Electronic effects in solvolysis reactions. III. Solvolysis of allyl-substituted cumyl derivatives

Abstract

Thermal Decomposition of -Hydroperoxytetrahydrofuran (I). A. Pyrolysis in the Gas Chromatograph.-A l-µ sample of a 4.3 X 10 ~2 M solution of I in THE was injected into a Beckman GC-5 gas chromatograph equipped with a flame ionization detector and a 6 ft X 0.125 in. Carbowax column on Chromosorb W. The gas chromatogram showed two major peaks for butyrolactone and -hydroxytetrahydrofuran in a ratio of ca. 1:3.B. Pyrolysis in a Sealed Tube.-A 5-ml solution of 8.6 X 10~2 I in THE was placed in a glass reaction tube which was connected to a vacuum line. The solution was thoroughly outgassed by conventional freeze-pump-thaw techniques. After a final check for noncondensable gases, the glass reaction tube was isolated by sealing off from the line and then allowed to reach room temperature. The sealed tube was then heated in a furnace at 100°for 30 min. The reaction mixture was analyzed and found to contain III as the only major products.Photodecomposition of -Hydroperoxytetrahydrofuran.-A solution of 9.1 X 10 ~2 I in THE was placed in a 3-ml uv spec-trophotometric cell. The irradiation procedure used was identical with that described before8 except that, instead of bubbling oxygen through the solution, a slow stream of nitrogen was maintained. The products were identified by ir and vpc and the progress of the reaction was followed as described above. For each set of data, five or more experiments were required for the points on the curve for the range of 0 to 65% decomposition of I. The irradiation of I under oxygen was performed and analyzed in a similar manner.Registry No.-I, 4676-82-8; THF, 109-99-9.Acknowledgment. -We gratefully acknowledge the research support of the National Science Foundation (Grants GP-5312 and GP-8564) for their financial contributions to this project.

Aromatic Allylation via Diazotization: Metal-Free C−C Bond Formation

“…Column chromatography (pentane) gave 200 mg (34%) of 1l as a colorless oil: 1 H NMR (CDCl 3 , 400 MHz) δ 7.42 (m, 2H, J = 8.3 Hz), 7.07 (m, 2H, J = 8.3 Hz), 6.00−5.88 (m, 1H), 5.11−5.04 (m, 2H), 3.34 (d, 2H, J = 6.7 Hz); 13 C NMR (CDCl 3 , 100 MHz) δ 139.0, 136.8, 131.5, 130.4, 119.7, 116.3, 39.6; HRMS (EI + ) calcd for C 9 H 9 Br (M) 195.9888, found 195.9887. 1 H NMR data were in agreement with literature data …”

Polystyrene‐Supported 2‐Arylindenyl Zirconocene Catalysts for Propylene Polymerization

“…~100 mL THF was then added to the addition *The broader molecular weight distribution of the homogeneous catalyst system (7) is likely due to higher conversion for this polymerization. funnel, followed by p-allylbromobenzene 40 (52.279g, 265 mmol). ~20 mL of the THF/aryl halide solution was added to the magnesium, and the mixture stirred for ~5 min until the solution warmed and turned green, then the remaining aryl halide was added slowly.…”