PL94801B1 - METHOD OF MAKING 2-AMINOMETHYLPYROLIDINE - Google Patents

METHOD OF MAKING 2-AMINOMETHYLPYROLIDINE Download PDF

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Publication number
PL94801B1
PL94801B1 PL1975178472A PL17847275A PL94801B1 PL 94801 B1 PL94801 B1 PL 94801B1 PL 1975178472 A PL1975178472 A PL 1975178472A PL 17847275 A PL17847275 A PL 17847275A PL 94801 B1 PL94801 B1 PL 94801B1
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PL
Poland
Prior art keywords
aminomethylpyrrolidine
aminomethylpyrolidine
making
benzyl
yield
Prior art date
Application number
PL1975178472A
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Polish (pl)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Publication of PL94801B1 publication Critical patent/PL94801B1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D207/00Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02Heterocyclic 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
    • C07D207/18Heterocyclic 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
    • C07D207/22Heterocyclic 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
    • C07D207/24Oxygen or sulfur atoms
    • C07D207/262-Pyrrolidones
    • C07D207/2632-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/2672-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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D207/00Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02Heterocyclic 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
    • C07D207/04Heterocyclic 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
    • C07D207/08Heterocyclic 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
    • C07D207/09Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D207/00Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02Heterocyclic 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
    • C07D207/18Heterocyclic 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
    • C07D207/20Heterocyclic 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Przedmiotem wynalazku jest sposób wytwarzania 2-aminometylopirolidyny o wzorze 1 i jej soli addy¬ cyjnych z kwasami.Znany jest sposób wytwarzania aminometylopiro- lidyny z prolinamidu z wydajnoscia 50%. Taka wy¬ dajnosc w przemysle nie jest zadowalajaca.Obecnie stwierdzono, ze mozna powiekszyc wydaj¬ nosc do okolo 75% zmieniajac surowiec wyjsciowy na N-benzylo-2-nitrometylopirolidyne.Sposób wytwarzania 2-aminometylopirolidyny przedstawiony na schemacie charakteryzuje sie tym, ze poddaje sie redukcji katalitycznej lub najpierw chemicznej a nastepnie katalitycznej, N-benzylo-2- -nitixmetyleaijopiirolidyne o wzorze 2.Redukcji mozna dokonac za pomoca metalu, ta¬ kiego jak zelazo lub cynk w kwasie, takim jak solny lub octowy lub za pomoca wodoru w obecnosci kata¬ lizatora, takiego jak nikiel Raneya, pallad na weglu, czern platynowa, itp. Uwodornianie przeprowadza sie przy cisnieniu od atmosferycznego do 150 atmo¬ sfer.Otrzymana 2-aminometylopirolidyne mozna prze¬ prowadzic w sól z kwasami nieorganicznymi, takimi jak solny, bromowodorowy lub siarkowy lub organi¬ cznymi, takimi jak szczawiowy, winowy, maleinowy, itp.Zaleta sposobu wedlug wynalazku jest wysoka czy¬ stosc produktu. Wysoka czystosc 2-aminometylópiro- lidyny jest cecha bardzo istotna, poniewaz zwiazek ten stosuje sie jako przejsciowy w syntezie zwiazków 2 o atrakcyjnych wlasciwosciach farmakodynamicz- nych.Przyklad. Do autoklawu o pojemnosci 1 litra wprowadza sie 61 g N-benzylo-2-nitrometylenopiro- lidyny, 300 m etanolu, etanolowy roztwór chlorowo¬ doru, w takiej ilosci, by liczba moli chlorowodoru byla dwukrotnie wieksza od liczby moli N-benzylo- -2-nitrometylenopirolidyny, okolo 150 g niklu Raneya i wodór do cisnienia 50 atmosfer. Autoklaw wstrzasa sie w ciagu godziny, a nastepnie dopelnia wodorem do cisnienia 145 atmosfer i w ciagu 5 godzin utrzy¬ muje w 100°C. Po oziebieniu z mieszaniny reakcyjnej odsacza sie nikiel, a przesacz pod zmniejszonym ci¬ snieniem odparowuje do sucha. Pozostalosc rozpu- szcza sie w 200 ml chlorku metylenu, a do roztworu dodaje 40% wodorotlenku sodu lub potasu w postaci pastylek.Po zdekantowaniu warstwe organiczna suszy sie i przesacza, po czym odparowuje rozpuszczalniki. De- stylacja daje 17 g 2-aminometylopirolidyny o tempe¬ raturze wrzenia przy 32 mm Hg 86—89°C. Wydaj¬ nosc 60,7%. PL PL PL PL PL PL PL PL PL PLThe subject of the invention is a method for preparing 2-aminomethylpyrrolidine of formula I and its acid addition salts. A method for preparing aminomethylpyrrolidine from prolinamide with a yield of 50% is known. This yield is not satisfactory in industry. It has now been found that the yield can be increased to about 75% by changing the starting material to N-benzyl-2-nitromethylpyrrolidine. The process for preparing 2-aminomethylpyrrolidine shown in the scheme is characterized in that N-benzyl-2-nitromethylpyrrolidine of formula II is subjected to catalytic reduction, or first chemically and then catalytically. The reduction can be carried out with a metal such as iron or zinc in an acid such as hydrochloric or acetic acid, or with hydrogen in the presence of a catalyst such as Raney nickel, palladium on carbon, platinum black, etc. The hydrogenation is carried out at pressures ranging from atmospheric pressure to 150 atmospheres. 2-Aminomethylpyrrolidine can be converted into a salt with inorganic acids such as hydrochloric, hydrobromic or sulfuric, or with organic acids such as oxalic, tartaric, maleic, etc. The advantage of the process according to the invention is the high purity of the product. The high purity of 2-aminomethylpyrrolidine is a very important feature, because this compound is used as an intermediate in the synthesis of compounds 2 with attractive pharmacodynamic properties. Example. To a 1-liter autoclave are introduced 61 g of N-benzyl-2-nitromethylenepyrrolidine, 300 mL of ethanol, an ethanolic solution of hydrogen chloride in such a quantity that the number of moles of hydrogen chloride is twice as great as the number of moles of N-benzyl-2-nitromethylenepyrrolidine, approximately 150 g of Raney nickel, and hydrogen to a pressure of 50 atmospheres. The autoclave is shaken for one hour, then filled with hydrogen to a pressure of 145 atmospheres and held at 100°C for 5 hours. After cooling, the nickel is filtered off from the reaction mixture, and the filtrate is evaporated to dryness under reduced pressure. The residue is dissolved in 200 ml of methylene chloride, and 40% sodium or potassium hydroxide pellets are added to the solution. After decantation, the organic layer is dried and filtered, and the solvents are evaporated. Distillation gives 17 g of 2-aminomethylpyrrolidine, boiling at 32 mm Hg, 86-89°C. Yield: 60.7%. PL PL PL PL PL PL PL PL PL PL

Claims (1)

1.1.
PL1975178472A 1974-03-04 1975-03-03 METHOD OF MAKING 2-AMINOMETHYLPYROLIDINE PL94801B1 (en)

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
PL94801B1 true PL94801B1 (en) 1977-08-31

Family

ID=9135811

Family Applications (1)

Application Number Title Priority Date Filing Date
PL1975178472A PL94801B1 (en) 1974-03-04 1975-03-03 METHOD OF MAKING 2-AMINOMETHYLPYROLIDINE

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) FI750558A7 (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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
FR2263239A1 (en) 1975-10-03
NO145439C (en) 1982-03-24
FR2263239B1 (en) 1977-03-04
NL7502425A (en) 1975-09-08
AU7848675A (en) 1976-08-26
ZA751072B (en) 1976-01-28
CA1047041A (en) 1979-01-23
JPS5948825B2 (en) 1984-11-29
LU71947A1 (en) 1976-02-04
AT358569B (en) 1980-09-25
DD117450A5 (en) 1976-01-12
ATA160575A (en) 1980-02-15
YU67675A (en) 1982-02-25
FI750558A7 (en) 1975-09-05
BG25077A3 (en) 1978-07-12
HK27878A (en) 1978-06-09
ZM2775A1 (en) 1975-12-22
SE7502340L (en) 1975-09-05
OA04856A (en) 1980-10-31
ES435139A1 (en) 1977-02-01
CS179935B2 (en) 1977-12-30
AR207350A1 (en) 1976-09-30
RO64007A (en) 1978-08-15
BE825728A (en) 1975-08-20
SE401367B (en) 1978-05-02
DE2506515A1 (en) 1975-09-11
SU591139A3 (en) 1978-01-30
JPS50121264A (en) 1975-09-23
GB1481251A (en) 1977-07-27
NO145439B (en) 1981-12-14
NO750699L (en) 1975-09-05
MW875A1 (en) 1975-10-08
DK83875A (en) 1975-09-05
PH11269A (en) 1977-11-02
HU169274B (en) 1976-10-28
YU36500B (en) 1984-02-29
CH602636A5 (en) 1978-07-31
IE40685L (en) 1975-09-04
EG11753A (en) 1978-06-30
IL46657A (en) 1977-12-30
IE40685B1 (en) 1979-08-01

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