The α-chlorophosphonates (OCH
2CMe
2CH
2O)P(O)CHCl-C
6H
4-4-R [R=H (4), Me (5), OMe (6)], which are now readily accessible, react with ketones R′C(O)R″ in the presence of NaH (without recourse to the more expensive
t-BuLi) to afford trisubstituted vinyl halides R′C(R″)=CCl(C
6H
4-4-R) in good yields. The corresponding α-bromophosphonates [R=H (7), Me (8)] failed to react with ketones and gave the symmetrical acetylenes 4-R-C
6H
4-C
C-C
6H
4-4-R as isolable products in low yield. We have found that K
2CO
3 in refluxing xylene is a good base for the synthesis of chlorostilbenes; using this base the bromostilbenes ArCH=CBr(C
6H
4-4-R) can be prepared in significantly higher yields than by using NaH. The stereochemistry of two of the trisubstituted vinyl chlorides is unambiguously proven by X-ray structure determination. Thus for (Cl)PhC=CPh(Me), the isomer with the upfield NMR shift for the C
H3 protons and for (Cl)PhC=C(Ph)(C
6H
4-4-Me), the isomer with the downfield NMR shift for the -C
6H
4-4-C
H3 protons have
Z stereochemistry.