72 J. Org. Chem., Vol. 39, No. 1, 1974
Harris, Cleary, and Harris
l-Acetoxyspiro[c~clopentane-1,3'-indoline] (14). Two grams of the spiro indolenine compound 9 was treated with 2.0 g of LiAlH4 in refluxing diethyl ether for 3 hr, then 0.5 ml of water, 0.5 ml of 15% NaOH, and 1.5 ml of water were added in succession. The ether phase was removed by filtration and to it 4.0 ml of pyridine and 2.0 ml of AczO were added. After standing overnight at lo",. the solvent was evaporated to give 1.4 g (65%) of white crystals, which when recrystallized from hexane melted at 122-123.5: ir 1660, 1600, 1480, 1460, 1410, 755 cm-l; nmr 6 6.927.32 (4 H, aromatic), 3.82 (singlet, 2 H, aliphatic), 2.22 (singlet 3 H, Ac), 1.83 (singlet, 8 H, aliphatic, spiro); mass spectrum m / e 215, 173, 130; uv 222 nm (6 20001, 252 (8600), 280 (2300), 290 (1950). Anal. Calcd for C14H17NO: C, 78.14; H, 7.91; N, 6.51. Found: C, 78.85; H, 8.28; N, 6.22. l-Methoxy-1,2,3,4-tetrahydrocarbazole (16). To 1,2,3,4tetrahydrocarbazole (3.00 g) and pyridine (3.6 ml) in benzene (60 ml) was added at once N-bromosuccinimide (3.3 g) and dibenzoyl peroxide (1 mg), and the mixture was stirred overnight at room temperature. The clear benzene layer was decanted from the oily product which separated, and the oil was dissolved in methanol (20 ml) and run into excess sodium methoxide in methanol at room temperature. This mixture was stirred for 1 hr, then evaporated under vacuum, and the residue was dissolved in CHC13. -The CHC13 layer was washed with water twice, dried over NaZS04 and evaporated to an oil which crystallized on standing (1.85 g, 52% yield). Recrystallization from hexane gave pale yellow rosettes melting at 74-76:: ir 3300, 1390, 1335, 1065, 910, 740; nmrI3 6 8.13 (singlet, 1 H, NH), 6.92-7.50 (multiplet, 4 H, aromatic), 4.48 (1 H, a to OCH3 at C-l), 3.38 (singlet, 3 H, OCHs), 2.67 (multiplet, 2 H, aliphatic a t C-4), 1.93 (multiplet, 4 H, aliphatic at C-2,3); mass spectrum m / e 201, 185, 170, 168; uv 230 nm (C 17,800), 276 (7650), 283 (8150), 291 (6700). Anal. Calcd for C13H15NO: C, 77.61; H, 7.46; N, 6.97. Found: C, 77.73; H, 7.53; N, 6.89.
Acknowledgments. We thank Miss Carol Hartke for technical assistance, Dr. C. H. Robinson for advice, and the Mass Spectrometry Laboratory, Department of Pharmacology and Experimental Therapeutics, Johns Hopkins School of Medicine. We also extend our thanks to the
NIH Gerontology Research Center for the use of their nmr facilities. We acknowledge support by NCI Grant CA06973 and the Eli Lilly Co. Registry No. 8, 942-01-8; 9, 42540-51-2; 10, 42540-52-3; 11, 42540-53-4; 12, 42540-54-5; 13, 41058-67-7; 14, 42540-56-7; 16, 42540-57-8. Supplementary Material Available. Full nmr data for compounds 10, 12, and 16 will appear following these pages in the microfilm edition of this volume of the journal. Photocopies of the supplementary material from this paper only or microfiche (105 X 148 mm, 24X reduction, negatives) containing all of the supplementary material for the papers in this issue may be obtained from the Journals Department, American Chemical Society, 1155 16th St., N.W., Washington, D.C. 20036. Remit check or money order for $3.00 for photocopy or $2.00 for microfiche, referring to code number JOC-74-69.
References and Notes W. 0. Godtfredsen and S. Vanaedal, Acta Chem. Scand., 10, 1414 (1956).
P. G. Gassman and R. L. Cryberg, J. Amer. Chem. SOC., 91, 2047
11969). ~.., P. G. Gassman, G. A. Campbell, and G. Mehta, Tetrahedron, 28, 2749 (1972). G. Buchi and R. E. Manning, J. Amer. Chem. SOC., 88, 2532 (1966), H. Zinnes and J. Shavel, J r . , J. Org. Chem., 31, 1765 (1966). N. Finch and W. I. Taylor.,J. Amer. Chem. SOC., 84, 3871 (1962). J. B. Patrick and B. Witkop, J. Amer. Chem. SOC.,72, 633 (1950). S. G. P. Plant, R. Robinson, and M. Tomlinson, Nature (London), 165, 928 (1950). B. Witkop and J . B. Patrick,J. Amer. Chem. SOC.,75, 2572 (1953). R. F. Moore and S. G. P. Plant, J. Chem. SOC.,3475 (1951). H . Sakakibara and T. Kobayoshi, Tetrahedron, 22, 2475 (1966). I
Melting points were determined on a Fisher-Johns apparatus and are uncorrected. N m r spectra were obtained on a Varian A-60 spectrometer in CDC13 with TMS as internal standard. Mass spectra were determined on a CEC-110 spectrometer. Microanalyses were performed by Gaibraith Laboratories. lr spectra were run on a Perkin-Elmer 700 spectrometer. Uv spectra were obtained on a Beckman DB spectrometer. See paragraph at end of paper regarding supplementary material.
Condensations of Enol Ethers of P-Dicarbonyl Compounds with Dimethylsulfonium Methylide and Dimethyloxosulfonium Methylide Constance M. Harris, Joseph J . Cleary, and Thomas M. Harris* Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235 Received June 27. 1973 Condensations of dimethylsulfonium methylide with &alkoxy-a,P-unsaturated ketones have been studied. The reactions of this ylide with the enol ethers of acyclic @ diketones gave 2,4-disubstituted furans. Attack by the ylide occurred at the carbonyl carbon atoms. Easily rearranged epoxides are postulated as intermediates in furan formation. With the enol ether of a cyclic @ diketone, 1,3-indandione, furanization of the epoxide intermediate was sterically prohibited and the condensation gave 3-(hydroxymethy1)indenone. The enol ethers of pketo aldehydes reacted with dimethylsulfonium methylide to give two products. In addition to 3-substituted fuFormation of the latter compounds rans. the condensations gave 5-substituted 3,6-dihydro-(2H)-pyran-2-01~. has been rationalized to involve attack by one molecule of the ylide at the positions of the unsaturated carbonyl compounds followed by a second molecule attacking the carbonyl groups. Rearrangement and hydrolysis of the resulting cyclopropyloxiranes would give the dihydropyran derivatives. p attack by dimethylsulfonium methylide on cu,p-unsaturated ketones does not normally occur but is facilitated with the enol ethers of @-keto aldehydes by the reduced steric hindrance at the p positions. The condensations of dimethyloxosulfonium methylide with enol ethers of @ diketones were also investigated. Twofold attacks occurred here, as well, but both attacks were by the same ylide molecule. Initial attack by the ylide at the P position, followed by formation of a new ylide by ionization of one of the remaining methyl groups, and finally intramolecular attack of the new ylides on the carbonyl groups, led to 3,5-disubstituted 1-methylthiabenzene 1-oxides.
The reactions of sulfonium ylides with a$-unsaturated ketones have been employed widely subsequent to the observations by Corey and Chaykovsky that dimethylsulfonium methylide preferentially attacks the carbonyl group to give epoxides, whereas dimethyloxosulfonium methylide attacks the (? position to give cyclopropyl ketones.l.2
The corresponding reactions of P-alkoxy-cu,P-unsaturated ketones were of interest to us because both the epoxide and cyclopropane products should be capable of rearrangement to furans or to the related 1,4-dicarbonyl compounds. The reactions of both of the ylides with these enol ethers have now been i n ~ e s t i g a t e d . ~
J,Org. Chem., Vol. 39, No. I, 1974 73
Condensations of Enol Ethers with Methylides Dimethylsulfonium Methylide (DSM). The initial studies were undertaken with unsaturated methoxy ketone la, which is readily available by methylation of dibenzoylmethane. Treatment of la with 1 equiv of DSM gave 56% of a furanoid product, readily identified as the known4 2,4-diphenylfuran (2a, Scheme I). A similar conScheme I
R
OCH,
C6H&cd=&& la,R=H b, R = CH3
0- R
f
(cH,),s+-CH
