Peroxides from alkyl halides

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

The stannylenes from either source will insert into the Sn- Sn, Sn-R, or Sn-H bonds of organotin compounds, and react with alkyl halides, disulfides, or peroxides as shown in the reaction scheme below, but only the stannylenes that are generated photolytically will react with carbonyl compounds, and it appears that the stannylenes may exist in two forms, perhaps related as singlet and triplet, or a com-plexed and uncomplexed species. 

Literature procedures for the synthesis of hydroperoxides include the preparation from hydrogen peroxide (via reaction with alkyl halides, -phosphites, -suEonates, alkenes. 

Chemically induced dynamic nuclear polarization (CIDNP) was first reported in 1967 in independent work from three different laboratories. The effects of free radicals on NMR spectra were revealed (Fig. 6) in studies of radicals from peroxides (equation 62) and azo compounds, as well as radicals generated from the reaction of alkyl halides and organolithium compounds. ... 

Sodium thiosulfate reacts with alkyl halides to form salts of the type RSSOjNa (Bunte salts). Alkyl disulfides may be obtained from these salts by pyrolysis or reaction with iodine or hydrogen peroxide. The yields range from 47% to 6S>%. Cyano and carboxyl groups do not interfere. Benzoylation of sodium thiosulfate produces benzoyl disulfide in 58% yield. ... 

Synthesis of secootkiry eokois from l-aOtynes. Dihydroboration at room temperature of a terminal alkyne with either (I) or 9-BBN gives a 1,1-diborylalkane (3) this is treated at 0-5° with I eq. of methyllithium in ether. The product (4) rearranges to (S). An alkyl halide (100 excess) is then added, and the resultant secondary organo-borane (6) is oxidized with alkaline hydrogen peroxide. Secondary alcohols (7) are obtained in 70-85% yield. 

The nucleophilicity of O2 - toward primary alkyl halides (Scheme 7-2) results in an Sn2 displacement of halide ion from the carbon center. The normal reactivity order, benzyl>primary>secondary>tertiary, and leaving-group order, I>Br>OTs>Cl, are observed, as are the expected stereoselectivity and inversion at the carbon center. In dimethylformamide the final product is the dialkyl peroxide. The peroxy radical (ROO), which is produced in the primary step and has been detected by spin trapping,25 is an oxidant that is readily reduced by O2 -to form the peroxy anion (ROO ). Because the latter can oxygenate Me2SO to its sulphone, the main product in this solvent is the alcohol (ROH) rather than the dialkyl peroxide. 

Functional group filters are applied to exclude from a chemical database those structures that possess undesired functionalities. These can be structures having more than one aldehyde group, structures containing metals, reactive alkyl halides, peroxides, carbazides. 

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