Ethyl chloromalonate

Deoxy 1,2 3,4-di-0-isopropylidene- 3-L-flra6i o-hex-5-enopyranose reacted with the radical generated from ethyl chloromalonate by tributyltin hydride, producing a small quantity of compound 40 together with products derived from reduction of the double bond in 40. (See Chapter 3 for an application of this method in preparing C-glycosides). 

Ethyl chloromalonate added slowly with stirring during 30 min. to an aq. soln. of acetaldehyde and K-carbonate, stirring continued 12-15 hrs. ethyl hydroxy-ethylchloromalonate. Y 84%. F. e. s. H. Gault and P. Bouvier, C. r. 254, 2179 (1962). 

Isocyanoacrylic acid esters are useful as precursors of heterocyclic and unsaturated amino-acids. These compounds are prepared in a stereoselective manner and in good yield using the Wittig-Horner reaction of t-butyl(diphenylphosphinyl)isocyanoacetate with aldehydes. cw-Enoates have been prepared by the reaction of a-diazoesters with Rh(OAc)2. An interesting one-pot synthesis of a-fluoro-a,/3-unsaturated esters from ethyl chloromalonate and carbonyl compounds works well using spray dried potassium fluoride but not with other forms of this salt (Scheme 47) the E-ester was the major product with a stereoselectivity of 86—96%. 

Analogously, l-brcano-3-oxiininobutan-2-one yields the 4-oximino-ethyl compound (67), while chloromalonic dialdehyde gives rise to the S-formylthiazole (68) (Scheme 31) (618). 

Saalfrank, Hoffmann and co-workers performed a number of reactions with tetra-alkoxyallenes such as 196 (Scheme 8.47) [1, 41, 105, 114—116] and demonstrated that this class of donor-substituted allenes can serve as a 1,3-dianion equivalent of malonic acid. Treatment of 196 with cyclopropyldicarboxylic acid dichloride 197 produces 2,4-dioxo-3,4-dihydro-2H-pyran 198 through release of two molecules of ethyl chloride [115]. Similarily, the reaction of this allene 196 with oxalyl chloride gives 3-chloromalonic acid anhydride derivative 199. This intermediate is a reactive dieno-phile which accepts 2,3-dimethyl-l,3-butadiene in a subsequent [4+2] cycloaddition to afford cycloadduct 200 in good yield [116]. 

Diethyl chloromalonate and acetaldehyde give diethyl -chloro-<%-(l-hydroxy-ethyl)malonate analogously.695... 

R = CHO) by the action of the dimethylformamide-phosphorus oxychloride complex, and 0-(p-nitrophenyl)hydroxylamine and ethyl benzoylacetate yield, inter alia, the benzofuran (77 R = COaEt). Sodium salts of 2-hydroxyben-zofuran-esters, e.g. (78), are produced by the action of dimethyl chloromalonate on hydroquinones. ... 

Yavari I, Hosseini N, Moradi L (2008) Efficient synthesis of highly functionalized thi-azolidine-4-ones under solvent-free conditions. Monatsh Chem 139 133-136 Yavari I, Hajinasiri R, Sayyed-Alangi Z, Iravani N (2008) Efficient synthesis of ethyl 3-alkyl-4-oxo-2-thioxo-l,3-thiazolane-5-carboxylates from the reaction of carbon disulfide and primary amines in the presence of diethyl 2-chloromalonate. Monatsh Chem 139 1029-1031... 

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