92787-70-7

Usage

Preparation

Following the method reported by Zinner [78c] to 29.2 g (0.4 mole) of isobutylamine dissolved in 40 ml benzene (suggest toluene instead) is added a solution of 48.4 g (0.2 mole) of dibenzoyl peroxide in 200 ml benzene (suggest toluene instead), with stirring and cooling to 0°C. The yellow-colored reaction was first heated for 30 min at 30°C and then 30 min at 50°C. After cooling to 0° N-isobutylammonium benzoate separates as a white precipitate. The filtrate is washed with water and dried over mag-nesium sulfate. The mixture is filtered, and then anhydrous hydrogen chloride is bubbled through the solution to give 12.1 g (26% yield) of a white precipitate of TV-isobutyl-O-benzoylhydroxylamine hydrochloride, m.p. 120-128°C. The infrared spectrum in Nujol indicated an absorbtion band at 1760 cm-1. Treatment of the latter product with IN aqueous sodium carbonate and then extraction with ether, drying over sodium sulfate and evaporation gave N-isobutyl-O-benzoylhydroxylamine. Precipitation of the latter by Kugelrohr distillation gave product b.p. 58-65°C (0.04-0.03 mm Hg). The IR (CCU) indicated 3235, 1725, 1267, 1088, 1067, 1027 cm-1; and the NMR (CCI4) indicated δ, 0.99(rf, J = 6.5Hz. 6H), 1.83 (m, J = 6.5Hz, 1H), 2.87 (d, J = 6.5 Hz, 2H), 7.47 and 7.98 (aromatic m and NH). K. Reactions of Grignard Reagents A variety of nitrogen-containing compounds have been treated with Grignard reagents in an effort to produce substituted hydroxylamines. Many of these reactions have not been explored extensively and no reasoned judgement as to general applicability can be made. These methods were presented in outline form in Schemes 2 and 3. L. Reaction of Chloramine with Alcoholates The reaction of chloramine and an alcoholate according to Eq. (46) appears attractive since it involves the direct formation of the oxygen-to-nitrogen bond in an O-alkylated hydroxylamine.

Upstream product

• 78-81-9 isobutylamine 
• 94-36-0 dibenzoyl peroxide 

Downstream Products

• 624-64-6 trans-2-Butene 
• 774-65-2 benzoic acid tert-butyl ester 
• 4909-81-3 s-butyl benzoate 
• 120-50-3 isobutyl benzoate 
• 65-85-0 benzoic acid 
• 115-11-7 isobutene 
• 92844-60-5 N-isobutyl-N-nitro-O-benzoylhydroxylamine 
• 588-47-6 N-isobutylaniline 

Relevant academic research and scientific papers

Copper-Catalyzed Dihydroquinolinone Synthesis from Isocyanides and O-Benzoyl Hydroxylamines

A copper-catalyzed protocol has been realized for the rapid assembly of dihydroquinolinones from readily accessible isocyanides and O-benzoyl hydroxylamines. The reactions (10 mol % of CuOAc, 10 mol % of dppe, 3 equiv of PhONa, 30 °C) deliver various stru

Rhodium(III)-catalyzed C–H amination of 2-arylquinazolin-4(3H)-one with N-alkyl-O-benzoyl-hydroxylamines

N-benzoate alkylamines were used as the aminating agents, a efficient Rh-catalyzed ortho C–H amination of 2-arylquinazolin-4(3H)-one has been reported. The reactions exhibit high efficient and good functional group tolerance. Exclusive 2,6-bis-aminated pr

Transition-metal-free electrophilic amination of arylboroxines

A transition-metal-free strategy to construct C(sp2)-N bonds using arylboroxines and O-benzoyl hydroxylamines as coupling partners has been developed. This transformation provides a useful method to access various aromatic amines.

Copper-catalyzed electrophilic amination of organozinc nucleophiles: Documentation of O-benzoyl hydroxylamines as broadly useful R2N(+) and RHN(+) synthons

This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents using O-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases, the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl-H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.

Synthesis and Decomposition of the N-Alkyl-N-nitro-O-benzoylhydroxylamines

Nitration of N-alkyl-O-benzoylhydroxylamines yields the correspondng N-nitro derivatives.At modest temperatures these compounds decompose to yield alkyl benzoates, alkenes, benzoic acid, and nitrous oxide.In the case of primary alkylnitrohydroxylamines, nitroalkanes and alkyl nitrates are also formed.The alkyl benzoates are products of ionic reactions since skeletal rearrangements characteristics of carbonium ions occur.The insensivity of the rates of decomposition to solvent polarity suggests that the rate-determining step is a rearrangement rather than direct ionization.