3- Methyl-3,4-epoxy esters

Bicyclic orthoesters. Together with a catalytic amount of AgClO zirconocene dichloride converts 3-methyl-3,4-epoxy esters to the 2,7,8-trioxabicyclo[3.2.1]octane derivatives. These orthoesters are less susceptible to acid hydrolysis than Corey s 2,6,7-trioxabicyclo[2.2.2]octanes. 

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-... 

Shibasaki et al. have reported a new approach to a,/3-epoxy esters the epoxidation of cv. j-unsaturated carboxylic acid imidazolides with a La(OPr )3, BINOL, Ph3As=0, and TBHP system provides epoxy-peroxy-esters (41), which are generated in situ from the intermediary epoxy acid imidazolide and converted to the corresponding methyl ester (42) upon treatment with methanol (Scheme 27).134... 

The required epoxy esters are obtained by reaction of the free acid (0.96 mmol) with 3,4-epoxy-3-methylbutanol (1.1 mmol), DCC (1.1 mmol), and DMAP (0.048 mmol) in CH2C12/DMF (9 1, 10 mL, 1 h at 0 °C and 2 h at r. t.). Alternatively, they can be synthesized from acid chlorides using 3-methyl-3-butenol and triethylamine (1 1 2 ratio CH2C12, 0°C), followed by epoxidation with m-chloroperbenzoic acid (1.2 equivalents, CH2C12, 0°C). 

Conversion of lodolactones into the corresponding epoxy esters- is often one of the major steps in their utilization for the purposes of stereo-control. Methanolysis of the cis isomer of 4,5-dihydro-5-iodomethyl-4-phenyl-2(3H)-furanone to methyl (3RS,4RS)-4,5-epoxy-3-phenylpentanoate is a representative procedure for this transformation. 

Methyl-tertiobutyl-ether / acetone was found to be a good solvent of the racemic epoxy-ester, and thus is used for the reaction, as for triglycerides hydrolysis. 

Chemical Name Morphinan-6-ol, 6,7-didehydro-4,5-epoxy-3-methoxy-17-methyl-, acetate (ester), (5a)-... 

Remotely unsaturated epoxy acids undergo fission rearrangement when treated with BF3 Et20. Hence, cis and trans ketocyclopropane esters are produced from the unsaturated epoxy ester methyl vernolate (Eq. 46) [88]. 

Bohlmann has isolated another naturally occurring thymol epoxy-ester (c/. Vol. 1, p. 34 Vol. 3, p. 46), this time from Wedelia forsteriana Compound (137)has been isolated from Pluchea odorata. Pseudomonas fluorescens converts (-)-menthone into cis- and trans-(138). In addition to known (Vol. 2, p. 31) p-menthane-8-thiol-3-ones in Buchu leaf oil, 5-methyl dnd S-acetyl derivatives have been isolated... 

Moreover, a-cyano-a-epoxy esters are easily reduced to a-cyano-a-epoxy alcohols by NaBH4 in aqueous THF [MR4]. Ethanedithiol can also be an additive for the reduction of esters by NaBH4, except r-butyl esters. Nitrile groups remain unperturbed under these conditions [GEl]. Methyl benzoate is reduced to benzylalcohol by NaBH4-ZrCl4 in THF [ISl],... 

Fission-rearrangement of epoxides. Following his suggestion that epoxy-acids may be important intermediates in biosynthesis,19 Gunstone with Conacher 20 found that when the unsaturated epoxy ester methyl vemolate (1) is treated with boron trifluoride etherate in cold benzene solution it is converted into a number of products, two of which cannot be separated from each other but, together, account for a yield of 34%. On the basis of chemical properties, infrared, NMR, and mass spectra they are believed to be the cis and trans forms of the ketocyclopropane ester (2). 

Bellstein Handbook Reference) AI3-08678 BRN 0878263 CCRIS 876 DImethoxymethyl-phosphIne oxide Dimethyl methanephosphonate Di-methyl methylphosphonate DMMP EINECS 212-062-3 Fyrol DMMP HSDB 2590 Methyl phosphonic acid, dimethyl ester NCI-C54762 NSC 62240 Phosphonic add, methyl-, dimethyl ester Pyrol dmmp. Flame retardant for applications where high phosphorus content, good solvency, and low viscosity are desired lowers viscosity of epoxy resins and unsaturated polyesters filled with hydrated alumina oxide. Liquid bp = 181 , bp20 = 79.6" d ° = 1.4099 Am = 217 nm (e = 13, EtOH) soluble in H2O, Et20, EtOH LDsO (rat orl) > 5000 mg/kg. Akzo Chemie. 

This reaction involves the condensation of an aldehyde or ketone with an a-halo ester in the presence of a basic condensing agent (sodium ethoxide, sodamide, finely divided sodium or potassium teri.-butoxide) to give a glycidic (or p-epoxy) ester. Thus acetophenone and ethyl chloroacetate yield phenyl-methyl glycidic ester (I) ... 

Epoxidized soybean oil, methyl ester CAS 68082-35-9 EINECS/ELINCS 268-371-3 Synonyms Fatty acids, soya, epoxidized, methyl esters Methyl epoxy soyate Uses Plasticizer lubricant additives surfactants curing agents epoxy reactive diluents source of epoxidized organic chem. Trade Name Synonyms Vikoflex 7010 [Atofina http //www.atofinachemicais.com, Ceca SA http //WWW. ceca. fi]... 

See P-Caryophyllene Methylenium ceruleum. See Basic blue 9 Methyl epi-jasmonate. See Methyl jasmonate Methyl epoxy soyate. See Epoxiidized soybean oil, methyl ester... 

N-lsopropyl-N -phenyl-p-phenylenediamine I-Limonene Methylal Salicylic acid Sorbitol 1,3,5-Trihydroxybenzene resin mfg., alkyd Linseed acid resin mfg., artificial Benzyl chloride Maleic acid resin mfg., epoxy ester Linseed acid resin mfg., food-contact 2,6-Xylenol resin mfg., oil-soluble p-t-Amyl phenol... 

Clearly, none of these approaches are suitable for efficient preparation of the correct optical antipode of LTA, and all further non-biomimetic preparations have utilized the formyl epoxy-ester (366) as a key synthon. / n example of this strategy is shown in Scheme 56 where (-)-LTA/i methyl ester was efficiently... 

Methyl oleate produces small amounts of allylic keto-oleates (with CO on carbons 8-, 9-, 10- and 11), epoxy-stearate or epoxy-oleates (8,9-, 9,10- and 10,11-epoxy), dihydroxy-oleates (8,9-, 9,10-, and 10,11-diOH) and dihydroxy-stearates (between carbon-9 and carbon-11). The allyhc keto-oleates may be derived by dehydration of the corresponding hydroperoxides. 9,10-Epoxystearate may be produced by the reaction of oleate and the hydroperoxides. The other epoxy products can be formed by cychzation of an alkoxy radical formed from the corresponding hydroperoxides of oleate (Figure 4.1). Accordingly, the 11-hydroperoxide forms the 10,11-epoxy ester, the 8-hydroperoxide forms the 8,9-epoxy ester, and the 9- and 10-hydroperoxides form the 9,10-epoxy ester. The 1,2- and 1,4-dihydroxy esters may be formed from a similar alkoxyl radical that undergoes hydroxyl and hydrogen radical substitution via an allylic hydroxy ester radical (Figure 4.1). 

Efficient Synthesis of Cardenolides. A general and efficient method has been described for the synthesis of cardenolides, consisting of (1) a-methylsulfenylation of pregnen-20-one, (2) Refor-matsky reaction, and (3) butenolide formation by alumina chromatography of the epoxy ester obtained from the S-methylated Reformatsky product (eq 4). ... 

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