Hydroxymethylation of cyclohexanone

Hydroxydibenzoylmethane, 32, 74 /3-Hydroxyethylphthalimide, 32, 19 Hydroxylammonium chloride, 32, 36 Hydroxymethylation of cyclohexanone,... 

Photoreactions of pyridazine N-oxides have been misinterpreted in part. Thus, the reported hydroxymethylation of some pyridazine N-oxides ° with concomitant loss of oxygen is probably due to secondary reaction of the parent pyridazine. Igeta et al. reported on the photochemistry of several pyridazine N-oxides that resulted mainly in deoxygenation " in the presence of benzene, toluene, or cyclohexane, the hydrocarbons were oxygenated to give phenols or cyclohexanol in moderate yield. Cyclohexene gave cyclohexene oxide and cyclohexanone in a ratio of 5 1 and polymethylbenzenes, the corresponding phenols or hydroxymethyl derivatives. ... 

The condensation of cyclohexanone (13) and cyclopentanone (14) with formaldehyde produced the corresponding tetrakis-(hydroxymethyl) -ketones in 37 and 90% yields, respectively. When the tetramethylolcyclohexanone was treated with cyclohexanone, a 77% yield of the model keto spiro ketal was formed. In this compound the carbonyl group located between the two quaternary carbon atoms is so hindered that no ketal formation apparently takes place. 

Tetraoxatetraspiro [5. 2. 2, 2. 5. 2. 2.2 ] hexacosane. Into a 300-ml, round-bottomed flask equipped with a magnetic stirrer, a Dean-Stark trap and a reflux condenser was added 2,04 g (0.01 mol) of 1,1, 4, 4-tetrakis(hydroxymethyl) cyclohexane, mp 223-224 [reported (12)mp 219-222°C], 2.16 g (0.022 mol) of cyclohexanone, 0.1 g of p-toluenesulfonic acid, and 300 ml of benzene. After the mixture had been heated under reflux until no more water collected in the Dean-Stark trap, the benzene was removed by distillation under reduced pressure. The resulting solid was dissolved in abs ethanol and treated with several grams of de-... 

Melamine is soluble only in water and has low solubility in dimethylsulfoxide (DMSO) and in other aprotic dipolar solvents (9% at 120 °C), in glycerol or ethylene glycol (10% at 140 °C). In the majority of other usual solvents it is insoluble. Kucharski and Lubczak discovered a new class of reactive solvents for melamine [36] poly (hydroxymethyl) derivatives of cyclohexanone, acetone, nitromethane which are able to dissolve 50-60% melamine. Melamine can be totally propoxylated or ethoxylated at lower temperatures (70-90 °C), in aprotic dipolar solvents (for example DMSO, dimethylformamide, N-methyl pyrrolidone and so on), in the presence of quaternary ammonium hydroxides as catalysts [for example tetrabutyl ammonium hydroxide (TBAH)], at a low reaction rate (reaction 15.35), for a very long reaction time (40-50 hours) [31, 37]. The resulting hexafunctional polyols give very thermostable rigid PU (up 200 °C). 

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. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide... 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide 1-Hydroxyethyl ethyl peroxide 1 -Hydroperoxy-1 -acetoxycyclodecan-6-one Isopropyl percarbonate Isopropyl hydroperoxide Methyl ethyl ketone peroxide Methyl hydroperoxide Methyl ethyl peroxide Monoperoxy succinic acid Nonanoyl peroxide (75% hydrocarbon solution) 1-Naphthoyl peroxide Oxalic acid ester of t-butyl hydroperoxide Ozonide of maleic anhydride Phenylhydrazone hydroperoxide Polymeric butadiene peroxide Polymeric isoprene peroxide Polymeric dimethylbutadiene peroxide Polymeric peroxides of methacrylic acid esters and styrene... 

Cyclohexanone, 2-hydroxymethyl-ene-, preparation of, 54, 38 reaction with alkylenedithio-tosylates, 54, 37 Cyclohexanone, 2,2-trimethy1-enedithio-, 54, 39 4-CYCLOHEXENE—1,2-DICARBOXYLIC ACID, DIETHYL ESTER, trans-, 50, 43... 

For formaldehyde reacting to give fert-butylperoxymethanol, the reaction enthalpy is —66.5 kJmol and for cyclohexanone reacting to give 1-fert-butylperoxycyclohexanol, the enthalpy of reaction is ca —45 kJmol. The average of these is compatible with the value reported from Reference 28. By contrast, the gas phase formal reaction 11 to produce bis(hydroxymethyl) peroxide is calculated to be exothermic by some —218 kJmol for the case of formaldehyde. 

This procedure for the preparation of 1 -(hydroxymethyl)cyclohexanol is a modification of that reported by the submitters.4 While 1 -(hydroxymethyl)cyclohexanol has been conventionally prepared from methylenecyclohexane by dihydro xylation53 or from cyclohexanone in three steps through the cyanohydrin,5b the present method consists of an alternative route from cyclohexanone via nucleophilic hydroxymethylation. 

Silyl enol ether of 2-methyl cyclohexanone reacts readily in the presence of ytterbium triflate to form 2-hydroxymethyl-2-methyl cyclohexanone [153,154], Yields ranged from... 

The present aryloxymethylation may be regarded as hy-droxymethylation of enones. In fact, 3-(3,4-methylenedi-oxyphenoxymethyl)cyclohexan-l-one (74d) can be converted to 3-(hydroxymethyl)cyclohexanone (75) in 88% yield by treatment with cerium(rV) ammonium nitrate (CAN) (Scheme 32). 

When cyclohexanone was condensed with the tetrakis-(hydroxymethyl)-cyclohexane, an 80% yield of the model spiro ketal was formed. 

Also in our previous work, the tetrol, 1,2,4,5-tetrakis-(hydroxymethyl) cyclohexane (17,18) of unknown stereochemistry was obtained. When this tetrol was condensed with cyclohexanone, a 92% yield of the bicyclic ketal containing the seven-membered ring was obtained. 

Since the seven-membered rings formed so readily to produce the ketals, an investigation was undertaken to see if eight-membered cyclic ketals would form as readily. A model compound was prepared from 1,8-bis(hydroxymethyl) naphthalene and cyclohexanone in a nearly quantitative yield of the cyclic ketal containing the eight-membered ring. 

---