NOVEMBER
1961
4781
COMft4UhTCA'ITONS
%phenyl phosphite resets with ICto give the The Reactions of 4-Bromocyclohexadienonienones tetrakyloxy phosphonium salt 111 as a white, with Esters of Phosphorous Acids intensely hygroscopic solid which reacts rapidly with water or alcohols to give 2,4,&tribromophenol Sir: and triphenyl phosphate. The reactions of quinones* and a-halocarbonyl Theoretical elementary analyses were obtained compounds2 with esters of phosphorous acid have for all new compounds. recently attracted appreciable interest. We now CHEMISTBY~ S I & A R C HDEPT. BERNARD MILLER' wish to report that certain features of these two A a r u c a ~ w Drv~sxori a~ types of reactions have been combined to af!ford a h R I c A N CYANco. novel synthetic route to the biologically active aTAMFoRD, corn. dialkyl aryl phosphates. Received September 8, 1961 Dialkyl phosphonates react with 2,4,&tribromo, Fmethyl-cyclohexadienone (Ia) in a manner similar to other reducing agents,s giving 2,6dibromo, 4(4) Present Address: Amencan Cyanamid Company, Agricultural Research Center, Princeton, N. J. methylphenol in high yield. stereospeci6c synthesis of 6-Methyl- tra~-5-cyclodecenone 1a.R = B r ; R ' = C & I I a . R = B r ; R ' C1; R' = C& c. R = R' = Br
b. R
P
= C&; R; f b. R C1* R' CE4; R c. R = R' = Br; R' = Et d. R = Br; R' = C&; R' = E t
Br
I11
Trialkyl phosphites, however, react with Ia-c in benzene solution to give the dialkyl aryl phosphates IIa-d in quantitative yields. The reactions a t room temperatures are apparently instantaneous, as judged by the disappearance of the yellow cyclohexadienone colors. Evaporation of the solvent leaves IIa-d in essentially pure statea, as determined by comparisons of their vapor phase chromatograms with those of distilled products. The structure of IId was confirmed by comparison of its infrared spectrum with that of a sample prepared by condensation of dry sodium 2,6dibromo, 4-methyl phenoxide with 0,Odiethylphosphorochloridate. In contrast to the very rapid reactions of the 4hromocyclohexadienones, neither Pphenylamino, 2,6-dibromo1 Pmethylcyclohexsdienone nor 2,4,6trimethyl, 6-acetoxy cyclohexadienone would react with trimethyl phosphite even on prolonged refluxing in benzene.
Sir: We wish to report the preparation of &methyltrans-kyclodecenone (III) by a sequence of reactions which exemplihs an effective approach, of wide applicability, to the Synthesis of various polyfunctions1 medium-sized carbocyclic ring systems of interest.' The key reaction of the sequence is the facile fragmentation of the 1,3401 monomesylate 11.Concomitantly, the ten-membered ring
a OMes
I
OH
0
I1
I11
(1) The simplest syatema, the cis and trum-ti-cyclodecenonea and the corresponding alcohole have been s y t h e a i d and studied. See H. L. Goering and W. D. Closson, J . Am. Chem. Soc., 83,3511 (1961), and ref. 9. Seealso D. J. Cram and L. K. Gaston, J. Am. Chem.Soc., 82,6386 (1960). The more complex systems belong to a subgroup of the sesquiterpenes which continues to grow in number at a rapid rate. For leading references see the following: J. P. devilliers, J. Chem-. Soc., 2049 (1961); J. Hochmannova, V. Herout, and F. Sorn, Cdl. Czcclr. Chcm. Comm., 26,1826 (1961); M. Suchf, V. Herout and F. &rm, Cdl. C d . C?. Comm., 26, 1358 (1961)! M. SouEek, V. Herout, and F. Sorm, Cdl. Czed. Chem. Comm., 26, 803 (1961); D. H. (1) (a) F. Ramirez and S. Dershowitz, J. Am. Chcm. R. Barton, 0.C. Biickman, and P. de Mayo, J. C h . Soc., Soc., 78, 5614 (1956). (b) F. Ramirez and S. Derahowitz, 2263 (1960); M. Suchy, V. BeneSov6, V. Herout, and F. J . otg. C h . , 22, 857 (1957). (c) F. Ramires and S. Der- krm, Ber, 93, 2449 (1960); M. Suchf, V. Herout, and showita, 22, 1282 (1957). (d) F. Ramirez, E. Chen, and S. F. &rm, Cdl. C d . Chcm. Comm., 24, 1512 (1959); 6. C. Dershowitz, J. Am. C h . Sa., 81, 4338 (1959). (e) B. A. Bhattacharyya, G. R. Kelkar, and A. 8.Rao,Chem. & I d . , Arbumv, N. A. Polezhaeva, and V. S. Viiogradova, 1069 (1959); V. Herout and F. &rm, Chem. & Znd., 1067 I m t . A M . Nauk S.S.S.R. OMel. Khim. Nauk., No. 7, (1959); S. Dev, T&ah&on, 9, 1 (1960); 8. h v , Chem. & 1219 (1960). Id.,8, 171 (1860); M. Holub, V. Herout, M. Horsk, and F (2) See B. A. Arbuzov, V. S. Vinogradova, and M. A. 24,3730 (1959). For a SUE Zvemva, Izvcsl. A M . Nauk S.S.S.R. otdcl Khim. Nauk., brm, CoU. C d .C h .Comm., 9 mary of the above, see F. Sorm, Pure and Applied Chm.,2, No. 10, 1772 (1960), for leading references. 533 (1961). (3) I(.Fries and G. Oehmke, Ann., 462,1(1928).
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