CA1047041A - Process for the preparation of 2-aminomethyl-pyrrolidine - Google Patents
Process for the preparation of 2-aminomethyl-pyrrolidineInfo
- Publication number
- CA1047041A CA1047041A CA220,855A CA220855A CA1047041A CA 1047041 A CA1047041 A CA 1047041A CA 220855 A CA220855 A CA 220855A CA 1047041 A CA1047041 A CA 1047041A
- Authority
- CA
- Canada
- Prior art keywords
- pyrrolidine
- aminomethyl
- benzyl
- pyrrolidone
- catalytic reduction
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
- C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
A B S T R A C T
The invention relates to a process for preparing 2-aminomethyl-pyrrolidine whereby 2-pyrrolidone is reacted with a reactive benzylated compound having the formula X-CH2-C6H5, in which X represents a reactive group, and that the N-benzyl-2-pyrrolidone formed is treated with a lower alkyl sulphate, an alkaline alcoholate and nitromethane, and that the N-benzyl-2-nitromethylene-pyrrolidine produced is reduced to 2-aminomethyl-pyrrolidine, either directly by catalytic reduction or the intermediate of N-benzyl-2-aminomethyl-pyrrolidine formed is further reduced by chemical or catalytic reduction to form 2-aminomethyl-pyrrolidine.
The invention relates to a process for preparing 2-aminomethyl-pyrrolidine whereby 2-pyrrolidone is reacted with a reactive benzylated compound having the formula X-CH2-C6H5, in which X represents a reactive group, and that the N-benzyl-2-pyrrolidone formed is treated with a lower alkyl sulphate, an alkaline alcoholate and nitromethane, and that the N-benzyl-2-nitromethylene-pyrrolidine produced is reduced to 2-aminomethyl-pyrrolidine, either directly by catalytic reduction or the intermediate of N-benzyl-2-aminomethyl-pyrrolidine formed is further reduced by chemical or catalytic reduction to form 2-aminomethyl-pyrrolidine.
Description
~4`-~4~
The present invention concerns a novel process for the preparation of 2-aminomethyl-pyrrolidine (V) and the :.
synthesis intermediates.
The process of the invention comprises reacting 2-pyrrolidone (I) with a reactive benzylated compound, then reacting the resulting N-benzyl-2-pyrrolidone (II~ with a lower alkyl sulphate, an alkaline alcoholate, and nitromethane, ~ -to form N-benzyl-2-nitromethylene-pyrrolidine (III), which by reduction results in N-benzyl-2-aminomethyl-pyrrolidine (IV), then 2-aminomethyl-pyrrolidine (V).
The process of the invention can be illustrated by the following diagram:
= 1- X-CH2~
(I) (II) :
(1) S04(Rl)2 ¦ ¦ ;
~, ~ ~=CHN02 ~ : :
The present invention concerns a novel process for the preparation of 2-aminomethyl-pyrrolidine (V) and the :.
synthesis intermediates.
The process of the invention comprises reacting 2-pyrrolidone (I) with a reactive benzylated compound, then reacting the resulting N-benzyl-2-pyrrolidone (II~ with a lower alkyl sulphate, an alkaline alcoholate, and nitromethane, ~ -to form N-benzyl-2-nitromethylene-pyrrolidine (III), which by reduction results in N-benzyl-2-aminomethyl-pyrrolidine (IV), then 2-aminomethyl-pyrrolidine (V).
The process of the invention can be illustrated by the following diagram:
= 1- X-CH2~
(I) (II) :
(1) S04(Rl)2 ¦ ¦ ;
~, ~ ~=CHN02 ~ : :
(2) R20M CH2 ~ H2/catalyst
(3) CH3N02 (III) \=/
CH2 - NH21 ~ CH2 - NH2 CH2 ~ H
(IV) ~==~J , (V) in which X is a reactive group or atom such as a halogen atom or a tosyl group, Rl is a lower alkyl group containing from 1 to 3 carbon atoms, R2 iS an alkyl group, M is an alkali metal.
~. ~
The following can be mentioned as examples of the reactive benzylated compound used in the first stage of the process: benzyl halides such as chloride, bromide or iodide, or benzyl p-toluene sulphonate. The action oF these compounds on pyrrolidone occurs in a solvent such as benzene, toluene or xylene, in a basic medium such as an alkaline alcoholate.
In accordance with the process oF the invention, a lower alkyl sulphate, an alkaline alcoholate and nitromethane are reacted on N-benzyl-2-pyrrolidone (II) to produce compound 10 (III). The following can be mentioned as examples oF a lower alkyl sulphate: dimethyl, diethyl, dipropyl or diisopropyl sulphates. The alkali metal alcoholate is produced by the action of an alcohol such as methanol, ethanol, propanol, isopropanol, butanol, etc., on an alkali metal such as sodium or potassium. ~
The product produced, having the formula: ~ .
l ;~`
IH2~
Rl and R2 being as defined above, can be isolated and purified.
It can also be used for the following reaction, without being isolated.
Reduction of N-benzyl-2-nitromethylene-pyrrolidine (III) results in 2-aminomethyl-pyrrolidine (V) through the intermediary of N-benzyl-2-aminomethyl-pyrrolidine (IV) which can be isolated and purified.
In this latter case, reduction of the compound (III) to the compound (IV) can be effected by chemical reduction by means of metals such as iron or zinc, in the presence of acids ' ' ' , ?
~0~704~L
such as hydrochloric or acetic acid, or by reduction by means of hydrogen in the presence of catalysts such as Raney nickel, palladium-bearing carbon, platinum black, etc. The hydrogen-ation pressure used varies from atmospheric pressure to 150 atmospheres.
It is also possible to effect the reduction of N-benzyl-2-nitromethylene-pyrrolidine (III) to 2-aminomethyl-pyrrolidine (V) without isolating N-benzyl-2-aminomethyl-pyrrolidine (IV).
Reduction is effected in an acid medium by hydrogen in the presence of catalysts, as described above.
The 2-aminomethyl-pyrrolidine produced can be con-verted into salts by the addition of a mineral acid such as hydrochloric, hydrobromic or sulphuric acid, or an organic acid such as oxalic acid, tartric acid, maleic acid, etc.
The process of the present invention has the advantage of producing 2-aminomethyl-pyrrolidine from 2-pyrrolidone, a widely available product at moderate cost, in `~
a reduced number of stages (three stages, or four stages if the intermediate (IV) is isolated), in a very good yield andin a very high state of purity.
As 2-aminomethyl-pyrrolidine is used as an inter-mediate in the synthesis of substances having attractive pharmacodynamic properties, the purity criterion is here essential.
The following examples illustrate the present invention but without limiting it.
~4~
2-aminomethyl-pyrrolidine a) N-benzyl-2-pyrrolidone 138 g of sodium are introduced into a 6 litre balloon flask containing 2,100 ml of ethanol. At the end of the reaction, the mixture is cooled to from 15 to 20C and 510 9 of 2-pyrrolidone is introduced. After evaporation of the alcohol under reduced pressure, 2,400 ml of xylene is added. A part of the solvent is distilled in order completely to remove the alcohol.
With the mixture at reflux temperature, 759 g of benzyl chloride is introduced. After the reaction temperature has been maintained for 8 hours at the reflux temperature, the ~ -mixture is cooled and filtered. The solvent is distilled under vacuum and after purification by distillation, 862 g of N-benzyl-2-pyrrolidone is produced (yield: 82%; boiling point/
23 mm Hg: 148 to 150C).
b) N-benzyl-2-nitromethylene-pyrrolidine 875 g of N-benzyl-2-pyrrolidone and 630 9 of dimethyl sulphate are introduced into a 6 litre balloon flask.
After this mixture has been heated for 1 1/2 hours at 65C, followed by cooling to about 15C, the solution of 115 9 of sodium in 3500 ml of methanol is introduced. The reaction mixture is left with agitation for 30 minutes at ambient temperature and then 460 g of nitromethane is added. Agitation is maintained for 1 hour, then the solution is left at rest for about 12 hours. The solvent is then evaporated under vacuum.
After the addition of 800 ml of water to the residue, crystallization, filtration of the crystals formed, washing with water and drying in a drying oven at 50C, 764 9 of N-~L~4~V~ :
benzyl-2-nitramethylene-pyrrolidine is produced (yield: 71%i melting point: 99C).
c) 2-aminomethyl-pyrrolidine Introduced into a 1 litre autoclave are 61 g of N- -benzyl-2-nitromethylene-pyrrolidine, 300 ml of ethanol, hydro-chloric ethanol in an amount sufficient for the number of hydrochloric acid mols introduced to be double the number of ~ ;
nitromethylene-pyrrolidine, approximately 150 9 Raney nickel, and hydrogen, until a pressure of 50 kg ;s produced. The autoclave is left under agitation for 1 hour, then further hydrogen is introduced until the pressure reaches 145 kg.
After the mixture has been heated for 5 hours at 100C, followed by cooling and filtration of the nickel, the solvent is evaporated to dryness at reduced pressure. The residue is dissolved in 200 ml of methylene chloride, then 40% sodium hydroxide and potassium hydroxide in pellet form are added.
After decantation, the organic phase is dried and .
filtered, and the solvent is evaporated.
Distillation is effected to produce 17 9 of 2-aminomethyl-pyrrolidine (boiling point/32 mm Hg: 86 to 89C;
yield: 60.7%).
2-aminomethyl-pyrrolid1ne .
a) identical to Example 1 b) identical to Example 1 c) N-benzyl-2-aminomethyl-pyrrolidine Introduced into a 5 litre autoclave are 218 9 of N-benzyl-2-nitromethylene-pyrrolidine, 900 ml of methanol, 120 9 of Raney nickel, and hydrogen, until the pressure reaches 40 kg. The autoclave is left under agitation for 1 1/2 hours.
The mixture is then cooled. After filtration, and washing of . .
. .
, . . . .
- ` ~
7~
the nickel with methanol, evaporation of the solvent and distillation of the residue, 179 9 of N-benzyl-2-aminomethyl-pyrrolidine is produced (yield: 94%; boiling point/7 mm Hg:
137 to 140C~.
d) 2-aminomethyl-pyrrolidine Introduced into a 1 litre autoclave is 190 9 of N-benzyl-2-aminomethyl-pyrrolidine, a solution of 160 ml of hydrochloric acid (d = 1.18) in 140 ml of water and approxi- ;
mately 75 9 of Raney nickel, and hydrogen until a pressure of 10 130 kg is reached. The autoclave is agitated and then heated ;~ ~ -to 100C. Further hydrogen is introduced until the pressure reaches 100 kg, and the autoclave is left under agitation for 1 hour.
After cooling of the mixture, the nickel is filtered and washed with water. The filtrate is evaporated to dryness under reduced pressure, then the residue is dissolved in 500 ml of ethanol and the solution is neutralized by means of a solution of 128 g of potassium hydroxide in pellet form, in 600 ml of ethyl alcohol.
AftPr filtration of the potassium chloride formed and distillation of the solvent under vacuum, the residue is dissolved in benzene. The benzene solution is dried and filtered and the solvent is distilled under reduced pressure.
Distillation of the residue provides 78 9 of 2-aminomethyl-pyrrolidine (yield: 78%i boiling point: 167 to 170C; purity by gas chromatography: 97.6%).
CH2 - NH21 ~ CH2 - NH2 CH2 ~ H
(IV) ~==~J , (V) in which X is a reactive group or atom such as a halogen atom or a tosyl group, Rl is a lower alkyl group containing from 1 to 3 carbon atoms, R2 iS an alkyl group, M is an alkali metal.
~. ~
The following can be mentioned as examples of the reactive benzylated compound used in the first stage of the process: benzyl halides such as chloride, bromide or iodide, or benzyl p-toluene sulphonate. The action oF these compounds on pyrrolidone occurs in a solvent such as benzene, toluene or xylene, in a basic medium such as an alkaline alcoholate.
In accordance with the process oF the invention, a lower alkyl sulphate, an alkaline alcoholate and nitromethane are reacted on N-benzyl-2-pyrrolidone (II) to produce compound 10 (III). The following can be mentioned as examples oF a lower alkyl sulphate: dimethyl, diethyl, dipropyl or diisopropyl sulphates. The alkali metal alcoholate is produced by the action of an alcohol such as methanol, ethanol, propanol, isopropanol, butanol, etc., on an alkali metal such as sodium or potassium. ~
The product produced, having the formula: ~ .
l ;~`
IH2~
Rl and R2 being as defined above, can be isolated and purified.
It can also be used for the following reaction, without being isolated.
Reduction of N-benzyl-2-nitromethylene-pyrrolidine (III) results in 2-aminomethyl-pyrrolidine (V) through the intermediary of N-benzyl-2-aminomethyl-pyrrolidine (IV) which can be isolated and purified.
In this latter case, reduction of the compound (III) to the compound (IV) can be effected by chemical reduction by means of metals such as iron or zinc, in the presence of acids ' ' ' , ?
~0~704~L
such as hydrochloric or acetic acid, or by reduction by means of hydrogen in the presence of catalysts such as Raney nickel, palladium-bearing carbon, platinum black, etc. The hydrogen-ation pressure used varies from atmospheric pressure to 150 atmospheres.
It is also possible to effect the reduction of N-benzyl-2-nitromethylene-pyrrolidine (III) to 2-aminomethyl-pyrrolidine (V) without isolating N-benzyl-2-aminomethyl-pyrrolidine (IV).
Reduction is effected in an acid medium by hydrogen in the presence of catalysts, as described above.
The 2-aminomethyl-pyrrolidine produced can be con-verted into salts by the addition of a mineral acid such as hydrochloric, hydrobromic or sulphuric acid, or an organic acid such as oxalic acid, tartric acid, maleic acid, etc.
The process of the present invention has the advantage of producing 2-aminomethyl-pyrrolidine from 2-pyrrolidone, a widely available product at moderate cost, in `~
a reduced number of stages (three stages, or four stages if the intermediate (IV) is isolated), in a very good yield andin a very high state of purity.
As 2-aminomethyl-pyrrolidine is used as an inter-mediate in the synthesis of substances having attractive pharmacodynamic properties, the purity criterion is here essential.
The following examples illustrate the present invention but without limiting it.
~4~
2-aminomethyl-pyrrolidine a) N-benzyl-2-pyrrolidone 138 g of sodium are introduced into a 6 litre balloon flask containing 2,100 ml of ethanol. At the end of the reaction, the mixture is cooled to from 15 to 20C and 510 9 of 2-pyrrolidone is introduced. After evaporation of the alcohol under reduced pressure, 2,400 ml of xylene is added. A part of the solvent is distilled in order completely to remove the alcohol.
With the mixture at reflux temperature, 759 g of benzyl chloride is introduced. After the reaction temperature has been maintained for 8 hours at the reflux temperature, the ~ -mixture is cooled and filtered. The solvent is distilled under vacuum and after purification by distillation, 862 g of N-benzyl-2-pyrrolidone is produced (yield: 82%; boiling point/
23 mm Hg: 148 to 150C).
b) N-benzyl-2-nitromethylene-pyrrolidine 875 g of N-benzyl-2-pyrrolidone and 630 9 of dimethyl sulphate are introduced into a 6 litre balloon flask.
After this mixture has been heated for 1 1/2 hours at 65C, followed by cooling to about 15C, the solution of 115 9 of sodium in 3500 ml of methanol is introduced. The reaction mixture is left with agitation for 30 minutes at ambient temperature and then 460 g of nitromethane is added. Agitation is maintained for 1 hour, then the solution is left at rest for about 12 hours. The solvent is then evaporated under vacuum.
After the addition of 800 ml of water to the residue, crystallization, filtration of the crystals formed, washing with water and drying in a drying oven at 50C, 764 9 of N-~L~4~V~ :
benzyl-2-nitramethylene-pyrrolidine is produced (yield: 71%i melting point: 99C).
c) 2-aminomethyl-pyrrolidine Introduced into a 1 litre autoclave are 61 g of N- -benzyl-2-nitromethylene-pyrrolidine, 300 ml of ethanol, hydro-chloric ethanol in an amount sufficient for the number of hydrochloric acid mols introduced to be double the number of ~ ;
nitromethylene-pyrrolidine, approximately 150 9 Raney nickel, and hydrogen, until a pressure of 50 kg ;s produced. The autoclave is left under agitation for 1 hour, then further hydrogen is introduced until the pressure reaches 145 kg.
After the mixture has been heated for 5 hours at 100C, followed by cooling and filtration of the nickel, the solvent is evaporated to dryness at reduced pressure. The residue is dissolved in 200 ml of methylene chloride, then 40% sodium hydroxide and potassium hydroxide in pellet form are added.
After decantation, the organic phase is dried and .
filtered, and the solvent is evaporated.
Distillation is effected to produce 17 9 of 2-aminomethyl-pyrrolidine (boiling point/32 mm Hg: 86 to 89C;
yield: 60.7%).
2-aminomethyl-pyrrolid1ne .
a) identical to Example 1 b) identical to Example 1 c) N-benzyl-2-aminomethyl-pyrrolidine Introduced into a 5 litre autoclave are 218 9 of N-benzyl-2-nitromethylene-pyrrolidine, 900 ml of methanol, 120 9 of Raney nickel, and hydrogen, until the pressure reaches 40 kg. The autoclave is left under agitation for 1 1/2 hours.
The mixture is then cooled. After filtration, and washing of . .
. .
, . . . .
- ` ~
7~
the nickel with methanol, evaporation of the solvent and distillation of the residue, 179 9 of N-benzyl-2-aminomethyl-pyrrolidine is produced (yield: 94%; boiling point/7 mm Hg:
137 to 140C~.
d) 2-aminomethyl-pyrrolidine Introduced into a 1 litre autoclave is 190 9 of N-benzyl-2-aminomethyl-pyrrolidine, a solution of 160 ml of hydrochloric acid (d = 1.18) in 140 ml of water and approxi- ;
mately 75 9 of Raney nickel, and hydrogen until a pressure of 10 130 kg is reached. The autoclave is agitated and then heated ;~ ~ -to 100C. Further hydrogen is introduced until the pressure reaches 100 kg, and the autoclave is left under agitation for 1 hour.
After cooling of the mixture, the nickel is filtered and washed with water. The filtrate is evaporated to dryness under reduced pressure, then the residue is dissolved in 500 ml of ethanol and the solution is neutralized by means of a solution of 128 g of potassium hydroxide in pellet form, in 600 ml of ethyl alcohol.
AftPr filtration of the potassium chloride formed and distillation of the solvent under vacuum, the residue is dissolved in benzene. The benzene solution is dried and filtered and the solvent is distilled under reduced pressure.
Distillation of the residue provides 78 9 of 2-aminomethyl-pyrrolidine (yield: 78%i boiling point: 167 to 170C; purity by gas chromatography: 97.6%).
Claims (3)
1. A novel process for the preparation of 2-aminomethyl-pyrrolidine having the formula:
characterized in that 2-pyrrolidone is reacted with a reactive benzylated compound having the formula X-CH2-C6H5, in which X
represents halogen or tosyl, and that the N-benzyl-2-pyrroli-done formed is treated with a lower alkyl sulphate, an alkaline alcoholate and nitromethane, and that the N-benzyl-2-nitro-methylene-pyrrolidine produced is reduced to 2-aminomethyl-pyrrolidine, either directly by catalytic reduction or the intermediate of N-benzyl-2-aminomethyl-pyrrolidine formed is further reduced by chemical or catalytic reduction to form 2-aminomethyl-pyrrolidine.
characterized in that 2-pyrrolidone is reacted with a reactive benzylated compound having the formula X-CH2-C6H5, in which X
represents halogen or tosyl, and that the N-benzyl-2-pyrroli-done formed is treated with a lower alkyl sulphate, an alkaline alcoholate and nitromethane, and that the N-benzyl-2-nitro-methylene-pyrrolidine produced is reduced to 2-aminomethyl-pyrrolidine, either directly by catalytic reduction or the intermediate of N-benzyl-2-aminomethyl-pyrrolidine formed is further reduced by chemical or catalytic reduction to form 2-aminomethyl-pyrrolidine.
2. The process of Claim 1, where X is halogen.
3. The process of Claim 1, where X is a tosyl group.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7407342A FR2263239B1 (en) | 1974-03-04 | 1974-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047041A true CA1047041A (en) | 1979-01-23 |
Family
ID=9135811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,855A Expired CA1047041A (en) | 1974-03-04 | 1975-02-26 | Process for the preparation of 2-aminomethyl-pyrrolidine |
Country Status (33)
| Country | Link |
|---|---|
| JP (1) | JPS5948825B2 (en) |
| AR (1) | AR207350A1 (en) |
| AT (1) | AT358569B (en) |
| BE (1) | BE825728A (en) |
| BG (1) | BG25077A3 (en) |
| CA (1) | CA1047041A (en) |
| CH (1) | CH602636A5 (en) |
| CS (1) | CS179935B2 (en) |
| DD (1) | DD117450A5 (en) |
| DE (1) | DE2506515A1 (en) |
| DK (1) | DK83875A (en) |
| EG (1) | EG11753A (en) |
| ES (1) | ES435139A1 (en) |
| FI (1) | FI750558A (en) |
| FR (1) | FR2263239B1 (en) |
| GB (1) | GB1481251A (en) |
| HK (1) | HK27878A (en) |
| HU (1) | HU169274B (en) |
| IE (1) | IE40685B1 (en) |
| IL (1) | IL46657A (en) |
| LU (1) | LU71947A1 (en) |
| MW (1) | MW875A1 (en) |
| NL (1) | NL7502425A (en) |
| NO (1) | NO145439C (en) |
| OA (1) | OA04856A (en) |
| PH (1) | PH11269A (en) |
| PL (1) | PL94801B1 (en) |
| RO (1) | RO64007A (en) |
| SE (1) | SE401367B (en) |
| SU (1) | SU591139A3 (en) |
| YU (1) | YU36500B (en) |
| ZA (1) | ZA751072B (en) |
| ZM (1) | ZM2775A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772459A (en) * | 1986-09-09 | 1988-09-20 | Erbamont, Inc. | Method for controlling emesis caused by chemotherapeutic agents and antiemetic agents useful therein |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1785124A1 (en) * | 1968-08-13 | 1971-11-11 | Prym Werke William | Zipper |
| JPS5146901B2 (en) * | 1971-08-24 | 1976-12-11 | ||
| CH556836A (en) * | 1971-09-30 | 1974-12-13 | Fratmann Ag | PROCESS FOR THE PREPARATION OF 1-ALKENYL-2-AMINOMETHYLPYRROLIDINES. |
| NL7304089A (en) * | 1972-03-30 | 1973-10-02 | ||
| CH573404A5 (en) * | 1972-07-28 | 1976-03-15 | Inventa Ag |
-
1974
- 1974-03-04 RO RO7400081539A patent/RO64007A/en unknown
- 1974-03-04 FR FR7407342A patent/FR2263239B1/fr not_active Expired
- 1974-03-04 CH CH272675A patent/CH602636A5/xx not_active IP Right Cessation
-
1975
- 1975-01-01 AR AR257827A patent/AR207350A1/en active
- 1975-02-15 DE DE19752506515 patent/DE2506515A1/en active Pending
- 1975-02-18 IL IL46657A patent/IL46657A/en unknown
- 1975-02-20 ZA ZA00751072A patent/ZA751072B/en unknown
- 1975-02-20 BE BE1006472A patent/BE825728A/en not_active IP Right Cessation
- 1975-02-24 IE IE377/75A patent/IE40685B1/en unknown
- 1975-02-24 GB GB7645/75A patent/GB1481251A/en not_active Expired
- 1975-02-25 EG EG93/75A patent/EG11753A/en active
- 1975-02-26 CA CA220,855A patent/CA1047041A/en not_active Expired
- 1975-02-26 FI FI750558A patent/FI750558A/fi not_active Application Discontinuation
- 1975-02-27 ES ES435139A patent/ES435139A1/en not_active Expired
- 1975-02-28 MW MW8/75A patent/MW875A1/en unknown
- 1975-02-28 NL NL7502425A patent/NL7502425A/en not_active Application Discontinuation
- 1975-03-03 BG BG7500029132A patent/BG25077A3/en unknown
- 1975-03-03 LU LU71947A patent/LU71947A1/xx unknown
- 1975-03-03 AT AT160575A patent/AT358569B/en not_active IP Right Cessation
- 1975-03-03 PL PL1975178472A patent/PL94801B1/en unknown
- 1975-03-03 SE SE7502340A patent/SE401367B/en not_active IP Right Cessation
- 1975-03-03 NO NO750699A patent/NO145439C/en unknown
- 1975-03-03 DK DK83875*#A patent/DK83875A/da not_active Application Discontinuation
- 1975-03-03 DD DD184512A patent/DD117450A5/xx unknown
- 1975-03-03 SU SU752111076A patent/SU591139A3/en active
- 1975-03-03 HU HUSO1136A patent/HU169274B/hu not_active IP Right Cessation
- 1975-03-03 PH PH16855A patent/PH11269A/en unknown
- 1975-03-04 OA OA55432A patent/OA04856A/en unknown
- 1975-03-04 CS CS7500001451A patent/CS179935B2/en unknown
- 1975-03-04 JP JP50026947A patent/JPS5948825B2/en not_active Expired
- 1975-03-04 ZM ZM27/75A patent/ZM2775A1/en unknown
- 1975-03-19 YU YU00676/75A patent/YU36500B/en unknown
-
1978
- 1978-06-01 HK HK278/78A patent/HK27878A/en unknown
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