A 13.8-g. sample of this material was chromatographed on a column of alumina which was partially deactivated by slurrying with alcohol and drying at steam bath temperature.The first 2 g. of product eluted from the column by petroleum ether comprised 90-95% tri-sec-butyl phosphite and the balance di-sec-butyl phosphonate, by infrared spectral analysis. Because of the very similar boiling points and consequential difficulty in separating the diester (10) The chemical shifts relative to 85% phosphoric acid for tri sec-butyl phosphite, di-sec-butyl phosphonate, and the unknown phos" phate were -139.8 p.p.m., -9.9 p.p.m., and +2.0 p.p.m., respectively. The spin-spin interaction of the P and H atoms in di-sec-butyl phosphonate resulted in a splitting of 660 c.p.s.(11) The determination of tri-sec-butyl phosphite was based on absorption at 10.7 µ. It is not possible to draw a precise base line for this band because of other strong absorption bands in this region of the spectrum. The similarity between phosphonate and phosphate spectra in the infrared region precluded the determination of phos-from the triester by distillation,12 no physical constants were obtained. Since the triester forms a solid cuprous chloride complex while the dies ter does not, separation and identification by this route were chosen. The crude tri-sec-butyl phosphite thus obtained gave a cuprous chloride complex melting 161.5-162.5°. An analogous complex prepared from the known phosphite melted at 162-163°and tinmixture melting point of the two complexes was 161.5-163.0°. These complexes were somewhat sticky and oxidized readily if not kept in an inert atmosphere.(12) The same is true for the n-butyl esters. (BuO)íPOH, b.p. 124-5°(12 mm): (BuO)3P, b.p. 122-3°(12 mm), see G. M. Kosolopoff, "Organophosphorus Compounds," Wiley, N. Y. 1950, pp. 202, 204.
III in 150 ml. of anhydrous acetone. The temperature rose to 0°. When the temperature had fallen again to -10°, the balance of the sodium methoxide solution was added and the stirring continued for 30 min. at -10°and for 1 hr. at 25°. The mixture was neutralized with dilute sulfuric acid, diluted with water, and extracted with benzene to yield 17 g.(74%), b.p. 175-177°( 1 mm.); \IT 292 µ (log e 3.40); *x 1675 cm.-1 (carbonyl).Anal. Caled, for CigHigO: C, 84.9; , 8.0. Found: C, 84.3 ;H, 8.2.The 2,4-dinitrophenylhydrazone precipitated as an oil which crystallized on trituration with butyl alcohol. From the same solvent or from ethanol, orange-red crystals, m.p. 112-114°; ""01 2' 385 mM (log e 4.45). l-Butadienyl-S-phenylcyclohex-4-ene (XVI). The ketone IX (14 g.) was reduced in the usual manner -with 14 g. of aluminum isopropoxide and 100 ml. of isopropyl alcohol. The product, which boiled at 150-153°(2 mm.) (yield, 8 g., 57%) showed in the infrared no residual carbonyl absorption and the hydroxyl band at 3400 cm.-1 It was heated with 1.5 g. of freshly fused potassium hydrogen sulfate at 140°i n vacuo. The desired diene distilled at 130-132°(3 mm.); yield, 4.2 g. (52%). \IT 230 µ (log e 4.06); 292 µ (log e 2.72). f"!x (cm.-1) 1600; 1650 (substituted butadiene);19 660 (terminal=CH2).20Anal.
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