JPH01294650A - Production of ester compound - Google Patents

Abstract

PURPOSE:To readily obtain an ester compound useful as solvents, plasticizers, etc., from a single raw material at a low cost by oxidatively dimerizing two molecules of a primary alcohol with an organic peracid in the presence of a halogen compound. CONSTITUTION:An alcohol having one primary OH group (preferably a saturated alkanol having a relatively large number of carbon atoms) is oxidatively dimerized with an organic peracid (preferably peracetic acid in 5-30wt.% concentration) in the presence of a halogen compound at 0-100 deg.C to afford an ester compound. A hydrogen halide, alkaline (earth) metal halogenide or a mixture thereof is preferred as the halogen compound and an optimum solvent is selected depending on the acidity thereof. The peracetic acid is obtained by oxidizing acetaldehyde to provide industrially useful acetic acid as a by-product of the above-mentioned reaction. Thereby, cost of the peracetic acid as the oxidizing agent equals to zero.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an ester compound by oxidatively converting two primary alcohol molecules into 21-molecules. More specifically, in the presence of a halogen compound.

This is a method for producing an ester compound, which is characterized by oxidatively dimerizing two primary alcohol molecules using an organic peracid.

Ester compounds are important compounds used in many applications such as solvents and plasticizers.

[Prior Art] Conventionally, methods for producing esters include a method of heating and dehydrating an acid and an alcohol in the presence of an acid catalyst, a method of reacting an acid anhydride with an ester, and a method of dimerizing a corresponding aldehyde by a Tischenko reaction. There are known ways to do this.

According to these methods, ester compounds can be obtained easily and in good yields, but thermal dehydration methods and methods using acid anhydrides require both acid and alcohol raw materials corresponding to the desired ester compound. , the corresponding aldehyde compound is required when using the Tiscienko reaction.

However, in many cases, aldehydes cannot be easily obtained at the same time as these acids and alcohols, and the methods for synthesizing these ester compounds are only used industrially when the corresponding raw materials are easily available at the same time. do not have.

In addition, the esters obtained are expensive, which greatly limits the scope of their industrial use.

As a means to solve these problems, a method of producing an ester compound by oxidative dimerization of two alcohol molecules without using an acid can be considered.

An example of this reaction is not a method for producing chain esters, but for example, a method discovered by Fetizon et al. in which a lactone, which is a cyclic ester compound, is synthesized from diols at both ends using silver carbonate-celite. [Tet
raheadron, Vo 16.171 [197
5)].

Furthermore, as a similar synthesis reaction for lactones, a method for synthesizing lactones using an oxoaminium salt as an oxidizing agent has been reported by Endo et al. cj, org, cherO.

, Vo150, 3930. (1985)] and the method using tail sodium bromite reported by Kageyama et al.
i, Lett, 1097 (1983)].

Although these reactions are relatively easy and the yields are good, the oxidizing agent used is expensive, so it is impossible to carry out the reaction industrially as it is.

In addition, Oka et al. developed a lactone synthesis technology using a gas phase reaction using a copper-zinc solid catalyst as an industrially viable technology [Bul 1. chen, soc, jpn, ,
Vol. 135.988 (1962)] However, this reaction has a short catalyst life of only a few hours, needs to be reacted in a hydrogen atmosphere, and is not suitable for high-boiling alcohols because the reaction is carried out in the gas phase. It has drawbacks such as being difficult to use.

As described above, there is no precedent for producing chain esters by oxidative dimerization of two alcohol molecules using a relatively inexpensive organic peracid, and the desired product is also a lactone. However, there has never been an example of an oxidative dimerization reaction of two alcohol molecules for the purpose of industrially producing a chain ester.

[Objective of the Invention] The object of the present invention is to simplify raw material management by unifying the raw materials used in the industrial production of chain esters, and to produce various esters at low cost. The aim is to develop possible technologies.

[Structure of the Invention] That is, the present invention provides ``Production of an ester compound characterized by oxidative dimerization of two alcohol molecules containing one primary hydroxyl group using an organic peracid in the presence of a halogen compound. method”.

The method for producing an ester compound according to the present invention will be described in detail below.

The chemical change of the compound used in the method of the present invention is expressed by the formula -a as follows.

RCHOH+ R' CH20H (alcohol)
(Alcohol) + 2 R”C00H (Organic peracid) (L・Hitosenben 6p -RCH20CR' + 2H20(R')
(R) (Ester) (Water) + 2 R"COH (I) (81M) "In the above formula (I), Ro is hydrogen or a hydrocarbon residue, and R and R' are each a hydrogen or hydrocarbon residue. and R and Ro may be the same residue.'' The primary alcohol that can be used is methanol.

Ethanol: Saturated alkanols such as decanol and their isomers containing at least one primary hydroxyl group, alicyclic alcohols such as cyclohexane dimetatool, aromatic alcohols such as benzyl alcohol There are alcohols having substituents such as

Among these, saturated alkanols having a relatively large number of carbon atoms are particularly suitable.

Although the active species in this reaction has not been confirmed, Weaver et al. reported that hypohalous acid derivatives are active species as shown in formula (II) in the halogenation reaction of aromatic compounds with halogen ions and peroxides. (J, An,
Soc, Discipline, 261 (1964)).

Oo RCOOH+ RCOH+Br −” RCOBr + RCO+ H2
O (hypohalous acid derivative) (II) In addition, Koiriki et al. suggested that the bromination of benzene with peracetic acid and bromine produces hypobromite acetate/L as shown in formula (II). [Bull, Chem, Soc, Jpn,
, 37.960. (1964)].

o 01/2
CH3C0OH+ 1/2 CH3COH+ 1
/2Br2 − CHC0Br + 1/2H20(II
I) These hypohalous acid derivatives are unstable;
It is not easy to isolate and confirm.

Although reactive species in this reaction have not been confirmed, the present inventors estimate that this reaction involves hypohalous acid derivatives similar to those in the above reaction.

The halogen component of the hypohalous acid derivative compound has cationic properties, and is thought to abstract hydrogen at the α-position of the primary alcohol, as shown in the formula <mV).

RCOBr + RI CH20H-RCO+
RCeHOH 10 HBr (1) Examples of organic peracids that can be used include performic acid, peracetic acid, perpropionic acid, metachloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid.

These organic peracids oxidize the corresponding aldehyde compounds,
Alternatively, it can be obtained by reacting a peroxide such as hydrogen peroxide with a corresponding organic acid.

In addition, as can be judged from formula (I), the raw organic peracid becomes a useful organic acid when the reaction is completed, and it is possible to sell it as a product by recovering and purifying it. The oxidizing agent used in the reaction has the advantage that it can be evaluated at a very low cost.

In particular, when the organic peracid is peracetic acid, it can be produced by oxidizing acetaldehyde with molecular oxygen.
Acetic acid is obtained as a byproduct of this reaction.

Known industrial methods for producing acetic acid include carbonylation of methanol, air oxidation of hydrocarbons, and oxidation of acetaldehyde, and judging from the fact that all of these methods are currently in use industrially, the present invention is applicable. When peracetic acid is used as an embodiment of the oxidative dimerization reaction, the cost as an oxidizing agent can be reduced to substantially zero.

Bromine and iodine can be used as the halogen ion, but bromine is preferable from the viewpoint of ease of mounting and unit cost.

Further, the form of the halogen compound charged into the reaction system is preferably hydrogen halide, a salt of an alkali metal or alkaline earth metal, or a mixture thereof. Specific examples of hydrogen halide include hydrogen bromide, halogen Examples of salts include sodium bromide, potassium bromide, lithium bromide, calcium bromide, magnesium bromide, and the like.

Having a solvent coexist is effective in reducing the viscosity of the reaction crude liquid and the reaction heat per unit volume, and it is effective for reducing the viscosity of the reaction crude liquid and the reaction heat per unit volume. halogen compounds, ester compounds such as ethyl acetate and butyl acetate, ketone compounds such as acetone and methyl isobutyl ketone, ether compounds such as 1-2 dimethoxyethane, nitrile compounds such as acetonitrile, basic compounds such as pyridine, etc. can be used, and a mixture of these may also be used.

However, the optimal solvent differs depending on the acidity of the halogen compound used as a catalyst; when hydrogen halide is used, the reaction proceeds even when pyridine, which is a basic solvent, is used, but when a halide salt is used, the reaction proceeds in neutral. The yield is higher when a neutral solvent is used.

This is thought to be due to the stability of hypohalous acid, which is considered to be a reactive species.

The solvent is preferably selected based on the above conditions and ease of separation from products of subsequent steps.

When using an organic peracid produced by oxidation of an aldehyde in an inert solvent, using the solvent contained in the organic peracid as it is as a reaction solvent will not cause any problems.

When an organic peracid contains a large amount of the corresponding organic acid, such as when synthesized from the corresponding organic acid anhydride and peroxide, the organic acid serves as a solvent, but an ester of the organic acid and alcohol is formed. There are drawbacks to doing so.

Taking the case of using peracetic acid as an organic peracid as an example, peracetic acid synthesized from hydrogen peroxide and anhydrous #acid uses acetic acid as a solvent, and is produced by the reaction between the solvent acetic acid and the raw alcohol. The amount of acetate ester increases considerably and the yield of the ester, which is the object of the present invention, decreases.

However, if both the ester obtained by oxidative dimerization of the target alcohol and the acetate ester are required, the ability to co-produce these two types of products is considered to be an advantage, and the present invention The scope is not limited.

Furthermore, the presence of a solvent is not necessarily an essential condition of the present invention.

When the reaction is carried out in a batch manner, a predetermined amount of a primary alcohol and a halogen compound are charged into a reaction vessel, and a solvent is added therein as required.

At this time, even if the halogen compound is in a dissolved state.

Alternatively, it may be in a suspended state.

Thereafter, the organic peracid is added dropwise at a rate that allows the reaction heat generated as the reaction progresses to be removed.

The reaction molar ratio between the organic peracid and the raw alcohol is theoretically 1, but may be even smaller depending on the production amount or external conditions such as the size of the reactor.

Further, from the viewpoint of yield, it is preferable to use an excess amount of peracid.

That is, the reaction molar ratio between the organic peracid and the raw material alcohol is 0.
It is in the range of 1 to 10, preferably in the range of 0.5 to 5, more preferably in the range of 1.5 to 3. When the molar ratio of the organic peracid to the raw material primary alcohol exceeds 10, it is preferable from the viewpoint of conversion rate and reaction rate of the raw material primary alcohol, but side reactions due to excess organic peracid and selection of the organic peracid may be avoided. This is not preferable because problems such as a decrease in the reaction rate and disposal of unreacted organic peracid occur.

On the other hand, if the molar ratio of the organic peracid to the raw material primary alcohol is 0.1 or less, it is preferable from the viewpoint of the conversion rate and selectivity of the organic peracid, but it requires a large amount of cost to recover the unreacted primary alcohol. It has disadvantages such as being required.

If it is less than 0.1, it is preferable from the point of view of the conversion rate and selectivity of the organic peracid, but it is not preferable because it causes drawbacks such as requiring a large amount of cost to recover unreacted primary alcohol.

The molar ratio of the halogen compound to the raw material primary alcohol is not particularly limited, but is 10 or less, preferably 4 or less.

If the usage ratio of the halogen compound exceeds the above value, equipment efficiency will decrease, which is not preferable.

The amount of halogen required to generate hypohalous acid derivatives, which are considered to be active species, is not particularly limited because it is regenerated by the reaction.

In particular, when halogenated salts are used in the reaction, the reaction may be heterogeneous depending on the type of solvent and raw material alcohol used, and the amount of halogen ions dissolved in the reaction system cannot be quantified, and a very small amount is required for the reaction. It is considered good.

For example, sodium bromide dissolves in acetic acid.

Not soluble in ethyl acetate.

However, if the molar ratio of the halogenated compound to the primary alcohol exceeds 10, the proportion of halogenated compounds as by-products in the product will increase, and this will also hinder the separation and purification of the product. Undesirable.

The reaction temperature is preferably below the upper limit at which the oxidation reaction takes precedence over the decomposition reaction of the organic peracid, that is, below 100°C.

If the reaction temperature is low, it will take a long time to complete the reaction, so it is generally preferable to carry out the reaction at a lower limit of 0°C or higher.

The optimum reaction temperature is determined by the type of primary alcohol used as a raw material, the type of organic peracid, the type of halogen compound, the molar ratio of these reaction reagents, etc.

The reaction according to the invention can be carried out under various pressures.

Generally, it is carried out under normal pressure, but it can also be carried out under increased pressure or reduced pressure.

Although it is possible to carry out the present invention according to only the above-mentioned requirements, it is preferable to add a stabilizer when the yield or selectivity can be improved by adding a stabilizer for the organic peracid.

Examples of such stabilizers include tripolyphosphate, pyrophosphate, potassium tripolyphosphate, potassium pyrophosphate,
Examples include phosphorus compounds such as tripolyphosphate.

The concentration of the stabilizer in the reaction system is preferably about 1 to 11,000 pp.

Usually, the reaction crude liquid at the end of the second reaction contains, in addition to the ester compound which is the target product, alcohol which is the starting material, the reaction solvent used, the halogen compound which is the catalyst, side reaction products, etc. .

The reaction crude liquid is separated by ordinary chemical synthesis processes such as filtration, distillation, and extraction.

The separated catalyst halogen compound can be reused.

EXAMPLES The effects of the present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

(Method for analyzing reaction products) Analysis of reaction products was mainly performed by gas chromatography.

Chroll using a GC-6A device manufactured by Shimadzu Corporation.

5% PEG 20M in 5orb WAI4-DHC8
An FID was used in the analyzer equipped with a 4 mmφ x 2 m glass column packed with the supported material, and nitrogen was used as a carrier gas at a rate of 30 mj/min.

The temperature of the sample chamber and the detector was maintained at 200''C, and the thermostat was heated at a temperature appropriate for each product for temperature-programming analysis.

The content distribution was determined from the area of the peak of each product thus obtained, and the conversion rate of the raw alcohol and the yield of each product were determined.

Unless otherwise stated, product analysis was performed as described above.

(Reaction using acetic acid solvent peracetic acid-HBr system) [Example 1] After heating 50 mj (0.12 mol) of 30% hydrogen peroxide solution to 35 to 40°C on a hot water bath, 338 g of acetic anhydride was added while stirring. <3.31 mol) at a temperature of 35 to 40
The mixture was added dropwise over 2 to 2.5 hours while maintaining the temperature at °C.

After dropping acetic anhydride, the reaction was continued for 1 hour while maintaining the same temperature.

1.3M peracetic acid was obtained as evaluated with 0.0, IN-sodium thiosulfate.

Experiments were conducted using this peracetic acid according to the method described below.

Octyl alcohol 0 in a three-day flask with a content of 20 m1
．． 5 g (3.8 mmol) and 3 mj of acetic acid as a solvent, hydrogen bromide was selected as the halogen compound, and 47%
The molar ratio of hydrobromic acid aqueous solution to alcohol is 0.1
It was added so that

The mixture thus prepared was kept at 40°C, and under an argon atmosphere, the above peracetic acid was added to the starting alcohol at 1:1.
, 1 times the amount over 1 hour, and then allowed to react for an additional 1 hour.

During this time, the inside of the reactor was maintained at 40°C.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 85%, the selectivity for octyl octylate was 20%, and the selectivity for octyl acetate was 74%.

[Example 2] The same operation as in Example 1 was performed except that a 47% aqueous solution of hydrobromic acid was added at a molar ratio of 0.5 to the alcohol. The selectivity for octyl was 22% and for octyl acetate was 73%.

[Example 3] The same operation as in Example 1 was performed except that a 47% aqueous solution of hydrobromic acid was added at a molar ratio of 1.0 to the alcohol. As a result, the conversion rate of octatool was 95% and octyl acid The selectivity for octyl was 16% and for octyl acetate was 82%.

(Reaction using ethyl acetate solvent peracetic acid-HBr system) [Example 4] Octyl alcohol 0
．． 5 g <3.8 mmol) and ethyl acetate 3 as solvent
Prepare mJ, choose hydrogen bromide as the halogen compound,
A 47% aqueous solution of hydrobromic acid was added at a molar ratio to alcohol of 1.0.

The mixture thus prepared was kept at 40°C, and under an argon atmosphere, a solution of peracetic acid [manufactured by Daicel Chemical Industries, Ltd. (2.1M)] in ethyl acetate was added at a ratio of 1.1% to the raw alcohol.
After doubling the amount over 1 hour, the reaction was continued for another 1 hour.

During this time, the inside of the reactor was maintained at 40°C.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 63%, the selectivity of octyl octylate was 51%, and the selectivity of octyl acetate was 43%.

[Example 5] The reaction was carried out in the same manner as in Example 4 except that pyridine was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 26%, the selectivity for octyl octylate was 73%, and the selectivity for octyl acetate was 7%.

[Example 6] The reaction was carried out in the same manner as in Example 4 except that carbon tetrachloride was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 70%, the selectivity of octyl octylate was 59%, and the selectivity of octyl acetate was 26%.

[Example 7] The reaction was carried out in the same manner as in Example 4 except that benzene was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 88%, the selectivity for octyl octylate was 20%, and the selectivity for octyl acetate was 64%.

[Example 8] The reaction was carried out in the same manner as in Example 4 except that acetonitrile was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 82%, the selectivity for octyl octylate was 25%, and the selectivity for octyl acetate was 55%.

(Reaction using ethyl acetate solvent peracetic acid-NaBr system) [Example 9] Octyl alcohol 0 was added to a Nilo flask with an internal capacity of 20 mj.
．． 5 g (3.8 mmol) and 3 m pyridine as solvent
Sodium bromide was selected as the halogen compound, and solid sodium bromide was added so that the molar ratio to alcohol was 1.0.

The mixture thus prepared was kept at 40°C, and peracetic acid [manufactured by Daicel Chemical Industries, Ltd. (2.1M)], which was an ethyl acetate solvent, was added at a ratio of 1.1% to the raw material alcohol under an argon atmosphere.
After preparing twice the amount over 1 hour, the reaction was continued for another 1 hour.

During this time, the inside of the reactor was maintained at 40°C.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 5%, the selectivity of octyl octylate was 46%, and the selectivity of octyl acetate was 0%.

[Example 10] The reaction was carried out in the same manner as in Example 9 except that carbon tetrachloride was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 77%, the selectivity of octyl octylate was 60%, and the selectivity of octyl acetate was 3%.

[Example 11] The reaction was carried out in the same manner as in Example 9 except that ethyl acetate was used as the solvent.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 76%, the selectivity of octyl octylate was 97%, and the selectivity of octyl acetate was 2%.

[Example 12] The reaction was carried out in the same manner as in Example 9, except that benzene was used as a solvent and sodium bromide was charged twice in mole relative to the raw material alcohol.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 75%, the selectivity for octyl octylate was 92%, and the selectivity for octyl acetate was 0.4%.
Met.

[Example 13] The reaction was carried out in the same manner as in Example 9, except that benzene was used as a solvent, sodium bromide was charged twice in mole relative to the raw material alcohol, and peracetic acid was charged twice in mole relative to the raw material alcohol.

Analysis of the resulting reaction solution by gas chromatography showed that the conversion rate of octatool was 99.5% and the selectivity of octyl octylate was 93%.

Octyl acetate was 0.5%.

[Example 14] The reaction was carried out in the same manner as in Example 9, except that ethyl acetate was used as the solvent and sodium bromide was charged twice in mole relative to the starting alcohol.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 98.1% and the selectivity of octyl octylate was 95%.

Octyl acetate was 1.5%.

[Example 15] The reaction was carried out in the same manner as in Example 9, except that ethyl acetate was used as the solvent and peracetic acid was charged twice in mole relative to the raw material alcohol.

When the resulting reaction solution was analyzed by gas chromatography, the conversion rate of octatool was 100%, and the selectivity of octyl octylate was 86%.

Octyl acetate was 0%.

[Example 16] The reaction was carried out in the same manner as in Example 9, except that pyridine was used as a solvent and peracetic acid was charged twice in mole relative to the raw material alcohol.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 10%, the selectivity of octyl octylate was 61%, and the selectivity of octyl acetate was 16%.

[Example 17] A reaction similar to that of Example 9 was carried out without using a solvent in the reaction.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 76% and the selectivity of octyl octylate was 97%.

Add 50 ml of saturated brine to this reaction crude solution, and add 1 ml of ether.
Extracted 3 times with 5mj.

The collected ether solution was mixed with 30% saturated saline solution.
once with mj, twice with 30 mj of 10% sodium carbonate aqueous solution
After washing twice and drying with anhydrous sodium sulfate, the weight of the product was determined to be 80% compared to the weight of the raw alcohol.
% recovery was obtained.

[Example 18] The reaction was carried out in the same manner as in Example 17 except that the reaction was continued for 23 hours after charging peracetic acid.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 83% and the selectivity of octyl octylate was 94%.

When this reaction crude liquid was subjected to the same operation as in Example 17, a recovery rate of 92% based on the weight of the raw alcohol was obtained.

[Example 19] The reaction was carried out in the same manner as in Example 17 except that peracetic acid was charged in a molar amount 2.2 times that of the raw material alcohol.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of octatool was 99.3% and the selectivity of octyl octylate was 96%.

When this reaction solution i was subjected to the same operation as in Example 17, a recovery rate of 88% based on the weight of the raw alcohol was obtained.

[Example 20] The reaction was carried out in the same manner as in Example 17, except that 2.2 times the mole of co-peracetic acid and 2 times the mole of sodium bromide were charged relative to the raw material alcohol. Analysis of the resulting reaction solution by gas chromatography revealed that the conversion of octatool was 99.5% and the selectivity of octyl octylate was 98.5%.

When this reaction crude liquid was subjected to the same operation as in Example 17, a recovery rate of 64% based on the weight of the raw alcohol was obtained.

[Example 21] The reaction was carried out in the same manner as in Example 20, except that 1-hexanol was used as the raw material.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion of hexanol was 97.1% and the selectivity of hexyl hexylate was 99.9%.

When this reaction solution a was subjected to the same operation as in Example 17, a recovery rate of 82% based on the weight of the raw alcohol was obtained.

[Example 22] The reaction was carried out in the same manner as in Example 20, except that 1-decanol was used as the raw material.

Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of decanol was 99.8% and the selectivity of decyl decanoate was 99.2%.

When this reaction crude liquid was subjected to the same operation as in Example 17, a recovery rate of 65% based on the weight of the raw alcohol was obtained.

[Example 23] The reaction was carried out in the same manner as in Example 22, except that the amount of sodium bromide was 1.6 with respect to the raw material alcohol. Analysis of the resulting reaction solution by gas chromatography revealed that the conversion rate of decanol was 98.4%, the selectivity of decyl decanoate was 58.5%, and the unidentified substance was 33.5%.

When this reaction crude liquid was subjected to the same operation as in Example 17, a recovery rate of 98% based on the weight of the raw alcohol was obtained.

This recovered solution did not contain the unidentified substance mentioned above, and decyl decanoate was isolated by silica gel flash chromatography using a developing solvent of n-hexane/ethyl acetate = 9/1. Molar yield 74
I got %.

Claims (9)

[Claims] (1) A method for producing an ester compound, which comprises oxidatively dimerizing two alcohol molecules containing one primary hydroxyl group using an organic peracid in the presence of a halogen compound. (2) Claim 1, characterized in that the halogen compound is charged into the reaction system in the form of hydrogen halide, an alkali metal or alkaline earth metal halide, or a mixture thereof. the method of. (3) The method according to claim (1), wherein the halogen compound is selected from bromine and iodine. (4) The method according to claim (1), wherein the organic peracid is peracetic acid. (5) The method according to claim (4), characterized in that peracetic acid with a concentration of 5 to 30% by weight is charged into the reaction system. (6) The method according to claim (3), wherein the halide salt is a sodium salt. (7) Claim No. 1, characterized in that peracetic acid is a solution of a solvent selected from esters and ketones.
The method described in section. (8) The method according to claim (3), wherein the halide salt is sodium bromide. (9) The method according to claim (1), wherein the peracetic acid is a solution of ethyl acetate.