• 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:
    Aromatic compounds of the general formula <IMAGE> in which R and Ro represents a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms are hydroxylated by reaction with hydrogen peroxide in the presence of a catalytic amount of a strong acid and the reaction is carried out in the presence of an activator which is a juxtanuclear aromatic aldehyde or derivative thereof selected from an acetal or a benzhydrol.
    公开号:SU784757A3
    申请号:SU762432954
    申请日:1976-12-24
    公开日:1980-11-30
    发明作者:Костантини Мишель；Дромар Андриан；Жуффре Мишель；Нантерме Ролан
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING HYDROCHINON AND PYROCATECHINE
    The invention relates to the field of hydroxylation of aromatic compounds, in particular, to an improved method for producing hydroquinone and catechol by hydroxylation of phenol with hydrogen peroxide. A known method for producing hydruquinone and pyrocatechol is by hydroxylation of phenol with hydrogen peroxide in the presence of an acid catalyst, for example, trifluoroacetic acid, acids with a pH of 0.7-3 and organic moncarboxylic acids. The yield of the target products is 80-95% in terms of C. The disadvantage of this method is the use of significant amounts of carboxylic acids, which must be recycled with unconverted phenol (the conversion of phenol is less than 10%), which reduces productivity. The closest to the proposed method to the technical essence and the achieved result is the method of producing pyrocatechol and hydroquinone by hydroxylation of phenol with hydrogen peroxide in the presence of catalytic amounts of strong acid with pKI. O is not more than 0.1 and the complexing agent with the initial water content in the reaction mass more than 20% 2. The disadvantage of this method is the considerable duration of the process. The purpose of the invention is to reduce the duration of the process. The goal is achieved by the fact that upon receipt of hydroquinone and pyrocatechol by hydroxylation of phenol with hydrogen peroxide in the presence of a strong acid catalyst and an agent forming a complex with transition metals, the process is proposed to be carried out in the presence of an aromatic aldehyde activator of the general formula where RJ is hydroxyl, alkoxyl, alkyl CfC i / halogen, —CH — CH — CH — CH— group, n —L — CH — CH — CH CH- group substituted with hydroxyl, halo, alkyl or alkoxy
    alkyortophosphates, mono- or dialkyl aryl orthophosphates, ethyl or diethyl phosphate, hexyl phosphate, cyclohexyl phosphate, benzyl phosphate.
    The amount of complexing agent depends on the content of metal ions in the reaction medium. The most appropriate amount is 0.0001-5% by weight of the medium.
    The temperature at which the method can be carried out is in the range of 20-150 C.
    The reaction can be carried out in the presence of solvents that are stable with respect to hydrogen peroxide, such as aliphatic and cycloaliphatic hydrocarbons or their halogen derivatives (chloroform, dichloroethane), nitrated aromatic hydrocarbons like nitrobenzene or nitrotoluene, especially when the temperature is below the melting point of the aromatic compound.
    The method can be carried out by continuous or periodic technology.
    At the end of the reaction, the unconverted aromatic compound and the activator are separated from the hydroxylation products by conventional methods, in particular by distillation, and reintroduced into the reaction zone.
    Example 1. In a three-neck flask with a capacity of 250 cm, equipped with a thermometer, a stirrer, a reflux condenser, a heating system and the introduction of nitrogen, after purging with nitrogen, load, g:
    Molten phenol containing 1100 hours per 1 million waters96
    85% phosphoric acid 0, 791 Benzaldegy; (0.985 70% perchloric acid 1.008 Maintain the contents of the flask at 45 ° C, then add 2.028 g (84.7% by weight) of hydrogen peroxide. Observe the disappearance of active oxygen by iodometric determination of samples kept at a temperature of a mixture of acetone and dry ice. After a minute, 50% of the active oxygen is converted under these conditions. The reaction ends in 44 minutes. The reaction mixture is neutralized with a 0.5N solution of potassium hydroxide in methanol, then it is diluted by adding volume of meth anola. The reaction products are determined by gas-liquid chromatography. The following yield is obtained, g:
    Hydroquinone2,57
    Pyrocatechin .1.98 The yields of hydroquinone and pyrocatechin are increased to 46.4 and 35.6%, respectively, relative to the hydrogen peroxide used. Ratio
    between the resulting hydroquinone and pyrocatechin is 1.3.
    As a comparison, the previous experiment is repeated, but it is carried out without benzal1: | degida. Under these conditions, it takes 19 minutes for the 50% active oxygen to disappear and 3 hours and 12 minutes for its complete conversion. The yield of hydroquinone and pyrocatechin in relation to the used hydrogen peroxide, respectively, but are 33.7 and 52.3%. The ratio
    o hydroquinone-pyrocatechin is 0.64.
    Comparing this experience with the previous one, it is possible to establish the influence of benzaldehyde on the reaction rate and on the distribution of the products formed.
    S
    Examples 2-9. The procedure described in Example 1 is carried out, various experiments are carried out, the nature of the activators is changed, the reaction conditions are as follows:
    0
    Temperature, C
    45
    Phenol containing
    In quantity
    1100 h for -1 ppm, sufficient for
    water per 1 mole of the introduction
    85% H-PO 0.5 wt.% Acid into the reaction medium
    84.7% 2.07
    .g
    (0.051 mol) 71% HCO, G 0.0975
    (0.00065 mol)
    0 Activator mol 0,011
    Molar
    The ratio of reagents is as follows:
    Phenol / LD Od
    20) Ndr-g.
    0,0127
    five
    Activator / H, fp2 0,22
    For practical reasons, and in order to show the comparative nature of various experiments, the determination of active oxygen is carried out iodometrically before the decomposition of 50% of active oxygen. This time is further referred to as half reaction time and is denoted as. in tab. 1. The effect of the tested activators is shown as the time taken to disappear
    5 50% hydrogen peroxide. However, the yield of diphenol relative to that used 2 is determined as in example 1 at the end of the reaction. The results are shown in Table. one.
    0
    Table 1
    55
    60
    权利要求:
    Claims (2)
    [1]
    1.Patent of France No. 2146195,
    0 Cl. C 07 C 37/00, published 1973.
    [2]
    2. The patent of France 2071464, cl, C 07 C 37/00, published. 1971.
    类似技术:
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    同族专利:
    公开号 | 公开日
    RO70266A|1982-10-11|
    JPS5647891B2|1981-11-12|
    FR2336364B1|1979-07-06|
    CA1069538A|1980-01-08|
    ATA958676A|1978-01-15|
    NL177746C|1985-11-18|
    PL105048B1|1979-09-29|
    NL177746B|1985-06-17|
    LU76462A1|1978-01-18|
    DE2658545A1|1977-07-07|
    CH617416A5|1980-05-30|
    BE849860A|1977-06-24|
    CS194681B2|1979-12-31|
    BR7608678A|1978-01-03|
    GB1521400A|1978-08-16|
    DD127489A5|1977-09-28|
    NL7614357A|1977-06-28|
    US4208536A|1980-06-17|
    SE435053B|1984-09-03|
    AT345269B|1978-09-11|
    DE2658545B2|1980-08-28|
    JPS5289625A|1977-07-27|
    FR2336364A1|1977-07-22|
    SE7614536L|1977-06-25|
    DE2658545C3|1981-05-07|
    IT1065507B|1985-02-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2439812A|1944-11-30|1948-04-20|Socony Vacuum Oil Co Inc|Method for making phenol|
    US3850995A|1969-09-22|1974-11-26|Celanese Corp|Conversion of aromatic aldehydes to phenolic compounds|
    FR2071464A5|1969-12-30|1971-09-17|Rhone Poulenc Sa|
    DE2150657C3|1971-07-17|1978-10-26|Brichima S.P.A., Mailand |Process for the preparation of a mixture of catechol and hydroquinone|
    DE2138735A1|1971-08-03|1973-03-01|Haarmann & Reimer Gmbh|PROCESS FOR THE MANUFACTURING OF POLYHYDROXYBENZENE|
    BE791582A|1971-11-19|1973-05-17|Rhone Poulenc Sa|PROCESS FOR THE PREPARATION OF PHENOLS BY OXIDATION OF AROMATIC ALDEHYDES|
    IT964049B|1972-08-18|1974-01-21|Brichima Spa|PROCESS FOR THE PREPARATION OF DIPHENOLS|
    US3839467A|1972-08-31|1974-10-01|Universal Oil Prod Co|Preparation of hydroxylated aromatic compounds|
    JPS4930330A|1973-03-23|1974-03-18|
    DE2410742C3|1974-03-06|1981-01-08|Bayer Ag, 5090 Leverkusen|Process for the production of catechol and hydroquinone by nuclear hydroxylation of phenol|
    GB1448358A|1974-04-04|1976-09-08|Ube Industries|Process for preparint dihydric phenol derivatives|DE2928743A1|1979-07-17|1981-02-05|Bayer Ag|METHOD FOR PRODUCING MULTIPLE PHENOLES|
    DE2942366A1|1979-10-19|1981-04-30|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING MULTIPLE PHENOLES|
    US4588845A|1983-07-18|1986-05-13|Fmc Corporation|Oxidation of unsaturated organic compounds with hydrogen peroxide|
    DE3643206C1|1986-12-18|1988-03-24|Degussa|Process for the preparation of substituted dihydroxybenzenes|
    FR2649695A1|1989-07-11|1991-01-18|Rhone Poulenc Chimie|PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS|
    FR2655332A1|1989-12-05|1991-06-07|Rhone Poulenc Chimie|PROCESS FOR HYDROXYLATION OF PHENOLS AND ETHERS OF PHENOLS|
    FR2700332B1|1993-01-08|1995-03-10|Rhone Poulenc Chimie|Process for the hydroxylation of phenolic compounds.|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7540382A|FR2336364B1|1975-12-24|1975-12-24|
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