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DE2309986A1 - N-benzoyl-4-dialkylaminoethoxyanilines - antispasmodics etc - Google Patents

N-benzoyl-4-dialkylaminoethoxyanilines - antispasmodics etc

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Publication number
DE2309986A1
DE2309986A1 DE19732309986 DE2309986A DE2309986A1 DE 2309986 A1 DE2309986 A1 DE 2309986A1 DE 19732309986 DE19732309986 DE 19732309986 DE 2309986 A DE2309986 A DE 2309986A DE 2309986 A1 DE2309986 A1 DE 2309986A1
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Prior art keywords
benzoyl
phenylamine
bromide
aminophenol
diethylaminoethoxy
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DE19732309986
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German (de)
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Mario Prof Ghelardoni
Vittorio Dr Pestellini
Nicola Dr Pisanti
Giovanna Dr Volterra
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A Menarini SAS
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A Menarini SAS
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Priority to DE19732309986 priority Critical patent/DE2309986A1/en
Priority to JP3312873A priority patent/JPS49126643A/ja
Priority to BE129408A priority patent/BE797498A/en
Publication of DE2309986A1 publication Critical patent/DE2309986A1/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/16Amides, e.g. hydroxamic acids
    • A61K31/165Amides, e.g. hydroxamic acids having aromatic rings, e.g. colchicine, atenolol, progabide
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/12Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compounds of formulae (I), (II) and (III) are new: (R= H, 1-8C alkyl or aralkyl; R1= 1-2C alkyl; X= Br, Cl, I, or sulphate; R2= 1-8C alkyl or aralkyl).

Description

N-(o-Hydroxybenzoyl)-p-(2-dialkylaminoäthoxy)-phenylamine sowie o-substituierte Derivate und quartäre Salze derselben Die Erfindung betrifft N-(o-Hydroxybenzoyl)-p-(2-dialkylaminoäthoxy) -phenylamine sowie o-substituierte Derivate derselben der allgemeinen Formel in der R ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 8 Kohlenstoffatomen oder eine Arylalkylgruppe wie Benzyl, Phenyläthyl und Phenylpropyl und R1 eine Alkylgruppe mit 1 oder 2 gohlenstoffatomen bedeuten.N- (o-Hydroxybenzoyl) -p- (2-dialkylaminoethoxy) -phenylamines and o-substituted derivatives and quaternary salts thereof. The invention relates to N- (o-hydroxybenzoyl) -p- (2-dialkylaminoethoxy) -phenylamines and o-substituted ones Derivatives thereof of the general formula in which R is a hydrogen atom or an alkyl group with 1 to 8 carbon atoms or an arylalkyl group such as benzyl, phenylethyl and phenylpropyl and R1 is an alkyl group with 1 or 2 carbon atoms.

Die Erfindung betrifft weiterhin quartäre Salze der genannten Phenylamine bzw. der betreffenden genannten Derivate der allgemeinen Formel in der R und R1 wie oben definiert sind und X ein Anion wie Bromid, Chlorid, Jodid oder Sulfat ist.The invention further relates to quaternary salts of the phenylamines mentioned or the respective derivatives mentioned of the general formula in which R and R1 are as defined above and X is an anion such as bromide, chloride, iodide or sulfate.

Die Erfindung betrifft weiterhin N-/ o-Alkyloxy (oder -Arylalkyloxy)]-benzoyl-p-aminophenole. Diese Verbindungen sind Zwischenprodukte zur Herstellung der Verbindungen der allgemeinen Formel (I) und weisen die folgende allgemeine Pormel auf; in der R2 eine Alkylgruppe mit 1 bis 8 Kohlenstoffatomen oder eine Arylalkylgruppe wie Benzyl, Phenyläthyl und Phenylpropyl bedeutet.The invention further relates to N- / o-alkyloxy (or arylalkyloxy)] benzoyl-p-aminophenols. These compounds are intermediates for the preparation of the compounds of the general formula (I) and have the following general formula; in which R2 is an alkyl group with 1 to 8 carbon atoms or an arylalkyl group such as benzyl, phenylethyl and phenylpropyl.

Die Erfindung betrifft weiterhin pharmazeutisch bzw. The invention further relates to pharmaceutical or

therapeutisch verträgliche Additionssalze der Phenylamine der allgemeinen Formel (I) mit anorganischen oder organischen Säuren.therapeutically acceptable addition salts of the general phenylamines Formula (I) with inorganic or organic acids.

Im folgenden wird eine Aufstellung über hergestellte Phenylamine der allgemeinen Formel (I) der Erfindung gegeben. The following is a list of manufactured phenylamines given the general formula (I) of the invention.

1) N-(o-Hydroxybenzoyl)-p-( 2-diäthylaminoäthoxy)-phenylamin (R = H; R1 = C2H5) (Smp. 108 - 110°C).1) N- (o-Hydroxybenzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = H; R1 = C2H5) (m.p. 108-110 ° C).

2) N-(o-Kethoxybenzoyl)-p-(2-diäthylaminoäthoxy)-phenylPman (R = CH3; R1 = C2H5) (Hydrochlorid, Smp. 132 - 133°C).2) N- (o-Kethoxybenzoyl) -p- (2-diethylaminoethoxy) -phenylPman (R = CH3; R1 = C2H5) (hydrochloride, m.p. 132-133 ° C).

3) N-(o-Äthoxybenzoyl)-p-(2-dimethylaminoäthoxy)-phenylamin (R = C2H5; R1 = CH3) (Smp. 72 - 74°C).3) N- (o-ethoxybenzoyl) -p- (2-dimethylaminoethoxy) -phenylamine (R = C2H5; R1 = CH3) (m.p. 72-74 ° C).

4) B-(o-Äthoxybensoyl)-p-(2-diäthylaminoäth ( = C2R5; R1 - C2H5) (Smp. 48 - 49°C).4) B- (o-ethoxy likewiseyl) -p- (2-diethylaminoeth (= C2R5; R1 - C2H5) (m.p. 48 - 49 ° C).

5) N-g o-(n-Propoxy)-benzoyl 7-p- (2-diäthylaminoäthoxy)-phenylamin (R = nC3H7; R1 = C2H5) (Smp. 63 - 65°C).5) N-g o- (n-propoxy) benzoyl 7-p- (2-diethylaminoethoxy) phenylamine (R = nC3H7; R1 = C2H5) (m.p. 63-65 ° C).

6) N-Co-(n-Butoxy )-benzoyl~7-p-( 2-diäthylaminoäthoxy)-phenylamin (R = nC4Hs; R1 = C2H5) (Smp. 74 - 75°C). 6) N-Co- (n-butoxy) -benzoyl ~ 7-p- (2-diethylaminoethoxy) -phenylamine (R = nC4Hs; R1 = C2H5) (m.p. 74-75 ° C).

7) N-/-o-(n-Amyloxy)-benzoyl 7-p-(2-diäthylaminoäthoxy)-phenylamin (R = nC5H11; R1 = C2H5) (Smp. 54 - 56°C). 7) N - / - o- (n-Amyloxy) benzoyl 7-p- (2-diethylaminoethoxy) phenylamine (R = nC5H11; R1 = C2H5) (m.p. 54-56 ° C).

8) N-[o-(n-Heptyloxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin (R = nC7H15; R1 = C2H5) (Smp. 44 - 46°C). 8) N- [o- (n-heptyloxy) benzoyl] -p- (2-diethylaminoethoxy) phenylamine (R = nC7H15; R1 = C2H5) (m.p. 44-46 ° C).

9) N- [o-(n-Octyloxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin (R = nC8H17; R1 = C2H5) (Smp. 56 - 58°C). 9) N- [o- (n-Octyloxy) -benzoyl] -p- (2-diethylaminoethoxy) -phenylamine (R = nC8H17; R1 = C2H5) (m.p. 56-58 ° C).

10) N-(o-Benzyloxy-benzoyl)-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH2C6H5; R1 = C2H5) (Smp. 66 - 6800).10) N- (o-Benzyloxy-benzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = CH2C6H5; R1 = C2H5) (m.p. 66-6800).

11) N-Jo-(ß-Phenyläthoxy)-benzoyl~7-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH2CH2C6H5; R1 = C2H5) (Smp. 98 - 10000).11) N-Jo- (ß-phenylethoxy) -benzoyl ~ 7-p- (2-diethylaminoethoxy) -phenylamine (R = CH2CH2C6H5; R1 = C2H5) (m.p. 98-10,000).

12) N- o-(g-Phenyl-n-propoxy)-benzoyl 7-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH2CH2CH2C6H5; R1 = C2H5) (Smp. 58 - 60°C).12) N- o- (g-Phenyl-n-propoxy) -benzoyl 7-p- (2-diethylaminoethoxy) -phenylamine (R = CH2CH2CH2C6H5; R1 = C2H5) (m.p. 58-60 ° C).

Quartäre Salze gemäß der allgemeinen Formel (II) können die folgenden sein: 13) N-(o-Hydroxybenzoyl)-p-(2-diäthyl-methyl-anunonio-äthoxy) phenylamin-bromid (R = H; R1 = C2H5; X = Br) (Smp. 198 - 200°C). Quaternary salts according to the general formula (II) can include the following be: 13) N- (o-Hydroxybenzoyl) -p- (2-diethyl-methyl-anunonio-ethoxy) phenylamine bromide (R = H; R1 = C2H5; X = Br) (m.p. 198-200 ° C).

14) N-(o-Methoxybenzoyl)-p-(2-diäthyl-methyl-nmmonio-äthoxy)-phenylamin-bromid (R = CH3; R1 = C2H5; X = Br) (Smp. 149 - 15100).14) N- (o-methoxybenzoyl) -p- (2-diethyl-methyl-nmmonio-ethoxy) -phenylamine-bromide (R = CH3; R1 = C2H5; X = Br) (m.p. 149-15100).

15) N-(o-Äthoxybenzoyl)-p-(2-triäthyl-ammonio-äthoxy) phenylamin-bromid (R = C2H5; R1 CH3; X = Br) (Smp. 217 - 219°C).15) N- (o-Ethoxybenzoyl) -p- (2-triethylammonioethoxy) phenylamine bromide (R = C2H5; R1 CH3; X = Br) (m.p. 217-219 ° C).

16) N-(o-Äthoxybenzoyl)-p-(2-diäthyl-methyl-ammonio-äthoxy)-phenylamin-bromid (R = C2H5; R1 = C2H5; X = Br) (Smp. 148 - 149°C).16) N- (o-Ethoxybenzoyl) -p- (2-diethyl-methyl-ammonio-ethoxy) -phenylamine-bromide (R = C2H5; R1 = C2H5; X = Br) (m.p. 148-149 ° C).

17) N-[o-(n-Propoxy)-benzoyl]-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = nC3H7; R1 = C2H5; X = Br) (Smp. 132 - 133°C).17) N- [o- (n-propoxy) -benzoyl] -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = nC3H7; R1 = C2H5; X = Br) (m.p. 132-133 ° C).

18) N-g o-(n-Butoxy)-benzoyl 7-p-(2-diäthyl-methyl-nmmonioäthoxy)-phenylamin-bromid (R = nC4Hg; R1 = C2H5; X = Br) (Smp. 121 - 123°C).18) N-g o- (n-butoxy) -benzoyl 7-p- (2-diethyl-methyl-nmmonioethoxy) -phenylamine-bromide (R = nC4Hg; R1 = C2H5; X = Br) (m.p. 121-123 ° C).

19) N-[o-(n-Amyloxy)-benzoyl]-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = nC5H11; R1 = C2H5; X = Br) (Smp. 146 - 147°C).19) N- [o- (n-amyloxy) -benzoyl] -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = nC5H11; R1 = C2H5; X = Br) (m.p. 146-147 ° C).

20) N-[o-(n-Heptyloxy)-benzoyl]-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = nC7H15; R1 = C2H5; X = Br) (Smp. 124 - 125°C).20) N- [o- (n-heptyloxy) -benzoyl] -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = nC7H15; R1 = C2H5; X = Br) (m.p. 124-125 ° C).

21) N-[o-(n-Octyloxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC8H17; R1 = C2H5; X = Br) (Smp. 133 - 135°C).21) N- [o- (n-Octyloxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC8H17; R1 = C2H5; X = Br) (m.p. 133-135 ° C).

22) N-(o-Benzyloxy-benzoyl)-p-(2-diäthyl-methyl-ammonioätholcy)-phenylamin-bromid (R = CH2C6H5; R1 = X = Br) (Smp. 161 - 162°C).22) N- (o-Benzyloxy-benzoyl) -p- (2-diethyl-methyl-ammonioethyl) -phenylamine-bromide (R = CH2C6H5; R1 = X = Br) (m.p. 161-162 ° C).

23) N-[o-(ß-Phenyläthoxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = CH2CH2C6H5; R1 = C2H5; X = Br) (Smp. 147 - 1500C).23) N- [o- (β-phenylethoxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = CH2CH2C6H5; R1 = C2H5; X = Br) (m.p. 147-1500C).

24) N-[o-(γ-Phenyl-n-propoxy)-benzoyl]-p-(2-diäthylmethyl-ammonio-äthoxy)-phenylamin-bromid (R = CH2CH2CH2C6H5; R1 = C2H5; X = Br) (Smp. 137 - 140°C).24) N- [o- (γ-phenyl-n-propoxy) -benzoyl] -p- (2-diethylmethyl-ammonio-ethoxy) -phenylamine-bromide (R = CH2CH2CH2C6H5; R1 = C2H5; X = Br) (m.p. 137-140 ° C).

Zwischenprodukte der allgemeinen Formel (III) zur Herstellung der Verbindungen der allgemeinen Formel (I) können die folgenden sein: 25) N-(o-Methoxybenzoyl)-p-aminophenol (R2 = CH3) (Smp. 169 - 170°C). Intermediates of the general formula (III) for the preparation of Compounds of the general formula (I) can be the following: 25) N- (o-methoxybenzoyl) -p-aminophenol (R2 = CH3) (m.p. 169-170 ° C).

26) N-(o-Äthoxybenzoyl)-p-aminophenol (R2 = C2H5) (Smp. 161 - 163°C).26) N- (o-Ethoxybenzoyl) -p-aminophenol (R2 = C2H5) (m.p. 161-163 ° C).

27) N-[o-(n-Propoxy)-benzoyl]-p-aminophenol (R2 = nC3H7) (Smp. 144 - 145°C).27) N- [o- (n-Propoxy) benzoyl] p-aminophenol (R2 = nC3H7) (m.p. 144 - 145 ° C).

28) N-[o-(n-Butoxy)-benzoyl]-p-aminophenol (R2 = nC4Hg) (Smp. 146 - 14800).28) N- [o- (n-Butoxy) -benzoyl] -p-aminophenol (R2 = nC4Hg) (m.p. 146 - 14800).

29) N-[o-(n-Amyloxy)-benzoyl]-p-aminophenol (R2 = nC5H11) (Smp. 129 - 1310C).29) N- [o- (n-Amyloxy) -benzoyl] -p-aminophenol (R2 = nC5H11) (m.p. 129 - 1310C).

30) N-[o-(n-Heptyloxy)-benzoyl]-p-aminophenol (R2 = nC7H15) (Smp. 98 - 10000).30) N- [o- (n-heptyloxy) -benzoyl] -p-aminophenol (R2 = nC7H15) (m.p. 98 - 10000).

31) N-[o-(n-Octyloxy)-benzoyl]-p-aminophenol (R2 = n08H17) (Smp. 104 - 10600).31) N- [o- (n-Octyloxy) -benzoyl] -p-aminophenol (R2 = n08H17) (m.p. 104 - 10600).

32) N-(o-Benzyloxy-benzoyl)-p-aminophenol (R2 = CH2C6H5) (Smp. 174 - 1760C).32) N- (o-Benzyloxy-benzoyl) -p-aminophenol (R2 = CH2C6H5) (m.p. 174 - 1760C).

33) N-[o-(ß-Phenyläthoxy)-benzoyl]-p-aminophenol (R2 = CH2CH2C6H5) (Smp. 156 - 158°C).33) N- [o- (ß-Phenylethoxy) -benzoyl] -p-aminophenol (R2 = CH2CH2C6H5) (M.p. 156-158 ° C).

34) N-[o-(γ-Phenyl-n-propoxy)-benzoyl]-p-aminophenol (R2 = CH2CH2CH2C6H5) (Smp. 124 - 126°C).34) N- [o- (γ-Phenyl-n-propoxy) -benzoyl] -p-aminophenol (R2 = CH2CH2CH2C6H5) (M.p. 124-126 ° C).

Die oben genannten Verbindungen zeigen eine bemerkenswerte pharmakologische Wirksamkeit und können zu verschiedenen therapeutischen Zwecken angewendet werden. The above compounds show a remarkable pharmacological Efficacy and can be used for various therapeutic purposes.

Die Verbindungen gemäß den allgemeinen Formeln (I) und (II) weisen insbesondere spasmolytische wirkungen und gefäßerweiternde Eigenschaften auf. In den Verbindungen, in denen R eine Alkylgruppe ist, ist die spasmolytische Aktivität (Vermögen zum Antagonisieren Bariumchlorid-induzierter Spasmen) proportional zu der Länge der Alkylkette. The compounds according to the general formulas (I) and (II) have in particular spasmolytic effects and vasodilating properties. In the compounds in which R is an alkyl group is spasmolytic activity (Ability to antagonize barium chloride-induced spasms) proportional to the length of the alkyl chain.

Die Verbindungen gemäß der allgemeinen Formel (III), die Zwischenprodukte zur Herstellung der Verbindungen der allgemeinen Formel (I) sind, weisen selbst eine analgetische, antiphlogistische und antipyretische Wirksamkeit auf. The compounds according to the general formula (III), the intermediates for the preparation of the compounds of general formula (I) are themselves an analgesic, anti-inflammatory and antipyretic activity.

Die Erfindung betrifft weiterhin Verfahren zur Herstellung der oben genannten Verbindungen. The invention further relates to methods of making the above named compounds.

Die Verbindungen der allgemeinen Formel (I) können erhalten werden, indem man geeignete Benzoylhalogenide oder geeignete Ester oder Anhydride mit p-(2-Diäthylaminoäthoxy )-phenylamin oder mit p- ( 2-Dimethylaminoäthoxy ) -phenylamin kondensiert oder die geeignet substituierten p-Aminophenole der allgemeinen Formel (III) mit 2-Diäthylaminoäthylhalogeniden oder 2-Dimethylaminoäthylhalogeniden in einem alkalischen Medium veräthert oder indem man ein geeignetes N-Jo-Alkyloxy (oder -Arylalkyloxy)-benzoyl 7-p- ( 2-halogenäthoxy)-phenylamin mit Diäthylamin oder Dimethylamin kondensiert. The compounds of the general formula (I) can be obtained by mixing suitable benzoyl halides or suitable esters or anhydrides with p- (2-diethylaminoethoxy ) -phenylamine or condensed with p- (2-dimethylaminoethoxy) -phenylamine or the suitably substituted p-aminophenols of the general formula (III) with 2-diethylaminoethyl halides or etherified or 2-dimethylaminoethyl halides in an alkaline medium by adding a suitable N-Jo-alkyloxy (or -arylalkyloxy) -benzoyl 7-p- (2-haloethoxy) -phenylamine condensed with diethylamine or dimethylamine.

Die Verbindungen der allgemeinen Formel (II) können erhalten werden, indem man die entsprechenden Verbindungen der allgemeinen Formel (1) in einem Quartärnierungverfahren unter Verwendung von Chlorid, Bromid, Jodid bzw. ethylchlorid, Methylbromid, Methyljodid oder Dimethylsulfat umsetzt. The compounds of the general formula (II) can be obtained by converting the corresponding compounds of general formula (1) in a quaternization process using chloride, bromide, iodide or ethyl chloride, methyl bromide, methyl iodide or dimethyl sulfate.

Die Verbindungen der allgemeinen Formel (III) können hergestellt werden, indem man p-Aminophenol mit geeigneten Benzoylhalogeniden, Estern oder Anhydriden umsetzt. The compounds of the general formula (III) can be prepared by mixing p-aminophenol with suitable benzoyl halides, esters or anhydrides implements.

Im folgenden wird über einige Verfahren zur Herstellung von N-(o-Äthoxybenzoyl)-p-(2-diäthylaminoäthoxy)-phenylRmin (Verbindung 4) und dessen Zwischenprodukt N-(o-Äthoxybenzoyl)-p-aminophenol (Verbindung 26) berichtet. The following describes some processes for the preparation of N- (o-ethoxybenzoyl) -p- (2-diethylaminoethoxy) -phenylRmin (Compound 4) and its intermediate N- (o-ethoxybenzoyl) -p-aminophenol (Compound 26) reported.

Beispiele 1a) und 1b) Herstellung von N- ( o-Äthoxybenzoyl )-p-( 2-diäthylaminoäthoxy)-phenylamin (Verbindung 4).Examples 1a) and 1b) Preparation of N- (o-ethoxybenzoyl) -p- (2-diethylaminoethoxy) phenylamine (Compound 4).

a) Zu 4 g Natriumhydroxid, gelöst in 100 ml Äthanol, werden 25,7 g N-(o-Äthoiybenzoyl)-p-aminophenol (26) gegeben. Die Mischung wird 1 Stunde am Rückfluß erhitzt. Nach dem Abkühlen werden 14,5 g N-Diäthylaminoäthylchlorid zugegeben. Die Mischung wird 6 Stunden lang am Rückfluß gekocht. Das Lösung mittel wird unter vermindertem Druck durch Destillation entfernt. Der RUckstand wird mit wasser aufgearbeitet. Der erhaltene Niederschlag wird filtriert und getrocknet, aus Hexan umkristallisiert und weist einen Schmelzpunkt von 4 - 49°C auf. a) To 4 g of sodium hydroxide dissolved in 100 ml of ethanol, 25.7 g N- (o-Äthoiybenzoyl) -p-aminophenol (26) added. The mixture is 1 hour on Heated to reflux. After cooling, 14.5 g of N-diethylaminoethyl chloride are added. The mixture is refluxed for 6 hours. The solution medium is below removed by distillation under reduced pressure. The arrears will worked up with water. The precipitate obtained is filtered and dried, recrystallized from hexane and has a melting point of 4-49 ° C.

b) Zu 20,8 g p-(2-Diäthylaminoäthoxy)-anilin in 200 ml wasserfreiem Benzol werden tropfenweise langsam und unter Rühren 18,4 g o-Äthoxybenzoylchlorid gegeben. Die Mischung wird 30 Minuten am Rückfluß gekocht. Nach dem Abkühlen wird der erhaltene Niederschlag filtriert, getrocknet und mit 5 einem Natriumhydroxid behandelt. Das erhaltene Produkt wird filtriert, getrocknet, aus Hexan umkristallisiert und weist einen Schmelzpunkt von 48 - 490C auf. b) To 20.8 g of p- (2-diethylaminoethoxy) aniline in 200 ml of anhydrous Benzene are slowly added dropwise and with stirring 18.4 g of o-ethoxybenzoyl chloride given. The mixture is refluxed for 30 minutes. After cooling it will the precipitate obtained is filtered, dried and treated with a sodium hydroxide treated. The product obtained is filtered, dried and recrystallized from hexane and has a melting point of 48 - 490C.

Beispiel 2 Herstellung von N-( o-Äthoxybenzoyl ) -p-aminophenol (Verbindung 26).Example 2 Preparation of N- (o-Ethoxybenzoyl) -p-aminophenol (compound 26).

18,4 g o-Äthoxybenzoylchlorid werden langsam unter Rühren in eine Lösung eingetropft, welche aus 500 ml wasserfreiem Dioxan, 7,9 g wasserfreiem Pyridin und 10,9 g p-Aminophenol besteht. 18.4 g of o-ethoxybenzoyl chloride are slowly stirred into a Dripped solution, which consists of 500 ml of anhydrous dioxane, 7.9 g of anhydrous pyridine and consists of 10.9 grams of p-aminophenol.

Nach Beendigung der Zugabe wird die Mischung 1,5 Stunden auf einem Wasserbad erhitzt. Nach dem Abkühlen wird die Reaktionamischung in verdünnte Salzsäure eingegossen. Der ausgeschiedene Niederschlag wird abfiltriert, mit Wasser gewaschen und mit 5 %igem Natriumhydroxid behandelt. Beim Ansäuern der erhaltenen filtrierten Lösung mit verdünnter Salzsäure scheidet sich ein Niederschlag ab, der aus Äthanol umkristallisiert einen Schmelzpunkt von 161 - 16300 aufweist. After the addition is complete, the mixture is left on for 1.5 hours Heated water bath. After cooling, the reaction mixture is dissolved in dilute hydrochloric acid poured. The deposited precipitate is filtered off and washed with water and treated with 5% sodium hydroxide. Upon acidification of the obtained filtered Solution with dilute hydrochloric acid separates a precipitate, which consists of ethanol recrystallized has a melting point of 161 - 16,300.

Claims (42)

Patent ansprüche Patent claims #. N-(o-Hydroxybenzoyl)-p-(2-dialkylaminoäthoxy)-phenylamine sowie o-substituierte Derivate derselben der allgemeinen Formel in der R ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 8 Kohlenstoffatomen oder eine Arylalkylgruppe wie Benzyl, Phenyläthyl und Phenylpropyl und R1 eine Alkylgruppe mit 1 oder 2 Kohlenstoffatomen bedeuten.#. N- (o-Hydroxybenzoyl) -p- (2-dialkylaminoethoxy) -phenylamines and o-substituted derivatives thereof of the general formula in which R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or an arylalkyl group such as benzyl, phenylethyl and phenylpropyl and R1 is an alkyl group having 1 or 2 carbon atoms. 2. Quartäre Salze der Verbindungen nach Anspruch 1 der allgemeinen Formel in der R und R1 wie oben definiert sind und X ein Anion wie Bromid, Chlorid, Jodid oder Sulfat bedeutet.2. Quaternary salts of the compounds according to Claim 1 of the general formula in which R and R1 are as defined above and X is an anion such as bromide, chloride, iodide or sulfate. 3. N-[o-Alkyloxy (oder -Arylalkyloxy) 7-benzoyl-paminophenole der allgemeinen Formel in der R2 eine Alkylgruppe mit 1 bis 8 Kohlenstoffatomen oder eine Arylalkylgruppe wie Benzyl, Phenyläthyl und Phenylpropyl bedeutet.3. N- [o-alkyloxy (or -arylalkyloxy) 7-benzoyl-paminophenols of the general formula in which R2 is an alkyl group with 1 to 8 carbon atoms or an arylalkyl group such as benzyl, phenylethyl and phenylpropyl. 4. N-(o-Hydroxybenzoyl)-p-(2-diäthylaminoäthoxy)-phenylamin (R = H, R1 = C2H5). 4. N- (o-Hydroxybenzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = H, R1 = C2H5). 5. N-(o-Methoxybenzoyl)-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH3, R1 = C2H5). 5. N- (o-Methoxybenzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = CH3, R1 = C2H5). 6. N-(o-ithoxybenzoyl)-p-(2-dimethylaminoäthoxy)-phenylamin (R = C2H5, R1 = CH3). 6. N- (o-Ithoxybenzoyl) -p- (2-dimethylaminoethoxy) -phenylamine (R = C2H5, R1 = CH3). 7. N-(o-Äthoxybenzoyl)-p-(2-diäthylaminoäthoxy)-phenylamin (R = C2E5, R1 = C2H5)- 7. N- (o-Ethoxybenzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = C2E5, R1 = C2H5) - 8. N-g o-(n-Propoxy)-benzoyl 7-p-(2-diäthylaminoäthoxy)-phenylamin = nC3H7, R1 = C2H5).8. N-g o- (n-propoxy) benzoyl 7-p- (2-diethylaminoethoxy) phenylamine = nC3H7, R1 = C2H5). 9. N-[o-(n-Butoxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin (R = nC4Hg, R1 = C2H5). 9. N- [o- (n-Butoxy) benzoyl] p- (2-diethylaminoethoxy) phenylamine (R = nC4Hg, R1 = C2H5). 10. N-[o-(n-Amyloxy)-benzoyl]-p-(2-diäthylaminoäthoxy) phenylamin ( R = nC5H11, R1 = C2H5) 10. N- [o- (n-Amyloxy) -benzoyl] -p- (2-diethylaminoethoxy) phenylamine (R = nC5H11, R1 = C2H5) 11. N-[o-(n-Heptyloxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin (R = nC7H15, R1 2 C2H5).11. N- [o- (n-Heptyloxy) -benzoyl] -p- (2-diethylaminoethoxy) -phenylamine (R = nC7H15, R1 2 C2H5). 12. N-[o-(n-Octyloxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin ( R = nC8H17, R1 = C2H5). 12. N- [o- (n-Octyloxy) -benzoyl] -p- (2-diethylaminoethoxy) -phenylamine (R = nC8H17, R1 = C2H5). 13. E-(o-Benzyloxy-benzoyl)-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH2C6H5, R1 = C2H5). 13. E- (o-Benzyloxy-benzoyl) -p- (2-diethylaminoethoxy) -phenylamine (R = CH2C6H5, R1 = C2H5). 14. N-[o-(ß-Phenyläthoxy)-benzoyl]-p-(2-diäthylaminoäthoxy)-phenylamin (R = CH2CH2C6H5, R1 = C2H5). 14. N- [o- (β-Phenylethoxy) -benzoyl] -p- (2-diethylaminoethoxy) -phenylamine (R = CH2CH2C6H5, R1 = C2H5). 15. N-[o-(γ-Phenyl-n-propoxy)-benzoyl]-p-(2-diäthylaminoäthoiy)-phenylamin (R = CH2CH2CH2C6H5, R1 = C2H5). 15. N- [o- (γ-Phenyl-n-propoxy) -benzoyl] -p- (2-diethylaminoethyl) -phenylamine (R = CH2CH2CH2C6H5, R1 = C2H5). 16. N-(o-Hydroxybenzoyl)-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = H, R1 = C2H5, X = Br). 16. N- (o-Hydroxybenzoyl) -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = H, R1 = C2H5, X = Br). 17. N-(o-Methoxybenzoyl)-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = CH3, R1 = C2H5, X = Br). 17. N- (o-Methoxybenzoyl) -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = CH3, R1 = C2H5, X = Br). 18. N-(o-Äthoxybenzoyl)-p-(2-triäthyl-ammonio-äthoxy)-phenylamin-bromid (R = C2H5, R1 = CH3, X = Br). 18. N- (o-Ethoxybenzoyl) -p- (2-triethyl-ammonio-ethoxy) -phenylamine-bromide (R = C2H5, R1 = CH3, X = Br). 19. N-(o-Äthoxybenzoyl)-p-(2-diäthyl-methyl-ammonio äthoxy)-phenylamin-bromid (R = C2H5, R1 = C2H5, X = Br). 19. N- (o-Ethoxybenzoyl) -p- (2-diethyl-methyl-ammonio ethoxy) -phenylamine-bromide (R = C2H5, R1 = C2H5, X = Br). 20. N-[o-(n-Propoxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC3H7, R1 = C2H5, X = Br). 20. N- [o- (n-Propoxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC3H7, R1 = C2H5, X = Br). 21. N-[o-(n-Butoxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC4Hg, R1 = C2H5, X = Br). 21. N- [o- (n-Butoxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC4Hg, R1 = C2H5, X = Br). 22. N-[o-(n-Amyloxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC5H11, R1 = C2H5, X = Br). 22. N- [o- (n-Amyloxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC5H11, R1 = C2H5, X = Br). 23. N-[o-(n-Heptyloxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC7H15, R1 = C2H5, X = Br). 23. N- [o- (n-Heptyloxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC7H15, R1 = C2H5, X = Br). 24. N-[o-(n-Octyloxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = nC8H17, R1 = C2H5, X = Br). 24. N- [o- (n-Octyloxy) -benzoyl] -p- (2-diethyl-methylammonio-ethoxy) -phenylamine-bromide (R = nC8H17, R1 = C2H5, X = Br). 25. N-(o-Benzyloxy-benzoyl)-p-(2-diäthyl-methyl-ammonioäthoxy)-phenylamin-bromid (R = CH2C6H5, R1 = C2H5, X = Br). 25. N- (o-Benzyloxy-benzoyl) -p- (2-diethyl-methyl-ammonioethoxy) -phenylamine-bromide (R = CH2C6H5, R1 = C2H5, X = Br). 26. N-[o-ß-Phenyläthoxy)-benzoyl]-p-(2-diäthyl-methylammonio-äthoxy)-phenylamin-bromid (R = CH2CH3C6H5, R1 = C2H5, X = Br). 26. N- [o-ß-phenylethoxy) benzoyl] p- (2-diethylmethylammonioethoxy) phenylamine bromide (R = CH2CH3C6H5, R1 = C2H5, X = Br). 27. N-[o-(γ-Phenyl-n-propoxy)-benzoyl]-p-(2-diäthylmethyl-ammonio-äthoxy)-phenylamin-bromid (R = CH2CH2CH2C6H5, R1 = C2H5, X = Br). 27. N- [o- (γ-Phenyl-n-propoxy) -benzoyl] -p- (2-diethylmethyl-ammonio-ethoxy) -phenylamine-bromide (R = CH2CH2CH2C6H5, R1 = C2H5, X = Br). 28. N-(o-Methoxybenzoyl)-p-aminophenol (R2 = CH3). 28. N- (o-Methoxybenzoyl) -p -aminophenol (R2 = CH3). 29. N-(o-Äthoxybenzoyl)-p-aminophenol (R2 = 02H5). 29. N- (o-Ethoxybenzoyl) -p-aminophenol (R2 = 02H5). 30. N-[o-(n-Propoxy)-benzoyl]-p-aminophenol (R2 = nC3H7). 30. N- [o- (n-Propoxy) benzoyl] p -aminophenol (R2 = nC3H7). 31. N-[o-(n-Butoxy)-benzoyl]-p-aminophenol (R2 = nC4H9). 31. N- [o- (n-Butoxy) benzoyl] p -aminophenol (R2 = nC4H9). 32. N-[o-(n-Amyloxy)-benzoyl]-p-aminophenol (R2 = nC5H11). 32. N- [o- (n-Amyloxy) -benzoyl] -p-aminophenol (R2 = nC5H11). 33. N-[o-(n-Heptyloxy)-benzoyl]-p-aminophenol (R2 = nC7H15). 33. N- [o- (n-Heptyloxy) -benzoyl] -p -aminophenol (R2 = nC7H15). 34. N-[o-(n-Octyloxy)-benzoyl]-p-aminophenol (R2 = nC8H17). 34. N- [o- (n-Octyloxy) -benzoyl] -p-aminophenol (R2 = nC8H17). 35. N-(o-Benzyloxy-benzoyl)-p-aminophenol (R2 = CH2C6H5). 35. N- (o-Benzyloxy-benzoyl) -p-aminophenol (R2 = CH2C6H5). 36. N-[o-(ß-Phenyläthoxy)-benzoyl]-p-aminophenol (R2 = CH2CH2C6115). 36. N- [o- (β-Phenylethoxy) -benzoyl] -p-aminophenol (R2 = CH2CH2C6115). 37. N-[o-(γ-Phenyl-n-propoxy)-benzoyl]-p-aminophenol (R2 = CH2CH2CH2C6H5). 37. N- [o- (γ-Phenyl-n-propoxy) -benzoyl] -p-aminophenol (R2 = CH2CH2CH2C6H5). 38. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch g e k e n n z e i c h n e t , daß man geeignete Benzoylhalogenide oder geeignete Ester oder Anhydride mit p-(2-Diäthylaminoäthoxy)-phenylamin oder p-(2-Dimethylaminoäthoxy) -phenylamin kondensiert. 38. Process for the preparation of the compounds according to claim 1, characterized in that it is not noted that suitable benzoyl halides or suitable Esters or anhydrides with p- (2-diethylaminoethoxy) phenylamine or p- (2-dimethylaminoethoxy) -phenylamine condensed. 39. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch g e k e n n z e i c h n e t , daß man geeignet substituierte p-Aminophenole der allgemeinen Pormel (III) mit 2-Diäthylaminoäthyl-halogeniden oder 2-Dimethylaminoäthyl-halogeniden in alkalischem Medium veräthert. 39. Process for the preparation of the compounds according to claim 1, characterized in that it is not noted that suitably substituted p-aminophenols are used general formula (III) with 2-diethylaminoethyl halides or 2-dimethylaminoethyl halides etherified in an alkaline medium. 40. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch g e k e n n z e i c h n e.t , daß man ein geeignetes N-Jo-Alkyloxy (oder -Arylalkyloxy)-benzoyl 7-p-(2-halogenäthoxy)-phenylamin mit Diäthylamin oder Dimethylamin kondensiert. 40. Process for the preparation of the compounds according to claim 1, characterized in that G e k e n n n z e i c h n e.t that one a suitable N-Jo-alkyloxy (or -Arylalkyloxy) -benzoyl 7-p- (2-haloethoxy) -phenylamine with diethylamine or Dimethylamine condenses. 41. Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (II), dadurch g e k e n n z e i c h II e t daß man die entsprechenden Verbindungen der allgemeinen Formel (I) mit Methylchlorid, Methylbromid, Methyljodid, Methylsulfat oder Dimethylsulfat quartärniert. 41. Process for the preparation of the compounds of the general formula (II), it is indicated that the corresponding compounds are used of the general formula (I) with methyl chloride, methyl bromide, methyl iodide, methyl sulfate or quaternized dimethyl sulfate. 42. Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (III), dadurch g e k e n n z e i c h n e t daß man p-Aminophenol mit geeigneten Benzoylhalogeniden, Estern oder Anhydriden acyliert. 42. Process for the preparation of the compounds of the general formula (III), it is noted that p-aminophenol is mixed with suitable Benzoyl halides, esters or anhydrides acylated.
DE19732309986 1973-02-28 1973-02-28 N-benzoyl-4-dialkylaminoethoxyanilines - antispasmodics etc Pending DE2309986A1 (en)

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