CH522642A - N-(4-chloro)-cinnamoyl-(4'-hydroxy)-piperid- - ine, antiphlogistic antipyretic - Google Patents

N-(4-chloro)-cinnamoyl-(4'-hydroxy)-piperid- - ine, antiphlogistic antipyretic

Info

Publication number
CH522642A
CH522642A CH144672A CH144672A CH522642A CH 522642 A CH522642 A CH 522642A CH 144672 A CH144672 A CH 144672A CH 144672 A CH144672 A CH 144672A CH 522642 A CH522642 A CH 522642A
Authority
CH
Switzerland
Prior art keywords
formula
hydroxy
chloro
cinnamoyl
piperid
Prior art date
Application number
CH144672A
Other languages
German (de)
Inventor
Manfred Dr Kleemann
Wolfgang Dr Grell
Gerhard Dr Dahms
Hans Dr Machleidt
Albrecht Dr Eckenfels
Original Assignee
Thomae Gmbh Dr K
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 AT494669A external-priority patent/AT288388B/en
Application filed by Thomae Gmbh Dr K filed Critical Thomae Gmbh Dr K
Priority claimed from CH1604469A external-priority patent/CH522640A/en
Publication of CH522642A publication Critical patent/CH522642A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/52—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen
    • C07C57/58—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
    • C07C57/60—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/02—Preparation by ring-closure or hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
    • C07D211/38—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

New N-(4-chloro)cinnamoyl-(4'-hydroxy)-piperazine is prepared by a) reacting a cinnamic acid deriv. of formula p-Cl-C6H4-CH=CH-COX (in which X is OH, NH, mono- or dialkylamino, or a reactive group) with 4-hydroxypiperidine, or a reactive deriv. of 4-hydroxypiperidine; b) or by reacting a cpd. of formula: (in which R is lower alkyl or (R1)3-P=CH-, where R1 is aryl or alkyl) with 4-chlorobenzaldehyde.

Description

  

  
 



  Verfahren zur Herstellung von neuen   Zimtsäureamiden   
Die Erfindung betrifft ein Verfahren zur Herstellung neuer Zimtsäureamide der Formel 1
EMI1.1     
 in der Hal ein Chlor-, Brom- oder Jodatom bedeutet, das dadurch gekennzeichnet ist, dass man eine Verbindung der Formel 2 2
EMI1.2     
 in der X1 das Anion einer anorganischen Säure darstellt, mit dem Acrylsäureamid der Formel 3
EMI1.3     
 und anschliessend mit einer Base umsetzt.



   Die Umsetzung einer Verbindung der Formel 2, welche durch Diazotierung des entsprechenden Anilins hergestellt wurde, mit einer Verbindung der Formel 3 erfolgt zweckmässigerweise in saurer Lösung, z. B. in Salzsäure/Aceton, und vorteilhafterweise in Gegenwart von Kupfer-(II)-chlorid vorzugsweise bei Temperaturen zwischen 20 und 400C und anschliessende Behandlung mit einer Base, z.B. Triäthylamin, zweckmässigerweise bei erhöhter Temperatur, z.B. bei 900C (C.A. 68, 77 903 [1968]).



   Die bei dem erfindungsgemässen Verfahren verwendeten Ausgangsstoffe lassen sich nach bekannten Methoden darstellen.



   Ein Acrylsäureamid der Formel 3 lässt sich beispielsweise durch Halogenwasserstoffabspaltung aus einem entsprechenden   B-Halogenpropionsäureamid    herstellen.



   Bei dem erfindungsgemässen Verfahren erhält man in überwiegendem Masse trans-Verbindungen der Formel 1.



   Die erfindungsgemäss hergestellten neuen Zimtsäureamide der Formel 1 besitzen wertvolle pharmakologische Eigenschaften, insbesondere eine antiphlogistische und antipyretische Wirkung.



  Die Substanzen A = 4-Chlor-zimtsäure-(4-hydroxypiperidid) und B = 4-Brom-zimtsäure-(4-hydroxypiperidid) wurden hinsichtlich ihrer antiphlogistischen Wir kung im Vergleich zu C = Phenylbutazon und hinsichtlich ihrer temperatursenkenden Wir kung im Vergleich zu D = Aminopyrin und E = Phenacetin untersucht
1. Die antiphlogistische Wirkung der zu untersuchenden Substanzen wurde als antiexsudative Wirkung gegenüber dem Carrageeninödem der Rattenhinterpfote nach der Methode von Winter et   al. [Proc.    Soc. exper.



  Biol Med. 111, 544- 547 (1962)] und gegenüber dem Kaolinödem der Rattenhinterpfote nach der Methode von Hillebrecht (Arzneimittelforschung, 4,   607 - 614    [1954]) nach oraler Gabe von mindestens 3 Dosen an mindestens 14 Tieren pro Dosis getestet.



   Die Messung erfolgte nach der Methode von Doepfner und Cerletti (Int. Arch. Allergy al appl. Immun. 12,     89-97 tl958]),    es wurde die Dosis graphisch ermittelt, welche eine 35%ige Abschwächung (ED35) der jeweiligen Schwellung bewirkt:   
Carrageenin - ödem Kaolin-ödem Substanz EDs5 mg/kg EDs5 mg/kg   
A 31 55
B 51 73
C 74 62
2. Die Prüfung auf eine temperatursenkende Wirkung der zu untersuchenden Substanzen erfolgte an normothermen Ratten nach oraler Gabe von mindestens 4 Dosen an mindestens 10 Tieren pro Dosis.



   Aus den mit den verschiedenen Dosen erzielten gemittelten Werten für maximale Temperaturerniedrigung des Einzeltieres wurde durch graphische Interpolation die Dosis bestimmt, die eine Senkung der Körpertemperatur um 1,50C   (ED-1,SOG)    bewirkt:
Substanz   ED-1,SOC    mg/kg
A 5,5
B 7,0
D 70
E 80
3. Die akute Toxizität der Substanzen A bis D wurde an Gruppen zu mindestens je 10 Ratten mit mindestens 3 Dosen pro Gruppe bestimmt.

  Es wurde die   LDso,    die Dosis bei deren peroralen Verabreichung 50% der Tiere innerhalb 14 Tagen verstarben, graphisch bestimmt:
Substanz   LDso    g/kg
A   ¯5,0   
B   5,0   
C 0,98
D 1,1
E 2,3
Das nachfolgende Beispiel soll die Erfindung näher erläutern:
Beispiel    4-Brom-zimtsäure-(4-hydroxy-piperidid)   
Zu 8,4 g (0,049 Mol) 4-Bromanilin im Gemisch aus 10 ml Wasser und 10 ml konz. Salzsäure wird bei 0 bis   3CC    die Lösung von 3,4 g (0,049 Mol) Natriumnitrit in 5 ml Wasser getropft.

  Man filtriert, gibt zu der klaren Diazoniumsalzlösung 2,0 g   Kupfer-(II) -chlorid-monohy-    drat und fügt langsam 12,5 g (0,081 Mol) Acrylsäure-(4 -hydroxy-piperidid)   föl    (Rohrprodukt); hergestellt durch   HCl-Eliminierung    aus   8      -Chlor-propionsäure-(4-hydroxy-    -piperidid)mittels Triäthylamin] in 40 rnl Aceton bei   50C    zu. Man erwärmt 5 Stunden auf 25 bis   300C    bis zur Beendigung der Stickstoff-Entwicklung. Die untere Phase wird im Scheidetrichter abgetrennt (21,5 g) und mit 21,5 g Triäthylamin versetzt. Man erhitzt das Gemisch 16 Stunden unter Rückfluss, dampft i. Vak. ein, löst den Rückstand in Chloroform und extrahiert die Lösung mit verd. Salzsäure, verd. Natronlauge und   Was--    ser. 

  Aus der Chloroformlösung wird beim Einengen ein dunkles öl erhalten. Das beim Anreiben mit Essigester/Äther auskristallisierende 4-Brom-zimts,ure-(4-hydroxy-piperidid) wird unter Verwendung von Aktivkohle aus Essigester umkristallisiert.



   Ausbeute: 1,2 g (8% d. Th.); Schmp.:   157-1590C.    



  
 



  Process for the preparation of new cinnamic acid amides
The invention relates to a process for the preparation of new cinnamic acid amides of the formula 1
EMI1.1
 in which Hal denotes a chlorine, bromine or iodine atom, which is characterized in that a compound of the formula 2 2
EMI1.2
 in which X1 represents the anion of an inorganic acid with the acrylic acid amide of the formula 3
EMI1.3
 and then reacted with a base.



   The reaction of a compound of formula 2, which has been prepared by diazotization of the corresponding aniline, with a compound of formula 3 is conveniently carried out in acidic solution, e.g. In hydrochloric acid / acetone, and advantageously in the presence of copper (II) chloride, preferably at temperatures between 20 and 40 ° C. and subsequent treatment with a base, e.g. Triethylamine, conveniently at elevated temperature, e.g. at 900C (C.A. 68, 77903 [1968]).



   The starting materials used in the process according to the invention can be prepared by known methods.



   An acrylic acid amide of the formula 3 can be prepared, for example, by splitting off hydrogen halide from a corresponding B-halopropionic acid amide.



   In the process according to the invention, trans compounds of the formula 1 are predominantly obtained.



   The new cinnamic acid amides of formula 1 prepared according to the invention have valuable pharmacological properties, in particular an anti-inflammatory and anti-pyretic effect.



  The substances A = 4-chloro-cinnamic acid (4-hydroxypiperidide) and B = 4-bromo-cinnamic acid (4-hydroxypiperidide) were compared to C = phenylbutazone in terms of their anti-inflammatory effect and in terms of their temperature-lowering effect D = aminopyrine and E = phenacetin investigated
1. The anti-inflammatory effect of the substances to be examined was determined as an anti-exudative effect against the carrageenin edema of the rat hind paw by the method of Winter et al. [Proc. Soc. exper.



  Biol Med. 111, 544-547 (1962)] and tested against kaolin edema of the rat hind paw according to the Hillebrecht method (Arzneimittelforschung, 4, 607-614 [1954]) after oral administration of at least 3 doses to at least 14 animals per dose.



   The measurement was carried out according to the method of Doepfner and Cerletti (Int. Arch. Allergy al appl. Immun. 12, 89-97 tl958]); the dose was determined graphically which causes a 35% reduction (ED35) of the respective swelling :
Carrageenin - edema Kaolin edema Substance EDs5 mg / kg EDs5 mg / kg
A 31 55
B 51 73
C 74 62
2. The test for a temperature-lowering effect of the substances under investigation was carried out on normothermic rats after oral administration of at least 4 doses to at least 10 animals per dose.



   From the averaged values achieved with the various doses for the maximum decrease in temperature of the individual animal, the dose was determined by graphical interpolation that causes a decrease in body temperature by 1.50C (ED-1, SOG):
Substance ED-1, SOC mg / kg
A 5.5
B 7.0
D 70
E 80
3. The acute toxicity of substances A to D was determined in groups of at least 10 rats with at least 3 doses per group.

  The LD 50, the dose of which 50% of the animals died within 14 days of oral administration, was determined graphically:
Substance LDso g / kg
A ¯5.0
B 5.0
C 0.98
D 1.1
E 2.3
The following example is intended to explain the invention in more detail:
Example 4-bromo-cinnamic acid- (4-hydroxypiperidide)
To 8.4 g (0.049 mol) of 4-bromoaniline in a mixture of 10 ml of water and 10 ml of conc. Hydrochloric acid is added dropwise to the solution of 3.4 g (0.049 mol) of sodium nitrite in 5 ml of water at 0 to 3CC.

  It is filtered, 2.0 g of copper (II) chloride monohydrate are added to the clear diazonium salt solution and 12.5 g (0.081 mol) of acrylic acid (4-hydroxypiperidide) oil (crude product) are slowly added; produced by HCl elimination from 8-chloropropionic acid (4-hydroxy-piperidide) using triethylamine] in 40 ml of acetone at 50C. The mixture is heated to 25 to 30 ° C. for 5 hours until the evolution of nitrogen has ended. The lower phase is separated off in a separating funnel (21.5 g) and treated with 21.5 g of triethylamine. The mixture is refluxed for 16 hours and evaporated i. Vac. , dissolve the residue in chloroform and extract the solution with dilute hydrochloric acid, dilute sodium hydroxide solution and water.

  A dark oil is obtained from the chloroform solution on concentration. The 4-bromo-cinnamon, ure- (4-hydroxy-piperidide) which crystallizes out when rubbed with ethyl acetate / ether is recrystallized from ethyl acetate using activated charcoal.



   Yield: 1.2 g (8% of theory); M.p .: 157-1590C.

Claims (1)

PATENTANSPRUCH PATENT CLAIM Verfahren zur Herstellung neuer Zimtsäureamide der Formel 1 EMI2.1 in der Hal ein Chlor-, Brom- oder Jodatom bedeutet, dadurch gekennzeichnet, dass man eine Verbindung der Formel 2 EMI2.2 in der X1 das Anion einer anorganischen Säure darstellt, mit dem Acrylsäureamid der Formel 3 EMI2.3 und anschliessend mit einer Base umsetzt. Process for the preparation of new cinnamic acid amides of formula 1 EMI2.1 in which Hal denotes a chlorine, bromine or iodine atom, characterized in that a compound of the formula 2 EMI2.2 in which X1 represents the anion of an inorganic acid with the acrylic acid amide of the formula 3 EMI2.3 and then reacted with a base. UNTERANSPRÜCHE 1. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man die Umsetzung in einem Lösungsmittel durchführt. SUBCLAIMS 1. The method according to claim, characterized in that the reaction is carried out in a solvent. 2. Verfahren nach Patentanspruch und Unteranspruch 1, dadurch gekennzeichet, dass man die Umsetzung in Gegenwart eines Kupfer-(II)-halogenids durchführt. 2. The method according to claim and dependent claim 1, characterized in that the reaction is carried out in the presence of a copper (II) halide. 3. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man 4-Chlor-zimtsäure-(4-hydroxy-piperidid) herstellt. 3. The method according to claim, characterized in that 4-chloro-cinnamic acid (4-hydroxy-piperidide) is produced. 4. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man 4- Brom-zimtsäure-(4.hydroxy-pipe- ridid) herstellt. 4. The method according to claim, characterized in that 4-bromocinnamic acid (4th hydroxy-piperidide) is produced.
CH144672A 1969-05-23 1969-10-28 N-(4-chloro)-cinnamoyl-(4'-hydroxy)-piperid- - ine, antiphlogistic antipyretic CH522642A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT494669A AT288388B (en) 1969-05-23 1969-05-23 Process for the preparation of a new cinnamic acid amide
CH1604469A CH522640A (en) 1967-12-01 1969-10-28 Cinnamic acid amide

Publications (1)

Publication Number Publication Date
CH522642A true CH522642A (en) 1972-06-30

Family

ID=25601705

Family Applications (8)

Application Number Title Priority Date Filing Date
CH144572A CH532043A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144972A CH522645A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144672A CH522642A (en) 1969-05-23 1969-10-28 N-(4-chloro)-cinnamoyl-(4'-hydroxy)-piperid- - ine, antiphlogistic antipyretic
CH144872A CH522644A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH145172A CH532045A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144772A CH522643A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144472A CH532042A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH145072A CH532044A (en) 1967-12-01 1969-10-28 Process for the preparation of new cinnamic acid amides

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CH144572A CH532043A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144972A CH522645A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides

Family Applications After (5)

Application Number Title Priority Date Filing Date
CH144872A CH522644A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH145172A CH532045A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144772A CH522643A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH144472A CH532042A (en) 1969-05-23 1969-10-28 Process for the preparation of new cinnamic acid amides
CH145072A CH532044A (en) 1967-12-01 1969-10-28 Process for the preparation of new cinnamic acid amides

Country Status (1)

Country Link
CH (8) CH532043A (en)

Also Published As

Publication number Publication date
CH522645A (en) 1972-06-30
CH532043A (en) 1972-12-31
CH532044A (en) 1972-12-31
CH532045A (en) 1972-12-31
CH522643A (en) 1972-06-30
CH522644A (en) 1972-06-30
CH532042A (en) 1972-12-31

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