1,3-DIPOLAR CYCLOADDITIONS OF ETHOXYCARBONYL-NITRILE BENZYLIMINE, ETOOC C-N-N- CH2C6H5, AND SYNTHESIS OF BETA-AMINO ACIDS - SYNTHESIS AND REACTIONS OF ETHYL 2-CHLORO-2-ETHOXYACETATE AND 2-CHLORO-2-ETHOXYACETYLCHLORIDE()

The principles of 1,2-cyano-hydroxylation of olefins were applied to t he preparation of 1,2-cyano-amines. The dipole component of this cyclo addition was nitrile imines, which formed pyrazolines with olefins. Ri ng cleavage was accomplished by thermolysis of 3-carboxypyrazolines, w hich gave 1,2-cyano-amines and subsequent hydrolysis gave beta-amino a cids. The syntheses of the title reagents were described. Ethyl 2-chlo ro-2-ethoxy-acetate gave selectively oximes, hydrazones, nitrones, and phosphonium salts with hydroxylamine, hydrazines, N-substituted hydro xylamines and triphenylphosphine respectively. The phosphonium salt wa s used in a Wittig reaction with aldehydes to give alpha-ketoesters. T reatment of the acid chloride with allyl alcohols and subsequently wit h a monosubstituted hydroxylamine gave the allylic eater nitrone, whic h underwent intramolecular cyclization. Similarly, intramolecular cycl izations were carried out with the allylic ester - nitrile oxide and a llylic ester - nitrile imine systems.