Ring medium

Cyclopropanes can also be obtained by the reaction of vinyltrialkylborates with aldehydes followed by treatment with phosphoms pentachloride and base (300), and by the rearrangement of 5-substituted alkynyltrialkylborates (308). It is also possible to utilize this approach for the synthesis of five- and six-membered rings (3). Trans-1,4-elimination ia cycHc systems leads to the formation of stereodefined acycHc 1,5-dienes or medium-ring dienes, depending on the starting compound (309). 

The racemization of medium-ring trans-cycloalkenes depends upon ring size and substitution, as indicated by the data below. Discuss these relative reactivities in terms of the structures of the cycloalkenes and the mechanism of racemization. 

Rearrangements are also observed during halojluonnanons with cyclic medium ring dienes [70, 93] (equations 4 and 5) and with the monoepoxide of 1,5-cyclooctadiene [94] (equation 6) during halofluonnations Again, there are differences in product mixture with apparently minor variations in reagents (equation 4)... 

Extension of these studies to medium rings produced interesting results (73). The mercuric acetate oxidation of 1-methyl-1-azacyclooctane (64), when worked up in the usual manner, gave no distillable material. When an equivalent amount of hydrochloric acid was added to the solution which had been saturated with hydrogen sulfide to precipitate the excess mercuric acetate and filtered, evaporation of the solution to dryness gave a solid which was subsequently identified as 2,4,6-tris(6 -methylaminohexyl)-trithiane trihydrochloride (65). Two plausible routes to the observed... 

This method provides a route to certain medium-ring sized enamines (106,107) not obtainable by other methods, l-Methyl-2-phenyl-l-azacyclo-hcpt-2-ene (124) can be prepared by the reaction of N-methylcaprolactam... 

Figure 4.3 Cycloalkane strain energies, calculated by taking the difference between cycloalkane heat of combustion per CH2 and acyclic alkane heat of combustion per CH2, and multiplying by the number of CH2 units in a ring. Small and medium rings are strained, but cyclohexane rings are strain-free.

The assembly of medium-ring ethers using C-0 or C-C bond forming protocols can be a profitable enterprise 13 nevertheless, it was of interest to determine if medium-ring ethers could be derived... 

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