writeup by bandil, taken from the vespiary!! i am aware theres another thread 4 the DOx series as a whole, but this seems 2 b a different method from the one listed there. feel free 2 delete this thread if im wrong tho >_<
About 30 grams of dimethoxytoluene, were prepared as described in an earlier post, via the TMP route in high yields. While the dimethoxytoluene was distilling, the Vilsmeier complex was prepared in the following manner:
A very old can of DMF was dried by dumping several grams of dry sodium sulfate in it and shaking for a few minutes. After settling, 45 mL's of DMF were placed in an 500 mL RBF and stirred magnetically. 40 mL's of not so new POCl3 were added in one portion to the DMF via an addition funnel. The solution was stirred for 1½ hours at room temperature where it gradually turned deep orange, which indicated a successful formation of the Vilsmeier complex.
To this mixture was added 15 grams of the freshly distilled dimethoxytoluene in one portion. The addition funnel was replaced with a condenser with attached drying tube. The whole lot was stirred at RT for 15 mins, and placed in boiling water afterwards for two hours. It gradually darkened and by the end of the two hour period it was pitch black. The whole mess was dumped into 1½ L of cold tap water with lots of ice in it. This turned a nice orange color immediately and smelled like the substituted benzaldehydes tend to do (sweet). This was filtered when the ice had melted. This whole solution was suction filtered to give 4 grams of 2,5-dimethoxy-4-methyl-benzaldehyde. The yield was on the low side, but subsequent examination of the filtered water sludge showed that a lot more had precipitated. It's always hard to judge how much is floating around in a slurry mess, but it just might be enough to bring the yield closer to 12 grams or so, making it quite a feasible synth. As always patience is a great asset in these types of operations - maybe swim will also learn someday
The final yield will be posted once measured properly filtered, measured etc.
The BA was without further purification subjected to condensation alá Barium. 4 grams Ba, 1.9 grams nitroethane, ½ mL 40% methylamine, 10 mL methanol and worked up in the usual manner. Worked like a charm and gave 4.6 g (87% yield) of quite purified nitropropene [fidelis note: i think he means P2NP when he says nitropropene].
3.7 g LAH was placed in 64.5 mL's of THF and placed on a magnetic stirrer. To this I added 4.6 grams of the nitropropene in 64.5 mL's THF. This mixture was left to reflux overnight and will be purified in a few hours. This will -in theory- of course be tested severely during the forthcoming festival. Swim will report the results back.
All in all, DOM was prepared from scratch (almost) in one day's work. Pretty neat if you ask swim
If anyone has some comments of the somewhat modified Vilsmeier reagent that was prepared, please do post them. It was a combination of the indole Vilsmeier from rh's page [fidelis note: rhodium's page? not sure] and some from PIHKAL etc... Seems it worked ok though!
Final yield was 3.2 grams of the hydrochloride as -not so white- substance.
About 30 grams of dimethoxytoluene, were prepared as described in an earlier post, via the TMP route in high yields. While the dimethoxytoluene was distilling, the Vilsmeier complex was prepared in the following manner:
A very old can of DMF was dried by dumping several grams of dry sodium sulfate in it and shaking for a few minutes. After settling, 45 mL's of DMF were placed in an 500 mL RBF and stirred magnetically. 40 mL's of not so new POCl3 were added in one portion to the DMF via an addition funnel. The solution was stirred for 1½ hours at room temperature where it gradually turned deep orange, which indicated a successful formation of the Vilsmeier complex.
To this mixture was added 15 grams of the freshly distilled dimethoxytoluene in one portion. The addition funnel was replaced with a condenser with attached drying tube. The whole lot was stirred at RT for 15 mins, and placed in boiling water afterwards for two hours. It gradually darkened and by the end of the two hour period it was pitch black. The whole mess was dumped into 1½ L of cold tap water with lots of ice in it. This turned a nice orange color immediately and smelled like the substituted benzaldehydes tend to do (sweet). This was filtered when the ice had melted. This whole solution was suction filtered to give 4 grams of 2,5-dimethoxy-4-methyl-benzaldehyde. The yield was on the low side, but subsequent examination of the filtered water sludge showed that a lot more had precipitated. It's always hard to judge how much is floating around in a slurry mess, but it just might be enough to bring the yield closer to 12 grams or so, making it quite a feasible synth. As always patience is a great asset in these types of operations - maybe swim will also learn someday
The final yield will be posted once measured properly filtered, measured etc.The BA was without further purification subjected to condensation alá Barium. 4 grams Ba, 1.9 grams nitroethane, ½ mL 40% methylamine, 10 mL methanol and worked up in the usual manner. Worked like a charm and gave 4.6 g (87% yield) of quite purified nitropropene [fidelis note: i think he means P2NP when he says nitropropene].
3.7 g LAH was placed in 64.5 mL's of THF and placed on a magnetic stirrer. To this I added 4.6 grams of the nitropropene in 64.5 mL's THF. This mixture was left to reflux overnight and will be purified in a few hours. This will -in theory- of course be tested severely during the forthcoming festival. Swim will report the results back.
All in all, DOM was prepared from scratch (almost) in one day's work. Pretty neat if you ask swim
If anyone has some comments of the somewhat modified Vilsmeier reagent that was prepared, please do post them. It was a combination of the indole Vilsmeier from rh's page [fidelis note: rhodium's page? not sure] and some from PIHKAL etc... Seems it worked ok though!
Final yield was 3.2 grams of the hydrochloride as -not so white- substance.
