JPH11236362A - Production of dichloroglyoxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely and easily obtain the subject compound useful as an industrial bactericide and an antiseptic, etc., by treating glyoxime in an aqueous suspension with a chlorinating agent in the presence of a specific water- immiscible organic solvent. SOLUTION: (D) Dichloroglyoxime is obtained by treating (A) glyoxime in an aqueous suspension with (C) a chlorinating agent (preferably chlorine gas or chlorine generated from an alkali salt of hypochlorite) in the presence of (B) a water-immiscible organic solvent (preferably aliphatic di- or mono- carboxylic esters). The component A is a reaction mixture obtained by reacting glyoxal with hydroxylamine in an aqueous medium and glyoxime is usable without isolation. The generating component D is obtained as a solution of the used component B. Preferably, an effective chlorine amount of the component C of 1.5-6 mol equivalent based on the glyoxime of the component A is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for safely and easily producing dichloroglyoxime, which is useful as a bactericide, in particular, an industrial bactericide, a preservative, and a slime control agent for a paper and pulp mill.

[0002]

2. Description of the Related Art Dichloroglyoxime is known to be useful as a bactericide, in particular, an industrial bactericide, preservative, slime control agent and the like (see, for example, JP-A-8-2).
No. 0505).

Hitherto, dichloroglyoxime has been produced by a method of chlorinating glyoxime (GB 1307223 and Dirasat-Univ. Jorda).
n, 13 (7) , 185-188 (1986)). In this method, dichloroglyoxime is obtained by blowing chlorine gas into a suspension of glyoxime and a dilute aqueous hydrochloric acid solution. However, the yield of dichloroglyoxime obtained by this method was as low as 33.5% according to the former description and 33.5% according to the latter description.

On the other hand, in Japanese Patent Application Laid-Open No. 7-33728,
It has been pointed out that treating glyoxime and dichloroglyoxime as crystals is likely to cause explosion due to mechanical shock or friction, and is extremely dangerous. Therefore, this publication discloses that an aqueous glyoxal solution is oximated to obtain a glyoxime reaction solution (aqueous suspension), the reaction solution is distilled or azeotropically distilled to remove water, and the obtained glyoxime is once dissolved in an organic solvent. Solution and
A method of obtaining an organic solvent solution of dichloroglyoxime by reacting chlorine with this is disclosed.

However, in this method, distillation by heating or azeotropic distillation is indispensable to remove water from an aqueous glyoxime suspension obtained by oximation of an aqueous glyoxal solution. Therefore, this method has a danger of ignition by an organic solvent and requires a very complicated operation, so that there is a problem as an industrial production method.

[0006]

An object of the present invention is to provide a method for obtaining dichloroglyoxime safely and easily without removing water from an aqueous glyoxime suspension.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, treated glyoxime in an aqueous suspension with a chlorinating agent in the presence of a specific non-water-miscible organic solvent. As a result, they have found that dichloroglyoxime can be obtained safely and easily, and have completed the present invention.

Thus, according to the present invention, glyoxime in an aqueous suspension is treated with a chlorinating agent in the presence of a non-water-miscible organic solvent to obtain dichloroglyoxime. A manufacturing method is provided.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The raw material glyoxime is generally produced by reacting glyoxal with hydroxylamine in an aqueous medium. In the treatment with the chlorinating agent of the present invention (hereinafter referred to as chlorination), Glyoxime can be used without isolation from the reaction mixture (glyoxime aqueous suspension) obtained in this reaction.
That is, two steps of oximation and chlorination are continuously performed for 1
Can be done in a pot.

The chlorination according to the method of the present invention is characterized in that it is carried out in the presence of a non-water-miscible organic solvent. That is,
The resulting dichloroglyoxime is obtained as a solution of the non-water miscible organic solvent used. As the non-water-miscible organic solvent, those which have substantially no or low compatibility with water, can dissolve 1% or more of dichloroglyoxime, and are inert to chlorine are preferable. Specifically, succinic acid dimethyl ester, succinic acid diethyl ester, glutaric acid dimethyl ester, glutaric acid diethyl ester, adipic acid dimethyl ester, adipic acid diethyl ester and 7,12-dimethyl-7,11-octadecadien-1, Examples include aliphatic dicarboxylic esters such as 18-dicarboxylic dimethyl ester, and aliphatic monocarboxylic esters such as ethyl acetate and butyl acetate. Hydrocarbons such as benzene, xylene, toluene and kerosene can also be used, and these non-water-miscible organic solvents can be used alone or in combination of two or more.

Among the above-mentioned non-water-miscible organic solvents, dimethyl succinate, dimethyl glutarate, dimethyl adipic acid or mixtures thereof as aliphatic dicarboxylic esters, and acetic acid as aliphatic monocarboxylic esters are exemplified. Ethyl, butyl acetate or mixtures thereof are preferred. More specifically, a mixed solution of succinic acid dimethyl ester, glutaric acid dimethyl ester, and adipic acid dimethyl ester (for example, DBE manufactured by DuPont) and ethyl acetate can be suitably used. Note that chloroform has low solubility of dichloroglyoxime, and is not preferred as the non-water-miscible organic solvent of the present invention.

The amount of the non-water-miscible organic solvent used depends on the type of the organic solvent, that is, its ability to dissolve in dichloroglyoxime, but the resulting dichloroglyoxime can be substantially dissolved at the reaction temperature. Preferably, the amount is not less than the amount. For example, DBE is used as a non-water miscible organic solvent.
When DBE is used, the DBE may be about 3.8 to 76 kg per 1 kg of glyoxime. When ethyl acetate is used, it may be about 3.8 to 76 kg similarly. There is no particular upper limit to the above-mentioned amount of use, but it is desirable that the required amount be as small as possible in terms of reaction efficiency and economy. In addition, when the obtained organic solvent solution of dichloroglyoxime is used as it is as a bactericide, the concentration can be adjusted to the concentration at the time of use.

As the chlorinating agent, chlorine gas or chlorine generated from alkali hypochlorite is used, and a non-water-miscible organic solvent solution is also used. The non-water-miscible organic solvent solution is, for example, a non-aqueous layer obtained by acidifying and separating a mixture of an aqueous solution of an alkali metal hypochlorite and the above-mentioned non-water-miscible organic solvent. In this acidification,
Mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid and acetic acid can be used.

The chlorinating agent is used as an effective chlorine in an amount of usually 1.5 to 6 molar equivalents, preferably 3 to 6 glyoximes.
It is used in an amount of from 5 to 5 molar equivalents, for example, 3, 4, and 5 molar equivalents are preferred.

[0015] The chlorination of the present invention is desirably performed in an acidic region. This acidic region is preferably formed by adding a mineral acid, such as sulfuric acid, to the aqueous glyoxime suspension.
By making the aqueous glyoxime suspension an acidic region,
Chlorination is not hindered, and the yield is improved, which is preferred. Particularly, an acidic region having a pH of about 2 or less is preferred.

The reaction temperature in the method of the present invention is not higher than room temperature, preferably -20 ° C to 25 ° C, more preferably -10 ° C to 10 ° C. The reaction time varies depending on the type and concentration of the chlorinating agent, the reaction temperature, and the like.
Time.

Thus, according to the method of the present invention, dichloroglyoxime is obtained as a solution of the used non-water-miscible organic solvent, and can be stored as it is or optionally after dehydration treatment. Here, as the dehydration treatment, a dehydration treatment by adsorption using an anhydride such as anhydrous sodium sulfate, which does not involve the danger of heating, is preferable.

As described above, the method of the present invention does not perform any dangerous heating operation, and treats glyoxime and dichloroglyoxime not as crystals but as a solution in which water coexists. An oxime can be obtained. In addition, since the reaction environment in the method of the present invention consists of a mixed system of an aqueous layer and a non-aqueous layer, hydrochloric acid generated in the chlorination reaction is dissolved (extracted) in the aqueous layer in the reaction mixture to convert dichloroglyoxime. It is removed from the contained non-aqueous layer (organic solvent solution). Therefore, there is no need to add an acid acceptor to the reaction mixture, the reaction can proceed smoothly, and when the resulting organic solvent solution of dichloroglyoxime is used as a bactericide or stored, hydrochloric acid is used. Harmful effects (corrosiveness to metals) can be avoided.

Further, the method of the present invention has good chlorination efficiency, so that dichloroglyoxime can be obtained in a yield of 60% or more based on glyoxime. The resulting organic solvent solution of dichloroglyoxime can be used as a bactericide, particularly an industrial bactericide, as it is or by mixing other bactericides as needed.

[0020]

The present invention will be described in more detail with reference to the following examples, which do not limit the scope of the present invention.

Reference Example 1 (Synthesis of glyoxime) 65 g of water was placed in a three-necked flask equipped with a thermometer and a stirrer.
And 50 g (0.75 mol) of a 50% aqueous hydroxylamine solution were added. The mixture is cooled with stirring and
55 g (0.38 mol) of 0% glyoxal aqueous solution
The mixture was added dropwise over about 5 minutes while maintaining at １５15 ° C., and stirred at 10 ° C. for 1 hour. Then, 20g of 62.5% sulfuric acid aqueous solution
Was added, and the mixture was stirred for 1 hour to obtain 190 g of an acidic aqueous glyoxime suspension (yield: 99%).

Reference Example 2 (Preparation of chlorine-containing non-water-miscible organic solvent solution) In a three-necked flask equipped with a thermometer and a stirrer, 460 g of an aqueous sodium hypochlorite solution (53 g of available chlorine,
0.75 mol) and 690 g of a mixed solution of dimethyl succinate, dimethyl glutarate and dimethyl adipic acid (DBE, manufactured by DuPont) were added. The mixture was cooled while stirring, and 150 g of a 35% hydrochloric acid aqueous solution was added dropwise over about 20 minutes while maintaining the temperature at 0 to 5 ° C. After the completion of the dropwise addition, the stirring was stopped and the mixture was allowed to stand, whereby the mixture was separated into two layers. D containing chlorine in yellow layer (non-aqueous layer)
760 g of a BE solution were obtained.

Reference Example 3 (Preparation of Non-Water-miscible Organic Solvent Containing Chlorine) In the same manner as in Reference Example 2 except that 1400 g of ethyl acetate was used instead of DBE, a non-water-miscible organic solvent containing chlorine was used. An organic solvent solution was obtained.

Example 1 The acidic glyoxime aqueous suspension 19 obtained in Reference Example 1
To 0 g, 760 g of the chlorine-containing DBE solution obtained in Reference Example 2 (containing an effective chlorine amount of 0.75 mol equivalent to glyoxime) was added dropwise at -10 to 5 ° C. over about 2 hours under strong stirring conditions. did. The DE contained in the DBE solution
690 g of BE correspond to 21 kg for 1 kg of glyoxime in aqueous suspension. After completion of the dropping, stirring was stopped and the mixture was allowed to stand, whereby the mixed solution was separated into two layers. Pale yellow DBE
The solution was separated, and the dichloroglyoxime therein was replaced with ¹ H-
It was identified and quantified by NMR and HPLC (liquid chromatography).

The results are as follows: ¹ H-NMR (DMSO) δ
And showed absorption of a hydroxy proton at 13.11 ppm, whereby the substance was determined to be dichloroglyoxime. In addition, HPLC confirmed that the obtained DBE solution contained 5.1 w / w% of dichloroglyoxime. The yield was 68% (converted value based on glyoxime, the same applies hereinafter).

Example 2 The aqueous acidic glyoxime suspension 19 obtained in Reference Example 1
0 g, 35% hydrochloric acid 20 at 0-5 ° C under strong stirring conditions.
0 g and 550 g of DBE were added, and 560 g of an aqueous solution of sodium hypochlorite (64 g, 0.9 mol as effective chlorine, containing 0.75 mol equivalent of effective chlorine relative to glyoxime) was added dropwise over about 2.5 hours. DBE55
0 g is 1 per kg of glyoxime in aqueous suspension
Equivalent to 7 kg. After completion of the dropping, stirring was stopped and the mixture was allowed to stand, whereby the mixed solution was separated into two layers. The pale yellow DBE solution was separated, and dichloroglyoxime therein was identified and quantified by ¹ H-NMR and HPLC.

The results are as follows: ¹ H-NMR (DMSO) δ
And showed absorption of a hydroxy proton at 13.11 ppm, whereby the substance was determined to be dichloroglyoxime. In addition, HPLC confirmed that the obtained DBE solution contained 6.4 w / w% of dichloroglyoxime. The yield was 65%.

Example 3 Dichloroglyoxime was added in an amount of 6.0% w / w in the same manner as in Example 2 except that the holding temperature of the reaction mixture was changed to 5 to 10 ° C. (the dropping time was about 2 hours). A contained DBE solution was obtained. The yield was 60%.

Example 4 The acidic glyoxime aqueous suspension 19 obtained in Reference Example 1
0 g of the total solution (chlorine-containing ethyl acetate solution layer and aqueous solution layer) obtained in Reference Example 3 under strong stirring conditions.
At 0 to 5 ° C., about 2.
It was added dropwise over 5 hours. In addition, 1400 g of ethyl acetate contained in the ethyl acetate solution layer is equivalent to 42 kg with respect to 1 kg of glyoxime in the aqueous suspension, and contains 0.75 molar equivalents of available chlorine relative to glyoxime. After completion of the dropping, stirring was stopped and the mixture was allowed to stand, whereby the mixed solution was separated into two layers. The pale yellow ethyl acetate solution was separated, and monochloroglyoxime therein was identified and quantified by ¹ H-NMR and HPLC.

The results are as follows: ¹ H-NMR (DMSO) δ
And showed absorption of a hydroxy proton at 13.11 ppm, whereby the substance was determined to be dichloroglyoxime. In addition, HPLC confirmed that the obtained ethyl acetate solution contained 3.2 w / w% of dichloroglyoxime. The yield was 75%.

Example 5 Aqueous suspension of acidic glyoxime obtained in Reference Example 1 19
1000 g of the DBE solution was added to 0 g, and chlorine gas was blown little by little at -10 to 5 ° C under strong stirring conditions. In addition, 1000 g of DBE is equivalent to 33 kg for 1 kg of glyoxime in the aqueous suspension. While measuring dichloroglyoxime in the reaction mixture over time with HPLC, chlorine gas was blown until the amount of dichloroglyoxime did not increase. The blowing time of chlorine gas was about 4 hours. When the stirring was stopped and the mixture was allowed to stand, the mixture was separated into two layers. The pale yellow DBE solution was separated, and monochloroglyoxime therein was identified and quantified by ¹ H-NMR and HPLC.

As a result, ¹ H-NMR (DMSO) δ
And showed absorption of a hydroxy proton at 13.11 ppm, whereby the substance was determined to be dichloroglyoxime. In addition, HPLC confirmed that the obtained DBE solution contained 3.6 w / w% of dichloroglyoxime. The yield was 62%.

Comparative Example 1 (Synthesis of dichloroglyoxime without using aqueous solution of water-miscible organic solvent during chlorination) Aqueous aqueous suspension of acidic glyoxime obtained in Reference Example 19
20 g of 35% hydrochloric acid was added to 0 g, and 0-g was added under strong stirring conditions.
At 5 ° C., 560 g of an aqueous sodium hypochlorite solution (64 g, 0.9 mol as effective chlorine, containing 0.75 mol equivalent of effective chlorine relative to glyoxime) was added dropwise over about 2.5 hours. Thereafter, 550 g of DBE was added. In addition,
550 g of DBE is 1 kg of glyoxime in aqueous suspension
17 kg. When the stirring was stopped and the mixture was allowed to stand, the mixture was separated into two layers. The pale yellow DBE solution was separated, and the monochloroglyoxime therein was analyzed by ¹ H-NMR.
And quantified by HPLC.

The results are as follows: ¹ H-NMR (DMSO) δ
And showed absorption of a hydroxy proton at 13.11 ppm, whereby the substance was determined to be dichloroglyoxime. In addition, HPLC confirmed that the obtained DPE solution contained 2.6% w / w of dichloroglyoxime. The yield was 24%.

[0035]

The process for producing dichloroglyoxime of the present invention is characterized in that an aqueous suspension of glyoxime is reacted with a chlorinating agent in the presence of a non-water-miscible organic solvent to obtain dichloroglyoxime. Therefore, since there is no risk of heating in operation, and the solution is treated as a solution coexisting with water, dichloroglyoxime can be safely obtained as a non-water-miscible organic solvent solution.

The reaction environment in the method of the present invention comprises a mixed system of an aqueous layer and a non-aqueous layer. Hydrochloric acid generated by the chlorination reaction is dissolved (extracted) in the aqueous layer of the reaction mixture, and Removed from non-aqueous layer containing glyoxime (organic solvent solution). Therefore, there is no need to add an acid acceptor to the reaction mixture, and the reaction can proceed smoothly. Further, when the obtained organic solvent solution of dichloroglyoxime is used as a bactericide or stored, the harmful effects of hydrochloric acid can be avoided.

Furthermore, the process of the present invention has good chlorination efficiency, so that dichloroglyoxime can be obtained in a yield of 60% or more based on glyoxime. In addition, the resulting organic solvent solution of dichloroglyoxime is
It can be used as it is or as a bactericide, particularly an industrial bactericide, if necessary, by blending another bactericide.

Claims (8)

[Claims] 1. A process for producing dichloroglyoxime, comprising treating glyoxime in an aqueous suspension with a chlorinating agent in the presence of a non-water-miscible organic solvent to obtain dichloroglyoxime. 2. The glyoxime in the aqueous suspension is a reaction mixture obtained by reacting glyoxal with hydroxylamine in an aqueous medium, and the resulting dichloroglyoxime is a mixture of the non-water-miscible organic solvent used. 2. The method according to claim 1, which is obtained as a solution. 3. The method according to claim 1, wherein the non-water-miscible organic solvent is an aliphatic dicarboxylic acid ester or an aliphatic monocarboxylic acid ester. 4. An aliphatic dicarboxylic acid ester comprising succinic acid dimethyl ester, glutaric acid dimethyl ester,
Adipic acid dimethyl ester or a mixture thereof,
The method according to claim 3, wherein the aliphatic monocarboxylic acid ester is ethyl acetate, butyl acetate or a mixture thereof. 5. The chlorinating agent is used in an effective chlorine amount of 1.5 to 6 molar equivalents relative to glyoxime.
The method according to any one of Items 1 to 4, wherein 6. The method according to claim 1, wherein the chlorinating agent is chlorine gas or chlorine generated from an alkali salt of hypochlorite. 7. The method according to claim 1, wherein the chlorinating agent is used as a non-water-miscible organic solvent solution. 8. A non-water-miscible organic solvent solution of a chlorinating agent,
The method according to claim 7, wherein the non-aqueous layer is obtained by acidifying and separating a mixture of an aqueous solution of an alkali hypochlorite and a non-water-miscible organic solvent.