DE887815C - Process for the preparation of disubstituted carboxylic acid diamides - Google Patents

Process for the preparation of disubstituted carboxylic acid diamides

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Publication number
DE887815C
DE887815C DE1951P0006232 DEP0006232D DE887815C DE 887815 C DE887815 C DE 887815C DE 1951P0006232 DE1951P0006232 DE 1951P0006232 DE P0006232 D DEP0006232 D DE P0006232D DE 887815 C DE887815 C DE 887815C
Authority
DE
Germany
Prior art keywords
carboxylic acid
preparation
acid diamides
acid
disubstituted carboxylic
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
DE1951P0006232
Other languages
German (de)
Inventor
Wilhelm Dr Irion
Heinrich Otto Dr Marwitz
Otto Dr Moldenhauer
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.)
Phrix Werke AG
Original Assignee
Phrix Werke 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 Phrix Werke AG filed Critical Phrix Werke AG
Priority to DE1951P0006232 priority Critical patent/DE887815C/en
Application granted granted Critical
Publication of DE887815C publication Critical patent/DE887815C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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

Description

Verfahren zur Herstellung von disubstituierten Carbonsäurediamiden Es ist bekannt, daB Methylolamide bei Umsetzung mit Brenzschleimsäureestern in Gegenwart von konzentrierter Schwefelsäure unter Wasseraustritt mit dem Furanring kondensieren. So sind bereits Kondensate zwischen Brenzschleimsäureäthylester einerseits und Methylolphthalimid, Methylolbenzamid oder Methylolchloracetamid andererseits beschrieben.Process for the preparation of disubstituted carboxylic acid diamides It is known that methylolamides are present when reacted with pyrocucic acid esters of concentrated sulfuric acid condense with the furan ring with the escape of water. There are already condensates between ethyl pyrocate and methylolphthalimide, On the other hand, methylolbenzamide or methylolchloroacetamide is described.

Es wurde nun gefunden, daB in Analogie zu diesem Verfahren auch Dimethylolverbindungen von Carbonsäurediamiden,wie z. B. Dimethylolharnstoff oder Dimethyloloxamid, unter denselben Bedingungen mit Brenzschleimsäureestern unter Bildung entsprechender Difurfurylverbindungen reagieren. Zum Beispiel erhält man aus Brenzschleimsäuremethylester und Dimethylolharnstoff den Difurfurylharnstoff-5, 5'-dicarbonsäuredimethylester vom Schmelzpunkt r87° Der entsprechende Äthylester hat einen Schmelzpunkt von 154 bis =55°, während die freie Säure, die durch Verseifung der Ester mit Na OH erhalten wird, einen Schmelzpunkt von 2,61 bis 268° zeigt. Entsprechend entsteht aus Dioxymethyloxamid und Brenzschleimsäuremethylester der Oxalyl-di-(2-aminomethylfuran-5-carbonsäuremethylester) Die Reaktion kann, unter Verwendung von Harnstoff als .Ausgangssubstanz, durch folgende Gleichungen ausgedrückt werden: . wobei R1 Wasserstoff, Alkyl oder Aryl und R2 einen Alkylrest mit nicht mehr als 6 C-Atomen bedeuten.It has now been found that, in analogy to this process, dimethylol compounds of carboxylic acid diamides, such as e.g. B. Dimethylolurea or Dimethyloloxamid, react under the same conditions with pyrocucic acid esters to form the corresponding difurfuryl compounds. For example, methyl pyrogenic acid and dimethylolurea give dimethyl difurfurylurea-5,5'-dicarboxylate with a melting point of 87 ° The corresponding ethyl ester has a melting point of 154 to = 55 °, while the free acid, which is obtained by saponification of the ester with Na OH, has a melting point of 2.61 to 268 °. Accordingly, the oxalyl-di- (2-aminomethylfuran-5-carboxylic acid methyl ester) is formed from dioxymethyloxamide and methyl pyrogenic acid. Using urea as the starting substance, the reaction can be expressed by the following equations:. where R1 is hydrogen, alkyl or aryl and R2 is an alkyl radical with not more than 6 carbon atoms.

Es ist in gleicher Weise möglich, zur Kondensation mit den Dimethylolverbindungen an Stelle der Furancarbonsäureester die entsprechenden Nitrile zu verwenden und die erhaltenen Kondensationsprodukte durch Verseifen in die freien Säuren überzuführen.It is possible in the same way for condensation with the dimethylol compounds to use the corresponding nitriles in place of the furancarboxylic acid esters and to convert the condensation products obtained into the free acids by saponification.

Im Gegensatz zu den eingangs beschriebenen bekannten Kondensationsprodukten lassen sich die erfindungsgemäßen neuen Verbindungen überraschenderweise durch Erhitzen auf Temperaturen von etwa i7o bis 2oo° zu Hochpolymeren kondensieren.In contrast to the known condensation products described at the outset surprisingly, the new compounds according to the invention can be obtained by heating condense to high polymers at temperatures of about 170 to 200 °.

Beispiel i 5oo ccm konzentrierte Schwefelsäure werden mit Eis-Kochsalz-Mischung gekühlt und bei o bis - io° tropfenweise mit 145 g Brenzschleimsäuremethylester versetzt. Dann wird eine Lösung von 69 g symm. Dimethylolharnstoff in 320 ccm Eisessig ebenfalls bei o bis - io° zugetropft. Nach 1/2stündigem Rühren bei der gleichen Temperatur wird die Masse auf Eis gegossen und abgesaugt.; Ausbeute 175 g = gi °/o. Durch Umkristallisieren aus einem Methanol-Benzol-Gemisch erhält man den Difurfurylharnstoff-5, 5'-dicarbon säuredimethylester mit dem Schmelzpunkt i87° in reiner Form. Beispiel 2 In 555 ccm konzentrierte Schwefelsäure, die auf o bis - io° gekühlt wurde, werden allmählich z26 g Brenzschleimsäuremethylester unter Rühren eingetragen. Dann werden auf dieselbe Weise 85 g Dimethyloloxamid zugegeben; anschließend wird 1/2 Stunde bei derselben Temperatur weitergerührt.EXAMPLE I 500 cc of concentrated sulfuric acid are cooled with a mixture of ice and table salt and 145 g of methyl pyrogenic acid are added dropwise at 0 to -10 °. Then a solution of 69 g of symm. Dimethylolurea in 320 cc of glacial acetic acid was also added dropwise at 0 to - 10 °. After stirring for 1/2 hour at the same temperature, the mass is poured onto ice and filtered off with suction. Yield 175 g = g / o. Recrystallization from a methanol-benzene mixture gives dimethyl difurfurylurea-5,5'-dicarboxylate with a melting point of 187 ° in pure form. EXAMPLE 2 Z26 g of methyl pyrogenic acid are gradually introduced into 555 cc of concentrated sulfuric acid, which has been cooled to 0 to -10 °. Then 85 g of dimethyloloxamide are added in the same way; then stirring is continued for 1/2 hour at the same temperature.

Die Reaktionsmasse wird auf Eis gegossen, das ausgeschiedene Produkt abfiltriert, mit Wasser gewaschen und aus Eisessig umkristallisiert. Ausbeute : 155 g Oxalyl-di-(2-aminomethylfuran-5-carbonsäuremethylester); entsprechend 88 °/a der Theorie. F. = z82,5°.The reaction mass is poured onto ice, the precipitated product filtered off, washed with water and recrystallized from glacial acetic acid. Yield: 155 g of oxalyl-di- (2-aminomethylfuran-5-carboxylic acid methyl ester); corresponding to 88 ° / a the theory. F. = z82.5 °.

Claims (2)

PATENTANSPRÜCHE: i. Verfahren zur Herstellung von disubstituierten Carbonsäurediamiden, dadurch gekennzeichnet, daß Dimethylolverbindungen von Carbonsäurediamiden in Gegenwart wasserentziehender Mittel mit Furan-2-carbonsäureestern oder -nitrilen kondensiert werden. PATENT CLAIMS: i. Process for the preparation of disubstituted carboxylic acid diamides, characterized in that dimethylol compounds of carboxylic acid diamides are condensed with furan-2-carboxylic acid esters or nitriles in the presence of dehydrating agents. 2. Verfahren nach Anspruch i, dadurch gekennzeichnet, daß als wasserentziehendes Mittel Schwefelsäure, vorzugsweise bei Temperaturen von o bis - io°, verwendet wird.2. The method according to claim i, characterized in that as dehydrating agent sulfuric acid, preferably at temperatures from o to - io °, is used.
DE1951P0006232 1951-09-25 1951-09-25 Process for the preparation of disubstituted carboxylic acid diamides Expired DE887815C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1951P0006232 DE887815C (en) 1951-09-25 1951-09-25 Process for the preparation of disubstituted carboxylic acid diamides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1951P0006232 DE887815C (en) 1951-09-25 1951-09-25 Process for the preparation of disubstituted carboxylic acid diamides

Publications (1)

Publication Number Publication Date
DE887815C true DE887815C (en) 1953-08-27

Family

ID=580742

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1951P0006232 Expired DE887815C (en) 1951-09-25 1951-09-25 Process for the preparation of disubstituted carboxylic acid diamides

Country Status (1)

Country Link
DE (1) DE887815C (en)

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