Cyano acetamides

Manufacture. Malononitiile can be produced batchwise by elimination of water from cyano acetamide [107-91-5] with phosphorous... 

The observation that a carboxyl derivative of a pyrimidinoquinol ine shows mediator release inhibiting activity is in consonance with the earlier generalization. Knoevenagel condensation of nitroaldehyde 138 with cyano-acetamide gives the product 139. Treatment with iron in... 

There has been considerable interest in hydroxy-3,3 -bipyridines and 3,3 -bipyridinones. Following from some very early work on the oxidation of citrazinic acid (2,6-dihydroxypyridine-4-carboxylic acid), which was considered to give some polyhydroxy-3,3 -bipyridines, it has been shown that the 3,3 -bipyridinone 59, a product of the hydrolysis of a natural blue pigment from Corynehacterium insidiosum, is obtained by oxidation of 2-hydroxy-5-aminopyridine (60) or 2,6-dihydroxypyridine-4-carboxylic acid 61) 80,83 similar oxidation of 2,6-dihydroxy-3-aminopyridine-4-carboxylic acid affords the natural product indigoidine (20). Numerous related oxidative condensations have been reported subsequently. Cyano-acetamide condensations analogous to those discussed in the synthesis of 2,3 -bipyridines afford, for example, the cyano-substituted 3,3 -bipyridinone 62 588 v, lereas condensation of 3-pyridylacetonitrile with ethyl phenyl-propiolate and ethanol affords compound 63. To complete the section on... 

The procedure used for preparing the sodium salt of formyl-acetone is a modification of a previously described procedure.2 3-Cyano-6-methyl-2(l)-pyridone has been prepared by the condensation of /3-ethoxycrotonaldehyde diethyl acetal with cyano-acetamide 6 and by condensation of the sodium salt of formyl-acetone with cyanoacetamide.7... 

Condensation, of paraldehyde with diethyl malonate, 32, 54 of a-phene thyl chloride with diphenylacetonitrile, 39, 74 of phenylacetylene with ethyl orthoformate, 39, 59 of 1-phenylbiguanide with ethyl chloroacetate, 38,1 of potassium diphenylacetonitrile with benzyl chloride, 39, 73 of potassium trithiocarbonate with potassium chloroacetate, 39, 77 of sodium acetylacetonate to tetraacetylethane, 39, 61 of sodium formylacetone with cyano-acetamide, 32, 32 of tetracyanoethylene with N,N-dimethylaniline, 39, 68 of thiophene, paraldehyde, and hydrogen chloride, 38, 86 of thiourea with furfuryl alcohol, 36,66... 

Atkinson, R.G., Schroder, R., Hallett, I.C., Cohen, D., and MacRae, E.A. 2002. Overexpression of polygalacturonase in transgenic apple trees leads to a range of novel phenotypes involving changes in cell adhesion. Plant Physiol. 129 122-133. Bach, E. and Schollmeyer, E. 1992. An ultraviolet-spectrophotometric method with 2-cyano-acetamide for the determination of the enzymatic degradation of reducing polysaccharides. Anal. Biochem. 203 335-339. 

Condensation of JV-methyl-3-formyl-4-piperidone (47) with cyano-acetamide afforded the tetrahydro-l,6-naphthyridine (48). This compound was converted into the 5,6,7,8-tetrahydro-6-methyl-1,6-naphthyridine (49) by the transformations shown.92... 

A one-pot synthesis of 3,5-disubstituted 7-hydroxy-3//-l,2,3-triazolo[4,5-d]pyrimidines (130) has been carried out by using benzyl azide, cyano-acetamide, ethyl or methyl esters of the appropriate carboxylic acid, and sodium ethoxide as catalyst. The reaction proceeds via a 5-amino-l-benzyltriazole-4-carboxamide intermediate (85JHC1607). 7-Amino-3H-l,2,3-triazolo[4,5-d]pyrimidines 133 (R2 = H) were prepared starting from benzyl azide, malononitrile, and an aliphatic or aromatic nitrile, or by reaction of 130 with phosphorus oxychloride followed by amination. Compound 132 was formed in most reactions from two molecules of the 5-amino-4-cyano-l-benzyltriazole intermediate by an intermolecular nucleophilic at-... 

A new approach to the abe ring system of the pentacyclic C20 diterpenoid alkaloids has been reported by van der Baan and Bickelhaupt.51 For the model system of major interest, (134) was prepared from (133) by reaction with cyano-acetamide. Treatment of (134) with allyl bromide gave almost exclusively C-alkylation, to afford (135). On heating (135) at 100—110°C, a Cope-type rearrangement to (136) was effected. This compound was then N-alkylated with ethyl iodide-DMF, the product being (137). Treatment of (137) with IV-bromosucc-... 

S-Methylglutaric anhydride is obtained from the acid, which has been prepared by condensation of acetaldehyde with cyano-acetamide.7 8 The present method, which is a simplification of that published by Stallberg-Stenhagen,9 gives a higher yield and is much better adapted to the preparation of large quantities. 

Condensation, of 1-phenylbiguanide and ethyl chloroacetate, 38, 1 of sodium formylacetone with cyano-acetamide, 32, 32... 

Some reactions of 2,3,4-trisubstituted isoxazolium salts (exemplified by 70) leading to ring transformations, are summarized in Scheme 14.180 Other active methylene compounds such as ethyl acetoacetate and cyano-acetamide give analogous results to those with diethyl malonate products of base-induced ring opening by ethoxide are also obtained. When the reaction with phenylhydrazine is carried out in the presence of sodium hydroxide in ethanol the product is 71, presumably formed via the im-inoketene 72. 

The condensation of 30 (via 69) with a-amino-a-cyano-acetamide in alcohol, using hydrogen chloride as catalyst, probably gave 2-carbamido-3-aminopyrrolo[2,3-6]indole (70) (Scheme 23) a possible normal reaction product128 would possess the structure 2-carba-mido-3-aminoimidazo[ 1,2-ajindoline (71). 

The reaction of (f /Z)-4-arylidenepyrazol-3-ones 491a-c with reactive methylene compounds such as diethyl or dimethyl malonate, ethyl cyanoacetate or cyano-acetamide in alcoholic solution containing sodium hydroxide afforded the corresponding addition products 492c-j. These adducts were found to be almost exclusively enol tautomers (79AP478) (Scheme 151). 

There have been several reports of the use of cyano-acetamides as C-C-N synthons in pyridone synthesis. The C-C-C component that is required for the formation of a six-membered ring may be either an 0 /3-unsaturated carbonyl compound or a dicarbonyl compound. Alternatively, pyridones have been formed by base-promoted cyclocondensation of cyano-acetamides with a-keto-ketene 5,A -acetals (Scheme 10). ... 

Substituted 2-iminochromenes (130), which have anti-tumour properties, have been synthesized from the salicylaldehydes (129) and N-substituted cyano-acetamides. ... 

Cyclocondensation of sulfamide and arylidenemalononitriles 282 in hydrochloric acid-saturated diglyme, following a described procedure <1988J(P1)1271>, failed to give the desired 283 only cyano acetamides 284 were obtained (Scheme 38) <1999AF759>. 

Pyridines are formed from the interaction between a 1,3-dicarbonyl compound and a 3-amino-enone or 3-aminoacrylate 3-cyano-2-pyridones result if cyano-acetamide is used instead of an amino-enone. 

Diphenyl-1,3-pentanedione, condensation with cyano-acetamide, 621... 

Ethyl 2-keto-3-phenyllevulinate, condensation with cyano— acetamide, 622 N-Ethyllutidone, 615... 

Eor examples of variation of the nitrile compound (cyano-acetamides) in the preparation of the starting thiophenes used in the synthesis of heterocycles with potential biological... 

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