Ethyl cyano acetate

Diethyl malonate is prepared commercially by hydrolysis and estenfication of ethyl cyano acetate... 

The reaction mixture is filtered through a Hirsch or Buchner funnel, and the bottle is rinsed with 50 ml. of benzene, which is also poured through the funnel. The filtrate is washed with two 50-ml. portions of 10% sodium chloride solution and three 2S-ml. portions of water (Note 4). The washings are extracted with three 10-ml. portions of benzene, and the combined benzene solutions are distilled under reduced pressure from a 250-ml. modified Claisen flask. The yield of ethyl -butylcyanoacetate, b.p. 108-109°/9 mm., is 79-81 g. (94-96%, based on the ethyl cyano-acetate used) (Note 5). 

This index is divided into two parts. Part 1 gives the names of compounds as used in these volumes as well as general terms for classes of compounds, types of reactions, synthetic applications, special apparatus, and unfamiliar methods. The complete names of all specific compounds are given in normal order as written in the text (e.g., ethyl cyano-acetate appears under ethyl). Some entries are common names and others are systematic Chemical Abstracts names, whichever was used in the text. 

Into a 3-1., three-necked flask (Note 1) equipped with a reflux condenser and an efficient stirrer is placed 11. of absolute (99.8%) ethanol. To this is added 39.4 g. (1.72 g. atom) of sodium metal, and, after solution is complete (Note 2), 91.5 ml. (97.2 g., 0.86 mole) of ethyl cyano-acetate (Note 3) and 51.5 g. (0.86 mole) of urea are added. The mixture is heated under reflux on a steam bath with vigorous stirring for 1 hours. After about 2 hours, the reaction mixture becomes practically solid, and the stirrer may have to be stopped. At the end of the reac-I ion time, 1 1. of hot (80°) water is added to the reaction mixture, and si i rring is resumed. After complete solution has taken place, the stirred mixture is heated at 80° for 15 minutes and is then neutralized to litmus with glacial acetic acid (Note 4). Additional glacial acetic acid (75 ml.) is then added, followed by cautious addition of a solution of 64.8 g. (0.94 mole) of sodium nitrite dissolved in 70 ml. of water. The rose-red nitroso compound separates almost immediately as an expanded precipitate which almost stops the stirrer. After a few minutes the ni-... 

The one-step condensation to convert 2-butanone, ethyl cyano-acetate, and hydrocyanic acid to ethyl 2,3-dicyano-3-methyl-pentanoate is a modification of the procedure described by Smith and Horowitz 6 in which pyridine acetate was employed as the catalyst. Higson and Thorp 6 employed a two-step procedure in which butanone was converted to its cyanohydrin, which in turn was condensed with ethyl cyanoacetate. 

Mettler and colleagues reported an alternative synthesis of malonate 16 in the same paper (Griffiths et al., 1991) in which they condensed cyclohexanone with ethyl cyano-acetate instead of diethyl malonate in the Knoevenagel reaction to give ethyl cyano(cyclohexylidene)-acetate (18). In the presence of a catalytic amount of sodium cyanide, the Michael addition of HCN to cyanoacetate 18 proceeded in good yield at room temperature to generate the dicyanoester 19. Intermediate 19 was selectively converted to malonate 16 with pressurized HCI treatment in ethanol (Scheme 16.4). 

Preparation of dihydropyridones by the condensation of ethyl cyano-acetate, cyanoacetamide, or malononitrile with a,j8-unsaturated ketones [186]. 

Cyclohexenylacetonitrile has been prepared by the decarboxylation of cyclohexylidenecyanoacetic acid 4-5 by the dehydration of 1-cyclohexenylacetamide 5 by the condensation of cyclohexanone and cyanoacetic acid in the presence of piperidine 6 by the condensation of cyclohexanone and ethyl cyano-acetate in the presence of sodium ethoxide 4-7 and by the condensation of cyclohexanone and cyanoacetic acid in the presence of ammonium acetate followed by decarboxylation.8 Ammonium acetate also has been used as a catalyst for the condensation of ketones with ethyl cyanoacetate.3-9... 

Head-to-tail dimerisation of methyl acrylate to the dimethyl ester of 2-methylenepentane-dioic acid (126) occurred in 82-85% yield in the presence of catalytic amounts of P(RNCH2CH2)3N with R = PP, Bu or Bz but the less sterically hindered proazaphosphatrane with R = Me, gave oligomer or pol-ymer. The proazaphosphatrane, P(RNCH2CH2)3N with R = Bu also acts as an effective ligand for the palladium-catalyzed direct arylation of ethyl cyano-acetate (127) with aryl bromides (e.g. 128) to form (129) in high yield. ... 

Sodium ethoxide is prepared from 46 g. (2 gram atoms) (Note 1) of sodium and 800 ml. of absolute ethanol in a 2-1. threenecked flask equipped with stirrer and a reflux condenser. To the hot solution is added 113 g. (106 ml., 1 mole) of ethyl cyano-acetate followed by 108 g. (98 ml., 1 mole) of phenylhydrazine (Note 2), and the mixture is stirred and heated in an oil bath at... 

Various approaches to the synthesis of 2,7-naphthyridines are available. Thus, the dianilide of 3-oxoglutaric acid 133 reacted with malononitrile in the presence of sodium acetate to give pyridone derivative 134, whereas the reaction of 133 with ethyl cyano-acetate in pyridine afforded tetrahydropyridinedione derivative 135. The compounds 134 and 135 underwent cyclization upon heating with triethylamine in DMF to form substituted 2,7-naphthyridine-3,6-diones 136 and 137, respectively (1989JPR745). 

This ring may be constructed from an aminoaldehyde and either ethyl cyano-acetate or triethyl phosphonoacetate in the presence of a strong base. 

Figure 1. Condensation of benzaldehyde and ethyl cyano-acetate on exchanged X zeolites LiX (X), NaX ( ), KX (O) and CsX ( ).

The reaction of N-aminoazonium salts with aliphatic and aromatic aldehydes in the absence of base gives the Schiff base type compounds 28.151,153-156 Some aliphatic ketones also react with N-aminoazonium salts.40,155 Hexane-2,5-dione reacts with N-aminopyridinium perchlorate to give l-(l -pyrrolyl)pyridinium cation 29 together with some of the bisper-chlorate 30.157 Certain esters such as diethyl malonate and ethyl cyano-acetate react with N-aminopyridinium salts in the presence of base to give the corresponding N-acylimines 31.48 However, the reaction of ethyl aceto-acetate and acetylacetone with N-aminoazonium salts in the presence of base gives 1,3-dipolar cycloaddition products (Section IV,C,1).36,154,158 The reaction of ethyl acetoacetate with 1-alkyl-l,2,4-triazole 4-imine affords zwitterionic triazolo[4,3-/>]pyridazines 32.139,159... 

The addition of the Sodio-derivative of ethyl acetoacetate, ethyl malonate, or ethyl cyano acetate to an olefine function that is specifically activated by a keto, nitrile or O... 

The condensation of a-bromoacetophenone azines with dimethyl malonate in the presence of NaOMe affords 5,5-bis(methoxycarbonyl)-3,7-diaryl-5,6-dihydro-4//-l,2-diazepines <77BCJ2153, 92M1904-01 > this method has been extended to reactions involving malononitrile and ethyl cyano-acetate in the presence of NaOEt to give similar 5,6-dihydro-3,7-diphenyl-4//-l,2-diazepines in 70 and 75% yields, respectively <86JHC557>. 

A soln. of 2-methylimidazole, ethyl 2-cyano-3-ethoxyacrylate, and ethyl cyano-acetate in ethanol refluxed 4 days diethyl 3 amino-2-cyano-4-[(2-methyl-l-imidazolyl)methylene]glutaconate. Y 91%. F. e., mostly with benzimidazole derivatives, s. R. K. Howe, J. Org. Chem. 34, 2983 (1969). 

Tetrabutyl ammonium bromide (TBAB) was found to be an efficient phase-transfer catalyst for the synthesis of pyrido[2,3 -d]pyrimidines by the one-pot reaction of 6-aminouracils (132), aromatic aldehydes (134), and malononitrile or ethyl cyano-acetate in water under ultrasonic irradiation (Scheme 8.45). The advantages of this method are the use of an inexpensive and readily available catalyst, short reaction times, easy workup, improved yields, and the use of water as a solvent that is environmentally benign (Hussein, 2012). 

Vinyl ketones, 630 condensation with ethyl cyano-acetate, 630... 

Pentane-2,4-dione reacts with 3-chloro-l,2-benzisothiazole in the presence of sodium ethoxide to form 2-acetyl-3-aminobenzo[6]thiophen (71%). Under similar conditions, ethyl acetoacetate and diethyl malonate each give mainly ethyl 3-aminobenzo[6]thiophen-2-carboxylate (160). Under modified conditions diethyl malonate gives, in addition, some of the expected diethyl (l,2-benzisothiazol-3-yl)malonate, whereas ethyl cyano-acetate forms only ethyl (l,2-benzisothiazol-3-yl)cyanoacetate, irrespective of conditions. Mechanisms were considered involving iS-substituted o-cyanothiophenols as possible intermediates in the reactions leading to benzo[6]thiophen (see Scheme 8). The reactions constitute a useful... 

Azeotropic water entrainment. A mixture of 1-naphthaldehyde, ethyl cyano-acetate, some piperidine, and some benzoic acid in benzene refluxed into a phase-separating head until after 1 hr. the theoretical amount of water has been collected ethyl 1-naphthylidenecyanoacetate. Y 88.8%. F. e. s. M. S. Newman et al., J. Org. Ghem. 23, 796 (1958) Am. Soc. 81, 3667 (1959). 

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