WO1998003483A1 - Procede de preparation de piperidines - Google Patents

Procede de preparation de piperidines Download PDF

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Publication number
WO1998003483A1
WO1998003483A1 PCT/JP1997/002495 JP9702495W WO9803483A1 WO 1998003483 A1 WO1998003483 A1 WO 1998003483A1 JP 9702495 W JP9702495 W JP 9702495W WO 9803483 A1 WO9803483 A1 WO 9803483A1
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WO
WIPO (PCT)
Prior art keywords
pyridine
catalyst
catalytic reduction
pyridin
nickel
Prior art date
Application number
PCT/JP1997/002495
Other languages
English (en)
Japanese (ja)
Inventor
Katsutoshi Harada
Original Assignee
Koei Chemical Co., Ltd.
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 Koei Chemical Co., Ltd. filed Critical Koei Chemical Co., Ltd.
Publication of WO1998003483A1 publication Critical patent/WO1998003483A1/fr

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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
    • C07D295/02—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 containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • 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

Definitions

  • Raney nickel is an inexpensive catalyst and is especially useful, but when it is used to catalytically reduce pyridin bases, the reaction is difficult to complete. In addition, even if the reaction is performed under a high hydrogen pressure, unreacted pyridin bases remain. To complete the reaction, you need the Raney Nickel.
  • Noble metal catalysts such as platinum catalysts, palladium catalysts, ruthenium catalysts, and rhodium catalysts are also used for the catalytic reduction of pyridin bases. Catalysts are expensive and, for example, when a ruthenium catalyst is used for the catalytic reduction of pyridin bases, the ring of formed piperidines may be reduced.
  • Amylamines in which the bond between a nitrogen atom and a carbon atom has been cleaved are likely to be formed. Since the by-product amiramines have a boiling point close to that of piperidines, when they are formed, high-purity piramines from the reaction mixture after the reaction is completed. Recovery of peridines becomes difficult
  • the present inventor has conducted intensive studies in order to solve the above problems. As a result, in producing piperidines by catalytic reduction of pyridin bases, they can be obtained at low cost as a commercial product, and they are easy to handle. When a stabilized nickel catalyst (hereinafter, referred to as a stabilized nickel catalyst) is used as a catalyst, the reaction is completed with a relatively small amount of catalyst.
  • a stabilized nickel catalyst hereinafter, referred to as a stabilized nickel catalyst
  • the present inventors have also found that piperidines can be produced in a high yield by suppressing the cleavage of the piperidin ring, and have completed the present invention.
  • the present invention relates to the production of pyridines by catalytic reduction of pyridin bases, in which a stabilized nickel catalyst is used as a catalyst.
  • the present invention relates to a method for producing piperidines characterized by the following.
  • the stabilized nickel catalyst used in the present invention is obtained by stabilizing a flammable nickel catalyst that ignites when it comes into contact with air. It is a catalyst that is easy to handle.
  • the stabilized nickel catalyst may be produced from a ignitable nickel catalyst by any conventionally known stabilization method. Examples of the stabilization method include a method of oxidizing a ignitable nickel catalyst by contacting it with air in the presence of gaseous or liquid phase water, Nickel catalyst A method of contacting with air and oxidizing in the presence of an inert gas such as nitrogen or carbon dioxide can be cited. Examples of the ignitable nickel catalyst used for the stabilization treatment include nickel such as nickel nickel, nickel nickel nitrate, nickel nickel carbonate, and the like.
  • the amount of the stabilized nickel catalyst used in the present invention is usually not less than 2% by weight, preferably not more than 3% by weight, based on the pyridin bases. To 30% by weight. If the amount of the nickel catalyst used is less than 2% by weight with respect to the pyridin bases, it takes a long time to complete the reaction.
  • pyridin bases used in the present invention include pyridin, 2-methynolepyridin, and 3-methynoleviridine.
  • Examples of piperidines produced according to the method of the present invention include pyridin, 2-methylbiperidine, and 3-perpidin.
  • the reaction temperature of the catalytic reduction in the present invention is usually 140-
  • reaction temperature 250 ° C, preferably 1502 ° C.
  • reaction temperature is lower than 140 ° C, it takes a long time to complete the reaction, and when the reaction temperature is higher than 250 ° C, amiamines are formed. It gets so good.
  • the hydrogen pressure at the contact area is usually
  • the method of the present invention does not particularly require a solvent, but does not support the use of a solvent at all.
  • Solvents that can be used are not particularly limited as long as they are inert to the catalytic reduction of the present invention.
  • the solvent include water, dioxane, and tetrahydro.
  • esters such as flavones and acetate esters.
  • a pressurized anti-fc pyridin base, a stabilized nickel catalyst and, if desired, a solvent are charged, and hydrogen is added under stirring.
  • the reaction may be carried out while maintaining the above reaction temperature and hydrogen pressure while introducing.
  • hydrogen is no longer consumed, but usually stirring is continued at the same temperature for about 0.51 hour.
  • the unreacted pyridin bases do not remain, and piperidines are selectively produced in high yield.
  • the reaction solution after the completion of the reaction is unreacted. Since almost no pyridin bases and by-products are present, high-purity pyridins can be obtained from the reaction solution after the reaction by a simple operation. Can be obtained. For example, after completion of the reaction, the reaction solution is cooled to about room temperature, the internal pressure is returned to normal pressure, the reaction solution is filtered, the catalyst is filtered off, and then the filtrate is distilled. As a result, high-purity piperidines can be easily obtained.
  • BEST MODE FOR CARRYING OUT THE INVENTION the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. No.
  • a mixture of 10 parts by weight of nickel nitrate hexahydrate, 2 parts by weight of water and 2 parts by weight of gay alga earth was dried, roasted, and then hydrogenated. It was reduced at around 50 ° C. Water is added to the obtained nickel Z gay algae soil by spraying at 50% by weight with respect to the nickel, and 80- The mixture was oxidized with air at 90 ° C. for 5 hours to obtain a stabilized nickel catalyst having a nickel content of 50% by weight supported on gay algae soil.
  • the obtained stabilized nickel catalyst (12 g) and 400 g of 2—methyl pyridine were supplied to a 1-liter electromagnetic stirring type autoclave. The temperature was raised to 170 ° C. while introducing hydrogen while stirring, heating and stirring, and maintained at the same temperature for 2 hours. During the reaction, the hydrogen pressure was kept at 40 kgf Z cm 2 (3.9 ⁇ 10. Pa). Thereafter, the introduction of hydrogen was terminated, the reaction solution was cooled to room temperature, returned to normal pressure, and then the reaction solution was filtered to remove the catalyst. When the obtained filtrate was separated by gas chromatography, the conversion of 2-methylpyridin was 100%, and the conversion was 2%. — The yield of methyl biperidine was 98%. The production of 1-hexylamine or 2-hexylamine by ring cleavage was not recognized.
  • Example 2 The procedure was as in Example 1, except that the pyridyl was used in place of the methylpyridin. As a result, the conversion of pyridin was 100%, and the yield of pyridin was 95%. The formation of amiramin by ring cleavage was not observed.

Landscapes

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

Abstract

Un procédé de préparation de piperidines par réduction catalytique de pyridines, consiste à mener à son terme la réduction catalytique d'une pyridine, même avec une quantité relativement faible d'un catalyseur, et à empêcher la formation de produits dérivés ayant des points d'ébullition proches de celui de la piperidine que l'on veut obtenir, afin d'obtenir une préparation de piperidines à rendement élevé. Le procédé se caractérise par le chargement d'une pyridine et d'au moins 2 % en poids (sur la base de la pyridine) d'un catalyseur au nickel stabilisé dans un réacteur de pression, et l'exécution de la réduction catalytique de la pyridine sous agitation à une température de réaction comprise entre 140 et 250 °C, sous une pression d'hydrogène maintenue entre 30 et 100 kgf/cm2 (2.9 x 106 à 9.8 x 106 Pa) par introduction d'hydrogène dans le réacteur.
PCT/JP1997/002495 1996-07-22 1997-07-18 Procede de preparation de piperidines WO1998003483A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8/211917 1996-07-22
JP21191796 1996-07-22

Publications (1)

Publication Number Publication Date
WO1998003483A1 true WO1998003483A1 (fr) 1998-01-29

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ID=16613810

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/002495 WO1998003483A1 (fr) 1996-07-22 1997-07-18 Procede de preparation de piperidines

Country Status (2)

Country Link
CN (1) CN1113866C (fr)
WO (1) WO1998003483A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101723877B (zh) * 2009-11-24 2011-10-05 南京第一农药集团有限公司 吡啶碱催化加氢制备哌啶类化合物的方法
CN106824205A (zh) * 2017-03-10 2017-06-13 中触媒新材料股份有限公司 一种镍基非晶态催化剂及其制备方法和催化吡啶类化合物加氢反应的应用
CN108840840A (zh) * 2018-07-18 2018-11-20 安徽国星生物化学有限公司 一种用n-氧化吡啶及其同系物合成哌啶及其同系物的方法
CN113264867A (zh) * 2021-06-08 2021-08-17 安徽星宇化工有限公司 一种顺式2,6-二甲基哌啶的制备方法
CN116162055B (zh) * 2023-03-10 2023-09-12 山东汇智药物研究有限公司 一种用n-氧化吡啶衍生物制备哌啶衍生物的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145274A (ja) * 1986-12-09 1988-06-17 Mitsui Toatsu Chem Inc ピペリジンの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145274A (ja) * 1986-12-09 1988-06-17 Mitsui Toatsu Chem Inc ピペリジンの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 91, 1979, (Columbus, Ohio, USA), Abstract No. 211221, SOGATOVA Ya. K. et al., "Study of the Catalytic Activity of Raney Hydrogenation of Pyridine to Piperidine"; & VINITI 1682-78, 11p. AVEIL. VINITI (RUSS), 1978. *

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CN1198155A (zh) 1998-11-04
CN1113866C (zh) 2003-07-09

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