PHENYLATION WITH DIPHENYLIODONIUM CHLORIDE: 1-PHENYL-2,4-PENTANEDIONE

PHENYLATION WITH DIPHENYLIODONIUM CHLORIDE l-PHENYL-2,4-PENTANEDIONE... 

Pentanedione, with sodium amide and diphenyliodonium chloride to give 1-phenyl-... 

Sodium, with l-bromo-3-chloro-cyclobutane to give bicyclo [l.l.O]butane, 51, 55 Sodium amalgam, 50, 50, 51 Sodium amide, with 2,4-pentane-dione and diphenyliodonium chloride to give l-phenyl-2, 4-pentanedione, 51, 128 Sodium azide, 50, 107 with mixed carboxylic-carbonic anhydrides, 51, 49 Sodium borohydride, reduction of erythro-3-methanesulfony-loxy-2-butyl cyclobutanecar-boxylate, 51, 12 reduction of 2-(1-phenylcyclo-pentyl)-4,4,6-trimethyl-5,6-dihydro-1,3(4H)-oxazine to 2-(1-phenylcyclopentyl)-4,4, 6-trimethyltetrahydro-l,3-oxazine, 51, 25 Sodium cyanoborohydride, used... 

Diphenyliodonium chloride, with 2,4-pentanedione and sodium amide to give 1-phenyl-2,4-pentanedione, 51,128... 

Ethereal acetylacetone added in small portions with Dry Ice-acetone cooling under Ng to 2 moles NaNH2 in liq. NH3, the cooling bath removed and the N2 flow stopped, after 0.5 hr. diphenyliodonium chloride added, after 1 hr. ether added while the NH3 is cautiously evaporated on a steam bath, finally the ethereal suspension refluxed 1 hr. crude l-phenyl-2,4-pentanedione. Y 92%.— The reaction of diaryliodonium chlorides with disodio-/ -diketones appears to be a good method for the prepn. of y-arylated y -diketones. F. e. s. K. G. Hampton, T. M. Harris, and G. R. Hauser, J. Org. Ghem. 29, 3511 (1964) cation specificity, monoalkylation, s. J. Org. Ghem. 30, 61 (1965) alkylation with dibromides s. J. Org. Ghem. 30, 1413. 

---