• 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. A process of preparation of R.S. 5-p-hydroxyphenyl hydantoin, characterized by hot condensing in an acid medium R.S. p-hydroxymandelic acid on urea in excess.
    公开号:SU854272A3
    申请号:SU792790706
    申请日:1979-08-02
    公开日:1981-08-07
    发明作者:Кристидис Йани
    申请人:Сосьете Франсэз Хехст (Фирма)；
    IPC主号:
    专利说明:

    The invention is from (| osit to a novom method of producing racemic p-oxiphenyl-5-hydantoin. RS p-hydroxyphenyl-5-hydantoin is used to produce either RS amino-2-p-hydroxyphenylacetic acid, or after separation of R amino-2-n -oxiphenylacetic acid. RS p-hydroxyphenyl-5-hydantoin can be obtained by demethylation of RS p-methoxyphenyl-5-hydantoin with 48% hydrobromic acid at 100 ° C. Methods are known for producing RS aryl-5-hydantoins by cyclizing racemic CX / - amino acids Cll (either from aromatic aldehydes, for example p-hydroxybenz ldehyde by Bucherer 2 reaction or by the interaction of arylglyoxal with urea The disadvantage of all known methods is the inaccessibility of the starting materials. The purpose of the invention is to simplify the process. The goal is achieved by obtaining RS p-hydroxyphenyl-5-hydantoin by condensing an airless p- oximindal acid or e monohydrate with an excess of urea, pr 60-1180s, followed by reaction with an organic or inorganic acid at 90-118 C. For 1 mol of RS monohydrate of p-oximindal acid, usually 1-7 moles of urine are taken iny. The following acids can be used: hydrochloric, sulfuric, nitric, p-toluenesulfonic acid monohydrate, acetic acid, but this list is not restrictive. In general, the concentration of the aqueous acid solution is 5 n., But a lower concentration or even a concentrated mineral acid can be used. If the reaction is carried out in a solvent, in order to achieve a greater yield, it is desirable to remove the solvent before introducing the aqueous acid solution. Acetic or formic acid is usually used as a solvent. If the reaction is carried out in an acetic acid medium, it is advisable, but not necessary, to introduce an aqueous solution of a strong acid. Similarly, it is advisable at the end of the reaction to remove the acid either by distillation under vacuum, if volatile acid has been introduced, or by neutralization with aqueous
    alkali metal bicarbonate solution.
    Some acids form insoluble salts in the reaction medium, at the end of the reaction such salt should be filtered, then replaced with an aqueous solution of an alkali metal bicarbonate.
    Example 1. Heat for 4 hours at 18.6 g (0.1 mol) of RS monohydrate of p-hydroxyindic acid with 30 g (0.5 mol) of urea. Then, after cooling, SOO-cm 5 and hydrochloric acid are introduced into the reaction mixture and heating is continued with reflux for 3 hours. After cooling, 15 g (yield 78.1%) of RS p-hydroxyphenyl-5-hydantoin are obtained, t. square 26Rs
    Example 2. Heated for 5 hours at 90 ° C 18.6 g (0.1 mol) of RS monohydrate of p-hydroxyindic acid with 30 g (0.5 mol) of urea. Then, after cooling, 100 cm 5 of hydrochloric acid salt are introduced into the reaction mixture and the heating is continued with reflux for 17 f. Then, the resulting solution is evaporated to dryness in vacuo, and the crystalline residue is dissolved in 50 cm of water. Get 16 g (yield 83.3%) RS p-hydroxyphenyl-5-hydantoin, so pl. 261-262 ° C.
    Example 3. Heated for 150 minutes at 90 ° C 18.6 g (0.1 mol) of RS monohydrate of p-hydroxyindic acid with 30 g (0.5 mol) of urea. Then, after cooling, 100 cm 5N of sulfuric acid are introduced into the reaction mixture and continue heating with reflux for 1 hour. After cooling, 13.1 th (yield 68.2%) of p-hydroxyphenyl-5-hydantoin RS was separated.
    Example 4. According to the method described in example 3, but using 2.5 M phosphoric acid instead of 5 N. sulfuric acid, 8.2 g (yield 42.7%) of RS p-hydroxyphenyl-5-hydantoin are obtained.
    Example 5. The experiment was carried out according to the procedure described in example 3, but using 5 n nitric acid instead of 5 N. sulfuric acid. At the end of the reaction, the resulting suspension is filtered and the crystalline product is dissolved in a saturated aqueous solution of potassium bicarbonate. Thus, 13.5 g (yield: 70.3%) of RS p-hydroxyphenyl-5-hydantoin are recovered.
    Example 6: 18.6 g (0.1 mol) of p-oximindal acid RS monohydrate and 18 g (0.3 mol) urea in 125 cm of acetic acid being heated are heated for 5 hours at 60 ° C to 100 cm. 3.5 N hydrochloric acid and continue heating with reflux for 1 hour. After cooling, 12 g (yield 62.5%) of RS p-hydroxyphenyl-5-g dantoin are isolated.
    Example 7. According to the method described in example 3, but using 7.5 n. Instead of 5 N. of sulfuric acid. hydrochloric acid, 11.5 g (yield: 59.9%) of RS p-hydroxyphenyl-5-hydantoin are obtained.
    EXAMPLE 8 18.6 g (0.1 mol) of RS monohydrate of p-oximinedal acid and 30 g (0.5 mol) of urea in 125 cm of crystallizing acetic acid are heated for 5 hours at 70 ° C with stirring. The acetic acid is then removed by distillation in vacuo, and the residue is heated with reflux for 1 hour in 100 cm of 5N hydrochloric acid. Leave for 16 hours at ambient temperature and filter the resulting crystalline product. 14.5 g (yield 75.5%) of RS p-hydroxyphenyl-5-hydantoin are obtained.
    Example 9. A reflux of 37.2 g (0.2 mol) of RS monohydrate of p-oximindal acid and 24 g (0.4 mol) of urea in 250 cm of acetic acid being heated is heated for 4 hours. Then, 0.5 cm of concentrated hydrochloric acid (d 1.18) is introduced and the heating is continued with reflux for approximately 150 minutes. After cooling, 22 g (yield 57.42%) of RS p-hydroxyphenyl-5-hydantoin were isolated.
    Example 10. A reflux of 37.2 g (0.2 mol) of RS n-oxides of indal acid and 36.0 g (0.6 mol) of urea in 250 cm of Crystallizing acetic acid is heated for 2 hours. After cooling, 21.4 g (yield 55.7%) of RS p-hydroxyphenyl-5-hydantoin is obtained.
    EXAMPLE 11 A reflux of 18.6 g (0.1 mol) of RS monohydrate of p-oximindal acid and 18.0 g, 3 miles of urea in 125 cm of acetic acid being crystallized is heated for 2 hours during the first hour of reflux slowly. 3.06 g (0.3 mol) of acetic anhydride are added. After cooling, 10 g (yield 52%) of RS p-hydroxyphenyl-5-hydantoin are obtained.
    Example 12. Heat for 3 hours at 90 ° C 18, B g (0.1 mol) of RS monohydrate p-hydroxy-apnic acid and 12 g (0.2 mol) of urea in 70 cm 2.5 n, hydrochloric acid / 10 cm of concentrated hydrochloric acid (d 1.18) are then introduced and heating is continued for 2 hours at. After cooling, 3.5 g (yield 18.2%) of p-hydroxyphenyl-5-hydantoin RS are obtained,
    权利要求:
    Claims (3)
    [1]
    - Example 13. According to the procedure described in Example 3, but using 100 cm of acetic acid instead of sulfuric acid containing 2 g of p-toluenesulfonic acid monohydrate, 7.6 g (39.6% yield) of RS p-hydroxyphenyl are obtained after cooling. -5-hydantoin Formula of the invention. A method for producing racemic p-hydroxyphenyl-5-hydantoin, characterized in that, for the purpose of improving the process, anhydrous p-hydroxyindal acid or its monohydrate 2 rt is subjected to condensation with an excess of urea at 6 O-118 0 followed by interaction with organic or iorganic acid at 90-1180С. Sources of information taken into account in the examination 1.F. Urech, Onn 1872, 164, 268.
    [2]
    2.Chem.Ulestr. 1965, 62, p. 4105
    [3]
    3.J. umer. Chem. Soc 1942, 64, 1434.
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP0008547A1|1980-03-05|
    EP0008547B1|1982-11-10|
    JPS5522691A|1980-02-18|
    FR2432510B1|1981-01-30|
    DE2964015D1|1982-12-16|
    FR2432510A1|1980-02-29|
    ES483042A1|1980-05-16|
    AT1778T|1982-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE4301244A1|1993-01-19|1994-07-21|Chemie Linz Deutschland|Prepn. of 5-aryl hydantoin derivs.|JPS5522474B2|1977-03-18|1980-06-17|ES2018743A6|1989-11-29|1991-05-01|Etilo Derivados|Preparing 5-hydantoin|
    AU6612990A|1989-12-14|1991-07-18|Hoechst Celanese Corporation|Production of 5-hydantoin and d-p-hydroxyphenylglycine from 4-hydroxyacetophenone|
    JP2974742B2|1990-09-04|1999-11-10|鐘淵化学工業株式会社|Method for producing 5-arylhydantoins|
    AT398199B|1992-11-27|1994-10-25|Chemie Linz Gmbh|METHOD FOR PRODUCING ARYLHYDANTOINES|
    US7073815B2|2002-04-24|2006-07-11|Graco Children's Products Inc.|Stroller with drop-down basket|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7822989A|FR2432510B1|1978-08-03|1978-08-03|
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