DE942510C - Process for the preparation of aminothiocarboxylic acids containing imino groups - Google Patents

Process for the preparation of aminothiocarboxylic acids containing imino groups

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Publication number
DE942510C
DE942510C DEV7525A DEV0007525A DE942510C DE 942510 C DE942510 C DE 942510C DE V7525 A DEV7525 A DE V7525A DE V0007525 A DEV0007525 A DE V0007525A DE 942510 C DE942510 C DE 942510C
Authority
DE
Germany
Prior art keywords
preparation
imino groups
acids containing
aminothiocarboxylic
containing imino
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
Application number
DEV7525A
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German (de)
Inventor
Dr Rudolf Lotz
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.)
Glanzstoff AG
Original Assignee
Glanzstoff AG
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 Glanzstoff AG filed Critical Glanzstoff AG
Priority to DEV7525A priority Critical patent/DE942510C/en
Application granted granted Critical
Publication of DE942510C publication Critical patent/DE942510C/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Description

Verfahren zur Herstellung von Iminogruppen enthaltenden Aminothiocarbonsäuren Die Erfindung betrifft ein Verfahren zur Herstellung von neuartige Iminogruppen enthaltenden Aminothiocarbonsäuren der allgemeinen Formel worin R = Wasserstoff, Methyl oder Phenyl bedeutet. Diese Aminothiocarbonsäuren erhält man, wenn man heterocyclische, stickstoffhaltige Verbindungen der allgemeinen Formel worin R die obengenannte Bedeutung hat, mit wasserfreien Hydrosulfiden, insbesondere mit Ammoniumhydrosulfid, umsetzt. Die heterocyclischen Verbindungen sind nach folgender, bereits bekannter Reaktionsweise leicht zugänglich: Aldehyde, wie Formaldehyd, Acetaldehyd oder Benzaldehyd, reagieren mit Acrylsäurenitrü; Chlorwasserstoff und Wasserdampf in der Gasphase und in Gegenwart von Katalysatoren, wie Borphospi:at;-unter Entstehung von Alkyliden- bzw. Aralkylidenbis-chlorpropionsäureamiden der allgemeinen Formel worin R die obengenannte Bedeutung hat.Process for the preparation of aminothiocarboxylic acids containing imino groups The invention relates to a process for the preparation of novel aminothiocarboxylic acids containing imino groups of the general formula where R = hydrogen, methyl or phenyl. These aminothiocarboxylic acids are obtained by using heterocyclic, nitrogen-containing compounds of the general formula wherein R has the abovementioned meaning with anhydrous hydrosulfides, in particular with ammonium hydrosulfide. The heterocyclic compounds are easily accessible by the following, already known reaction mode: Aldehydes, such as formaldehyde, acetaldehyde or benzaldehyde, react with acrylic acid nitrate; Hydrogen chloride and water vapor in the gas phase and in the presence of catalysts such as Borphosphi: at; - with formation of alkylidene or aralkylidenebis-chloropropionic acid amides of the general formula wherein R has the abovementioned meaning.

LäBt man auf diese Dichloride flüssiges Ammoniak bei Raumtemperatur einwirken, so erhält man die diesen Verbindungen entsprechenden Monoamine. Aus diesen Monoaminen erhält man dann obengenannte, stickstoffhaltige, heterocyclische Verbindungen, wenn man im Vakuum quantitativ Chlorwasserstoff abspaltet. Die entstehenden heterocyclischen Verbindungen reagieren dann erfindungsgemäß mit Hydrosulfiden, wie Ammoniumhydrosulfid, unter Bildung von Aminothiocarbonsäuren,welche Iminogruppen in der Kette enthalten. Zur Auslösung der Reaktion ist die Anwesenheit von geringen Mengen Wasser, . welches zusätzlich zugeführt wird, unerläßlich. Es konnte nämlich die Beobachtung gemacht werden, daß die Reaktion nicht durchführbar ist, wenn entweder wasserfreie Hydrosulfide in Abwesenheit von Wasser zur Reaktion verwendet werden oder aber wenn der Reaktion zu viel Wasser zugeführt wird. Es ist zweckmäßig, nicht mehr als etwa io °/o Wasser - bezogen auf die Menge der Ausgangsverbindung - zu verwenden.If liquid ammonia is allowed to act on these dichlorides at room temperature act, the monoamines corresponding to these compounds are obtained. From these Monoamines are then obtained from the nitrogen-containing heterocyclic compounds mentioned above, when hydrogen chloride is split off quantitatively in vacuo. The resulting heterocyclic According to the invention, compounds then react with hydrosulfides, such as ammonium hydrosulfide, with the formation of aminothiocarboxylic acids which contain imino groups in the chain. The presence of small amounts of water is necessary to trigger the reaction. which is additionally supplied, indispensable. The observation could be made that the reaction is not feasible when either anhydrous hydrosulfides can be used for the reaction in the absence of water or if the reaction occurs too much water is being supplied. It is advisable not to use more than about 10 per cent of water - based on the amount of the starting compound - to be used.

Die gebildeten Aminothiocarbonsäuren eignen sich als Ausgangssubstanzen für Polykondensations-Re-. aktionen oder als Hitzestabilisatoren für thermoplastische Verbindungen. Beispiel z io g der heterocyclischen Verbindung mischt man mit io g festem Ammoniumhydrosulfid und fügt etwa i ccm Wasser zu dieser Mischung hinzu. Schon nach einigen Minuten tritt vollkommene Lösung ein, aus welcher sich alsbald Kristalle ausscheiden. Die aus Äthanol umkristallisierte Substanz 'stellt das gewünschte Imino-(ß-thiopropionsäure) - (ß - propionsäureaminomethylamid) der Formel HS-OC-CH2-CHZ-NH-CH2-CHZ-CO-NH-CHZ-NH2-dar und weist einen Schmelzpunkt von i77° auf. Beispiel 2 5 g der heterocyclischen Verbindung werden .mit etwa 5 g festem, wasserfreiem Ammoniumhydrosulfid gemischt und zu dieser Mischung etwa 5 0,5 ccm Wasser hinzugefügt. Schon nach kurzer Zeit tritt vollkommene Lösung dieser Mischung ein, aus welcher sich alsbald Kristalle abscheiden. Das entstandene Imino - (ß -.thiopropionsäure) - (ß - propionsäure-a-arninoäthylamid) der Formel wird aus Äthanol umkristallisiert.The aminothiocarboxylic acids formed are suitable as starting substances for polycondensation Re-. actions or as heat stabilizers for thermoplastic compounds. Example z io g of the heterocyclic compound it is mixed with 10 g of solid ammonium hydrosulphide and about 1 cc of water is added to this mixture. After just a few minutes, complete solution occurs, from which crystals soon precipitate. The substance recrystallized from ethanol represents the desired imino- (ß-thiopropionic acid) - (ß-propionic acid aminomethylamide) of the formula HS-OC-CH2-CHZ-NH-CH2-CHZ-CO-NH-CHZ-NH2- and has a Melting point of 177 °. Example 2 5 g of the heterocyclic compound are mixed with about 5 g of solid, anhydrous ammonium hydrosulphide and about 5 0.5 cc of water are added to this mixture. After a short time, this mixture completely dissolves, from which crystals soon separate out. The resulting imino - (ß-thiopropionic acid) - (ß-propionic acid-a-arninoethylamide) of the formula is recrystallized from ethanol.

Claims (2)

PATENTANSPRÜCHE: i. Verfahren zur Herstellung von Iminogruppen enthaltenden Aminothiocarbonsäuren der allgemeinen Formel dadurch gekennzeichnet, daß man heterocyclische Verbindungen der allgemeinen Formel worin R = Wasserstoff, Methyl oder Phenyl. bedeutet, mit Hydrosulfiden in Anwesenheit geringer Mengen Wasser umsetzt. PATENT CLAIMS: i. Process for the preparation of aminothiocarboxylic acids containing imino groups of the general formula characterized in that there are heterocyclic compounds of the general formula where R = hydrogen, methyl or phenyl. means, reacts with hydrosulfides in the presence of small amounts of water. 2. Verfahren nach Anspruch i, dadurch gekennzeichnet, daß man als Hydrosulfid Ammoniumhydrosulfid verwendet.2. The method according to claim i, characterized in that that ammonium hydrosulfide is used as the hydrosulfide.
DEV7525A 1954-07-15 1954-07-15 Process for the preparation of aminothiocarboxylic acids containing imino groups Expired DE942510C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEV7525A DE942510C (en) 1954-07-15 1954-07-15 Process for the preparation of aminothiocarboxylic acids containing imino groups

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEV7525A DE942510C (en) 1954-07-15 1954-07-15 Process for the preparation of aminothiocarboxylic acids containing imino groups

Publications (1)

Publication Number Publication Date
DE942510C true DE942510C (en) 1956-05-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEV7525A Expired DE942510C (en) 1954-07-15 1954-07-15 Process for the preparation of aminothiocarboxylic acids containing imino groups

Country Status (1)

Country Link
DE (1) DE942510C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004089297A2 (en) * 2003-04-02 2004-10-21 Suntory Pharmaceutical Research Laboratories, Llc Compounds and methods for treatment of thrombosis

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004089297A2 (en) * 2003-04-02 2004-10-21 Suntory Pharmaceutical Research Laboratories, Llc Compounds and methods for treatment of thrombosis
WO2004089297A3 (en) * 2003-04-02 2006-03-30 Suntory Pharmaceutical Res Lab Compounds and methods for treatment of thrombosis

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