A New Synthesis of the Cyclopentane Ring with Notes on the Biological Origin of Terpenes and Sterols

Abstract

New Synthesis of the Cyclopentane Ring 1687 eluate (B), Table I, in vacuo to a dry sirup and acetylation of this sirup resulted in the isolation of a colorless sirup rotating +93.4°(c, 2 in chloroform). This acetate, dissolved in ethanol, crystallized overnight at 25°. The total yield of pure octaacetyl-6 -[ a -d -glucopyranosyl ] -/3 -D-glucose, [a]25d +98.0°(c, 2 in chloroform), m. p. 143°, was 9.2 g. or 77%. e Crystallization of 6-[a-D-Glucopyranosyl]-D-glucose.-Six grams of (IV), [«¡25°d +98.0°in chloroform, was deactylated catalytically with barium methylate at 0°. The barium was precipitated with 0.5 TV sulfuric acid and removed by filtration as barium sulfate. A colorless solution, pH 7.0, resulted. Concentrated in vacuo to a sirup and taken up in ethanol the deacetylated material crystallized during several days as long prisms. Recrystallized under similar conditions the sugar was separated by filtration, washed and dried to constant weight at 98°. The dry crystalline substance melted at 120 °and had an equilibrium [<*]2Sd value (c, 1.2 in water) of +120°mutarotating downwards. Its Jlfcu value (c, 1) was 97%; yield, 2.3 g.

Thiyl radical induced cyclizations of dienes. Cyclization of .alpha.-acoradiene, .alpha.-bulnesene, and geranyl acetate to cedrane, patchulane, and cyclogeranyl acetate products

“…Fractions 2 and 3 showed molecular ions of m/e 208 (tetrahydrobulnesene). Of fractions 4 and 5 with m/e 206 (dihydropatchulenes) the latter could be matched in mass fragmentation with a dihydro-a.y-patchulene sample obtained by hydrogenation (below). A corresponding reaction sequence using benzene as photolysis solvent also gave these four product fractions in similar amounts in addition to two minor components.…”

“…C, 19, m/e 258,260; NMR (CDC13) 6 5.58 (t, «7 = 8 Hz, 1 H), 4.78 (d, «7 = 8 Hz, 2 H), 2.76-2.2 (complex pattern, 4-5 ), 1.02 (doublet of doublets, =7 = 4 and 8 Hz, 6 H). D, 18, m/e 258; NMR (CDClg) 5.58 (t, J = 7 Hz, 1 H), 4.76 (d, J = 7 Hz, 2 H), 2.S-2.2 (complex pattern, 4-5 ), 2.12 (s, 3 ), 1.80 (s, 3 ), 1.28 (t, J = 7 Hz, 3-4 ), 1.01 (t, «7 = 6 Hz, 6 H). (Small m/e 260 peaks.are due to contamination of geranyl acetate with small amounts of citronellyl acetate in this but not in subsequent experiments.)…”

“…m/e 244 (M+); NMR (CDC13) 5.24 (t,=7 = 7 Hz, 1 H), 4.48 (d,«7 = 7 Hz, 2 ), 2.08-2.28 (m, 3 ), 2.04 (s, [8][9] ), 1.68 (s, [3][4] ), 0.96 (doublet of doublets, «7 = 8 and 4 Hz, 6 H). D, E, and F, m/e 244 (M+).…”

“…Caled for Ci2Hi402: Preparation of Methyl 2-Phenyl-5-methyl-4-hexenoate (24). Using the preceding procedure and 7.64 g (31.3 mmol) of triphenylmethane, 1.22 g (0.0313 g-atom) of potassium, 35 mL of 1,2-dimethoxyethane, 2 mL of butadiene, 4.69 g (31.3 mmol) of methyl phenylacetate, and l-bromo-3-methyl-2-butene (4.69 g, 31. mmol), gave 4.85 g (71%) of a clear, colorless, chromatographed liquid: bp 79-80 °C (0.025 mm); NMR (CDC13) 7.14 (s, 5 H), 4.94 (t, J = 6 Hz, 1 H), 3.56 (s, 3 H), 3.48 (t,J = 8 Hz, 1 ), 1.6 (s, 3 ), 1.54 (s, 3 H); IR (liquid film) 3020, 2960, 2950, 2910,1735,1600 cm-1.…”

Composition of United States Crude Oils

“…Only California and West Texas areas produce oil of less than 15 API gravity, and there only in limited quantities. The heavier characteristics of California and West Texas oils are shown by rather large quantities of oil in the 15 to 25 API gravity group, and California is the only area that has less than 20% of its production in the 35 to 45 API gravity class. Gulf Coast oils are about equally divided between those oils in the 35 to 45 and 25 to 35 API gravity groups.…”