Methylsulfonation

A suspension of 3.90 g (19.6 mmol) of p-(bromomethyl)benzaldehyde (2.8) and 4.00 g (31.7 mmol) of sodium sulfite in 40 ml of water was refluxed for two hours, after which a clear solution was obtained. The reaction mixture was cooled on an ice bath resulting in precipitation of some sodium sulfite. After filtration, the solvent was evaporated. Ethanol was added to the remaining solid and the suspension was refluxed for 10 minutes. After filtering the hot solution, the filtrate was allowed to cool down slowly to -18 °C whereupon sodium (p-oxomethylphenyl)methylsulfonate (2.9) separated as colourless crystals. The extraction procedure was repeated two more times, affording 2.29 g (10.3 mmol, 53%) of the desired product. H-NMR (200 MH D2O) 5(ppm) =4.10 (s,2H) 7.44 (d,2H) 7,76 (d,2H) 9.75 (s,lH). 

Fig. 1 Absorption scan of a chromatogram track with 150 ng of each substance per chromatogram zone 1 = demeton-S-methylsulfone, 2 = dimethoate, 3a = transmevinphos,...

Alternatively, hydration of the acetylenes in cold concentrated sulfuric acid, or with mercury(II) sulfate in formic acid, yields 1-aryl-3,4-dihydro-5//-2-benzazepin-5-ones which are isolated as their methylsulfonate salts.79 If, however, acetylene 4 is stirred with pyrrolidine at room temperature then cyclization is accompanied by amination to give 8-chloro-l-(2-chlorophenyl)-4-(pyrrolidin-l-yl)-3i/-2-benzazepine (5) in high yield. 

Lediglich beim Methylsulfon (R3 = CH3) entstehen nennenswerte Mengen dimere Ketone (bis zu 20% bei einer Keton-Ausbeute von 57-95% d.Th.). 

Dehydrocorticosterone 221 Demeton-S-methyl 362 Demeton-S-methylsulfone 362 Deoxynivalenol 89,147,148 Derivatization, aims 56, 57 -, during development 57 -, for clean up 56 -, in situ 56... 

Synthesis of 5,10,15,20-Tetrakis(4-(polyethyleneoxy)phenyl)) porphyrin. A slurry of polyethylene methylsulfonic ester (PEvoo-OMs) (20.0 g, 69% functionalized, Mn -780 Daltons) and anhydrous cesium carbonate (CS2CO3) (9.05 g, 27 mmol) in dry toluene (75 ttiL) was prepared and to this mixture a purple solution of 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphine (2.9 g, 4.27 mmol) in 75 mL A. A-DMF was added. The reaction mixture was warmed to 95°C with stirring for 18 hours, then the temperature increased to 130°C for a further 5 hours before coohng. The purple-brown solid was collected by filtration, washed thoroughly with methanol and dried under vacuum to yield 21.0 g of the crude ligand, h NMR (toluene-dg, 80°C) 5 8.96 (s), 8.10 (d), 7.22 (d), 4.05 (t), 1.88 (quia), 1.58 (quin.), 1.31 (br. s), 0.88 (t). 

Phenyl methyl ketone 1 was brominated to give l-phenyl-2-bromoethanone 2. Compound 2 was treated with methylsulfonic acid to yield the corresponding methylsulfonate 3. Etherification of 3 gave the a-benzyloxy derivative 4 and compound 4 was then chlorinated to give the 2,4-dichlorinated derivatives in both aromatic ring systems 5. Compound 5 reacted with imidazole in dimethylformamide to give miconazole 6 [7], which is converted to miconazole nitrate. 

Methyl succinyl chloride, ml95 Methylsulfonic acid, m34 Methyl theobromine, cl... 

Synthesis of the oxadiazolopyrimidone 358 was accomplished by reaction of the amide 357 with phosphorus pentoxide and methylsulfonic acid in low yield <1994PHA880>. Also, its benzologue 360 could only be obtained in very modest yield <2004TL8741> in the case, reaction of the benzonitrile derivative 359 with acetylhydrazine resulted in formation of the bicyclic product 360. 

Chlorinated acetones Chloroform Dichloromethane Trichloroethene Chloropropenal Chlorofuranone 1,1-dichloro-methylsulfone Aldehydes Ketones... 

Ki = 0.009 xM CDK2 K[ = 0.007 xM), that was as active as 7b, with the N,N-dimethylsulfonamide 7d (CDKl Ki = 0.077 xM CDK2 Ki = 0.056 xM) that was substantially less potent. These results indicate that at least one sulfonamide H-bond interaction was required for optimal binding to the enzyme. Consistent with this conclusion, the methylsulfone 7e was equipotent (CDKl Ki = 0.08 xM CDK2 K = 0.063 xM) to 7d. 

Japanese workers have also displaced a methyl sulfone group with a variety of nucleophiles. Thus they were able to introduce, ethoxy, thiophenyl, aniline, and malonic acid groups in to the pyridine A -oxide derivative (105). Acid hydrolysis produced the 2-one compound, while reduction with sodium borohydride cleaved off the methylsulfone group <87CPB1030>. 

Domariska, U. and Mazurowska, L., Solubility of 1,3-dialkylimidazolium chloride or hexafluorophosphate or methylsulfonate in organic solvents. Effect of the anions on solubility. Fluid Phase Equilib., 221, 73, 2004. 

Illustrative of the use of methylsulfonate caters for epoxide synthesis are several preparations drawn from the steroid litera-tnj-oMH-ww. i ot, ls 3 j nd depicted in Eqs. (23fi)-(24l). Although other... 

Methylesculetol-6,7-dinicotinate (32) is useful as an antiinflammatory and vasodilator oflow toxicity (101). The synthesis of asarone [5555-15-1] (2,4,5-trimethoxy-l-propenylbenzene), which is used as a tranquilizer, has been patented (102). It occurs in calamus root, Acorns calamus L.y and is a chemosterilant for insects (103). 6,7-Dihydroxycoumarin-4-methylsulfonic acid and its salts are useful in the treatment of capillary permeability and fragility and for protecting oxidizable metabolites and drugs against biooxidation (104). Certain chromones derived from hydroxyhydroquinone, eg (33), and its salts, esters, and amides are valuable in the prophylactic treatment of asthma (105) (see Antiasthmatic agents). 2-Methoxy-6-multiprenyl-l,4-benzoquinones are intermediates in the microbiological synthesis of coenzyme Q compounds (106). 

The New Zealand bryozoan Cribicellina cribraria was the source of several P-carboline alkaloids. One of these examples, compound 34, has a unique methylsulfone substituent. Spectroscopic studies identified 34 as 1-ethyl-4-methylsulfone-P-carboline [34]. Hyrtiomanzamine (35) represents the first example of a 6-OH-P-carboline ring associated with a betaine unit to be obtained from a natural source. This compound was isolated from the Red Sea sponge Hyrtios erecta and its structure was determined on the basis of its spectral data [35]. Compound 35 displayed immunosuppressive activity with an ED50 of 2 mg/ml in the B lymphocytes reaction assay. The lack of cytotoxicity against KB cells indicated that the immunosuppressive activity of 35 is specific and not due to a general cytotoxic effect. 

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