The correct way to mdp2p via performic

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Author	Topic: The correct way to mdp2p via performic
gyrogearloose Member	posted 09-03-99 01:47 AM Courtesy of Mr. LabTop, the elves followed this RXN to sucess . COmbine 16.25 grams of Iso with 50 ml DCE plus 5 Grams sodium BiCarb(sodium Hydrogen Carbonate) let it stirr for 3 hours. Slowly combine 25 grams 86%formic and 38% Hudrogen peroxide and cool to 0 C. then drip slowly(keeping to less than 40 C. until in and stir vigerously for 10 hours. let it sit for one hour in seperatory funnel it will be orange juice color on top and clearish peracid mix on bottom, seperate into new FBF and add 180 grams of 15% H2SO4, boil it to reflux with slight addition of methanol and condenser added. let it cool and extract with DCM, boil off solvent for brown oil that is peppery and cardamon smell. Around 16 grams MDP2P/. aminate to you choice or use it to cure athlete foot. it works easy and is clean and uses less solvents.
Osmium Member	posted 09-03-99 05:47 AM then drip slowly... Which solution is added to which one?
Micr-O-NNN-2 Junior Member	posted 09-03-99 09:07 AM How Much H2O2? 25g?
Acme Member	posted 09-03-99 04:43 PM Gyro you are my new hero. Could you maybe clarify {25 grams 86%formic and 38% Hudrogen peroxide} Is that a 1/1 mixture, 12.5 g 86% formic + 12.5 g 38% H2O2??
samoza Junior Member	posted 09-03-99 05:40 PM This is a direct copy of the Ritter performic as found on Rhodium's site under Peracid methods: performic oxidation with DCM as solvent.
Semtex Enigma Member	posted 09-04-99 12:39 AM If one can use a mixture like 90% GAA and 10% formic, this would lower the cost of the formic considerably. Rhodium, didn't you mention a method(email) that used/uses GAA instead of formic? Was that theoretical or real world? If I remember correctly SWIM tried it once, but something broke, so it couldn't be finished. Thoughts??? Anyone???
Semtex Enigma Member	posted 09-04-99 12:44 AM Opps, wrong thread, I think I meant the good Dr. Sorry...
Rhodium Administrator	posted 09-04-99 09:27 AM Semtex: It was real world, but it was performed by french chemists in the 1800's
gyrogearloose Member	posted 09-05-99 07:44 AM While it is essentially the same info it is not a direct copy, if you follow the directions there you will not get a good yeild. If you follow these directions IE letting the iso, DCE, and sodium bi carb stir for three hours it will all work, You drip the performic into the iso-DCE-SBC mix you have been stiring for three hours. Indeed drip very slowly, took the elves overnight to get it alkl in on a big run. 15.1 grams of the h202 sorry for that leaving out small details drive the elves round the bend but I seem to be prone to it, and the yeild was stomping on this and easy since it seperates on its own when you stop the stirring, Extract the orange juice by vacumn and then go on to easy sucess. Acme no read it again. 25 grams formic and 15.1 grams H202 PS it is very vigerous reaction this way ..
r2d3 Member	posted 09-05-99 02:09 PM Gyro:Why did you change to sodium carbonate to sodium bicarbonate as originally mentioned in the CA? Also you are using over triple the amount of buffer. Was this neccessary?
hellman Member	posted 09-05-99 08:02 PM Gyro, Your post is truly great, as was labtop information, The big questions. 1) Do you know if we can play switcharoo with dce/dcm to say xylene or toluene? 2) What are the rules of scaling, in this reaction. hellman
hellman Member	posted 09-05-99 08:05 PM Oh yeh gyro, A super dumb question, When you seperate the orangey top, You do evap of the dce, before hydrolizing in h2so4, right?. hellman
gyrogearloose Member	posted 09-06-99 01:31 AM R2D3, those were LaBtops instructions and the elves did try the other way as posted in the CA ref, but this way works like stink so they go with it. not being a trained chemist I coulden't say. Still it works out fine. mikey likes it.
dpHarma Member	posted 09-13-99 10:00 PM Gyro very nice! cupl'a q's. 1. time at reflux? 2. amt. methanol? 3. washes after extraction from hydrolysis? 4. yeild of 'crude' or 'distilled' propanone is ~ 16 gm.? 1st. attempt. at dreaming above: starting w/ chilled peracid, stirred flask in ice bath and 'micro-drop' pippette attached to addition funnel provides a 'set and walk away' rxn which dips to ~4^C then slowly rises and peaks at ~23 - 26^C and gradually drops to RT "or less" that's using 50 ml. DCM the stirred sol'n before peracid addition which was done in < 10 min. and dropped temp from RT to ~6 ^C. the ice bath was allowed to melt. 2hrs. after addition complete, temp was 13^C. melted bath water drained reducing thermal mass. 3.5hrs. to peak temp then a loss of 1^C every 35 - 40 min. love those walk away dynamics. noticed iso/DCM/bicarb stirred mixture dropped ~ 2^C below RT!!????? after about 2 hrs. stirring. await your clarifications. way to go. dpHarma
gyrogearloose Member	posted 09-15-99 07:03 AM dpHarma, I suppose you mean reflux at hydrolysis? 2 hrs. methanol 60ml. one wash after hydrolisis elves got 16 grms. on teh temp drop who knows the elves are not chemist, just fun loving elves who like to stay high. otherwise did it go well? The elves like to stir the iso bicarband dce 3 hours first,then go on, nice that drip item, the elves have to sit by and watch it.
dpHarma Member	posted 09-16-99 01:54 AM vac distillation of the peth extraction product yeilded pretty much some isosafrol. as this was the third performic failure in a row, iso-safrol is suspect. must perform tests to verify iso before anything else. can't get to first base if iso ain't. dpHarma
r2d3 Member	posted 09-16-99 02:12 AM Gyro: What good does it do to stir the iso-dce-bicarb solution for three hours, it does't seem to me like too much would be happening, as far as a reaction goes?
gyrogearloose Member	posted 09-16-99 02:47 AM Try the iso method posted by osmium with aliquat 336 and KOH + 80 C for five min. it goes fast and sure. Onec you get good Iso taste it and smell it and keep some on side for comparisons in future, when its right the reaction goes very hot, not as you mentioned, cool then cooler. that says no good iso only saf. You will know when its right its so damn hot you must pay attention all the while its going in or it will get out of control, when your finished the smell of the ketone will stay with you, it smells like vinilla and candy and good things, taste it once just half a drop, I know people think you are crazy, but taking the finished product is just about the same as far as physical effects to your body. If you do this way right you don't need to distill the final product, just wash it once then use.
gyrogearloose Member	posted 09-16-99 02:51 AM r2d3 I don't know, but it works like this, also I observed that the solution color is different this way, and from the start of the peracid addition it is damn hot, slow, slow, slow dripping, the elves want one of the pipettes he talked about, they have to sit and watch this way until its done adding.
dpHarma Member	posted 09-17-1999 12:22 AM Got some glass tubing and a torch? heat a short length in the middle until soft. remove from flame , grasp an end in each hand and pull firmly apart. snap the thin section in half, adjust the length at the wide end w/ a file, scoring a mark and snapping off. adjust legth of thin end by snapping off. if temp was right when pulled out, a capillary of about .01mm will be formed. this will auto regulate the flow from a sep or addition funnel just like an IV system with the little half-full cup just under the bag. if the flow is too slow snap off a bit more. it will be slightly wider as you go up. if too fast, try again. I'll leave off the ice bath next time, til needed. I've always tried to keep performic rxns' below 35^. maybe I should let it get 'closer' to 40. your advice and assistance appreciated dpHarma
dpHarma Member	posted 09-17-1999 01:19 AM may I presume that 16.4gms of 35% H2O2 would suffice? how critical is the conc. of the acid? dpHarma
MERLIN Junior Member	posted 09-18-1999 08:41 AM The maximum result is obtained by using these concentrations,chemicals and procedure. In case you can not obtain the desired concentrations, try to get as close as you can to it. The 3 hour pre mixing is compelling to form a small but highly effective intermediate (discussed before !) which let the following reaction yield so high and clean. Answers: 1.If you use DCM,xylene or toluene you get a not so high yield then with DCE or it even do'nt work at all. 2.Sodiumbicarbonate works way better then sodiumcarbonate. 3.Scale up as far as you want. Batches of 250 kg isosafrole were done this way. 4.Before hydrolizing in 15% H2SO4, you evaporate (no vacuum) off the DCE and stock it for future use. 5.The addition of the peracid must be done in such a way (manual !,do not try to mechanise it), that the dripping rate controls the reaction temperature (36-40C), so use a good tap. If as usual anybody is too impatient, an icebath kept at hand is only used to get the reaction temperature at 36-40C again, then removed. The now convinced experimenter will hopefully not make the same error (hurry) again. 6.To perform your saffrole/isosafrole switch, it is strongly suggested to forget all other methods but the one proposed by Osmium (aliquat) which was excellently performed by Gyrogearloose, as is this one. Quote: Nearly all literature references are worked out under the pressure of a demanding prof/result and that way full of possible enhancements. Believe in your own skills more then that of the publishing chemist, and you will find out better ways to do the hastely writeups and possibly find totally new pathways to the desired endresult. And many officially published refs have blatently errors in them...... ------------------ quote: WISDOMwillWIN
MERLIN Junior Member	posted 09-18-1999 10:21 AM For the safrole/isosafrole swap, go to: http://hive.lycaeum.org/ubb_board/Forum3/HTML/000853.html For safrole proprietors,this is the sure way to success: 1.Buy safrole >98% 2.Make isosafrole as above. 3.Make MDP2P as per this thread. 4.Make MDMA/MDA/MDEA/MDE etc. as per One Pot NaBH4.For maximum results, dry all your solvents extensively. The one's who can buy their MDP2P will know what to do with it by now. ------------------ quote: WISDOMwillWIN
dpHarma Member	posted 09-18-1999 04:08 PM how much of the chilled performic aicd is dripped in 'initially' or is the same slow steady rate perfomed from start to finish? How likely is DCM to fail completely, and how much less yeild is expected using it? thanks for the kind answers. btw re: DCM see new thread in Aquistions dpHarma
Jiggs Member	posted 09-18-1999 06:54 PM Thanks for the tips on improving the performic. Merlin or somebody: please post a brief 4 line review of the NaBH4 recipe. I have a hassle with the many different variations of it.
Jiggs Member	posted 09-18-1999 06:59 PM Can you use the NaBH4 with methylamine hydrochloride rather than 40% aq.?
gyrogearloose Member	posted 09-18-1999 11:07 PM The drip rate must be controlled by the thermic reaction rate.Keep in mind that the reaction time will lag behind the drip rate. Be careful at first, until you find a good rate, the elves use a pressure equalized addition funnel , they watch it very carefully until all is in, even then they continue the watch for latent exothermic reactions. The danger in cold addition is that when it warms to RT it may have a violent thermic reaction, so care must be taken when using cold. The elves never leave the reaction until it starts to cool on its own. As for the DCM question the elves have used both, same results. ON the methylamine HCL question, yes you can but better to put it in some methanol, then add NaOH slowly, the HCL will go off as a salt in the bottom and you will have methanolic methylamine solution, you will get a lot of salt so use big flask.
hellman Member	posted 09-19-1999 09:26 PM Thankyou Merlin,er.... Your response is exactly what we need to hear,. Man, Dpharma question rings strong,. Why can't we use dcm,. And what happens?. Even if we condense the escaping vapour?. thankyou MERLIN, hellman
hellman Member	posted 09-19-1999 09:28 PM Please ignore the bottom half of my question, about the dcm subs. gyro answered it, hellman
sparks Junior Member	posted 09-22-1999 07:12 AM Is it normal for the postoxidation/prehydrolysis product from this oxidation to be of a more pale yellow/orange colour than from the more traditional performic method. Very little raise in temp was also noted. Maybe this turns out to be a fruitless dream (like Emerdale farm).
sparks Junior Member	posted 09-22-1999 07:15 AM Oh, btw, anethole was (not) used.
dpHarma Member	posted 09-22-1999 11:31 AM ". Around 16 grams MDP2P/. aminate to you choice or use it to cure athlete foot." May one assume that the results after only a single wash may be aminated 'as if' it were 16 gms. pure ketone. what is a 'typical' yeild on a 'typical' reduction? are we getting damn close to a 'quantitative' yeild from safrol or what? regarding the carbonate(hydrogen), almost exactly a year ago, Beagle Boy posted a reaction which "he overheard in a bar". it had the alkene, DCM, carbonate stirring, H2O2 was added and heated to 40^C then formic added SLOWELY through the condensor. to my knowledge, no one ever discussed this at any length. I recently stumbled accross an Aldrich product called Hydrogen Percarbonate adduct. perhaps, it works like this.(remember I'm not a chemist) the carbonate stirred with the iso-alkene, forms some intermediate, with the carbonate attached to the double bond. the H2O2 when added and heated, forms the percarbonate, which directs the formic to the double bond, and keeps it from acting as a reducing agent. just some probably pointless ideas, but what the hey? a second wild idea is the addition of a bit of PTC to the stirring DCM/iso/bicarb. could improve miscibility when peracid is added. any comments? dpHarma

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