CH222734A - 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.

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Publication number
CH222734A
CH222734A CH222734DA CH222734A CH 222734 A CH222734 A CH 222734A CH 222734D A CH222734D A CH 222734DA CH 222734 A CH222734 A CH 222734A
Authority
CH
Switzerland
Prior art keywords
benzene
amino
para
derivative
preparation
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 CH222734A publication Critical patent/CH222734A/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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (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 et qui fond à 237-238" C, est sus  ceptible d'application thérapeutique.  



  Selon la présente invention, la composé  mentionné ci-dessus est préparé comme suit:  On condense du     2-amino-4-méthylthiazol     avec un     p-nitro-benzène-halogénure    de soufre,  ayant pour formule  
EMI0001.0006     
    Ce dernier composé est facile à préparer  d'après     Zincke    A.. 400 9.    Le produit de la condensation mentionnée  a pour formule  
EMI0001.0008     
    Ce dernier composé est oxydé, par exem  ple, par le permanganate de potasse ou des  oxydants équivalents, en     2(para-nitro-benzène-          sulfamido)-4-méthylthiazol.     



  On réduit ensuite le groupe nitro en       amino,    par exemple avec du fer et de l'acide  acétique à 95-100   selon la méthode bien  connue de     Béchamp    (A. ch.     [3]    42 190), et  on obtient du     2(para-amino-benzéne-sulfamido)-          4-méthylthiazol.     



  Voici des exemples d'exécution du pro  cédé de l'invention:  <I>Exemple 1:</I>  On dissout 11,4 gr de     2-amino-4-méthyl-          thiazol    dans 60 cm' d'éther sec et on ajoute      f> gr de carbonate de sodium anhydre. En  refroidissant à     10--15'l,    on ajoute alors len  tement une solution de 14 gr de     p-nitro-          benzéne-chlorure    de soufre  
EMI0002.0004     
    dans 100 cm' d'éther séché, en agitant bien  le mélange. Un précipité     résineux    est formé.  Après une heure, on ajoute 100 cm" d'eau  en agitant et ensuite on sépare le précipité  de l'eau et de l'éther.  



  Ce composé a la formule  
EMI0002.0006     
    La réaction peut aussi être mise en     oeuvre     en solution benzénique.  



  Pour l'oxydation de ce dernier composé  en dérivé     sulfamino,    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<B>10-15',</B> on l'agite  tout en ajoutant lentement du permanganate  de potasse pulvérisé jusqu'à ce qu'un petit       excés    de cet oxydant soit présent et que la  solution reste rouge.

   Le mélange est ensuite       versé        dans        100        cm"        d'acide        sulfurique        1%     et décoloré par un peu de bisulfite de sodium.  Le précipité est séparé par filtration. Il con  siste en     2(para    -     nitro    -benzène -     sulfamido)-    4     -          méthy1thiazol.     



  10 gr de ce composé nitré brut sont  versés dans un mélange bien agité de 100 gr  de limaille de fer et de 300 cm" d'acide acé  tique à une température de 95-100 0. Après  une heure d'agitation à 95 0, le mélange est  refroidi à 20 0 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     2(para-          amino-benzéne-sulfamido)-4-méthylthiazol    et  fond à     237-238".       <I>Exemple 2:</I>  5,7 gr de 2 -     amino    - 4     -méthylthiazol    sont  dissous dans 35 cm" de     pyridine    sèche.

   On  ajoute à cette solution en refroidissant à  10--15 0 et agitant, 9,5 gr de     p-nitro-benzène-          chlorure    de soufre  
EMI0002.0032     
    Après une heure de repos à 20', la solution  jaune est versée dans 500 cm" d'eau. Le  précipité est filtré et séché. Après     recristalli-          sation    à l'alcool ou au 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 len  tement a<B>10-151</B> un petit excès de per  manganate de potasse.

   Le     mélange    est alors       versé        dans        100        cm"        d'acide        sulfurique        10%     et décoloré à l'aide de     bisulfite    de sodium.  Le précipité est filtré. Par réduction selon  l'exemple 1, on obtient du     2(para-amino-          benzène-sulfamido)-4-méthylthiazol.  



  Process for the preparation of a derivative of para-amino-benzene-sulfonamide. The present invention relates to a process for the preparation of a derivative of para-amino-benzenesulfonylurea, having the formula
EMI0001.0003
    This known compound, which forms a white powder and melts at 237-238 ° C, is capable of therapeutic application.



  According to the present invention, the above-mentioned compound is prepared as follows: 2-amino-4-methylthiazol is condensed with a p-nitro-benzene-sulfur halide, having the formula
EMI0001.0006
    The latter compound is easy to prepare according to Zincke A .. 400 9. The product of the mentioned condensation has the formula
EMI0001.0008
    The latter compound is oxidized, for example, by potassium permanganate or equivalent oxidants, to 2 (para-nitro-benzene-sulfamido) -4-methylthiazol.



  The nitro group is then reduced to amino, for example with iron and 95-100 acetic acid according to the well-known method of Béchamp (A. ch. [3] 42 190), and 2 (para. -amino-benzenesulfamido) - 4-methylthiazol.



  Here are examples of execution of the process of the invention: <I> Example 1: </I> 11.4 g of 2-amino-4-methyl-thiazol are dissolved in 60 cm 3 of dry ether and add f> g of anhydrous sodium carbonate. While cooling to 10--15'l, 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 formed. After one hour, 100 cm 3 of water are added with stirring and then the precipitate is separated from the water and ether.



  This compound has the formula
EMI0002.0006
    The reaction can also be carried out in benzene solution.



  For the oxidation of the latter compound to a sulfamino derivative, 1 g of the crude material is dissolved in 15 cm 3 of dioxane and this solution is diluted with 5 cm 3 of water. This solution being cooled to <B> 10- 15 ', </B> stir while slowly adding powdered potassium permanganate until a small excess of this oxidant is present and the solution remains red.

   The mixture is then poured into 100 cm 3 of 1% sulfuric acid and decolorized with a little sodium bisulfite. The precipitate is separated by filtration. It consists of 2 (para - nitro -benzene - sulfamido) - 4 - methylthiazol .



  10 g of this crude nitro compound are poured into a well-stirred mixture of 100 g of iron filings and 300 cm 3 of acetic acid at a temperature of 95-100 0. After stirring for one hour at 95 0, the mixture is cooled to 20 ° C. 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 2 (para-amino-benzenesulfamido) - 4-methylthiazol and melts at 237-238 ". <I> Example 2: </I> 5.7 g of 2 - amino - 4 -methylthiazol are dissolved in 35 cm "of dry pyridine.

   To this solution is added, cooling to 10--15 0 and stirring, 9.5 g of p-nitro-benzene-sulfur chloride
EMI0002.0032
    After standing at 20 'for one hour, the yellow solution is poured into 500 cm 3 of water. The precipitate is filtered off and dried. After recrystallization with alcohol or 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. While stirring, a small excess of potassium per manganate is slowly added to <B> 10-151 </B>.

   The mixture is then poured into 100 cm 3 of 10% sulfuric acid and decolorized with sodium bisulphite. The precipitate is filtered. By reduction according to Example 1, 2 (para-amino-benzene- sulfamido) -4-methylthiazol.

Claims (1)

REVENDICATION Procédé de préparation d'un dérivé de la para-amino-benzène-sulfamide, caractérisé en ce que l'on fait réagir du 2-amino-4-méthyl- thiazol avec un p-nitro-benzène-halogénure de soufre de formule EMI0002.0052 pour former le composé de formule EMI0002.0053 puis en ce que l'on soumet ce dernier com posé à une oxydation de façon à obtenir le 2(para-nitro-beiizène - sulfamido)-4-méthylthia- zol, que l'on soumet â une réduction pouf obtenir le 2(para-amino-benzène-sulfamido) CLAIM Process for the preparation of a derivative of para-amino-benzene-sulfonylurea, characterized in that 2-amino-4-methyl-thiazol is reacted with a p-nitro-benzene-sulfur halide of formula EMI0002.0052 to form the compound of formula EMI0002.0053 then in that the latter compound is subjected to oxidation so as to obtain 2 (para-nitro-beiizene - sulfamido) -4-methylthia-zol, which is subjected to reduction to obtain 2 ( para-amino-benzene-sulfamido) - 4-méthylthiazol. - 4-methylthiazol.
CH222734D 1941-08-08 1941-08-08 Process for the preparation of a derivative of para-amino-benzene-sulfonamide. CH222734A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH220046T 1941-08-08
CH222734T 1941-08-08

Publications (1)

Publication Number Publication Date
CH222734A true CH222734A (en) 1942-07-31

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ID=25726388

Family Applications (1)

Application Number Title Priority Date Filing Date
CH222734D CH222734A (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) CH222734A (en)

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