o-Iodo-p'-nitrobenzoyl Peroxide¹

Abstract

MARCH 196lO-IODO-p'-NITROBENZOYL PEROXIDE 733 distilling head.. The product was analyzed by gas chromatography without further purification. Yields were generally between 30 and 60%. Table III summarizes the analyses and melting points of the biphenyl products.Vapor phase chromatographic method. The gas chromatography was carried out with either a Perkin-Elmer Model 154C or a Pye Argon instrument. The Perkin-Elmer was equipped with a 2-m. stainless steel column packed with fire brick C-22 (mesh 40-60) impregnated with Dow Corning Silicone Fluid 550 (10%). The eluent was helium and the column temperature was in the range of 180-200°. The Pye Argon was equipped with a 4.5-foot column packed with Celite (mesh 80-100) impregnated with Dow Corning Silicone Fluid 550 (5%). The eluent was argon and the column temperature was in the range of 150-160°. Oxidation of biphenyl derivatives. General method. One gram of biphenyl derivative was dissolved in 20 ml. of acetic acid (gl.). Three grams of chromic anhydride was added to a solution of 1 ml. of water in 20 ml. of acetic acid. The two preparations were combined and heated on a steam bath for 2 hr. The reaction mixture was then poured into excess ice water and the precipitate collected and recrystallized from benzene. The benzoic acid product was then identified by mixed melting point with authentic sample or by infrared analysis.

A Nonaromatic Route to a Paracyclophane: A Study of the 1,2,4,5-Tetramethylenecyclohexane to Tetramethyl[2.2]paracyclophane Conversion

“…Isolation of 1,2,4,5-Tetramethylenecyclohexane (3).-Heptane layers (from the standardized dehydroiodinations) containing monomers 3 and 4 were concentrated under reduced pressure at room temperature to ca. one-tenth of their original volume.…”

“…Re-injection of a small portion of monomer 3 in heptane solution into the same column gave a chromatogram free from spurious fractions. When monomer 3 directly from the column or in heptane solution was treated with a benzene solution of maleic anhydride, pure dianhydride 12, identified by comparison of its melting point and infrared spectrum with those of an authentic sample, was obtained. The following bands are present in the infrared spectrum (CC14) of 3: 3082m, 2980sh, 2955m, 2870w, 2814w, 1802m, 1643s, 1610m, 1426vs, 1389w, 1282m, 1204w, 1175w, 1157w, 1020w, 948w, and 891 vs (cm.-1).…”

“…We viewed2 1,2,4,5-tetramethylenecyclohexane (3) as the primary product in the dehydroiodination of 1 and the formation of 2 as arising from dimerization of the />-xylylene 5, the latter generated from 3 via 1-methyl-3,4,6-trimethylenecyclohexene (4). Although alternative, more complex, routes to 2 were considered, the simple combination of base-catalyzed proto tropic shifts6 and a p-xylylene dimerization appeared attractive.…”

Laser Raman Investigation of Solid State Rearrangement of bis(O-lodobenzoyl) peroxide into 1-(2'-Iodobenzoyloxy)-1, 2-benziodoxolin-3-one

“…The /3-phase of I1 crystallizes in space group P2,/c, 2 = 4. For this space group,12 Raman-active phonon modes are expected. We observe fifteen transitions within the spectralTABLE 1Observed vibrational frequencies (cm-') of the reactant and the product in the Raman 0-200 cm-'.…”

The synthesis of organic polymers containing hypervalent Iodine

“…They suggest (4) that a compound prepared by Willgerodt and Boegel (5) in 1905 and at that time given a cyclic structure is actually [(-N = CH-C &i 4-1 +-C 6H 4-CH = N-)(X -)In. More recently, in 1961, Honsberg and Leffler (6) suggested that heating a p-nitrobenzoyl derivative of o-iodosobenzoic acid caused it to alter to a polymer with the empirical formula C 14HsIN0 6, although no structure was suggested for the polymer. In the most recent review (7) of organic higher valence iodine compounds there is no mention of polymers.…”