Development of a new method for the conversion of alcohols into chlorides

A list of reagent systems is given below. Reagent systems (1) through (4) have been designed to afford as much unrearranged product as possible. The reactive intermediates of systems (2) through (5) are analogous to those of the Arbuzov reaction and will be discussed in Chapter 2.

(1) ROH + CH₃SO₂CI + LiCI in DMF/collidine ¹

(2) ROH + CH₃-S-CH₃ + N-chlorosuccinimide ²

(3) ROH + Ph₃P + CCI₄^{3, 4}

(4) ROH + Ph₃P + hexachloroacetone ^{5, 9}

(5) ROH + Ph₃P + diethylazodicarboxylate + HCI ⁶

The major goal of this work has been to find an efficient, mild method for converting alcohols into chlorides. Allylic alcohols provide a formidable challenge for any method and therefore help define the scope and usefulness of this reaction. The underlying logic in the choice of reagents came from analogy with the reactive intermediates in the reagent systems previously listed.