23058-07-3

Upstream product

• 98-53-3 4-tercbutyl-cyclohexanone 
• 19980-19-9 4-t-butyl-1-trimethylsilyloxy-1-cyclohexene 

Downstream Products

• 62845-84-5 4-(tert-butyl)cyclohex-1-en-1-yl diisopropyl phosphate 
• 62845-82-3 Phosphoric acid 4-tert-butyl-cyclohex-1-enyl ester dimethyl ester 
• 62845-83-4 4-(tert-butyl)cyclohex-1-en-1-yl diethyl phosphate 
• 128298-81-7 2-hydroxy-4-t-butylcyclohexanone 
• 89237-17-2 cis-ethylα-cyano-2-oxo-5-t-butylcyclohexane acetate 
• 89237-16-1 [(1R,5S)-5-tert-Butyl-2-(phenyl-hydrazono)-cyclohexyl]-cyano-acetic acid ethyl ester 

Relevant academic research and scientific papers

Axial/equatorial proportions for 2-substituted cyclohexanones

Axial-equatorial conformational proportions have been measured for 2- substituted cyclohexanones in chloroform by the Eliel method for F, Cl, Br, I, MeO, MeS, Me2N, MeSe, and Me. For the first seven of these, at least five experimentally independent measurables were used and the resulting conformational preferences appear to be accurate to within 10%. Systematic errors degraded the results for MeSe and Me. For Me2N, the conformational preference also was measured for the first time at slow exchange in the low- temperature 13C spectrum in several solvents. In chloroform, steric and polar effects contribute to the conformational preferences, with steric effects dominant for large groups such as I and MeS.

Halogenation of ketones with N-halosuccinimides under solvent-free reaction conditions

Several aryl substituted ketones, cyclic ketones, 1,3-diketones and a β-ketoamide were halogenated with N-halosuccinimides under solvent-free reaction conditions (SFRC) at various temperatures (20-80 °C), whereas less enolized ketones required the presence of an acid catalyst (p-toluenesulfonic acid, PTSA). Bromination of substituted acetophenones obeys first order kinetics v=kBr[ketone] and the following correlation with the keto-enol equilibrium constant: log kBr=0.3pKE+C1, less enolized substrates being more reactive; the moderate positive charge developed in the rate determining step was confirmed by the Hammett correlation (ρ=-0.5). On the other hand, in cyclic ketones an opposite relation was observed: log kBr=-0.6pKE+C2, indicating higher reactivity of substrates with higher enolization constant (KE). The important role of the nature of the solvent (MeCN, MeOH) in preorganization of the ketone-NBS-PTSA mixture prior to SFRC bromination was found.

2-Bromocyclohexanone perhydrate - X-ray crystal structure and conformational effects on reactivity in sulfoxidations

The remarkably stable crystalline perhydrate 1 derived from a-bromocyclohexanone has been characterised by X-ray crystallography providing the first example of a perhydrate crystal structure. Perhydrate 1 exists in alternative chair conformations in chloroform and tetrahydrofuran with the bromine substituent occupying equatorial and axial positions, respectively. The perhydrate 1 can oxidise sulfides to sulfoxides in good yields in dichloromethane but not in tetrahydrofuran. The requirement for bromine to be equatorial for a stable perhydrate to form is demonstrated using conformationally locked cis and trans 2-bromo-4-tert-butylcyclohexanones in which case only the cis isomer 4a forms a perhydrate. (C) 2000 Elsevier Science Ltd.

Synthesis of substituted 2-bromo phenols using a novel bromination-dehydrobromination reaction

Substituted 2-bromo-phenols can be synthesised by heating substituted cyclohexanones in neat diethyl dibromomalonate at 100°C. We discuss the efficiency of such a procedure and comment on the possible mechanism.