EP0613473A1 - Procede de fabrication de la 1-amino-2,6-dimethylpiperidine - Google Patents

Procede de fabrication de la 1-amino-2,6-dimethylpiperidine

Info

Publication number
EP0613473A1
EP0613473A1 EP92923140A EP92923140A EP0613473A1 EP 0613473 A1 EP0613473 A1 EP 0613473A1 EP 92923140 A EP92923140 A EP 92923140A EP 92923140 A EP92923140 A EP 92923140A EP 0613473 A1 EP0613473 A1 EP 0613473A1
Authority
EP
European Patent Office
Prior art keywords
dimethylpiperidine
surfactant
nitroso
amino
catalyst
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP92923140A
Other languages
German (de)
English (en)
Inventor
Wolfgang Rybczynski
Wolfgang Bauer
Eckard Kujath
Manfred Schrod
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Cassella AG
Hoechst AG
Cassella Farbwerke Mainkur AG
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 Cassella AG, Hoechst AG, Cassella Farbwerke Mainkur AG filed Critical Cassella AG
Publication of EP0613473A1 publication Critical patent/EP0613473A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/30—Nitrogen atoms non-acylated

Definitions

  • the invention relates to a process for the preparation of ⁇ . l-amino-2,6-dimethylpiperidine.
  • l-Amino-cis-2,6-dimethylpiperidine is a key intermediate in the synthesis of the loop saluretic clopamide (chlorine-N- (cis-2,6-dimethylpiperidino) sulfo and amoylbenzamide) and the cardiovascular agent Pirsidomine (3- (cis-2,6-dimethylpiperidino) -N- (4-methoxybenzoyl) sydnonimine).
  • a process for the preparation of substituted hydrazines such as, for example, N-aminopiperidine, is known from ÜSP 2 979 505, in which the corresponding nitrosoamines are hydrogenated in the presence of a palladium catalyst which contains a certain amount of a soluble iron salt.
  • the preparation of l-amino-cis-2,6-dimethylpiperidine by this process is unsatisfactory, both in terms of yield (65%) and selectivity (60 to 70%), as stated in Hungarian patent 15614.
  • l-amino-cis-2,6-dimethylpiperidine is therefore obtained by nitrosating cis-2,6-dimethylpiperidine and hydrogenating the resulting nitroso compound in aqueous ammoniacal solution in the presence of a solvent Fe (II) salt poisoned Palladiumkataly ⁇ produced, both reactions being carried out in the absence of chloride ions.
  • This method has considerable problems both in the implementation and in the working up of the reaction mixture obtained. For example, the use of ammonia requires additional procedural measures to avoid corrosion and emissions. The amount of ammonia used is also high (100 to 150 g of ammonia per 1 kg of product).
  • the invention thus relates to a process for the preparation of l-amino-2,6-dimethylpiperidine by catalytically hydrogenating l-nitroso-2,6-dimethylpiperidine using a palladium catalyst partially poisoned with iron ions.
  • the process according to the invention is characterized in that it is carried out in an aqueous solvent in the presence of a surfactant or surfactant mixture.
  • Water is preferably used as the aqueous solvent.
  • anionic surfactants are divided into anionic, nonionic, cationic and amphoteric types, of which the anionic and nonionic are particularly preferred in the process according to the invention.
  • Suitable anionic surfactants are e.g. sulfonated aromatic hydrocarbons such as the sodium salt of dodecylbenzenesulfonic acid; sulfonated aliphatic hydrocarbons, such as the sodium salt of sec. pentadecane sulfonic acid; sulfonated olefins, such as the sodium salt of ⁇ -hexadecenesulfonic acid; sulfated fatty alcohols such as sodium lauryl sulfate; sulfated
  • Fatty alcohol ethers such as sodium lauryl polyglycol ether sulfate; sulfonated fatty acid methyl esters, such as palm kernel sulfo fatty acid methyl ester sodium salt; carboxy ethylated fatty alcohol polyglycol ethers, such as lauryl polyglycol ether acetate sodium salt.
  • Suitable nonionic surfactants are, for example, fatty alcohol oxyethylates, alkylphenol oxyethylates, fatty acid oxyethylates, fatty acid alkylolamides, fatty amine oxyethylates, polyalkylene oxide block polymers, fatty acid esters of sorbitan and ethoxylated fatty acid esters of sorbitan.
  • Suitable surfactants depending on their intended use, for example also referred to as emulsifiers or detergents, are marketed by numerous companies.
  • a surfactant with low foaming power, good environmental compatibility and good biodegradability is preferably used.
  • surfactant or surfactant mixture is added to the aqueous solvent, in particular the water, preferably 0.1 to 10% by weight, very particularly preferably 1 to 6% by weight.
  • Sufficient palladium catalyst is preferably used in such a way that the amount of Pd is 0.1 to 10 mol%, based on the l-nitroso-2,6-dimethylpiperidine.
  • the palladium catalysts used are, in particular, those in which the palladium is supported on a support, preferably carbon or aluminum oxide, and which have a Pd content of 1 to 10% by weight.
  • the catalyst is partially poisoned by the addition of a soluble iron salt before or during the reaction.
  • Fe (II) sulfate is particularly suitable as the soluble iron salt.
  • the molar ratio Pd: Fe is preferably (20 to 0.5): 1.
  • the hydrogenation is carried out at normal temperature or preferably at an elevated temperature, for example at 20 to 80 ° C, and e.g. a hydrogen pressure of 1 to 100 bar.
  • a reaction temperature of 30 to 50 ° C. and / or a hydrogen pressure of 2 to 25 bar is particularly preferred.
  • the process according to the invention achieves a virtually complete conversion of over 99%.
  • the trace product l-nitroso-2,6-dimethylpiperidine if at all, can then only be detected in traces using sensitive detection methods.
  • the reaction mixture remaining after filtering off the catalyst in the process according to the invention generally contains, based on the l-nitroso-2,6-dimethylpiperidine used, over 90% l-amino-2,6-dimethylpiperidine, 9% 2 , 6-dimethylpiperidine and, as already mentioned, at most traces of l-nitroso-2,6-dimethylpiperidine.
  • the selectivity is therefore 90%.
  • the by-product and the water as the top product can be partially separated off by rectification, preferably under reduced pressure.
  • the substances remaining in the sump in addition to the desired 1-amino-2,6-dimethylpiperidine do not interfere with further processing.
  • the process according to the invention is equally suitable for the preparation of l-amino-cis-2,6- or trans-2,6-dimethyl-piperidine.
  • the by-product and the water can be partially separated off by rectification.
  • the substances remaining in the product have no negative effect on its further use.
  • Example 1 In a repetition of Example 1, the Hostapur ® SAS 93 by 3 g of the surfactant E ulgator NW (aryl polyglycol ethers, manufacturer Bayer AG, Leverkusen) replaced. The conversion and the selectivity are the same as in Example 1.
  • E ulgator NW aryl polyglycol ethers, manufacturer Bayer AG, Leverkusen
  • Example 1 In a repetition of Example 1, the Hostapur ® SAS 93 by 3 g of the surfactant Dispersogen®P (Hoechst AG, Frankfurt am Main) er ⁇ sets. The conversion and the selectivity are as good as in Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de fabrication de la 1-amino-2,6-diméthylpipéridine par hydrogénation catalytique de la 1-nitroso-2,6-diméthylpipéridine, avec utilisation d'un catalyseur au palladium partiellement empoisonné par des ions fer, selon lequel l'hydrogénation est effectuée dans un solvant aqueux, en présence d'un agent tensioactif ou d'un mélange d'agents tensioactifs.
EP92923140A 1991-11-20 1992-11-12 Procede de fabrication de la 1-amino-2,6-dimethylpiperidine Withdrawn EP0613473A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4138143A DE4138143C2 (de) 1991-11-20 1991-11-20 Verfahren zur Herstellung von 1-Amino-2,6-dimethylpiperidin
DE4138143 1991-11-20
PCT/EP1992/002594 WO1993010110A1 (fr) 1991-11-20 1992-11-12 Procede de fabrication de la 1-amino-2,6-dimethylpiperidine

Publications (1)

Publication Number Publication Date
EP0613473A1 true EP0613473A1 (fr) 1994-09-07

Family

ID=6445181

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92923140A Withdrawn EP0613473A1 (fr) 1991-11-20 1992-11-12 Procede de fabrication de la 1-amino-2,6-dimethylpiperidine

Country Status (6)

Country Link
US (1) US5510489A (fr)
EP (1) EP0613473A1 (fr)
JP (1) JPH07501065A (fr)
CA (1) CA2123989A1 (fr)
DE (1) DE4138143C2 (fr)
WO (1) WO1993010110A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19719524C1 (de) * 1997-05-09 1998-11-12 Autoliv Dev Faltverfahren für einen Gassack einer Airbageinrichtung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2979505A (en) * 1957-08-06 1961-04-11 Fmc Corp Process for hydrogenation of nitrosamines
US3102887A (en) * 1959-04-13 1963-09-03 Du Pont Preparation of unsymmetrically disubstituted hydrazines
DE1141292B (de) * 1959-09-23 1962-12-20 Dresden Arzneimittel Verfahren zur Herstellung von unsymmetrisch disubstituierten Hydrazinen
DE1155138B (de) * 1962-02-28 1963-10-03 Dresden Arzneimittel Verfahren zur Herstellung unsymmetrisch disubstituierter Hydrazine
US3154538A (en) * 1962-03-09 1964-10-27 Fmc Corp Process for hydrogenating nitrosamines
GB1060160A (en) * 1964-08-05 1967-03-01 Allen & Hanburys Ltd 4-phenylpiperidine derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9310110A1 *

Also Published As

Publication number Publication date
US5510489A (en) 1996-04-23
JPH07501065A (ja) 1995-02-02
WO1993010110A1 (fr) 1993-05-27
DE4138143A1 (de) 1993-05-27
CA2123989A1 (fr) 1993-05-27
DE4138143C2 (de) 1996-05-30

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