BE890221A - NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE - Google Patents

NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE Download PDF

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Publication number
BE890221A
BE890221A BE2/59338A BE2059338A BE890221A BE 890221 A BE890221 A BE 890221A BE 2/59338 A BE2/59338 A BE 2/59338A BE 2059338 A BE2059338 A BE 2059338A BE 890221 A BE890221 A BE 890221A
Authority
BE
Belgium
Prior art keywords
emi
acid
methoxy
methyl
naphthaleneacetique
Prior art date
Application number
BE2/59338A
Other languages
French (fr)
Original Assignee
Bago Sa Labor
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 Bago Sa Labor filed Critical Bago Sa Labor
Priority to BE2/59338A priority Critical patent/BE890221A/en
Publication of BE890221A publication Critical patent/BE890221A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

       

   <EMI ID=1.1>   <EMI ID=2.1> 

  
 <EMI ID=3.1> 

  
traitement de l'inflammation., de la fièvre et de la douleur chez

  
 <EMI ID=4.1> 

  
quement de composés qui présentent la formule générale suivante (I)

  

 <EMI ID=5.1> 


  
 <EMI ID=6.1> 

  
ment la partie bivalente de la formule (II)

  

 <EMI ID=7.1> 


  
Les composés suivants sont représentatifs de la formule (I) : <EMI ID=8.1>  naphtalène-acétate.
- pivaloxyloxyméthyl (+) 6-méthoxy-a-méthyl-2-naphtalèneacetate. L'utilisation de l'acide (+) 6-méthoxy-a-méthyl-2-naphtalène- <EMI ID=9.1> 

  
analgésique de certains états pathologiques, est bien connu (Brogden R.N., Heel, R.C., Speight, T.M. et Avery,.G.S. Drugs, 18, 24L;

  
 <EMI ID=10.1> 

  
des, ce produit acide peut provoquer de l'irritation de la muqueuse gastrique lorsqu'il est administré par la bouche. Le comportement acide de la molécule est déterminé par groupe carboxylique et se manifeste par des troubles gastriques et dans certains cas par des hémorragies graves (Uthgermant H., Proceedings of 8th European  <EMI ID=11.1> 

  
Les composes de la formule (I) présentés ici ne manifestent pas seulement une efficacité pharmacologique en tant qu'agents anti-inflammatoires et analgésiques, mais ils ont encore l'avantage de ne pas avoir d'activité ulcérogénique.

  
Avant la présente invention, plusieurs chercheurs ont fait

  
 <EMI ID=12.1> 

  
naphtalène. Parmi eux, on trouve : sel de pipérazine (Brevet

  
 <EMI ID=13.1> 

  
japonais n[deg.] 54-079.258; 1979), ester de pyridoxine (brevet belge

  
 <EMI ID=14.1> 

  
n[deg.] 2.726.561; 1977).

  
Les esters de la présente invention - en particulier l'ester

  
 <EMI ID=15.1> 

  
analgésique, anti-inflammatoire et antipyrétique que l'acide dont ils sont dérivés. Ils ne présentent pas d'action irritante sur la muqueuse gastrique.

  
Les composés de la formule générale (I) de la présente invention sont préparés par réaction de l'acide (+) 6-méthoxy-a-méthyl2-naphtalèneacétique de la formule (III), salifié au préalable

  
et du composé de la formule (IV) .

  
Le schéma de synthèse est illustré par la formule :

  

 <EMI ID=16.1> 


  
dans laquelle R- et R2 sont définis comme plus haut, A peut être un atome d'hydrogène ou une base et B peut être hydroxyle ou halogène. 

  
La salification peut être effectuée à l'aide d'une base or-

  
 <EMI ID=17.1> 

  
 <EMI ID=18.1> 

  
 <EMI ID=19.1> 

  
laires. La base organique utilisée de préférence est la triêthy lamine. La raison de masse des éléments de la réaction pourra être de 1,3-2 masses de base pour chaque masse d'acide, et la réaction s'effectuera de préférence dans des solvants polaires tels que

  
 <EMI ID=20.1> 

  
Après salification de l'acide, le sel produit est mis en réac-

  
 <EMI ID=21.1> 

  
du composé- (IV) pour chaque .,masse de l'acide de formule (III) pour

  
 <EMI ID=22.1> 

  
comme composé (IV) 3-bromophtalide. 3-Bromophthalide est un compost

  
 <EMI ID=23.1> 

  
 <EMI ID=24.1> 

  
laires de paraformaldéhyde et de chlorure de pivaloyl en présence d'un catalyseur tel que le chlorure de zinc (Ulich L.H., Adams,

  
 <EMI ID=25.1>  acétiques est effectuée avantageusement dans un milieu comprenant un solvant ou un mélange de solvants dans lequel les matières mises en réaction et le composé produit sont parfaitement solubles. De plus, étant donné que la présence d'eau hydrolise 3-bromophta-

  
 <EMI ID=26.1> 

  
 <EMI ID=27.1> 

  
tion est parfaitement anhydre.

  
 <EMI ID=28.1> 

  
réaction qui les produisent se fait par extraction, après addition

  
 <EMI ID=29.1> 

  
tates d'éthyl, de.propyl de butyl, dichlorométhane et similaires.

  
Les exemples ci-dessous sont donnés comme illustration de l'invention 

  
Exemple 

  
 <EMI ID=30.1> 

  
dition, le mélange a subi un reflux pendant deux heures puis a été refroidi à la température ambiante. Toujours sous agitation,

  
 <EMI ID=31.1> 

  
 <EMI ID=32.1> 

  
 <EMI ID=33.1> 

  
enlevée. Pour la phase organique suivante, on a ajoute du sulfate de magnésium anhydre. Le sulfate de magnésium a été séparé par filtration et le filtrat concentré jusqu'à dessication. Rendement

  
 <EMI ID=34.1>   <EMI ID=35.1> 

  
obtenue : C, 72,95; H, 5,07.

Exemple II 

  
 <EMI ID=36.1> 

  
 <EMI ID=37.1> 

  
de pivaloyloxyméthyl , le mélange formant la réaction a été soumis au reflux durant 210 minutes.. La solution a ensuite été rafraîchie à la température ambiante puis versée dans de l'eau distillée (1500 ml) refroidie au préalable et le tout a reposé 30 minutes. Le mélange de réaction a alors été extrait à l'aide de

  
 <EMI ID=38.1> 

  
ajouté l'éther. L'autre solution a pu reposer et le composé cristallisé qui en a résulté a été filtre et desséché sous vide. Ren-

  
 <EMI ID=39.1> 



   <EMI ID = 1.1> <EMI ID = 2.1>

  
 <EMI ID = 3.1>

  
treatment of inflammation, fever and pain in

  
 <EMI ID = 4.1>

  
only of compounds which have the following general formula (I)

  

 <EMI ID = 5.1>


  
 <EMI ID = 6.1>

  
ment the bivalent part of formula (II)

  

 <EMI ID = 7.1>


  
The following compounds are representative of formula (I): <EMI ID = 8.1> naphthalene-acetate.
- pivaloxyloxymethyl (+) 6-methoxy-a-methyl-2-naphthaleneeacetate. The use of (+) 6-methoxy-a-methyl-2-naphthalene- acid <EMI ID = 9.1>

  
analgesic of certain medical conditions is well known (Brogden R.N., Heel, R.C., Speight, T.M. and Avery, .G.S. Drugs, 18, 24L;

  
 <EMI ID = 10.1>

  
This acidic product may cause irritation of the gastric mucosa when administered by mouth. The acid behavior of the molecule is determined by carboxylic group and is manifested by gastric disorders and in some cases by severe hemorrhages (Uthgermant H., Proceedings of 8th European <EMI ID = 11.1>

  
The compounds of formula (I) presented here do not only demonstrate pharmacological efficacy as anti-inflammatory and analgesic agents, but they also have the advantage of not having ulcerogenic activity.

  
Before the present invention, several researchers have made

  
 <EMI ID = 12.1>

  
naphthalene. Among them are: piperazine salt (Patent

  
 <EMI ID = 13.1>

  
Japanese n [deg.] 54-079.258; 1979), pyridoxine ester (Belgian patent

  
 <EMI ID = 14.1>

  
n [deg.] 2,726,561; 1977).

  
The esters of the present invention - in particular the ester

  
 <EMI ID = 15.1>

  
analgesic, anti-inflammatory and antipyretic as the acid from which they are derived. They do not have an irritant action on the gastric mucosa.

  
The compounds of general formula (I) of the present invention are prepared by reaction of the (+) 6-methoxy-a-methyl2-naphthalene acetic acid of formula (III), previously salified

  
and the compound of formula (IV).

  
The summary diagram is illustrated by the formula:

  

 <EMI ID = 16.1>


  
wherein R- and R2 are defined above, A can be a hydrogen atom or a base and B can be hydroxyl or halogen.

  
Salification can be carried out using an or-

  
 <EMI ID = 17.1>

  
 <EMI ID = 18.1>

  
 <EMI ID = 19.1>

  
laires. The organic base preferably used is triethyl lamin. The mass reason of the reaction elements may be 1.3-2 base masses for each acid mass, and the reaction will preferably be carried out in polar solvents such as

  
 <EMI ID = 20.1>

  
After salification of the acid, the salt produced is reacted

  
 <EMI ID = 21.1>

  
of the compound- (IV) for each., mass of the acid of formula (III) for

  
 <EMI ID = 22.1>

  
as compound (IV) 3-bromophthalide. 3-Bromophthalide is a compost

  
 <EMI ID = 23.1>

  
 <EMI ID = 24.1>

  
paraformaldehyde and pivaloyl chloride liquors in the presence of a catalyst such as zinc chloride (Ulich L.H., Adams,

  
 <EMI ID = 25.1> acetic acid is advantageously carried out in a medium comprising a solvent or a mixture of solvents in which the materials reacted and the compound produced are perfectly soluble. In addition, since the presence of water hydrolyzes 3-bromophta-

  
 <EMI ID = 26.1>

  
 <EMI ID = 27.1>

  
tion is perfectly anhydrous.

  
 <EMI ID = 28.1>

  
reaction which produces them is done by extraction, after addition

  
 <EMI ID = 29.1>

  
tates of ethyl, butyl propyl, dichloromethane and the like.

  
The examples below are given as illustration of the invention

  
Example

  
 <EMI ID = 30.1>

  
The mixture was refluxed for two hours and then cooled to room temperature. Still under agitation,

  
 <EMI ID = 31.1>

  
 <EMI ID = 32.1>

  
 <EMI ID = 33.1>

  
removed. For the next organic phase, anhydrous magnesium sulfate was added. The magnesium sulfate was separated by filtration and the filtrate concentrated until drying. Yield

  
 <EMI ID = 34.1> <EMI ID = 35.1>

  
obtained: C, 72.95; H, 5.07.

Example II

  
 <EMI ID = 36.1>

  
 <EMI ID = 37.1>

  
of pivaloyloxymethyl, the reaction-forming mixture was refluxed for 210 minutes. The solution was then cooled to room temperature then poured into distilled water (1500 ml) previously cooled and rested for 30 minutes . The reaction mixture was then extracted using

  
 <EMI ID = 38.1>

  
added ether. The other solution could stand and the resulting crystalline compound was filtered and dried in vacuo. Ren-

  
 <EMI ID = 39.1>


    

Claims (1)

<EMI ID=40.1>  <EMI ID = 40.1> de la fièvre et de la douleur chez les mammifères qui présentent fever and pain in mammals with <EMI ID=41.1>  <EMI ID = 41.1> <EMI ID=42.1>  <EMI ID = 42.1> <EMI ID=43.1>  <EMI ID = 43.1> <EMI ID=44.1>  <EMI ID = 44.1> forment la partie bivalente de la formule (II) form the bivalent part of formula (II) <EMI ID=45.1>  <EMI ID = 45.1> <EMI ID=46.1>  <EMI ID = 46.1>
BE2/59338A 1981-09-04 1981-09-04 NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE BE890221A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BE2/59338A BE890221A (en) 1981-09-04 1981-09-04 NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE890221 1981-09-04
BE2/59338A BE890221A (en) 1981-09-04 1981-09-04 NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE

Publications (1)

Publication Number Publication Date
BE890221A true BE890221A (en) 1982-01-04

Family

ID=25659703

Family Applications (1)

Application Number Title Priority Date Filing Date
BE2/59338A BE890221A (en) 1981-09-04 1981-09-04 NOVEL ESTERS OF ACID (+) 6-METHOXY-ALPHA-METHYL-2-NAPHTHALENEACETIQUE

Country Status (1)

Country Link
BE (1) BE890221A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939455A (en) * 1997-03-11 1999-08-17 Beacon Laboratories, Inc. Therapeutic augmentation of oxyalkylene diesters and butyric acid derivatives
US6110955A (en) * 1997-03-11 2000-08-29 Beacon Laboratories, Inc. Metabolically stabilized oxyalkylene esters and uses thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939455A (en) * 1997-03-11 1999-08-17 Beacon Laboratories, Inc. Therapeutic augmentation of oxyalkylene diesters and butyric acid derivatives
US6110955A (en) * 1997-03-11 2000-08-29 Beacon Laboratories, Inc. Metabolically stabilized oxyalkylene esters and uses thereof

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RE Patent lapsed

Owner name: LABORATORIOS BAGO S.A.

Effective date: 19890930