BE865898A - PROCESS FOR THE PREPARATION OF ACID (CHLOROBENZOYL-4) PHENOXY-4) METHYL-2 PROPIONIC-2 AND SOME OF ITS ESTERS - Google Patents

PROCESS FOR THE PREPARATION OF ACID (CHLOROBENZOYL-4) PHENOXY-4) METHYL-2 PROPIONIC-2 AND SOME OF ITS ESTERS

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Publication number
BE865898A
BE865898A BE2056864A BE2056864A BE865898A BE 865898 A BE865898 A BE 865898A BE 2056864 A BE2056864 A BE 2056864A BE 2056864 A BE2056864 A BE 2056864A BE 865898 A BE865898 A BE 865898A
Authority
BE
Belgium
Prior art keywords
methyl
phenoxy
emi
chlorobenzoyl
esters
Prior art date
Application number
BE2056864A
Other languages
French (fr)
Original Assignee
Sigurta S P A
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sigurta S P A filed Critical Sigurta S P A
Publication of BE865898A publication Critical patent/BE865898A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

       

  "Procédé pour la préparation de l'acide ((chlorobenzoyl-4) phénoxy-4) méthyl-2 propionique-2 et de quelques-uns de ses esters" La présente invention se rapporte à un procédé pour la préparation de l'acide ((chlorobenzoyl-4) phénoxy-4) méthyl-2 propionique-2 et de ses esters méthylique, éthylique et isopropylique par oxydation de l'acide "chlorobenzyl-4) phénoxy-4) méthyl-2 propionique-2 et par l'estérification successive par les alcools aliphatiques correspondants.

  
L'oxydation a lieu sur un groupe méthylénique qui se transforme en groupe carbonylique; toutefois, la réaction ne doit pas être trop outrée pour éviter que l'agent d'oxydation n'agisse ultérieurement sur le groupe carbonylique qui s'est formé en donnant origine, au lieu du benzophénone-dérivé, à des produits indésirés, tels que l'acide chlorobenzolque-4.

  
Les oxydants employés sont le permanganate de potassium, le bichromate de sodium et le persulfate d'ammonium. La réaction a lieu en milieu acide dans le cas du bichromate de sodium, en solution aqueuse avec le permanganate de potassium et en solution aqueuse en présence d'un catalyseur, tel que le nitrate d'argent, avec le persulfate d'ammonium.

  
Le tableau ci-après illustre la synthèse de l'acide

  
 <EMI ID=1.1> 

  
esters. 

  

 <EMI ID=2.1> 
 

  
En ce qui concerne le degré de réactivité des oxydants utilisés, on a observé l'échelle suivante:

  

 <EMI ID=3.1> 


  
avec des rendements de transformation de l'acide (1) en acide (2) de 50% avec le permanganate de potassium, de 35% avec la bichromate de sodium et de 10% avec le persulfate d'ammonium.

  
EXEMPLE 1

  
Acide ((chlorobenzoyl-4) phénoxy-4) méthyl-2 propionique-2

  
,en 5 g d'acide ((chlorobenzyl-4) phénoxy-4) méthyl-2 propionique-2 dans 100 ml d'eau on ajoute, par portions, 15 g

  
de permanganate de potassium en agitant vigoureusement: d'abord la réaction est faiblement exothermique. L'addition terminée, l'agitation est poursuivie pendant 24 heures. Le bioxyde de manganèse qui s'est séparé est éliminé par filtration et la solution aqueuse est acidifiée par l'acide chlorhydrique concentré, ce qui fait précipiter un produit blanc qui est filtré, séché, lavé au benzène chaud et de nouveau filtré. Par dessèchement du filtrat,on obtient un produit blanc qui, après recristallisation dans l'acide acétique, se fond à 181-183[deg.]. Rendement 2,6 g.

  
La matière de départ est préparée de la manière suivante: à 15 g de hydroxy-4 chloro-4' diphénylméthane dans 240 ml d'acétone anhydre on ajoute 48 g de sodium solide. Après la formation du sel de sodium,, on ajoute au milieu réactionnel un mélange de 60 ml d'acétone anhydre et 24 ml de chloroforme anhydre; lorsque la réaction exothermique est terminée, on chauffe à reflux pendant quelques heures. Après avoir chassé le solvant, <EMI ID=4.1> 

  
duit à la formation d'un; précipité constitué de l'acide 

  
 <EMI ID=5.1> 

  
 <EMI ID=6.1> 



  "Process for the preparation of ((chlorobenzoyl-4) phenoxy-4) 2-methyl-2-propionic acid and some of its esters" The present invention relates to a process for the preparation of ( (4-chlorobenzoyl) 4-phenoxy) 2-methyl-2-propionic and its methyl, ethyl and isopropyl esters by oxidation of "4-chlorobenzyl) phenoxy-4) 2-methyl propionic-2 and by esterification successively by the corresponding aliphatic alcohols.

  
Oxidation takes place on a methylene group which turns into a carbonyl group; however, the reaction should not be too extreme to prevent the oxidizing agent from subsequently acting on the carbonyl group which has formed giving origin, instead of the benzophenone-derivative, to unwanted products, such as 4-chlorobenzolque acid.

  
The oxidants used are potassium permanganate, sodium dichromate and ammonium persulfate. The reaction takes place in an acidic medium in the case of sodium dichromate, in aqueous solution with potassium permanganate and in aqueous solution in the presence of a catalyst, such as silver nitrate, with ammonium persulfate.

  
The table below illustrates the synthesis of the acid

  
 <EMI ID = 1.1>

  
esters.

  

 <EMI ID = 2.1>
 

  
Regarding the degree of reactivity of the oxidants used, the following scale was observed:

  

 <EMI ID = 3.1>


  
with conversion yields of acid (1) into acid (2) of 50% with potassium permanganate, 35% with sodium dichromate and 10% with ammonium persulfate.

  
EXAMPLE 1

  
((4-chlorobenzoyl) phenoxy-4) 2-methyl-2-propionic acid

  
, in 5 g of ((4-chlorobenzyl) phenoxy-4) 2-methyl-2-propionic acid in 100 ml of water, 15 g are added in portions.

  
of potassium permanganate with vigorous stirring: first the reaction is weakly exothermic. When the addition is complete, stirring is continued for 24 hours. The manganese dioxide which has separated is removed by filtration and the aqueous solution is acidified with concentrated hydrochloric acid, which precipitates a white product which is filtered, dried, washed with hot benzene and again filtered. By drying the filtrate, a white product is obtained which, after recrystallization from acetic acid, melts at 181-183 [deg.]. Yield 2.6 g.

  
The starting material is prepared as follows: to 15 g of 4-hydroxy-4-chloro-diphenylmethane in 240 ml of anhydrous acetone is added 48 g of solid sodium. After the formation of the sodium salt, a mixture of 60 ml of anhydrous acetone and 24 ml of anhydrous chloroform is added to the reaction medium; when the exothermic reaction is complete, the mixture is heated under reflux for a few hours. After removing the solvent, <EMI ID = 4.1>

  
leads to the formation of a; precipitate consisting of acid

  
 <EMI ID = 5.1>

  
 <EMI ID = 6.1>

Claims (1)

traitement par le cyclohexane, se fond à 78-80[deg.]. Rendement treatment with cyclohexane, melts at 78-80 [deg.]. Yield 12 g. 12 g. L'hydroxy-4 chloro-4' diphénylméthane est obtenu par la réaction du p-chlorobenzylchlorure avec le phénol en présence de chlorure de zinc comme catalyseur. 4-hydroxy-4-chloro-diphenylmethane is obtained by reacting p-chlorobenzylchloride with phenol in the presence of zinc chloride as a catalyst. EXEMPLE 2 EXAMPLE 2 Ester isopropylique de l'acide ((chlorobenzoyl-4) phénoxy-4) méthyl-2 propionique-2 ((4-chlorobenzoyl) phenoxy-4) 2-methyl-2-propionic acid isopropyl ester On ajoute 36 g d'acide ((chlorobenzoyl-4) phénoxy-4) méthyl-2 propionique-2 à un mélange de 40 ml d'alcool isopropylique et 7 ml d'acide sulfurique concentré. Le mélange est chauffé à reflux pendant 60 heures; l'excès d'alcool isopropylique est alors chassé, le résidu est traité par l'eau et est extrait au chloroforme. Les extraits sont lavés plusieurs fois 36 g of ((chlorobenzoyl-4) phenoxy-4) 2-methyl-2-propionic acid are added to a mixture of 40 ml of isopropyl alcohol and 7 ml of concentrated sulfuric acid. The mixture is heated at reflux for 60 hours; the excess isopropyl alcohol is then driven off, the residue is treated with water and is extracted with chloroform. The extracts are washed several times à la soude 10%, séchés par le sulfate de sodium anhydre, filtrés et évaporés. with 10% sodium hydroxide, dried with anhydrous sodium sulfate, filtered and evaporated. On a obtenu 35 g d'un produit blanc se fondant à 79-80[deg.]. 35 g of a white product was obtained, melting at 79-80 [deg.]. Le même procédé a été utilisé pour la préparation des esters méthylique, (point de fusion = 88-89[deg.]), et éthylique (point de fusion = 78-79[deg.]). The same process was used for the preparation of the methyl esters (melting point = 88-89 [deg.]), And ethyl esters. (melting point = 78-79 [deg.]). REVENDICATIONS 1.- Procédé pour la préparation de l'acide ((chlorobenzoyl-4)phénoxy-4) méthyl-2 propionique-2 par oxydation de l'acide ((chlorobenzyl-4) phénoxy-4) méthyl-2 propionique par des agents d'oxydation tels que le permanganate de potassium, le dichromate de sodium ou le persulfate d'ammonium, tel que décrit <EMI ID=7.1> 1.- Process for the preparation of ((chlorobenzoyl-4) phenoxy-4) 2-methyl propionic-2 by oxidation of ((4-chlorobenzyl) phenoxy-4) 2-methyl propionic acid with agents oxidation agents such as potassium permanganate, sodium dichromate or ammonium persulfate, as described <EMI ID = 7.1> <EMI ID=8.1> <EMI ID = 8.1> <EMI ID=9.1> <EMI ID = 9.1> <EMI ID=10.1> <EMI ID = 10.1> benzoyl-4) phénoxy-4) mêthyl-2-propionique-2 et de quelques-uns de ses esters, substantiellement tel que décrit précédemment. <EMI ID=11.1> benzoyl-4) phenoxy-4) methyl-2-propionique-2 and some of its esters, substantially as described above. <EMI ID = 11.1>
BE2056864A 1978-02-10 1978-04-12 PROCESS FOR THE PREPARATION OF ACID (CHLOROBENZOYL-4) PHENOXY-4) METHYL-2 PROPIONIC-2 AND SOME OF ITS ESTERS BE865898A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT6726378A IT1203166B (en) 1978-02-10 1978-02-10 Chlorobenzoyl-phenoxymethyl-propionic acid and its ester(s) - obtd. by oxidising chlorobenzyl-phenoxymethyl-propionic acid using e.g. potassium permanganate and esterifying

Publications (1)

Publication Number Publication Date
BE865898A true BE865898A (en) 1978-07-31

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Country Status (2)

Country Link
BE (1) BE865898A (en)
IT (1) IT1203166B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104276950A (en) * 2014-09-19 2015-01-14 徐州工业职业技术学院 Method for preparing fenofibrate by virtue of intelligent temperature control and remote monitoring

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104276950A (en) * 2014-09-19 2015-01-14 徐州工业职业技术学院 Method for preparing fenofibrate by virtue of intelligent temperature control and remote monitoring
CN104276950B (en) * 2014-09-19 2016-04-20 徐州工业职业技术学院 A kind of intelligent temperature control, remote monitoring prepare the method for fenofibrate

Also Published As

Publication number Publication date
IT7867263A0 (en) 1978-02-10
IT1203166B (en) 1989-02-15

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