MC896A1 - Process for the preparation of 1-alkyl-2-aminomethylpyrrolidines - Google Patents
Process for the preparation of 1-alkyl-2-aminomethylpyrrolidinesInfo
- Publication number
- MC896A1 MC896A1 MC953A MC953A MC896A1 MC 896 A1 MC896 A1 MC 896A1 MC 953 A MC953 A MC 953A MC 953 A MC953 A MC 953A MC 896 A1 MC896 A1 MC 896A1
- Authority
- MC
- Monaco
- Prior art keywords
- alkyl
- solvent
- added
- reduction
- temperature
- Prior art date
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
- C07D207/04—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
- C07D207/10—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 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
- C07D207/12—Oxygen or sulfur atoms
-
- 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)
- Catalysts (AREA)
Description
BREVET D'INVENTION PATENT FOR INVENTION
Procédé de préparation de l-alkyl-2-aminométhylpyrrolidines Process for the preparation of l-alkyl-2-aminomethylpyrrolidines
FR AT MANN S. A. FR AT MANN S. A.
La. présente invention a trait à un nouveau procédé de préparation des l-alkyl~ 2-aminométhylpyrrolidines et leurs intermédiaires. The present invention relates to a new process for preparing l-alkyl~ 2-aminomethylpyrrolidines and their intermediates.
Ce procédé est caractérisé essentiellement en ce que l'on fait réagir en milieu solvant une 1-alkyl-2-pyrrolidone avec le phosgène à une température comprise entre - 5°C et + 10°C, que l'on ajoute au produit obtenu dont la température a été rabaissé entre 0°C et - 20 C un alcoolate alcalin, que l'on ajoute du nitrométhane au mélange ramené à température ambiante, et que l'on réduit le groupement nitrométhylene obtenu en groupement aminométhyl. This process is essentially characterized in that a 1-alkyl-2-pyrrolidone is reacted in solvent medium with phosgene at a temperature between -5°C and +10°C, an alkali alkoxide is added to the product obtained, the temperature of which has been lowered to between 0°C and -20°C, nitromethane is added to the mixture brought back to room temperature, and the resulting nitromethylene group is reduced to an aminomethyl group.
- 2 - - 2 -
r <. r <.
Ceci permet la fabrication d'un corps chimique, utilisé notamment comme intermédiaire de synthèse, en évitant d'utiliser des procédés connus longs et délicats partant de la pyrrolidine comme matière première. This allows the manufacture of a chemical compound, used in particular as a synthetic intermediate, avoiding the use of known long and delicate processes starting from pyrrolidine as a raw material.
Le procédé objet de la présente invention est illustré par la suite des réaction suivantes: The process that is the subject of the present invention is illustrated by the following sequence of reactions:
(1) + coci2 (1) + coci2
(2) + 2MeOR, (2) + 2MeOR,
(3) + CH NO 3 2 (3) + CH NO 3 2
(1) (1)
(2) (2)
(3) (3)
VN' VN'
I I
R R
LGHNO. f métal + acide ou LGHNO. f metal + acid or
(II) (II)
H /hydrogénation 2 H /hydrogenation 2
cataly tique catalytic
SN' SN'
1 1
R. R.
CH NH 2 2 CH NH 2 2
(III) (III)
où R et R sont des groupements alkyles. where R and R are alkyl groups.
X Là X There
Me un métal alcalin tel que sodium, potassium, etc. Me an alkali metal such as sodium, potassium, etc.
(10) (10)
$ $
Suivant le procédé de l'invention ont fait récigir une 1-alkyl- 2-pyrrolidone (I) avec le phosgène, un alcoolate alcalin et le nitrométhane de façon à obtenir le composé (II). According to the process of the invention, a 1-alkyl-2-pyrrolidone (I) was reacted with phosgene, an alkali alkoxide and nitromethane to obtain compound (II).
- 3 - - 3 -
Comme exemple de groupement alkyle (R^) dans les 1-alkyl-2-pyr-rolidones on peut citer les groupements méthyle, éthyle, propyle, isolpropyle, butyle, ou iso etc. Examples of alkyl groups (R^) in 1-alkyl-2-pyr-rolidones include methyl, ethyl, propyl, isolpropyl, butyl, or iso groups, etc.
La réaction de la l-alkyl-2-pyrrolidone avec le phosgène peut être menée au sein d'un solvant tel que le benzène, le toluène, le xylène, etc. La réaction est menée à basse température entre - 5°C et + 10 C par exemple. Le produit obtenu a la structure chimique suivante: The reaction of l-alkyl-2-pyrrolidone with phosgene can be carried out in a solvent such as benzene, toluene, xylene, etc. The reaction is conducted at low temperatures, for example, between -5°C and +10°C. The resulting product has the following chemical structure:
© ©
C I C I
où R^ a la même signification qu'indiqué plus haut. Il peut être isolé et purifié. Il peut toutefois être utilisé pour la réaction suivante avec l'alcoolate alcalin et le nitrométhane sans isolement et sans purification. Le solvant utilisé au stade précédent est couramment conservé. Le traitement à l'alcoolate alcalin doit être mené à basse température, des températures comprises entre 0°C et - 20 C sont préférables. La réaction du produit obtenu: where R^ has the same meaning as indicated above. It can be isolated and purified. However, it can be used for the following reaction with alkali alkoxide and nitromethane without isolation or purification. The solvent used in the previous stage is usually retained. The alkali alkoxide treatment should be carried out at low temperatures; temperatures between 0°C and -20°C are preferable. The reaction of the product obtained:
CH CIL CH CIL
2 £■ £2■
CH. CH.
.CH, .CH,
CH CH
,„C — C 1 ,„C — C 1
r © r ©
R, R,
oùRj et R^ ont les mêmes significations qu'indiqué plus haut avec le nitrométhane, se fait à température ambiante. where Rj and R^ have the same meanings as indicated above with nitromethane, is done at room temperature.
Les l-alkyl^2-.nitrométhylènepyrrolidines (II) peuvent être isolées et purifiées, mais elles peuvent être également utilisées telles quelles, sans isolement et sans purification, pour la réaction suivante: la réduction des 1-alkyl-2-nitrométhylènepyrrolidines (II) est obtenue par action d'un acide sur un métal ou par l'hydrogène en présence d'un catalyseur métallique d'hydrogénation. Comme métaux, dans le cas de la réduction par un moyen chimique, on utilise principalement le fer et le zinc avec l'acide chlorhydrique ou acétique. La réaction est menée dans un solvant, l'acide utilisé jouant le rôle de solvant, et l'opération est menée avec chauffage. Dans le cas de l'hydrogénation cata-lytique, on utilise comme catalyseur d'hydrogénation des noirs d'oxydes métalliques, des métaux, des métaux colloi'daux, des métaux sur support approprié. Les catalyseurs les plus fréquemment employés sont: le noir de platine, le rhodium sur alumine, le palladium sur charbon et le nickel de Raiïey. L'hydrogénation catalytique est menée au sein d'un solvant tel que l'eau, le méthanol, l'éthanol, l'isopropanol, le butanol, ie tétrahydro-furane, le dioxane ou d'autres solvants inertes. Ces solvants peuvent être utilisés seuls ou en combinaison. La pression d'hydrogénation peut varier de la pression atmosphérique à de hautes pressions. On utilise en général des pressions allant de la pression atmosphérique à quelques atmosphères. • Il est préférable d'arrêter la réaction quand la quantité d'hydrogène calculée a été absorbée. Le produit réactionnel (III) est isolé après filtration t ■' 1-Alkyl-2-nitromethylenepyrrolidines (II) can be isolated and purified, but they can also be used as is, without isolation or purification, for the following reaction: the reduction of 1-alkyl-2-nitromethylenepyrrolidines (II) is achieved by the action of an acid on a metal or by hydrogen in the presence of a metallic hydrogenation catalyst. For chemical reduction, iron and zinc are primarily used as metals with hydrochloric or acetic acid. The reaction is carried out in a solvent, with the acid acting as the solvent, and the operation is performed with heating. For catalytic hydrogenation, metal oxide blacks, metals, colloidal metals, or metals on suitable supports are used as hydrogenation catalysts. The most frequently used catalysts are platinum black, rhodium on alumina, palladium on carbon, and Railly's nickel. Catalytic hydrogenation is carried out in a solvent such as water, methanol, ethanol, isopropanol, butanol, tetrahydrofuran, dioxane, or other inert solvents. These solvents can be used alone or in combination. The hydrogenation pressure can range from atmospheric pressure to high pressures. Pressures ranging from atmospheric to a few atmospheres are generally used. It is preferable to stop the reaction when the calculated amount of hydrogen has been absorbed. The reaction product (III) is isolated after filtration.
du catalyseur, suivie d'une évaporation du solvant. of the catalyst, followed by evaporation of the solvent.
Les 1-alkyl-2-aminométhylpyrrolidines (III) ainsi obtenues peuvent être transformées en sels, par addition d'un acide minéral tel que l'acide chlorhydrique, l'acide bromhydrique, l'acide sulfurique ou d'un acide organique tel que l'acide oxalique, l'acide tartrique, The 1-alkyl-2-aminomethylpyrrolidines (III) thus obtained can be transformed into salts, by the addition of a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid or an organic acid such as oxalic acid, tartaric acid,
l'acide maléique et l'acide picrique. maleic acid and picric acid.
L'exemple suivant est donné pour illustrer la présente invention, The following example is given to illustrate the present invention,
mais ce, sans limiter en rien cette dernière. but this, without limiting the latter in any way.
a) Préparation de la 1-éthyl-2-nitrométhylènepyrrolidine Dans un ballon à deux tubulures muni d'un agitateur mécanique, d'une ampoule à brome et d'un thermomètre on met 23 g de 1-éthylpyrroli-done dissouts dans 100 ml de toluène anhydre. On refroidit à 0°C et introduit en maintenant la température entre 0 et 5 C 90 ml d'une solution benzénique à 21% de phosgène. A chaque goutte versée, il précipite un produit blanc et on note un dégagement gazeux de gaz carbonique. La durée de l'introduction est de une heure environ. L'introduction du phosgène terminée on maintient l'agitation pendant 3 heures à 0°C, puis refroidit à - 15°G est introduit goutte à goutte en maintenant la température entre - 5 et - 15 C une solution de 170 ml d'éthanol absolu dans lesquels ont été dissouts 9, 5 g de sodium. La durée d'introduction est d'une heure environ, car la réaction est très exothermique. Après dix minutes d'introduction de l'éthylate de soflium le chlorure de sodium commence à précipiter. Après la fin de la réaction, on laisse le mélange sous agitation jusqu'à ce qu'il a) Preparation of 1-Ethyl-2-Nitromethylenepyrrolidine: In a two-tubed round-bottom flask equipped with a mechanical stirrer, a bromine funnel, and a thermometer, 23 g of 1-ethylpyrrolidone dissolved in 100 mL of anhydrous toluene are placed. The flask is cooled to 0°C, and 90 mL of a 21% phosgene benzene solution is added while maintaining the temperature between 0 and 5°C. With each drop added, a white precipitate is formed, and carbon dioxide gas is released. The introduction lasts approximately one hour. After the phosgene has been added, the flask is stirred for 3 hours at 0°C, then cooled to -15°C. Finally, while maintaining the temperature between -5 and -15°C, 170 mL of absolute ethanol in which 9.5 g of sodium has been dissolved is added dropwise. The introduction time is approximately one hour, as the reaction is highly exothermic. After ten minutes of introducing sodium ethoxide, sodium chloride begins to precipitate. After the reaction is complete, the mixture is stirred until it
atteigne la température ambiante. On introduit alors sans refroidir et en dix minutes 18 g. de nitrométhane. On laisse agiter pendant deux heures puis laisse reposer pendant 12 heures environ. On dilue alors le mélange avec un litre d'eau. La couche organique qui est décantée est séparée. La phase aqueuse est extraite à trois reprises avec de chaque fois 150 ml/chloroforme. On réunit les phases organiques, les sèche sur sulfate de sodium, filtre, évapore sous vide à sec. Le résidu, bien cristallisé est repris par 100 ml d'éther ordinaire. Le produit est essoré et séché à 40°C. On obtient 25 g de 1-éthyl-2-nitrométhylènepyrrolidine (F : 131°C - Rt : 78%). The mixture reaches room temperature. Then, without cooling, 18 g of nitromethane are introduced over ten minutes. The mixture is stirred for two hours and then left to stand for approximately 12 hours. It is then diluted with one liter of water. The organic layer, which has settled, is separated. The aqueous phase is extracted three times, each time with 150 mL of chloroform. The organic phases are combined, dried over sodium sulfate, filtered, and evaporated under vacuum until dry. The well-crystallized residue is collected with 100 mL of ordinary ether. The product is drained and dried at 40°C. 25 g of 1-ethyl-2-nitromethylenepyrrolidine (F: 131°C - Rt: 78%) are obtained.
Analyse Analysis
Calculé : C % 53, 84 H % 7, 69 N % 17, 95 Trouvé : C % 53, 60 H % 7, 39 N % 18, 04 Calculated: C % 53.84 H % 7.69 N % 17.95 Found: C % 53.60 H % 7.39 N % 18.04
b) Préparation de la 1-éthyl-2-aminométhylpyrrolidine Aune solution de 25 g de 1-éthyl-2-nitrométhylènepyrrolidine dans 500 ml de méthanol, on ajoute enviton 5g de nickel de Raney et le mélange réactionnel est hydrogéné à la pression et à la température ambiante jusqu'à absorption de 4 équivalents moléculaires d'hydrogène ce qui demande environ 5 heures. Le nickel de Raney est séparé par filtration et le solvant est évaporé sous pression réduite. Par distillation du ré-sidu, on obtient 17g de 1-éthyl-2-aminométhylpyrrolidine, sous la forme d'huile (EU/2Q mm : 60 - 61° C), avec rendement de 65 pour cent. b) Preparation of 1-Ethyl-2-Aminomethylpyrrolidine: To a solution of 25 g of 1-Ethyl-2-nitromethylenepyrrolidine in 500 mL of methanol, approximately 5 g of Raney nickel are added, and the reaction mixture is hydrogenated at ambient temperature and pressure until the absorption of 4 molecular equivalents of hydrogen, which takes about 5 hours. The Raney nickel is separated by filtration, and the solvent is evaporated under reduced pressure. Distillation of the residue yields 17 g of 1-Ethyl-2-Aminomethylpyrrolidine as an oil (EU/2Q mm: 60–61°C), with a yield of 65 percent.
Les produits préparés selon le procédé de l'invention constituent un stade intermédiaire, permettant la fabrication de principes actifs utilisables, notamment dans l'industrie pharmaceutique et particulier ment en gastro entérologie, en neurologie et en toutes autres applications. The products prepared according to the process of the invention constitute an intermediate stage, enabling the manufacture of usable active ingredients, particularly in the pharmaceutical industry and especially in gastroenterology, neurology and all other applications.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1662870A CH532035A (en) | 1970-11-10 | 1970-11-10 | New process for the preparation of 1-alkyl-2-amino-methylpyrrolidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MC896A1 true MC896A1 (en) | 1972-06-22 |
Family
ID=4418871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MC953A MC896A1 (en) | 1970-11-10 | 1971-10-26 | Process for the preparation of 1-alkyl-2-aminomethylpyrrolidines |
Country Status (27)
| Country | Link |
|---|---|
| AT (1) | AT311952B (en) |
| AU (1) | AU464960B2 (en) |
| BE (1) | BE773979A (en) |
| BG (1) | BG21605A3 (en) |
| CA (1) | CA940533A (en) |
| CH (1) | CH532035A (en) |
| CS (1) | CS186206B2 (en) |
| DE (1) | DE2152371A1 (en) |
| DK (1) | DK145573C (en) |
| ES (1) | ES396293A1 (en) |
| FI (1) | FI54471C (en) |
| FR (1) | FR2111371A5 (en) |
| GB (1) | GB1374818A (en) |
| HU (1) | HU162787B (en) |
| IE (1) | IE35775B1 (en) |
| IL (1) | IL37994A (en) |
| IT (1) | IT1043845B (en) |
| LU (1) | LU64227A1 (en) |
| MC (1) | MC896A1 (en) |
| NL (1) | NL7114901A (en) |
| OA (1) | OA03823A (en) |
| PH (1) | PH12022A (en) |
| PL (1) | PL81412B1 (en) |
| SE (1) | SE376415B (en) |
| YU (1) | YU34672B (en) |
| ZA (1) | ZA716998B (en) |
| ZM (1) | ZM15171A1 (en) |
-
1970
- 1970-11-10 CH CH1662870A patent/CH532035A/en not_active IP Right Cessation
-
1971
- 1971-10-14 FR FR7136940A patent/FR2111371A5/fr not_active Expired
- 1971-10-15 BE BE773979A patent/BE773979A/en not_active IP Right Cessation
- 1971-10-19 ZA ZA716998A patent/ZA716998B/en unknown
- 1971-10-20 AU AU34790/71A patent/AU464960B2/en not_active Expired
- 1971-10-21 DE DE19712152371 patent/DE2152371A1/en active Pending
- 1971-10-22 IL IL37994A patent/IL37994A/en unknown
- 1971-10-22 ES ES396293A patent/ES396293A1/en not_active Expired
- 1971-10-26 MC MC953A patent/MC896A1/en unknown
- 1971-10-26 CA CA126,128A patent/CA940533A/en not_active Expired
- 1971-10-26 BG BG018861A patent/BG21605A3/en unknown
- 1971-10-26 IE IE1354/71A patent/IE35775B1/en unknown
- 1971-10-27 ZM ZM151/71A patent/ZM15171A1/en unknown
- 1971-10-28 NL NL7114901A patent/NL7114901A/xx unknown
- 1971-10-29 IT IT30520/71A patent/IT1043845B/en active
- 1971-11-04 CS CS7100007753A patent/CS186206B2/en unknown
- 1971-11-04 GB GB5122571A patent/GB1374818A/en not_active Expired
- 1971-11-05 OA OA54406A patent/OA03823A/en unknown
- 1971-11-08 PL PL1971151433A patent/PL81412B1/pl unknown
- 1971-11-08 FI FI3193/71A patent/FI54471C/en active
- 1971-11-08 LU LU64227D patent/LU64227A1/xx unknown
- 1971-11-09 YU YU2823/71A patent/YU34672B/en unknown
- 1971-11-09 SE SE7114274A patent/SE376415B/xx unknown
- 1971-11-09 HU HUFA897A patent/HU162787B/hu unknown
- 1971-11-09 DK DK548871A patent/DK145573C/en not_active IP Right Cessation
- 1971-11-10 AT AT969071A patent/AT311952B/en not_active IP Right Cessation
- 1971-11-10 PH PH13000A patent/PH12022A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU3479071A (en) | 1973-05-03 |
| PH12022A (en) | 1978-10-06 |
| LU64227A1 (en) | 1972-05-29 |
| IE35775L (en) | 1972-05-10 |
| CH532035A (en) | 1972-12-31 |
| FI54471C (en) | 1978-12-11 |
| AU464960B2 (en) | 1975-09-11 |
| YU34672B (en) | 1979-12-31 |
| NL7114901A (en) | 1972-05-15 |
| ES396293A1 (en) | 1974-05-01 |
| ZA716998B (en) | 1972-07-26 |
| IL37994A0 (en) | 1971-12-29 |
| BG21605A3 (en) | 1976-07-20 |
| IE35775B1 (en) | 1976-05-12 |
| CA940533A (en) | 1974-01-22 |
| DE2152371A1 (en) | 1972-06-22 |
| SE376415B (en) | 1975-05-26 |
| FI54471B (en) | 1978-08-31 |
| GB1374818A (en) | 1974-11-20 |
| IL37994A (en) | 1974-10-22 |
| HU162787B (en) | 1973-04-28 |
| CS186206B2 (en) | 1978-11-30 |
| AT311952B (en) | 1973-12-10 |
| FR2111371A5 (en) | 1972-06-02 |
| YU282371A (en) | 1979-07-10 |
| ZM15171A1 (en) | 1972-07-21 |
| PL81412B1 (en) | 1975-08-30 |
| OA03823A (en) | 1971-12-24 |
| DK145573B (en) | 1982-12-13 |
| BE773979A (en) | 1972-04-17 |
| DK145573C (en) | 1983-05-30 |
| IT1043845B (en) | 1980-02-29 |
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