Isopropyl methanesulfonate

W. Li, Trace analysis of residual methyl methanesulfonate, ethyl methanesulfonate and isopropyl methanesulfonate in pharmaceuticals by capillary gas chromatography with flame ionization detection. Journal of Chromatography A, 2004,1046(1-2), 297-301. 

The only detailed method of prepn, by distilling a mixt of isopropyl methanesulfonate, KOH in water S hydrogen peroxide at 51° is that of Pryor (Ref 10). Its elemental analysis is dangerous. Ptyor (Ref 8) reported an accidental expl of Di(iso-propyl) -peroxide in the gas phase at ca 200° in an O stream Refs 1) Beil, not found 2) W. Rocke-muller St L Pfeuffer, Ann 537, 178(1939) St CA not found, . ... 

Some or all events leading to sex-chromosome loss or nondisjunction are either not inducible in or not recoverable from some of the germ cell stage.378 However, very few chemicals have been tested, and none in all germ cell stages. Sex-chromosome loss has been shown to be induced by triethylenemelamine in spermatids and spermatozoa, 55 by isopropyl methanesulfonate in primary oocytes within 6 wk of being ovulated,138 and by hycanthone methanesulfonate in primary oocytes within 1 wk of being ovulated.38 ... 

The only detailed method of prepn, by distilling a mixt of isopropyl methanesulfonate,... 

SEC X C57BL)Fi strain can be seen in Table 3 and Fig. 2, showing data obtained from three batches of control mice and two batches of mice treated with 75 mg/kg of isopropyl methanesulfonate at different times. The three control batches involved 18, 24, and 29 females, while the two experimental groups involved 29 and 30 females. As can be seen, the three controls exhibited remarkably similar results, as did the two experimental groups. 

Reactions of ar>l or alkyl bis(siloxy)isopropyl ethers with tetrabutyl-ammoninm fluoride-mesyl fluoride reagent lead to replacement of one siloxy group by fluorine and dehydrosiloxylation, providing an efficient access to fluoroisopropenyl ethers, which are useful as specific building blocks in drug design The reactions proceed via the intermediate allyl methanesulfonates [30, 31] (equation 23)... 

Potassium cyanide has been caused to react with salts and esters of sulfonic acids to give nitriles. Thus, an intimate mixture of finely powdered potassium cyanide with the compound may be fused 422 this method was successfully applied428 to tetrahydrofurfuryl p-toluenesul-fonate and methanesulfonate, but failed with l,2 3,4-di-0-isopropylidene-6-O-tosyl-D-galactose. Another method, consisting of treatment of the ester with a stirred, boiling, saturated, aqueous solution of potassium cyanide gave885 a 70 to 83% yield of nitrile with primary p-toluenesul-fonates (ethyl, n-butyl, and n-octyl) and a 43% yield with a secondary p-toluenesulfonate (isopropyl). Similar methods had been applied earlier98 841 to such simple esters, but have not apparently found use with sulfonic esters of carbohydrates. 

In parallel fashion, compound 267, made from 2,3 5,6-di-<9-isopropyl-idene-D-mannono-1,4-lactone by Reformatsky addition using ethyl bromo-acetate and zinc-silver graphite, undergoes ready elimination when converted to the methanesulfonic ester to give a separable mixture of the E- and Z-alkenes (268).251 Quite a different approach involves treatment of the 1-C-nitromannofuranosyl chloride, derived from the oxime of 2,3 5,6-di-O-isopropylidene-D-mannose, with the anion of diethyl malonate to give the disubstituted alkene 269.252... 

Other studies of selective sulfonylation at a primary hydroxyl group of sugars were made with 5-deoxy-l,2-0-isopropylidene-a-D-xy/o-hexofuranose at —12° to give the 6-p-toluenesulfonate and 6-methanesulfonate. On wanning the reaction mixture to 25°, these derivatives were converted into 3,6-anhydro-5-deoxy-l,2-0-isopropyl-idene-a-D-xyio-hexofuranose. The formation of 2,5-anhydrides on p-toluenesulfonylation of dialkyl dithioacetals of pentoses probably proceeds similarly, through the 5-p-toluenesulfonates. 

Photolysis of 3-thietanone involves both singlet and triplet excited states the initial products are sulfene and ketene, as determined by IR spectroscopy at liquid nitrogen temperatures in a pentane matrix.When the photolysis is done in methanol, isopropyl alcohol, or r-butyl alcohol, these intermediates are trapped as the acetate and methanesulfonate esters. In diphenylmethanol solvent, the bis-diphenylmethyl ether is formed by displacement of the alcohol on the sulfonate ester. Photolysis of tetramethyl-3-thietanone 1,1-dioxide gives dimethylketene. ... 

Isopropyl acetate (IPAc) is much more resistant to hydrolysis than EtOAc in the preparation of the methanesulfonate salts 3 (Figure 4.3) significant amounts of the acetic acid solvates were formed when the solvent was EtOAc, and IPAc was preferred [12], Crixivan intermediate 4 was prepared under Schotten-Baumann conditions by using IPAc at elevated temperatures (Figure 4.4) [13], which suggests the resistance of IPAc to hydrolysis. 

Butyl alcohol t-Butyl alcohol, Isopropyl alcohol, Methanesulfonic acid Silica gel Succinic anhydride dehydrating agent, paints Slllporite ... 

Methyi ester of diethyi borinic acid. See Diethyiboron methoxide Methyi ester of methanesulfonic acid. See Methyl methanesulfonate Methyl ester of rosin, partially hydrogenated CAS 67893-02-1 EINECS/ELINCS 267-605-1 Synonyms Methyl dihydroabietate Methyl 1, 2, 3, 4, 4a, 4b, 5, 6, 7, 8,10,10a- dodecahydro- 7-isopropyl-1, 4a- dimethylphenanthren-1-carboxylate Methyl rosinate, partially hydrogenated Partially hydrogenated methyl rosinate... 

Butyl alcohol t-Butyl alcohol Calcium bromide Isopropyl alcohol Methanesulfonic acid... 

Secondary isotope effects, as we have seen particularly in cormec-tion with eqs. (III-9) and (III-15), are regarded as being predomi nantly zero-point enei y effects. It is thus something of a shock to learn, from the careful investigation of the temperature dependence of the j3-effect on water solvolysis of the isopropyl sulfonates and bromide, performed by Leffek et al. (151), that virtually all of the effect is on the entropy of activation. At 50 C., AAF /n = 46, 47, and 29 cal., respectively, for the tosylate, methanesulfonate, and bromide, of which 45, 50, and 35 cal. are due to This is temperature... 

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