Synthesis of Substituted Vinylic Chloroformates
This clean conversion,
was surprising since lossof the chloroformate anion could have been competitivewith
of chloride (when Favorskii treated 2,2,2-tri-chloroethyl acetate with zinc in 1899, he made 1,l-di-chloroethylene in a very exothermic process13). Chloro-formate also could have been lost in a subsequent elimi-nation1*
give the explosive chloroacetylene. Finally, thehigh reactivity of acid chlorides toward zinc and theZnC1,-catalyzed decomposition of
pres-ented other potential problems.In this paper, we describe the even more surprisingformation of 2,2-dichlorovinyl chloroformate
by directtreatment of a mixture of chloral and phosgene with zincdust. Most of the factors favoring a negative outcome forthe scheme
also apply to this new process. Also,under some conditions, zinc reacts exothermically withphosgene. In addition, complications from the powerfulacceptor properties of the aldehyde carbonyl and thepreference for reaction at carbon in Reformatsky typeprocesses would be expected. Nevertheless, the desiredreaction occurred.
these reactions were successful. However,many were not, and several experiments were performedbefore a predictively useful pattern
is hydrogen, alkyl, or aryl, the chloroformate
isobtained only when
alkyl but nothydrogen.
In the preferred process, a little zinc dust was added toa stirred solution of chloral and phosgene in MeOAc/ether.
more zinc was added until this was consumed, andinitiation of the reaction was certain (usually 5-30 min butsometimes 1-2 h). Then the remaining zinc was added inportions, being sure that most was consumed before morewas added. Otherwise the reaction could end in an un-controllable exotherm. After removal of much of thesolvent by vacuum evaporation, the remaining liquid wastriturated with pentane to eliminate the insoluble zincsalts. Vacuum distillation then gave pure
yield.Less satisfactory was a workup in which volatiles firstwere collected by vacuum distillation with 1,2,4-tri-chlorobenzene as a chaser. Then
was isolated by re-distillation in
yield. The yield was 44% in EtOAc,42% in EtOAc/ether (2:1), 19% in ether, 26% in dioxane,and 10% in diethyl oxalate. With magnesium instead ofzinc, reaction was rapid (after 40 min, 16% of the chloralremained) but the yield was only 6%.The reaction of bromal and phosgene with zinc was veryslow, and
could not be separated from remaining bromalby simple distillation. The distilled product after a 7-dayreaction still contained bromal and
in a 57:43
ratio(26% yield of
few reactions of
can be performedin the presence of bromal. In an attempt to extend thesynthesis of
to include dihalovinyl carbonates, vinylchloroformate was substituted for phosgene. Then
wasisolated, but only in 6% yield (see the supplementarymaterial).Efforts also were made to generalize the synthesis byreplacing the chloral by other a-halo carbonyl compounds
778. For nucleofugacityof C1C02-, see: Wong, C.-P.; Jackman,
M.; Portman, R. G.
921.(14) See, e.g.: Ballester,
., Jr.; Baril,
Martin, R. H.; Robinson, R.
497. Also seepreparation of
While bromoacetone, chloroacetone, and 1,l-dichloro-acetone all reacted with zinc and phosgene, no chloro-formate
was found. However,
afforded pure chloroformate
in 23% yield. Similarlya-bromo and
but trichloroa~etophenone'~as converted tothe styryl chloroformate
in 66% distilled yield. Reac-tion of
n EtOAc gave 54% ofthe desired chloroformate
along with 34% of thechlorostyrene
This process was difficult to reproduceand usually gave low yields of
along with more
(fromZnC1,-catalyzed decomposition of
The reaction failedusing 2-chlorocyclohexanone but 2-chloro-2-methylcyclo-hexanonelg gave
in 68% distilled yield.
In other successful reactions,
ere convertedto the chloroformates,
(59%). The lowyield of
is partly attributed to its volatility. Similarly,
were obtained from the corresponding a-chloroaldehydes.BIn the only experiment which did not fit the pattern es-tablished for A,
no enol chloroformate wasobtained from
lthoughthe zinc was consumed. The reason for this failure is notknown, but further reaction is suspected.
far, this outline of the scope of the scheme
hasbeen confined to systems
is H, alkyl,
aryl.Examples with other
residues include 2,2-dichloro-1,3-cycl~hexanedione,~~hich was converted to the chloro-formate
distilled yield. Thus, the reaction seemsto tolerate electron-withdrawing functions as
is unstable at room temperature. Over
daysit cleanly decomposed to the previously unknown di-
1189.(17) Hiegel, G. A.; Peyton, K. B.
W.; Martin, D. G.; Johnson, W.
(20) Stevens, C.
3448.(21) Stork, G.; Worrall, W.
erhe, R.; DeKimpe, N.; Courtheyn, D.; Schamp,
Wiley: New York, 1963; Collec. Vol. IV, p 162.(23) Wanzlick, H.-W.; Mohrmann,