US3658824A - Process for the preparation of piperidine - Google Patents
Process for the preparation of piperidine Download PDFInfo
- Publication number
- US3658824A US3658824A US23981A US3658824DA US3658824A US 3658824 A US3658824 A US 3658824A US 23981 A US23981 A US 23981A US 3658824D A US3658824D A US 3658824DA US 3658824 A US3658824 A US 3658824A
- Authority
- US
- United States
- Prior art keywords
- piperidine
- autoclave
- ammonia
- cyanobutyraldehyde
- methanol
- 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.)
- Expired - Lifetime
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
- C07D295/02—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
- C07D295/027—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 containing only one hetero ring
-
- 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
Definitions
- the present invention relates to a process for the preparation of piperidine.
- piperidine can be prepared quite economically according to the process of the present invention, whereby 4-cyanobutyraldehyde is hydrogenated in the presence of a hydrogenation catalyst and ammonia.
- the 4-cyanobutyraldehyde starting material for this process may be prepared in a suitable maner from relatively inexpensive basic materials such as acetaldehyde and acrylonitrile by a process, for example, according to application U.S. Ser. No. 8,704 filed Feb. 4, 1970 by the present applicants.
- the amount of ammonia required in practicing the present invention is not critical, and may be varied over a wide range. A favorable influence on the yield can be noticed at an ammonia to 4-cyanobutyraldehyde molar ratio as low as about 2:1. For optimum results, however, it is preferable to use an ammonia to 4-cyanobutyraldehyde molar ratio within a range from about 5:1 to 25:1.
- various known and typical hydrogenation catalysts may be employed, such as nickel or cobalt on a carrier or in the form of a Raney-catalyst and catalysts containing a platinum-metal such as platinum and palladium.
- the present process can be carried out with or without an inert solvent.
- suitable solvents include water, lower alkanols such as methanol, ethanol and isopropanol, and lower alkyl ethers, or mixtures of any of the above.
- the present process is preferably carried out at a temperature in the range of between about 50 C. up to about 200 C., but most preferably at a temperature of about 80 to 150 C.
- a pressure in the range from about -1 to 300 atmospheres may be used but a pressure of 25 to 125 atmospheres is preferable.
- the resulting reaction product obtained by the present process consists primarily of piperidine. There may also be some by-product formation of 1,5-diaminopentane, but this is not objectionable in that 1,5-diaminopentane can be recovered and easily converted to piperidine, for example by a process as disclosed in Chemische Berichte, volume 95, 1962, page 1992.
- the process of the present invention can be carried out either continuously or as a batch process by any of a number of known hydrogenation methods.
- a batch process it is preferably carried out by adding the 4- cyanobutyraldehyde to the ammonia-catalyst mixture whilethe latter is kept under hydrogen pressure. In this way, the'by-product formation of 1,5-diaminopentane is minimized.
- EXAMPLE 1 Methanol (250 ml.) and ammonia (425 g., 25 moles) were introduced into a 5 l. autoclave provided with a stirrer and a feed line, along with a Raney nickel catalyst (30 g.). The ammonia was introduced by connecting the autoclave with a bomb containing liquid ammonia. Hydrogen was fed into the autoclave until a pressure of 55 atmospheres was reached whereupon this mixture in the autoclave was heated to 125 C. A solution of 4-cyanobutyraldehyde (121.3 g., 1.25 moles) in methanol (750 ml.) was then added to the autoclave with simultaneous stirring over a period of 1.5 hours while maintaining the mixture temperature at 125 C.
- EXAMPLE 2 Methanol (350 ml.) and ammonia (170 g., 10 moles) were introduced into a 5 l. autoclave provided with a stirrer and fed line, along with a Raney nickel catalyst (40 g.). Hydrogen was fed into the autoclave until a pressure of 80 atmospheres Wes reached whereupon the mixture in the autoclave was heated to 120 C. A solution of 4- cyanobutyraldehyde (121.3 g., 1.25 moles) in methanol (750 ml.) was then added to the autoclave with simultaneous stirring over a period of 2 hours while maintaining the mixture temperature at 120 C. An additional ml. of methanol was fed to the autoclave in order to wash out the feed line.
- EXAMPLE 3 Methanol (400 ml.) and ammonia (380 g., 22.5 moles) were introduced into a l. autoclave provided with a stirrer and feed line, along with a Raney nickel catalyst (30 g.). Hydrogen was fed into the autoclave until a pressure of 115 atmospheres was reached whereupon this mixture in the autoclave was heated to 95 C. A solution of 4-cyanobutyraidehyde (120 g. of impure 4-cyanobutyraldehyde, equivalent to 1.16 moles of pure 4-cyan'obutyraldehyde) in methanol (700 ml.) was then added to the autoclave with simultaneous stirring over a period of 2 hours while maintaining the mixture at temperature of 95 C.
- 4-cyanobutyraidehyde 120 g. of impure 4-cyanobutyraldehyde, equivalent to 1.16 moles of pure 4-cyan'obutyraldehyde
- EXAMPLE 4 4-cyanobutyraldehyde (121.3 g., 1.25 moles) dissolved in methanol (750 ml.), and ammonia (425 g., 25 moles) were fed into a 5 l. autoclave provided with a stirrer and feed line, along with a Raney nickel catalyst (40 g.). Hydrogen was fed into the autoclave until a pressure of 60 atmospheres was reached. The mixture in the autoclave was then heated to 105 C. with simultaneous stirring over a period of 1 hour and thereafter maintained at this temperature for an additional hour with continuous stirring. The mixture was then cooled to room temperature. The autoclave was opened, the catalyst recovered by filtration, and the filtrate was dried with sodium sulphate.
- the dried filtrate was then distilled to recover the methanol, and the remaining product contained 73.3 g. of piperidine (0.86 mole) having a boiling point of 103-1104 C. and 30.6 g. of 1,5-diaminopentane (0.3 mole) having a boiling point of 174-177" C.
- the yield calculated on the basis of A-cyanobutyraldehyde was 69% for the piperidine, and 24%. for the 1,5-diaminopentane.
- a process for the preparation of piperidine consisting essentially in the hydrogenation of 4-cyanobutyraldehyde in the presence of a hydrogenation catalyst and ammonia wherein said hydrogenation is carried out at a temperature of between and 200 C. and at a pressure of between 1 and 300 atmospheres.
Landscapes
- 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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL6904908A NL6904908A (de) | 1969-03-29 | 1969-03-29 | |
US2398170A | 1970-03-30 | 1970-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3658824A true US3658824A (en) | 1972-04-25 |
Family
ID=26644418
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US23981A Expired - Lifetime US3658824A (en) | 1969-03-29 | 1970-03-30 | Process for the preparation of piperidine |
Country Status (7)
Country | Link |
---|---|
US (1) | US3658824A (de) |
BE (1) | BE748143A (de) |
CH (1) | CH531514A (de) |
DE (1) | DE2014837A1 (de) |
FR (1) | FR2040098A5 (de) |
GB (1) | GB1243327A (de) |
NL (1) | NL6904908A (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3971792A (en) * | 1970-03-23 | 1976-07-27 | Ciba-Geigy Ag | Process for the manufacture of 4-amino-3-aminomethylpiperidine |
US4207260A (en) * | 1978-12-20 | 1980-06-10 | Uop Inc. | Preparation of tertiary amines |
CN116041278A (zh) * | 2022-12-30 | 2023-05-02 | 摩珈(上海)生物科技有限公司 | 一种使用微反应器装置和含钌催化剂制备哌啶的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116041279A (zh) * | 2022-12-30 | 2023-05-02 | 摩珈(上海)生物科技有限公司 | 一种使用高压釜装置和含钌催化剂制备哌啶的方法 |
-
1969
- 1969-03-29 NL NL6904908A patent/NL6904908A/xx unknown
-
1970
- 1970-03-24 GB GB04339/70A patent/GB1243327A/en not_active Expired
- 1970-03-26 CH CH463270A patent/CH531514A/de not_active IP Right Cessation
- 1970-03-26 DE DE19702014837 patent/DE2014837A1/de active Pending
- 1970-03-27 FR FR7011196A patent/FR2040098A5/fr not_active Expired
- 1970-03-27 BE BE748143D patent/BE748143A/xx unknown
- 1970-03-30 US US23981A patent/US3658824A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3971792A (en) * | 1970-03-23 | 1976-07-27 | Ciba-Geigy Ag | Process for the manufacture of 4-amino-3-aminomethylpiperidine |
US4207260A (en) * | 1978-12-20 | 1980-06-10 | Uop Inc. | Preparation of tertiary amines |
CN116041278A (zh) * | 2022-12-30 | 2023-05-02 | 摩珈(上海)生物科技有限公司 | 一种使用微反应器装置和含钌催化剂制备哌啶的方法 |
Also Published As
Publication number | Publication date |
---|---|
NL6904908A (de) | 1970-10-01 |
DE2014837A1 (de) | 1970-10-08 |
CH531514A (de) | 1972-12-15 |
GB1243327A (en) | 1971-08-18 |
BE748143A (fr) | 1970-09-28 |
FR2040098A5 (de) | 1971-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2368366A (en) | Process for the production of lactones | |
US3322815A (en) | Aminoalkanenitriles and process for preparing the same | |
CA2015251A1 (en) | Amination of carbonyls | |
US4847394A (en) | Preparation of 2,2-di-[lycidyloxycyclohexyl]-propane | |
US3448118A (en) | Preparation of n-substituted alpha-pyrrolidones | |
US3225066A (en) | Process for the preparation of tetrahydrofuran-cis, 2,5-dicarboxylic acid and salts thereof | |
US3658824A (en) | Process for the preparation of piperidine | |
KR100404287B1 (ko) | 카프로락탐의제조방법 | |
US3230259A (en) | Preparation of o-phenylenediamines | |
KR20000071062A (ko) | ε-카프로락탐과 ε-카프로락탐 전구물질의 수성 혼합물의 연속제조방법 | |
US3812148A (en) | Preparation of 2-pyrrolidone | |
US3709881A (en) | Preparation of n-alkylmorpholines from diethylene glycol and alkylamines | |
US2088633A (en) | Process for preparing hydroaromatic lactones | |
US2846449A (en) | Production of tetrahydrofuran | |
US3520934A (en) | Hydrogenation of cinnamaldehyde | |
US3377374A (en) | 4-(aminomethyl)cyclohexane-carbonitrile | |
US2908722A (en) | Process for preparing saturated monohydric alcohols | |
US3745164A (en) | Preparation of butyrolactam and valerolactam | |
US3048580A (en) | Preparation of a-aminolactams by cata- | |
US3900522A (en) | Production of catechol | |
US3812149A (en) | Preparation of 2-pyrrolidinone | |
US3148202A (en) | Diisocyanato tricyclodecane | |
US3401161A (en) | Preparation of epsilon-caprolactam | |
US2782191A (en) | Nitrogen containing carbinols | |
US4045484A (en) | Process for preparing N'-methyl acethydrazide |