CH501004A - Theophylline 7-(beta-ethane sulphonic acid) Salts of (I) with mineral and organic bases. (I) and its salts have anti-fungal and anti-bacterial activ - Google Patents

Theophylline 7-(beta-ethane sulphonic acid) Salts of (I) with mineral and organic bases. (I) and its salts have anti-fungal and anti-bacterial activ

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Publication number
CH501004A
CH501004A CH2870A CH2870A CH501004A CH 501004 A CH501004 A CH 501004A CH 2870 A CH2870 A CH 2870A CH 2870 A CH2870 A CH 2870A CH 501004 A CH501004 A CH 501004A
Authority
CH
Switzerland
Prior art keywords
salts
sep
theophylline
fungal
beta
Prior art date
Application number
CH2870A
Other languages
French (fr)
Inventor
Clemence Francois
Martret Odile Le
Original Assignee
Roussel Uclaf
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
Priority claimed from FR116130A external-priority patent/FR6525M/fr
Application filed by Roussel Uclaf filed Critical Roussel Uclaf
Publication of CH501004A publication Critical patent/CH501004A/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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/16Purine radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Theophylline 7-(beta-ethane sulphonic acid) - Salts of (I) with mineral and organic bases. - (I) and its salts have anti-fungal and anti-bacterial activity. The salts are used in the paper- and textile industry against (fungi-, bacteria and unpleasant odours stemming from fermentation. They may be used in pharmaceuticals because of their high solubility in water, esp. for neutral aqueous injectable solutions or preparations for aerosols. The salts with basic antibiotics give improved activity. They may also be used for medical dressings of cellulose- or synthetic fibres for external application.

Description

  

  Procédé de préparation de sels de l'acide théophylline 7-[ss-éthane sulfoniquel  avec les antibiotiques basiques    La présente invention a pour objet un procédé de  préparation de nouveaux sels de l'acide théophylline     7-          [(3-éthane    sulfonique] avec les antibiotiques basiques.  



  L'acide théophylline 7-[ss-éthane sulfonique] répond  à la formule  
EMI0001.0002     
    Ledit acide est un acide fort qui, par     salification,     fournit des sels bien définis et stables, les sels ainsi       formés    sont solubles dans l'eau.  



  L'invention a donc pour objet un     procédé    d'obten  tion des sels hydrosolubles de l'acide     théophylline    7-[P  éthane sulfonique] avec les antibiotiques basiques et  notamment les     sels    d'antibiotiques basiques comme par  exemple les sels de néomycine B ou de néomycine C,  le sel de tétracycline, le sel de streptomycine, le sel  d'érythromycine, le :sel de kanamycine, le sel de     coli-          mycine,    le sel d'hygromycine ou le sel     d'hydroxy-          mycine.     



  Les sels de l'acide théophylline 7-[ss-éthane     sulfo-          nique]    avec les antibiotiques basiques peuvent être uti  lisés dans l'industrie pharmoceutique grâce à leur solu  bilité dans l'eau. Ils permettent la préparation de solutés  injectables aqueux neutres ou de préparations pour  aérosols.    Les formes injectables tirent de cette hydrosolubilité  une activité, une diffusibilité ou une vitesse d'action  nettement     améliorées.     



  Ils peuvent enfin servir à la préparation de panse  ments médicamenteux en fibres cellulosiques ou en fibres  artificielles lorsqu'une action thérapeutique externe est  préconisée.  



  Parmi les sels susceptibles d'être préparés par le  procédé selon l'invention, le théophylline 7-[ss-éthane     sul-          fonate]    de tétracycline présente un intérêt particulier. Il  est doté, en effet, de propriétés pharmacologiques inté  ressantes,     notamment    une action antibiotique et anti  bactérienne importante.  



  Il peut être     utilisé    pour le traitement des staphylo  coccies, des     streptococcies    et des infections provoquées  par des germes à Gram négatif,     comme    par exemple, les  bacilles typhiques.  



  Le théophylline 7-(ss-éthane sulfonate) de tétracycline  est utilisé par voie buccale,     transcutanée    ou par voie  locale en application topique sur     la    peau et les muqueu  ses ou par voie rectale.  



  Il peut se présenter sous forme de solutions injec  tables, conditionnées en ampoules, en flacons à prises  multiples ou de poudre stérile pour préparation extem  poranée de solutions injectables, de comprimés, de com  primés enrobés, de poudre aromatisée, de granulés,  d'émulsions, de sirops, de suppositoires, d'ovules, de  comprimés     intravaginaux,    de pommades, de crèmes, de  gouttes nasales et auriculaires, de collyre, de collutoire  et de poudres topiques en pulvérisations.  



  La posologie utile s'échelonne entre 200 mg et 800 mg  par prise et 1 à 4 g par jour chez l'adulte en fonction de  la voie d'administration.  



  Les formes     pharmaceutiques    telles que solutions in  jectables, poudre stérile pour préparation extemporanée  de solutions injectables,     comprimés,        comprimés        enrobés,         poudre aromatisée, granulés, émulsions, sirops, suppo  sitoires, ovules, comprimés intravaginaux, pommades,  crèmes, gouttes nasales et auriculaires, collyre, collutoire  et poudres topiques en pulvérisations, sont préparées se  lon les procédés usuels.  



  Les sels de l'acide théophylline 7-[ss-éthane     sulfoni-          que]    avec les antibiotiques basiques sont préparés par  réaction dudit acide avec un antibiotique basique, dans  un solvant inerte, après quoi l'on isole le sel formé.  



  La salification est effectuée de préférence dans l'eau.  Elle peut également être effectuée dans un solvant orga  nique en présence ou en l'absence d'eau.  



  L'acide théophylline 7-[ss-éthane sulfurique] est ob  tenu en soumettant le théophylline 7-[ss-chloroéthyle] à  l'action d'un     sulfite    métallique, puis en     acidifiant    au  moyen d'un acide minéral fort la solution de théophyl  line 7-[ss-éthane sulfonate] métallique ainsi obtenue.  



  <I>Préparation de l'acide théophylline</I>  7-[ss-éthane sulfonique]  On porte au reflux, pendant sept heures, une solu  tion de 72,6 g de théophylline 7(ss-chloro éthyle) (obtenu  selon le procédé décrit par G. di Paco, Ann. chim.     Ro-          ma,    47, 698-704, 1957) dans 1000 cm3 d'eau et une solu  tion de 41,6 g de sulfite de sodium dans 200 cm  d'eau ;  on filtre et la solution est évaporée à sec sous pression  réduite.  



  Le résidu est repris par 200 cm3 d'acide chlor  hydrique ; on filtre le précipité minéral et évapore à  sec le filtrat. On lave le résidu à l'alcool et sèche; on  obtient 68 g d'acide théophylline 7 (ss-éthane.sulfonique)  que l'on purifie par dissolution dans l'eau et précipita  tion par l'acétone (Rendement: 65 %).  



  L'acide théophylline 7 (ss-éthane sulfonique) se pré  sente sous forme de cristaux incolores, très solubles  dans l'eau, insolubles dans l'alcool, l'acétone, l'éther et  le benzène, fondant à 3200 C.  
EMI0002.0006     
  
    Analyse: <SEP> C9H12N405S <SEP> = <SEP> 288,29
<tb>  Calculé <SEP> : <SEP> C <SEP> % <SEP> 37,50 <SEP> H <SEP> % <SEP> 4,19 <SEP> N <SEP> % <SEP> 19,44
<tb>  Trouvé <SEP> : <SEP> C <SEP> % <SEP> 37,3 <SEP> H <SEP> % <SEP> 4,3 <SEP> N <SEP> % <SEP> 19,1       Spectre I.R. (Nujol)  Absence de NH vers 3300-3500 cm-Ú  Présence de C=O à 1675 cm-'  Présence de R-S03(-) à 1150 et l060 cm-1  Pour autant que l'on sache, ce composé n'est pas  décrit dans la littérature.  



  Exemple  Théophylline 7-(ss-éthane sulfonate) de tétracycline  On dissout<B>26,31</B> g de tétracycline base dans  1050 cm  de méthanol et ajoute 16,72 g d'acide théophyl  line 7-(ss-éthane sulfonique) ; on évapore à sec sous pres  sion     réduite,    lave le résidu à l'éther et sèche, on obtient  43 g de théophylline 7-(ss-éthane sulfonate) de tétra  cycline sous forme d'une poudre microcristalline jaune  clair, soluble dans l'eau et le méthanol, peu soluble dans  l'éthanol, insoluble dans l'éther, fondant vers 2500 C  avec décomposition, son pouvoir rotatoire est  
EMI0002.0008     
  
    [a]20D= <SEP> -168  <SEP>   <SEP> 1 <SEP> (c <SEP> = <SEP> 1%, <SEP> eau).
<tb>  Analyse <SEP> : <SEP> C31H36N6013S <SEP> = <SEP> 732,71
<tb>  Calculé <SEP> : <SEP> N% <SEP> 11,47
<tb>  Trouvé <SEP> :

   <SEP> N <SEP> % <SEP> 11,49       Pour autant que l'on sache, ce composé n'est pas  décrit dans la littérature.



  Process for the preparation of salts of theophylline 7- [ss-ethane sulfonic acid with basic antibiotics The present invention relates to a process for the preparation of new salts of theophylline 7- [(3-ethanesulfonic acid] with the basic antibiotics. basic antibiotics.



  Theophylline 7- [ss-ethanesulfonic acid] has the formula
EMI0001.0002
    Said acid is a strong acid which, on salification, provides well-defined and stable salts, the salts thus formed are soluble in water.



  The subject of the invention is therefore a process for obtaining the water-soluble salts of theophylline 7- [P ethanesulfonic acid] with basic antibiotics and in particular the salts of basic antibiotics such as for example the salts of neomycin B or of neomycin C, tetracycline salt, streptomycin salt, erythromycin salt, kanamycin salt, colimycin salt, hygromycin salt or hydroxymycin salt.



  The salts of theophylline 7- [ss-ethanesulfonic acid] with basic antibiotics can be used in the pharmaceutical industry due to their water solubility. They allow the preparation of neutral aqueous injectable solutions or aerosol preparations. The injectable forms derive from this water solubility a markedly improved activity, diffusibility or speed of action.



  Finally, they can be used for the preparation of medicated dressings made from cellulose fibers or artificial fibers when an external therapeutic action is recommended.



  Among the salts capable of being prepared by the process according to the invention, tetracycline theophylline 7- [ss-ethane sulphonate] is of particular interest. It is endowed, in fact, with interesting pharmacological properties, in particular an important antibiotic and anti-bacterial action.



  It can be used for the treatment of staphylococcal disease, streptococcal disease and infections caused by gram-negative germs, such as, for example, typhoid bacilli.



  Tetracycline theophylline 7- (ss-ethanesulphonate) is used orally, transcutaneously or locally as topical application to the skin and mucous membranes or rectally.



  It can be in the form of injectable solutions, packaged in ampoules, in multi-dose vials or as sterile powder for external preparation of injectable solutions, tablets, coated tablets, flavored powder, granules, emulsions. , syrups, suppositories, ova, intravaginal tablets, ointments, creams, nasal and ear drops, eye drops, mouthwash and topical powder sprays.



  The useful dosage ranges between 200 mg and 800 mg per dose and 1 to 4 g per day in adults depending on the route of administration.



  Pharmaceutical forms such as injectable solutions, sterile powder for extemporaneous preparation of injectable solutions, tablets, coated tablets, flavored powder, granules, emulsions, syrups, suppositories, ova, intravaginal tablets, ointments, creams, nasal and ear drops, eye drops , mouthwash and topical spray powders are prepared according to the usual methods.



  The salts of theophylline 7- [ss-ethanesulfonic acid] with basic antibiotics are prepared by reacting said acid with a basic antibiotic, in an inert solvent, after which the salt formed is isolated.



  The salification is preferably carried out in water. It can also be carried out in an organic solvent in the presence or absence of water.



  The theophylline 7- [ss-ethane sulfuric acid] is obtained by subjecting the theophylline 7- [ss-chloroethyl] to the action of a metal sulphite, then by acidifying the solution with a strong mineral acid. theophyl line 7- [ss-ethane sulfonate] metal thus obtained.



  <I> Preparation of theophylline acid </I> 7- [ss-ethane sulfonic] A solution of 72.6 g of theophylline 7 (ss-chloroethyl) (obtained according to the process described by G. di Paco, Ann. chim. Ro- ma, 47, 698-704, 1957) in 1000 cm3 of water and a solution of 41.6 g of sodium sulphite in 200 cm3 of water ; it is filtered and the solution is evaporated to dryness under reduced pressure.



  The residue is taken up in 200 cm3 of hydrochloric acid; the inorganic precipitate is filtered off and the filtrate evaporated to dryness. The residue is washed with alcohol and dried; 68 g of theophylline 7 (ss-ethane.sulfonic acid) are obtained, which is purified by dissolving in water and precipitating with acetone (yield: 65%).



  Theophylline 7 (ss-ethanesulphonic acid) occurs as colorless crystals, very soluble in water, insoluble in alcohol, acetone, ether and benzene, melting at 3200 C.
EMI0002.0006
  
    Analysis: <SEP> C9H12N405S <SEP> = <SEP> 288.29
<tb> Calculated <SEP>: <SEP> C <SEP>% <SEP> 37.50 <SEP> H <SEP>% <SEP> 4.19 <SEP> N <SEP>% <SEP> 19.44
<tb> Found <SEP>: <SEP> C <SEP>% <SEP> 37.3 <SEP> H <SEP>% <SEP> 4.3 <SEP> N <SEP>% <SEP> 19.1 IR spectrum (Nujol) Absence of NH around 3300-3500 cm-Ú Presence of C = O at 1675 cm- 'Presence of R-S03 (-) at 1150 and l060 cm-1 As far as we know, this compound is not described in the literature.



  Example Theophylline 7- (ss-ethane sulfonate) of tetracycline <B> 26.31 </B> g of tetracycline base is dissolved in 1050 cm 3 of methanol and 16.72 g of theophyl line 7- (ss-ethane sulfonic); evaporated to dryness under reduced pressure, the residue washed with ether and dried, 43 g of tetra cyclin theophylline 7- (ss-ethane sulfonate) are obtained in the form of a light yellow microcrystalline powder, soluble in water and methanol, sparingly soluble in ethanol, insoluble in ether, melting at around 2500 C with decomposition, its optical rotation is
EMI0002.0008
  
    [a] 20D = <SEP> -168 <SEP> <SEP> 1 <SEP> (c <SEP> = <SEP> 1%, <SEP> water).
<tb> Analysis <SEP>: <SEP> C31H36N6013S <SEP> = <SEP> 732.71
<tb> Calculated <SEP>: <SEP> N% <SEP> 11.47
<tb> Found <SEP>:

   <SEP> N <SEP>% <SEP> 11.49 As far as we know, this compound has not been described in the literature.

 

Claims (1)

REVENDICATION Procédé de préparation de sels de l'acide théophyl line 7-[ss-éthane sulfonique] avec les antibiotiques basi ques, caractérisé en ce que l'on fait réagir ledit acide avec un antibiotique basique, dans un solvant inerte, et isole le sel formé. SOUS-REVENDICATIONS 1. Procédé suivant la revendisation, caractérisé en ce que le solvant inerte est l'eau, ou un solvant orga nique en présence ou en l'absence d'eau. 2. CLAIM Process for the preparation of salts of theophyl line 7- [ss-ethanesulphonic acid] with basic antibiotics, characterized in that said acid is reacted with a basic antibiotic, in an inert solvent, and isolates the salt formed. SUB-CLAIMS 1. A process according to claim, characterized in that the inert solvent is water, or an organic solvent in the presence or absence of water. 2. Procédé suivant la revendication, caractérisé en ce que l'on prépare le théophylline 7-[ss-éthane sulfonate] de tétracycline, de streptomycine, de théomycine B, de néomycine C, d'érythromycine, de kanamycine, de co- limycine, d'hygromycine et d'hydromycine. Process according to claim, characterized in that theophylline 7- [ss-ethanesulfonate] of tetracycline, streptomycin, theomycin B, neomycin C, erythromycin, kanamycin, co-limycin, d is prepared. 'hygromycin and hydromycin.
CH2870A 1967-05-23 1968-05-20 Theophylline 7-(beta-ethane sulphonic acid) Salts of (I) with mineral and organic bases. (I) and its salts have anti-fungal and anti-bacterial activ CH501004A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR107454 1967-05-23
FR116130A FR6525M (en) 1967-05-23 1967-07-28
CH746368A CH496015A (en) 1967-05-23 1968-05-20 Process for obtaining a novel acid derived from theophylline

Publications (1)

Publication Number Publication Date
CH501004A true CH501004A (en) 1970-12-31

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CH2870A CH501004A (en) 1967-05-23 1968-05-20 Theophylline 7-(beta-ethane sulphonic acid) Salts of (I) with mineral and organic bases. (I) and its salts have anti-fungal and anti-bacterial activ

Country Status (1)

Country Link
CH (1) CH501004A (en)

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