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DE1283241B - N- (ªÏ-phenoxyalkyl) -4-alkoxy-4-phenyl-piperidines, their acid addition salts and processes for their preparation - Google Patents

N- (ªÏ-phenoxyalkyl) -4-alkoxy-4-phenyl-piperidines, their acid addition salts and processes for their preparation

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Publication number
DE1283241B
DE1283241B DEN21349A DEN0021349A DE1283241B DE 1283241 B DE1283241 B DE 1283241B DE N21349 A DEN21349 A DE N21349A DE N0021349 A DEN0021349 A DE N0021349A DE 1283241 B DE1283241 B DE 1283241B
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Prior art keywords
parts
general formula
phenylpiperidine
hydrochloride
mixture
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DEN21349A
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German (de)
Inventor
Paul Adriaan Jan Janssen
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Janssen Pharmaceutica NV
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Janssen Pharmaceutica NV
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06Heterocyclic 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
    • C07D211/08Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06Heterocyclic 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
    • C07D211/08Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18Heterocyclic 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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06Heterocyclic 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
    • C07D211/36Heterocyclic 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
    • C07D211/40Oxygen atoms
    • C07D211/44Oxygen atoms attached in position 4
    • C07D211/46Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D211/00Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06Heterocyclic 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
    • C07D211/36Heterocyclic 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
    • C07D211/56Nitrogen atoms
    • C07D211/58Nitrogen atoms attached in position 4

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

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

Deutsche Kl.:German class:

Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:
Number:
File number:
Registration date:
Display day:

C07dC07d

AOIk ·AOIk

12 ρ-1/01
30 h-2/36
12 ρ -1/01
30 h-2/36

P 12 83 241.6-44 (N 21349)P 12 83 241.6-44 (N 21349)

20. März 1962March 20, 1962

21. November 1968November 21, 1968

Gegenstand der Erfindung sind N-(r»-Phenoxyalkyl)-4-alkoxy-4-phenylpiperidine der allgemeinen Formel IThe invention relates to N- (r »-phenoxyalkyl) -4-alkoxy-4-phenylpiperidines of the general formula I.

in der R einen Methyl-, Äthyl- oder Propylrest und (0 // eine der Zahlen 2, 3 oder 4 bedeutet, deren Säureadditionssalze sowie ein Verfahren zu ihrer Herstellung. in which R is a methyl, ethyl or propyl radical and (0 // is one of the numbers 2, 3 or 4, their acid addition salts and a process for their preparation.

Diese Verbindungen sind wirksame Hemmstoffe für durch Pentamethylentetrazol hervorgerufene ,5 Krämpfe. Diese Wirksamkeit ist unerwartet, da die entsprechenden Alkohole, nämlich die N-(fj-Phenoxyalkyl)-4-phenylpiperidin-4-ole, diese Antikrampfwirksamkeit nicht besitzen.These compounds are potent inhibitors of induced pentamethylenetetrazole, 5 cramps. This activity is unexpected because the corresponding alcohols, namely the N- (fj-phenoxyalkyl) -4-phenylpiperidin-4-ols, do not have this anti-seizure activity.

Gegenüberstellung der therapeutischen Eigenschäften der erfindungsgemäßen Verbindungen der allgemeinen Formel IComparison of the therapeutic properties of the compounds of the general formula I according to the invention

O-(CH2),,O- (CH 2 ) ,,

mit der Vergleichssubstanz 5-Phenyl-5-äthylbarbitursäure. with the comparison substance 5-phenyl-5-ethylbarbituric acid.

1111 Niederes
Alkyl
Lower
Alkyl
Pcntamothylen-
tetrazohest:
ED51, in
mg kg s. c.
Pcntamothylene
tetrazohest:
ED 51 , in
mg kg sc
Toxizitäl
bei Mäusen
Toxicity
in mice
Therapeuti
sches
Verhältnis
Therapeuti
sches
relationship
■)■) CH:! CH :! 1515th >160*)> 160 *) >11> 11 33 CH:5 CH: 5 1212th >160*)> 160 *) >13> 13 44th CH3 CH 3 1010 >320*)> 320 *) >32> 32 ->-> C2H5 C 2 H 5 2020th 180180 9,09.0 33 CiH5 CiH 5 8.58.5 200200 2424 44th C2H5 C 2 H 5 2525th 210210 8.48.4 22 nGjHvnGjHv 1818th >160*)> 160 *) >8.9> 8.9 33 nCsHTnCsHT 9.09.0 >160*)> 160 *) >18> 18 44th nG)HT nG) H T 1515th >160*)> 160 *) >11> 11 5-Äthyl-
5-phenyl-
barbitursäure
(Phenobarbital)
5-ethyl
5-phenyl-
barbituric acid
(Phenobarbital)
1818th 150150 8,38.3

N-(w-Phenoxyalkyl)-4-alkoxy-4-phenylpiperidine, ihre Säureadditionssalze sowie
Verfahren zu ihrer Herstellung
N- (w-phenoxyalkyl) -4-alkoxy-4-phenylpiperidines, their acid addition salts and
Process for their manufacture

Anmelder:Applicant:

Janssen Pharmaceutica,Janssen Pharmaceutica,

Naamlozevennootschap, Beerse (Belgien)Naamlozevennootschap, Beerse (Belgium)

Vertreter:Representative:

Dipl.-Chem. Dr. Arthur UllrichDipl.-Chem. Dr. Arthur Ullrich

und Dipl.-Chem. Dr. Thurmod Ullrich,and Dipl.-Chem. Dr. Thurmod Ullrich,

Patentanwälte, 6900 HeidelbergPatent Attorneys, 6900 Heidelberg

Als Erfinder benannt:Named as inventor:

Paul Adriaan Jan Janssen, Vosselaar, TurnhoutPaul Adriaan Jan Janssen, Vosselaar, Turnhout

(Belgien)(Belgium)

Beanspruchte Priorität:Claimed priority:

V. St. v. Amerika vom 22. März 1961 (97 424) -V. St. v. America March 22, 1961 (97 424) -

*l Höchste getestete Dosis ohne tödliche Wirkung.* l Highest dose tested with no lethal effect.

TestbeschreibungTest description

(Durch Pentamethylentetrazol erzeugte
Anfälle bei Mäusen)
(Generated by pentamethylenetetrazole
Seizures in mice)

Es wurden erwachsene Albinomäuse von- 18 bis g Körpergewicht verwendet, um die krampfhemmende Wirkung der erfindungsgemäßen Verbindungen zu erproben.Adult albino mice weighing -18 to g. Body weight were used to give the anticonvulsant To test the effect of the compounds according to the invention.

Die krampfartigen Anfälle wurden durch intravenöse Einspritzung einer 5°/oigen wäßrigen Lösung von Pentamethylentetrazol bei einer Geschwindigkeit von 0,0625 ml je 10 Sekunden durch die Schwanzvene ausgelöst.The seizures were cured by intravenous injection of a 5% aqueous solution of pentamethylenetetrazole at a rate of 0.0625 ml per 10 seconds through the tail vein triggered.

Die zu prüfende erfindungsgemäße Verbindung wurde auf subkutanem Wege (0,1 ml einer wäßrigen Lösung auf 10 g Körpergewicht) 1 Stunde vor der Verabfolgung des krampfauslösenden Mittels an die Mäuse verabreicht.The compound according to the invention to be tested was administered subcutaneously (0.1 ml of an aqueous Solution to 10 g body weight) 1 hour before the administration of the anticonvulsant agent to the Administered to mice.

Die krampfhemmende Wirkung jeder Verbindung wurde statistisch (P <0,05) unter Anwendung des »Kolmogorov-Smirnov-Zweiprobentests« (Siegel, S., Nonparametric Statistics for the Behavioural Sciences, 1956, S. 127) zusammengestellt. Die ED.50-Werte geben die Dosen (in mg/kg) an, die 50% der Tiere gegen die durch Pentamethylentetrazol erzeugten Anfälle schützen. (Literatur: Chen, G. and Bohner, B., J. Pharmacol., 117, 142 [1956].)The anticonvulsant effect of each compound was statistically (P <0.05) using the "Kolmogorov-Smirnov two-sample tests" (seal, S., Nonparametric Statistics for the Behavioral Sciences, 1956, p. 127). The ED.50 values indicate the doses (in mg / kg) produced by 50% of the animals against those produced by pentamethylenetetrazole Protecting seizures. (Literature: Chen, G. and Bohner, B., J. Pharmacol., 117, 142 [1956].)

809 638/1707809 638/1707

Die erfindungsgemäßen basischen Verbindungen bilden nichttoxische Säureadditionssalze mit einer Anzahl organischer und anorganischer Säuren, wie Schwefel-, Phosphor-, Chlorwasserstoff-, Bromwasserstoff-, Jodwasserstoff-, Sulfamin-, Citronen-, Milch-, Malein-, Äpfel-, Bernstein-, Wein-, Zimt-,', Essig-, Benzoe-, Glukon- und Ascorbinsäure.The basic compounds of the invention form non-toxic acid addition salts with a Number of organic and inorganic acids, such as sulfur, phosphorus, hydrogen chloride, hydrogen bromide, Hydrogen iodide, sulfamine, lemon, milk, male, apple, amber, wine, cinnamon, ', Acetic, benzoic, gluconic and ascorbic acids.

Die erfindungsgemäßen Verbindungen können durch Kondensation des entsprechenden w-Phenoxyalkylhalogenids mit einem 4-Alkoxy-4-phenylpiperidin hergestellt werden. Die Reaktion wird in einem geeigneten inerten Lösungsmittel, wie z. B. 4-Methyl-2-pentanol oder Toluol, ausgeführt. Die Reaktion kann durch Erhitzen der Mischung bei atmosphärischem Druck oder in zugeschmolzenem Rohr beschleunigt werden.The compounds according to the invention can be prepared by condensation of the corresponding w-phenoxyalkyl halide with a 4-alkoxy-4-phenylpiperidine. The response is in a suitable inert solvent, such as. B. 4-methyl-2-pentanol or toluene performed. the Reaction can be carried out by heating the mixture at atmospheric pressure or in sealed Tube to be accelerated.

Die Herstellung der neuen Verbindungen wird an folgenden Beispielen erläutert.The preparation of the new compounds is illustrated by the following examples.

Beispiell 2Q Example 2Q

Eine wäßrige Lösung von 6,83 Teilen 4-Methoxy-4-phenylpiperidin-hydrochlorid wird alkalisch gemacht und mit Benzol extrahiert. Nach dem Abdampfen des Lösungsmittels wird der Rückstand in 120 Teilen 4 - Methyl - 2 - pentanon zusammen mit 8,4 Teilen l-Brom-2-phenoxyäthan, 9,5 Teilen Natriumcarbonat und 0,1 Teil Kaliumiodid gelöst. Die Mischung wird 40 Stunden unter Rückfluß gehalten und heiß filtriert. Das Lösungsmittel wird aus dem Filtrat abgedampft und der ölige Rückstand in 400 Teilen wasserfreiem Diisopropyläther gelöst. Durch Einleiten von Chlorwasserstoffgas in die ätherische Lösung wird das Hydrochlorid niedergeschlagen, das abfiltriert und aus 2-Propanol umkristallisiert wird. Man erhält so das l-(^-Phenoxyäthyl) - 4 - methoxy -A- phenylpiperidin - hydrochlorid. Schmelzpunkt 207,5 bis 208,20C. Die freie Base dieser Verbindung hat die FormelAn aqueous solution of 6.83 parts of 4-methoxy-4-phenylpiperidine hydrochloride is made alkaline and extracted with benzene. After evaporation of the solvent, the residue is dissolved in 120 parts of 4 - methyl - 2 - pentanone together with 8.4 parts of 1-bromo-2-phenoxyethane, 9.5 parts of sodium carbonate and 0.1 part of potassium iodide. The mixture is refluxed for 40 hours and filtered hot. The solvent is evaporated from the filtrate and the oily residue is dissolved in 400 parts of anhydrous diisopropyl ether. By introducing hydrogen chloride gas into the ethereal solution, the hydrochloride is precipitated, which is filtered off and recrystallized from 2-propanol. Is obtained as the l - (^ - phenoxyethyl) - 4 - methoxy -A- phenylpiperidin - hydrochloride. Melting point 207.5 to 208.2 0 C. The free base of this compound has the formula

4-Methyl-2-pentanon wird gerührt und 50 Stunden unter Rückfluß gehalten. Die heiße Reaktionsmischung wird filtriert und das Lösungsmittel aus dem Filtrat abgedampft. Eine Lösung des Rückstands in 2-Propanol wird mit einer Lösung von 2,1 Teilen Oxalsäure-dihydrat in 300 Teilen 2-Propanol gemischt. Der sich bildende Niederschlag besteht aus l-(/?-Phenoxyäthyl)-4-propoxy-4-phenylpiperidin-oxalat, Schmelzpunkt 174 bis 176,4° C.4-methyl-2-pentanone is stirred and refluxed for 50 hours. The hot reaction mixture is filtered and the solvent is removed evaporated from the filtrate. A solution of the residue in 2-propanol is mixed with a solution of 2.1 parts of oxalic acid dihydrate mixed in 300 parts of 2-propanol. The precipitate that forms consists of l - (/? - phenoxyethyl) -4-propoxy-4-phenylpiperidine oxalate, Melting point 174 to 176.4 ° C.

B eisp iel 4Example 4

Aus' einer wäßrigen Lösung von 11,5 Teilen 4-Methoxy-4-phenylpiperidin-hydrochlorid wird die Base durch Alkalischmachen mit Natriumhydroxyd in Freiheit gesetzt. Die erhaltene Mischung wird mit Toluol extrahiert, das Lösungsmittel aus der Toluollösung abgedampft und der Rückstand in einem zugeschmolzenen Rohr mit 4,3 Teilen 1-Chlor-3-phenoxypropan und 0,1 Teil Kaliumiodid in 120 Teilen wasserfreiem Toluol 88 Stunden auf 1500C erhitzt. Die gekühlte Reaktionsmischung wird mit Wasser gewaschen und über Magnesiumsulfat getrocknet. Nach dem Abdampfen des Lösungsmittels wird der Rückstand in 32 Teilen Petroläther gelöst und 50 Teile 1 : 1 verdünnter Chlorwasserstoffsäure zugesetzt. Der sich bildende Niederschlag wird abfiltriert, aus Wasser umkristallisiert und stellt l-(y-Phenöxypropyl)-4-methoxy-4-phenylpiperidin-hydrochlorid vom Schmelzpunkt 219 bis 22O0C dar. Die freie Base dieses Produkts hat die FormelThe base is liberated from an aqueous solution of 11.5 parts of 4-methoxy-4-phenylpiperidine hydrochloride by making it alkaline with sodium hydroxide. The mixture obtained is extracted with toluene, the solvent from the toluene solution evaporated and the residue in a sealed tube with 4.3 parts of 1-chloro-3-phenoxypropane and 0.1 part of potassium iodide in 120 parts of anhydrous toluene, 88 hours at 150 0 C. heated. The cooled reaction mixture is washed with water and dried over magnesium sulfate. After evaporation of the solvent, the residue is dissolved in 32 parts of petroleum ether and 50 parts of 1: 1 dilute hydrochloric acid are added. The precipitate which forms is filtered off, recrystallised from water and provides l- (y-Phenöxypropyl) -4-methoxy-4-phenylpiperidine hydrochloride of melting point 219 to 22O 0 C. The free base of this product has the formula

OCH,OCH,

OCH, CH, CH, — NOCH, CH, CH, - N

Beispiel 5Example 5

OCH,OCH,

OCH2CH2 OCH 2 CH 2

Beispiel2Example2

Eine Mischung aus 8,04 Teilen l-Brom-2-phenoxyäthan, 7,2"Teilen 4-Äthoxy-4-phenylpiperidin, isoliert aus dem Hydrochlorid durch Verdampfen des Lösungsmittels aus der benzolischen Lösung einer wäßrigen alkalischen Lösung des Salzes, 10,6 Teilen Natriumcarbonat und 0,1 Teil Kaliumjodid in 280 Teilen 4-Methyl-2-pentanon wird gerührt und etwa 100 Stunden unter Rückfluß gehalten. Die Reaktionsmischüng wird heiß filtriert und das Lösungsmittel aus dem Filtrat abgedampft. Der ölige Rückstand wird in 560 Teilen Diisopropyläther gelöst und Chlorwasserstoffgas in diese Lösung eingeleitet. Das niedergeschlagene Hydrochlorid wird abfiltriert, aus Äthylacetat umkristallis'iert und stellt l-(ß- Phenoxyäthyl) - 4 - äthoxy - 4 - phenylpiperidinhydrochlorid vom Schmelzpunkt 147 bis 148 0C dar.A mixture of 8.04 parts of 1-bromo-2-phenoxyethane, 7.2 "parts of 4-ethoxy-4-phenylpiperidine, isolated from the hydrochloride by evaporation of the solvent from the benzene solution of an aqueous alkaline solution of the salt, 10.6 Parts of sodium carbonate and 0.1 part of potassium iodide in 280 parts of 4-methyl-2-pentanone are stirred and refluxed for about 100 hours. The reaction mixture is filtered hot and the solvent is evaporated from the filtrate. The oily residue is dissolved in 560 parts of diisopropyl ether and hydrogen chloride gas is introduced into this solution, the precipitated hydrochloride is filtered off, umkristallis'iert of ethyl acetate and is l- (.beta.-phenoxyethyl) -. 4 - ethoxy - 4 - phenylpiperidine hydrochloride of melting point 147-148 0 C represents.

B eispiel 3Example 3

Eine Mischung aus' 8,05 Teilen l-Brom-2-phenoxyäthan, 7,66 Teilen 4-Propoxy-4-phenylpiperidin, isoliert aus dem Hydrochlorid, 10,6 Teilen Natriumcarbonat und 0,1 Teil Kaliumiodid in 280 Teilen Eine Mischung aus 3,3 Teilen l-Chlor-3-phenoxypropan, 3,6 Teilen 4-Äthoxy-4-phenylpiperidin, isoliert aus dem Hydrochlorid, 5,3 Teilen Natriumcarbonat und 0,1 Teil Kaliumiodid in 280 Teilen 4-Methyl-2-pentanon wird gerührt und 50 Stunden unter Rückfluß gehalten. Die gekühlte Reaktionsmischung wird filtriert und das Lösungsmittel aus dem Filtrat abgedampft. Der Rückstand wird in 400 Teilen Diisopropyläther gelöst. Durch Einleiten von Chlorwasserstoffgas in die ätherische Lösung fällt das Hydrochlorid aus, das abfiltriert und aus Äthylacetat umkristallisiert wird. Man erhält so 1 - (y- Phenoxypropyl) - 4 - äthoxy - 4 - phenylpiperidinhydrochlorid, Schmelzpunkt 173 bis 174,50C.A mixture of 8.05 parts of 1-bromo-2-phenoxyethane, 7.66 parts of 4-propoxy-4-phenylpiperidine, isolated from the hydrochloride, 10.6 parts of sodium carbonate and 0.1 part of potassium iodide in 280 parts 3.3 parts of 1-chloro-3-phenoxypropane, 3.6 parts of 4-ethoxy-4-phenylpiperidine, isolated from the hydrochloride, 5.3 parts of sodium carbonate and 0.1 part of potassium iodide in 280 parts of 4-methyl-2-pentanone is stirred and refluxed for 50 hours. The cooled reaction mixture is filtered and the solvent is evaporated from the filtrate. The residue is dissolved in 400 parts of diisopropyl ether. By introducing hydrogen chloride gas into the ethereal solution, the hydrochloride precipitates, which is filtered off and recrystallized from ethyl acetate. One obtains 1 - (y-phenoxypropyl) - 4 - ethoxy - 4 - phenylpiperidine, mp 173 to 174.5 0 C.

B e i s ρ i e 1 6B e i s ρ i e 1 6

Eine Mischung aus 6,6 Teilen l-Chlor-3-phenoxypropan, 7,66 Teilen 4-Propoxy-4-phenylpiperidin, isoliert aus dem Hydrochlorid, 10,6 Teilen Natriumcarbonat und 0,1 Teil Kaliumiodid in 280 Teilen 4-Methyl-2-pentanon wird gerührt und 50-Stunden unter Rückfluß gehalten. Die Reaktionsmischung wird abfiltriert und das Lösungsmittel aus dem Filtrat abgedampft: Chlorwasserstoffgas wirdiri die ätherische Lösung des Rückstandes eingeleitet. Beim Stehenlassen fällt l-(y-Phenoxypropyl)-4-propoxy-4-phenylpiperidin-hydrochlorid aus der ätherischen Lösung aus. Das Produkt schmilzt bei 168,5 bis 169,50C.A mixture of 6.6 parts of 1-chloro-3-phenoxypropane, 7.66 parts of 4-propoxy-4-phenylpiperidine, isolated from the hydrochloride, 10.6 parts of sodium carbonate and 0.1 part of potassium iodide in 280 parts of 4-methyl 2-pentanone is stirred and refluxed for 50 hours. The reaction mixture is filtered off and the solvent is evaporated from the filtrate: hydrogen chloride gas is introduced into the ethereal solution of the residue. When left to stand, 1- (γ-phenoxypropyl) -4-propoxy-4-phenylpiperidine hydrochloride precipitates from the ethereal solution. The product melts at 168.5 to 169.5 0 C.

Beispiel 7Example 7

Aus 11,5 Teilen 4 - Methoxy - 4 - phenylpiperidinhydrochlorid wird die Base gemäß Beispiel 4 in Freiheit gesetzt. Die rohe Base wird mit 4,6 Teilen 1 -Chlor-4-phenoxybutan, 0,1 Teil Kaliumiodid und 120 Teilen wasserfreiem Toluol gemischt und in einem zugeschmolzenen Rohr 92 Stunden auf 1500C erhitzt. Die gekühlte Reaktionsmischung wird mit Wasser gewaschen und das organische Lösungsmittel abgedampft. Der Rückstand wird mit 82 Teilen Petroläther behandelt und 50 Teile 1 : 1 verdünnter Chlorwasserstoffsäure zugesetzt. Der ausfallende Niederschlag wird abfiltriert, aus Wasser umkristallisiert und stellt 1 - (<) - Phenoxybutyl) - 4 - methoxy-· 4-phenylpiperidin-hydrochlorid vom Schmelzpunkt 196 bis 1970C dar. Die freie Base dieser Verbindung hat die FormelThe base according to Example 4 is liberated from 11.5 parts of 4 - methoxy - 4 - phenylpiperidine hydrochloride. The crude base is mixed with 4.6 parts of 1-chloro-4-phenoxybutane, 0.1 part of potassium iodide and 120 parts of anhydrous toluene and heated to 150 ° C. for 92 hours in a sealed tube. The cooled reaction mixture is washed with water and the organic solvent is evaporated. The residue is treated with 82 parts of petroleum ether and 50 parts of 1: 1 dilute hydrochloric acid are added. The precipitate is filtered off, recrystallised from water and provides 1 - (<) - phenoxybutyl) - 4 -. Methoxy- · 4-phenylpiperidine hydrochloride of melting point 196-197 0 C represents The free base of this compound has the formula

OCH2CH2CH2CH2 — NOCH 2 CH 2 CH 2 CH 2 -N

carbonat und 0,1 Teil Kaliumjodid in 280 Teilen 4-Methyl-2-pentanon wird gerührt und 50 Stunden unter Rückfluß gehalten. Die heiße Reaktionsmischung wird filtriert und das Lösungsmittel aus dem Filtrat abgedampft. Zu einer Lösung des Rückstandes in 2-Propanol wird eine Lösung von 3,5 Teilen Oxalsäure-dihydrat in 320 Teilen 2-Propanol zugesetzt. Beim Stehen bei Raumtemperatur fällt - (() - Phenoxybutyl) - 4 - propoxy- 4- phenylpiperidinoxalat vom Schmelzpunkt 191,8 bis 192,6°C aus.carbonate and 0.1 part of potassium iodide in 280 parts of 4-methyl-2-pentanone is stirred and refluxed for 50 hours. The hot reaction mixture is filtered and the solvent is evaporated from the filtrate. A solution of 3.5 parts of oxalic acid dihydrate in 320 parts of 2-propanol is added to a solution of the residue in 2-propanol. When standing at room temperature, - ( () - phenoxybutyl) - 4 - propoxy- 4-phenylpiperidine oxalate with a melting point of 191.8 to 192.6 ° C. precipitates.

Claims (3)

Patentansprüche:Patent claims: 1. N - {c> - Phenoxyalkyl) - 4 - alkoxy -A- phenylpiperidine der allgemeinen Formel I1. N - {c> - phenoxyalkyl) - 4 - alkoxy -A- phenylpiperidines of the general formula I Beispiel 8Example 8 Eine Mischung aus 3,7 Teilen l-Chlor^-plienoxybutan, 3,6 Teilen 4-Äthoxy-4-phenylpiperidin, isoliert aus dem Hydrochlorid, 5,3 Teilen Natriumcarbonat und 0,1 Teil Kaliumjodid in 280 Teilen 4-Methyl-2-pentanon wird gerührt und 50 Stunden unter Rückfluß gehalten. Die gekühlte Reaktionsmischung wird abfiltriert und das Lösungsmittel aus dem Filtrat abgedampft. Der Rückstand wird mit einer Mischung aus 400 Teilen Diisopropyläther und 40 Teilen 2-Propanol behandelt. Der sich bildende Niederschlag wird abfiltriert und Chlorwasserstoffgas in das Filtrat eingeleitet. Das Lösungsmittel wird aus dem Filtrat abgedampft, der Rückstand zuerst aus 2-Propanol und dann aus Äthylacetat umkristallisiert. Man erhält so l-(o-Phenoxybutyl)-4-äthoxy-4-phenylpiperidin-hydrochlorid, Schmelzpunkt 136 bis 138,8°C.A mixture of 3.7 parts of l-chloro ^ -plienoxybutane, 3.6 parts of 4-ethoxy-4-phenylpiperidine, isolated from the hydrochloride, 5.3 parts of sodium carbonate and 0.1 part of potassium iodide in 280 parts of 4-methyl-2-pentanone is stirred and 50 hours held under reflux. The cooled reaction mixture is filtered off and the solvent is removed evaporated from the filtrate. The residue is with a mixture of 400 parts of diisopropyl ether and Treated 40 parts of 2-propanol. The precipitate which forms is filtered off and hydrogen chloride gas introduced into the filtrate. The solvent is evaporated from the filtrate, the residue first recrystallized from 2-propanol and then from ethyl acetate. This gives l- (o-phenoxybutyl) -4-ethoxy-4-phenylpiperidine hydrochloride, Melting point 136-138.8 ° C. Beispiel 9Example 9 Eine Mischung aus 7,1 Teilen l-Chlor-4-phenoxybutan, 7,66 Teilen 4 - Propoxy - 4 - phenylpiperidin, isoliert aus dem Hydrochlorid, 10,6 Teilen Natrium-A mixture of 7.1 parts of l-chloro-4-phenoxybutane, 7.66 parts of 4 - propoxy - 4 - phenylpiperidine, isolated from the hydrochloride, 10.6 parts of sodium 3030th 3535 4040 4545 in der R einen Methyl-, Äthyl- oder Propylrest und η eine der Zahlen 2, 3 oder 4 bedeutet, und deren Säureadditionssalze.in which R is a methyl, ethyl or propyl radical and η is one of the numbers 2, 3 or 4, and their acid addition salts. 2. Verfahren zur Herstellung von N-(o;-Phenoxyalkyl)-4-alkoxy-4-phenylpiperidine der allgemeinen Formel I, dadurch gekennzeichnet, daß man eine Verbindung der allgemeinen Formel II2. Process for the preparation of N- (o; -phenoxyalkyl) -4-alkoxy-4-phenylpiperidines of the general formula I, characterized in that that a compound of the general formula II HNHN in der R einen Methyl-, Äthyl- oder Propylrest bedeutet, mit einer Verbindung der allgemeinen Formel IIIin which R is a methyl, ethyl or propyl radical, with a compound of the general Formula III O —- (CH2), — Halogen (III)O - (CH 2 ), - halogen (III) in der η eine der Zahlen 2, 3 oder 4 bedeutet, in Gegenwart eines inerten organischen Lösungsmittels erhitzt.in which η is one of the numbers 2, 3 or 4, heated in the presence of an inert organic solvent. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man eine Verbindung der allgemeinen Formel I mit einer Säure in das entsprechende pharmazeutisch wirksame Säureadditionssalz überführt.3. The method according to claim 1 and 2, characterized in that there is a compound of general formula I with an acid into the corresponding pharmaceutically active acid addition salt convicted. SO» 638/1707 11.68 O Bundesdruckeroi BerlinSO »638/1707 11.68 O Bundesdruckeroi Berlin
DEN21349A 1961-03-22 1962-03-20 N- (ªÏ-phenoxyalkyl) -4-alkoxy-4-phenyl-piperidines, their acid addition salts and processes for their preparation Pending DE1283241B (en)

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