Nitrobenzenesulfonyl Peroxides as Reagents for Aromatic Substitution¹

Abstract

Compd. 7-Benzylidenebutyryl peroxide r(p-Ch1orobenzylidene)butyric acid 7-(p-Chlorobenzy1idene)butyryl peroxide a-(p-Fluoropheny1)allyl alcohol p-Fluorocinnamyl bromide y-(p-F1uorobenzylidene)butyric acid 7-( pFluorobenzy1idene)butyryl peroxide y-(p-Methylbenzy1idene)butyric acid 7-(p-MethyIbenzy1idene)butyryl peroxide 7-( p-Methoxybenzy1idene)butyric acid 6-(pMethoxyphenyl)valeryl peroxide Wave length region, w 0.0-3.0 5.5-6.0 6.0-7.0 8.0-10.0 5.55-5.64 (s) 9.38 (s)6.82 (s) 6.67 (s) (doublet) 5.50-5.60 (9) 6.70 (5) 9.13-9.40 (s) (doublet) (doublet) 2.30 (m) 6.22 (s) 8.13 (s) 3.40 (s) 6.62 (s) 8.63 (s) 6.22 (s) 8.11 (s) 6.62 (s) 8.31 (s) 8.61 (s) 5.61 (s) 6.20 (m) 8 . 1 0 (s) 6.60 (s) 8.60 (s) 5.5-5.59 (s) 6.22 (m) 8.21 ( 8 ) (doublet) 6.62 (9) 8.62 (m) 5.86 (s) 7.10 (m) 5.51-5.61 (s) 9.43 (m) 5.98 (s) 6.28 (m) 8.07 (s) 5.54-5.61 (s) 6.64 (s) 8.04 (s) (doublet) (donblet) 6.22 (m) 8.56 (m) 6.86 (m) 9.67 (m)acid separated as a white, creamy solid. It was extracted into ether; the latter was washed with water and dried over magnesium sulfate, and the ether was removed. The resulting solid was recrystallized from toluene. The over-all yield of y -( p methoxybenzylidene)butyric acid from the ethyl ester of the keto acid was 67%. Some chemical and physical properties of this acid are listed in Table VI; its infrared spectrum is described in Table VII.

The Chemistry of Organomettallic and Organometalloid Peroxides

“…, Et, n-Pr, I-Pr,PhCH2 Dannley and Corbett(45) prepared nitro derivatives of benzenesulfonyl peroxides, XCVIII, by the reaction of nitrobenzenesulfonyl chlorides with hydrogen peroxide in ethanol at -20°in the presence of potassiumcarbonate. K.CO, x-NOiPhSOiCl + HiO* ->-(z-N02PhS020)2 XCVIII xo, m, p…”

“…PhS020)2 + CeHe -* PhS020Ph + PhS020HXCVIIThe decomposition of nitro derivatives of benzenesulfonyl peroxide (XCVIII) in aromatic solvents yields the corresponding nitrosulfonic acids, CXIII, and a mixture of the ortho and para derivatives of the sulfonic esters, CXIV, exclusively(45).…”

Arylsulfonoxylation of aromatic compounds. VI. Decomposition of m-trifluoromethylbenzenesulfonyl peroxide in the absence of solvent and in the presence of ethylbenzene and cumene

“…When ethanol was added to the reaction mixture, 3 was found and the yield of 2 approximately doubled. Inasmuch as 6 does not undergo alcoholysis under these mild conditions, 3 possibly may have some type of anhydride precursor. The following scheme (eq 4-6) includes a possible concerted mechanism for the decomposition similar to the carboxyl inversion observed with p-methoxy-p'-nitrobenzoyl peroxide.…”

Sulfur and Phosphorus Peroxides

“…Mixed sulfonyl acyl peroxides are qualitatively less stable than bissulfonyl peroxides. Sulfonyl alkyl peroxides are somewhat less stable and decompose violently in a few minutes at 25 • C. Bissulfonyl peroxides can be prepared by reacting arylsulfonyl chloride with H 2 O 2 in aqueous EtOH/CHCl 3 mixture in the presence of K 2 CO 3 at −20 • C in high purity (>98%) (equation 4) 37 2 45…”