WO2018139485A1 - Method for producing dichloroglyoxime - Google Patents
Method for producing dichloroglyoxime Download PDFInfo
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- WO2018139485A1 WO2018139485A1 PCT/JP2018/002116 JP2018002116W WO2018139485A1 WO 2018139485 A1 WO2018139485 A1 WO 2018139485A1 JP 2018002116 W JP2018002116 W JP 2018002116W WO 2018139485 A1 WO2018139485 A1 WO 2018139485A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/38—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/02—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by halogen atoms
Definitions
- the present invention relates to a method for producing dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc. safely and more efficiently than before.
- dichloroglyoxime is known to be used as an excellent active ingredient such as an industrial disinfectant, preservative, slime control agent, etc. (Patent Document 1).
- dichloroglyoxime As a manufacturing method of dichloroglyoxime (Dichloroglyoxime), it is common to produce
- glyoxime Glyoxime
- Glyoxal Glyoxal
- glyoxal glyoxal
- glyoxal glyoxal
- chlorinate this For example, in Patent Document 2, an aqueous solution of glyoxal and hydroxylamine hydrochloride are mixed by adding water, and sodium carbonate is added as an alkali to form glyoxime, which is isolated as crystals and then dissolved in ethanol.
- a method for obtaining dichloroglyoxime by blowing chlorine at 20 ° C. is disclosed.
- Patent Document 3 an organic solvent having a boiling point higher than that of water is added to a glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt with an alkali, and water is removed by distillation.
- a method is disclosed in which a dichloroglyoxime organic solvent solution is efficiently obtained in a high yield by being simultaneously injected into a container and reacted. By this method, industrial mass production of dichloroglyoxime organic solvent solution has been realized.
- the object of the present invention is to produce dichloroglyoxime, which solves the above-mentioned problems and can obtain dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc. more safely and efficiently. Is to provide a method.
- the configuration of the present invention is as follows.
- Glyoxal is reacted with hydroxylamine or a salt thereof to prepare a glyoxime solution containing a water-miscible organic solvent, and the glyoxime solution and the chlorinating agent are simultaneously injected into the reaction vessel to react.
- a method for producing dichloroglyoxime which comprises the following steps.
- (A) A step of containing a low-boiling organic solvent that is immiscible with water and has a boiling point at 760 mmHg of 200 ° C. or lower.
- the glyoxime solution is a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with hydroxylamine under acidity and containing a water-miscible organic solvent.
- the manufacturing method of the dichloroglyoxime of description (4) A glyoxime solution containing a water-miscible organic solvent having a boiling point higher than that of water was added to a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with a hydroxylamine inorganic acid salt or organic acid salt and an alkali.
- the method for producing dichloroglyoxime according to (1) above wherein (6)
- the glyoxime solution contains a water-miscible organic solvent in a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with a hydroxylamine inorganic acid salt or organic acid salt and an alkali, and then the above (1)
- the method for producing dichloroglyoxime according to (1) above which is an organic layer obtained by liquid-liquid extraction (separation) with the low-boiling organic solvent described in (a).
- the glyoxime solution contains a water-miscible organic solvent in the glyoxime reaction solution obtained by reacting the aqueous solution of glyoxal with hydroxylamine under acidic conditions, the low boiling point described in the above (1)
- the chlorinating agent is chlorine or sulfuryl chloride.
- One raw material glyoxal used for the oximation is usually supplied as a 40% aqueous solution.
- the other raw material hydroxylamine a commercially available hydroxylamine hydrochloride, an inorganic acid salt such as sulfate or nitrate, or an organic acid salt such as acetate may be used, or free hydroxylamine may be used.
- a commercially available inorganic acid salt or organic acid salt of hydroxylamine a free hydroxylamine aqueous solution is prepared by neutralizing with alkali at the time of use. This neutralization reaction is performed simultaneously with the oximation reaction.
- an oxime reaction is carried out while neutralizing with an aqueous solution or solid of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate in a hydroxylamine inorganic acid salt or organic acid salt aqueous solution and a 40% glyoxal aqueous solution.
- an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate in a hydroxylamine inorganic acid salt or organic acid salt aqueous solution and a 40% glyoxal aqueous solution.
- a commercially available 50% hydroxylamine aqueous solution (manufactured by BASF, etc.) is mixed with 40% glyoxal aqueous solution under acidic conditions with hydrochloric acid to prevent polymerization, and the same as described above.
- the glyoxime after the reaction is obtained in the form of a suspension.
- the reaction solution is filtered to separate solids, which are washed and dried to obtain glyoxime crystals.
- this crystal has a risk of explosion due to mechanical shock and friction.
- the glyoxime of the target product inevitably partially escapes together with the inorganic salt, resulting in a decrease in yield. Therefore, the present invention employs a method of obtaining a glyoxime solution by adding a water-miscible organic solvent to the glyoxime suspension, as in the following method.
- ⁇ Method 1> By adding a water-miscible organic solvent to the glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt and an alkali before or after the reaction.
- Method 2> A method for obtaining a glyoxime solution by adding a water-miscible organic solvent to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction.
- a water-miscible organic solvent having a boiling point higher than water is added to a glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt and an alkali before or after the reaction. And then removing the water by distillation, and then removing the precipitated salt by filtration to obtain a glyoxime solution.
- ⁇ Method 4> A water-miscible organic solvent having a boiling point higher than that of water is added to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction, and then distilled.
- a glyoxime solution by removing water.
- a water-miscible organic solvent was added to the glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt or hydroxyl acid salt of hydroxylamine and an alkali before or after the reaction. Thereafter, a liquid-liquid extraction (separation) with a water-immiscible low-boiling organic solvent yields a glyoxime solution as an organic layer.
- a water-miscible organic solvent is added to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction.
- a method for obtaining a glyoxime solution as an organic layer by liquid-liquid extraction (separation) with a boiling organic solvent is obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction.
- examples of the water-miscible organic solvent used in the methods 1 to 6 for obtaining the glyoxal solution include the following.
- Ethylene glycol type For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples include dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.
- Propylene glycol type For example, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methoxypropanol, 2-ethoxypropanol, 2-methoxypropyl acetate, 2-ethoxypropyl acetate, dipropylene glycol monomethyl ether, dipropylene Examples include glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate.
- Alkanol type For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, etc. .
- Examples include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-octylpyrrolidone, and dimethyl sulfoxide. It is done.
- a water-miscible organic solvent having a boiling point higher than that of water is preferably used.
- diethylene glycol monomethyl is used.
- Ether, diethylene glycol monoethyl ether or diethylene glycol may be used.
- a water-miscible organic solvent having a relatively low boiling point such as methanol, ethanol or 2-propanol can be used.
- the boiling point of the water-immiscible low-boiling organic solvent used for liquid-liquid extraction (separation) after the water-miscible organic solvent is contained in the glyoxime reaction solution is 760 mmHg.
- the boiling point should be 200 ° C. or lower, and preferably 150 ° C. or lower.
- Examples of such low boiling point organic solvents include benzene, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, octanol, ethyl acetate, propyl acetate, butyl acetate, and carbon disulfide.
- the glyoxime solution obtained as an organic layer after liquid-liquid extraction may be used for the next chlorination reaction as it is, and a dehydrating agent such as anhydrous sodium sulfate or magnesium sulfate is used.
- the chlorination reaction may be carried out after dehydration.
- a molar ratio of the glyoxime solution prepared by the oximation and the chlorinating agent is 1: 2 or more in a reaction vessel such as a reaction vessel equipped with a stirrer and a cooling device according to the cooling capacity. It is recommended to inject at the same time. At this time, one or both of them are intermittently injected while maintaining the molar ratio of 1: 2 or more within a short limited time.
- the injection molar ratio of the glyoxime solution and the chlorinating agent is preferably 1: 2 to 1: 4.
- the reaction temperature is +20 to ⁇ 20 ° C., preferably +10 to ⁇ 10 ° C.
- a water-immiscible low-boiling organic solvent is added to the dichloroglyoxime reaction solution and sufficiently stirred and mixed.
- the water-immiscible low-boiling organic solvent used at this time has a boiling point at 760 mmHg of 200 ° C. or lower, preferably 150 ° C. or lower.
- low boiling point organic solvents examples include benzene, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, octanol, ethyl acetate, propyl acetate, butyl acetate, and carbon disulfide.
- ethyl acetate and chloroform more preferably.
- the water-immiscible low boiling point organic solvent is already contained in the dichloroglyoxime reaction solution, so the amount added accordingly Or the addition thereof can be omitted.
- water is adjusted so that the water content in the dichloroglyoxime reaction solution in the reaction vessel is in the range of 20 to 90% by weight, preferably in the range of 30 to 80% by weight in the reaction mixture. .
- an appropriate amount of salt such as sodium chloride or potassium chloride may be added to promote the salting out effect.
- two layers are separated into an organic layer and an aqueous layer, and the organic layer is separated. Since most of the hydrogen chloride by-produced by chlorination of glyoxime is transferred to the aqueous layer, the residual hydrogen chloride in the organic layer containing dichloroglyoxime is considerably reduced.
- the yield of dichloroglyoxime can also be improved by further adding the above-mentioned water-immiscible low-boiling organic solvent to the aqueous layer and performing liquid-liquid extraction (separation). Thereafter, the separated organic layer can be dehydrated with a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate.
- a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate.
- the dichloroglyoxime crystals are converted into a water-miscible organic solvent having a boiling point higher than that of water.
- an organic solvent solution of dichloroglyoxime can be obtained.
- the water may be removed at a low temperature under reduced pressure.
- part means part by mass.
- Example 1 A 300 ml four-necked flask is charged with 32.8 g (0.2 mol) of hydroxyammonium sulfate, 29 g (0.2 mol) of 40% aqueous glyoxal solution, and 35 g of water. 45.9 g (0.4 mol) of an aqueous sodium solution was added dropwise. After stirring and aging overnight, 150 g of ethanol was added and stirred until uniform to obtain 290 g of a yellow glyoxime ethanol (water-containing) solution.
- Example 2 To a 300 ml four-necked flask, 29 g (0.2 mol) of 40% aqueous glyoxal solution, 0.35 g of concentrated hydrochloric acid and 105 g of ethanol are added, and 26.4 g (0.4 mol) of 50% aqueous hydroxylamine solution is added dropwise at 20 ° C. did. After stirring and aging overnight, 160 g of a yellow glyoxime ethanol (water-containing) solution was obtained. In a 1 liter four-necked flask, 70 g of ethanol is added, and the ethanol (water-containing) solution of glyoxime and chlorine are added at ⁇ 5 to 0 ° C.
- Example 3 A 300 liter glass-lined reaction kettle is charged with 32.8 kg (200 mol) of hydroxyammonium sulfate, 29.0 kg (200 mol) of 40% aqueous glyoxal solution, and 35.0 kg of water. 45.9 kg (400 mol) of an aqueous sodium oxide solution was added dropwise. After stirring and aging overnight, 130 kg of diethylene glycol monomethyl ether was added, and water was distilled off under reduced pressure (internal temperature: 60 ° C. or lower). After cooling to 10 ° C. or lower, the precipitated sodium sulfate crystals were filtered under reduced pressure.
- Example 4 To a 300 liter glass-lined reaction kettle, 29.0 kg (200 mol) of 40% glyoxal aqueous solution, 0.35 kg of concentrated hydrochloric acid and 105 kg diethylene glycol monomethyl ether were added, and 26.4 kg (400 mol) of 50% hydroxylamine aqueous solution was added at 20 ° C. It was dripped. After stirring and aging overnight, water was distilled off under reduced pressure (internal temperature: 60 ° C. or lower). 125 kg of a diethylene glycol monomethyl solution of brown glyoxime was obtained.
- Example 5 A 300 ml four-necked flask is charged with 32.8 g (0.2 mol) of hydroxyammonium sulfate, 29 g (0.2 mol) of 40% aqueous glyoxal solution, and 35 g of water. 45.9 g (0.4 mol) of an aqueous sodium solution was added dropwise. After stirring and aging overnight, 70 g of diethylene glycol monomethyl ether was added, and then the glyoxime white solid precipitated was dissolved while stirring. Further, 7 g of sodium chloride was added, and 70 g of ethyl acetate was added for extraction.
- the organic layer (upper layer) was separated to obtain 105 g of a pale yellow glyoxime ethyl acetate / diethylene glycol monomethyl ether solution (hereinafter also referred to as glyoxime solution).
- glyoxime solution was analyzed for glyoxime content by HPLC, it was 11% (yield: 65.6%).
- Into a 1 liter four-necked flask add 40 g of diethylene glycol monomethyl ether, and simultaneously inject the glyoxime solution and chlorine at ⁇ 5 to 0 ° C. so that the molar ratio of glyoxime and chlorine in the solution is 1: 3. did. After completion of the reaction, 70 g of 10% brine was added and stirred.
- Example 6 To a 300 ml four-necked flask, 29 g (0.2 mol) of 40% glyoxal aqueous solution, 0.35 g of concentrated hydrochloric acid and 70 g of diethylene glycol monomethyl ether were added, and 26.4 g (0.4 mol) of 50% aqueous hydroxylamine solution at 20 ° C. was dripped. After stirring and aging overnight, 7 g of sodium chloride was added, and 70 g of ethyl acetate was added for extraction.
- the organic layer (upper layer) was separated to obtain 101 g of a pale yellow glyoxime solution in ethyl acetate / diethylene glycol monomethyl ether (hereinafter also referred to as glyoxime solution).
- glyoxime solution a pale yellow glyoxime solution in ethyl acetate / diethylene glycol monomethyl ether
- the glyoxime content of this glyoxime solution was analyzed by the HPLC method, it was 11.8% (yield: 67.5%) 40 g of diethylene glycol monomethyl ether was placed in a 1 liter four-necked flask, and -5 to The glyoxime solution and chlorine were simultaneously injected at 0 ° C. so that the injection molar ratio of glyoxime and chlorine in the solution was 1: 3.
- 70 g of 10% brine was added and stirred.
- the precipitated sodium sulfate crystals were filtered off with 5A filter paper, the crystals on the filter paper were washed with 64 g of diethylene glycol monomethyl ether, and the filtrate and the washing solution were combined to obtain a diethylene glycol monomethyl solution of brown glyoxime.
- 60 g of diethylene glycol monomethyl ether is added, and the glyoxime diethylene glycol monomethyl ether solution and chlorine are added at ⁇ 5 to 0 ° C. so that the molar ratio of glyoxime and chlorine in the solution is 1: 3.
- the present invention relates to a method for safely and more efficiently producing dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc., and harmful microorganisms such as water treatment and paper industry are problematic. It is used in the industrial field.
- the time for completing the production of dichloroglyoxime can be significantly shortened, and dichloroglyoxime can be produced efficiently.
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Abstract
Description
本発明は、工業用殺菌剤、防腐剤、スライムコントロール剤等として用いられるジクロログリオキシムを安全に、且つ従来より効率よく製造する方法に関する。 The present invention relates to a method for producing dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc. safely and more efficiently than before.
従来よりジクロログリオキシムは、工業用殺菌剤、防腐剤、スライムコントロール剤等の優れた有効成分として使用されることが知られている（特許文献１）。 Conventionally, dichloroglyoxime is known to be used as an excellent active ingredient such as an industrial disinfectant, preservative, slime control agent, etc. (Patent Document 1).
そして、ジクロログリオキシム（Dichloroglyoxime）の製造方法としては、グリオキサール（Glyoxal）を出発原料としてグリオキシム（Glyoxime）を生成し、これを塩素化することが一般的である（式Ｉ）。例えば、特許文献２では、グリオキサールの水溶液とヒドロキシルアミン塩酸塩とを水を加えて混合し、さらにアルカリとして炭酸ナトリウムを加えてグリオキシムを生成させ、結晶として単離した後、エタノールに溶解し、－２０℃で塩素を吹き込んでジクロログリオキシムを得る方法が開示されている。
しかし、この方法は、少なくとも中間体のグリオキシムを結晶として取り扱うことになるが、グリオキシムの結晶は機械的な衝撃や摩擦に対して爆発を起こしやすく、危険性が極めて高い。又、特許文献２の方法は、グリオキシム１７．６ｇのエタノール２００ｍｌの溶液に塩素を－２０℃を維持しつつ３０分という短時間で吹き込んで初めてジクロログリオキシムが得られるというものであり、実験室の少量生産ならともかく、大規模生産の場合には明らかに不向きであると言える。 However, this method treats at least the intermediate glyoxime as crystals, but the crystals of glyoxime are prone to explosion due to mechanical impact and friction, and are extremely dangerous. The method of Patent Document 2 is that dichloroglyoxime can be obtained only by blowing chlorine into a solution of 17.6 g of glyoxime in 200 ml of ethanol in a short time of 30 minutes while maintaining −20 ° C. This is obviously unsuitable for large-scale production.
一方、特許文献３では、グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させ得られたグリオキシム反応溶液に、水より高い沸点を持つ有機溶媒を加えて、蒸留により水を除去し、次いで析出した塩を濾過によって除去して得られたグリオキシム溶液（又は、グリオキサール水溶液を、酸性下ヒドロキシルアミン水溶液と反応させて得られたグリオキシム反応溶液に、水より高い沸点を持つ有機溶媒を加えてから、蒸留によって水を除去して得られたグリオキシム溶液）と、塩素化剤とを、グリオキシム：塩素化剤＝１：２～１：４の比率（モル比）を維持しながら反応容器に同時に注入して反応させ、効率的に高収率でジクロログリオキシム有機溶剤溶液を得る方法が開示されている。この方法により、ジクロログリオキシム有機溶媒溶液の工業的量産が実現されている。 On the other hand, in Patent Document 3, an organic solvent having a boiling point higher than that of water is added to a glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt with an alkali, and water is removed by distillation. An organic solvent having a boiling point higher than that of water in a glyoxime solution (or a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with an acidic hydroxylamine aqueous solution under acidic conditions) And a chlorinating agent obtained by removing water by distillation while maintaining a ratio (molar ratio) of glyoxime: chlorinating agent = 1: 2 to 1: 4. A method is disclosed in which a dichloroglyoxime organic solvent solution is efficiently obtained in a high yield by being simultaneously injected into a container and reacted. By this method, industrial mass production of dichloroglyoxime organic solvent solution has been realized.
しかしながら、特許文献３の方法では、大量の水を蒸留により除去する必要があり、しかも中間体のグリオキシムの分解や着色を防止するために減圧下に低い温度で蒸留を行わなければならず、多大な電力・エネルギーコストと作業時間を余儀なくされる。 However, in the method of Patent Document 3, it is necessary to remove a large amount of water by distillation, and in order to prevent decomposition and coloring of the intermediate glyoxime, distillation must be performed at a low temperature under reduced pressure. Power and energy costs and work hours are forced.
さらに、塩素化終了後は、ジクロログリオキシム有機溶剤反応液から、グリオキシムと塩素化剤との反応により副生した溶存塩化水素を高真空下に除去しなければならず、例えば、ジクロログリオキシム１０％のジエチレングリコールモノメチルエーテル溶液を２トン製造した場合は、この最終工程での塩化水素除去に３日～７日を要するなど、膨大な作業時間を強いられている。又、塩化水素を高真空下吸引除去する際には、塩化水素の一部がアルカリトラップを通過して真空ポンプの気密性に関わる部品を腐食し、真空ポンプの能力低下あるいはその寿命を著しく損ねるという問題も深刻である。すなわち、生産効率の面において、副生塩化水素の除去方法の改善が大きな課題となっている。 Further, after completion of chlorination, dissolved hydrogen chloride by-produced by the reaction of glyoxime and chlorinating agent must be removed from the dichloroglyoxime organic solvent reaction solution under a high vacuum, for example, dichloroglyoxime 10 When 2 tons of 2% diethylene glycol monomethyl ether solution is produced, enormous work time is required, such as removing 3 to 7 days for removing hydrogen chloride in this final process. In addition, when removing hydrogen chloride under high vacuum, part of the hydrogen chloride passes through the alkali trap and corrodes the parts related to the airtightness of the vacuum pump, and the capacity of the vacuum pump is reduced or its life is significantly impaired. The problem is also serious. That is, in terms of production efficiency, improvement of a method for removing by-product hydrogen chloride is a major issue.
本発明の課題は、上記の問題点を解決し、工業用殺菌剤、防腐剤、スライムコントロール剤等として用いられるジクロログリオキシムをより安全に且つより効率的に得ることのできるジクロログリオキシムの製造方法を提供することである。 The object of the present invention is to produce dichloroglyoxime, which solves the above-mentioned problems and can obtain dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc. more safely and efficiently. Is to provide a method.
上記課題を解決するため、本発明者らは鋭意検討した結果、特許文献３に記載のジクロログリオキシム有機溶剤溶液の製造方法を基礎として、水非混和性の低沸点有機溶剤を含有させる工程と、塩素化終了後に水を２０～９０％含有させ、二層分離させた後、有機層を分取する工程と、有機層から水混和性の低沸点有機溶剤を除去する工程とを追加することにより、従来の方法に比べて、より安全に且つより効率的にジクロログリオキシムを製造できることを見出し、本発明を完成させるに至った。 In order to solve the above-mentioned problems, the present inventors have intensively studied and, as a result, based on the method for producing a dichloroglyoxime organic solvent solution described in Patent Document 3, a step of containing a water-immiscible low-boiling organic solvent; Adding 20 to 90% of water after chlorination is completed, separating the two layers, separating the organic layer, and removing the water-miscible low boiling point organic solvent from the organic layer. Thus, it has been found that dichloroglyoxime can be produced more safely and more efficiently than the conventional method, and the present invention has been completed.
すなわち、本発明の構成は、以下のようになる。
（１）グリオキサールとヒドロキシルアミン又はその塩とを反応させ、水混和性の有機溶剤を含有させたグリオキシム溶液を調製し、該グリオキシム溶液と塩素化剤とを反応容器に同時に注入して反応させてジクロログリオキシムを製造する方法であって、以下の工程を含むことを特徴とするジクロログリオキシムの製造方法。
（ａ）水と非混和性であり、且つその７６０ｍｍＨｇにおける沸点が２００℃以下である低沸点有機溶剤を含有させる工程。
（ｂ）塩素化終了後の反応容器内の水含有量が反応混合物中２０～９０重量％となるように調整し、有機層と水層に二層分離させた後、有機層を分取する工程。
（ｃ）前記（ｂ）の有機層から前記（ａ）の低沸点有機溶剤を除去する工程。
（２）グリオキシム溶液が、グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させ得られたグリオキシム反応溶液に、水混和性の有機溶剤を含有させたものであることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（３）グリオキシム溶液が、グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られたグリオキシム反応溶液に、水混和性の有機溶剤を含有させたものであることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（４）グリオキシム溶液が、グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させて得られたグリオキシム反応溶液に、水より沸点の高い水混和性の有機溶剤を含有させた後、蒸留によって水を除去し、次いで析出した塩を濾過によって除去したものであることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（５）グリオキシム溶液が、グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られたグリオキシム反応溶液に、水より沸点の高い水混和性の有機溶剤を含有させた後、蒸留によって水を除去したものであることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（６）グリオキシム溶液が、グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させ得られたグリオキシム反応溶液に、水混和性の有機溶剤を含有させた後、前記（１）（ａ）記載の低沸点有機溶剤で液液抽出（分液）して得られた有機層であることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（７）グリオキシム溶液が、グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られたグリオキシム反応溶液に、水混和性の有機溶剤を含有させた後、前記（１）（ａ）記載の低沸点有機溶剤で液液抽出（分液）して得られた有機層であることを特徴とする前記（１）に記載のジクロログリオキシムの製造方法。
（８）塩素化剤が、塩素または塩化スルフリルであることを特徴とする前記（１）～（７）のいずれかに記載のジクロログリオキシムの製造方法。
That is, the configuration of the present invention is as follows.
(1) Glyoxal is reacted with hydroxylamine or a salt thereof to prepare a glyoxime solution containing a water-miscible organic solvent, and the glyoxime solution and the chlorinating agent are simultaneously injected into the reaction vessel to react. A method for producing dichloroglyoxime, which comprises the following steps.
(A) A step of containing a low-boiling organic solvent that is immiscible with water and has a boiling point at 760 mmHg of 200 ° C. or lower.
(B) The water content in the reaction vessel after completion of chlorination is adjusted to 20 to 90% by weight in the reaction mixture, and the organic layer and the aqueous layer are separated into two layers, and then the organic layer is separated. Process.
(C) A step of removing the low-boiling organic solvent (a) from the organic layer (b).
(2) The glyoxime solution is characterized by containing a water-miscible organic solvent in a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with a hydroxylamine inorganic acid salt or organic acid salt and an alkali. The method for producing dichloroglyoxime according to (1) above.
(3) In the above (1), the glyoxime solution is a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with hydroxylamine under acidity and containing a water-miscible organic solvent. The manufacturing method of the dichloroglyoxime of description.
(4) A glyoxime solution containing a water-miscible organic solvent having a boiling point higher than that of water was added to a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with a hydroxylamine inorganic acid salt or organic acid salt and an alkali. The method for producing dichloroglyoxime according to (1) above, wherein water is removed by distillation, and then the precipitated salt is removed by filtration.
(5) After the glyoxime solution contained a water-miscible organic solvent having a boiling point higher than water in the glyoxime reaction solution obtained by reacting the aqueous solution of glyoxal with hydroxylamine under acidic conditions, water was removed by distillation. The method for producing dichloroglyoxime according to (1) above, wherein
(6) The glyoxime solution contains a water-miscible organic solvent in a glyoxime reaction solution obtained by reacting a glyoxal aqueous solution with a hydroxylamine inorganic acid salt or organic acid salt and an alkali, and then the above (1) The method for producing dichloroglyoxime according to (1) above, which is an organic layer obtained by liquid-liquid extraction (separation) with the low-boiling organic solvent described in (a).
(7) After the glyoxime solution contains a water-miscible organic solvent in the glyoxime reaction solution obtained by reacting the aqueous solution of glyoxal with hydroxylamine under acidic conditions, the low boiling point described in the above (1) (a) The method for producing dichloroglyoxime according to (1) above, which is an organic layer obtained by liquid-liquid extraction (separation) with an organic solvent.
(8) The method for producing dichloroglyoxime according to any one of (1) to (7) above, wherein the chlorinating agent is chlorine or sulfuryl chloride.
本発明によれば、従来の方法に比べて、より安全に且つ時間とエネルギーをより節約して効率的にジクロログリオキシムを製造することができる。 According to the present invention, it is possible to produce dichloroglyoxime more safely and efficiently while saving time and energy as compared with the conventional method.
以下、本発明のジクロログリオキシムの製造方法について詳細に説明する。 Hereinafter, the manufacturing method of the dichloroglyoxime of this invention is demonstrated in detail.
まず、本発明におけるオキシム化反応について述べる。オキシム化に使用する一方の原料グリオキサールは通常、市販品は４０％水溶液で供給される。他方の原料ヒドロキシルアミンについては、市販のヒドロキシルアミン塩酸塩、硫酸塩若しくは硝酸塩のような無機酸塩又は酢酸塩のような有機酸塩を使用する場合とフリーのヒドロキシルアミンを使用する場合がある。市販のヒドロキシルアミンの無機酸塩又は有機酸塩を使用する場合、使用時アルカリで中和して遊離のヒドロキシルアミン水溶液を調製して使用する。この中和反応は、オキシム化反応と同時に行う。すなわち、ヒドロキシルアミン無機酸塩又は有機酸塩水溶液と４０％グリオキサール水溶液中に、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等のアルカリの水溶液又は固形物で中和しながらオキシム化反応を行う。反応後グリオキシムは、一部は水に溶けており、懸濁液の状態で得られる。 First, the oximation reaction in the present invention will be described. One raw material glyoxal used for the oximation is usually supplied as a 40% aqueous solution. As the other raw material hydroxylamine, a commercially available hydroxylamine hydrochloride, an inorganic acid salt such as sulfate or nitrate, or an organic acid salt such as acetate may be used, or free hydroxylamine may be used. When using a commercially available inorganic acid salt or organic acid salt of hydroxylamine, a free hydroxylamine aqueous solution is prepared by neutralizing with alkali at the time of use. This neutralization reaction is performed simultaneously with the oximation reaction. That is, an oxime reaction is carried out while neutralizing with an aqueous solution or solid of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate in a hydroxylamine inorganic acid salt or organic acid salt aqueous solution and a 40% glyoxal aqueous solution. Do. After the reaction, part of the glyoxime is dissolved in water and is obtained in the form of a suspension.
又、フリーのヒドロキシルアミンを用いる場合は、市販の５０％のヒドロキシルアミン水溶液（ＢＡＳＦ社製など）を４０％グリオキサール水溶液に、重合防止のため塩酸等により酸性下として混合させ、前記したのと同様に、反応後のグリオキシムは懸濁液の状態で得られる。 When using free hydroxylamine, a commercially available 50% hydroxylamine aqueous solution (manufactured by BASF, etc.) is mixed with 40% glyoxal aqueous solution under acidic conditions with hydrochloric acid to prevent polymerization, and the same as described above. In addition, the glyoxime after the reaction is obtained in the form of a suspension.
特許文献２に開示されている方法では、反応後、反応液を濾過して固形物をろ別し、これを洗浄、乾燥してグリオキシムの結晶を得ている。しかし、この結晶は機械的衝撃や摩擦により爆発の危険性がある。そして、ろ液には無機塩と共に不可避的に目的物のグリオキシムが一部逃げ収率低下をもたらしている。そこで、本発明では、以下に挙げる方法のように、グリオキシム懸濁液に水混和性有機溶媒を添加することにより、グリオキシム溶液を得る方法を採用する。 In the method disclosed in Patent Document 2, after the reaction, the reaction solution is filtered to separate solids, which are washed and dried to obtain glyoxime crystals. However, this crystal has a risk of explosion due to mechanical shock and friction. In the filtrate, the glyoxime of the target product inevitably partially escapes together with the inorganic salt, resulting in a decrease in yield. Therefore, the present invention employs a method of obtaining a glyoxime solution by adding a water-miscible organic solvent to the glyoxime suspension, as in the following method.
＜方法１＞ グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させて得られるグリオキシム反応溶液に、水混和性の有機溶剤を反応前又は反応後に添加して含有させることによりグリオキシム溶液を得る方法。
＜方法２＞ グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られるグリオキシム反応溶液に、水混和性の有機溶剤を反応前又は反応後に添加して含有させることによりグリオキシム溶液を得る方法。
＜方法３＞ グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させて得られたグリオキシム反応溶液に、水より沸点の高い水混和性の有機溶剤を反応前又は反応後に添加して含有させた後、蒸留によって水を除去し、次いで析出した塩を濾過によって除去することによりグリオキシム溶液を得る方法。
＜方法４＞ グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られたグリオキシム反応溶液に、水より沸点の高い水混和性の有機溶剤を反応前又は反応後に添加して含有させた後、蒸留によって水を除去することによりグリオキシム溶液を得る方法。
＜方法５＞ グリオキサール水溶液とヒドロキシルアミンの無機酸塩あるいは有機酸塩とアルカリとを反応させて得られたグリオキシム反応溶液に、水混和性の有機溶剤を反応前又は反応後に添加して含有させた後、水非混和性の低沸点有機溶剤で液液抽出（分液）することにより有機層としてグリオキシム溶液を得る方法。
＜方法６＞ グリオキサール水溶液を、酸性下ヒドロキシルアミンと反応させて得られたグリオキシム反応溶液に、水混和性の有機溶剤を反応前又は反応後に添加して含有させた後、水非混和性の低沸点有機溶剤で液液抽出（分液）することにより有機層としてグリオキシム溶液を得る方法。
<Method 1> By adding a water-miscible organic solvent to the glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt and an alkali before or after the reaction. A method for obtaining a glyoxime solution.
<Method 2> A method for obtaining a glyoxime solution by adding a water-miscible organic solvent to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction.
<Method 3> A water-miscible organic solvent having a boiling point higher than water is added to a glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt of hydroxylamine or an organic acid salt and an alkali before or after the reaction. And then removing the water by distillation, and then removing the precipitated salt by filtration to obtain a glyoxime solution.
<Method 4> A water-miscible organic solvent having a boiling point higher than that of water is added to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction, and then distilled. To obtain a glyoxime solution by removing water.
<Method 5> A water-miscible organic solvent was added to the glyoxime reaction solution obtained by reacting an aqueous solution of glyoxal with an inorganic acid salt or hydroxyl acid salt of hydroxylamine and an alkali before or after the reaction. Thereafter, a liquid-liquid extraction (separation) with a water-immiscible low-boiling organic solvent yields a glyoxime solution as an organic layer.
<Method 6> A water-miscible organic solvent is added to a glyoxime reaction solution obtained by reacting an aqueous glyoxal solution with hydroxylamine under acidity before or after the reaction. A method for obtaining a glyoxime solution as an organic layer by liquid-liquid extraction (separation) with a boiling organic solvent.
本発明では、グリオキサール溶液を得る方法１～６において用いられる水混和性の有機溶剤としては、次のようなものが挙げられる。
エチレングリコール系： 例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、２－メトキシエタノール、２－エトキシエタノール、２－メトキシエチルアセテート、２－エトキシエチルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等が挙げられる。
In the present invention, examples of the water-miscible organic solvent used in the methods 1 to 6 for obtaining the glyoxal solution include the following.
Ethylene glycol type: For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples include dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.
プロピレングリコール系： 例えば、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、２－メトキシプロパノール、２－エトキシプロパノール、２－メトキシプロピルアセテート、２－エトキシプロピルアセテート、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート等が挙げられる。 Propylene glycol type: For example, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methoxypropanol, 2-ethoxypropanol, 2-methoxypropyl acetate, 2-ethoxypropyl acetate, dipropylene glycol monomethyl ether, dipropylene Examples include glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate.
アルカノール系： 例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、イソブタノール、ターシャリーブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ドデカノール等が挙げられる。 Alkanol type: For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, etc. .
その他： Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－オクチルピロリドンなどのピロリドン系、ジメチルスルホキシド等が挙げられる。 Others: Examples include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-octylpyrrolidone, and dimethyl sulfoxide. It is done.
これらの水混和性の有機溶剤のうち、最終のジクロログリオキシムを有機溶剤溶液の形態として得たい場合は、水より沸点の高い水混和性の有機溶剤を用いるのがよく、好ましくは、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル又はジエチレングリコールを用いるのがよい。 Of these water-miscible organic solvents, when it is desired to obtain the final dichloroglyoxime in the form of an organic solvent solution, a water-miscible organic solvent having a boiling point higher than that of water is preferably used. Preferably, diethylene glycol monomethyl is used. Ether, diethylene glycol monoethyl ether or diethylene glycol may be used.
又、最終のジクロログリオキシムを結晶として得る必要がある場合は、メタノール、エタノール又は２－プロパノール等の比較的沸点の低い水混和性の有機溶剤を用いることもできる。 If it is necessary to obtain the final dichloroglyoxime as crystals, a water-miscible organic solvent having a relatively low boiling point such as methanol, ethanol or 2-propanol can be used.
前記の方法５又は６において、グリオキシム反応溶液に水混和性の有機溶剤を含有させた後に液液抽出（分液）をするために用いる水非混和性の低沸点有機溶剤の沸点は、７６０ｍｍＨｇにおける沸点が２００℃以下であるのがよく、好ましくは、１５０℃以下であるのがよい。そのような低沸点有機溶剤としては、例えば、ベンゼン、トルエン、キシレン、四塩化炭素、クロロホルム、ジクロロメタン、１，２－ジクロロエタン、ジエチルエーテル、オクタノール、酢酸エチル、酢酸プロピル、酢酸ブチル、二硫化炭素が好ましく用いられ、より好ましくは、酢酸エチル、クロロホルムを用いるのがよい。 In the above method 5 or 6, the boiling point of the water-immiscible low-boiling organic solvent used for liquid-liquid extraction (separation) after the water-miscible organic solvent is contained in the glyoxime reaction solution is 760 mmHg. The boiling point should be 200 ° C. or lower, and preferably 150 ° C. or lower. Examples of such low boiling point organic solvents include benzene, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, octanol, ethyl acetate, propyl acetate, butyl acetate, and carbon disulfide. Preferably, it is good to use ethyl acetate and chloroform more preferably.
前記の方法５又は６において、水非混和性の低沸点有機溶剤で液液抽出（分液）をする際には、抽出効率を向上させるために、塩化ナトリウムや塩化カリウムなどの塩を適量添加して塩析を行ってもよい。 When performing liquid-liquid extraction (separation) with a water-immiscible low-boiling organic solvent in method 5 or 6, an appropriate amount of salt such as sodium chloride or potassium chloride is added to improve extraction efficiency. Then, salting out may be performed.
前記の方法５又は６において、液液抽出（分液）後に有機層として得られたグリオキシム溶液は、そのまま次の塩素化反応に供してもよく、無水硫酸ナトリウム、硫酸マグネシウム等の脱水剤を用いて脱水してから塩素化反応に供してもよい。 In the above method 5 or 6, the glyoxime solution obtained as an organic layer after liquid-liquid extraction (separation) may be used for the next chlorination reaction as it is, and a dehydrating agent such as anhydrous sodium sulfate or magnesium sulfate is used. The chlorination reaction may be carried out after dehydration.
次に、前記において得られたグリオキシム溶液の塩素化とその後の処理について述べる。 Next, the chlorination of the glyoxime solution obtained above and the subsequent treatment will be described.
本発明の方法では、撹拌装置と冷却装置を備えた反応釜等の反応容器に、冷却能力に応じて、前記オキシム化で調製されたグリオキシム溶液と塩素化剤とを、モル比１：２以上の比率で同時に注入するとよい。このとき、短く限られた時間内では前記モル比１：２以上を維持しつつ、どちらか一方あるいは双方が間欠的に注入されることを含む。グリオキシム溶液と塩素化剤の注入モル比は、好ましくは、１：２～１：４で行うのがよい。反応温度は、＋２０～－２０℃、好ましくは＋１０～－１０℃で行うとよい。 In the method of the present invention, a molar ratio of the glyoxime solution prepared by the oximation and the chlorinating agent is 1: 2 or more in a reaction vessel such as a reaction vessel equipped with a stirrer and a cooling device according to the cooling capacity. It is recommended to inject at the same time. At this time, one or both of them are intermittently injected while maintaining the molar ratio of 1: 2 or more within a short limited time. The injection molar ratio of the glyoxime solution and the chlorinating agent is preferably 1: 2 to 1: 4. The reaction temperature is +20 to −20 ° C., preferably +10 to −10 ° C.
次に、塩素化終了後のジクロログリオキシム反応溶液の後処理について述べる。 Next, the post-treatment of the dichloroglyoxime reaction solution after completion of chlorination will be described.
グリオキシム溶液を得る方法１～４にて得られたグリオキシム溶液を用いた場合は、ジクロログリオキシム反応溶液に、水非混和性の低沸点有機溶剤を添加して十分に撹拌・混合する。このとき使用される水非混和性の低沸点有機溶剤は、７６０ｍｍＨｇにおける沸点が２００℃以下であるのがよく、好ましくは、１５０℃以下であるのがよい。そのような低沸点有機溶剤としては、例えば、ベンゼン、トルエン、キシレン、四塩化炭素、クロロホルム、ジクロロメタン、１，２－ジクロロエタン、ジエチルエーテル、オクタノール、酢酸エチル、酢酸プロピル、酢酸ブチル、二硫化炭素が好ましく用いられ、より好ましくは、酢酸エチル、クロロホルムを用いるのがよい。なお、グリオキシム溶液を得る方法５及び６にて得られたグリオキシム溶液を用いた場合は、水非混和性の低沸点有機溶剤がジクロログリオキシム反応溶液に既に含まれているので、その分添加量を減らすか又はその添加を省略することができる。 When the glyoxime solution obtained in methods 1 to 4 for obtaining a glyoxime solution is used, a water-immiscible low-boiling organic solvent is added to the dichloroglyoxime reaction solution and sufficiently stirred and mixed. The water-immiscible low-boiling organic solvent used at this time has a boiling point at 760 mmHg of 200 ° C. or lower, preferably 150 ° C. or lower. Examples of such low boiling point organic solvents include benzene, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, octanol, ethyl acetate, propyl acetate, butyl acetate, and carbon disulfide. Preferably, it is good to use ethyl acetate and chloroform more preferably. In addition, when using the glyoxime solution obtained in the methods 5 and 6 for obtaining the glyoxime solution, the water-immiscible low boiling point organic solvent is already contained in the dichloroglyoxime reaction solution, so the amount added accordingly Or the addition thereof can be omitted.
続いて、反応容器内のジクロログリオキシム反応溶液中の水含有量が反応混合物中２０～９０重量％の範囲内、好ましくは３０～８０重量％の範囲内となるように水を加えて調整する。このとき、塩析効果を促進するために、塩化ナトリウム、塩化カリウム等の塩を適量添加してもよい。その後、有機層と水層に二層分離するので、有機層を分取する。グリオキシムの塩素化により副生した塩化水素のほとんどは、水層へ移動するので、ジクロログリオキシムを含有する有機層中の残留塩化水素はかなり少なくなっている。又、水層に、前記した水非混和性の低沸点有機溶剤をさらに加えて液液抽出（分液）すると、ジクロログリオキシムの収率を向上させることもできる。又、この後、分取した有機層に無水硫酸ナトリウム、無水硫酸マグネシウム等の脱水剤で脱水することもできる。 Subsequently, water is adjusted so that the water content in the dichloroglyoxime reaction solution in the reaction vessel is in the range of 20 to 90% by weight, preferably in the range of 30 to 80% by weight in the reaction mixture. . At this time, an appropriate amount of salt such as sodium chloride or potassium chloride may be added to promote the salting out effect. Thereafter, two layers are separated into an organic layer and an aqueous layer, and the organic layer is separated. Since most of the hydrogen chloride by-produced by chlorination of glyoxime is transferred to the aqueous layer, the residual hydrogen chloride in the organic layer containing dichloroglyoxime is considerably reduced. Moreover, the yield of dichloroglyoxime can also be improved by further adding the above-mentioned water-immiscible low-boiling organic solvent to the aqueous layer and performing liquid-liquid extraction (separation). Thereafter, the separated organic layer can be dehydrated with a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate.
続いて、前記した有機層から低沸点有機溶剤を減圧下除去することにより、低沸点の水混和性有機溶剤を使用した場合はジクロログリオキシムの結晶を、水より高沸点の水混和性有機溶剤を使用した場合はジクロログリオキシムの有機溶剤溶液を得ることができる。このとき、さらに水分含有量を低減させたいときは、減圧下低温にて水分を除去してもよい。 Subsequently, by removing the low-boiling organic solvent from the organic layer under reduced pressure, when a low-boiling water-miscible organic solvent is used, the dichloroglyoxime crystals are converted into a water-miscible organic solvent having a boiling point higher than that of water. When is used, an organic solvent solution of dichloroglyoxime can be obtained. At this time, when it is desired to further reduce the water content, the water may be removed at a low temperature under reduced pressure.
以下、実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。なお、以下の説明において、「部」は質量部を示す。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples. In the following description, “part” means part by mass.
＜実施例１＞
３００ｍｌの四つ口フラスコに、硫酸ヒドロキシアンモニウム３２．８ｇ（０．２モル）と４０％グリオキサール水溶液２９ｇ（０．２モル）と、水３５ｇを入れ、冷却下、１５℃以下で３５％水酸化ナトリウム水溶液４５．９ｇ（０．４モル）を滴下した。一晩撹拌熟成後、エタノール１５０ｇを加えて均一になるまで撹拌し、黄色のグリオキシムのエタノール（含水）溶液２９０ｇを得た。１リットルの四つ口フラスコに、エタノール７０ｇを入れ、－５～０℃で前記グリオキシムのエタノール（含水）溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、酢酸エチル２００ｇを添加して撹拌し、続いて５％食塩水１２０ｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。分取した有機層に無水硫酸ナトリウム１０ｇを添加して約１時間脱水した後５Ａろ紙でろ過し、ろ液中の酢酸エチルとエタノールとを減圧下留去することにより、白色固体２２ｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、９５．２％であった（収率：６６．７％）。このジクロログリオキシムの白色固体からは塩化水素臭は感じられなかったことから、副生した塩化水素は十分除去されていた。塩素化反応終了後にジクロログリオキシムの白色固体を得るまでに要した時間は、約２．５時間であった。
<Example 1>
A 300 ml four-necked flask is charged with 32.8 g (0.2 mol) of hydroxyammonium sulfate, 29 g (0.2 mol) of 40% aqueous glyoxal solution, and 35 g of water. 45.9 g (0.4 mol) of an aqueous sodium solution was added dropwise. After stirring and aging overnight, 150 g of ethanol was added and stirred until uniform to obtain 290 g of a yellow glyoxime ethanol (water-containing) solution. In a 1 liter four-necked flask, 70 g of ethanol is added, and the ethanol (water-containing) solution of glyoxime and chlorine are added at −5 to 0 ° C. so that the injection molar ratio of glyoxime and chlorine in the solution is 1: 3. Were injected simultaneously. After completion of the reaction, 200 g of ethyl acetate was added and stirred, and then 120 g of 5% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. 10 g of anhydrous sodium sulfate was added to the separated organic layer, dehydrated for about 1 hour, filtered through 5A filter paper, and ethyl acetate and ethanol in the filtrate were distilled off under reduced pressure to obtain 22 g of a white solid. . When the dichloroglyoxime content was analyzed by the HPLC method, it was 95.2% (yield: 66.7%). Since the hydrogen chloride odor was not felt from the white solid of dichloroglyoxime, the by-produced hydrogen chloride was sufficiently removed. The time required to obtain a white solid of dichloroglyoxime after completion of the chlorination reaction was about 2.5 hours.
＜実施例２＞
３００ｍｌの四つ口フラスコに、４０％グリオキサール水溶液２９ｇ（０．２モル）と濃塩酸０．３５ｇとエタノール１０５ｇを加え、２０℃で５０％ヒドロキシルアミン水溶液２６．４ｇ（０．４モル）を滴下した。一晩撹拌熟成後、黄色のグリオキシムのエタノール（含水）溶液１６０ｇを得た。１リットルの四つ口フラスコに、エタノール７０ｇを入れ、－５～０℃で前記グリオキシムのエタノール（含水）溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、酢酸エチル２００ｇを添加して撹拌し、続いて１０％食塩水１７０ｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。分取した有機層に無水硫酸ナトリウム１０ｇを添加して約１時間脱水した後５Ａろ紙でろ過し、ろ液中の酢酸エチルを減圧下留去することにより、白色固体２６ｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、９４．０％であった（収率：７７．８％）。このジクロログリオキシムの白色固体からは塩化水素臭は感じられなかったことから、副生した塩化水素は十分除去されていた。このとき、塩素化反応終了後にジクロログリオキシムの白色固体を得るまでに要した時間は、約２．５時間であった。
<Example 2>
To a 300 ml four-necked flask, 29 g (0.2 mol) of 40% aqueous glyoxal solution, 0.35 g of concentrated hydrochloric acid and 105 g of ethanol are added, and 26.4 g (0.4 mol) of 50% aqueous hydroxylamine solution is added dropwise at 20 ° C. did. After stirring and aging overnight, 160 g of a yellow glyoxime ethanol (water-containing) solution was obtained. In a 1 liter four-necked flask, 70 g of ethanol is added, and the ethanol (water-containing) solution of glyoxime and chlorine are added at −5 to 0 ° C. so that the injection molar ratio of glyoxime and chlorine in the solution is 1: 3. Were injected simultaneously. After completion of the reaction, 200 g of ethyl acetate was added and stirred, and then 170 g of 10% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. 10 g of anhydrous sodium sulfate was added to the separated organic layer, dehydrated for about 1 hour, filtered through 5A filter paper, and ethyl acetate in the filtrate was distilled off under reduced pressure to obtain 26 g of a white solid. When the dichloroglyoxime content was analyzed by HPLC, it was 94.0% (yield: 77.8%). Since the hydrogen chloride odor was not felt from the white solid of dichloroglyoxime, the by-produced hydrogen chloride was sufficiently removed. At this time, it took about 2.5 hours to obtain a white solid of dichloroglyoxime after completion of the chlorination reaction.
＜実施例３＞
３００リットルのグラスライニング反応釜に、硫酸ヒドロキシアンモニウム３２．８ｋｇ（２００モル）と４０％グリオキサール水溶液２９．０ｋｇ（２００モル）と、水３５．０ｋｇを入れ、冷却下、１５℃以下で３５％水酸化ナトリウム水溶液４５．９ｋｇ（４００モル）を滴下した。一晩撹拌熟成後、ジエチレングリコールモノメチルエーテル１３０ｋｇを加え、水を減圧留去（内温６０℃以下）した。１０℃以下に冷却後、析出硫酸ナトリウムの結晶を減圧ろ過し、この結晶をジエチレングリコールモノメチルエーテル２０．０ｋｇで洗浄し、ろ液と洗液とを合わせて、褐色のグリオキシムのジエチレングリコールモノメチル溶液１４７．３ｋｇを得た。１０００リットルのグラスライニング反応釜に、ジエチレングリコールモノメチルエーテル７０．０ｋｇを入れ、５℃以下で前記グリオキシムのジエチレングリコールモノメチルエーテル溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、酢酸エチル２００ｋｇを添加して撹拌し、続いて５％食塩水２００ｋｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。有機層中の酢酸エチルを減圧下留去することにより、淡黄色透明溶液１６０ｋｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、１８．１％であった（収率：９２．２％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．４であり、副生した塩化水素は十分除去されていた。このとき、塩素化反応終了後に淡黄色透明溶液を得るまでに要した時間は、約３時間であった。
<Example 3>
A 300 liter glass-lined reaction kettle is charged with 32.8 kg (200 mol) of hydroxyammonium sulfate, 29.0 kg (200 mol) of 40% aqueous glyoxal solution, and 35.0 kg of water. 45.9 kg (400 mol) of an aqueous sodium oxide solution was added dropwise. After stirring and aging overnight, 130 kg of diethylene glycol monomethyl ether was added, and water was distilled off under reduced pressure (internal temperature: 60 ° C. or lower). After cooling to 10 ° C. or lower, the precipitated sodium sulfate crystals were filtered under reduced pressure. The crystals were washed with 20.0 kg of diethylene glycol monomethyl ether, and the filtrate and the washings were combined to give a brown glyoxime diethylene glycol monomethyl solution of 147.3 kg. Got. 70.0 kg of diethylene glycol monomethyl ether is put into a 1000 liter glass-lined reaction kettle, and the molar ratio of glyoxime and chlorine in the solution of glyoxime and diethylene glycol monomethyl ether solution and chlorine is 1: 3 at 5 ° C. or lower. Were injected at the same time. After completion of the reaction, 200 kg of ethyl acetate was added and stirred, and then 200 kg of 5% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. Ethyl acetate in the organic layer was distilled off under reduced pressure to obtain 160 kg of a pale yellow transparent solution. When the dichloroglyoxime content was analyzed by the HPLC method, it was 18.1% (yield: 92.2%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.4, and hydrogen chloride produced as a by-product was sufficiently removed. At this time, it took about 3 hours to obtain a pale yellow transparent solution after completion of the chlorination reaction.
＜実施例４＞
３００リットルのグラスライニング反応釜に、４０％グリオキサール水溶液２９．０ｋｇ（２００モル）と濃塩酸０．３５ｋｇとジエチレングリコールモノメチルエーテル１０５ｋｇを加え、２０℃で５０％ヒドロキシルアミン水溶液２６．４ｋｇ（４００モル）を滴下した。一晩撹拌熟成後、水を減圧留去（内温６０℃以下）した。褐色のグリオキシムのジエチレングリコールモノメチル溶液１２５ｋｇを得た。１０００リットルのグラスライニング反応釜に、ジエチレングリコールモノメチルエーテル７０ｋｇを入れ、５℃以下で前記グリオキシムのジエチレングリコールモノメチルエーテル溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。１０時間の反応後、酢酸エチル２００ｋｇを添加して撹拌し、続いて１０％食塩水２００ｋｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。有機層中の酢酸エチルを減圧下留去することにより、淡黄色透明溶液１４２ｋｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、２０．０％であった（収率：９０．４％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．３であり、副生した塩化水素は十分除去されていた。このとき、塩素化反応終了後に淡黄色透明溶液を得るまでに要した時間は、約３時間であった。
<Example 4>
To a 300 liter glass-lined reaction kettle, 29.0 kg (200 mol) of 40% glyoxal aqueous solution, 0.35 kg of concentrated hydrochloric acid and 105 kg diethylene glycol monomethyl ether were added, and 26.4 kg (400 mol) of 50% hydroxylamine aqueous solution was added at 20 ° C. It was dripped. After stirring and aging overnight, water was distilled off under reduced pressure (internal temperature: 60 ° C. or lower). 125 kg of a diethylene glycol monomethyl solution of brown glyoxime was obtained. Into a 1000 liter glass-lined reaction kettle, 70 kg of diethylene glycol monomethyl ether is put, and the diethylene glycol monomethyl ether solution of glyoxime and chlorine are added at 5 ° C. or less so that the molar ratio of glyoxime and chlorine in the solution is 1: 3. Injected simultaneously. After the reaction for 10 hours, 200 kg of ethyl acetate was added and stirred, and then 200 kg of 10% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. Ethyl acetate in the organic layer was distilled off under reduced pressure to obtain 142 kg of a pale yellow transparent solution. When the dichloroglyoxime content was analyzed by the HPLC method, it was 20.0% (yield: 90.4%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.3, and hydrogen chloride produced as a by-product was sufficiently removed. At this time, it took about 3 hours to obtain a pale yellow transparent solution after completion of the chlorination reaction.
＜実施例５＞
３００ｍｌの四つ口フラスコに、硫酸ヒドロキシアンモニウム３２．８ｇ（０．２モル）と４０％グリオキサール水溶液２９ｇ（０．２モル）と、水３５ｇを入れ、冷却下、１５℃以下で３５％水酸化ナトリウム水溶液４５．９ｇ（０．４モル）を滴下した。一晩撹拌熟成後、ジエチレングリコールモノメチルエーテル７０ｇを加えた後撹拌しながら析出したグリオキシムの白色固体を溶解した。さらに食塩７ｇを加え、酢酸エチル７０ｇを加えて抽出した。有機層（上層）を分取して、淡黄色のグリオキシムの酢酸エチル／ジエチレングリコールモノメチルエーテル溶液（以下、グリオキシム溶液ともいう。）１０５ｇを得た。このグリオキシム溶液をＨＰＬＣ法によりグリオキシム含有量を分析したところ、１１％であった（収率：６５．６％）
１リットルの四つ口フラスコに、ジエチレングリコールモノメチルエーテル４０ｇを入れ、－５～０℃で前記グリオキシム溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、１０％食塩水７０ｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。分取した有機層に無水硫酸ナトリウム１０ｇを添加して約１時間脱水した後５Ａろ紙でろ過し、ろ液中の酢酸エチルを減圧下留去することにより、淡黄色液体１０７ｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、１７．７％であった（出発原料からの収率：６０．１％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．５であり、副生した塩化水素は十分除去されていた。塩素化反応終了後にジクロログリオキシムの白色固体を得るまでに要した時間は、約２．５時間であった。
<Example 5>
A 300 ml four-necked flask is charged with 32.8 g (0.2 mol) of hydroxyammonium sulfate, 29 g (0.2 mol) of 40% aqueous glyoxal solution, and 35 g of water. 45.9 g (0.4 mol) of an aqueous sodium solution was added dropwise. After stirring and aging overnight, 70 g of diethylene glycol monomethyl ether was added, and then the glyoxime white solid precipitated was dissolved while stirring. Further, 7 g of sodium chloride was added, and 70 g of ethyl acetate was added for extraction. The organic layer (upper layer) was separated to obtain 105 g of a pale yellow glyoxime ethyl acetate / diethylene glycol monomethyl ether solution (hereinafter also referred to as glyoxime solution). When this glyoxime solution was analyzed for glyoxime content by HPLC, it was 11% (yield: 65.6%).
Into a 1 liter four-necked flask, add 40 g of diethylene glycol monomethyl ether, and simultaneously inject the glyoxime solution and chlorine at −5 to 0 ° C. so that the molar ratio of glyoxime and chlorine in the solution is 1: 3. did. After completion of the reaction, 70 g of 10% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. 10 g of anhydrous sodium sulfate was added to the separated organic layer, dehydrated for about 1 hour, filtered through 5A filter paper, and ethyl acetate in the filtrate was distilled off under reduced pressure to obtain 107 g of a pale yellow liquid. When the dichloroglyoxime content was analyzed by HPLC, it was 17.7% (yield from starting material: 60.1%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.5, and the by-produced hydrogen chloride was sufficiently removed. The time required to obtain a white solid of dichloroglyoxime after completion of the chlorination reaction was about 2.5 hours.
＜実施例６＞
３００ｍｌの四つ口フラスコに、４０％グリオキサール水溶液２９ｇ（０．２モル）と濃塩酸０．３５ｇとジエチレングリコールモノメチルエーテル７０ｇを加え、２０℃で５０％ヒドロキシルアミン水溶液２６．４ｇ（０．４モル）を滴下した。一晩撹拌熟成後、食塩７ｇを加え、酢酸エチル７０ｇを加えて抽出した。有機層（上層）を分取して、淡黄色のグリオキシムの酢酸エチル／ジエチレングリコールモノメチルエーテル溶液（以下、グリオキシム溶液ともいう。）１０１ｇを得た。このグリオキシム溶液をＨＰＬＣ法によりグリオキシム含有量を分析したところ、１１．８％であった（収率：６７．５％）１リットルの四つ口フラスコに、ジエチレングリコールモノメチルエーテル４０ｇを入れ、－５～０℃で前記グリオキシム溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、１０％食塩水７０ｇを添加して撹拌した。撹拌を止めた後、反応混合溶液が二層に分離したら、有機層（上層）を分取した。分取した有機層に無水硫酸ナトリウム１０ｇを添加して約１時間脱水した後５Ａろ紙でろ過し、ろ液中の酢酸エチルを減圧下留去することにより、淡黄色液体１０２ｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、１８．３％であった（出発原料からの収率：５９．４％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．６であり、副生した塩化水素は十分除去されていた。塩素化反応終了後にジクロログリオキシムの白色固体を得るまでに要した時間は、約２．５時間であった。
<Example 6>
To a 300 ml four-necked flask, 29 g (0.2 mol) of 40% glyoxal aqueous solution, 0.35 g of concentrated hydrochloric acid and 70 g of diethylene glycol monomethyl ether were added, and 26.4 g (0.4 mol) of 50% aqueous hydroxylamine solution at 20 ° C. Was dripped. After stirring and aging overnight, 7 g of sodium chloride was added, and 70 g of ethyl acetate was added for extraction. The organic layer (upper layer) was separated to obtain 101 g of a pale yellow glyoxime solution in ethyl acetate / diethylene glycol monomethyl ether (hereinafter also referred to as glyoxime solution). When the glyoxime content of this glyoxime solution was analyzed by the HPLC method, it was 11.8% (yield: 67.5%) 40 g of diethylene glycol monomethyl ether was placed in a 1 liter four-necked flask, and -5 to The glyoxime solution and chlorine were simultaneously injected at 0 ° C. so that the injection molar ratio of glyoxime and chlorine in the solution was 1: 3. After completion of the reaction, 70 g of 10% brine was added and stirred. After the stirring was stopped, when the reaction mixture solution separated into two layers, the organic layer (upper layer) was separated. 10 g of anhydrous sodium sulfate was added to the separated organic layer, dehydrated for about 1 hour, filtered through 5A filter paper, and ethyl acetate in the filtrate was distilled off under reduced pressure to obtain 102 g of a pale yellow liquid. When the dichloroglyoxime content was analyzed by HPLC, it was 18.3% (yield from starting material: 59.4%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.6, and the by-produced hydrogen chloride was sufficiently removed. The time required to obtain a white solid of dichloroglyoxime after completion of the chlorination reaction was about 2.5 hours.
＜比較例１＞
３００ｍｌの四つ口フラスコに、硫酸ヒドロキシアンモニウム３２．８ｇ（０．２モル）と４０％グリオキサール水溶液２９ｇ（０．２モル）と、水３５ｇを入れ、冷却下、１５℃以下で３５％水酸化ナトリウム水溶液４５．９ｇ（０．４モル）を滴下した。一晩撹拌熟成後、ジエチレングリコールモノメチルエーテル１００ｇを加え、ロータリーエバポレーターで水を減圧留去した。析出した硫酸ナトリウムの結晶を５Ａろ紙でろ別し、ろ紙上の結晶をジエチレングリコールモノメチルエーテル６４ｇで洗浄し、ろ液と洗液を合わせて褐色のグリオキシムのジエチレングリコールモノメチル溶液を得た。５００ｍｌの四つ口フラスコに６０ｇのジエチレングリコールモノメチルエーテルを入れ、－５～０℃で前記グリオキシムのジエチレングリコールモノメチルエーテル溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。反応終了後、真空ポンプを用いて減圧下、副生した塩化水素を反応混合混合物が発煙しなくなるまで脱気し、淡黄色液体２５１ｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、１１．０％であった（収率：８７．９％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．２であり、副生した塩化水素は十分除去されていたが、塩素化反応終了後に、塩化水素を十分に除去して（塩化水素の発煙のない）ジクロログリオキシムの淡黄色液体を得るまでに約３６時間を要した。又、脱気中にアルカリトラップの詰まりや、アルカリトラップで捕捉しきれなかった塩化水素により真空ポンプの吸引能力の低下などの不具合が見られた。
<Comparative Example 1>
A 300 ml four-necked flask is charged with 32.8 g (0.2 mol) of hydroxyammonium sulfate, 29 g (0.2 mol) of 40% aqueous glyoxal solution, and 35 g of water. 45.9 g (0.4 mol) of an aqueous sodium solution was added dropwise. After stirring and aging overnight, 100 g of diethylene glycol monomethyl ether was added, and water was distilled off under reduced pressure using a rotary evaporator. The precipitated sodium sulfate crystals were filtered off with 5A filter paper, the crystals on the filter paper were washed with 64 g of diethylene glycol monomethyl ether, and the filtrate and the washing solution were combined to obtain a diethylene glycol monomethyl solution of brown glyoxime. In a 500 ml four-necked flask, 60 g of diethylene glycol monomethyl ether is added, and the glyoxime diethylene glycol monomethyl ether solution and chlorine are added at −5 to 0 ° C. so that the molar ratio of glyoxime and chlorine in the solution is 1: 3. Were injected simultaneously. After completion of the reaction, by-product hydrogen chloride was deaerated under reduced pressure using a vacuum pump until the reaction mixture did not emit smoke to obtain 251 g of a pale yellow liquid. When the dichloroglyoxime content was analyzed by the HPLC method, it was 11.0% (yield: 87.9%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.2 and hydrogen chloride produced as a by-product was sufficiently removed. However, after completion of the chlorination reaction, hydrogen chloride was sufficiently removed (hydrogen chloride). It took about 36 hours to obtain a light yellow liquid of dichloroglyoxime (without smoking). In addition, problems such as clogging of the alkali trap during deaeration and reduction of the suction capacity of the vacuum pump due to hydrogen chloride that could not be captured by the alkali trap were observed.
＜比較例２＞
３００リットルのグラスライニング反応釜に、４０％グリオキサール水溶液２９．０ｋｇ（２００モル）と濃塩酸０．３５ｋｇとジエチレングリコールモノメチルエーテル１０５ｋｇを加え、２０℃で５０％ヒドロキシルアミン水溶液２６．４ｋｇ（４００モル）を滴下した。一晩撹拌熟成後、水を減圧留去（内温６０℃以下）した。褐色のグリオキシムのジエチレングリコールモノメチル溶液１２５ｋｇを得た。３００リットルのグラスライニング反応釜に、ジエチレングリコールモノメチルエーテル７０ｋｇを入れ、－５～０℃で前記グリオキシムのジエチレングリコールモノメチルエーテル溶液と塩素とを、溶液中のグリオキシムと塩素の注入モル比率が１：３となるように同時に注入した。１０時間の反応後、真空ポンプを用いて減圧下、溶存塩化水素を反応混合物が発煙しなくなるまで脱気し、淡黄色液体２５０ｋｇを得た。ＨＰＬＣ法によりジクロログリオキシム含有量を分析したところ、１１．１％であった（収率：８８．４％）。このジクロログリオキシム溶液のｐＨ（１％精製水溶液）は２．１であり、副生した塩化水素は十分除去されていたが、塩素化反応終了後に、塩化水素を十分に除去して（塩化水素の発煙のない）ジクロログリオキシムの淡黄色液体を得るまでに約５日間を要した。脱気作業中には、アルカリトラップの詰まりや、アルカリトラップで捕捉しきれなかった塩化水素によると思われる真空ポンプの吸引能力の低下などの不具合が見られた。
<Comparative example 2>
To a 300 liter glass-lined reaction kettle, 29.0 kg (200 mol) of 40% glyoxal aqueous solution, 0.35 kg of concentrated hydrochloric acid and 105 kg diethylene glycol monomethyl ether were added, and 26.4 kg (400 mol) of 50% hydroxylamine aqueous solution was added at 20 ° C. It was dripped. After stirring and aging overnight, water was distilled off under reduced pressure (internal temperature: 60 ° C. or lower). 125 kg of a diethylene glycol monomethyl solution of brown glyoxime was obtained. In a 300 liter glass-lined reaction kettle, 70 kg of diethylene glycol monomethyl ether is charged, and the diethylene glycol monomethyl ether solution of glyoxime and chlorine at −5 to 0 ° C. The injection molar ratio of glyoxime and chlorine in the solution is 1: 3. Were injected at the same time. After the reaction for 10 hours, the dissolved hydrogen chloride was deaerated under reduced pressure using a vacuum pump until the reaction mixture no longer smoked to obtain 250 kg of a pale yellow liquid. When the dichloroglyoxime content was analyzed by HPLC, it was 11.1% (yield: 88.4%). The pH of this dichloroglyoxime solution (1% purified aqueous solution) was 2.1, and the hydrogen chloride produced as a by-product was sufficiently removed. However, after the chlorination reaction was completed, the hydrogen chloride was sufficiently removed (hydrogen chloride). It took about 5 days to obtain a light yellow liquid of dichloroglyoxime (without smoking). During the deaeration work, problems such as clogging of the alkali trap and a decrease in the suction capacity of the vacuum pump, which seems to be caused by hydrogen chloride that could not be captured by the alkali trap, were observed.
実施例１～６においては、比較例１又は２と比べ、塩素化反応後の脱塩化水素の時間が著しく短縮されており、効率的にジクロログリオキシム又はジクロログリオキシムの有機溶剤溶液が得られていることがわかる。 In Examples 1 to 6, the time for dehydrochlorination after the chlorination reaction is remarkably shortened as compared with Comparative Example 1 or 2, and dichloroglyoxime or an organic solvent solution of dichloroglyoxime can be obtained efficiently. You can see that
本発明は、工業用殺菌剤、防腐剤、スライムコントロール剤等として用いられるジクロログリオキシムを安全に、且つ従来より効率よく製造する方法に関するものであり、水処理、製紙工業などの有害微生物が問題となる産業分野で利用されるものである。特に、本発明においては、ジクロログリオキシムの製造を完結させるための時間を著しく短縮することができ、ジクロログリオキシムを効率的に製造することができる。
The present invention relates to a method for safely and more efficiently producing dichloroglyoxime used as an industrial disinfectant, preservative, slime control agent, etc., and harmful microorganisms such as water treatment and paper industry are problematic. It is used in the industrial field. In particular, in the present invention, the time for completing the production of dichloroglyoxime can be significantly shortened, and dichloroglyoxime can be produced efficiently.
Claims (8)
（ａ）水と非混和性であり、且つその７６０ｍｍＨｇにおける沸点が２００℃以下である低沸点有機溶剤を含有させる工程。
（ｂ）塩素化終了後の反応容器内の水含有量が反応混合物中２０～９０重量％となるように調整し、有機層と水層に二層分離させた後、有機層を分取する工程。
（ｃ）前記（ｂ）の有機層から前記（ａ）の低沸点有機溶剤を除去する工程。 Dichloroglyoxime is prepared by reacting glyoxal with hydroxylamine or a salt thereof to prepare a glyoxime solution containing a water-miscible organic solvent, and simultaneously injecting the glyoxime solution and the chlorinating agent into a reaction vessel. A process for producing dichloroglyoxime comprising the following steps:
(A) A step of containing a low-boiling organic solvent that is immiscible with water and has a boiling point at 760 mmHg of 200 ° C. or lower.
(B) The water content in the reaction vessel after completion of chlorination is adjusted to 20 to 90% by weight in the reaction mixture, and the organic layer and the aqueous layer are separated into two layers, and then the organic layer is separated. Process.
(C) A step of removing the low-boiling organic solvent (a) from the organic layer (b).
The method for producing dichloroglyoxime according to any one of claims 1 to 7, wherein the chlorinating agent is chlorine or sulfuryl chloride.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539405A (en) * | 1984-04-16 | 1985-09-03 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of 1,4-dinitrofurazano(3,4-b)piperazine |
| JPH0733728A (en) * | 1993-07-27 | 1995-02-03 | Jiyunsei Kagaku Kk | Production of organic solvent solution of dichloroglyoxime |
| JPH11236362A (en) * | 1998-02-23 | 1999-08-31 | Katayama Chem Works Co Ltd | Production of dichloroglyoxime |
| JP2003012628A (en) * | 2001-07-06 | 2003-01-15 | Katayama Chem Works Co Ltd | Method for producing glyoxime and dichloroglyoxime |
| JP2014076985A (en) * | 2012-09-18 | 2014-05-01 | Fuji Sangyo Co Ltd | Industrial microbicide composition having improved safety |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539405A (en) * | 1984-04-16 | 1985-09-03 | The United States Of America As Represented By The Secretary Of The Navy | Synthesis of 1,4-dinitrofurazano(3,4-b)piperazine |
| JPH0733728A (en) * | 1993-07-27 | 1995-02-03 | Jiyunsei Kagaku Kk | Production of organic solvent solution of dichloroglyoxime |
| JPH11236362A (en) * | 1998-02-23 | 1999-08-31 | Katayama Chem Works Co Ltd | Production of dichloroglyoxime |
| JP2003012628A (en) * | 2001-07-06 | 2003-01-15 | Katayama Chem Works Co Ltd | Method for producing glyoxime and dichloroglyoxime |
| JP2014076985A (en) * | 2012-09-18 | 2014-05-01 | Fuji Sangyo Co Ltd | Industrial microbicide composition having improved safety |
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