2- Cyano-2 acetates

A concentrated solution of monochloroacetic acid is neutralised with sodium bicarbonate, and then heated with potassium cyanide, whereby sodium cyano-acetate is obtained ... 

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). 

To minimize the gradual embrittlement that can occur on aging of cyanoacrylate adhesives, plasticizers are added. Some of the materials, which have been used as plasticizers, include phthalates, phosphonates, acyl esters, succinates, and cyano-acetates. The use of allyl, methallyl, and crotyl phthalates is also claimed to improve thermal resistance properties in addition to plasticizing the adhesive [23]. 

The final step in the synthesis of all barbiturates consists in either condensation of a suitably substituted malonic or cyano-acetic ester with urea by means of sodium ethoxide (scheme a) or... 

Then, ethyl methyl(3-benzoylphenyl)cyanoacetate employed as an intermediate material is prepared as follows The sodium derivative of ethyl (3-benzoylphenyl)cyanoacetate (131 g) is dissolved in anhydrous ethanol (2 liters). Methyl iodide (236 g) is added and the mixture is heated under reflux for 22 hours, and then concentrated to dryness under reduced pressure (10 mm Hg). The residue is taken up in methylene chloride (900 cc) and water (500 cc) and acidified with 4N hydrochloric acid (10 cc). The methylene chloride solution is decanted, washed with water (400 cc) and dried over anhydrous sodium sulfate. The methylene chloride solution is filtered through a column containing alumina (1,500 g). Elution is effected with methylene chloride (6 liters), and the solvent is evaporated under reduced pressure (10 mm Hg) to give ethyl methyl(3-benzoylphenyl)cyano-acetate (48 g) in the form of an oil. 

In the final production preparation, a mixture of ethyl methyl(3-benzoylphenyl)cyano-acetate (48 g), concentrated sulfuric acid (125 cc) and water (125 cc) is heated under reflux under nitrogen for 4 hours, and water (180 cc) is then added. The reaction mixture is extracted with diethyl ether (300 cc) and the ethereal solution is extracted with N sodium hydroxide (300 cc). The alkaline solution is treated with decolorizing charcoal (2 g) and then acidified with concentrated hydrochloric acid (40 cc). An oil separates out, which is extracted with methylene chloride (450 cc), washed with water (100 cc) and dried over anhydrous sodium sulfate. The product is concentrated to dryness under reduced pressure (20 mm Hg) to give a brown oil (33.8 g). 

A solution of 69g of sodium in 1,380 ccof absolute alcohol is mixed with 257.4 g of /3-methyl-thioethyl-d -methyl)-n-butvl-cyano-acetic acid ethyl ester and 114 g of thiourea and the whole mass boiled under reflux with stirring for six hours. After concentration under vacuum the residue is taken up in 1.5 liters of water and shaken up thrice, each time with 300 cc of ether. The aqueous alcoholic layer is stripped, under vacuum, of the dissolved ether and mixed with 300 cc of 30% acetic acid under stirring and ice cooling. The precipitated material is sucked off, washed with water, dried and recrystallized from isopropyl alcohol. The thus obtained j3-methvl-thioethyl-(1 -methyD-n-butyl-cyano-ecetyl thiourea forms yellowish green crystals having a melting point of 229°C to 230°C. 

Ammonium acetate as catalyst for condensation ot furfural with cyano-acetic add, 40, 47... 

By coelectrolysis of polymethacrylic acid with e-acetaminocaproic acid or cyano-acetic acid the alkylacetamido- or cyanomethyl group can be grafted on to the main chain of the polymer [205]. 

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. 

Jautze S, Peters R (2010) Catalytic asymmetric Michael additions of a-cyano acetates. Synthesis 365-388... 

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. 

Olefination of the Aldehyde 178 using a stabilized Wittig reagent followed by protecting group chemistry at the lower branch and reduction of the a,p-unsaturated ester afforded the allylic alcohol 179 (Scheme 29). The allylic alcohol 179 was then converted into an allylic chloride and the hydroxyl function at the lower branch was deprotected and subsequently oxidized to provide the corresponding aldehyde 161 [42]. The aldehyde 161 was treated with trimethylsilyl cyanide to afford the cyanohydrin that was transformed into the cyano acetal 180. The decisive intramolecular alkylation was realized by treatment of the cyano acetal 180 with sodium bis(trimethylsi-lyl)amide. Subsequent treatment of the alkylated cyano acetal 182 with acid (to 183) and base afforded the bicyclo[9.3.0]tetradecane 184. 

The first asymmetric synthesis of (-)-monomorine I, an enantiomer of the natural alkaloid, by Husson and co-workers starts with the chiral 2-cyano-6-oxazolopiperidine synthon (385) prepared from (-)-phenylglycinol (384), glu-taraldehyde (383), and KCN (443). Alkylation of 385 with an iodo ketal led to the formation of a single product (386). The cyano acetal (386) was treated with silver tetrafluoroborate and then zinc borohydride to afford a 3 2 mixture of C-6 epimeric oxazolidine (387) having the (2S) configuration. Reaction of 387 with... 

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]. 

This treatment removes ethyl (l-ethylpropylidene)-cyano-acetate as a water-soluble sodium bisulfite addition product (p. 46). 

ETHYL (l-ETHYLPROPYLIDENE)-CYANO ACETATE (2-Pentenoic acid, 2-cyano-3-ethyl-, ethyl ester)... 

A stirred mixture of 72 (41.9 g, 181 mmol), ethyl (acetylamino)(cyano)acetate (30.9 g, 182 mmol), acetone (300mL), anhyd K2C03 (17.3 g), and KI (1.6g) was refluxed overnight, cooled, and filtered. The solid was washed with acetone, and the combined filtrates were evaporated under reduced pressure. The residue was crystallized (EtOH, 70 mL) by cooling to 5°C. The resulting product (59 g) was dissolved in hot EtOH (900 mL), treated with activated charcoal, filtered, and diluted with hexanes (900mL) to give colorless crystals yield 45.6g (70%) mp 151-152°C. 

A mixture of ethyl (acetylamino)(cyano)acetate (5.10 g, 30 mmol), 80 (5.46 g, 20 mmol), 18-crown-6 (528 mg, 2 mmol), and finely powdered K2C03 (8.28 g, 60 mmol) in MeCN (60 mL) was stirred overnight at rt. The mixture was filtered through a Celite bed and the cake was washed with CHC13. The residue obtained after rotary evaporation was dissolved in hot EtOH (100 mL), treated with activated charcoal, filtered, and diluted with hexanes (100 mL) affording 81 as bright yellow crystals yield 6.01 g (83%) mp 162-163°C. 

A stirred mixture of 94 (798 mg, 2 mmol), ethyl (acetylamino)(cyano)acetate (701 mg, 4.12 mmol), K2C03 (382 mg, 2.76 mmol), and KI (8.3 mg, 0.05 mmol) in acetone was refluxed in the dark under argon for 20 h. After cooling, the solid precipitate was filtered and washed with acetone. The crude product was purified by preparative TLC (fy0.24, CHCIs/EtOH 94 6) to give 95 as a glassy solid yield 360 mg (47%). [TLC purification resulted in loss of material, apparently because the crude material also contained the phenolic ester of A-acetyl-2-cyano-4-(4-hydroxybenzoyl)phenylalanine.]... 

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