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WO2018139485A1 - Procédé de production de dichloroglyoxime - Google Patents

Procédé de production de dichloroglyoxime Download PDF

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Publication number
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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Prior art keywords
solution
glyoxime
water
dichloroglyoxime
organic solvent
Prior art date
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Ceased
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PCT/JP2018/002116
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English (en)
Japanese (ja)
Inventor
川島竜一
金山正博
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Fuji Sangyo Co Ltd
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Fuji Sangyo Co Ltd
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Publication of WO2018139485A1 publication Critical patent/WO2018139485A1/fr
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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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un procédé de production de dichloroglyoxime par lequel la dichloroglyoxime, qui peut être utilisée en tant qu'agent antibactérien industriel, conservateur, agent de lutte contre les boues ou analogues, peut être obtenue avec une plus grande sécurité et une efficacité améliorée. La solution, selon l'invention porte sur un procédé de production de dichloroglyoxime par la réaction du glyoxal avec de l'hydroxylamine suivie d'une chloration. Selon l'invention, le procédé comprend en outre les étapes consistant à : incorporer un solvant organique à bas point d'ébullition non miscible dans l'eau ; incorporer de 20 à 90 % d'eau après l'achèvement de la chloration de manière à provoquer la séparation en deux couches, puis, séparer la couche organique ; et éliminer le solvant organique à bas point d'ébullition miscible dans l'eau à partir de la couche organique.
PCT/JP2018/002116 2017-01-30 2018-01-24 Procédé de production de dichloroglyoxime Ceased WO2018139485A1 (fr)

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JP2017014045A JP6229244B1 (ja) 2017-01-30 2017-01-30 ジクロログリオキシムの製造方法
JP2017-014045 2017-06-29

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Citations (5)

* Cited by examiner, † Cited by third party
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 (ja) * 1993-07-27 1995-02-03 Jiyunsei Kagaku Kk ジクロログリオキシム有機溶剤溶液の製造法
JPH11236362A (ja) * 1998-02-23 1999-08-31 Katayama Chem Works Co Ltd ジクロログリオキシムの製造方法
JP2003012628A (ja) * 2001-07-06 2003-01-15 Katayama Chem Works Co Ltd グリオキシムおよびジクロログリオキシムの製造方法
JP2014076985A (ja) * 2012-09-18 2014-05-01 Fuji Sangyo Co Ltd 安全性の改善された工業用殺菌剤組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
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 (ja) * 1993-07-27 1995-02-03 Jiyunsei Kagaku Kk ジクロログリオキシム有機溶剤溶液の製造法
JPH11236362A (ja) * 1998-02-23 1999-08-31 Katayama Chem Works Co Ltd ジクロログリオキシムの製造方法
JP2003012628A (ja) * 2001-07-06 2003-01-15 Katayama Chem Works Co Ltd グリオキシムおよびジクロログリオキシムの製造方法
JP2014076985A (ja) * 2012-09-18 2014-05-01 Fuji Sangyo Co Ltd 安全性の改善された工業用殺菌剤組成物

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JP6229244B1 (ja) 2017-11-15

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