-butadiene, change the bubbling gas composition to nitrogen at 50 NmL/min to complete the oxidation reaction, immediately stop the suspension stirring, and remove the flask from the oil bath. The temperature of the liquid was lowered to around room temperature. Thereafter, a portion of the liquid in the flask was taken out and the products etc. were analyzed by the method described above.

When 1,3-butadiene is oxidized in the presence of acetic acid, the following compounds are mainly produced. 3,
4-diacetoxy-1-butene (abbreviated as 3,4-DABE), 3-hydroxy-4-acetoxy-1-butene (abbreviated as 3,4-HABE), 3-acetoxy-4-hydroxy-1
-butene (abbreviated as 3,4-HABE), 3,4-dihydroxy-1-butene (3,4-B
(abbreviated as EG). These are combined to form a vicinal diol derivative.
Also, 1,4-diacetoxy-2-butene (abbreviated as 1,4-DABE), 1-hydroxy-4-acetoxy-2-butene (abbreviated as 1,4-HABE), 1,4-dihydroxy-
2-Butene (abbreviated as 1,4-HABE) is also produced. These are combined to form a non-adjacent diol derivative.
Furthermore, acetoxybutene and butenol may also be produced. These are referred to as monoalcohol derivatives.

The reaction solution after 6 hours of reaction was analyzed, and the reaction rate and selectivity were determined from the following equations.
Reaction rate (mol/h・g-cat) = (Amount of adjacent diol derivative in reaction solution (mol)
+Amount of non-adjacent diol derivative (mol)+Amount of monoalcohol derivative (mol))/(Amount of catalyst (g) x Reaction time (h))
Adjacent diol derivative selectivity = amount of adjacent diol derivative in reaction solution (mol) / (amount of adjacent diol derivative in reaction solution (mol) + amount of non-adjacent diol derivative (mol) + amount of monoalcohol derivative (mol)) x 100

Details of the catalyst used and reaction results are shown in Table 1.

(Example 2)
In the catalyst preparation of Example 1, the order of supporting Te and Au on a silica carrier was changed, and the catalyst containing Au (Group 11 element) and Te (Group 16 element) was changed, and Te was supported on silica first. A Te⇒Au catalyst (Au: 2 wt%, Te: 2 wt%) was prepared. Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

(Example 3)
In the catalyst preparation of Example 1, a catalyst containing Rh in addition to Au (Group 11 element) and Te (Group 16 element) was prepared as follows.
First, Au ethylenediamine nitrate was prepared as follows. An aqueous silver nitrate solution of the same molar amount as the chlorine ion of the Au ethylenediamine chloride obtained in Example 1 was added until no silver chloride precipitated. The produced silver chloride was removed by filtration, and ethanol was added to the filtrate to cause reprecipitation. The obtained precipitate was dissolved in a small amount of water, reprecipitated with ethanol, and the resulting precipitate was filtered. After repeating this reprecipitation operation three times, the resulting precipitate was mixed with 90 vol of ethanol.
% aqueous solution and finally with acetone, the resulting solid was vacuum dried for 24 hours, and A
U ethylenediamine nitrate was obtained.

Next, the catalyst was prepared as follows. Obtained Au ethylenediamine nitrate 173m
g, 96 mg of nitric acid solution containing 7.35 wt% rhodium, and 4 mg of telluric acid were dissolved in demineralized water,
A 5 ml solution was prepared. 2.5 g of silica carrier (Carryact Q15 75-500 μm, manufactured by Fuji Silysia) was placed in a glass container without a lid, and the above aqueous solution was added. After mixing to a uniform state, the container was heated in a hot water bath to remove moisture from the mixture. The obtained dried product was loaded into a glass firing tube, dried at 100° C. for 7 hours under air circulation at 200 mL/min, and then heated to 200° C. over 2 hours. After maintaining the temperature at 200° C. for 4 hours, the temperature was lowered to room temperature. Furthermore, the obtained baked product was heated for 40 minutes under hydrogen flow of 75 mL/min.
The temperature was raised to 0°C over 2 hours, and the temperature was maintained at 400°C for 2 hours to perform a reduction treatment.
89 wt%). Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

(Comparative example 1)
A catalyst in which Pd (group 10 element) and Te (group 16 element) instead of Au (group 11 element) were supported on silica was prepared as shown below. 2.5 g of a silica carrier (Carryact Q15 75-500 μm, manufactured by Fuji Silysia) was placed in a glass container without a lid, and a mixed aqueous solution of telluric acid dissolved in a nitric acid solution of palladium nitrate was added. After mixing to a uniform state, the container was heated in a hot water bath to remove water from the mixture. The obtained dried product was loaded into a glass baking tube and dried at 100°C for 7 hours under air flow of 200 mL/min.
The temperature was raised to 00°C over 2 hours. After maintaining the temperature at 200° C. for 4 hours, the temperature was lowered to room temperature. Furthermore, the temperature of the obtained calcined product was raised to 400°C over 2 hours under a hydrogen flow of 75 mL/min, and the temperature was maintained at 400°C for 2 hours to perform a reduction treatment.
A catalyst (Pd: 5.0 wt%, Te: 1.5 wt%) was obtained. Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

A comparison between Example 1-3 and Comparative Example 1 shows that the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) exhibits high catalytic activity, and shows that the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) exhibits high catalytic activity. It can be seen that the reaction rate of the oxidation reaction is accelerated and high selectivity toward adjacent diol derivatives is exhibited.

(Example 4)
First, silica supporting 5 wt% MgO, which will serve as a carrier precursor, was prepared as follows. Dissolve 2.68 g of magnesium acetate in a suitable amount of water, and add 1 silica powder (Carryact Q15).
0g was added and impregnated by the pore filling method. It was transferred to a glass container without a lid, and the water was evaporated in a hot water bath. Further, it was transferred to a tubular firing tube, dried at 110°C for 7 hours under an air flow, then fired at 600°C for 4 hours, left to cool, taken out, and silica-supported MgO (MgO
:5 wt%).

2.0 g of the above silica-supported MgO was added to 50 mL of a chloroauric acid aqueous solution heated to 85°C. Au was adsorbed on the silica in the form of ion exchange with Mg hydroxided in an aqueous solution.
Stirring was continued for about 30 minutes while heating, then stirring was stopped and the mixture was allowed to cool. After the temperature dropped, decantation was performed, and filtration and water washing were repeated until Cl- was no longer detected by the silver nitrate aqueous solution method. The filtered and washed product was transferred to a glass container without a lid, the water was evaporated in a hot water bath, and then transferred to a tubular baking tube, dried at 110°C for 7 hours under an air flow, and then heated at 400°C.
It was baked at ℃ for 4 hours. After cooling, it was taken out to obtain silica-supported Au (Au: 2.0 wt%).
Next, tellurium was introduced as follows. Obtained silica-supported Au (2.0wt%) 1.0
g was immersed in an aqueous telluric acid solution, transferred to a glass container without a lid, and the water was evaporated while stirring to ensure uniformity. Further, it was transferred to a tubular firing tube, dried at 110°C for 7 hours under an air flow, and then fired at 400°C for 4 hours. After cooling, take out the silica-supported Au⇒Te
A catalyst (Au: 2.0 wt%, Te: 0.5 wt%) was obtained. Using the prepared catalyst,
In the same manner as in Example 1, the oxidation reaction of 1,3-butadiene in the presence of acetic acid and the analysis of the product were performed. Table 1 shows the contents of the catalyst used and the reaction results.

(Example 5)
In the catalyst preparation of Example 4, a silica-supported Au⇒Te catalyst (Au: 2.0 wt%, Te: 0.1 wt%) was obtained in the same manner as in Example 4, except that the amount of supported telluric acid was changed. . Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

(Comparative example 2)
In the catalyst preparation of Examples 4 and 5, the silica-supported Au catalyst (Au
:2.0wt%). Using the catalyst, 1 in the presence of acetic acid in the same manner as in Example 1.
, 3-butadiene oxidation reaction and product analysis were carried out. Table 1 shows the contents of the catalyst used and the reaction results.

A comparison between Examples 4 and 5 and Comparative Example 2 shows that the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) exhibits high catalytic activity, and shows that the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) exhibits high catalytic activity. It can be seen that the reaction rate of the oxidation reaction is accelerated and high selectivity toward adjacent diol derivatives is exhibited.

(Example 6)
2.0 g of powdered Monoclinic ZrO ₂ (Saint-Gobain Norpro SZ31164) was added to 30 mL of chloroauric acid aqueous solution heated to 70°C, and 0.1 M sodium hydroxide was added for about 20 minutes while vigorously stirring with a stirrer tip. The pH was adjusted to 8-9 by dropwise addition. Stirring was continued for about 20 minutes while heating, then stirring was stopped and the mixture was allowed to cool. After the temperature dropped, decantation was performed, and filtration and water washing were repeated until Cl- was no longer detected by the silver nitrate aqueous solution method. The filtered and rinsed product was transferred to a glass container without a lid, the water was evaporated in a hot water bath, and then transferred to a tubular baking tube, dried at 110°C for 7 hours under an air flow, and then heated at 400°C for 4 hours.
Baked for an hour. After being left to cool, it was taken out to obtain zirconia-supported Au (2.0 wt%).

Next, tellurium was introduced as follows. The obtained zirconia-supported Au (2.0 wt%),
1.0 g was immersed in an aqueous telluric acid solution, transferred to a glass container without a lid, and the water was evaporated while stirring to make it uniform. Further, it was transferred to a tubular firing tube, dried at 110°C for 7 hours under an air flow, and then fired at 350°C for 4 hours. After cooling, it was taken out to obtain a zirconia-supported Au⇒Te catalyst (Au: 2.0 wt%, Te: 0.75 wt%). Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

(Comparative example 3)
In the catalyst preparation of Example 6, the zirconia-supported Au catalyst (Au
:2.0wt%). Using the catalyst, 1 in the presence of acetic acid in the same manner as in Example 1.
, 3-butadiene oxidation reaction and product analysis were carried out. Table 1 shows the contents of the catalyst used and the reaction results.

A comparison between Example 6 and Comparative Example 3 shows that the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) exhibits high catalytic activity and is effective in the oxidation reaction of 1,3-butadiene in the presence of acetic acid. It can be seen that the reaction rate can be increased and at the same time, high selectivity to adjacent diol derivatives can be obtained.

(Example 7)
4.0 g of powdered monoclinic zirconia (Saint-Gobain Norpro SZ31164) was immersed in an aqueous telluric acid solution, transferred to a glass container without a lid, and the water was evaporated while stirring to ensure uniformity. Further, it was transferred to a tubular firing tube, dried at 110°C for 7 hours under an air flow, and then fired at 400°C for 4 hours. After cooling, it was taken out and zirconia-supported Te (1.
0 wt%) was obtained.
The above zirconia-supported Te (1.0 wt%
), and while stirring vigorously with a stirrer chip, 0.1M sodium hydroxide was added dropwise over about 20 minutes to adjust the pH to 8-9. Stirring was continued for about 20 minutes while heating, then stirring was stopped and the mixture was allowed to cool. After the temperature dropped, decantation was performed, and filtration and water washing were repeated until Cl- was no longer detected by the silver nitrate aqueous solution method. The filtered water was transferred to a glass container without a lid, and the water was evaporated in a hot water bath. Further, it was transferred to a tubular firing tube, dried at 110°C for 7 hours under an air flow, and then fired at 400°C for 4 hours. After cooling, it was taken out to obtain a zirconia-supported Te⇒Au catalyst (Au: 2.0 wt%, Te: 1.0 wt%). Using the prepared catalyst, oxidation reaction of 1,3-butadiene in the presence of acetic acid and analysis of the product were performed in the same manner as in Example 1. Table 1 shows the contents of the catalyst used and the reaction results.

(Comparative example 4)
In the catalyst preparation of Example 7, zirconia-supported Te (Te:1.
0 wt%) was obtained. Using this catalyst, in the same manner as in Example 1, 1,3-
The oxidation reaction of butadiene and the analysis of the products were carried out. Table 1 shows the contents of the catalyst used and the reaction results.

From the comparison between Example 7 and Comparative Example 4, the catalyst consisting of a combination of Au (Group 11 element) and Te (Group 16 element) showed high catalytic activity, and the oxidation reaction of 1,3-butadiene in the presence of acetic acid was confirmed. It can be seen that the reaction rate is accelerated and high selectivity toward adjacent diol derivatives is exhibited.

Claims (6)

In the presence of a catalyst and a carboxylic acid represented by formula (1),
The catalyst contains Group 11 elements and metalloid elements such as S, Se, Te, P, As, Sb,
Contains one or more elements selected from the group consisting of Bi, Sn and Pb,
Oxidizing the carbon adjacent to the unsaturated bond of the unsaturated hydrocarbon represented by the formula (2) using molecular oxygen to obtain a compound represented by any of the formulas (3) to (6). Method for producing oxygen compounds.

[In formula (1),
R ¹ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or 2 carbon atoms. ]

[In formula (2),
R ² , R ³ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group,
R ⁴ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ² and R ⁴ may be combined to form a ring. ]

[In formulas (3) to (6),
R ¹ to R ⁶ are each independent and have the same meaning as R ¹ to R ⁶ in formulas (1) and (2), respectively. ] The method for producing an oxygen-containing compound according to claim 1, wherein R ¹ in the formula (1) is an aliphatic hydrocarbon group having 1 or 2 carbon atoms. The method for producing an oxygen-containing compound according to claim 1 or 2, wherein the reaction temperature for oxidizing the carbon adjacent to the unsaturated bond is 25°C or more and 200°C or less. A catalyst that oxidizes a carbon adjacent to an unsaturated bond of an unsaturated hydrocarbon,
Group 11 elements, S, Se, Te, P, As, Sb, Bi, Sn and P as metalloid elements
A catalyst containing one or more elements selected from the group consisting of b. The catalyst according to claim 4, wherein the Group 11 element is Au. The catalyst according to claim 4 or 5, wherein the metalloid element is Te.