psyloxy (Hive Addict) 09-23-03 22:41 No 460607				DMS methylation of toluhydroquinone in 90%+ yield
						2,5-dimethoxytoluene In a dry 3-neck 1L rb flask equipped with a mag stirring bar, two stoppers, a reflux condensor, and a N2 inlet was placed 2,5-dihydroxymethylbenzene (49.6g, 0.4 mol). To the flask was added 300 ml of ethanol, and the soln was slightly heated with a mantle until the solid dissolved. The heating mantle was then removed and the soln was allowed to cool to room temp. Over a period of 20 min, DMS (? mol) and 100ml of an aqu. NaOH soln (~10 M) were added to the reaction mixture. The heat released was sufficient to bring the solution to boil. After this step was completed, NaOH (10g 0.25 ml) in 10 ml of water was added to the solution to make it alkaline. When the boiling subsided, the heating mantle was replaced and the reaction mixture refluxed for 7h. The reaction mixture was checked by TLC and then transferred to a separatory funnel. The organic fraction was extracted with Et2O and washed with sat. aqu. NaCl soln. The resulting solution was dried with MgSO4, filtered, and then concentrated on a Rotovap. The product was then subjected to flash chromatography (20% ether, 80% hexane), yielding a light yellow liquid: yield 53.3g (93,9%). Ref: Bae, I. T.; Sandifer, M.; Le, Y. W.; Tryk, D. A.; Sukenuk, C. N.; Scherson, D. A.;ANCHAM; Anal.Chem.; EN; 67; 24; 1995; 4508-4513. EDIT: I first believed this to be a methylation rxn using DMSO but apparently they used DMS, so this is nothing really exciting. --psyloxy--
		Bandil (you can always take some more) 09-23-03 23:01 No 460613				Is this for real??
						Do they really mean dimethylsulfoxide and not dimethylsulfate?? If it is, then i'd have to call that a seriously good find. Can you dig out the article so we can read the whole thing? It would be nice to know if it was a general methylating method. DMSO is practically drinkable compared to DMS Looking forward to read more about it! Edit: crap Regards Bandil I just love the smell of bromine in the morning!
		Lilienthal (Moderator) 09-23-03 23:54 No 460619				It's a typo in that paper...
						It's a typo in that paper... I'm pretty sure they used DMS = dimethylsulfate.
		psyloxy (Hive Addict) 09-24-03 00:33 No 460627				Oh well, no breakthru for today...
						God, I'm feelin so ashamed - that rxn scheme doesn't make any sense at all, now that I have a sobered look at it. Well I guess disillusionment really is a positive state of being. And I even thought I dug up the ultimate wonder-rxn --psyloxy--