• 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:
    Olefins are oxidized to produce the corresponding epoxides by means of an aryl thallic carboxylate in the presence of an inert polar organic solvent and in the presence of water, the novel compound thallic benzoate being a preferred reactant.
    公开号:SU715022A3
    申请号:SU772473621
    申请日:1977-04-21
    公开日:1980-02-05
    发明作者:Ф.Брилл Уильям
    申请人:Халкон Интернэшнл Инк (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to an improved CTBOBaHHoiviy method for producing epoxides, which are valuable intermediates or monomers.
    A known method of producing epoxides by reacting olefins (iobutylene, propylene) with trivalent thallium acetate. The process is carried out in the presence of an organic solvent (tetrahydrofuran). water and acetic acid at a temperature of 70 ° C and a pressure of 1.8-2.0 atm.
    In the case of epoxidation of isobutylene, 82% of isobutylene oxide is obtained, 15% of 1-acetoxy-2-methylpropanol-2 (the rest is aldehyde), and epoxidation of propylene produces 72% of propylene oxide, 16% of acetone (the rest is 1-acetoxypropanol-2) 1 .
    The disadvantage of this method is the low selectivity of the process for the desired product.
    The aim of the invention is to increase the yield of the target product.
    The goal is achieved by the method of producing EPOXIDES by reacting Cj-Cg olefins or Cg-Cg cycloolefins with thallium compounds in organic solvent and water at elevated temperature and
    pressure, a distinctive feature of which is the use of a poly-arylallium carboxylate as a compound.
    Ethylene or propylene is preferably used as the olefin, and thallium benzoate is used as the arylallium carboxylate.
    The process is preferably carried out at a temperature of 20-60s and a pressure of 7-10 atm.
    Example 1. A 0.1 M solution of thallium acetate in a mixture of 90% by volume of tetrahydrofuran and 10% by volume of water is added to benzoic acid, which is in a glass tube for reaction to obtain a clear solution of a golden brown color. The molar ratio between benzoic acid and thallium acetate is 1: 0.1. The tube is equipped with a cap with a capillary tube that reaches half its length. Then the truschet is placed in a pressure vessel and, having removed the air, a pressure of 7.03 kg / cm is created in the vessel with ethylene. After the vessel has risen in an oil bath at 60 ° C for 30 minutes, it is cooled, the pressure is reduced and clean liquid is removed from the tube. The analysis of the obtained substance by the method of gaeochromatographics during the use of olonkk: It is time to pack that it contains ethylene oxide in the amount of; corresponding to a yield of 89% with respect to the Thallium carboxyllag that entered into the reaction. Yodimetric titration indicates that approximately 36% of three. Peccalli thallium (+ 3) is eligible for monovalent thallium (+1), the selectivity of acetaldehyde delivers 9%. P J) and meer. 2,. The process is carried out as in Example 1, but propylene is used instead of ethylene. At the end of the reaction period, which lasts 30 minutes, the product obtained is analyzed. Oxylene propylene receive koliches (T 36), corresponding to a yield of 60% relative to the thallium carboxylate. Pr: 1, Approximately 70% of the trivalent thallium is converted to single-thallium. Selectivity otnitel7g. Acetone 19%, Example 3, The process is carried out as in Example 2. The molar ratio between benzoic acid and tall QBEiiM ag. tetom is 0.5: 0.1, OKOJio 4.Q% trivalent thallium conversion. from monovalent to thallium Vycode of propylene oxide with respect to the reacted thallium carboxy. patch 42%, selectivity for more to another tune of 17%. Г (р imper 4. The process is produced in example 2. The molar ratio of pec-h2 between benzoic acid and M a.): Tl and e c and t a t cm O, 7 3; Oh, 2 5. B: .1. The solvent is used to give 70 vol. 5 totrahydrofurin, iO vol,% Baud m 10 vol. Oh, viccycHoa t-system, Around 80 and three-site, tal-pi turns into single-stranded thallium, superior oxo-propylene, relative to the reacted carboxylate, selective bone refers to spruce to acetone he Example 5 (for comparison), Process is carried out as in npi-mspe 3, but the benoneug-o acid is replaced with acetic acid. The analysis of the obtained product shows that 54% of three-talented thallium transforms into univalent thallium. Propylene oxide is obtained in an amount corresponding to a yield of 28% relative to the reacted thallium carboxylate, selectivity with respect to acetone is 17%. Example 6 (for comparison). The process is carried out as in Example 1, except that benzoic acid is replaced with acetic acid. Analysis of the product obtained shows that only 11% of trivalent thallium is converted to monovalent thallium. The yield of propylene oxide, with respect to reacting with the Shem of the tallic carboxylate, is only 7.2%, the selectivity for acetaldehyde is 0.1%. EXAMPLE 7: A 0.1 M solution of thallium acetate, in a mixture of 90% by volume of tetrahydrofuran and 10% by volume of water, is mixed with 4-nitrobenzoic acid, and the molar ratio between this acid and tallow-acetate is liO-l, as described in Example B 1. Then, a pressure of 7.03 kg / cm is created in the vessel for the reaction using ethylene. After reacting for 30 minutes at 60 ° C, the reaction mixture is cooled and analyzed in accordance with Example 1. About 30% of trivalent thallium is converted to monovalent thallium. The yield of ethylene oxide is 37% with respect to the hydro-reacted taliyevo.1y carboxylate, the selectivity of acetaldehyde is 7%. Example 8, The process is carried out as in Example 7, but instead of 4-nitrobenzoic acid, o-toluic acid is used; 23% of trivalent thallium is converted to monovalent thallium. The yield of ethylene oxide is 82% with respect to the reacted thallium carboxylate, selectivity with respect to acetaldehyde is 11%. Example 9. The process is carried out as 3 npKi.iepe 7, except that benzenesulfonic acid is used instead of 4-nitrobenzoic acid. 9G% of trivalent thallium is transformed into 3 monovalent thallium. The yield of ethylene oxide is negligible (up to 5%), and the selectivity with respect to acetallegide is 18.8%, Example 10. The process is carried out as in Example 7, but instead of 4-nitro-benzoic acid, thioacetic acid is used. . The analysis shows that TO, a single ion of trivalent thallium is not converted to a monovalent thallium ion and ethylene oxide is not formed. Example 11. The process is carried out as in npnivsepe 7, but 4-nitrobenoic acid is replaced with p-toluic acid. A product is obtained in which 29% of the trivalent thallium is converted to monovalent thallium. Ethylene oxide is obtained in an amount corresponding to a yield of 81% relative to the reacted thallium carboxylate, the selectivity for acetaldehyde is 14%. Example 12. The process is carried out as in Example 7, but instead of 4-nitrobenzoic acid, flavic acid is taken, 58% of the trivalent thallium is converted to monovalent thallium. Ethylene oxide is obtained with a yield of | 11.5% relative to the reacted thalliesm carboxylate, selenium
    The potency for acetaldepde is 15%.
    Example 13. The process is carried out similarly to Examples 1 and 7. A solution of thallium acetate in a mixture of 90% by volume of tetrahydrofuran and 10% by volume of water is mixed with benzoic acid and the molar ratio between benzoic acid and tallka BbiNi acetate is 1: 0.1. Then, a pressure of 7.03 kg / cm was created in the reaction vessel with cis-butene 2 and the reaction was carried out for 30 minutes at 60 ° C. The oxide yield was 11.9% relative to the thallium carboxylate placed in the reaction vessel (10.2% cis-butene-2 oxide and 1.7% trans-butene-2 oxide).
    Example. 14 (for comparison), the process is carried out as in example 3, but acetic acid is used instead of benzoic acid. Olefin oxide is not formed.
    Example 15. The process is carried out as in Example 13, but the reaction time is increased to 60 minutes. The oxide yield is 15.6% with respect to the ishonic thallium carboxylate (12% cis-butene-2 oxide and 3.6% trans-butene-2 oxide).
    Example 16 (partial comparison).
    The process is carried out as in Examples 13, 14 and 15, except that trans butene-2 is used instead of cis-butene-2. When using acetic acid, no olefin oxide is formed. When benzoic acid is consumed, 19.8% of oxide (14., 2% of trans-butene-2 oxide and 5.6% of cis-butene-2 oxide) are obtained in 30 minutes, and 24.4 % oxide {18.5% oxide trans-butene-2 and 5.9% oxide cis-butene-2).
    In the examples above, thallium carboxylate is prepared by adding aryl carboxylic acid to thallium acetate directly during the reaction. However, the thallium carboxylate can be obtained in advance {before the start of the reaction).
    The following is an example of the preparation of pure thallium benzoate.
    Syringe 17. 85.44 g of thallium nitrate is dissolved in 200 ml of methyl alcohol, and 70.44 g of benzoic acid are separately dissolved in 200 ml of methyl alcohol. Then, the benzoic acid solution is slowly added to the thallium nitrate solution with stirring. The solution becomes cloudy and becomes dark brown. After stirring for 15-20 minutes, the solution becomes clear and has a faint yellow tint. Next, dissolve the solution for 15-10 minutes and, with stirring, add to it
    400 ml of water, after which stirring is continued until crystals begin to form. When water is added, the solution becomes turbid, but after settling, the turbidity disappears. When crystals begin to form, stirring is stopped and the solution is allowed to stand until the crystal formation (about 3 h) is completely stopped. The crystals are then separated by vacuum filtration and 40 ml of water are added to the filtrate with stirring until crystals begin to form, which occurs almost immediately.
    5 after adding water. At the end of the crystallization, the solution is allowed to stand and the crystals are removed by vacuum filtration. In the first case, 31.2 g of crystals are obtained, and in the second, 57.8 g (82% of the total yield). The resulting crystals are placed in a vacuum desiccator. Their melting point is 198 -1-2 ° C. They are poorly soluble in benzene and methanol, and well soluble in acetone, methyl ethylene glycol
    ketone, tetrahydrofuran and not soluble in water and carbon tetrachloride,
    At measure 18. Hexen-1 in the form
    0 1 M solution in a mixture of 90% tetrahydrofurac and 10% water is heated at 60 ° C together with 0.2 M tallyevEvJ benoeats, hg-t-genngm according to example 17, and a 0.5 M solution of free benzoyl acid, Gychod is 40.5% /. ,, 2-epoxide and 5.7% 2-hexanone after 30 and 48% epoxide and 7% ketone - through YO min. The side products are not processed but with
    0When Measure 19. The process is carried out,
    as 3 of example 17, Cyclohexene enters 3 to the reaction with thallium-benoate 3 in the presence of benzoic acid (molar ratio between cyclo5 hexene, thallium benzoate and.
    benzoic acid 1: 0.2: 1); benzoic acid is present as a 1 M solution in a mixture of 90% dioxane and 10% water. The reaction is carried out in
    0 for 30 min at 20 ° С, and then for 30 min at 60 ° С. Analysis of the field gene shows that 48% of the trivalent thallium is converted to monovalent thallium. The yield of oxidation products is 90% in relation to the reacted thallium carboxylate. The reaction product consists of 31% cyclohexene oxide and 69% cyclopentene carboxaldehyde.
    0 Example 20. The process is carried out as B npHNsepe 19, but no free benzoic acid is added to the reaction mixture. 32% trivalent thallium is converted to monovalent thallium. Product yield 40%
    (including cyclohexene oxide about 35%).
    Example 21 (for comparison) The process is carried out as in Example 10, with the exception that only dioxane is used as the solvent. The reaction practically does not proceed.
    Example 22 (for partial comparison). The process is carried out as in Example 1. Ethylene is used as an olefin at a pressure of 14, Ob kg / cm. Reaction duration is 30 minutes at 60 ° C. The process is carried out using tetragyrofuran as a solvent in the presence and in the absence of water.
    with benzoic or acetic acid (molar ratio v between added acid and thallium benzoate about 1: 1). If benzoic acid is added to a mixture of solvents consisting of 90% tetrahydrofuran and 10% water, the yield of ethylene oxide is 25% In the absence of water, the yield of this oxide is 0.4%. When acetic acid is introduced into the system containing 90S tetrahydrofuran and 10% water instead of benzoic acid, the yield of ethylene oxide is 15%. If no water is added, only a small amount of ethylene oxide is obtained.
    Below are data on the selectivity of the process in all examples.
    权利要求:
    Claims (4)
    [1]
    Claim
    1, Method for producing epoxides <
    by the interaction of olefins Cg. - С th or cycloolefins С§- С § with thallium compounds in an environment of an organic solvent and water at elevated temperature and pressure, characterized in that, in order to increase the yield of the target product, aryl potassium carboxylate is used as a thallium compound.
    [2]
    2. The method of pop. 1, characterized in that as the olefin use ethylene or propylene.
    TSNIIIPI Order 9325/63 may be indicated.
    [3]
    3. The method of pop. 1, which is due to the fact that thallium benzoate is used as an aryllium carboxylate.
    [4]
    4. The method according to PP. 1-3, about l and chaga sh and th with the fact that the process is carried out at a temperature of 20-60 ° C, a pressure of 7-10 atm.
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    同族专利:
    公开号 | 公开日
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    NL7703506A|1977-10-25|
    DE2718057A1|1977-11-17|
    IT1086595B|1985-05-28|
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    ES458081A1|1978-03-16|
    ZA772432B|1978-11-29|
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    DE2718057C3|1980-02-07|
    BE853863A|1977-10-24|
    AU2434277A|1978-10-26|
    JPS52131505A|1977-11-04|
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    RO74965A|1982-09-09|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3024253A|1956-09-14|1962-03-06|Scient Design Co|Process for oxidizing styrene to styrene oxide|
    US3020293A|1959-04-24|1962-02-06|Hoechst Ag|Process for the manufacture of olefin oxidation products from olefin-mercury complexes|
    US3436409A|1964-12-30|1969-04-01|Union Carbide Corp|Epoxidation process|
    US3641067A|1969-11-03|1972-02-08|Hercules Inc|Epoxidation of olefins with thallic carboxylates|US4290959A|1977-06-16|1981-09-22|Halcon Research And Development Corp.|Preparation of propylene oxide|
    FR2394537A1|1977-06-16|1979-01-12|Halcon Res & Dev|Thallium salt catalysed propylene oxide prepn. - by reacting propylene with water in presence of alkanoic carboxylic acids|
    IL63433A|1980-08-06|1986-04-29|Univ Leland Stanford Junior|Method of asymmetrical epoxidation|
    US4356311A|1981-12-21|1982-10-26|Allied Corporation|Producing epoxide from olefin using metal nitro complexes|
    JPS58183924A|1982-04-19|1983-10-27|Taikisha Ltd|Dry type dehumidifying body|
    US4483994A|1983-02-22|1984-11-20|The Halcon Sd Group, Inc.|Process for the production of alkylene carbonates and oxides|
    US4483996A|1983-02-22|1984-11-20|The Halcon Sd Group, Inc.|Process for production of olefin oxides and ketones|
    JPS6291225A|1985-10-18|1987-04-25|Nippon Chem Ind Co Ltd:The|Air-purifying agent|
    法律状态:
    优先权:
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