Methyl cyclohexanones, oxidation

Bis(trimethylsilyl)monoperoxysulfate 6 is also an excellent agent for oxygen transfer to nucleophilic substrates such as alkenes and heteroatoms. Compound 6 could oxidize alkenes such as 1-methylcyclohexene and fraw5-/3-methylstyrene, producing 2-methyl-cyclohexanone and benzyl methyl ketone, respectively, in high yield, most likely via the... 

The procedure reported here provides a convenient method for the a-hydroxylation of ketones which form enolates under the reaction conditions. The reaction has been applied successfully to a series of para-substituted acetophenones, 1-phenyl-1-propanone, 3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclododecanone, 2-methyl cyclohexanone, 2-norbornanone and benzalacetone. In the case of a steroidal example it was shown that a carbon-carbon double bond and a secondary hydroxyl group are not oxidized. A primary amino function, as in the case of p-aminoacetophenone, is not affected.5 Similarly, a tertiary amino ketone such as tropinone undergoes the a-hydroxy at ion reaction.5... 

When a mixture of finely powdered 1 1 inclusion compound of (-)-l and 4-methyl-cyclohexanone 2a (1.5 g) and (carbethoxymethyl)triphenylphosphorane 3 (2.59 g) was kept at 70 °C, the Wittig-Horner reaction was completed within 4 h. To the reaction mixture was added ether-petroleum (1 1), and the precipitated solid (triphe-nylphosphine oxide and excess 3) was removed by filtration. The crude product left after evaporation of die solvent of the filtrate was distilled in vacuo to give (-)-4-methyl-l-(carbethoxymediylene)cyclohexane 4 of 42.3% ee in 73% yield. 

Treatment of 2-butyne with ozone leads to unstable primary ozonides that cleave to cr-oxo-carbonyl oxides these could be trapped in the presence of aldehydes or ketones affording cross- -oxo-l, 2,4-trioxolanes. Subsequent cycloadditions between such cr-oxo-ozonides and cyclohexanone oxide, generated in situ from O-methylcyclohex-anone oxime (which affords methyl nitrite as a side-product), yield cr-diozonides 101 (Scheme 30) <1997J(P1)1601>. 

CO. CHa, CO2, acetone, ketene. ethene. propene, 1-butene, benzene, toluene, mesitylene. xylene, methyl ethyl ketone, diethyl ketone, methyl-n-propyt ketone, methyl-n-butyl ketone, ethyl vinyl ketone, methyl propenyl ketone (trace), ethyl propyl ketone (trace), 3-methyl-cydopenlanone, cyclohexanone (trace), cyclohexa-2-enone, 2-methyl-cyclohexanone, 1-methyl-cydohexa-1-ene-3-one (trace), acrolein, mesityl oxide, ethanal, propanal. butanal. chain fragments, some monomer... 

Plastic solid, d 1.406 n 1.54. Stabilizers are necessary to prevent discoloration from exposure to light or heat. Solvents for unmodified polyvinyl chloride of high mol wt cyclohexanone, methyl cyclohexanone, dimethyl formamide, nitrobenzene, tetrahydrofuran, isophorone, mesityl oxide. Solvents for lower polymers dipropyl ketone, methyl amyl ketone, methyl isobutyl ketone, acetonylacetone, methyl ethyl ketone, dioxane, methylene chloride. 

C (131°F) vapor density 3.9 (air = 1) fire-extinguishing agent dry chemical or CO2. o-Methyl cyclohexanone can react explosively with strong oxidizers at elevated temperatures. 

We are particularly interested in the Wacker oxidation of cyclohexene as the product, cyclohexanone, is a starting material in the synthesis of caprolactam, which is an intermediate in nylon production. Furthermore, we have strong interest in oxidation of acrolein in particular and acryhc compounds in general. Acrolein oxidation leads to a convenient route to 1,3-propanediol, while methyl acrylate oxidation leads to a starting material for adhesives. 

The reaction of (104) with acetone gives (107), from which the (/ )-sulphone (108) is obtained on oxidation, indicating that the steric course of hydroxyalkylation through this procedure is the same as that of deuteriation, but opposite to that of methylation. Cyclohexanone gives (109), in the... 

The oxidation of cyclohexanone is a reaction which has been the subject of considerable study over the years. Continued research in this area has given rise to many recent patents and papers. The product of the oxidation reaction is rather dependent on the metal complex which is used as a catalyst. When manganese(III) complexes are used the major reaction product is adipic acid [280-288]. Selectivity to adipic acid is about 70% in most cases. When copper(II) complexes are used, 5-formylvaleric acid predominates [289, 290] whereas iron complexes catalyze the formation of e-caprolactone [291,292] in up to 56% yield. In fact, liquid phase air oxidation of 2-methyl-cyclohexanone at 100 °C in the presence of copper stearate gave e-methyl- -caprolactone [292a]. Reaction scheme (190) shows the predominant reaction pathways. 

A reaction has been developed for the conversion of a 3-unsaturated ketones into 3-alkyl trans-1,2-diols. Previously it had been shown that addition of MejCuLi to cyclohex-2-enone followed by acid workup gives 3-methyl-cyclohexanone in high yidd. If, after Me2CuLi addition and separation from the black copper-containing precipitate, the reaction mixture is treated with borane, followed by oxidation with alkaline HjOj, a 55% yield of two diols (108) and (109) in a ratio of 87 13 is obtained. Likewise, isophorone (110) was converted into (111) after a two-day hydroboration step in 53% yield. 

Photolysis of pyridazine IV-oxide and alkylated pyridazine IV-oxides results in deoxygenation. When this is carried out in the presence of aromatic or methylated aromatic solvents or cyclohexane, the corresponding phenols, hydroxymethyl derivatives or cyclohexanol are formed in addition to pyridazines. In the presence of cyclohexene, cyclohexene oxide and cyclohexanone are generated. 

Clean examples of diaziridine to hydrazone rearrangements are rare. Diaziridine (119) mentioned above rearranges to the isomeric enhydrazone in boiling toluene, and 2,4-dinitrophenyldiaziridine (125) under the same conditions affords the 2,4-dinitrophenylhy-drazone (145) within 4 h. On blocking this rearrangement by iV-methyl, conversion with loss of cyclohexanone occurred to give benzotriazole iV-oxide (146) (72JOC2980). 

By oxidation with chromic acid, this is converted into cyclohexanone-3-carboxylic acid, in which the —CH. OH— group is converted into the —CO— group. This is converted into its ethyl ester and treated with magnesium methyl iodide, and the product, on hydrolysis, yields l-methyl-cyclohexane-l-ol-3-carboxylic acid, which is converted byhydro-bromic acid into 1-bromo-l - methyl - cyclohexane - 3 - carboxylic acid. When this is digested with pyridine, hydrobromic acid is eliminated and yields l-methyl-A -cyclohexane-3-carboxylic acid of the formula—... 

Cyclohexanone, 23,35 Cyclohexene oxide, 137 Cyclohcxyl methyl ether, 137 l-Cydohexyl-2-methylpropene, 68-9 ( )-l-Cyclohexyl-2-trimethyl ilylethene, 12 (Z)-l-Cyclohexyl-2-trimethylsilylelhene, 12 l-Cydohcxyl-2-trimethylsilylethyne, 12 (2-Cyclohexylidene-eihyl)trimethylsilane, 29 Cyclopentadec-2-ynone, 48 Cydopentadiene, 25 Cyclopentanone, 72 Cyclopentenones, 15 Cyclopropanone, 133... 

Optically pure (S)-benzyl methyl sulfoxide 139 can be converted to the corresponding a-lithio-derivative, which upon reaction with acetone gave a diastereomeric mixture (15 1) of the /S-hydroxysulfoxide 140. This addition reaction gave preferentially the product in which the configuration of the original carbanion is maintained. By this reaction, an optically active epoxy compound 142 was prepared from the cyclohexanone adduct 141181. Johnson and Schroeck188,189 succeeded in obtaining optically active styrene oxide by recrystallization of the condensation product of (+ )-(S)-n-butyl methyl sulfoxide 143 with benzaldehyde. 

For a number of applications curing at room temperature is desirable. This so-called cold cure is brought about by using a peroxy initiator in conjunction with some kind of activator substance. The peroxy compounds in these cases are substances such as methyl ethyl ketone peroxide and cyclohexanone peroxide, which as used in commercial systems tend not to be particularly pure, but instead are usually mixtures of peroxides and hydroperoxides corresponding in composition approximately to that of the respective nominal compounds. Activators are generally salts of metals capable of undergoing oxidation/reduction reactions very readily. A typical salt for this purpose is cobalt naphthenate, which undergoes the kind of reactions illustrated in Reactions 4.6 and 4.7. 

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