Malodinitrile

AU these results indicate that silylated amides and, in particular, silylated lactams such as 388 will react with methyl or ethyl cyanoacetate or malonate and malodinitrile in the presence of HMDS 2 (to convert the leaving group MeaSiOH 4 into HMDSO 7) via the O-silylated forms such as 384b or 389 to give similar products such as 385 and HMDSO 7 (Scheme 4.54). 

Additionally, the synthetic utility of this procedure was demonstrated by the efficient one-step synthesis of a 2,2 -bipyridine 176 starting from the corresponding tetrayne 175 and malodinitrile (Equation (35)). 

Keywords arylidene malodinitril, dimedone, Michael addition, cyclization, pyrane... 

Keywords cyanoacetamide, malodinitril, methyl cyanoacetate, aromatic aldehyde, Knoevenagel condensation, solid-solid reaction, base catalysis, melt reaction, uncatalyzed, cinnamamide, cinnamonitril, methyl cinnamate... 

There is no perfectly linear correlation between the basicity and nucleophilicity of carbanions [66], but higher basicity usually also implies higher nucleophilicity. Carbanions in which the negative charge is highly delocalized (e.g. diethylmalonate) will usually react more slowly with electrophiles than less extensively delocalized carbanions of similar basicity (e.g. malodinitrile) [66],... 

HFA has been found to insert into one of the acidic C—H bonds of malodinitrile (186). 

Malodinitrile (l-Methyl-2-phenyl-propyl)- E21c, 2242 (En + H3C —I/Cul/Zn) Naphthalin l-Diazo-4.4.6-trimethyl-... 

An acid-resistant protecting principle for carbonyl groups consists of the a,a-dicyanoethylene derivatives (96). They are obtained from carbonyl compounds, e.g. pyrrole aldehydes (95), by Knoevenagel condensation with malodinitrile. In general, mineral acids and Lewis acids, which are used in Friedel-... 

Analogously to conventional reactions 201-203), bis(trimethylsiloxy) alkenes form heterocycles of different classes l,2-bis(trimethylsiloxy)-l-cyclohexene (305) reacts with formamide urea malodinitrile and ethyl (J-amino-crotonate to afford 4,5,6,7-tetrahydrobenzunidazole (309) ° 2-oxo-l, 3,4,5,6,7-hexahydrobenzimidazoIe (317) , 2-aniino-3-cyano-4,5,6,7-tetra-hydro-coumarone (312) and 2-methyl-3-ethoxy-carbonyl-4,5,6,7-tetrahydro-in-dole (373) respectively. 

Similar reasoning applies to mixtures of solvents. The combination of a nonsolvent with a lower, and a nonsolvent with a higher, solubility parameter than that of the polymer often gives a good solvent for the polymer (Table 6-4). Conversely, a mixture of two solvents can be a nonsolvent. Poly(acrylonitrile) 62 = 12.8), for example, dissolves in both dimethyl-formamide (<5i = 12.1) and malodinitrile = 15.1), but not in a mixture of the two. 

An efficient method for the synthesis of dihydrothiophene ureidoformamides 149 from commercially available materials in a four-component domino process was reported by Cai et al. [82] (Scheme 12.58). The reaction efficiently assembled aromatic aldehydes 69, malodinitrile 71a, 1,3-thiazolidinedione 148, and anitines 102 with high yields by conducting the reaction in a cosolvent mixture of polyethylene glycol (PEG) 400/H2O (1 1) at 80 °C. Under optimized conditions, a wide range of aldehydes and amines were converted into the desired heterocycles with yields ranging from 27% to 90%. 

Retinaldehyde (2) underwent condensation with cyclopentadiene to give fulvene (614) (Haeck and Kraelt, 1966) and with malodinitrile to give (615) (Haeck and Kraelt, 1966b Schmieder et aL, 1980). 

Derivatives of the type 29 have also proved to be more suitable starting materials than the corresponding 0-analog for condensation reactions with carbanions like malodinitrile, ultimately enabling the formal replacement of O by... 

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