DE843406C - Process for the preparation of substituted ª ‡ -amino-acetic acid esters - Google Patents
Process for the preparation of substituted ª ‡ -amino-acetic acid estersInfo
- Publication number
- DE843406C DE843406C DEE1286A DEE0001286A DE843406C DE 843406 C DE843406 C DE 843406C DE E1286 A DEE1286 A DE E1286A DE E0001286 A DEE0001286 A DE E0001286A DE 843406 C DE843406 C DE 843406C
- Authority
- DE
- Germany
- Prior art keywords
- acetic acid
- acid esters
- amino
- preparation
- substituted
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von substituierten a-Amino-acetessigestern In "Berichte der Deutschen Chem. Ges. a, Jhg. 82, Heft 1 (1949), S. 6o bis 63, ist die Herstellung von acylierten a - Amino - acetessigestern beschrieben.Process for the preparation of substituted a-amino-acetic acid esters In "Reports of Deutsche Chem. Ges. A, Vol. 82, Issue 1 (1949), pp. 6o to 63 is the preparation of acylated a - amino - acetic acid esters is described.
Es wurde nun die überraschende Beobachtung gemacht, daß es gelingt, diese acylierten a-Amino-acetessigester in Gegenwart säurebindender Mittel, vorzugsweise Alkalien oder Erdalkalien, und zwar zweckmäßig in wäßrigem Medium, mit Säurehalogeniden, wie Benzoylchlorid, p-Nitrobenzoylchlorid, Chlorbenzoylchlorid, zu den entsprechenden a-Aroyl-a-acylamino-acetessigestern umzusetzen.The surprising observation has now been made that it succeeds these acylated α-amino-acetic acid esters in the presence of acid-binding agents, preferably Alkalis or alkaline earths, expediently in an aqueous medium, with acid halides, such as benzoyl chloride, p-nitrobenzoyl chloride, chlorobenzoyl chloride, to the corresponding to implement a-aroyl-a-acylamino-acetic acid esters.
Die neuen Verbindungen sollen als solche in der Chemotherapie verwendet werden oder als Zwischenprodukte für weitere Synthesen dienen. Beispiel i 26,3 g a-Phenacetylamino-acetessigsäureäthylester werden mit ioo ccm Wasser und einer Lösung von 18,5 g p-Nitrobenzoylchlorid in 50 ccm Benzol vereinigt und sofort unter kräftigem Rühren 7,5 g Calciumhydroxyd in Wasser hinzugefügt. Die Temperatur steigt sofort auf etwa. 4o bis 45°, und es scheidet sich bald ein weißer Niederschlag aus. Nach 1/$stündigem Rühren wird abgesaugt, mit Wasser und etwas Äther gewaschen und an der Luft getrocknet. Erhalten werden 27 g ' cc-(p-Nitrobenzoyl)-a-phenacetylamino-acetessigsäureäthylester der Formel welcher nach dem Umkristallisieren aus Essigester i : 6 einen Fp. von 147° zeigt. Beispiel 2 26,3 g a-Phenacetylamino-acetessigsäureäthylester werden mit ioo ccm Wasser und einer Lösung von 17,5 g p-Chlorbenzoylchlorid in 5o ccm Benzol vereinigt und sofort unter kräftigem Rühren 7,5 g Calciumhydroxyd in Form einer iväßrigen Suspension hinzugefügt. Es wird aufgearbeitet wie in Beispiel i.The new compounds are to be used as such in chemotherapy or as intermediates for further syntheses. Example i 26.3 g of a-phenacetylamino-acetic acid ethyl ester are combined with 100 cc of water and a solution of 18.5 g of p-nitrobenzoyl chloride in 50 cc of benzene and 7.5 g of calcium hydroxide in water are immediately added with vigorous stirring. The temperature immediately rises to about. 40 to 45 °, and a white precipitate soon separates out. After stirring for an hour, it is filtered off with suction, washed with water and a little ether and air-dried. 27 g of 'cc- (p-nitrobenzoyl) -a-phenacetylamino-acetic acid ethyl ester of the formula are obtained which after recrystallization from ethyl acetate i: 6 shows a melting point of 147 °. Example 2 26.3 g of a-phenacetylamino-acetic acid ethyl ester are combined with 100 cc of water and a solution of 17.5 g of p-chlorobenzoyl chloride in 50 cc of benzene and 7.5 g of calcium hydroxide in the form of an aqueous suspension are immediately added with vigorous stirring. It is worked up as in Example i.
Erhalten werden 26 g a-(p-Chlorbenzoyl)-a-phenacetv1amino-acetessigsäureäthylester der Formel welcher nach dem Umkristallisieren aus einem Gemisch von Benzol und Petroläther einen Fp. von 126 bis i27° zeigt.26 g of a- (p-chlorobenzoyl) -a-phenacetv1amino-acetic acid ethyl ester of the formula are obtained which, after recrystallization from a mixture of benzene and petroleum ether, has a melting point of 126 ° to i27 °.
Beispiel 3 Zu einer Mischung von 26,8g a-Phenacetylaminoacetessigsäureäthylester, ioo g Eis, ioo ccm Methylenchlorid und 14 g Benzoylchlorid wird unter kräftigem Rühren eine wäßrige Suspension von 7,5 g Calciumhydroxyd gegeben. Nach zweistündigem Rühren wird von wenig ungelöstem Kalk abgesaugt, die klare Methylenchloridlösung eingedampft, der festgewordene Rückstand mit wenig Äther digeriert und a4ü--saugt. Erhalten werden 16 g a-Benzoyl-a-phenacetylamino-acetessigsäureäthylester der Formel vom Fp. 96 bis 97°.EXAMPLE 3 An aqueous suspension of 7.5 g of calcium hydroxide is added to a mixture of 26.8 g of ethyl α-phenacetylaminoacetoacetate, 100 g of ice, 100 cc of methylene chloride and 14 g of benzoyl chloride with vigorous stirring. After two hours of stirring, a little undissolved lime is suctioned off, the clear methylene chloride solution is evaporated, the solidified residue is digested with a little ether and sucked off. 16 g of a-benzoyl-a-phenacetylamino-acetic acid ethyl ester of the formula are obtained from m.p. 96 to 97 °.
Beispiel 4 Man vermischt 25,6g a-Dichloracetylamino-acetessigsäureäthylester mit einer Lösung von 18,5g p-Nitrobenzoylchlorid in ioo ccm Benzol, gibt i g Calciumhydroxyd in 15 ccm Wasser hinzu und schüttelt '/$ Stunde lang kräftig. Dann wird von Ungelöstem abgesaugt, die benzolische Lösung abgetrennt und das Benzol abgedunstet. Der Rückstand wird mit Äther digeriert und abgesaugt. .EXAMPLE 4 25.6 g of a-dichloroacetylamino-acetic acid ethyl ester are mixed with a solution of 18.5 g of p-nitrobenzoyl chloride in 100 cc of benzene, calcium hydroxide in 15 cc of water is added and shaken vigorously for 1 hour. Then undissolved material is suctioned off, the benzene solution is separated off and the benzene is evaporated. The residue is digested with ether and filtered off with suction. .
Nach dem Umkristallisieren aus Alkohol erhält man 14g a-(p-Nitrobenzoyl)-a-dichloracetylamino-acetessigsäureäthylester vom Schmelzpunkt 136 bis i37°. Beispiel 5 26,3 g a-Phenacetylamino-acetessigsäureäthylester werden zu 18,5 g p-Nitrobenzoylchlorid in 5o ccm Benzol gegeben, 17 g Barythydrat in i5o ccm Wasser zugefügt und 1/4 Stunde kräftig geschüttelt.After recrystallization from alcohol, 14 g of a- (p-nitrobenzoyl) -a-dichloroacetylamino-acetic acid ethyl ester are obtained from melting point 136 to i37 °. Example 5 26.3 g of a-phenacetylamino-acetic acid ethyl ester are added to 18.5 g of p-nitrobenzoyl chloride in 50 cc of benzene, 17 g of baryta hydrate in 150 cc of water and shaken vigorously for 1/4 hour.
Es werden 28 g a-(p-Nitrobenzoyl)-a-phenacetylamino-acetessigsäureäthylester mit dem in Beispiel t angegebenen Schmelzpunkt erhalten.There are 28 g of a- (p-nitrobenzoyl) -a-phenacetylamino-acetic acid ethyl ester obtained with the melting point given in Example t.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEE1286A DE843406C (en) | 1950-06-06 | 1950-06-06 | Process for the preparation of substituted ª ‡ -amino-acetic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEE1286A DE843406C (en) | 1950-06-06 | 1950-06-06 | Process for the preparation of substituted ª ‡ -amino-acetic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE843406C true DE843406C (en) | 1952-07-07 |
Family
ID=7065190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEE1286A Expired DE843406C (en) | 1950-06-06 | 1950-06-06 | Process for the preparation of substituted ª ‡ -amino-acetic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE843406C (en) |
-
1950
- 1950-06-06 DE DEE1286A patent/DE843406C/en not_active Expired
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