• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD OF OBTAINING 0, L-DIMETHYL-S-
    公开号:SU1060117A3
    申请号:SU813261996
    申请日:1981-03-20
    公开日:1983-12-07
    发明作者:Руи Ноэль；Грос Жорж
    申请人:Рон-Пуленк Агрошими (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the chemistry of organophosphorus compounds, and specifically to a method for the preparation of 0,0-dimethyl 8- (1,2-dicarbethoxyethyl) di-tiophosphate (malathion), which is an effective neecotoxic insecticide, and is widely used in agriculture and forestry. and for hygiene purposes. A known method of producing malaTHOEia by the interaction of five-grained g6 phosphorus with methyl alcohol and diethyl ether of maleic acid in the presence of alkali or tertiary amine as a catalyst and as an inhibitor of the polymerization of hydroquinone Cl 3. The closest to the technical essence and the achieved result to the proposed method and obtaining 0,0-dimethyl-3- (1,2-dicarbethoxyethyl) dithiophosphate by the interaction of dimethyldithiophosphoric acid with ethyl maleate taken in. molar ratio, 15: 1, in an organic solvent medium, for example, di-a, benzene, or toluene at 70–107 ° C, followed by rapid distillation of the solvent and unreacted starting reagents at 121–182 ° C, pressure 1–30 mmHg. Art. and returning them to the cycle by treating the residue after the solvent and unreacted starting reagents is refined with an aqueous alkali solution, separating the target product by stripping from it light fractions in a thin-film evaporator with steam, 2, the disadvantage of this method is the use of a significant amount of solvent that reduces the productivity of the process, causes a limitation of the reaction rate | And reduces the degree of conversion of the-reactants. In addition, the return of unreacted ethyl maleate to the process increases the amount of ethyl fumarate (isomerization of ethyl maleate), which reacts slower than ethyl maleate and accumulates in the reaction mixture; its removal requires special operations. The purpose of the invention is to simplify the process. The purpose of the invention is achieved in that according to the method of producing O, p-dimethyl-S- (1, 2-dicarbethoxyethyl) dithium phosphate, which implies that dimethyldithiophosphoric acid is reacted with ethyl maleate at their molar ratio 1.05-2.0: 1.0 in the medium of an organic solvent, an "saturated hydrocarbon with a boiling point of 160-240 ° C, taken in an amount of 4.0-9.0% by weight, dimethyldithiophosphoric acid, with; -90 ° C. The solvent is distilled off and the unreacted reagents, the residue is treated with water The organic phase is separated, washed with water and the desired product is isolated by stripping light fractions from it in a thin-film evaporator with steam, the azeotropic mixture of dimethyldithiophosphoric acid and organic solvent resulting from the distillation of the solvent and uncorrected reagents is cooled. to 15-40 ° C; a phase containing mainly the solvent, which is recycled to the process, and a phase containing mainly dimethyldithiophosphoric acid, which is removed, are separated. Distinctive features of the described method are the use of a naked hydrocarbon with a boiling point of 160-240 ° C as an organic solvent, taking in an amount of 4.0-9.0 wt.% Of dimethyldithiophosphoric acid, and the distillation of the resulting. races of the solvent and unreacted reagents of the azeotropic mixture of dimethyldithiophosphoric acid with an organic solvent, cooling it to 15–40 ° С, separating the phase containing the main solvent, which is returned to the process, —I phase containing mainly dimethyldithiophosphoric acid, which removed. The method is carried out as follows. Ethyl maleate is reacted with an excess of dimethyl dithiophosphoric acid in the presence of a solvent capable of forming an azeotrope with dimethyldithiophosphoric acid. The azeotropic i mixture of dimethyldithiophosphoric acid and the solvent are distilled. The distillate obtained is cooled and decanted, the cooled and decanted distillate phase, containing mainly solvent, is returned to the process, the cooled and decanted distillate phase, containing mainly dimethyldithiophosphoric acid, is removed. Aliphatic hydrocarbons (decane, dodecane, tetradecane) or cycloaliphatic hydrocarbons, for example, decalin, Example 1, are used as an organic solvent. 8 1 liter reactor is charged with 240.8 g of crude dimethyldithiophosphoric acid containing Q% by weight dodecane, then 172 g of ethyl maleate is gradually added over 1 hour and 30 minutes.
    The resulting mixture was incubated for 4 hours at 90 ° C, then distilled under reduced pressure (approximately 5-10 mm Hg). The zeotropic dodecane + dimethyldithiophosphoric acid mixture is rendered in the form of steam, the distillate is cooled to 25 ° C, and it is divided into two layers. The upper layer containing mainly dodecane is reintroduced into the reactor.
    The residue after distilling off the solvent and unreacted starting reagents, containing halthion, is neutralized with an aqueous solution of sodium bicarbonate .-.
    Malathion is obtained with a yield of 98% relative to the ethyl maleate used. Malathion is purified by a single evaporation (in a film evaporator) with 50% by weight of water in the presence, then a second single evaporation (in a film evaporator) is carried out at 105 ° C and a pressure of 5.5 mm Hg. (residence time less than 1 min).
    Obtain 32.8 g of malathion 95% purity.
    Example 2. In a 1 liter reactor, 218.2 g of crude dimethyl dithiophosphoric acid containing 190 g of pure acid is loaded. (1.20 mol) and 8 g. dodecane, then 172 g of ethyl maleate (1 mol) is gradually added over 1 hour and 30 minutes.
    The mixture is incubated for 12 hours at 70 ° C. It is then distilled under reduced pressure (about 10 mm Hg). The azeotropic mixture, consisting of a solvent and dimethyldithiophosphoric acid, is distilled in the form of para-. The distillate is condensed, cooled to 15 ° C and pa: divided into two layers. The upper layer containing mainly solvent is returned to the reactor. ,,
    The residue containing malathion is neutralized using a sodium bicarbonate water solution. Crude Malathion is obtained in a yield of 94% relative to the ethyl maleate used. Malathion is purified by a single evaporation at 110 ° C in the presence of 50% by weight of water, and a second single evaporation is carried out at 105 ° C. and at an absolute reduced pressure of 6 mm Hg. (residence time less than 1 min.).
    Obtain 318 g of malathion 94% purity.
    PRI me R 3. In the reactor with a current of 1 l load. 250.8 g of crude dimethyldithiophosphoric acid containing 218 g of pure acid
    (1.38 mol) and 19.3 g of purified petroleum fraction-C C (m.p. 175-225 C)., Then 172 g of ethyl maleate (1 mol) is gradually added over 1 h 30 min. The reaction mixture was incubated for 4 hours at 90 ° C, and then distilled under reduced pressure of about 10 mm Hg.
    Azeotropic mixture (dissolved ± spruce +
    0 dimethyldithiophosphoric acid is distilled in the form of steam, the distillate is condensed, cooled to 35-40 ° C and separated into two layers, the upper layer, containing basic solvent, is returned to the reactor.
    The residue containing malathion is neutralized with an aqueous solution of sodium bicarbonate. Get raw Malathion with the release of 97.35%
    0 relative to the ethyl maleate used.
    Malathion is purified by a single evaporation in the presence of 50 wt.% Water; then carried out
    5 second single evaporation at 105 ° C and under reduced pressure b mm Hg. (residence time less than 1 min.).
    Obtain 326 g of malathion 95.7%
    0 cleanliness.
    Example 4. In a reactor with a capacity of 1 l load 228 g of crude dimethyldithiophosphoric acid containing 205.7 pure acid
    5 (1.30 mol) and 15 g of decalin, then 172 g of ethyl maleate is gradually added over 1 hour 30 minutes. The mixture was kept for 10 hours at 80 s. Distillation is carried out under reduced pressure of about 10 mm Hg.
    0
    The azeotropic mixture (solvent 4 dimethyldithiophosphoric acid) is distilled as a vapor; The distillate is condensed, cooled to 20 ° C and separated into two layers. Upper
    5 the layer containing mainly solvent is again returned to the reactor. The residue containing malathion is neutralized with an aqueous solution of sodium bicarbonate. Get raw
    0 malathion with a yield of 96.5% relative to the ethyl maleate used. Malathion is purified by a single evaporation at 110 ° C in the presence of 50 wt.% Water; then carry out the second
    5 single evaporation at and at a pressure of 6 mm Hg. (residence time less than 1 min.).
    Obtain 320 g of malathion36.2% purity.
    0
    P and measures 5. In the reactor with a capacity of 1 l load 240,8 g crude. dimethyldithiophosphoric acid containing 215.6 gcous acid 5 (1/35 mol) and 7 g of technical dodecane (hydrocarbons: linear and branched aliphatic, obtained by hydrogenation of prylene tetramer and condensation of hydrocarbons to), boiling point 160240 ° C, then gradually over 172 g of ethyl maleate (1 mol) are added in 1 hour 30 minutes. The mixture is held for 4 hours at. Then distillation is carried out under reduced pressure of about 10 mm Hg. The azeotropic mixture (solvent + dimethyldithiophosphoric acid) is distilled as steam. The distillate is condensed with, cooled to 20 ° C and separated into two layers, the upper layer containing mainly solvent is returned to the reactor. The residue containing malathion is neutralized with an aqueous solution of sodium bicarbonate. Crude Malathion is obtained with a yield of 98% relative to the ethyl acetate utilization. Malathion is purified by a single evaporation at 110 ° C in the presence of 50 wt.% Water, then a second single evaporation is carried out at a pressure of 6 mm Hg (residence time less than 2 minutes). 325.5 g of malathion are obtained 95.3% cleanliness. Thus, the proposed method allows to simplify the process i of obtaining 0,0-dimethyl-8- (1,2-dicarbethoxyethyl) dithiophosphate by using a much smaller amount of solvent in comparison with the known method and to obtain the target product with a high yield (94-98 %) and a high degree of purity (94-95%).
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 0,0-DIMETHYL-S- (1,2-DICARBETOXYETHYL) -DITHIOPHOSPHATE by reacting an excess of dimethyldithiophosphoric acid with ethyl maleate in an organic solvent medium at 70-90 ° C, followed by distillation of the solvent and unreacted starting reagents with alkaline treatment with an alkaline residue solution, separation of the organic phase, washing it with water and isolating the target product by distillation of light fractions from it in a thin-film evaporator with water vapor, characterized in that, in order to simplify the process, as an organic of solvent. use a saturated hydrocarbon with a boiling point of 160-240 ° C, taken in an amount of 4.0-9.0% by weight of dimethyldithiophosphoric acid, an azeotropic mixture resulting from the distillation of the solvent of unreacted reagents * distillate dimethyldithiophosphoric acid with an organic solvent, cool to 15 -40 ° C, separate the phase, containing mainly the solvent, which is returned to the process ^ and. a phase containing mainly dimethyldithiophosphoric acid, which is removed.
    SU 1060
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    同族专利:
    公开号 | 公开日
    EP0037349A1|1981-10-07|
    PL230260A1|1981-11-27|
    AU547037B2|1985-10-03|
    BR8101680A|1981-09-22|
    EP0037349B1|1983-02-09|
    DE3160055D1|1983-03-17|
    US4367180A|1983-01-04|
    ZA811794B|1982-03-31|
    CA1169432A|1984-06-19|
    IE51442B1|1986-12-24|
    NZ196554A|1983-06-17|
    FR2478644B1|1984-06-08|
    PT72713B|1982-11-15|
    RO81910B|1983-09-30|
    YU66181A|1983-12-31|
    PL126676B1|1983-08-31|
    ES500558A0|1982-01-01|
    DK126881A|1981-09-22|
    AU6847481A|1981-09-24|
    RO81910A|1983-10-15|
    IE810590L|1981-09-21|
    HU188284B|1986-03-28|
    DD157804A5|1982-12-08|
    ES8205415A1|1982-01-01|
    FR2478644A1|1981-09-25|
    PT72713A|1981-04-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR1427827A|1964-12-08|1966-02-11|Ministerul Ind Petrolului|Manufacturing process of o, o-dimethyl-s- dithiophosphate|
    FR1541883A|1966-11-01|1968-10-11|American Cyanamid Co|Improved process for preparing diethyl mercaptosuccinate o, o-dimethylphosphorodithioate|
    US3463841A|1966-11-01|1969-08-26|American Cyanamid Co|Malathion manufacture|US6524246B1|2000-10-13|2003-02-25|Sonocine, Inc.|Ultrasonic cellular tissue screening tool|
    US8158139B2|2004-07-12|2012-04-17|Taro Pharmaceuticals North America, Inc.|Topical gel formulation comprising organophosphate insecticide and preparation thereof|
    US8012498B2|2004-07-12|2011-09-06|Sandhya Goyal|Topical gel formulation comprising organophosphate insecticide and preparation thereof|
    WO2006017232A1|2004-07-12|2006-02-16|Taro Pharmaceuticals Industries Ltd.|Topical gel formulation comprising insecticide and its preparation thereof|
    US7560445B2|2005-07-06|2009-07-14|Taro Pharmaceuticals North America, Inc.|Process for preparing malathion for pharmaceutical use|
    EP2170078B1|2007-07-09|2014-03-26|Suven Life Sciences Limited|Process for the preparation of malathion and its intermediate|
    EP2360132B1|2010-01-20|2014-06-11|W.R. Grace & Co.-Conn.|High curing inducing surface applied setting retarder|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8007243A|FR2478644B1|1980-03-21|1980-03-21|
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