DD143426A1 - PROCESS FOR PREPARING 5,6-CONDENSED 4-AMINO-3-CYAN-PYRIDONES (2) - Google Patents

Abstract

The title compounds used as intermediates can find according to the invention by a simple method made accessible by carbocyclic or heterocyclic o-aminonitriles (I-III) in one step with cyanoacetic ester in Presence of sodium alkoxide be implemented. This results substituted or unsubstituted 5,6-benzo, thieno, -pyrrolo-, -Furo- and -pyrazolocondensed 4-7 \ "minO" 3 "cyanopyridones" (2) (V-VII),

Description

Field of use; the invention

The invention relates to a process for the preparation of 5,6 ~ -fused 4 ~ amino ~ 3-cyanopyridones - (2). Such compounds can be used as intermediates, for example for the production of pharmaceuticals and dyes,

Characteristic of the known technical solutions

5,6-benzo- and hetero-fused 4-amino-3-cyano-pyridones - (2) of the type specified herein are not known. Of the related compounds in question, only the preparation of the ^ -nino-benzo [b] pyridone- (2) from 2-acetylaminobenzonitrile in the presence of sodium amide in liquid ammonia is shown in Table 2. Chem. Soc. 71, 2205 (19 ^ 9) »as well as 2-quinolone-3-carboxylic acid esters in 4 stages according to Yak. Zasshi 80, 1806 (1960) J.O.A. 55, 9401 (1-951)

The starting materials I-III are either Ilandelsprodukte or easy to prepare according to Literatux regulations, · z * Bo after Jo Org _e Chem. 21 ^, 1240 (1955), Chem. Ber. 9B ₅ 357 "! (1965), S4 _S ^100? - (^ 966), J ₆ prakt. Chem. 3JiS ₅ 653 (Ί976).

Object of the invention

The aim of the invention is to produce 5> 6 ~ condensed 4-amino-3-cyanopyridone- (2) in a simple manner.

Explanation of the essence of the invention

The object of the invention is to prepare hitherto unknown 5 ₅ 6 -benzoic and heterocondensed 4-amino-3-cyanopyridone- (2) in a simple manner. ,

According to the invention the object is achieved in that o-aminonitriles., Type I-III, which are substituted and unsubstituted 2-Aiai nob en zo nitrile I, 2-aminothiophene, -pyrrole and furan-3-carbonitriles II and ^ -Aminopyrazole - ^ - carbo- • nitrile III,

"J

CN

IX

III

rn.it cyanoacetic ester XV

IV

be reacted in the presence of bases such as sodium and in polar solvents such as alcohol at temperatures between 70 ° and 120 ⁰ C. In this case, the compounds of the formula V are formed from I, from II products of the formula VI and from III the substances VII.

HH

VII

- 3 - '

In the formulas. I to VII, R is a hydrogen or halogen atom, an alkyl, aryl, acyl, alkoxy, cyano or.

12

Carbalkoxy, R and R are hydrogen, an aryl of the alkyl group, and X is a sulfur, oxygen or nitrogen atom.

embodiments

Example 1ί 4-Araino-3-cyano-quinolone- (2)

In a solution of 7 g of sodium in about 200 ml of abs »ethanol are dissolved 0.1 times Anthranilsäurenitril and 0.15 mol of ethyl cyanoacetate» Thereafter, the solution '2.5 St d. After cooling, the mixture is distilled off (if necessary) some alcohol, stirred into 500 ml of water, filtered and the filtrate acidified with hydrochloric acid · yield 70%, mp 325 ° 328 ° C. (from glacial acetic acid) *

Example Zx 4-araino-5-cyanothieno [2,3-b] pyridone- (6)

0.01 mol of 1 2-amino-3-cyanth.ioph.en be together with 0.02 mol Cyanessigsäureethy! Ester in a solution of 0.8 g of sodium in 25 ml of abs * ethanol for 2.5 hr _e in a boiling water under Reflux heated. After cooling, the mixture is stirred into 70 ml of water and filtered. The filtrate is rendered significantly acidic with dilute hydrochloric acid. After prolonged standing, the product is filtered off with suction. Yield 75%, mp 356 ~ 360 ° C (from Bisessig).

Example 3J 4-Amino-2,3-tetramethylene-5-cyanothieno [2,3-b] pyridone- (6)

A solution of 7-8 g of sodium in about * 200 ml abs. Ethanol is mixed with 0.1 mol of 2-amino-4-, 5-tetramethylene-3 - cyanothiophene and 0.17 mol Cyanesoigsäureethylestor and heated in a boiling water bath 2 ₄ 5 StcL under reflux. After the ericalten is in 500-600 ml of water, stirred (if necessary, before (Toll of Et ha no Is distilled off) "It is filtered, the filtrate is acidified with mineral acid, and the precipitate is filtered off with suction yield 72%, Schiap. -358 ⁰ G (from dimethylformamide) _o

4- Example 4: 4-Kmino-3-methyl-5-cyanothieno [2,3- "b] pyridone- (6)

As described in Example 2, 0.01 mol of 2-amino-4-methyl-3-cyanthiophen is reacted and worked up. Yield 80%, mp, from 36O ⁰ C decomposition (from formamide). -

Example 5: 4-Amino-3-ethyl-2-carbethoxy-5-cyanothieno [2,3-b] pyridone- (6)

After the given for Example 3, "provision 0.1 mol · 2-amino ~ 4-methyl-3-cyanothiophene-5-carboxylic acid ethyl ester are reacted and worked * Yield 80%, mp. 339-.341 ⁰ C (from dimethylformamide),

Example 6: 4-Amino-2-methyl-3-p-acyl-5-cyano-pyrrolo [2,3-b] pyridone- (6)

A solution of 6.8 g of sodium in 20 ml abs. Ethanol is treated with 0.1 mol of 2-amino-4-methyl-5-phenyl-3-cyanopyrrole and 0.18 mol of ethyl cyanoacetate and heated under reflux in a boiling water bath for 3 hours. After cooling, the sparingly soluble sodium salt is filtered off with suction and washed with abs. Washed ethanol. It is dissolved in hot water, filtered hot and acidified with acetic acid. The colorless product does not melt. up to 360 °. Yield 78%.

Example 7: 4-Amino-2,3-diphenyl-5-cyano-furo [2,3-b] pyridone- (6)

It is a solution of 0.8 g of sodium in 20 ml of abs. Ethanol and dissolved therein 0.18 mol of ethyl cyanoacetate and 0.01 mol of 2-amino- ⁱ l, 5-diphenyl-3-cyan-furan. The mixture is then heated under vigorous reflux for 4 hours. It is then diluted with 40-50 ml of water and acidified with hydrochloric acid. The precipitated product is filtered off with suction and boiled with ethanol for cleaning. Yield 72%, from 35O ⁰ C gradual decomposition. (If too short reaction time is das'Zwischenprodukt, the 2-Cyanacetylamino-4 _s ~ diphenyl-3 ~ cyano-5 furan mp, 184-187 ⁰ C isolated) ο

Example 5: 4-Araino-1-phenyl-i-cyano-pyrazolo [3,4-b] pyridone ~ (6)

Ια a solution of 0.8 g sodium in 20 ml abs "-ethanol 0.01 Biol ^ - ^ mino-i-phenyl ^ H-cyano-pyrazole and 0.02 mol of ethyl cyanoacetate 2.5 3td _e in a boiling water heated to reflux. After cooling, 40 ml of water are added and filtered after some time. "The filtrate is acidified with hydrochloric acid. When a gel separates, it is stirred until the product has become filterable. The mixture is filtered off with suction. Yield 70%, mp 284 ~ 287 ° C _e (When dissolved in hot, ethanolic KOH and allowed to cool, the potassium salt of mp. 34-5-355 ° C is formed _e

Claims (1)

Erfindungsansprucli "' Process for the preparation of 5> δ-fused 4-amino- 3 cyanopyridones ~ (2), ^ e ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Ή ² - II III with cyanoacetic ester NC-CH ₂ -GO ₂ -Altri IY in the presence of bases, preferably sodium alkoxide and in a polar solvent, preferably alcohol, are reacted at 70-120 °, wherein from I the compounds of formula V, from II the products of formula VI and III of the formula VII VI umd in formulas I, II, V and VI R is a hydrogen or halogen atom, an alkyl, aryl, acyl or oar Λ 2 balkoxy, in the formulas III and VII R and R represents a hydrogen atom, an alkyl or aryl group and in the formulas II and VI X represents an oxygen, sulfur or nitrogen atom.