638 Bruce A. McAndrew the elimination of ketene, but this behaviour has not been demonstrated by the com- pounds of type [21]. From a chemical point-of-view Hagemann's Ester has been demonstrated as a versatile intermediate in the synthesis of alkylated 3-methylcyclohex-2-en-l-ones. In contrast, it is difficult to draw any wide ranging conclusions from a perfumery stand- point. Although it is possible to outline a number of generalisations (Table V) where, e.g. line (1) represents decreasing mintiness and increasing salicylate character and line (5) represents decreasing softness and florality, none of the compounds depicted possess odour characteristics which approach closely to those of dihydrojasmone and Lyral. REFERENCES 1 Smith, L. I. and Rouault, G. F. Alkylation of 3-Methyl-4-carbethoxy-2-cyclohexen-l-one (Hage- mann's Ester) and related substances. J. Amer. Chem. Soc. 65 631 (1943). 2 Harris, T. M. and Harris, C. M. The y-Alkylation and y-Arylation of dianions of [I-Dicarbonyl compounds. Organic Reactions. 17 155 (1969). 3 Hogg, J. A. Synthetic sterols: Part I: Model experiments employing Hagemann's Ester. J. Amer. Chem. Soc. 70 161 (1948). 4 Nasipuri, D., Sarkar, G., Roy, R. and Guha, M. C-1 Alkylation of Hagemann's Ester. Tet. Letts. 927 (1966). 5 Nasipuri, D., Mitra, K. and Venkataraman, S. Cyclohexenone derivatives: Part VI: C-3 and C-1 Alkylation of Hageman's Ester with alkyl halides and Michael acceptors. J. Chem. Soc. 1836 (1972). 6 Horning, E. C., Denekas, M. O. and Field, R. E. The preparation of 4-Carbethoxy-3-methyl-5- alkyl-2-cyclohexen-l-ones and 3-methyl-5-alkyl-2-cyclohexen-l-ones. J. Org. Chem. 9 547 (1944). McCurry, P.M. and Singh, R. K. Cyclenones: Part IX: A convenient synthesis of 3-methyl-5-alkyl- 4-carbethoxycyclohex-2-enones. Synthetic Communications 6 75 (1976). 7 Julia, M. and Le Thuiller, G. Pr6paration d'alcools 0•-ph6noxy-2 (ou 6thoxy-2) cydopropaniques et leur transformation en ald6hydes 6thy16niques. Bull. Soc. Chim. Fr. 717 (1966). Yang, M., Ando, M. and Takase, K. Isoprene-magnesium compound: Part II: Reaction of isoprene- magnesium compound with some esters. Tet. Letts. 3529 (1971). Vinogradov, G. O., Ignatenko, II'ina A. V. and Nikishin, G. L. Free-radical reactions of carbonyl compounds initiated by manganese triacetate: Part III: Preparation of [i, y- and y, 8-unsaturated aldehydes by reacting alkanals with iso-olefins. Zhur. Org. Khim. 8 1403 (1972). 8 Hoaglin, R. L. and Hirsch, D. H. Production of unsaturated aldehydes. USP 2 628 257. 9 Baggiolini, E., Hamlow, H. P. and Schaffner, K. Photochemical reactions: LIX: On the mechanism of the photodecarbonylation of •, y-unsaturated aldehydes. J. Amer. Chem. Soc. 92 4906 (1970). Parker, K. A. and Johnson, W. S. The synthesis and cyclization of 4-(trans, trans-7, 12-dimethyl-3, 7, 11-tridecatrienyl)-3-methyl-2-cyclohexen-l-ol and of its allylic isomer. 96 2556 (1974). 10 Mongrain, H., Lafontaine, J., Belanger, A. and Deslongchamps, P. Stereoselective synthesis of (+) epihinesol (Agarospirol). Can. J. Chem. 48 3273 (1970). Markezich, R. L., Wally, W. E., McCarry, B. E. and Johnson, W. S. Direct formation of the steroid nucleus by a nonenzymic biogenetic-like cyclization: Preparation of the cyclization substrate. J. Amer. Chem. Soc. 95 4414 (1973). 11 Posner, G. Conjugate addition reactions or organocopper reagents. Organic Reactions. 19 1 (1972). 12 Marshall, J. A., Ruden, R. A., Hirsch, L. K. and Philippe, K. Regioselectivity in the conjugate addition of lithium dimethylcopper to cyclohexadienones. Tet. Letts. 3795 (1971). 13 Rathke, M. W. and Sullivan, D. The preparation and reactions of enolate anions derived from % [i-unsaturated esters. Tet. Letts. 4249 (1972). Herrmann, J. L., Kieczykowski, G. R. and Schlessinger, R. H. Deconjugative alkylation of the enolate anion derived from ethyl crotonate. Tet. Letts. 2433 (1793). Katzenellenbogen, J. A. and Crumrine, A. L. Regioselectivity in the alkylation of lithium and copper ester dienolates. An allylic transposition associated with y-alkylation of copper dienolates. J. Amer. Chem. Soc. 96 5662 (1974). 14 White, J. D. and Snug, W. L. Alkylation of Hagemann's Ester. Preparation of an intermediate for trisporic acid synthesis. J. Org. Chem. 39 2323 (1974).

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