DE887815C - Process for the preparation of disubstituted carboxylic acid diamides - Google Patents
Process for the preparation of disubstituted carboxylic acid diamidesInfo
- 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
Links
- -1 carboxylic acid diamides Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical class OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012024 dehydrating agents Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 3
- 229950005308 oxymethurea Drugs 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- HXZRHZUUJMJRJT-UHFFFAOYSA-N methyl 5-(aminomethyl)furan-2-carboxylate Chemical compound COC(=O)C1=CC=C(CN)O1 HXZRHZUUJMJRJT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GCNCKNGJEDEZKJ-UHFFFAOYSA-N n,n'-bis(hydroxymethyl)oxamide Chemical compound OCNC(=O)C(=O)NCO GCNCKNGJEDEZKJ-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RULWBFLPUAFFGY-UHFFFAOYSA-N 2-(hydroxymethyl)benzamide Chemical compound NC(=O)C1=CC=CC=C1CO RULWBFLPUAFFGY-UHFFFAOYSA-N 0.000 description 1
- ATGFZSOBDDZEEX-UHFFFAOYSA-N 2-chloro-3-hydroxypropanamide Chemical compound NC(=O)C(Cl)CO ATGFZSOBDDZEEX-UHFFFAOYSA-N 0.000 description 1
- QGGFJIALGORYME-UHFFFAOYSA-N 4-(hydroxymethyl)isoindole-1,3-dione Chemical compound OCC1=CC=CC2=C1C(=O)NC2=O QGGFJIALGORYME-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
Landscapes
- 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)
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) |
-
1951
- 1951-09-25 DE DE1951P0006232 patent/DE887815C/en not_active Expired
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