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()
Kk. Bach et al., 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(), Tetrahedron, 50(25), 1994, pp. 7543-7556
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.