Cyanohydrin synthesis of 2,3-dihydroxy-2,3-dimethylbutanoic acid

Journal Article · Fri Aug 04 04:00:00 EDT 1978 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00410a015· OSTI ID:6547409

Powell, J E; Osuch, C; Burkholder, H R; Kulprathipanja, S; Miller, J H; Stadtherr, L G; Baughman, R G

From 3-hydroxy-3-methyl-2-butanone (1) via cyanohydrin synthesis and subsequent hydrolysis, the intermediates 2,3-dihydroxy-2,3-dimethylbutanonitrile (2), 3-chloro-1,2-dihydroxy-2,3-dimethylbutanimine hydrochloride (3), 3-chloro-1,2-dihydroxy-2,3-dimethylbutanamide (4), and 2,3-dihydroxy-2,3-dimethylbutanamide (5) have been isolated en route to 2,3-dihydroxy-2,3-dimethylbutanoic acid (6). Compound 2 reverted to 1 in the presence of base. In aqueous NaOH or NaOMe in Et/sub 2/O, compounds 3 and 4 gave (by HCl abstraction) 2,3-epoxy-1-hydroxy-2,3-dimethylbutanimine (7), tautomeric with 2,3-epoxy-2,3-dimethylbutanamide (8). Acid hydrolysis of 2 (at 40 to 50/sup 0/C) led principally to 5, but at higher temperatures to 3-methyl-2-butanone (9) via a pinacol-pinacolone type rearrangement involving the intermediates 2,2-dimethyl-3-oxobutanamide (10) and 2,2-dimethyl-3-oxobutanoic acid (11), which decarboxylates spontaneously to 9. In the acid hydrolysis of 2 to obtain 5 and 6 directly, substantial amounts of the byproduct 2-hydroxy-2,3-dimethyl-3-butenoic acid (12) were encountered; better yields of the desired products were obtained when the dihydroxynitrile (2) was first treated with 2 mol of acetic anhydride per mole to form its diacetate and somewhat diluted hydrochloric acid was used in lieu of saturated aqueous HCl. 4 tables, 1 figure.

• Research Organization: Ames Lab., IA
• OSTI ID: 6547409
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 43:16; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETIC ACID
ACETIC ACID ESTERS
ALKALI METAL COMPOUNDS
AMIDES
BOND ANGLE
CARBOXYLIC ACID ESTERS
CARBOXYLIC ACIDS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CYANIDES
ESTERS
HEAT TREATMENTS
HYDROCYANIC ACID
HYDROGEN COMPOUNDS
HYDROXY ACIDS
IMINES
INORGANIC ACIDS
KETONES
MAGNETIC RESONANCE
MELTING POINTS
MOLECULAR STRUCTURE
MONOCARBOXYLIC ACIDS
NITRILES
NUCLEAR MAGNETIC RESONANCE
ORGANIC ACIDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHYSICAL PROPERTIES
POTASSIUM COMPOUNDS
QUENCHING
REACTION INTERMEDIATES
RESONANCE
SYNTHESIS
THERMODYNAMIC PROPERTIES
TRANSITION TEMPERATURE
YIELDS