Methyl sulfate, reactions

Reactions of the Hydroxyl Group. The hydroxyl proton of hydroxybenzaldehydes is acidic and reacts with alkahes to form salts. The lithium, sodium, potassium, and copper salts of sahcylaldehyde exist as chelates. The cobalt salt is the most simple oxygen-carrying synthetic chelate compound (33). The stabiUty constants of numerous sahcylaldehyde—metal ion coordination compounds have been measured (34). Both sahcylaldehyde and 4-hydroxybenzaldehyde are readily converted to the corresponding anisaldehyde by reaction with a methyl hahde, methyl sulfate (35—37), or methyl carbonate (38). The reaction shown produces -anisaldehyde [123-11-5] in 93.3% yield. Other ethers can also be made by the use of the appropriate reagent. 

The nitration of l,2,5-selenadiazolo[3,4-/] quinoline 77 with benzoyl nitrate affords the 8-nitro derivative 78, whereas methylation with methyl iodide or methyl sulfate afforded the corresponding 6-pyridinium methiodide 79 or methosulfate 80, respectively (Scheme 29). The pyridinium salt 80 was submitted to oxidation with potassium hexacyanoferrate and provided 7-oxo-6,7-dihydro derivative 81 or, by reaction of pyridinium salt 79 with phenylmagnesium bromide, the 7-phenyl-6,7-dihydro derivative 82. Nucleophilic substitution of the methiodide 79 with potassium cyanide resulted in the formation of 9-cyano-6,9-dihydroderivative 83, which can be oxidized by iodine to 9-cyano-l,2,5-selenadiazolo [3,4-/]quinoline methiodide 84. All the reactions proceeded in moderate yields (81IJC648). 

This procedure illustrates formylation by N,N-dimethylamino-methoxymethylium methyl sulfate, a compound which can be produced readily by reaction of easily available materials. 6-(Dimethylamino)fulvene is a useful intermediate for the synthesis of various f used-ring nonbenzenoid aromatic compounds. 

The reaction of alkyl sulfates with alkoxide ions is quite similar to 10-12 in mechanism and scope. Other inorganic esters can also be used. One of the most common usages of the reaction is the formation of methyl ethers of alcohols and phenols by treatment of alkoxides or aroxides with methyl sulfate. The alcohol or phenol can be methylated directly, by treatment with dimethyl sulfate and alumina in cyclohexane. Carboxylic esters sometimes give ethers when treated with alkoxides (Bal2 mechanism, p. 473) in a very similar process (see also 10-24). 

Amide 138 undergoes N-methylation by reaction with methyl iodide furnishing compound 139. However, the reaction with dimethyl sulfate provides O-methyl derivative 140 (Scheme 1) <2002CHE828>. 

Potassium 4-chloro-3,5-dinitrobenzene-sulfonate, 31, 46 Potassium cyanate, 31, 9 Potassium cyanide, 30,84 32,31,63 37,47 Potassium ethyl malonate, 37, 34 Potassium ethyl xanthate, 30, 56 Potassium fluoride, 36, 40 Potassium iodide, 30, 34 31, 31, 66 Potassium metal, 37, 29, 30 Potassium methyl sulfate, 31, 73 Potassium nitrate, 31, 46 Potassium 1-nitropropylnitronate, 37, 24 Potassium oxalate, 34, 83 Potassium permanganate, 30, 87 31, 59 Potassium sulfide, 32, 103 Potassium thiobenzoate, 32, 101 Potassium thiocyanate, 32, 39, 40 Prins reaction, 33, 72 Propane, 1, 3-dibromo-2, 2-Ws-(bromo-methyl)-, 31, 82... 

Agar may be acetylated with pyridine and acetic anhydride and the resultant acetyl derivative readily converted into the corresponding methyl ether by reaction with sodium hydroxide and methyl sulfate ... 

The lithio derivatives of dibenzofuran undergo the expected reactions. Carbonation yields carboxylic acids,reaction with sulfur dioxide yields sulfinic acids, and reaction with methyl sulfate yields methyl compounds. Alkylation can also be achieved by treatment of 4-lithio-dibenzofuran with alkyl halides. Silylation can be achieved with chlorotrimethyl- or chlorotriphenylsilane. " " Reaction of lithiodibenzo-furans with acetaldehyde and with benzonitrile take the expected course. 

Werner [10] suggested that, on heating, urea tautomerizes to the pseudourea structure which, on reaction with methyl sulfate, allows the isolation of 2-methylpseudourea (Eq. 22). The product was difficult to crystallize and it was isolated as the picric acid derivative. 

Werner [10] later found that urea reacts with methyl sulfate to give 2-methyl-pseudourea, but the isolation of the product from the syrup is difficult and is usually done via the picrate. The reaction is usually carried out at about 40°C (7 hr) because at temperatures above 100°C the reaction is too violent [11] (Eq. 5). 

To a flask containing 60 gm (1.0 mole) of urea is added 126 gm (1.0 mole) of methyl sulfate, and the stirred reaction mixture is warmed for 7 hr at 40°C. Stirring is continued until the reaction mixture is clear. The O-methylisourea is isolated as the picrate salt by adding 350-400 ml of 2 M lithium picrate in 300 ml of ethanol. The resulting mixture is boiled on the steam bath for 5 min. Most of the picrate dissolves but precipitates on slowly cooling to 0°C. The picrate is filtered, washed with ethanol, and air-dried to afford 182 gm (60%), m.p. 177°C. 

Methylfluorene has been prepared by cleavage of ethyl 9-methyl-9-fluorenylglyoxylate,4 by the decarboxylation of 9-methylfluorene-9-carboxylic acid,4 by the decarboxylation of 9-fluorenylacetic acid,6 by the cleavage of 9-methyl-9-acetyl-fluorene with alcoholic potassium hydroxide or soda-lime,6 by the reduction of 9-methyl-9-fluorenol with hydriodic acid in acetic acid,7 by the reaction of 9-fluorenyllithium 8 or -sodium 9 with methyl iodide or methyl sulfate,9 by the cyclization of diphenylmethyl carbinol over platinum-on-carbon at 300°,10 by the reaction of ethyl 9-methoxymcthyl-9-fluorcnylcarboxylate,11 by the diazotization and heating of 2-ethyl-2-aminobiphenyl,12 by the dehydration and then reduction of 9-mcthyl-9-fluorcnol,13... 

The methyl ether of cellulose has a methoxyl content which varies between 6 and 33 %. Methylcellulose can be prepared by the action of methyl chloride or methyl sulfate on cellulose that has been previously treated with alkali. Purification is accomplished by washing the reaction product with hot water. The degree of methylation can be controlled to yield products with varying viscosities. Seven viscosity types of methylcellulose are currently produced with centipoise values ranging from 10 to 4000. Methylated cellulose of low methoxy content is soluble... 

Lithiation of dibenzofuran with butyllithium and mercuration both occur at the 4-position. Thallation occurs at the 2-position, however (57IZV1391). The mercury and thallium derivatives serve as a source of the iodo compounds by reaction with iodine. Bromodibenzofurans undergo bromine/lithium exchange with butyllithium and the derived lithio compounds may be converted into phenols by reaction with molecular oxygen in the presence of a Grignard reagent, into amines by reaction with O-methylhydroxylamine, into sulfinic acids by reaction with sulfur dioxide, into carboxylic acids by reaction with carbon dioxide and into methyl derivatives by reaction with methyl sulfate (Scheme 100). This last reaction... 

To a solution of benzaldehyde (1.06g. lOmmol) in CH2CI2 (10ml) were added trimethylsulfonium methyl sulfate (2.17 g, 11.5 mmol) and 50% aqueous NaOH (5 ml). The reaction mixture was magnetically stirred at room temperature for 2.5 h. Water (20-30 ml) was added and the organic phase was decanted. The aqueous phase was extracted twice with ether (2 X 20ml). The combined organic solution was washed twice with water and dried (CaCl2). The solvents were evaporated under vacuum (rotatory evaporator, cold bath) and the epoxide distilled (l-2g, 80%), b.p. 82°C/38 torr. 

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