Franzen, Volker published the artcileMolecular rearrangement during the oxidation of acetylenic hydrocarbons with peracetic acid. A new route to ¦Á-branched carboxylic acids, Formula: C10H20O2, the publication is Chemische Berichte (1954), 1219-25, database is CAplus.
Reaction of RCú·CR’ with AcO2H (I) yields, in addition to RCO2H and R’CO2H, RR’CHCO2H, probably via RR’C:C:O, by a mechanism (details given) similar to that of the Wolff-Schroeter (C.A. 3, 2555) and Buckley-Levy (C.A. 46, 9055e) rearrangements. Degrading Bu2CHCO2H (II) to Bu2CO (III) proved its structure. Keeping 20 g. (EtCú·)2 and 3 equivalents 12% I 10 days, removing AcOH in vacuo, and esterifying residual Et2CHCO2H, b760 191-5¡ã, with MeOH-HCl gave 8.2 g. Et2CHCO2Me, b760 134¡ã, nD20 1.4052. (BuCú·)2 and I similarly (reaction kept at 25¡ã and followed by titration) gave by fractional distillation BuCO2Me, b760 125-7¡ã, nD20 1.3969, and Bu2CHCO2Me (IV), b9 90¡ã, nD23 1.4232. IV (16 g.) refluxed with KOH in MeOH 2 hrs. and dilute H2SO4 added gave 12 g. II, b12 137¡ã, nD20 1.4330, d20 0.8848, forming no urea adduct [p-toluidide of II, m. 115¡ã (from EtOH), prepared with SOCl2 and p-toluidine]. Bu2CHCH2OH, b12 107¡ã, nD20 1.4360, was prepared from IV with LiAlH4. The chilled Grignard reagent from 20 g. Mg and 140 g. PhBr in 250 cc. Et2O treated dropwise with 70 g. IV in 100 cc. Et2O, boiled 3 hrs., decomposed with dilute H2SO4, and Et2O residue distilled gave a trace of Ph2, then 56 g. Bu2CHC(OH)Ph2 (V), b0.5 168-70¡ã, nD20 1.5410. Heating 30 g. V with 20 g. KHSO4 at 230¡ã 1 hr., decanting from salt, and distilling gave 21.7 g. Bu 2CH:CHPh2 (VI), b4.8 183-4¡ã, nD21 1.5460. A solution of 17 g. VI in 60 cc. AcOH was ozonized at 0¡ã, treated with 4 g. Zn dust, concentrated to 0.5 volume, diluted with water, extracted with Et2O, the extract washed with 2N Na2CO3, and the Et2O residue fractionated, giving 4.8 g. III, b28 89-90¡ã, nD21 1.4200 (identical with compound prepared from Bu2CHOH with CrO3), forming urea adduct in MeOH [semicarbazone of III, m. 89¡ã (from EtOH)], and Ph2CO, b0.1 118-22¡ã [semicarbazone, m. 164¡ã]. PhCú·CMe treated with I gave, after esterifying, BzOMe, b24 96-8¡ã, and 20% PhCHMeCO2Me, b24 115¡ã, nD25 1.5010, which was saponified 2 hrs. with KOH in boiling MeOH, the acid treated with SOCl2, and the PhCHMeCOCl, b40 33¡ã, poured into concentrated NH4OH to give PhCHMeCONH2, m. 92¡ã (from MeOH). PhCú·CCH2Ph treated with I, AcOH evaporated, the mixture of acids extracted with 2N Na2CO3 and fractionally sublimed after addition of dilute H2SO4, gave below 160¡ã (1 mm.) BzOH and PhCH2CO2H [amide, m. 156¡ã], and at 200-10¡ã (0.1 mm.) 35% crude PhCH2CHPhCO2H [pure amide, m. 133¡ã (from aqueous EtOH)]. MeCú·CBu treated with I and product distilled gave BuCO2H, b12 87¡ã, and BuCHMeCO2H, b12 110-12¡ã, nD18 1.4200, d17 0.9085, no urea adduct. PrCú·CBu and I gave PrCO2H, b25 78-82¡ã, BuCO2H, b25 96-9¡ã [S-benzylthiuronium salts, m. 146¡ã and 156¡ã, resp.], and BuCHPrCO2H, b25 140-42¡ã, nD20 1.4297, no urea adduct [amide, m. 122¡ã]. MeCú·C(CH2)4Cú·CMe and I gave after esterification, distillation, and saponification HO2CCHMe(CH2)4CHMeCO2H (Steele, C.A. 25,919).
Chemische Berichte 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, Formula: C10H20O2.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia