Quantum-chemical investigation of chlorine-containing ethers

Ethers have found wide practical application in synthetic organic chemistry [i], but problems associated with the anomalously high reactivity of ~-chloro ethers and the appreciably lower reactivity of Band 7chloro ethers have been studied little. One can only cite the references [2, 3] where the electron-density distribution in chloromethyl and ~chlorodiethyl ethers is calculated by the extended HHckel method and the Del Re method, and the communication [4], which is devoted to a quantum-chemical study of s-halo-substituted anisoles, including a-chloroand ~-fluoromethyl phenyl ethers. In the present paper we study the electronic structure of a number of a-, B-, and y-chloro ethers, viz., CHaOCH2CI (i), CH3CHCIOCH3 (II), CH3CH2CHCIOCH3 (III), (CH3)~CHCHCIOCH3 (IV), (CHa)aCCHCIOCHa (V), C~HsCHCIOCHa (VI), (CHa)=CCIOCH3 (VII), CICH2CH2OCHa (VIII), CICH2CH2CH2OCH~ (IX). For comparison, a calculation has also been conducted for the chloroalkanes CHaCI (X) and (CHa)3CCI (XI) and the ethers ChaOCHa (XII), CH3CH=OOCHa (XIII), and CH~CH2CH=OCHa (XIV).