CA1050987A - Process for the production of 3-methyl piperidine - Google Patents
Process for the production of 3-methyl piperidineInfo
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- CA1050987A CA1050987A CA248,739A CA248739A CA1050987A CA 1050987 A CA1050987 A CA 1050987A CA 248739 A CA248739 A CA 248739A CA 1050987 A CA1050987 A CA 1050987A
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- diluent
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
3-Methyl piperidine is produced in high yields by hy-drogenating 2-methyl glutaric acid dinitrile in the presence of a nickel catalyst. The use of a nickel catalyst, such as finely divided nickel or nickel on a support, promotes the for-mation of 3-methyl piperidine and suppresses formation of the 2-methyl -1,5-diaminopentane which would normally be expected.
3-Methyl piperidine is used as a vulcanisation accelerator and as an additive for lubricating oils; it is also an interme-diate product for the production of nicotine acid.
3-Methyl piperidine is produced in high yields by hy-drogenating 2-methyl glutaric acid dinitrile in the presence of a nickel catalyst. The use of a nickel catalyst, such as finely divided nickel or nickel on a support, promotes the for-mation of 3-methyl piperidine and suppresses formation of the 2-methyl -1,5-diaminopentane which would normally be expected.
3-Methyl piperidine is used as a vulcanisation accelerator and as an additive for lubricating oils; it is also an interme-diate product for the production of nicotine acid.
Description
This invention relates to a process for the production of ~-methyl piperidine by the catalytic hydrogena-tion o~
2-methyl glutaric acid dinitrile (1~3 butane dicarbonitrile) in the liquid phase9 according to the following reaction soheme:
IH3~ 4H2 i ~ C~
NG--CE--CE2~ CH2--C~J ~ l l
IH3~ 4H2 i ~ C~
NG--CE--CE2~ CH2--C~J ~ l l
3 ~ ~ ~ (I) -(II) H
3-Methyl piperidine (I) may be obtained by the hydro-genation of~ -picoline (J. Amer. Chem9 Soc, 49, (1927)t (2837). Howevers 3-methyl piperidine may also be obtained from 2-methyl glutaric acid dinitrile (II), which can be formed ~rom 2-me-thylene glutaxic acLd dinltrile b~ hydro~enating the double bond, the 2-methylene glutar:lc acid clinltri:Le helng ln turn obtainable from acrylonitrile by dimerisa-tion. One method by which 3-methyl piperidine has been obtained from 2-me-thyl glutaric acid dinitrile is by reduction wi-th sodium in ethanol (Monatshefte fur Chemie 23, (1902) 878, 883) or in butanol (Zhur.
Obshchei Khim 24, tl954) 291-298; C.A 49 (1955) 4643, 8109).
In the latter case, 3 methyl plperidine was obtained in a yield of 21~ together wi-th 68~o o~ 2-methyl-1~5-dlaminopentane.
In another synthesi~, 2-methyl glutarlc acid dinitrile was initially cyclised with sodium amide to form the glutari-midine derivative in a yield of 70%. The glu-tarimidine deriva-tive thus ~ormed was then reduced with sodium in alcohol to form 3-methyl piperidine (~ull. Chemu Soc. Japan 35, (1962) 1438-1443; Japanese patent No~ 14 140/65)o ~he above syntheses are unsuitable for the production o~
3-methyl piperidine on a commercial scale bo-th on account of the poor yield and on account of the high consumption of 30dium or sodium amide~
9~ :
Conventionally, a cobalt ca-talyst has been used in the hydrogenation of 2-methyl glutaric acid dinitrile to produce 2-methyl-1,5-diaminopen-tane in high yields. Additives ~uch as ammonia or tertiary aliphatic amines containlng from 3 to 5 carbon atoms per molecule, or these compounds together with al~
cohols containing from 1 to 12 carbon atoms per molecule have : -been found to be ef~ective as solvents in increasing the yield of 2-me-thyl-1,5-diamino pentane in the catalytic hydrogenation process using cobalt catalysts.
Contrary to expectations, we made the surprising disco-very tha-t -the use of a nickel catalyst, such as finely divided nickel, for example Raney nickelt or nickel on a support, pro-motes the formation of 3-methyl piperidine and suppresse~ for-mation of the 2-methyl-1, 5-diaminopentane which would normally be e~pected.
Accordingly1 the present invention provides a process for the production of 3-methyl piperidine9 which process com-prises hydrogenating 2-meth.yl glutaric acid dinitrile in the presence o~ a nickel catalyst.
According to -the process of the invention, 3-methyl piperidine is produced in a yield of over 50 mol ~, based on the theoretical yield9 and yields of over 80 mol % are possible~
'~he hydrogenation gas i5 preferably hydrogen alone.
I-t has been found that the addition of considerable quantities of such substances as, for example, ammonia, which generally promote the formation of the linear diamine, do not . -prevent the formation of 3-methyl piperidine.
Experimental inves-tigations produced the following sur-prising results.
30i As indicated in Example 1, reported herei.naf-ter there ; :
wa~ obtained 2-methyl-1,5--diaminopentane in yields of up to 90~
of the theoretical in the h~drogenation of 2-methyl glutaric , ; , , ~ :;, -. , , : .
~os~
acid dinitrile in li~uid ammonia using commercial coball ca-taly3ts such as RCI-I 45/20* (a product of ~Ioechst A~G), or 0121 (a produc-t of ~Iarshaw Chem. ~V, de Meern/holland). After changing the cobalt catalyst for nickel-con~aining supported catalysts, such as RCH 55/10*(1Ioechst AG) or 3250 ~ (~Iarshaw), there was ob-tained 3-methyl piperidine as main product in a yield of up to 90% following exactly -the same procedure. ~e production of 3-methyl piperidine is not confined to the US8 uf supported catalysts or continuous workingO It can also be produced by carrying out hydrogenation in ~L-tches, for ex-ample in the presence of Raney nickel catalyst.
~he hydrogenation of 2-methyl glutaric acid dinitrile is preferably carried out in the presence of hydrophilic subs-tances as solvents or dlluents.
The proces~ may be carried out wit;h advantag~ the presence of liquid ammonia as diluent. However, the formation of 3-me-thyl piperidine is not confined to the presence of ammonia. Comparable quanti-ties are also obtained with admix-tures comprising ammonia and aliphatic or cycloaliphatic al-cohols, preferably having from 1 to about 8 carbon a-toms, such as methanol, ethanolt propanol, isopropanol, bu-tanol, hexanol or cyclohexanol. The hydrogenation o~ 2-methyl glutaric acid dinitrile to ~`orm 3 me-thyl piperidlne in the process o~ the in-vention may also be carried out in non-alcoholic solvents, such as dicyclohexane, dioxane, tetrahydrofuran and ether~ In ge-neral, the diluent ~enerally has to satisfy the requirement of at least acting a~ a solvent for the 3-me-thyl piperidene which is formed. }Iydrogenation may even be carried out in 3-methyl piperidine itself as reaction medium~
Although the presence of~ for example 9 ammonia, tertiary aliphatic amines and, op-tionally~ alkali hydroxide and/or al-kaline earth hydroxide is not absolutely essential9 it i~ of * Trademarks ,~s, advantage insofar as it reduces or eliminates the undesirable formation of relatively high boiling secondary products~ for example condensed secondar~ and tertiary amines '~he quantity o~ diluent, where presen-t, is not cri-tical.
It is preferable to use ratios by volume of ammonia or other diluents to nitrile in the range from 1:0.01 to 1:109 prefe-rably from 1:0.1 to 1: 10 The catalysts used for hydrogena-tion may be commercial nickel catalyst, for example, RC}I 55/10 ~rS~ a product of ~arb-werke E1oechst, G49A* a product of Girdler-Sudchemi Kat. GmbH, Ni 0104 P*or 3250 T* products of Harshaw ~hemie BoVo These cata]ysts are supported cataLyts based on kieselguhr or aLumi-nlum oxlde with Ypecial activators aclded. ~t ls also possible to use puxe metal catalysts such as raney nickel. The quantity in which the catalyst is usecl is not crucial to the rsaction, ~`he only requirement in this respect is that the catalyst should be present ~ a sufficie~tly larg~ quantity to keep reduction in process. ~his quan-tity is in the same order of magnitude as the quantities normally used in the hydrogenation of nitrile compounds, that i5, genèrally betwecn 0.5 and 10~ by weight, based on th0 dini-trile.
The process may be carried out in batches or continu-ously.
In cases where hydrogenation is carried out in a batch manner, the ~atalyst is preferably used ln powdered form. After the reaction solution has been filtered off, the catalyst may be used for further hydrogenation cycles~
For continuous liquid-phase hydrogena-tion in the sump phase or by the trickle process9 -the suitably shaped ca-talyst is arranged as a fixed bed in the reactor, It is preferred tha-t the process according to the in-ventlon takes place at a temperature in the range from 80 to * Trademarks ,~c, 098~
200C and pre~erably at a temperature in the range from 75 to 150C. It is preferred that the gas comprising molecular hy-drogen is used at a pressure of up to 500 atms preferably un-der a pressure of from 50 to 200 atms The continuous process may be worked for prolonged periods with high yields of 3-methyl pipeIidine. Ammonia may be distilled o~f from the reaction produc-t and recycled into the process irrespective o~ small quantities of 3-methyl pi-peridine present therein~
3-Methyl piperidine is used as a vulcanisation acce-lerator and as an additive for lubricating oils. It is also ~n intermediate product for the production of nicotinic acid which is of significance as a medicament and animal feed sup-plement.
'~he inventlon is illustrated by the following Examples.
EXAMPLE 1 (Comparison Example~
After the air present in it had been displaced by ni-trogen, a vertically arranged 0,5 litre capaci-ty pressure tube, filled with 0.3 litres (280 g) of cobalt catalyst of the RCH 45/20 * type in the form of tablets measuring 5 x 6 mm (~ product of ~arbwerke Hoechst) was filled with hydrogen gas to a pressure of 400 atms, 70 ml/h of 2-methyl glutaric acid dinitrile and 720 ml/h of li~uid ammonia were the~ introduced into the tube $rom the bottom at a temperature maintained at 110~. A pressure of 400 atms. was maintained by continuously replacing the hydrogen consumed, the hydrogen being recycled in order to dissipate the heat of reaction. ~he reaction mix-ture i~suing from the reactor passed through a cooling coil -into a receiver from which it was continuously removed, The removal o~ ammom a by distilla~ion g~70ml/h of a ~ixture which, according to analysis by gas chromatography, contai~ed 90~9 o~ 2-methyl-1,5-diamino pen-taneS 8.2% o~ 3-methyl plperidine * Trademark~
~ -5-. ~ , .
and 1 to 2~ of more highly condensed secondary and tertiary aminesO
~ he procedure was as in Example 1, except that -the ca-talyst used in that Example was replaced by the same volume t240 g) of a nickel catalys-t of the RC~I 55/10*type in the form of -tablets measuring 5 x 6 mm ( a product of Hoechst AG), Work-ing up in the same way produced a reaction mixture con-taining 3.9~ of 2~methyl-175-diaminopentane, 90.1% of 3~methyl piperi-dine and from 6 to 8% of more highl~ condensed polyamines.
Wiith this catalyst, it was found that the hydrogenpressure could be lowered to 130 atmosphere3 without any adverse effects upon the reaction, ~.
The procedure was as in the preceding Example3, except that the pressure tube was filled with 0.33 litres ~330 g) of ~ickel catalyst 32 50 T*in the fol~ of tablets measuring 3 x ~ mm, ~nd 100 ml/h of 2-methyl glutaric acid dinitr$1e and 720 ml/h of liquid ammonia were introduced -into it at 155~/400 atmos-pheres hydrogen pres3ure. Working up in -the same way as in Example 1 ga~e 100 ml/h of a mixture which, according -to ana-lysis by gas chromatography, consisted of 90.7~ of 3-mcthyl pi-peridine and 3.7~0 of 2-me-thyl-1,5-diaminopentane.
Examples 4 to 7, which illustra-te the batch-type process9 yielded results which axe set out in the following Table. ~he general procedure adopted for -these Examples was as follows:
A high-pressure autoclave was filled, under nitrogen, with -the quantities indicated of 2-methyl glutaric acid dinitrile (MGN) and sol~ent other than ammonia~ i~ any. After the auto-clave had been closed and purged wi-th hydrogen, the quan-tity of liquid ammonla indicated was in-troduced into i-t under pressure * Trademarks ,, ;, from a measuring ~es~el~ Hydrogen was introduced while stirring in the same way as before, and the reaction was initiated by heating. After reduction had commeneed, recognisable from the drop in the hydrogen pressure and the increase in reaction tem perature, the pressure was kept constant by the continuous in-troduction of hydrogen~ whilst the -temperature was kept 20 degrees C above the initiation temperature by controlling the stirring periods After the hydrogen ~ad been absorbed~ followed by cool-ing to 40 to 50C, the excess hydrogen was blown of~ with the free ammonia. The catalyst was then separated off through a pressure filter, washed with solven-t (where one was used) and the filtrate was ~ractionated under normal pressure through a 50 cm Vigreux column. ~he removal of dlssolved ammonia and solvent left a crude d-ist~lla-te~ boiling at a maximum o~
185C, which was separated by fractina-tion through a 1 20 m packed column into the components 3-methyl piperidine (MP) hav-ing a boiling point of 125 to 126~9 and 2-methyl-1,5-diami- -nopentane (MD) having a boiling point of 192C. ~he crude dis-tillation residue was a viscous product consisting of secon-dary and tertiary amines9 of which the quan-ti-ty corresponded -to the di~ference in yield in the Table.
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3-Methyl piperidine (I) may be obtained by the hydro-genation of~ -picoline (J. Amer. Chem9 Soc, 49, (1927)t (2837). Howevers 3-methyl piperidine may also be obtained from 2-methyl glutaric acid dinitrile (II), which can be formed ~rom 2-me-thylene glutaxic acLd dinltrile b~ hydro~enating the double bond, the 2-methylene glutar:lc acid clinltri:Le helng ln turn obtainable from acrylonitrile by dimerisa-tion. One method by which 3-methyl piperidine has been obtained from 2-me-thyl glutaric acid dinitrile is by reduction wi-th sodium in ethanol (Monatshefte fur Chemie 23, (1902) 878, 883) or in butanol (Zhur.
Obshchei Khim 24, tl954) 291-298; C.A 49 (1955) 4643, 8109).
In the latter case, 3 methyl plperidine was obtained in a yield of 21~ together wi-th 68~o o~ 2-methyl-1~5-dlaminopentane.
In another synthesi~, 2-methyl glutarlc acid dinitrile was initially cyclised with sodium amide to form the glutari-midine derivative in a yield of 70%. The glu-tarimidine deriva-tive thus ~ormed was then reduced with sodium in alcohol to form 3-methyl piperidine (~ull. Chemu Soc. Japan 35, (1962) 1438-1443; Japanese patent No~ 14 140/65)o ~he above syntheses are unsuitable for the production o~
3-methyl piperidine on a commercial scale bo-th on account of the poor yield and on account of the high consumption of 30dium or sodium amide~
9~ :
Conventionally, a cobalt ca-talyst has been used in the hydrogenation of 2-methyl glutaric acid dinitrile to produce 2-methyl-1,5-diaminopen-tane in high yields. Additives ~uch as ammonia or tertiary aliphatic amines containlng from 3 to 5 carbon atoms per molecule, or these compounds together with al~
cohols containing from 1 to 12 carbon atoms per molecule have : -been found to be ef~ective as solvents in increasing the yield of 2-me-thyl-1,5-diamino pentane in the catalytic hydrogenation process using cobalt catalysts.
Contrary to expectations, we made the surprising disco-very tha-t -the use of a nickel catalyst, such as finely divided nickel, for example Raney nickelt or nickel on a support, pro-motes the formation of 3-methyl piperidine and suppresse~ for-mation of the 2-methyl-1, 5-diaminopentane which would normally be e~pected.
Accordingly1 the present invention provides a process for the production of 3-methyl piperidine9 which process com-prises hydrogenating 2-meth.yl glutaric acid dinitrile in the presence o~ a nickel catalyst.
According to -the process of the invention, 3-methyl piperidine is produced in a yield of over 50 mol ~, based on the theoretical yield9 and yields of over 80 mol % are possible~
'~he hydrogenation gas i5 preferably hydrogen alone.
I-t has been found that the addition of considerable quantities of such substances as, for example, ammonia, which generally promote the formation of the linear diamine, do not . -prevent the formation of 3-methyl piperidine.
Experimental inves-tigations produced the following sur-prising results.
30i As indicated in Example 1, reported herei.naf-ter there ; :
wa~ obtained 2-methyl-1,5--diaminopentane in yields of up to 90~
of the theoretical in the h~drogenation of 2-methyl glutaric , ; , , ~ :;, -. , , : .
~os~
acid dinitrile in li~uid ammonia using commercial coball ca-taly3ts such as RCI-I 45/20* (a product of ~Ioechst A~G), or 0121 (a produc-t of ~Iarshaw Chem. ~V, de Meern/holland). After changing the cobalt catalyst for nickel-con~aining supported catalysts, such as RCH 55/10*(1Ioechst AG) or 3250 ~ (~Iarshaw), there was ob-tained 3-methyl piperidine as main product in a yield of up to 90% following exactly -the same procedure. ~e production of 3-methyl piperidine is not confined to the US8 uf supported catalysts or continuous workingO It can also be produced by carrying out hydrogenation in ~L-tches, for ex-ample in the presence of Raney nickel catalyst.
~he hydrogenation of 2-methyl glutaric acid dinitrile is preferably carried out in the presence of hydrophilic subs-tances as solvents or dlluents.
The proces~ may be carried out wit;h advantag~ the presence of liquid ammonia as diluent. However, the formation of 3-me-thyl piperidine is not confined to the presence of ammonia. Comparable quanti-ties are also obtained with admix-tures comprising ammonia and aliphatic or cycloaliphatic al-cohols, preferably having from 1 to about 8 carbon a-toms, such as methanol, ethanolt propanol, isopropanol, bu-tanol, hexanol or cyclohexanol. The hydrogenation o~ 2-methyl glutaric acid dinitrile to ~`orm 3 me-thyl piperidlne in the process o~ the in-vention may also be carried out in non-alcoholic solvents, such as dicyclohexane, dioxane, tetrahydrofuran and ether~ In ge-neral, the diluent ~enerally has to satisfy the requirement of at least acting a~ a solvent for the 3-me-thyl piperidene which is formed. }Iydrogenation may even be carried out in 3-methyl piperidine itself as reaction medium~
Although the presence of~ for example 9 ammonia, tertiary aliphatic amines and, op-tionally~ alkali hydroxide and/or al-kaline earth hydroxide is not absolutely essential9 it i~ of * Trademarks ,~s, advantage insofar as it reduces or eliminates the undesirable formation of relatively high boiling secondary products~ for example condensed secondar~ and tertiary amines '~he quantity o~ diluent, where presen-t, is not cri-tical.
It is preferable to use ratios by volume of ammonia or other diluents to nitrile in the range from 1:0.01 to 1:109 prefe-rably from 1:0.1 to 1: 10 The catalysts used for hydrogena-tion may be commercial nickel catalyst, for example, RC}I 55/10 ~rS~ a product of ~arb-werke E1oechst, G49A* a product of Girdler-Sudchemi Kat. GmbH, Ni 0104 P*or 3250 T* products of Harshaw ~hemie BoVo These cata]ysts are supported cataLyts based on kieselguhr or aLumi-nlum oxlde with Ypecial activators aclded. ~t ls also possible to use puxe metal catalysts such as raney nickel. The quantity in which the catalyst is usecl is not crucial to the rsaction, ~`he only requirement in this respect is that the catalyst should be present ~ a sufficie~tly larg~ quantity to keep reduction in process. ~his quan-tity is in the same order of magnitude as the quantities normally used in the hydrogenation of nitrile compounds, that i5, genèrally betwecn 0.5 and 10~ by weight, based on th0 dini-trile.
The process may be carried out in batches or continu-ously.
In cases where hydrogenation is carried out in a batch manner, the ~atalyst is preferably used ln powdered form. After the reaction solution has been filtered off, the catalyst may be used for further hydrogenation cycles~
For continuous liquid-phase hydrogena-tion in the sump phase or by the trickle process9 -the suitably shaped ca-talyst is arranged as a fixed bed in the reactor, It is preferred tha-t the process according to the in-ventlon takes place at a temperature in the range from 80 to * Trademarks ,~c, 098~
200C and pre~erably at a temperature in the range from 75 to 150C. It is preferred that the gas comprising molecular hy-drogen is used at a pressure of up to 500 atms preferably un-der a pressure of from 50 to 200 atms The continuous process may be worked for prolonged periods with high yields of 3-methyl pipeIidine. Ammonia may be distilled o~f from the reaction produc-t and recycled into the process irrespective o~ small quantities of 3-methyl pi-peridine present therein~
3-Methyl piperidine is used as a vulcanisation acce-lerator and as an additive for lubricating oils. It is also ~n intermediate product for the production of nicotinic acid which is of significance as a medicament and animal feed sup-plement.
'~he inventlon is illustrated by the following Examples.
EXAMPLE 1 (Comparison Example~
After the air present in it had been displaced by ni-trogen, a vertically arranged 0,5 litre capaci-ty pressure tube, filled with 0.3 litres (280 g) of cobalt catalyst of the RCH 45/20 * type in the form of tablets measuring 5 x 6 mm (~ product of ~arbwerke Hoechst) was filled with hydrogen gas to a pressure of 400 atms, 70 ml/h of 2-methyl glutaric acid dinitrile and 720 ml/h of li~uid ammonia were the~ introduced into the tube $rom the bottom at a temperature maintained at 110~. A pressure of 400 atms. was maintained by continuously replacing the hydrogen consumed, the hydrogen being recycled in order to dissipate the heat of reaction. ~he reaction mix-ture i~suing from the reactor passed through a cooling coil -into a receiver from which it was continuously removed, The removal o~ ammom a by distilla~ion g~70ml/h of a ~ixture which, according to analysis by gas chromatography, contai~ed 90~9 o~ 2-methyl-1,5-diamino pen-taneS 8.2% o~ 3-methyl plperidine * Trademark~
~ -5-. ~ , .
and 1 to 2~ of more highly condensed secondary and tertiary aminesO
~ he procedure was as in Example 1, except that -the ca-talyst used in that Example was replaced by the same volume t240 g) of a nickel catalys-t of the RC~I 55/10*type in the form of -tablets measuring 5 x 6 mm ( a product of Hoechst AG), Work-ing up in the same way produced a reaction mixture con-taining 3.9~ of 2~methyl-175-diaminopentane, 90.1% of 3~methyl piperi-dine and from 6 to 8% of more highl~ condensed polyamines.
Wiith this catalyst, it was found that the hydrogenpressure could be lowered to 130 atmosphere3 without any adverse effects upon the reaction, ~.
The procedure was as in the preceding Example3, except that the pressure tube was filled with 0.33 litres ~330 g) of ~ickel catalyst 32 50 T*in the fol~ of tablets measuring 3 x ~ mm, ~nd 100 ml/h of 2-methyl glutaric acid dinitr$1e and 720 ml/h of liquid ammonia were introduced -into it at 155~/400 atmos-pheres hydrogen pres3ure. Working up in -the same way as in Example 1 ga~e 100 ml/h of a mixture which, according -to ana-lysis by gas chromatography, consisted of 90.7~ of 3-mcthyl pi-peridine and 3.7~0 of 2-me-thyl-1,5-diaminopentane.
Examples 4 to 7, which illustra-te the batch-type process9 yielded results which axe set out in the following Table. ~he general procedure adopted for -these Examples was as follows:
A high-pressure autoclave was filled, under nitrogen, with -the quantities indicated of 2-methyl glutaric acid dinitrile (MGN) and sol~ent other than ammonia~ i~ any. After the auto-clave had been closed and purged wi-th hydrogen, the quan-tity of liquid ammonla indicated was in-troduced into i-t under pressure * Trademarks ,, ;, from a measuring ~es~el~ Hydrogen was introduced while stirring in the same way as before, and the reaction was initiated by heating. After reduction had commeneed, recognisable from the drop in the hydrogen pressure and the increase in reaction tem perature, the pressure was kept constant by the continuous in-troduction of hydrogen~ whilst the -temperature was kept 20 degrees C above the initiation temperature by controlling the stirring periods After the hydrogen ~ad been absorbed~ followed by cool-ing to 40 to 50C, the excess hydrogen was blown of~ with the free ammonia. The catalyst was then separated off through a pressure filter, washed with solven-t (where one was used) and the filtrate was ~ractionated under normal pressure through a 50 cm Vigreux column. ~he removal of dlssolved ammonia and solvent left a crude d-ist~lla-te~ boiling at a maximum o~
185C, which was separated by fractina-tion through a 1 20 m packed column into the components 3-methyl piperidine (MP) hav-ing a boiling point of 125 to 126~9 and 2-methyl-1,5-diami- -nopentane (MD) having a boiling point of 192C. ~he crude dis-tillation residue was a viscous product consisting of secon-dary and tertiary amines9 of which the quan-ti-ty corresponded -to the di~ference in yield in the Table.
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,. , .
': .
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Claims (25)
1. A process for the production of 3-methyl piperi-dine, which comprises hydrogenating 2-methyl glutaric acid dinitrile in the presence of a nickel catalyst.
2. A process according to claim 1, wherein the catalyst comprises nickel on a support.
3. A process according to claim 2, wherein the support is kieselguhr.
4. A process according to claim 2, wherein the support is aluminium oxide.
5. A process according to claim 1, wherein the catalyst comprises a Raney nickel catalyst.
6. A process according to claim 1, 2 or 4, wherein -the catalyst is present in a proportion of from 0.5 to 10% by weight based on the dinitrile.
7. A process according to claim 1, 2 or 4, wherein the catalyst is in powder form.
8. A process according to claim 1, wherein the hy-drogenation is carried out at a pressure which is not greater than 500 atmospheres.
9. A process according to claim 83 wherein the pressure is comprised between 50 and 200 atmospheres.
10. A process according to claim 1, wherein the hydrogena-tion is carried out at a temperature of from 80 to 200°C.
11. A process according to claim 10, wherein the tem-perature is comprised between 75 and 150°C.
12. A process according to claim 1, wherein the hydro-genation is carried out in the presence of 2 liquid diluent which is a solvent for the 3-methyl piperidine.
13. A process according to claim 12, wherein the i-nitial ratio by volume or diluent to dinitrile is from 1: 0.01 to 1:10.
14. A process according to claim 13, wherein the ini-tial ratio by volume of diluent to dinitrile is from 1:0.1 to 1: 1.
15. A process according to claims 12, 13 or 149 wherein the diluent comprises ammonia.
16. A process according to claims 12, 13 or 14, wherein the diluent comprises an aliphatic alcohol having from 1 to 8 carbon atoms.
17. A process according to claim 12, 13 or 14, wherein the diluent comprises methanol, ethanol, propanol, butanol or hexanol.
18. A process according to claims 12, 13 or 14, wherein the diluent comprises a cycloaliphatic alcohol having from 1 to 8 carbon atoms.
19. A process according to claims 12, 13 or 14 wherein the diluent comprises cyclohexanol.
20. A process according to claims 129 13 or 14, wherein the diluent comprises cyclohexane, dioxane, tetrahydrofuran or ether.
21. A process according to claim 12, wherein the diluent comprises ammonia in admixture with a solvent selected from the group comprising cyclohexane, dioxane, tetradrofuran, ether, aliphatic and cycloaliphatic alcohols having from 1 to 8 car-bon atoms.
22. A process according to claim 1, wherein the hy-drogenation is carried out in the presence of a tertiary ali-phatic amine.
23. A process according to claim 1, wherein the hy-drogenation is carried out in the presence of an alkali earth hydroxide and/or alkali metal hydroxide.
24. A process according to claim 1, wherein the hydro-genation is carried out in a batch manner.
25. A process according to claim 1, wherein the hydro-genation is carried out continuously.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752514004 DE2514004C3 (en) | 1975-03-29 | 1975-03-29 | Process for the preparation of 3-methylpiperidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050987A true CA1050987A (en) | 1979-03-20 |
Family
ID=5942726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA248,739A Expired CA1050987A (en) | 1975-03-29 | 1976-03-24 | Process for the production of 3-methyl piperidine |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS51122074A (en) |
| BE (1) | BE840151A (en) |
| BR (1) | BR7601871A (en) |
| CA (1) | CA1050987A (en) |
| CH (1) | CH607999A5 (en) |
| DD (1) | DD124474A5 (en) |
| DE (1) | DE2514004C3 (en) |
| ES (1) | ES446437A1 (en) |
| FR (1) | FR2306202A1 (en) |
| GB (1) | GB1488335A (en) |
| IT (1) | IT1057358B (en) |
| NL (1) | NL7603259A (en) |
| PL (1) | PL97986B1 (en) |
| SU (1) | SU569284A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI386395B (en) * | 2008-12-15 | 2013-02-21 | Taigen Biotechnology Co Ltd | Stereoselective synthesis of piperidine derivatives |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3028384A1 (en) * | 1980-07-26 | 1982-02-25 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING N-ALKYLPIPERIDINES AND N-ALKYLPYRROLIDINES |
| DE3104765A1 (en) * | 1981-02-11 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PYRIDINES OR PYRROLS FROM (ALPHA), (OMEGA) -DINITRILES |
| DE3329692A1 (en) * | 1983-08-17 | 1985-03-07 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING 5- TO 7-LINK CYCLIC IMINES |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2790804A (en) * | 1955-06-04 | 1957-04-30 | Ici Ltd | Catalytic hydrogenation |
| US3408397A (en) * | 1965-06-01 | 1968-10-29 | Nat Distillers Chem Corp | Methyl pentamethylene diamine process |
-
1975
- 1975-03-29 DE DE19752514004 patent/DE2514004C3/en not_active Expired
-
1976
- 1976-03-10 SU SU7602331901A patent/SU569284A3/en active
- 1976-03-24 CA CA248,739A patent/CA1050987A/en not_active Expired
- 1976-03-24 CH CH366576A patent/CH607999A5/en not_active IP Right Cessation
- 1976-03-25 GB GB1215476A patent/GB1488335A/en not_active Expired
- 1976-03-26 DD DD19206376A patent/DD124474A5/xx unknown
- 1976-03-26 FR FR7608961A patent/FR2306202A1/en active Granted
- 1976-03-26 IT IT4875076A patent/IT1057358B/en active
- 1976-03-26 BR BR7601871A patent/BR7601871A/en unknown
- 1976-03-27 ES ES446437A patent/ES446437A1/en not_active Expired
- 1976-03-27 PL PL18828776A patent/PL97986B1/en unknown
- 1976-03-29 BE BE165655A patent/BE840151A/en not_active IP Right Cessation
- 1976-03-29 NL NL7603259A patent/NL7603259A/en not_active Application Discontinuation
- 1976-03-29 JP JP3510776A patent/JPS51122074A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI386395B (en) * | 2008-12-15 | 2013-02-21 | Taigen Biotechnology Co Ltd | Stereoselective synthesis of piperidine derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| BE840151A (en) | 1976-09-29 |
| BR7601871A (en) | 1976-10-05 |
| JPS51122074A (en) | 1976-10-25 |
| ES446437A1 (en) | 1977-06-16 |
| DE2514004C3 (en) | 1981-09-10 |
| PL97986B1 (en) | 1978-04-29 |
| NL7603259A (en) | 1976-10-01 |
| GB1488335A (en) | 1977-10-12 |
| SU569284A3 (en) | 1977-08-15 |
| FR2306202A1 (en) | 1976-10-29 |
| DE2514004B2 (en) | 1979-03-29 |
| CH607999A5 (en) | 1978-12-15 |
| DD124474A5 (en) | 1977-02-23 |
| DE2514004A1 (en) | 1976-09-30 |
| IT1057358B (en) | 1982-03-10 |
| FR2306202B1 (en) | 1979-07-13 |
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