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Alcohol-free dichloromethane

For the asymmetric epoxidation reaction, dry alcohol-free dichloromethane (the use of dichloromethane stabilized with methanol must be avoided) is usually the solvent of choice It is inert to the reagents, has good solvent power for the components of the reaction, and supports good epoxidation rates. A fortunate consequence of the asymmetric epoxidation process is that ligation of the allylic alcohol to the Ti center aids in solubilization of the substrate. Substrates that normally may be only modestly soluble in the above-mentioned solvents will be brought into solution as they complex with the Ti-tartrate catalyst. [Pg.237]

Of the alkyl esters, methyl esters are the most useful because of their rapid hydrolysis. The acid is refluxed with one or two equivalents of methanol in excess alcohol-free chloroform (or dichloromethane) containing about O.lg of p-toluenesulfonic acid (as catalyst), using a Dean-Stark apparatus. (The water formed by the... [Pg.58]

An example of the efficient formation of an electron-deficient double bond by RCM was disclosed by a Japanese group in a novel total synthesis of the macrosphelides A (209) and B (208) (Scheme 41) [100]. When the PMB-pro-tected compound 204 was examined as a metathesis substrate, the ring closure did not proceed at all in dichloromethane using catalysts A or C. When the reaction was carried out using equimolar amounts of catalyst C in refluxing 1,2-dichloroethane, the cyclized product 205 was obtained in 65% yield after 5 days. On the other hand, the free allylic alcohol 206 reacted smoothly at room temperature leading to the desired macrocycle 207 in improved yield. [Pg.308]

Fluoride ion catalyzes the hydrosilylation of both alkyl and aryl aldehydes to silyl ethers that can be easily hydrolyzed to the free alcohols by treatment with 1 M hydrogen chloride in methanol.320 The most effective sources of fluoride are TBAF and tris(diethylamino)sulfonium difluorotrimethylsilicate (TASF). Somewhat less effective are CsF and KF. Solvent effects are marked. The reactions are facilitated in polar, aprotic solvents such as hexamethylphosphortriamide (HMPA) or 1,3-dimethyl-3,4,5,6-tetrahydro-2(l //)-pyrirnidinone (DMPU), go moderately well in dimethylformamide, but do not proceed well in either tetrahydrofuran or dichloromethane. The solvent effects are dramatically illustrated in the reaction of undecanal and dimethylphenylsilane to produce undecyloxyphenyldimethylsi-lane. After one hour at room temperature with TBAF as the source of fluoride and a 10 mol% excess of silane, yields of 91% in HMPA, 89% in DMPU, 56% in dimethylformamide, 9% in tetrahydrofuran, and only 1% in dichloromethane are obtained (Eq. 164).320... [Pg.60]

Another RP-HPLC procedure was applied for the study of the distribution and stability of steryl chlorin esters in copepod faecal pellets from diatom grazing. Pigments were sonicated for 15 min with acetone at 0°C and the procedure was repeated until the extract became colourless. The organic phase was evaporated and the fraction containing the free alcohols was separated by TLC (silica stationary and dichloromethane mobile phases) and analysed by gas chromatography. RP-HPLC measurements were performed in an ODS... [Pg.300]

Since a magnesium alkoxide undergoes rapid ligand exchange with free alcohols even in dichloromethane at ambient temperature, the regiocontrol of nitrile oxide cycloadditions of multisubstituted allylic alcohols can be effectively attained... [Pg.781]

Very recently, Hu et al. claimed to have discovered a convenient procedure for the aerobic oxidation of primary and secondary alcohols utilizing a TEMPO based catalyst system free of any transition metal co-catalyst (21). These authors employed a mixture of TEMPO (1 mol%), sodium nitrite (4-8 mol%) and bromine (4 mol%) as an active catalyst system. The oxidation took place at temperatures between 80-100 °C and at air pressure of 4 bars. However, this process was only successful with activated alcohols. With benzyl alcohol, quantitative conversion to benzaldehyde was achieved after a 1-2 hour reaction. With non-activated aliphatic alcohols (such as 1-octanol) or cyclic alcohols (cyclohexanol), the air pressure needed to be raised to 9 bar and a 4-5 hour of reaction was necessary to reach complete conversion. Unfortunately, this new oxidation procedure also depends on the use of dichloromethane as a solvent. In addition, the elemental bromine used as a cocatalyst is rather difficult to handle on a technical scale because of its high vapor pressure, toxicity and severe corrosion problems. Other disadvantages of this system are the rather low substrate concentration in the solvent and the observed formation of bromination by-products. [Pg.120]

Chromyl chloride, Cr202Cl2, a dark-red liquid (mp -96.5 °C, bp 117 °C, d 1.911), is prepared from chromium trioxide or sodium dichromate, hydrochloric acid, and sulfuric acid [665]. The reagent is used in solutions in carbon disulfide, dichloromethane, acetone, tert-butyl alcohol, and pyridine. Oxidations with chromyl chloride are often complicated by side reactions and do not always give satisfactory yields. The mechanism of the oxidation with chromyl chloride, the Etard reaction, is probably of free-radical nature [666]. Complexes of chromyl chloride with the compounds to be oxidized have been isolated [666, 667, 668]. [Pg.26]

Oxidation of hydrocarbons with a tertiary carbon, e.g. adamantane, with lead tetraacetate in trifluoroacetic acid-dichloromethane solution, in the presence of chloride ion, gave high yields of trifluoroacetate functionahzed bridgehead alcohols [57]. Subsequent hydrolysis yielded the free bridgehead alcohols (Scheme 13.34). Another important advantage of this method is the feasible conversion of the intermediate trifluoroacetate into an amide with acetonitrile. [Pg.735]

Alternatively, the substrate has been accessed by a free radical route starting from propargyl alcohol (6)21. The key step is the radical cyclization of 3-[(bromomethyl)dimethylsilyloxy]-l-propyne (7). This in turn is readily available in high yield by treatment of 6 with commercially available (bromomethyl)chlorodimethylsilane and triethylamine in dichloromethane tn the presence of a catalytic amount of 4-dimethylaminopyridine at 20 C. [Pg.809]

The cyclopentenones with functionality at the 4-position are listed in Table II. Those compounds with THP blocl g groups were prepared from the corresponding free alcohols using dihy-dropyran (pTSA catalysis) in dichloromethane solution (28). The TMS blocked cycldpentenones were obtained by treatment with chlorotrimethylsilane (TMS-Cl) and hexamethyldisilazane (HMDS) in pyridine solution (72). In these instances the Scheme reference of Table II refers to the parent hydroxy compound. [Pg.313]


See other pages where Alcohol-free dichloromethane is mentioned: [Pg.408]    [Pg.408]    [Pg.228]    [Pg.44]    [Pg.77]    [Pg.77]    [Pg.85]    [Pg.295]    [Pg.301]    [Pg.103]    [Pg.13]    [Pg.104]    [Pg.36]    [Pg.81]    [Pg.330]    [Pg.91]    [Pg.8]    [Pg.34]    [Pg.119]    [Pg.880]    [Pg.69]    [Pg.199]    [Pg.191]    [Pg.152]    [Pg.504]    [Pg.282]    [Pg.16]    [Pg.155]    [Pg.188]    [Pg.146]   
See also in sourсe #XX -- [ Pg.408 ]




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Alcohol-free

Asymmetric epoxidation alcohol-free dichloromethane

Dichloromethane

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