The formation of exo-trioyolo[4.4.1.12'5 )dodecs-3,7,9-trien-11-one by the therm81 addition of tropone and oyolopentsdiene, the first example of a 6+4 cycloaddition (l), has been described recently (2). We now wish to report the synthesis of pentacyclo 17 5 o o*,7.05*13.06,12
. . . Jtetradeca-3,10-dien-e-one (I), a novel cage-molecule produced by reaction of tropone and oycloheptatriene.
Cycloheptatriene and tropone when heated together without solvent at 200° for 5 hrs afforded, after chromatography on silica gel, a 15% yield of the adduot I, C14H140, with physical properties given in Table 1. Its NMR spectrum (Fig. 2a) proved too,complicated for a complete assignment, snd accordingly the monochloroadduct (II) and the trideuteriomonochloroadduct (III) were prepared from 2-chlorotropone and 2-chlorotropone-3,5,7-d3, respectively. The physical properties 8nd the method of preparation of these two derivatives are given in Table 1 which also records data for the alcohols IV, V and VI, obtained by reduction of I, II and III, VII and VIII of I and II, respectively. TABLE 1. Properties of Compdi t Mol. Afr?&H(E) No.
FOrmUl8 *.p. ("C) (mp) .I Cl4H140 150-2.5 301.5(220) II Cl4H13OC1 149-51 303(*4*) III C14HloD30C1 151.5-2.5 300(235) IV C14H160 -170(d)* end sbs. V Cl4H15OCl -l130(d)A end abs. VI C14H12D30C1 --1,0(d)' end abs. VII Cl4%0 -150(d)' *89(40) VIII C14"170C1 191-4' *94(47) respectively, 8nd for the tetrehydro derivatives the Adducts and their Derivatives v,": (cm') MS peaks (m/e) CMJ+ major peaks 3045, 1735, 1638, l9S 91, 9**