Baird, Richard; Winstein, S. published the artcile< Neighboring carbon and hydrogen. XLVI. Spiro[4.5]-deca-1,4-dien-3-one from Ar1--5 participation>, COA of Formula: C11H16O2, the main research area is .
The formation of I from 4-HOC6H4(CH2)4O3SC6H4Br-4 (II) by Ar1-5 participation in the phenoxide anion of II was designated Ar1–5. This reaction was studied by kinetic investigation of the behavior of II in basic solution The reaction was favored in tert-BuOH but not in MeOH. Solvolysis rates for II, the Me ether (III), and p-BrC6H4S(O3)( CH2)4OH (IV) were determined in various solvents at different temperatures and concentrations With II, Ar1-5 participation was slightly more important in formolysis than with III. With II, III, and IV in neutral MeOH, Ar1-5 assisted ionization was negligible. The rate of methanolysis of II was increased by the addition of NaOMe. II appeared to be initially at least 90% in the phenoxide ion form. From the basic solvolysis reactions of II in MeOH and tert-BuOH were obtained (by extraction with pentane) 20 and 50-60% yields, resp., of I, m. 34-5° (pentane at -70°), b1.3 83.5-5°, v 1594, 1617, 1655, 1707 cm.-1 (CHCl3), λ242 mμ, ε 16,000; semicarba zone m. 224-5.5°; 2,4-dinitrophenylhydrazone m. 140.5-3.5°, λ 390, 253, 223 mμ, log ε 4.53, 4.21, 2.92. Catalytic reduction of I (reduced PrO2) gave a tetrahydro ketone; 2,4-dinitrophenylhydrazone (V), C16H20N4O4, m. 161.9-2.8°, λ 363, 229 mμ, ε 22,500 and 17,000. I underwent dienonephenol rearrangement (Wilds and Djerassi, CA 40, 72239), to give an almost quant. yield of 5,6,7,8-tetrahydro-2-naphthol (VI). Treating I in buffered formic acid gave 95% VI. p-MeOC6H4(CH2)3CO2H (VII), b.9.9 194-5.5°, m. 56-6.5°, was prepared from succinic anhydride, anisole, and AlCl3 via p-MeC6H4CO(CH2)2CO2H by the procedures of Fieser (CA 32, 84345) and Martin (CA 30, 67262) in 78.5% yield. VII, was reduced with LiAlH4 to give 93% p-MeOC6H4(CH2)4OH b8 160-60.9°, m. 3.0-4.0°, n25D 1.5248. This was converted to the p-bromobenzenesulfonate. VII and HBr gave pHOC6H4(CH2)3CO2H (VIII), which was reduced with LiAlH4 (4 mol/mol acid and refluxing 1 wk) to p-HOC6H4(CH2)4OH (IX) (92% yield), b0.5 144-6°, m. 55.5-8°, 56.5-7.8° (purified by sublimation). IX (25 g.) in 300 mL. pyridine at -30° treated with 50 g. p-BrC6H4SO2Cl, the solution warmed to 0° 1 h., poured into ice water, the oil extracted with ether, the ether washed, concentrated, the residue (a solution in CH2Cl2 partly crystallized after 1-2 wk) dissolved in 350-400 mL. MeOH, diluted with ice water until a 2nd phase appeared, seeded, and cooled 24 h. at 0° gave 50% II, m. 59.5-61.5° (CH2Cl2-hexane). II was also prepared by treating VIII with excess dihydropyran and a trace of H2SO4 and reducing the solution with LiAlH4 to give 4-[p-(2-tetrahydropyranoxy)phenyl]-1-butanol, which was converted to the p-bromobenzenesulfonate (X), m. 57-60° (ether-pentane), in 77% yield. This was hydrolyzed by gentle acid hydrolysis (304 g. X, 2.5 1. MeOH, 200 mL. H2SO4, 400 mL. water, left overnight in ice box) to give II (68% yield from VIII).
Journal of the American Chemical Society published new progress about Solvolysis. 52244-70-9 belongs to class ethers-buliding-blocks, and the molecular formula is C11H16O2, COA of Formula: C11H16O2.
Referemce:
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem