BE883654A - PROCESS FOR THE PREPARATION OF BAMIFYLLIN. - Google Patents

PROCESS FOR THE PREPARATION OF BAMIFYLLIN. Download PDF

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Publication number
BE883654A
BE883654A BE0/200903A BE200903A BE883654A BE 883654 A BE883654 A BE 883654A BE 0/200903 A BE0/200903 A BE 0/200903A BE 200903 A BE200903 A BE 200903A BE 883654 A BE883654 A BE 883654A
Authority
BE
Belgium
Prior art keywords
emi
reaction
benzyltheophylline
approximately
parts
Prior art date
Application number
BE0/200903A
Other languages
French (fr)
Original Assignee
Christiaens Sa 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 Christiaens Sa A filed Critical Christiaens Sa A
Priority to BE0/200903A priority Critical patent/BE883654A/en
Publication of BE883654A publication Critical patent/BE883654A/en
Priority to ES502769A priority patent/ES502769A0/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D473/00Heterocyclic compounds containing purine ring systems
    • C07D473/02Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6
    • C07D473/04Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms
    • C07D473/06Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3
    • C07D473/08Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3 with methyl radicals in positions 1 and 3, e.g. theophylline

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

Description

       

  : Procédé de préparation de Bamifylline La présente invention est relative à un

  
 <EMI ID=1.1> 

  
line qui est un produit connu de formule

  

 <EMI ID=2.1> 


  
possédant-des propriétés pharmaceutiques intéressantes notamment pour le traitement de diverses maladies,

  
 <EMI ID=3.1> 

  
angine de poitrine, les dépressions respiratoires, l'asthme et diverses maladies pulmonaires.

  
 <EMI ID=4.1> 

  
 <EMI ID=5.1> 

  
de la N-éthyléthanolamine (formule III) en présence de carbonate de sodium anhydre, selon la réaction suivante :

  

 <EMI ID=6.1> 
 

  
Dans ce procédé connu, effectué à l'échelle Industrielle, on chauffait pendant 7 heures le mélange suivant : <EMI ID=7.1> 
(578,4 moles) obtenue de la manière décrite dans le brevet belge n[deg.] 602.887 ; <EMI ID=8.1> 
- 45 kg de carbonate de sodium anhydre (424,5 moles). Après isolement et purification du produit de la réaction, le rendement atteignait 57 à 65%. Outre les pertes mécaniques, cette réaction donnait lieu à la formation d'une proportion importante d'un <EMI ID=9.1> 

  

 <EMI ID=10.1> 


  
Ce produit secondaire était obtenu à raison de 25 à 30% et à raison de 40 à 45% respectivement

  
 <EMI ID=11.1> 

  
chloro- ou bromoéthylée en position 7. 

  
Or, on a trouvé à présent que l'on peut obtenir de la Bamifylline, en un seul stade, avec un rendement remarquable, c'est-à-dire sans production simultanée de 7-vinyl-8-benzylthéophylline.

  
Suivant l'invention, on prépare de la Bamifylline, en un seul stade, en chauffant au reflux un mélange réactionnel constitué de 8-benzylthéophylline et de N-éthyléthanolamine, de carbonate

  
de sodium et de 1,2-dichloroéthane.

  
Le rendement de la réaction atteint plus de
90% et, lorsque la réaction est terminée, on obtient  <EMI ID=12.1> 

  
8-benzylthéophylline qui est récupérable.

  
L'homme de métier ne pouvait s'attendre à ce que l'on puisse obtenir, en un seul stade réactionnel, de la Bamifylline, en partant directement de 8-benzylthéophylline et sans passer par la phase intermédiaire de préparation du composé de formule

  
 <EMI ID=13.1> 

  
benzylthéophylline.

  
L'exemple suivant illustre la préparation, à l'échelle industrielle, de Bamifylline par le procédé suivant l'invention.

EXEMPLE

  
On chauffe à reflux pendant 52 heures le mélange suivant

  
 <EMI ID=14.1> 

  
36 litres de N-éthyléthanolamine (environ 350 moles) ;
300 litres de 1,2-dichloroéthane (environ 738 moles) ;
71 kg de carbonate de sodium (environ 667,5 moles) ;

  
 <EMI ID=15.1> 

  
on ajoute encore 36 litres de N-éthyléthanolamine.

  
Lorsque la réaction estterminée, on refroidit le mélange réactionnel et on y ajoute

  
de l'eau pour dissoudre les sels minéraux.

  
La phase organique (1,2-dichloroéthane) est alors extraite avec de l'acide chlorhydrique, puis écartée. Cette phase organique contient environ

  
 <EMI ID=16.1> 

  
La phase acide est neutralisée avec du

  
 <EMI ID=17.1> 

  
hydroxyéthylamino-éthyl)-8-benzylthéophylline en est extraite par un hydrocarbure aliphatique halogéné, tel que le dichlorométhane.

  
Après évaporation à sec du dichlorométhane, la base est dissoute dans un alcanol, tel que le méthanol, puis transformée en chlorhydrate dans les conditions habituelles de tranformation d'un composé organique azoté en un sel d'addition avec un acide.

  
La chlorhydrate obtenu est purifié par cristallisation dans du méthanol. Le chlorhydrate

  
 <EMI ID=18.1> 

  
 <EMI ID=19.1> 

  
rendement atteignant 91% lorsqu'on utilise, le produit récupérable de formule II. 

REVENDICATIONS

  
1 .- Procédé de préparation de Bamifylline, caractérisé en ce qu'on chauffe au reflux un mélange de 8-benzylthéophylline, de N-éthyléthanolamine et de 1,2-dichloroéthane en présence d'une base miné-

  
 <EMI ID=20.1> 

  
éthylamino-éthyl)-8-benzylthéophylline obtenue en son chlorhydrate..



  : Process for the preparation of Bamifylline The present invention relates to a

  
 <EMI ID = 1.1>

  
line which is a known product of formula

  

 <EMI ID = 2.1>


  
having advantageous pharmaceutical properties in particular for the treatment of various diseases,

  
 <EMI ID = 3.1>

  
angina, respiratory depression, asthma and various lung diseases.

  
 <EMI ID = 4.1>

  
 <EMI ID = 5.1>

  
N-ethylethanolamine (formula III) in the presence of anhydrous sodium carbonate, according to the following reaction:

  

 <EMI ID = 6.1>
 

  
In this known process, carried out on an industrial scale, the following mixture was heated for 7 hours: <EMI ID = 7.1>
(578.4 moles) obtained in the manner described in Belgian patent n [deg.] 602,887; <EMI ID = 8.1>
- 45 kg of anhydrous sodium carbonate (424.5 moles). After isolation and purification of the reaction product, the yield was 57 to 65%. In addition to the mechanical losses, this reaction gave rise to the formation of a significant proportion of an <EMI ID = 9.1>

  

 <EMI ID = 10.1>


  
This secondary product was obtained at 25 to 30% and 40 to 45% respectively

  
 <EMI ID = 11.1>

  
chloro- or bromoethylated in position 7.

  
Now, it has now been found that Bamifylline can be obtained, in a single stage, with a remarkable yield, that is to say without simultaneous production of 7-vinyl-8-benzyltheophylline.

  
According to the invention, Bamifylline is prepared, in a single stage, by heating under reflux a reaction mixture consisting of 8-benzyltheophylline and N-ethylethanolamine, carbonate

  
sodium and 1,2-dichloroethane.

  
The reaction yield reaches more than
90% and, when the reaction is complete, we obtain <EMI ID = 12.1>

  
8-benzyltheophylline which is recoverable.

  
Those skilled in the art could not expect that Bamifylline could be obtained, in a single reaction stage, starting directly from 8-benzyltheophylline and without going through the intermediate phase of preparation of the compound of formula

  
 <EMI ID = 13.1>

  
benzyltheophylline.

  
The following example illustrates the preparation, on an industrial scale, of Bamifylline by the process according to the invention.

EXAMPLE

  
The following mixture is heated at reflux for 52 hours.

  
 <EMI ID = 14.1>

  
36 liters of N-ethylethanolamine (about 350 moles);
300 liters of 1,2-dichloroethane (about 738 moles);
71 kg of sodium carbonate (about 667.5 moles);

  
 <EMI ID = 15.1>

  
another 36 liters of N-ethylethanolamine are added.

  
When the reaction is complete, the reaction mixture is cooled and added to it.

  
water to dissolve the mineral salts.

  
The organic phase (1,2-dichloroethane) is then extracted with hydrochloric acid, then discarded. This organic phase contains approximately

  
 <EMI ID = 16.1>

  
The acid phase is neutralized with

  
 <EMI ID = 17.1>

  
hydroxyethylamino-ethyl) -8-benzyltheophylline is extracted therefrom by a halogenated aliphatic hydrocarbon, such as dichloromethane.

  
After evaporation to dryness of the dichloromethane, the base is dissolved in an alkanol, such as methanol, then transformed into hydrochloride under the usual conditions of transformation of an organic nitrogen compound into an addition salt with an acid.

  
The hydrochloride obtained is purified by crystallization from methanol. Hydrochloride

  
 <EMI ID = 18.1>

  
 <EMI ID = 19.1>

  
yield up to 91% when using the recoverable product of formula II.

CLAIMS

  
1 .- Process for preparing Bamifylline, characterized in that a mixture of 8-benzyltheophylline, N-ethylethanolamine and 1,2-dichloroethane is heated to reflux in the presence of a mineral base.

  
 <EMI ID = 20.1>

  
ethylamino-ethyl) -8-benzyltheophylline obtained as its hydrochloride.


    

Claims (1)

2.- Procédé suivant la revendication 1, caractérisé en ce que la base minérale est du carbonate de sodium. 2.- Method according to claim 1, characterized in that the mineral base is sodium carbonate. 3.- Procédé suivant l'une ou l'autre des revendications précédentes, caractérisé en ce qu'on extrait la phase organique obtenue à l'aide d'acide chlorhydrique, on neutralise la phase acide obtenue <EMI ID=21.1> 3.- Method according to either of the preceding claims, characterized in that the organic phase obtained is extracted with hydrochloric acid, the acid phase obtained is neutralized <EMI ID = 21.1> line de la phase neutralisée au moyen de dichlorométhane, et on transforme ce dernier composé en chlorhydrate. line of the neutralized phase using dichloromethane, and the latter compound is transformed into the hydrochloride. 4.- Procédé suivant l'une ou l'autre des revendications précédentes, caractérisé en ce qu'on chauffe au reflux un mélange contenant, par environ 100 parties en poids de 8-benzylthéophylline, environ 300 parties en volume de 1,2-dichloroéthane, environ 4.- Method according to either of the preceding claims, characterized in that a mixture containing, by approximately 100 parts by weight of 8-benzyltheophylline, approximately 300 parts by volume of 1,2-dichloroethane, approximately <EMI ID=22.1> <EMI ID = 22.1> ron 71 parties en poids de carbonate de sodium. 71 parts by weight of sodium carbonate. 5.- Procédé suivant la revendication 4, caractérisé en ce qu'une partie de la N-éthyléthanolamine est ajoutée au mélange réactionnel pendant la réaction. 5.- Method according to claim 4, characterized in that a part of the N-ethylethanolamine is added to the reaction mixture during the reaction. <EMI ID=23.1> <EMI ID = 23.1> substance, tel que décrit plus haut notamment dans l'exemple. substance, as described above in particular in the example. 7.- Bamifylline obtenue par le procédé suivant l'une ou l'autre des revendications précédentes. 7.- Bamifylline obtained by the process according to either of the preceding claims.
BE0/200903A 1980-06-05 1980-06-05 PROCESS FOR THE PREPARATION OF BAMIFYLLIN. BE883654A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BE0/200903A BE883654A (en) 1980-06-05 1980-06-05 PROCESS FOR THE PREPARATION OF BAMIFYLLIN.
ES502769A ES502769A0 (en) 1980-06-05 1981-06-04 PREPARATION PROCEDURE OF 7- (N-ETIL-N-B-HIDROXI-ETILA-MINO-ETIL) -8-BENCILTEOFILINA

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE0/200903A BE883654A (en) 1980-06-05 1980-06-05 PROCESS FOR THE PREPARATION OF BAMIFYLLIN.
BE883654 1980-06-05

Publications (1)

Publication Number Publication Date
BE883654A true BE883654A (en) 1980-12-05

Family

ID=25652101

Family Applications (1)

Application Number Title Priority Date Filing Date
BE0/200903A BE883654A (en) 1980-06-05 1980-06-05 PROCESS FOR THE PREPARATION OF BAMIFYLLIN.

Country Status (1)

Country Link
BE (1) BE883654A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017064A1 (en) 1993-01-21 1994-08-04 S.A. Nycomed Christiaens N.V. Method for converting a xanthine ring or derivatives thereof into dialkylamino-xanthine derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994017064A1 (en) 1993-01-21 1994-08-04 S.A. Nycomed Christiaens N.V. Method for converting a xanthine ring or derivatives thereof into dialkylamino-xanthine derivatives
BE1006613A3 (en) * 1993-01-21 1994-11-03 Nycomed Christiaens Nv Sa Conversion process xanthine cycle or derivatives derivatives in cycle xanthine dialkylamino xanthine-type.

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Legal Events

Date Code Title Description
RE20 Patent expired

Owner name: A. CHRISTIAENS S.A.

Effective date: 20000605