• 专利附录
  • 专利说明
  • 权利要求
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  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    This invention relates to a process for preparing cinnamic acid by hydrolysis of 1,1,1,3-tetrachloro-3-phenylpropane with acetic acid, trifluoroacetic acid or formic acid, optionally in the presence sulphuric acid, phosphoric acid, para-toluenesulphonic acid, or a cation exchange resin containing sulphonic acid groups. The mixture is heated at a temperature from about 80 DEG to about 150 DEG C. until hydrogen chloride evolution ceases, after which time the cinnamic acid is separated.
    公开号:SU1348334A1
    申请号:SU857773897
    申请日:1985-07-03
    公开日:1987-10-30
    发明作者:Милан Гайек；Пржемысл Шилгавы
    申请人:Ческословенска Академия Вед (Инопредприятие)；
    IPC主号:
    专利说明:

    This invention relates to a process for producing cinnamic acid.
    The cinnamic acid (3-phenylphenol) is used as a corrosion inhibitor for zinc surfaces in descaling and for inhibiting the corrosion of spray containers, as a temperature stabilizer of polyvinyl chloride, a structuring catalyst for dimethyl terephthalate-ethylene glycol polymers and polyurethanes, as remedy against burning of caprolactam and t, e “Sodium salt of cinnamic acid is known as an anti-corrosion agent. Cinnamic acid is also a valuable intermediate for the preparation of drugs and, in the form of esters, it is used in the cosmetic industry as a component of fragrant compositions. The greatest use of cinnamic acid has been found as a starting matic transformation in Alanya, which, next to a new acid, is a component of a new synthetic sugar preparation.
    the enzyme raw material in L-phenyl-b is asparagi, one of.
    The most used method for the production of cinnamic acid is Perkin synthesis, i.e. condensation of benzaldehyde with acetic anhydride in the presence of lithium acetates and / or reaction of benzalchloride with alkaline acetates in the presence of amines (Kirk-Othmer5 Encyclopedia of Chemical Technology, T. Sj c, 517, I.Wiley, New York, 1964, Japanese patent No. 73 081 830, Chem Abstr 80, 108 194 1974. A high temperature is required for the reaction (180-185 ° C) and with a reaction time of 8-17 hours, the yield of cinnamic acid is 80-85%. New Japanese patents originate from styrene , alcohol; carbon monoxide and oxygen in the presence of platinum or palladium catalysts in the formation of cinnamic acid esters s, but with lower selectivity (Japanese Patent No. 57 070 836, 1980) Japanese Patent No. 56 071 039, 1979, Chem. Abstr. 95, 186 892, 1981,
    The proposed method for the production of cinnamic acid originates from easily attainable styrene and carbon tetrachloride, which, in a radical reaction, provide an appropriate adduct of 1.151 ,, 3-tetrachloro 3-phenylpropane (Chel, author's certificate
    about
    W 209347). By hydrolysis of this adduct in an acidic medium, peric acid is obtained. So far, the described hydrolytic reactions of the adduct have been distinguished by low selectivity and low reaction rate. For example, hydrolysis of 1,1,1,3-tetrachloro 3-phenyl-propane with concentrated perchloric acid provided cinnamic acid in an amount of only 35% yield. (I. Chem, Soc, 1887 (1963)), In another case, it reached 90% of the yield of cinnamic acid using a stoichiometric amount of ferric chloride in an acetic acid medium (Tetrahedron 20, 1649, 1964) .. According to Czech. copyright certificate No. 217518 is based on the knowledge that hydrolysis of 1,515 1,3-tetrachloro-3-phenylpropane can be carried out (catalytically carried out in the presence of Lewis acids, such as zinc or tin compounds, in an acetic acid medium that proceeds with high selectivity and reaction rate with high yields of cinnamic acid (min. 90%).
    The subject of the invention is a process for the production of cinnamic acid by acid hydrolysis of 1,1,1,3-tetrachloro-3-phenylpropane, in that a mixture of 1 part May.1,1,1,3-tetrachloro-3-phenylpropane and 0.1-5 to-. Lei May 80-100% acid such as acetic acid, trifluoroacetic acid or formic acid, and / or using acetic acid or formic acid in the presence of up to 1 share of May. 50-100% acid such as sulfuric, phosphoric, / chlorine or p-toluenesulfonic acid, or up to 10 fractions of May. The cation exchange resin containing the SO H -group is heated at 80-150 ° C, if necessary with the gradual addition of up to 10 shares of May. water until hydrogen chloride is released o I
    If trifluoroacetic acid is used to convert 1, 3-tetrachloro-3-phenylpropane to cinnamic acid
    0 or formic acid, in which case no further amount of strong acid should be used. When the reaction is carried out in formic acid, occurs in all cases of its
    g partial decomposition to carbon monoxide and water; the remaining substantial portion of carboxylic acid can be recovered by distillation and returned to the process. When applied
    five
    0
    five
    1.5
    It is advantageous for the scientific research institute of acetic acid to add water or an inorganic acid containing water or p-toluenesulfonic acid and acetic acid in order to more uniformly dissolve hydrogen chloride.
    The advantage of converting 1,1,1,3-β-tetrachloro-3-phenylpropane to cinnamic acid according to the invention is easy Q feasibility, economic benefits and high yield and purity of the obtained product.
    The following examples describe a method for producing cinnamic acid, without limiting or determining the extent of its action.
    EXAMPLE 1: A mixture of 129 g of 1,1,1,3-tetrachloro-3-phenylpropane, 7 D of glacial acetic acid, and 4.9 g of 98% sulfuric acid are brought to a boil with stirring. 122 ° C-while simultaneously adding 18 g of water for 15 hours, when hydrogen chloride ceases to be released. 54.9 g of cinnamic acid are separated out from the reaction mixture by cooling, which are separated by filtration, washed with water and 7.4 g of cinnamic acid are obtained by condensation of the filtrate in 84% overall yield. The melting point of recrystallized cinnamic acid from dilute acetic acid is 133-134 ° C, purity at least 99%.
    acetic acid and 31.8 g of p-toluenesulfonic acid monohydrate are brought to a boil with stirring
    Or
    at 115-120 ° C while adding 18 g of water for 13 hours at the same time. From the reaction mixture, the crystals separated due to cooling off are filtered off, washed with water to obtain 59 g of cinnamic acid. Concentration of the filtrate, filtration of the crystals and their washing with water gives the following 11 g of cinnamic acid with a total yield of 94., 5%, melting point after recrystallization 131-1ЗЗ С and purity min, 98%,
    PRI me R 5. A mixture of 129 g 1.1. - tetrachloro-3-phenylpropane, 74 g of glacial acetic acid and 39 g of Wolfatit OK 80 cation-exchange resin are brought to a boil under stirring at 118-124 ° C for 15 hours. In the middle of the hot reaction mixture, the cation-exchange resin is filtered. and cooling the reaction mixture, filtering the crystals and washing them with water gives 56.5 g of cinnamic acid. The following 9.5 g of cinnamic acid are obtained with a total yield of 89%, a melting point after recrystallization of 128-135 ° C, and a purity of min. 98%.
    PRI me R 6. A mixture of 25.8 g of 1,1,1,3-tetrachloro-3-phenylpropane and
    20
    thirty
    Example 2. A mixture of 129 g of 1.1, 1.3-22 g of 80% trifluoroacetic acid
    - tetrachloro-3-phenylpropane, 74 g of 98% acetic acid, and 7.9 g
    70% perchloric acid is brought under stirring to boiling at 114-188 ° C while adding 18 g of water for 9 hours. By treating the reaction mixture of example 1, you get 57.4 parts and 9 g of cinnamic acid with a total yield of 89, 6%, mp. 133-135 ° C and purity min. 99%.
    Froze A mixture of 129 g of 1,1,1,3-tetrachloro-3-phenylpropane, 74 g of 98% acetic acid and 25.6 g of 85% phosphoric acid is brought to a boil at 120-130 ° C while stirring. Adding 18 g of water over 12.5 hours. By treating the reaction mixture by the method of Example 1, you get fractions of 62 and 7.5 g of cinnamic acid in a yield of 93.8%; %
    PRI me R A. A mixture of 129 g of 1,1,1,3-tetrachloro-3-phenylpropane, 74 g of le-,
    five
    Q
    acetic acid and 31.8 g of p-toluenesulfonic acid monohydrate are brought to a boil with stirring,
    Or
    at 115-120 ° C while adding 18 g of water for 13 hours at the same time. From the reaction mixture, the crystals separated due to cooling off are filtered off, washed with water to obtain 59 g of cinnamic acid. Concentration of the filtrate, filtration of the crystals and their washing with water give the following 11 g of cinnamic acid with a total yield of 94., 5%, melting point after recrystallization 131-1ЗЗ С and purity min, 98%,
    PRI me R 5. A mixture of 129 g 1.1. - tetrachloro-3-phenylpropane, 74 g of glacial acetic acid and 39 g of Wolfatit OK 80 cation-exchange resin are brought to a boil under stirring at 118-124 ° C for 15 hours. In the middle of the hot reaction mixture, the cation-exchange resin is filtered. and cooling the reaction mixture, filtering the crystals and washing them with water gives 56.5 g of cinnamic acid. The following 9.5 g of cinnamic acid are obtained with a total yield of 89%, a melting point after recrystallization of 128-135 ° C, and a purity of min. 98%.
    PRI me R 6. A mixture of 25.8 g of 1,1,1,3-tetrachloro-3-phenylpropane and
    0
    0
     22 g of 80% trifluoroacetic acid
    0
    five
    0
    five
    while stirring, boil at 80-90 ° C for 2 hours. Dilute the reaction mixture with 1: 1 water, cool, filter the crystals after washing them with water, 15.2 g of cinnamic acid with a yield of 96%, mp. . 127 - 133,5 ° C and purity min. 97%.
    , Example 7: A mixture of 12.9 g of 1,1,1,3-tetrachloro-3-phenylpropane and 100 g of 85% formic acid is brought to a boil at 100- 106 ° C with stirring for 10 h. At the reaction. carbon monoxide is also released along with hydrogen chloride. By cooling the reaction mixture, filtering the crystals and washing them with water, 60 g of cinnamic acid are obtained with a yield of 81%, mp. 126-132 C and clean min. 97%.
    Example 8. A mixture of 103.2 g of 1,1,1,3-tetrachloro-3-phenylpropane, 114 g of 85% formic acid and
    513483346
    4.2 g of 93% sulfuric acid is made up. Example 11. A mixture of 77.4 g with stirring is boiling at 100-1,1,1,3-tetrachloro-3-phenylpropane,
    110 ° C for 6 hours with hydrogen chloride and carbon monoxide. The reaction mixture is cooled, the separated crystals are filtered off, washed with water and thus receive 51.5 g of cinnamic acid with a yield of 98%, so pl. 127-133 With and purity of min, 97%. I
    PRI me R 9. A mixture of 103.2 g of 1,1,1,3-tetrachloro-3-phenylpropaNa, 120 g of 85% formic acid and 17 g of cation-exchange resin OSTION KSC 1 is brought to boil. at 100-105 ° C for 7 h with simultaneous release of hydrogen chloride and carbon monoxide. The cation-exchange resin is separated from the reaction mixture by filtration, the mixture is cooled, the separated crystals are filtered, washed with water and such
    ten
    15
    20
    7.7g 98% acetic acid and
    1.8 g of 98% sulfuric acid under stirring until boiling at 1,138 ° C while adding a mixture of 15.5 ml of water ,. 4 ml of acetic acid and 0.5 ml of sulfuric acid per 2.5.4 when it ceases to release with hydrogen chloride. By treating the reaction mixture in the manner described in Example 1, 33.6 cinnamic acid is obtained with a yield of 75.6%, mp 132-133 ° C and a purity of min.99%
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing cinnamic acid by acid hydrolysis of 1,1,1,3-tetrachloro-3-phenylpropane is different in that the mixture is 1 fraction of May. 1,1,1,3-tetrachloro-3-fe of propane with 0.1 - 5 shares of May. 80-10
    46.8 g of cinnamic acid-25 acid such as acetic acid, trifluoroacetic acid or formic, and / or using acetic acid or formic acid in the presence of up to 1 part may be obtained. or up to 10 shares of May. cation exchange
    lots with a yield of 79%, so pl. 127- 133.5 ° С and purity min. 97%.
    thirty
    on or formic, and / or when using acetic or formic acid in the presence of up to 1 part may.50-100% of an acid like sulfuric, phosphoric, perchloric or p-toluenesulfonic acid, or up to 10 parts of May. cation exchange
    Example 10. A mixture of 51.6 g of 1,1,1,3-tetrachloro-3-phenylpropane, 60 g of glacial acetic acid and 17.8 g of 55% sulfuric acid with stirring is brought to a boil at 115-122 ° C for 5 hours when hydrogen chloride ceases to be released.
    The reaction mixture is treated with hydrogen, bom ,. given in example 1, and obtained from the acquisition of 22.5 and 2.9 g of cinnamic acid there, the examination carried out according to the total yield of 85.8%, that is, 131.5 The Czechoslovak resins containing the SO H group are heated at 80-150 ° C, with possible gradual addition to 10 beats in May. as long as chlorine133 C and purity min. 99%.
    40
    Coy Social Republic.
    Compiled by A. Evetigneev Editor N. Kishtulinets Tehred M. Khodanych Corrector G. Reshetnik
    Order 5163/24 Circulation 371Subscription
    VNIIPI USSR State Committee
    JTO cases of inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    7.7g 98% acetic acid and
    1.8 g of 98% sulfuric acid is brought to a boil with stirring at 130-138 ° C while adding a mixture of 15.5 ml of water. 4 ml of acetic acid and 0.5 ml of sulfuric acid for 2.5.4 when hydrogen chloride ceases to be released. By treating the reaction mixture in the manner described in Example 1, 33.6 g of cinnamic acid was obtained with a yield of 75.6%, mp 132-133 ° C and a purity of min.99%.
    Invention Formula
    The method of producing cinnamic acid by acid hydrolysis of 1,1,1,3-tetrachloro-3-phenylpropane, characterized in that the mixture is 1 fraction of May. 1,1,1,3-tetrachloro-3-phenylpropane with 0.1–5 shares of May. 80-100%
    acids like acetic acid, trifluoroacetic acid
    on or formic, and / or when using acetic or formic acid in the presence of up to 1 part may.50-100% of an acid like sulfuric, phosphoric, perchloric or p-toluenesulfonic acid, or up to 10 parts of May. cation exchange
    This hydrogen is recognized from the acquisition according to the results of the examination carried out by the Office for the invention of the Czechoslovak resins containing the SO H group, is heated at 80–150 ° C, with possible gradual addition to 10 fractions in May. as long as chlorine 40 is selected
    Coy Social Republic.
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    同族专利:
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    法律状态:
    优先权:
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