Arndt, R. R. published the artcileAutoxidation. I. Liquid phase autoxidation of 5-methylnonane, Category: catalysis-chemistry, the publication is Journal of the Chemical Society (1959), 3258-64, database is CAplus.
The purpose was to determine the effect of a Me group, introduced into an otherwise straight-chain hydrocarbon, on the position of radical attack during autoxidation 5-Methylnonane (I), b655 160°, n21D 1.4122, was prepared Bu2C(OH)Me (500 g.), b24 103-4°, n25D 1.4328, was slowly distilled over 0.1 g. iodine at atm. pressure. The distillate was dried over CaCl2 and redist. to give 5-methyl-4-nonene (II), b655 155-6°. Hydrogenation of II at 100° and 150 lb./sq. in. in the presence of 2% Pd(CaCO3 yielded I (after fractional distillation). I was oxidized in O at 90°. Samples were withdrawn at intervals and reduced with LiAlH4 to give a mixture of corresponding alcs., which were analyzed by gas chromatography (flame ionization detector). Mixtures of 3- and 4-ols could not be resolved by gas chromatography, but the mixture of isomers in the fraction was determined by infrared absorption spectroscopy. The susceptibility of various carbon positions to attack was in the expected order (tertiary > secondary > primary). However, differences in the reactivity of secondary C’s were observed. Position 2 was slightly more reactive than 4, and both were 2-3 times as reactive as position 3. H was removed 19 times more readily from a tertiary than a secondary C and 4 times more readily from a secondary than a primary C. As oxidation proceeded, chain fission of the primary oxidation product (5-hydroperoxy-5-methylnonane) yielded EtOH, BuOH, and 2-hexanol as major substances. Removal of the Me group from I did not take place, since the expected alc. was not detected. Diols obtained on reduction of disubstituted autoxidation products were found in substantial amounts, indicating that the chain reaction step ROOâ?+ HR â?ROOH + â¢R was propagated to a large extent by intramolecular H transfer. A number of possible reduction products were synthesized in order to identify the gas chromatographic peaks. 5-Methyl-4-nonanone, prepared by a Grignard reaction from 2-methylhexanoyl chloride and PrBr, was reduced with LiAlH4, distilled, and purified by chromatography on alumina to yield 5-methyl-4-nonanol, b654 197.8-8.0°, n25D 1.4340, n30D 1.4320. 5-Methyl-3-nonanone, b655 194-6, prepared from 3-methylheptanoyl chloride and EtBr, gave 5-methyl-3-nonanol, b655 197.5-7.6°, n26D 1.4326, n30D 1.4312. Similarly prepared was 5-methyl-2-nonanol, b655 202-2.1°, n25D 1.4320, n30D 1.4312. 5-Methylnonanol, n30D 1.4340, was prepared by reduction of a 5-methylnonanoate with LiAlH4. 2-Butylhexanol, b655 209.40, n30D 1.4328, was prepared by LiAlH4 reduction of 2-butylhexanoic acid, b35 160-2°, n30D 1.4396. 5-Methyl-2,5-nonanediol, b0.25 93°, m. 70°, was prepared from 5-oxo-2-hexanol and the Grignard derivative of BuBr. Similarly prepared was 5-methyl-3,5-nonanediol, b0.1 77.5°, n30D 1.4407. Hydroxylation of 5-methyl-4-nonene with performic acid yielded 5-methyl-4,5-nonanediol, b0.5 86°, n30D 1.4463.
Journal of the Chemical Society published new progress about 3115-28-4. 3115-28-4 belongs to catalysis-chemistry, auxiliary class Aliphatic Chain, name is 2-Butylhexanoic acid, and the molecular formula is C10H20O2, Category: catalysis-chemistry.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia