• 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:
    1. Process for the production of 2-chloroacetoacetic esters, characterized in converting diketene at temperatures of from +10 to -40 degrees C in the presence of chlorinated aliphatic hydrocarbons as solvent by using hydrogen chloride into the acetoacetic chloride, forming the 2-chloroacetoacetic chloride by introducing of chlorine at temperature of from +10 to -40 degrees C, and converting the 2-chloroacetoacetic chloride by adding of alcohols having from 1 to 4 carbon atoms at temperatures of from +10 to -40 degrees C into the corresponding esters.
    公开号:SU988187A3
    申请号:SU813262355
    申请日:1981-03-30
    公开日:1983-01-07
    发明作者:Блюм Рене；Тенуд Леандер
    申请人:Лонца Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of alkyl C / j-C esters of 2-chloroacetoacetic acid, and may be used to obtain derivatives of cusyl acid, known as intermediates in the preparation of plant protection products and medicines such as cimetidine.
    A method of producing alkyl esters of 2-chloroacetoacetic acid is known by chlorinating the corresponding acetoacetic acid esters with sulfuryl chloride Cl.15
    Although chlorination with sulphuryl chloride gives a high conversion and yield (93-97%), it has the disadvantage that the -SO and HC1 gases released by the reaction of 2o react, it is necessary to separate the sulfur dioxide into a sulphuryl chloride as a separate operation.
    A disadvantage of the known method is also the necessity of preliminary preparation of the starting acetoacetic acid esters.
    The purpose of the invention is to simplify the process of obtaining the desired product.
    The goal is achieved by the fact that in the method of producing alkyl esters of 2-chloroacetoacetic acid, dicatene is reacted with hydrogen chloride in
     10, the chlorinated aliphatic hydrocarbon C -Ci2C is then treated by chlorine and esterifying the chloroacetoacetic acid chloride with the corresponding aliphatic alcohol by treating the resulting acetoacetic acid chloride with chlorine and esterification and the process is carried out at (+10) - (- Aos). As a rule, the chlorination stage is carried out in the presence of an acidic catalyst, and methylene chloride is used as the chlorinated aliphatic hydrocarbon.
    Chlorination is carried out in the presence of acidic catalysts, such as 398 Lewis acids, for example PCIj, FeCW, inorganic acids, for example sulfuric, perchloric, or strong organic carboxylic acids, for example acetic, trifluoroacetic, p-toluenesulfonic. These acids are used in catalytic amounts, preferably in amounts of 0-20 mol. in terms of dikeTen. Chlorinated aliphatic hydrocarbons, such as tetrachloro methane, ethyl chloride, dichloroethane, etc., are used as solvents. D., preferably methylene chloride. It is advisable to use 200-1000 g of solvent per mole of diketene. The molar ratio of hydrogen chloride and diketene in the first stage can vary within wide limits, it is advisable in the range of 1.1-10 mol, preferably 1.95-6.5 mol of hydrogen chloride, per 1 mol of diketene. , For chlorination with chlorine in the second stage, preferably 0.9 to 1.1 mol of chlorine per mole of acetoacetic acid chloride is used. In order to obtain the desired ester, the 2-chloroacetoacetic acid chloride at the third step of the process is reacted with a corresponding alcohol with a carbon number of 1 such as methanol, ethanol, propanol, butanol. The amount of alcohol added is usually stoichiometric. However, in some cases, alcohol is used in a slight excess, preferably in an amount of 0.1-0.3 mol. PRI me R 1. In a double-jacketed flask with a capacity of 500 ml equipped with a pneumatic stirrer, a thermometer, a pelvic inlet tube with a frit, a reflux condenser and a cryostat, 50.45 g (0.6 mol) of diketene are dissolved in 300 ml of methylene chloride. and cool until. After adding 0.11 mol. % sulfuric acid, in terms of diketene, and 3, g (1.2 mol) of hydrogen chloride in terms of diketene, and stirring for 3.5 hours, skip k2, S g (0.6 mol) of chlorine for 35 min and additionally stirred for 30 minutes Finally, dropping, maintaining the temperature -20 -, 27.6 g (0.6 mol) of absolute ethanol and stirred for 15 minutes. The solvent is then evaporated by means of a rotary evaporator. 98.7 g of 2-chloroacetoacetic acid ethyl ester are obtained (yield 83.% on the starting diketene). The table below shows the results of other experiments.
    Example7. In a double-55 flask with a capacity of 500 ml, equipped with a pneumatic stirrer, a thermometer, a gas tube with a frit, a reflux condenser and a cryostat, 50.5 g of Co 6 mol) diketene is dissolved in 300 ml of dichloroethane and cooled to -20 ° C. After adding 0.11 mol. % sulfuric acid (. in terms of diketene) and CH, g, 2 mol) of hydrogen chloride, in terms of diketene, and stirring for 3 h, 2.5 g (. 0.6 mol) of chlorine are passed in for 35 minutes and mix for an additional 30 minutes. Then, dropping maintaining the temperature -20 - -tO ° C 1912 g (, 0.6 mol) of methanol and stirred for 15 minutes. The solvent is then evaporated by means of a rotary evaporator. 97.8 g of methyl 2-chloroacetic acid ester are obtained {yield 91, i). Example B: A double-jacketed flask with a capacity of 500 ml equipped with a pneumatic stirrer, a thermometer, a gas-inlet tube with a frit, a reflux condenser, and a cryostat is dissolved in 50, g (0.6 mol) diketene in 300 ml of ethyl chloride and cooled to-20C. After adding 0, Pmol. % sulfuric acid, in terms of diketene, and, 8 g (1.2 mol) of hydrogen chloride, in terms of diketene, and stirring for 3.5 hours, pass «2.5 g (0.6 mol) of chlorine in 35 minutes and stir for an additional 30 minutes. Then, 59.2 g (0.8 mol) of butanol are added, maintaining the temperature at -20 - -10 ° C, and stirred for 15 minutes. Finally, the solvent is evaporated in a rotary evaporator. 115 g of 2-chloroacetoacetic acid butyl ester are obtained (yield 91.6). Example 9 In a double-jacketed flask with a capacity of 500 ml, equipped with a pneumatic stirrer, thermometer with a fritted gas tube, a reflux condenser, and a cryostat, 50, f g (0.6 mol) of diketene are dissolved in 300 ml of methylene chloride and cooled to 10 ° C. After adding 0.1 g of Nb50d (0.2 mol.) In terms of diketene, and one-hour treatment with 8 g of hydrogen chloride, after another 30 minutes, 4.0 g (0.62 mol) of chlorine are passed through and stirred for 30 minutes. Then, 27.6 g (0.6 mol) of absolute ethanol is added dropwise to the mixture and stirring is continued for 15 minutes. After that, the solvent is evaporated in a rotary evaporator. 2 g of chloroacetoacetic acid ethyl ester are obtained, which corresponds to the yield. Formula inventive 1. Method of producing alkyl esters of 2-chloroacetoacetic acid, characterized in that, in order to simplify the process, diketene is reacted with hydrogen chloride in a C-C 2 chlorinated aliphatic hydrocarbon followed by treatment of the acetic acid and acetic acid, hydrochloric acid C-C 2 followed by treatment of the acetic acid and acetic acid, hydrochloric acid C-C 2 followed by processing acetic acid acetic acid and acetic acid. chloroacetoacetic acid chloride with the corresponding aliphatic alcohol and the process is carried out at a temperature of (+10) - () ° C. 2. The method according to claim 1 is also characterized in that the chlorination step is carried out in the presence of an acid catalyst. 3. The method according to claim 1, of which is also the fact that methylene chloride is used as the chlorinated aliphatic hydrocarbon. Sources of information taken into account during the examination 1. Published for Germany No. 2709138, cl. C 07 C 69/72, 1978.
    权利要求:
    Claims (3)
    [1]
    Formula of Invention
    A method of producing 2-chloroacetoacetic acid alkyl esters, characterized in that, in order to simplify the process, diketene is reacted with hydrogen chloride in a chlorinated aliphatic hydrocarbon medium CC2, followed by treatment of the resulting acetoacetic acid chloride with chlorine and the esterification of the resulting chlorohydrochloride acid chloride hydrochloride hydrochloride hydrochloride C4 and the process are conducted at a temperature of (+ 10 ° C) - (- 40) ° C.
    [2]
    2. The method of pop. ^ characterized in that the chlorination stage is carried out in the presence of an acidic catalyst *.
    [3]
    3. The method according to p. ^ Characterized ’in that methylene chloride is used as a chlorinated aliphatic hydrocarbon.
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    同族专利:
    公开号 | 公开日
    CS217995B2|1983-02-25|
    PL230340A1|1981-11-27|
    EP0037015A3|1981-12-30|
    IN151753B|1983-07-23|
    DD157794A5|1982-12-08|
    AT3852T|1983-07-15|
    EP0037015B1|1983-06-22|
    MX152284A|1985-06-20|
    DE3160460D1|1983-07-28|
    PL134443B1|1985-08-31|
    EP0037015A2|1981-10-07|
    JPH0125735B2|1989-05-19|
    JPS56154438A|1981-11-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2209683A|1936-06-27|1940-07-30|Carbide & Carbon Chem Corp|Halogenation of diketene|
    CH492670A|1968-04-24|1970-06-30|Lonza Ag|Process for the preparation of γ-chloroacetoacetic acid ester|
    JPS5823373B2|1975-03-27|1983-05-14|Nippon Synthetic Chem Ind|IL65246A|1981-03-26|1985-11-29|Lonza Ag|Process for the preparation of 2-chloroacetoacetamides|
    JPS6025955A|1983-07-22|1985-02-08|Nippon Synthetic Chem Ind Co Ltd:The|Production of gamma-chloroacetoacetic acid ester|
    JP5960243B2|2011-04-01|2016-08-02|ロンザ リミテッドＬｏｎｚａ Ｌｉｍｉｔｅｄ|Production of 3,5-dioxohexanoic acid ester in two steps|
    KR20180084138A|2015-12-03|2018-07-24|바이엘 크롭사이언스 악티엔게젤샤프트|Methyl-1H-imidazo [1,2-a] pyridin-4-yl) -2- Oleate derivatives and related compounds|
    WO2018229202A1|2017-06-16|2018-12-20|Basf Se|Mesoionic imidazolium compounds and derivatives for combating animal pests|
    CN109503381A|2018-12-12|2019-03-22|安徽金禾实业股份有限公司|4- chloroacetyl acetacetic ester microchannel plate induction method and device|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH260680|1980-04-02|
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