• 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:
    A novel process for preparing alkyl esters which comprises reacting a homologous ester having one methylene group less in the alkyl group than the desired ester with carbon monoxide and hydrogen at high temperature and pressure in the presence of elemental cobalt, rhodium, ruthenium or iron, or a salt thereof as catalyst.
    公开号:SU791223A3
    申请号:SU782638051
    申请日:1978-07-14
    公开日:1980-12-23
    发明作者:Зауз Альфонс
    申请人:Имхаузен-Хеми Гмбх (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to organic synthesis, specifically, to a process for the preparation of alkyl esters of carboxylic acids, important industrial products.
    A method of producing carboxylic acid esters by reacting the corresponding acid with an alcohol is known.
    Methyl esters of carboxylic acids are more readily available because they are obtained by reacting carboxylic acids with methanol, which is obtained from synthesis gas 1.
    The production of higher esters according to this method is uneconomical due to the need to prepare higher alcohols.
    The purpose of the invention is to develop a new economical process for the preparation of carboxylic acid alkyl esters.
    The goal is achieved by the described method of producing alkyl esters of carboxylic acids of general formula I
    R ooSti aCM.ivn.
    R CH ,, or Ph,
    Where
    n 1-3,
    by treating alkyl ethers of carboxylic acids of general formula II
    RCOOCnM2m-f
    where R and p have the indicated values, with a mixture of carbon monoxide and hydrogen in a ratio of 1: 0.8-1.2 at a temperature of 180-250 ° C and a pressure of 200-1700 atm, in the presence of a catalyst, cobalt or ruthenium or iron salts, addition in the amount of 0.5-10% by weight relative to air.
    15
    The process is carried out in the presence of cocatalysis of a torus — triphenylphosphine or iodine or NaJ or N-methylpyrrolidine, taken in an amount of 2.5–9% by weight.
    20 relative to the air.
    The proposed method allows to obtain esters with high yield and selectivity.
    The process is carried out in steam or
    25 liquid phase at a temperature of 180-250 ° C. The most preferable, from an economic point of view, are the temperature, the temperature is not higher than 220 ° C and the pressure is 1200-1500 atm.
    The reaction time is not an essential parameter of the process and depends on the applied pressure and temperature. Usually n {the duration of the process does not exceed 20 hours. The increase in the duration of the process often leads to an increase in side processes and to a decrease in the yield of the target product.
    Example 1. In an autoclave equipped with a stirrer, methyl acetate and 5% by weight with respect to cobalt acetate tetrahydrate (11) and 2.5% by weight iodine are charged. After sealing the autoclave, a mixture of carbon monoxide - hydrogen in a molar ratio of 1: 0.8 to 1.2 is fed and the pressure is brought to 440 atm. The autoclave is heated to 180 ° C and then maintained at this temperature for 3 hours. The autoclave is cooled.
    Analysis by gas chromatography showed the following.
    When converting methyl ether. 71% by weight of such products as acetic acid ethyl ester - 78.5% by weight, acetic acid n-propyl ester - 6.7% by weight, isopropyl acetic acid ester - 0.5% by weight , methanol - 3.2 wt.%, ethanol - 8.0 wt.%, n-propanol 0, 4 wt.%, isopropanol - 0.2 wt.%, 3-methylbutanol - 10.5 wt. %, diethyl ether - 0.3 wt.%.
    Examples 2-6. The experiments were carried out 5 analogously to example 1, under the conditions described in table. 1. The results obtained herewith are also given in table. one.
    Table 1
    Example. In an autoclave equipped with a stirrer, 41.7 g of tert-butyl acetate and 1.26 g of tetrahydrate of cobalt acetate (I) are placed. After sealing the autoclave, a mixture of carbon monoxide - hydrogen in molar
    ratio of 1: 0.8 to 1.2 under pressure of 240 atm, heated to a temperature. The pressure rises to 370 atm. Depending on the time of the process, the results shown in Table 2 are obtained. 2
    The yield of the reaction product in wt.% On the unreacted ether
    Isobutane
    Isobutene
    Pee aal oh alde guide
    Rubs butanol
    3-methylbutanol
    Primary amyloacetate
    Neopentyl alcohol
    And 3 o amyl ats t at
    3 methylbutanol
    Example Experience . carried out as described in example 7, while
    equivalent amounts of ethyl acetate are used as starting material. As a result, a 100% conversion of the ester is achieved with the yield of 80 weight acetic acid propyl ester
    PRI me R 9. The experiment was carried out as described in example 7, with note as an initial product.
    T a fi l and c a 2
    4.9
    1.4
    3.9
    2.8
    4.1 2.3 0.7 0.2 0.1
    0.1 2.8 2.4 1.0
    0.1 O O 4.3 3.9 2D
    0.02 2.9 51.8
    21.5
    0.1
    0.08 0.3
    4.1
    4.6
    5.9 1.8
    2.1 1.0
    1.6
    1.6 6.2
    21.4
    59.3
    75.0
    77.7
    h 15.0 7.0
    14.0
    13.9
    acetic acid n-propyl ester is changed, as the final product is obtained from acetic acid n-butyl ester with the yield indicated in Example 8.
    Examples 11-16. The experiments were carried out as described in example 1 under the conditions indicated in Table. 3. Download 57.2 g of methyl acetate. The ratio of CO: H2 is 1: 0.8-1.2.
    The results are presented in table 4. (a) In all cases, the pressure is indicated in the cold state, i.e., the pressure before heating to the temperature (reaction temperature.
    b - Balance not determined.
    Note;
    权利要求:
    Claims (1)
    [1]
    1. Roberte Dis., Kaserio M .. Fundamentals of organic chemistry. M., Mir, 1968, vol. 1, p. 463..
    类似技术:
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    同族专利:
    公开号 | 公开日
    JPS5459212A|1979-05-12|
    GB2001070A|1979-01-24|
    IT7825640D0|1978-07-13|
    DE2731962A1|1979-02-01|
    BE868981A|1979-01-15|
    NL7807520A|1979-01-17|
    FR2397389A1|1979-02-09|
    IT1097227B|1985-08-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA1157038A|1979-11-15|1983-11-15|Erlind M. Thorsteinson|Manganese catalyzed carbonylation of aliphaticalcohols|
    FR2471965A1|1979-12-21|1981-06-26|Rhone Poulenc Ind|PROCESS FOR THE PREPARATION OF ALKYL CARBOXYLATES FROM THEIR LOWER COUNTERPARTS|
    JPS5925776B2|1980-06-09|1984-06-21|Mitsubishi Gas Chemical Co|
    JPS57114550A|1981-01-07|1982-07-16|Mitsubishi Chem Ind Ltd|Preparation of carboxylic acid ester|
    US4511741A|1983-12-02|1985-04-16|Union Carbide Corporation|Production of aldehydes from organic acid esters|
    JPH0641436B2|1986-12-22|1994-06-01|工業技術院長|Homologation of ester|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772731962|DE2731962A1|1977-07-15|1977-07-15|METHOD FOR MANUFACTURING CARBONIC ETHYLESTER|
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