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BE601394A - - Google Patents

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Publication number
BE601394A
BE601394A BE601394DA BE601394A BE 601394 A BE601394 A BE 601394A BE 601394D A BE601394D A BE 601394DA BE 601394 A BE601394 A BE 601394A
Authority
BE
Belgium
Prior art keywords
sep
piperazine derivatives
preparation
chlorophenyl
cough
Prior art date
Application number
Other languages
French (fr)
Publication of BE601394A publication Critical patent/BE601394A/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

       

   <Desc/Clms Page number 1> 
 
 EMI1.1 
 



  ?:!s¯Ltveaux de 1-: p.ipr=zine 
Le brevet 569.407 concerne des   dérives de   la piperazine parmi   lesquels   une substance de formule 
 EMI1.2 
 Ce produit possède une activité antitoux considérable 
 EMI1.3 
 et uns trs faible toxicité. Toutefois, il présente l'inconve- nient de ne pas pouvoir être conditionné sous toutes les forces   pharmaceutiques  scuhaitables. 



   La présente invention se rapporte à de nouveaux 
 EMI1.4 
 dérives de 1:, piprazine répondant à 1. --on.ule générale 
 EMI1.5 
 
 EMI1.6 
 'la:-..3 Le.zaélle R représente un atcWe 2- 1 ::y:.rogène ou un atone i's>1:1.lr:e se :rouv3nt en pcsition crthj, neta Du para. 

 <Desc/Clms Page number 2> 

 
 EMI2.1 
 



  Elle se rapporte J,a==...<;:: à la préparation 1e ces drives ainsi que ie le3 : d'acides minéraux en organiques. 



  Selcn :. 1 ir:ve!lticr¯: en prépare les composés de l-' !"'H:J.10 (I) en :ais3:-:.t réagir une '::'-:.2.-';.:?:../::')-ril,'?razine avec le 1,2i Oxß l : .rxj-¯7r0= .:e , R à=:#:-.= 1::: . ::e 3i?;i.:'ication qU"2 p2.s ;-..; J. -:; . 



  Les dérives de î'¯:=-,r=.tor foss9den une activité aatitoux considérable, ils scn' tr3 peu toxiques et présentent l' ,sa:tae due ne pas provoquer toxicomanie. 



  Dans le tableau I, on compare l'activité antitoux des produits préparas dans les exemples 1 et 2 à celle d'un produit de référence, er. l'occurrence le phosphate de codéine, désigné par produit A. La réduction ie l'amplitude de la toux a été déterminée suivant la aéthode de ¯?. Cu.¯sJvZ (nrcr.exp.:ath.u. 



  Pnaroeakoàyn.215,(1952),19-2±). i=elon re ité méthode, on observe le réflexe de la toux chez '1.."l cliat endorcd. au Nusial et dont le nerf laryngé supérieur est s2is à une excitation électrique. 



  1..-..=-3ri.U 
 EMI2.2 
 
<tb> 
<tb> Produits <SEP> Dose <SEP> Réduction <SEP> de
<tb> (per <SEP> os <SEP> en <SEP> mg/kg) <SEP> l'aplitude <SEP> de <SEP> la <SEP> toux
<tb> Exemple <SEP> 1 <SEP> 6 <SEP> 48%
<tb> Exemple <SEP> 2 <SEP> 6 <SEP> 33%
<tb> 6 <SEP> 38%
<tb> 
 
 EMI2.3 
 Dans le tableau II. cr- compare la toxicité du proinit préparé dans l'exemple 1 à celle du phosphate de codéine, administrés chez le rat, par 7G= cuccal e (v .. ) ou intraveineuse (V.I.). Les chiffres indi1et la toxicité D.L.50, autr-seni dit le nombre Óe iillijrai.:-es administres par kilograi#e d' animal ui tuent 507 des animaux sc=is aux 8?sais. 



  ?ÀlEa5 II 
 EMI2.4 
 
<tb> 
<tb> Produits <SEP> Toxicité
<tb> 
 
 EMI2.5 
 "Í . -z . 1J . 1. 



  Exemule 1 75= 20J 
 EMI2.6 
 
<tb> 
<tb> A <SEP> 85 <SEP> 54
<tb> 
 

 <Desc/Clms Page number 3> 

 
 EMI3.1 
 Lè3  hv;"' :.5 3ivants illustrent l'invention, ils ne 
 EMI3.2 
 la limitent en aucune façon. 
 EMI3.3 
 



  Exemple 1. Fr :û: ru tior de la 1-phn;rl-4-(2,3-dih,yàrox;ywrop,rl)- 1ÜD2razir:e. une solution de 64)u g de 1-pineniJlpipôrazin1e dans 00 c3 d'0tlLi':0:", on ajoute une solution de 34 g de 1,2-4};::oxy- 3-hy.roxy-propane dans 50 c3 d'eau, en tsaintenani la température en dessous de 502'-. On laisse reposer la solution pendant une nuit, on l'évapore à sec sous vide et on cristallise le residu sirupeux dais.-10C, ca3 d'acétone. 



  On obtient 60 g de 1-ph4nyl-4-(2,3-àihy-lroxypropyi)pip?r3zine fondant à 1C5 C et bouillant à 2059C/1 ma Hg. 



  Le onochlorhydrate correspondant préparé en milieu alcoolique a ur. point de fusion de 142QC. 



  Exemple 2. Préparation de la 1-p-chloronhényl-4-(Z,3-dih,yârox - 
 EMI3.4 
 propyl)-pipérazine. 
 EMI3.5 
 



  On opsre comme dans l'exemple 1, m:::is en utilisant la 1-p--ihlorqJh4nj,lpipérazine au lieu de la I-phénylpip'3L zine . 
 EMI3.6 
 On obtient la 1-p-chlorophényl-4-(2,3-dihydroxypropyl)- 
 EMI3.7 
 pipsrazine qui, cristallisée dans l'isopropanol, fond à 142±C. 



  Exemple 3 . Préparation de la 1-o-cnlorophén,yl-4-( Z , 3-:îih,ydrox,yprop.vl) -r;:i.p.jrazine . 



  On opère comme dans l'exemple 1, 3is en utilisant la 1-o-chlorophé :3>lpipérazine au lieu de la 1-phénylpipérazine. 



  On obtient la 1-c-chlorophényl-4-(2,3-dihydrcxypropyl)pipérazine qui bout à lîC/0,02 me: Hg.



   <Desc / Clms Page number 1>
 
 EMI1.1
 



  ?:! s¯ Levels of 1-: p.ipr = zine
Patent 569,407 relates to derivatives of piperazine, including a substance of formula
 EMI1.2
 This product has considerable anti-cough activity
 EMI1.3
 and a few very low toxicity. However, it has the disadvantage of not being able to be packaged under all the scuhaitable pharmaceutical forces.



   The present invention relates to new
 EMI1.4
 drifts of 1 :, piprazine responding to 1. --on.ule general
 EMI1.5
 
 EMI1.6
 'la: - .. 3 Le.zaélle R represents an atcWe 2- 1 :: y: .rogen or an atone i's> 1: 1.lr: e se: rouv3nt en pcsition crthj, neta Du para.

 <Desc / Clms Page number 2>

 
 EMI2.1
 



  It relates J, a == ... <; :: to the preparation of these drives as well as the 3: of mineral acids in organic.



  Selcn:. 1 ir: ve! Lticr¯: by preparing the compounds of l- '! "' H: J.10 (I) in: ais3: - :. t react a '::' - :. 2.- ';. :?: ../ :: ') - ril,'? razine with 1,2i Oxß l: .rxj-¯7r0 =.: e, R at =: #: -. = 1 :::. :: e 3i?; i.: 'ication qU "2 p2.s; - ..; J. - :; .



  The drifts of î'¯: = -, r = .tor foss9den a considerable aatitoux activity, they scn 'very little toxic and present the, its: tae due not to cause drug addiction.



  In Table I, the anti-cough activity of the products prepared in Examples 1 and 2 is compared with that of a reference product, er. the occurrence codeine phosphate, designated by product A. The reduction ie the amplitude of the cough was determined according to the method of ¯ ?. Cu.¯sJvZ (nrcr.exp.:ath.u.



  Pnaroeakoàyn. 215, (1952), 19-2 ±). According to the method, the cough reflex is observed in '1 .. "the endorced cliat at the Nusial and whose superior laryngeal nerve is subjected to electrical excitation.



  1 ..- .. = - 3ri.U
 EMI2.2
 
<tb>
<tb> Products <SEP> Dose <SEP> Reduction <SEP> of
<tb> (per <SEP> os <SEP> in <SEP> mg / kg) <SEP> the amplitude <SEP> of <SEP> the <SEP> cough
<tb> Example <SEP> 1 <SEP> 6 <SEP> 48%
<tb> Example <SEP> 2 <SEP> 6 <SEP> 33%
<tb> 6 <SEP> 38%
<tb>
 
 EMI2.3
 In Table II. cr- compares the toxicity of the proinit prepared in Example 1 to that of codeine phosphate, administered in rats, by 7G = cuccal e (v ..) or intravenously (V.I.). The figures indi1et the toxicity D.L.50, other says the number Óe iillijrai.:- administered per kilogram of animal that kill 507 of the animals sc = is to 8 know.



  ? ATlEa5 II
 EMI2.4
 
<tb>
<tb> Products <SEP> Toxicity
<tb>
 
 EMI2.5
 "Í. -Z. 1J. 1.



  Example 1 75 = 20J
 EMI2.6
 
<tb>
<tb> A <SEP> 85 <SEP> 54
<tb>
 

 <Desc / Clms Page number 3>

 
 EMI3.1
 Lè3 hv; "': .5 3ivants illustrate the invention, they do not
 EMI3.2
 limit it in any way.
 EMI3.3
 



  Example 1. Fr: û: ru tior of 1-phn; rl-4- (2,3-dih, yàrox; ywrop, rl) - 1ÜD2razir: e. a solution of 64) µg of 1-pineniJlpipôrazin1e in 00 c3 of 0tlLi ': 0: ", a solution of 34 g of 1,2-4}; :: oxy-3-hy.roxy-propane in 50 c3 of water, with the temperature below 502 ° C. The solution is left to stand overnight, it is evaporated to dryness in vacuo and the syrupy residue is crystallized in dais.-10 ° C., ca3 of acetone.



  60 g of 1-ph4nyl-4- (2,3-aihy-lroxypropyi) pipr3zine are obtained, melting at 1C5 C and boiling at 2059C / 1 ma Hg.



  The corresponding onochlorhydrate prepared in an alcoholic medium has ur. melting point of 142QC.



  Example 2. Preparation of 1-p-chloronhenyl-4- (Z, 3-dih, yârox -
 EMI3.4
 propyl) -piperazine.
 EMI3.5
 



  The procedure is as in Example 1, m ::: is using 1-p - ihlorqJh4nj, lpiperazine instead of I-phenylpip'3L zine.
 EMI3.6
 We obtain 1-p-chlorophenyl-4- (2,3-dihydroxypropyl) -
 EMI3.7
 pipsrazine which, crystallized from isopropanol, melts at 142 ± C.



  Example 3. Preparation of 1-o-chlorophen, yl-4- (Z, 3-: ilh, ydrox, yprop.vl) -r;: i.p.jrazine.



  The procedure is as in Example 1, 3is using 1-o-chlorophy: 3> lpiperazine instead of 1-phenylpiperazine.



  1-c-chlorophenyl-4- (2,3-dihydrcxypropyl) piperazine is obtained which boils at 1 C / 0.02 me: Hg.


    

Claims (1)

R é s u m é 1 Nouveaux dérivés de la pipérazine répandant à la formule générale EMI4.1 dans laquelle R représente un atome d'hydrogène ou un atome d'halogène se trouvant en position ortho, méta ou para. SUMMARY 1 New piperazine derivatives with general formula EMI4.1 in which R represents a hydrogen atom or a halogen atom located in the ortho, meta or para position. 2 Sels d'acides minéraux ou organiques des dérives de la pipérazine définis en le. 2 Salts of mineral or organic acids of piperazine derivatives defined in. 3 Procadé de préparation de dérivés de la pipérazine définis en 1 , caractérise en ce que l'on fait réagir le l,2-époxy-3- EMI4.2 hydroxy-propane avec une 1-(R-phényl)-piprazine, R ayant la même signification qu'au 1 . 3 Process for the preparation of piperazine derivatives defined in 1, characterized in that the 1,2-epoxy-3- EMI4.2 hydroxy-propane with a 1- (R-phenyl) -piprazine, R having the same meaning as in 1. 4 En tant que produits nouveaux : EMI4.3 1-phétiyl-4-(2,3-dihyuroxypropyl)-pipàrazine , i-p-chlorophényl-4-(2,3-àihyùroxypropyl)-nipérazine , 1-O-chlorcphényl-4-(2,3-àihyàroxypropyl)-pip4razine. 4 As new products: EMI4.3 1-phétiyl-4- (2,3-dihyuroxypropyl) -pipàrazine, i-p-chlorophenyl-4- (2,3-àihyùroxypropyl) -niperazine, 1-O-chlorcphenyl-4- (2,3-àihyàroxypropyl) -pip4razine.
BE601394D BE601394A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699911A (en) * 1983-12-29 1987-10-13 Dompe' Farmaceutici S.P.A. Levo and dextro dropropizine having antitussive activity
EP0349066A1 (en) * 1988-06-25 1990-01-03 Dsm N.V. Preparation of enantiomers of dropropizine
EP0409044A3 (en) * 1989-07-20 1991-05-29 Dompe' Farmaceutici S.P.A. A process for the optical resolution of dropropizine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699911A (en) * 1983-12-29 1987-10-13 Dompe' Farmaceutici S.P.A. Levo and dextro dropropizine having antitussive activity
EP0349066A1 (en) * 1988-06-25 1990-01-03 Dsm N.V. Preparation of enantiomers of dropropizine
EP0409044A3 (en) * 1989-07-20 1991-05-29 Dompe' Farmaceutici S.P.A. A process for the optical resolution of dropropizine

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