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DE1059911B - Process for the preparation of the chemotherapeutically active N-n-propyl-ª ‡, ª ‰ -dimethylsuccinimide - Google Patents

Process for the preparation of the chemotherapeutically active N-n-propyl-ª ‡, ª ‰ -dimethylsuccinimide

Info

Publication number
DE1059911B
DE1059911B DEP9151A DEP0009151A DE1059911B DE 1059911 B DE1059911 B DE 1059911B DE P9151 A DEP9151 A DE P9151A DE P0009151 A DEP0009151 A DE P0009151A DE 1059911 B DE1059911 B DE 1059911B
Authority
DE
Germany
Prior art keywords
propylamine
propyl
dimethylsuccinimide
dimethylsuccinic
intermediate product
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.)
Pending
Application number
DEP9151A
Other languages
German (de)
Inventor
Charles Alexis Miller
Loren Marlin Long
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Davis & Co
Parke Davis and Co LLC
Original Assignee
Davis & Co
Parke Davis and Co LLC
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.)
Filing date
Publication date
Application filed by Davis & Co, Parke Davis and Co LLC filed Critical Davis & Co
Publication of DE1059911B publication Critical patent/DE1059911B/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C07D207/30Heterocyclic 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 two double bonds between ring members or between ring members and non-ring members
    • C07D207/34Heterocyclic 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 two 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
    • C07D207/36Oxygen or sulfur atoms
    • C07D207/402,5-Pyrrolidine-diones
    • C07D207/4042,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C07D207/408Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung des chemotherapeutisch wirksamen N-n-Propyl- a, ß-dimethylsuccin.i.m.ids Die Erfindung betrifft die Herstellung des chemotherapeutisch wirksamen N-n-Propyl-a,ß-dimethylsuccinimids der Formel Nach der Erfindung wird das oben gekennzeichnete Produkt hergestellt, indem man a,ß-Dimethylbernsteinsäure oder a,ß-Dimethylbernsteinsäureanhydrid mit mindestens einem Moläquivalent n-Propylamin umsetzt und das so erhaltene Zwischenprodukt auf eine Temperatur zwischen 100 und 350° C erhitzt. Bei Durchführung der ersten Stufe des Verfahrens ist es vorteilhaft, aber nicht notwendig, ein inertes Lösungsmittel,. wie Wasser, niedrige aliphatische Alkohole oder deren Gemische, Äther, Benzol oder Toluol, zu verwenden, um die Reaktion der a,ß-Dimethylbernsteinsäure oder des a,ß-Dimethylbernsteinsäureanhydrides mit n-Propylamin zu erleichtern. Die relativen Mengen der Reaktionsteilnehmer sind nicht besonders kritisch, aber aus Wirtschaftlichkeitsgründen sollen mindestens ein und vorzugsweise mehrere Moläquivalente n-Propylamin für jedes Moläquivalent a,ß-Dimethylbernsteinsäure oder -anhydrid verwendet werden. Die auftretenden Zwischenprodukte unterscheiden sich je nach dem Ausgangsstoff, der verwendet wird, und auch je nach der verwendeten Menge n-Propylamin. Bei Umsetzung von a,ß-Dimethylbernsteinsäureanhydrid und einem Moläquivalent n-Propylamin, entsteht als Zwischenprodukt das Halbamid, während, wenn zwei oder mehr Moläquivalente n-Propylamin verwendet werden, als Zwischenprodukt das n-Propylaminsalz des Halbamides der a,ß-Dimethylbernsteinsäure entsteht.Process for the production of the chemotherapeutically active Nn-propyl-α, ß-dimethylsuccinimids The invention relates to the production of the chemotherapeutically active Nn-propyl-α, ß-dimethylsuccinimide of the formula According to the invention, the product identified above is prepared by reacting α, β-dimethylsuccinic acid or α, β-dimethylsuccinic anhydride with at least one molar equivalent of n-propylamine and heating the intermediate product thus obtained to a temperature between 100 and 350 ° C. When carrying out the first stage of the process, it is advantageous, but not necessary, to use an inert solvent. such as water, lower aliphatic alcohols or their mixtures, ether, benzene or toluene, to be used in order to facilitate the reaction of α, β-dimethylsuccinic acid or α, β-dimethylsuccinic anhydride with n-propylamine. The relative amounts of the reactants are not particularly critical, but for reasons of economy at least one and preferably several molar equivalents of n-propylamine should be used for each molar equivalent of α, β-dimethylsuccinic acid or anhydride. The intermediate products that occur differ depending on the starting material that is used and also depending on the amount of n-propylamine used. When α, ß-dimethylsuccinic anhydride and one molar equivalent of n-propylamine are reacted, the half-amide is formed as an intermediate, while when two or more molar equivalents of n-propylamine are used, the n-propylamine salt of the half-amide of α, ß-dimethylsuccinic acid is formed.

Falls a,ß-Dimethylbernsteinsäure als Ausgangsmaterial verwendet wird, entsteht als Zwischenprodukt entweder das Mono- oder Di-n-propylaminsalz der a,ß-Dimethylbernsteinsäure. Wie oben angegeben, können diese Zwischenprodukte in das N-n-Propyl-a,ß-Dimethylsuccinimid umgewandelt werden, indem man sie auf eine Temperatur zwischen etwa 100 und 350° C erhitzt. Die bevorzugte Temperatur für die Umwandlung liegt im Bereich von 190 bis 210° C, bei welcher Temperatur die Reaktion in etwa einer Stunde vollständig ist.If a, ß-dimethylsuccinic acid is used as the starting material, either the mono- or di-n-propylamine salt of α, ß-dimethylsuccinic acid is formed as an intermediate product. As indicated above, these intermediates can be converted into the N-n-propyl-α, β-dimethyl succinimide can be converted by bringing them to a temperature between about 100 and 350 ° C heated. The preferred temperature for the conversion is in the range of 190 to 210 ° C, at which temperature the reaction is complete in about an hour is.

Das N-n-Propyl-a,ß-dimethylsuccinimid besitzt wertvolle therapeutische Eigenschaften. Es ist besonders nützlich bei der Behandlung der Epilepsie in der petitmal-Form. Es ist bekannten analogen Succinimiden bei etwa gleicher krampflösender `Wirkung darin überlegen, daB es gleichzeitig stimulierend wirkt und dadurch Epilepsieanfälle schneller zu überwinden gestattet.N-n-propyl-α, ß-dimethylsuccinimide has valuable therapeutic properties Properties. It is particularly useful in treating epilepsy in the petitmal form. It is known analogous succinimides with about the same antispasmodic The effect is superior in that it simultaneously has a stimulating effect and thereby epilepsy attacks allowed to overcome faster.

Die Erfindung wird durch die folgenden Beispiele erläutert.The invention is illustrated by the following examples.

Beispiel 1 10 g a,ß-Dimethylbernsteinsäure werden allmählich zu 20 g wäBrigem n-Propylamin gegeben und das Wasser und der AminüberschuB durch Destillation entfernt. Die Temperatur des Rückstandes wird auf 200° C erhöht und hier gehalten, bis kein n-Propylamin mehr entwickelt wird. Der Rückstand wird in trockenem Äther gelöst, die Lösung mit Aktivkohle entfärbt und der Äther durch Destillation entfernt. Der Rückstand wird im Vakuum unter Gewinnung des N-n-Propyl-a,ß-dimethylsuccinimids destilliert; Kp. 18,3 119 bis 120° C; Ausbeute 60/0. Beispiel 2 10g a,ß-Dimethylbernsteinsäureanhydrid werden allmählich zu 10 g n-Propylamin in Äthylalkohol gegeben und der Alkohol und das überschüssige Amin durch Destillation entfernt. Der Rückstand wird auf 210° C erhitzt, bis kein n-Propylamin mehr entwickelt wird, dann abgekühlt und in trockenem Äther gelöst. Die ätherische Lösung wird mit Aktivkohle entfärbt und der Äther durch Destillation entfernt. Der Rückstand wird im Vakuum unter Gewinnung des N-n-Propyl-a,ß-di- methylsuccinimids destilliert ; Kp' e,s' 119 bis 120° C, Ausbeute 65 °/o. Example 1 10 ga, β-dimethylsuccinic acid are gradually added to 20 g of aqueous n-propylamine and the water and the excess amine are removed by distillation. The temperature of the residue is increased to 200 ° C. and held there until no more n-propylamine is evolved. The residue is dissolved in dry ether, the solution is decolorized with activated charcoal and the ether is removed by distillation. The residue is distilled in vacuo to give the Nn-propyl-α, ß-dimethylsuccinimide; B.p. 18.3 119 to 120 ° C; Yield 60/0. Example 2 10 g of α, β-dimethylsuccinic anhydride are gradually added to 10 g of n-propylamine in ethyl alcohol and the alcohol and the excess amine are removed by distillation. The residue is heated to 210 ° C. until no more n-propylamine is evolved, then cooled and dissolved in dry ether. The ethereal solution is decolorized with activated charcoal and the ether is removed by distillation. The residue is in vacuo to obtain the Nn-propyl-a, ß-di- methylsuccinimide distilled; Kp 'e, s' 119 to 120 ° C, Yield 65%.

Claims (1)

PATENTANSPRÜCHE.: 1. Verfahren zur Hersfellung'eines krärripflösenden und- zugleich stimulierend wirkenden chemothera- peutischen Mittels, dadurch gekennzeichnet, daB @a,ß-Dimethvlbernsteinsäur@eöder ä;ß-Dimethylbern- steinsäureanhydrid durch Umsetzen mit n-Propylamin und Erhitzen des so gebildeten Zwischenprodukts auf eine Temperatur zwischen etwa 100 und 350° C in- - N-n-Propyl-a,ß-dimethylsuccinimid übergeführt wird,-
2. - 'Verfs,llken nach Anspruch 1, dadurch gekenn- zeichnet, daB das Zwischenprodukt auf 190 bis 210° C erhitzt wird. 3, -Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daB ein ÜberschuB an n-Propylamin verwendet wird.
In Betracht gezogene Druckschriften: Deutsche Patentschrift Nr. 389 948; Hoppe-Seylers Zeitschrift für physiologische Chemie, Bd.226 [1934], S. 98, 103; Arch. Neurol. Psychiatry, 66, S. 156 bis 162; Journal of the American Chemical Society, Bd.73 [1951], S.5608- bis 5610.
PATENT CLAIMS .: 1. Process for the production of a skin dissolving and- at the same time stimulating chemothera- therapeutic means, characterized in that @ a, ß-dimethylsuccinic acid @ eöder ä; ß-dimethylsuccinic stinic anhydride by reacting with n-propylamine and heating the intermediate product so formed to a temperature between about 100 and 350 ° C in - Nn-propyl-a, ß-dimethylsuccinimide converted will,-
2. - 'Verfs, llken according to claim 1, characterized in that shows that the intermediate product is at 190 to 210 ° C is heated. 3, method according to claim 1 and 2, characterized indicated that there was an excess of n-propylamine is used.
Documents considered: German Patent No. 389 948; Hoppe-Seylers Zeitschrift für Physiologische Chemie, Vol. 226 [1934], pp. 98, 103; Arch. Neurol. Psychiatry, 66, pp. 156 to 162; Journal of the American Chemical Society, Vol. 73 [1951], pp. 5608 to 5610.
DEP9151A 1952-02-26 1953-02-05 Process for the preparation of the chemotherapeutically active N-n-propyl-ª ‡, ª ‰ -dimethylsuccinimide Pending DE1059911B (en)

Applications Claiming Priority (1)

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US1059911XA 1952-02-26 1952-02-26

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DE1059911B true DE1059911B (en) 1959-06-25

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE389948C (en) * 1922-08-01 1924-02-09 Hoechst Ag Process for the preparation of CíñC-substituted succinimides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE389948C (en) * 1922-08-01 1924-02-09 Hoechst Ag Process for the preparation of CíñC-substituted succinimides

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