CH222735A - Process for the preparation of a derivative of para-amino-benzene-sulfonamide. - Google Patents

Process for the preparation of a derivative of para-amino-benzene-sulfonamide.

Info

Publication number
CH222735A
CH222735A CH222735DA CH222735A CH 222735 A CH222735 A CH 222735A CH 222735D A CH222735D A CH 222735DA CH 222735 A CH222735 A CH 222735A
Authority
CH
Switzerland
Prior art keywords
para
benzene
amino
derivative
sulfonamide
Prior art date
Application number
Other languages
French (fr)
Inventor
Chemisches Industrielles Cilag
Original Assignee
Cilag Chemisches Ind Lab A G
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 Cilag Chemisches Ind Lab A G filed Critical Cilag Chemisches Ind Lab A G
Publication of CH222735A publication Critical patent/CH222735A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/64—X and Y being nitrogen atoms, e.g. N-sulfonylguanidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C07D277/52—Nitrogen atoms bound to hetero atoms to sulfur atoms, e.g. sulfonamides

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

Description

  

  Procédé de préparation d'un dérivé de la     para-amino-benzène-sulfamide.       La présente invention a pour objet un  procédé de préparation d'un dérivé de la  para-     amino-benzéne-sulfamide,    ayant la for  mule  
EMI0001.0003     
    Ce composé connu, qui forme une poudre  blanche, est susceptible d'application théra  peutique.  



  Selon la présente invention, le composé  mentionné ci-dessus est préparé comme suit:  On condense de la     guanidine,        préférable-          ment    sous     forme    d'un des sels, par exemple  le nitrate, avec un     p-nitro-benzèrre-halogénure     de soufre, ayant pour formule  
EMI0001.0009     
    Ce dernier composé est facile à préparer  d'après     Zinche    A. 400 9.

      Le produit de la condensation mentionnée  a pour formule  
EMI0001.0011     
    Ce dernier composé est oxydé, par exem  ple par le permanganate de potasse ou des  oxydants équivalents, en     p-nitro-benzéne-sul-          fonyle-guanidine.    On réduit ensuite le groupe  nitro en     amino,    par exemple avec du fer et  de l'acide acétique à     95-100"    selon la mé  thode bien connue de     Béchamp    (A. ch.     [3]     42 190), et on obtient de la     p-amino-benzène-          sulfonyle-guanidine.     



  Voici des exemples d'exécution du pro  cédé de l'invention.    <I>Exemple 1:</I>  On suspend 12,1 gr de nitrate de     gua-          nidine    dans 100 cm<B>3</B>  ' d'éther sec et on ajoute  8 gr de carbonate de sodium anhydre. En  refroidissant à<B>10-150</B> on ajoute alors len-           tentent    une solution de 14 gr de     p-nitro-          benzène-clilorure    de soufre  
EMI0002.0004     
    dans 100     cm'    d'éther     séché    en     agitant        bien     le mélange.

   Un précipité     résineux    est     fariné.     Après une     lieuse,    air ajoute     100        cm:\        d'e;iu     en agitant et ensuite air sépare le, précipité  de l'eau et de l'éther.  



  Ce composé a la formule  
EMI0002.0015     
    La     réaction        petit        aussi    être,     mise    en     02uvre     en solution benzénique.  



  Pour l'oxydation de ce dernier composé  en dérivé sulfamide, 1 gr de la     matière    brute  est dissous dans 15 cm'' de     dioxane    et cette  solution est diluée par 5 cm'' d'eau. Cette  solution étant refroidie à 10-15 ", air l'agite  tout en ajoutant     lentement        dit    permanganate  de potasse     pulvérisé    jusqu'à ce qu'un petit  excès de cet oxydant soit présent et que la  solution reste rouge.

   Le     mélange    est ensuite       versé    dans 100 cm" d'acide     sulfurique   <B>IV</B>     /0     et décoloré par un     peut    de     bisulfite    de sodium.  Le précipité est séparé par     filti, < ttioii.    Il con  siste en     para-nitro-benzènesulfonyle-guanidine.     



  10 gr de ce composé nitré brut sont       versés    dans     titi        méhinge    bien agité de 100 gr  de limaille de fer et de 300     cm'    d'acide acé  tique à une température de 95-100 ". Après  une heure d'agitation à 95 ", le mélange est  refroidi à 20" et rendu     alcalin    avec une  solution de soude caustique. Le     mélange    est       filtré    et le filtrat acidifié à     l'acide    acétique.  Le précipité est filtré. IL     consiste    en     para-          amino-benzène-sulforiyle-gti@uiidiiie.     



       Exemple   <I>2:</I>  6 gr de nitrate de     guanidine    sont sus  pendus dans 50     cm.1     ' de     pyridine        sèche.    Ors  ajoute à cette     solution    en refroidissant à         10-15"    et agitant, 9,5 gr de     p-nitro-beri-          zène-clilor        ure    de soufre  
EMI0002.0055     
         Après        mie    heure de repos à 20  , la solution       jmiue    est versée dans 500     cnt'    d'eau.

   Le  précipité est filtré et     séclié.    Après     recristalli-          sation    à l'alcool ou air benzène, le     composé     obtenu est oxydé à la manière suivante  1 gr du composé obtenu ainsi est dissous  dans 50 cm" d'acétone. La solution est diluée       par    10     cm:'    d'eau. En agitant, on ajoute     leu-          tentent    à     10--l5\    un petit excès de     per-          mauganate    de potasse.

   Le mélange est alors  versé dans 100 cm' d'acide sulfurique     10';'o     et décoloré à l'aide de bisulfite de sodium.  Le précipité est filtré. Par réduction selon       l'exemple    1, ors obtient de la     para-amino-          berr7,ène-stilforryle-guanidine.  



  Process for the preparation of a derivative of para-amino-benzene-sulfonamide. The present invention relates to a process for preparing a derivative of para-amino-benzenesulfonylurea, having the formula
EMI0001.0003
    This known compound, which forms a white powder, is capable of therapeutic application.



  According to the present invention, the above-mentioned compound is prepared as follows: Guanidine, preferably in the form of one of the salts, for example nitrate, is condensed with a p-nitro-benzere-sulfur halide, having for formula
EMI0001.0009
    The latter compound is easy to prepare according to Zinche A. 400 9.

      The product of the mentioned condensation has the formula
EMI0001.0011
    The latter compound is oxidized, for example by potassium permanganate or equivalent oxidants, to p-nitro-benzenesulfonyl-guanidine. The nitro group is then reduced to amino, for example with iron and acetic acid 95-100 "according to the well-known method of Béchamp (A. ch. [3] 42 190), and one obtains p-amino-benzenesulfonyl-guanidine.



  Here are examples of execution of the process of the invention. <I> Example 1: </I> 12.1 g of guanidine nitrate are suspended in 100 cm 3 of dry ether and 8 g of anhydrous sodium carbonate are added. While cooling to <B> 10-150 </B>, a solution of 14 g of p-nitro-benzene-sulfur chloride is then added slowly.
EMI0002.0004
    in 100 cm 3 of dried ether, stirring the mixture well.

   A resinous precipitate is floured. After a binder, air adds 100 cm 3 of e; iu while stirring and then air separates the precipitate from the water and ether.



  This compound has the formula
EMI0002.0015
    The reaction can also be carried out in benzene solution.



  For the oxidation of the latter compound to a sulfonamide derivative, 1 g of the crude material is dissolved in 15 cm “of dioxane and this solution is diluted with 5 cm“ of water. This solution being cooled to 10-15 ", air stirred while slowly adding said pulverized potassium permanganate until a small excess of this oxidant is present and the solution remains red.

   The mixture is then poured into 100 cm "of <B> IV </B> / 0 sulfuric acid and decolorized with a can of sodium bisulfite. The precipitate is separated by filtration, <ttioii. It consists of para-nitro -benzenesulfonyl-guanidine.



  10 g of this crude nitrated compound are poured into a well-stirred titi mixture of 100 g of iron filings and 300 cm 3 of acetic acid at a temperature of 95-100 ". After stirring for one hour at 95", the mixture is cooled to 20 "and made alkaline with caustic soda solution. The mixture is filtered and the filtrate acidified with acetic acid. The precipitate is filtered. It consists of para-amino-benzene-sulforiyl-gti @ uiidiiie. .



       Example <I> 2: </I> 6 g of guanidine nitrate are suspended in 50 cm.1 'of dry pyridine. Ors adds to this solution, cooling to 10-15 "and stirring, 9.5 g of p-nitro-berizene-sulfur chloride.
EMI0002.0055
         After standing for half an hour at 20, the jmiue solution is poured into 500 cc of water.

   The precipitate is filtered off and dried. After recrystallization with alcohol or air benzene, the compound obtained is oxidized as follows: 1 g of the compound thus obtained is dissolved in 50 cm 3 of acetone. The solution is diluted with 10 cm 3 of water. With stirring, a small excess of potassium permaganate is added to 10-15%.

   The mixture is then poured into 100 cm 3 of 10 'sulfuric acid and decolorized with sodium bisulfite. The precipitate is filtered off. By reduction according to Example 1, we obtain para-aminoberr7, ene-stilforryl-guanidine.

Claims (1)

REVENDICATION Procédé de préparation d'un dérivé de la p < ir:i-@iutino-benzèrie-stilfamide, caractérisé en ce que l'on fait réagir de la guanidine avec titi p-riitro-benzène-halogériure de soufre de formule EMI0002.0080 pour former le composé de formule EMI0002.0081 puis en ce que l'on soumet ce dernier com posé à une oxydation de façon à obtenir 1a p-niti-o-benzéne-sulfoiiyle-guairidine, que l'on soumet à une réduction pour obtenir la para- amino-lrenzèrie-sulfonyle-guanidine. CLAIM A process for preparing a derivative of p <ir: i- @ iutino-benzèrie-stilfamide, characterized in that guanidine is reacted with titi p-riitro-benzene-sulfur halide of formula EMI0002.0080 to form the compound of formula EMI0002.0081 then in that the latter compound is subjected to oxidation so as to obtain p-ni-o-benzenesulfolyl-guairidin, which is subjected to reduction to obtain the para-amino-lrenzere-sulfonyl -guanidine.
CH222735D 1941-08-08 1941-08-08 Process for the preparation of a derivative of para-amino-benzene-sulfonamide. CH222735A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH220046T 1941-08-08
CH222735T 1941-08-08

Publications (1)

Publication Number Publication Date
CH222735A true CH222735A (en) 1942-07-31

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ID=25726389

Family Applications (1)

Application Number Title Priority Date Filing Date
CH222735D CH222735A (en) 1941-08-08 1941-08-08 Process for the preparation of a derivative of para-amino-benzene-sulfonamide.

Country Status (1)

Country Link
CH (1) CH222735A (en)

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