1,6-Heptadiene chlorination

The use of 1,6-diene systems usually does not result in cyclization reactions with palladium ) salts. For example, with 1,6-heptadiene a /i-elimination takes place from the cqjr-intermediate to give diene 22 as the major product (equation 10)27. However, more recently Trost and Burgess21 have shown that with a 4,4-bis(phenylsulfonyl) derivative of 1,6-heptadiene (23) an insertion takes place to give a 5-membered ring product (24, equation 11). The final step of the latter reaction is oxidative cleavage of the palladium-carbon bond by CuCl2 to produce a carbon-chlorine bond. 

Manganese (III) acetate or chloride salts [Mn30(0Ac) H0Ac, MnCb] can react with alkenes to afford 1,2-dichlorides and chlorohydrin acetates (equation 16). i The manganese(III) reagent promotes the chlorination of 1,6-heptadiene (42) to afford almost equal amount of open chain and cycliz dichlorides... 

Results for some other halogenated unsaturated polyhydrocarbons were reported in literature. For example, poly(perfluoro-4-chloro-1,6-heptadiene) upon heating between 320° C and 400° C is reported to completely volatilize [12]. Also, reports on chlorinated rubber show that by heating from ambient to 500° C, it generates almost quantitatively HCI, and in the later stages of reaction CH4, C2H4, and H2 [13],... 

Cyclopropanone acetals can also be obtained by addition of dialkoxycarbenes to C — C double bonds (see Section 5.2.3.5.). Dialkoxycarbenes can be generated by thermolysis of chlorinated 7,7-dialkoxybicyclo[2.2.1]heptadiene derivatives by photolysis or thermolysis... 

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