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NO800660L - PROCEDURE FOR PREPARING PIPERIDE INGREDIENTS - Google Patents

PROCEDURE FOR PREPARING PIPERIDE INGREDIENTS

Info

Publication number
NO800660L
NO800660L NO800660A NO800660A NO800660L NO 800660 L NO800660 L NO 800660L NO 800660 A NO800660 A NO 800660A NO 800660 A NO800660 A NO 800660A NO 800660 L NO800660 L NO 800660L
Authority
NO
Norway
Prior art keywords
piperidine
formula
benzyloxy
preparing
procedure
Prior art date
Application number
NO800660A
Other languages
Norwegian (no)
Inventor
Christian Warolin
Roland Schneider
Original Assignee
Metabio Joullie Sa
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 Metabio Joullie Sa filed Critical Metabio Joullie Sa
Publication of NO800660L publication Critical patent/NO800660L/en

Links

Classifications

    • 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

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

Description

Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av 4-benzyloksy-piperidin med formel I The present invention relates to a method for the production of 4-benzyloxy-piperidine with formula I

og farmasøytisk tålbare syreaddisjonssalter derav, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er : a) 4-hydroksy-piperidin kondenseres med p-nitrobenzoyl-klorid i nærvær av et syrebindehde middel, til å gi et and pharmaceutically acceptable acid addition salts thereof, and the distinctive feature of the method according to the invention is: a) 4-hydroxy-piperidine is condensed with p-nitrobenzoyl chloride in the presence of an acid-binding agent, to give a

beskyttet piperidin, med formel IIprotected piperidine, of formula II

b) forbindelsen med formel II benzyleres med benzyl-klorid i nærvær av et kondenserende middel og et syrebindende b) the compound of formula II is benzylated with benzyl chloride in the presence of a condensing agent and an acid scavenger

middel, til å gi forbindelsen III med formelagent, to give the compound III of formula

c) aminogruppen i piperidinet frigis, og c) the amino group in the piperidine is released, and

d) om ønsket omdannes den resulterende base til et salt. d) if desired, the resulting base is converted to a salt.

Det følgende eksempel illustrerer fremstillingen av forbindelsen med formel I. The following example illustrates the preparation of the compound of formula I.

EKSEMPELEXAMPLE

a) l-p-Nitrobenzoyl-4-hydroksy-piperidina) 1-p-Nitrobenzoyl-4-hydroxy-piperidine

Til en Erlenmeyer-kolbe på 1 liter utstyrt mfed magnetisk To an Erlenmeyer flask of 1 liter equipped mfed magnetic

rørverk og anbragt i et vannbad, inneholdende en løsning av 30,34 g (0,3 mol) 4-hydroksy-piperidin og 58,04 g vannfritt kalium-karbonat (0,42 mol) i 260 ml vann tilsettes 260 kloroform. 48,43 g (0,261 mol) p-nitrobenzoyl-klorid tilsettes porsjonsvis til den omrørte reaksjonsblanding. pipework and placed in a water bath, containing a solution of 30.34 g (0.3 mol) 4-hydroxy-piperidine and 58.04 g anhydrous potassium carbonate (0.42 mol) in 260 ml of water, 260 chloroform is added. 48.43 g (0.261 mol) of p-nitrobenzoyl chloride are added in portions to the stirred reaction mixture.

Den heterogene blanding omrøres i 30 minutter ved tomtempera-tur og fortynnes så ved tilsetning av 260 ml eter. Etter omrøring i ytterligere 15 minutter avsuges bunnfallet på filter under et svakt undertrykk, hvoretter det vaskes med 5 x 50 ml vann, inntil det er fullstendig fravær av Cl ,ioner. The heterogeneous mixture is stirred for 30 minutes at room temperature and then diluted by adding 260 ml of ether. After stirring for a further 15 minutes, the precipitate is sucked off the filter under a slight negative pressure, after which it is washed with 5 x 50 ml of water, until there is a complete absence of Cl , ions.

Det blekgule produkt tørkes i vakuum i 2 til 10 timer ved oppvarming ved 40-50°C til å gi 52,39 g produkt (utbytte 80%). Smeltepunkt = 205-206°C.(Kofler-blokk). The pale yellow product is dried in vacuo for 2 to 10 hours by heating at 40-50°C to give 52.39 g of product (80% yield). Melting point = 205-206°C. (Kofler block).

b) 1-p-Nitrobenzoyl-4-benzyloksy-piperidinb) 1-p-Nitrobenzoyl-4-benzyloxy-piperidine

Under ett avtrekk tilsettes til en kraftig omrørt suspensjon Under one hood, add to a vigorously stirred suspension

av 33,21 g (0,133 mol) l-p-nitrobenzoyl-4-hydroksy-piperidin i 176 ml benzyl-klorid en o<p>pløsning av 53,2 g natrium-hydroksyd (50 vektprosent løsning. 0,665 mol) og 2,25 g TBAS (tetrabutylammonium-hydrogen-sulfat) tilsettes så porsjonsvis dertil, pga. den eksoterme karakter av reaksjonen. of 33.21 g (0.133 mol) of 1-p-nitrobenzoyl-4-hydroxy-piperidine in 176 ml of benzyl chloride a solution of 53.2 g of sodium hydroxide (50% by weight solution. 0.665 mol) and 2.25 g TBAS (tetrabutylammonium-hydrogen-sulphate) is then added in portions thereto, because the exothermic nature of the reaction.

Den godt omrørte blanding oppvarmes til 50°C i 4 timer, fortynnes så med 345 ml vann for å oppløse utfelt NaCl, og til slutt med 210 ml kloroform. The well-stirred mixture is heated to 50°C for 4 hours, then diluted with 345 ml of water to dissolve precipitated NaCl, and finally with 210 ml of chloroform.

Blandingen dékanteres. Den vandige fase ekstraheres med 100 ml CHC13og den totale organiske fase vaskes ved 3 x 100 ml vann og tørkes over natten .over MgS04. Etter filtrering fjernes kloroform under vakuum i en rotasjonsfordamper, og den resterende produktløsning i benzylklorid helles utover 1760 The mixture is decanted. The aqueous phase is extracted with 100 ml CHCl 3 and the total organic phase is washed with 3 x 100 ml water and dried overnight over MgSO 4 . After filtration, chloroform is removed under vacuum in a rotary evaporator, and the remaining product solution in benzyl chloride is poured over 1760

ml cykloheksan, under kraftig omrøring.ml of cyclohexane, with vigorous stirring.

Det resulterende meget blekgule bunnfall omrøres i omtrentThe resulting very pale yellow precipitate is stirred for approx

3 timer i blandingen, hvoretter det filtreres, vaskes med cykloheksan og tørkes vinder vakuum ved 40°C til å gi 39 ,24 g produkt (utbytte: 86,5%). Smeltepunkt = 119°C (Kofler-blokk). 3 hours in the mixture, after which it is filtered, washed with cyclohexane and dried under vacuum at 40°C to give 39.24 g of product (yield: 86.5%). Melting point = 119°C (Kofler block).

c) 4-benzyloksy-piperidin- hydrobromidc) 4-benzyloxy-piperidine hydrobromide

Til en omrørt suspensjon av 22,12 g (0,065 mol) 1-p-nitrobenzoyl-4-benzyloksy-piperidin i 390 ml 96% etanol tilsettes ION vandig kalium-hydroksyd (97,5ml/0,975 mol). Reaksjons-blandingen omrører over natten ved romtemperatur og den neste dag ved 50°C i 4 timer, under en nitrogenatmosfære. To a stirred suspension of 22.12 g (0.065 mol) of 1-p-nitrobenzoyl-4-benzyloxy-piperidine in 390 ml of 96% ethanol is added ION aqueous potassium hydroxide (97.5 ml/0.975 mol). The reaction mixture is stirred overnight at room temperature and the next day at 50°C for 4 hours, under a nitrogen atmosphere.

Etanol fjernes under vakuum i en rotasjonsfordamper (bad: 35-40°C). Resten oppløses på nytt i 160 ml vann og 60 g rent NaCl tilsettes for utsalting av produktet som ekstraheres Ethanol is removed under vacuum in a rotary evaporator (bath: 35-40°C). The residue is redissolved in 160 ml of water and 60 g of pure NaCl is added to salt out the product that is extracted

med 160 ml eter.with 160 ml of ether.

Blandingen av NaCl og natriumsaltet av p-nitrobenzosyren frafiltreres, filtratet dekanteres av og eterfasen tørkes over natten over MgS04etter ekstraksjon av den vandig fase med 3 x 160 ml eter. The mixture of NaCl and the sodium salt of the p-nitrobenzoic acid is filtered off, the filtrate is decanted off and the ether phase is dried overnight over MgSO 4 after extraction of the aqueous phase with 3 x 160 ml of ether.

Oppløsningsmidlet tørkes under vakuum, uten oppvarming. Det dannes lange blekgule nåler fra utgangsoljen og de gir 12,28 g produkt (98,8%) . The solvent is dried under vacuum, without heating. Long pale yellow needles are formed from the starting oil and they yield 12.28 g of product (98.8%).

Basen er sterkt hygroskopisk.The base is highly hygroscopic.

Den olje oppløses i 660 ml tørr de-peroksydert eter og 55 ml av en oppløsning (omtrent 1,3M) gassformet brom-hydrogensyre i tørr de-peroksydert eter tilsettes så dertil porsjonsvis The oil is dissolved in 660 ml of dry de-peroxidized ether and 55 ml of a solution (approximately 1.3 M) of gaseous hydrobromic acid in dry de-peroxidized ether is then added portionwise

(en sterkere konsentrert oppløsning, f.eks. med en konsentrasjon på omtrent 4M, kan fordelaktig anvendes) under avkjøling i et isbad. (a more highly concentrated solution, e.g. with a concentration of about 4M, can advantageously be used) while cooling in an ice bath.

Det resulterende hydrobromid-bunnfall filtreres hurtig, vaskes med eter og tørkes under vakuum, uten oppvarming. The resulting hydrobromide precipitate is quickly filtered, washed with ether and dried under vacuum, without heating.

Det tørre salt er ikke hygroskopisk.The dry salt is not hygroscopic.

Denne fremgangmsåte gir 16,75 g salt (95%).This progress yield 16.75 g of salt (95%).

Det noe beige produkt avfarges ved omkrystallisering fra omtrent 270 ml benzen (med filtrering om nødvendig i varm tilstand). Smeltepunkt = 134°C (Kofler-blokk). The somewhat beige product is decolorized by recrystallization from about 270 ml of benzene (with filtration if necessary while hot). Melting point = 134°C (Kofler block).

4-benzyloksy-piperidin og dets farmasøytisk -tålbare syrer har nyttige farmakologiske egenskaper. 4-Benzyloxy-piperidine and its pharmaceutically acceptable acids have useful pharmacological properties.

Spesielt har de en anti-spasmodisk virkning på den glatte muskulatur og er terepeutisk nyttige for behandling av arterielle (arteritis, angina pectoris), digestive, viscerale (hepatiske og nefretiske kolikker), vesikalske og uterine spasmer. In particular, they have an anti-spasmodic effect on the smooth muscles and are therapeutically useful for the treatment of arterial (arteritis, angina pectoris), digestive, visceral (hepatic and nephrotic colic), vesical and uterine spasms.

Resultatene av toksikologiske og farmakologiske undersøkelser som viser de nevnte egenskaper er gitt i det følgende. The results of toxicological and pharmacological investigations which show the aforementioned properties are given below.

a) Akutt giftigheta) Acute toxicity

LDj-q ble bestemt med Swiss NMRI mus med 4-benzyloksy-piperidin LDj-q was determined with Swiss NMRI mice with 4-benzyloxy-piperidine

hydrobromide:hydrobromide:

b) Antispasmodisk virkning b) Antispasmodic action

Testene gjennomføres med isolert duodenum fra rotter som The tests are carried out with isolated duodenum from rats that

holdes i live i oksygenert tyfode-væske ved en temperatur på 37°C (20 ml celle, Vålett type vannbad for isolerte organer). kept alive in oxygenated typhoid fluid at a temperature of 37°C (20 ml cell, Vålett type water bath for isolated organs).

Tonisitet og bevegelser av det isolerte -organ opptegnes under anvendelse av metoden i henhold til Magnus R. (Arch. Ges. Physiol. 1904, 102. 123) ved hjelp av en spenningsmåler for-bundet til en elektronisk rekorder av typen "Electromed". Tonicity and movements of the isolated organ are recorded using the method according to Magnus R. (Arch. Ges. Physiol. 1904, 102. 123) by means of a voltage meter connected to an electronic recorder of the "Electromed" type.

Antagonismen som utøves av testmaterialet undersøkes i forhold til de muskolotropiske kontrakterende virkninger av barium-kloridet. The antagonism exerted by the test material is examined in relation to the musculotropic contracting effects of the barium chloride.

Papaverin anvendes som sammenliknings-antagonistisk material. Papaverine is used as comparison-antagonistic material.

Den molare konsentrasjon av test-material som nedsetter virkningene av barium-klorid med en faktor på 50% bestemmes. The molar concentration of test material which reduces the effects of barium chloride by a factor of 50% is determined.

De oppnådde resultater er angitt i den følgende tabell. The results obtained are indicated in the following table.

Det fremgår av de oppnådde resultater at aktiviteten av 4-benzyloksy-piperidin stort sett tilsvarer aktiviteten av papaverin. It appears from the results obtained that the activity of 4-benzyloxy-piperidine largely corresponds to the activity of papaverine.

4-benzyloksy-piperidin og foretrukket dets farmasøytisk tålbare salter, tilføres mennesker oralt (typisk som kapsler inneholdende 10 mg aktiv bestanddel, 3-5 ganger daglig) eller parenteralt, typisk ved intramuskulær tilførsel (som en vandig op<p>løsning inneholdende 5 g aktiv bestanddel, 3-2 ganger daglig. 4-benzyloxy-piperidine and preferably its pharmaceutically acceptable salts, are administered to humans orally (typically as capsules containing 10 mg of active ingredient, 3-5 times daily) or parenterally, typically by intramuscular administration (as an aqueous solution containing 5 g active ingredient, 3-2 times daily.

Claims (1)

Fremgangsmåte for fremstilling av 4-benzyloksy-piperidin og dets farmasøytisk tålbare sålter, karakterisert ved : a) 4-hydroksy-piperidin kondenseres med p-nitrobenzoyl-klorid i nærvær av et .syrebindende middel, til å gi et be- skyttet piperidin II med formel Process for the preparation of 4-benzyloxy-piperidine and its pharmaceutically acceptable salts, characterized by : a) 4-hydroxy-piperidine is condensed with p-nitrobenzoyl chloride in the presence of an acid-binding agent, to give a capped piperidine II of formula b) forbindelsen med formel II benzyleres med benzyl-klorid i nærvær av et kondenserende middel og et syrebindende middel, til å gi en forbindelse med formel III b) the compound of formula II is benzylated with benzyl chloride in the presence of a condensing agent and an acid-binding agent, to give a compound of formula III c) amino-gruppen i piperidinet frigis, d) om ønsket omdannes den resulterende base til et salt.c) the amino group in the piperidine is released, d) if desired, the resulting base is converted to a salt.
NO800660A 1979-03-09 1980-03-07 PROCEDURE FOR PREPARING PIPERIDE INGREDIENTS NO800660L (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7906070A FR2450816A1 (en) 1979-03-09 1979-03-09 NOVEL PIPERIDINE DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR THERAPEUTIC APPLICATION

Publications (1)

Publication Number Publication Date
NO800660L true NO800660L (en) 1980-09-10

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ID=9222953

Family Applications (1)

Application Number Title Priority Date Filing Date
NO800660A NO800660L (en) 1979-03-09 1980-03-07 PROCEDURE FOR PREPARING PIPERIDE INGREDIENTS

Country Status (9)

Country Link
EP (1) EP0015817A1 (en)
JP (1) JPS55122761A (en)
AU (1) AU5594080A (en)
BE (1) BE882122A (en)
ES (1) ES489042A1 (en)
FR (1) FR2450816A1 (en)
GB (1) GB2044260A (en)
IT (1) IT8067364A0 (en)
NO (1) NO800660L (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE13425T1 (en) 1981-10-15 1985-06-15 Synthelabo PIPERIDINE DERIVATIVES, PROCESSES FOR THEIR PRODUCTION AND THEIR USE AS MEDICINAL PRODUCTS.
US4529730A (en) * 1981-10-21 1985-07-16 Synthelabo Piperidine derivatives, their preparation and pharmaceutical compositions containing them
GB8321157D0 (en) * 1983-08-05 1983-09-07 Fordonal Sa Piperidine derivatives

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260723A (en) * 1963-08-27 1966-07-12 Parke Davis & Co 4-phenoxy piperidines; alpha4-phenoxy piperideines

Also Published As

Publication number Publication date
FR2450816A1 (en) 1980-10-03
IT8067364A0 (en) 1980-03-07
GB2044260A (en) 1980-10-15
BE882122A (en) 1980-09-08
FR2450816B1 (en) 1981-05-22
EP0015817A1 (en) 1980-09-17
ES489042A1 (en) 1980-09-16
AU5594080A (en) 1980-09-11
JPS55122761A (en) 1980-09-20

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