CYCLOHEXANONE, 2,3-epoxy

Cyclohexane, methyl, 55, 112 CYCLOHEXANECARBOXYLIC ACID, 1 cyano-2-methyl-, ethyl ester, 55, 57 CYCLOHEXANONE, 2,3-epoxy- [7-Oxa-bityUo[4 1 0]heptan-2-one], 55, 52 2-Cyclohexen-l-one, 55, 52 5-Cyclohexene-l,4-dione, 2,3-dichloro-2,5-di-fm-butyl- [5-Cyclohexene-l,4-dione, 2,3-dichloro-2,5-bis( 1,1-di-methylethyl)-], 55, 32 5-Cyclohexene-l, 4-dione, 2,3,5-tnchloro-... 

Cyclohexanone, 2,3-dimethyl-, 56, 56 CYCLOHEXANONE, 2,3-epoxy-, 55, 52 Cyclohexanone, 3-methyl-, 56, 53 Cyclohexanone, 3 methyl 2-(phenyl methyl)-, 56, 56... 

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. 

The role of oxygen on the allyhc oxidation of cyclohexene over the FePcCli6-S/TBHP catalytic system was determined by using 2 labelled oxygen. Since more than 70% of the main cyclohexene oxidation products, 4,11, and 12, had labelled oxygen, we can assure that molecular oxygen acts as co-oxidant. However, under the reaction conditions the over-oxidation of 4 seems to be unavoidable. Labelled 2, 3- epoxy-l-cyclohexanone (13), 2-cyclohexen-l, 4-dione (14), and 4-hydroxy-2-cyclohexen-l-one (15) were detected as reaction products. 

Wittig-type olefination has been reported. The reaction is thought to involve the salt (47) and shows little stereoselectivity. 2.2.2 Ketones.- The stereochemistry of olefination of 2,3-epoxy- and protected 2-hydroxy cyclohexanones with ethylidenetriphenyl-... 

Titanium enolates.1 This Fischer carbene converts epoxides into titanium enolates. In the case of cyclohexene oxide, the product is a titanium enolate of cyclohexanone. But the enolates formed by reaction with 1,2-epoxybutane (equation I) or 2,3-epoxy butane differ from those formed from 2-butanone (Equation II). Apparently the reaction with epoxides does not involve rearrangement to the ketone but complexation of the epoxide oxygen to the metal and transfer of hydrogen from the substrate to the methylene group. 

Using diarylprolinol ether 55 in conjunction with an additional base, a domino Michael/aldol/intramolecular Sj 2 process has been developed that led to highly functionalised epoxy cyclohexanones 110, with excellent control of three of the chiral centres generated (Scheme 42) [169]. Despite the apparent complexity, these reactions proceed at room temperature in less than 24 h and the products contain significant potential for a host of further transformations. 

Materials. Epoxy novolac, DEN-431, obtained from Dow Chemical Co. was selected as the epoxy component. A 3,3 -diazidodiphenyl sulfone synthesized in our laboratory (5) was used as the azide compound. Poly(/7-vinyl phenol) obtained from Maruzen Oil Co. was used as the phenolic resin matrix. The coating solvent was cyclohexanone. The developer used in this study was 0.1 N tetramethylammonium hydroxide aqueous solution. 

Presence of a phenyl 6ubetitu nt at C(jj, as in 2,3-epoxy-3-phemy) -cyclohexanone caused a preponderance of acyl migration (Eq. 47. j. presumably by stabilizing the carbonium ion generated by Cjar bond rupture. Formation of a oerbonium ton at Ct ) rather than is favored also on electrostatic grounds by the proximity of C( to tlie positive terminal of the carbonyl dipole.8 ... 

In another study, 13-carotene was heated in aqueous medium at 90°C, 120°C and 150°C. More than 40 different compounds were found in the ether extracts by GC-MS as shown in Figure 3. Dihydroactinidiolide (sweet peachy aroma) was found in highest concentration at all temperatures studied. At 90°C, 5-6-epoxy-6-ionone (sweet, violet-like) was found in second highest quantity, while at 150°C, 2,6,6-trimethyl-2-hydroxy-cyclohexanone (green, citrusy) and 2,6,6-trimethyl-2-hydroxy-cyclohexan-1-aldehyde (floral, geraniol-like) were found in large quantity. At 120°C, these compounds were more evenly balanced than at 90°C or 150°C. A balance of ionone related compounds seem to contribute to an attractive green tea flavor. 

Other examples of solvent effects in casting blends include epoxy resin/copoly-ester/tetrachloroethane polyethersulphone/poly(ethylene oxide)/cyclohexanone and mixtures of PVC with various polyacrylates in solvents such as THF One particular pair of polymers PVC/poly(ethyl acrylate) appear to be miscible but no suitable solvent has been found as yet. Homogeneous blends can only be prepared by in situ polymerisation though it is possible that miscibility is enhanced by small amounts of graft copolymer which is inevitably formed by this technique. 

Oxidation of cyclohexanone. Oxidation of cyclohexanone with TTN in acetic acid at room temperature proceeds rapidly to give adipoin (5) in 84% yield. If the oxidation is performed at first at room temperature, the thallium(I) nitrate removed hy filtration, and then the filtrate heated to about 40° for a few minutes, the product is cyclopentanecarboxylic acid (4), obtained in 84% yield. McKillop et al. propose that both products are derived from a common precursor, an epoxy enol (3). 

Thiocyanato-2-cyclohexenone is formed regioselectively (Eq. 321a) from 2,3 -epoxy cyclohexanone. 

Treatment of the epoxy sulfones obtained thus with MgBr2 produces a-bromo ketones or a-bromo al-dehyde. This conversion can be applied to stereoselective preparations of a-bromo methyl ketones from cyclohexanone derivatives. Thus, treatment of 17-P-hydroxy-5-a-androstan-3-one (134) with 1-chloroethyl phenyl sulfone provides an epoxy sulfone (135), which is cleaved by MgBr2 to give a 99 1 mixture of 3-acetyl-3-bromoandrostanes (136 and 137 equation 33), whereas similar treatment of 17-p-hydroxy-5-B-androstan-3-one (138) gives a 4 96 mixture of 3-acetyl-3-bromoandrostanes (139 and 140 equation 34). These facts may reflect the steric course of the initial attack of the a-sulfonyl carbanion on the carbonyl face. 

Further work will be necessary to produce practical paints from the 2,6-divanillylidene cyclohexanone system, but as an example of the possibilities of the olefinic approach to cleavable epoxy resins, it has been reasonably successful. 

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