Author Topic: Antibody2's Acidic Al/Hg - MDOH vs MDA (Read 2339 times)

NeilPatrickHarris · « **Reply #20 on:** October 22, 2010, 07:08:34 PM »

Quote from: RoidRage on October 19, 2010, 07:38:51 PM

Damnit....Retried the oxime formation and only got 2g of Wet oxime from 9g of ketone...There is definitly a problem somewhere...Anybody got ideas...I'd rather ask here than start a new thread lol

that's the recovered ketone from the failed AcOH al/hg? maybe the low yields were because if the oxime reverted back to ketone + hydroxylamine then the ketone was reduced to alcohol, leaving only a little bit of actual unreacted ketone. taking a guess. swim has never had an oxime revert back to ketone before and he's put his oxime in neutral water and slightly acidic water with no change in the oxime. swim has very limited experience here though and it was a different oxime, an aldoxime not a ketoxime

RoidRage · « **Reply #21 on:** October 22, 2010, 11:11:33 PM »

Quote from: NeilPatrickHarris on October 22, 2010, 07:08:34 PM

Quote from: RoidRage on October 19, 2010, 07:38:51 PM
Damnit....Retried the oxime formation and only got 2g of Wet oxime from 9g of ketone...There is definitly a problem somewhere...Anybody got ideas...I'd rather ask here than start a new thread lol

that's the recovered ketone from the failed AcOH al/hg? maybe the low yields were because if the oxime reverted back to ketone + hydroxylamine then the ketone was reduced to alcohol, leaving only a little bit of actual unreacted ketone. taking a guess. swim has never had an oxime revert back to ketone before and he's put his oxime in neutral water and slightly acidic water with no change in the oxime. swim has very limited experience here though and it was a different oxime, an aldoxime not a ketoxime

No It's only with retry of the oxime formation. I only tried the AcOH al/hg once with what I though was the oxime, but seems like it wasn't the oxime since it dissolved in water. I still got like 100mg of MDA/MDOH but it's probably because the product I reduced was probably contaminated with some actual oxime. This reaction is starting to give me headaches. It's so straightforward on paper but I've ran it 6 times so far with differents reactions conditions, and it failed. Actually I'm not sure it failed on the last try, I've got some white goo currently drying lol.

NeilPatrickHarris · « **Reply #22 on:** October 23, 2010, 12:54:06 AM »

have you used this same exact olefin from the same bottle to successfully make mdxx using a different procedure? so you know the oil is what it's supposed to be

what was the procedure you used to make the ketone and did you do a bisulfite test? supply as many details as you can or at least a general overview. i'm guessing you vacuum distilled the ketone as the purification method right?

do a mp on the oxime after it's completely solidified the mp is supposed to be 86-87C

RoidRage · « **Reply #23 on:** October 23, 2010, 01:09:47 AM »

Good question...

I never actually did MDxx with this batch of olefin. Melting and boiling points are on par though so I don't think it's the problem. I used the wacker oxidation to synth. my ketone, as I always did. I didn't use the bisulfite test, never had. My thermometer is broken so I don't know at which temp the ketone came over, but it was strangely high. Odor is normal. Color is a bit clear though. Always have been kinda clear with previous successful runs though when it has been extracted with toluene instead of DCM. Never had a neon green ketone with toluene extraction for unknown reasons.

Thanks for helping

NeilPatrickHarris · « **Reply #24 on:** October 23, 2010, 03:04:41 AM »

swim always uses toluene to extract ketone and it comes over fluorescent yellow also, swim has never had green. a friend of swim's used to have a relatively weak vacuum pump and distilled ketone at around 180C or maybe even a little higher, can't remember exactly. but i recall him saying it would distill over clear, it was made via benzo wacker and extracted with DCM same as MM's writeup except it was distilled at a high temp and came over clear. it reduced to amine just fine. you can test for the md bridge with h2so4 if i remember correctly, somebody may have to post some more info b/c i don't remember the expected color change of the test. another option is to take a little bit of that starting oil if there is any left and do a congealing test. the mp is 11C for pure safrole

best thing to do in this situation is to start from the start and test each step of the way. so test to see if it's really safrole by doing a mp test or if we can dig up more info on the old h2so4 test that i can't remember the exact details of it off the top of my head. then take a sample of the ketone and do a bisulfite test, you only need to sacrifice a few drops, and as stated above test a little sample of the suspected oxime to see what the mp is. problem is, all this stuff will require a thermometer and if yours is broken then there isn't much you can do aside from reagent tests

RoidRage · « **Reply #25 on:** October 23, 2010, 04:25:38 AM »

Thanks for your fast reply

I'm currently exactly doing that. I'm distilling safrole from the start (I got this batch directly as safrole, not as sassy oil, so I didn't bother distilling it.) I'm not too sure if I can trust the guy so it's a good idea to redistill it. My vacuum pump is pretty strong so It distill a lot lower than that. It distilled at a really high temperature last time as I said though. I was worried it was my vacuum pump but it isn't. I can't exactly tell you the temp at which it came over since my thermometer is broken as I already said, but the oil pump bath was at about 205, which is anormaly high. I tested everything with H2SO4 and marquis reagent and everything is alright.Troubleshooting this all isn't evident without a damn thermometer though. I don't have access to GC/MS, HPLC, NMR right now some it's sometimes tricky to confirm. The safrole did crystallize at fridge temp though.

As I said though, I have some white paste that is drying that I suppose is the oxime. I don't have bisulte in stock right now to try the test.

Did you try the oxime reaction yourself ? I'm embarassed to admit that I wasted mucho ketone on this reaction without any success. I'm no newbie and never had any problems with other reaction, but this one is puzzling me. Strange since it's so straightforward on paper. Troubleshooting an organic reaction is fun but tricky

NeilPatrickHarris · « **Reply #26 on:** October 23, 2010, 04:33:02 AM »

swim has only done oximations on an aldehyde, he's never done the oximation on mdp2p. if you're interested in finding bisulfite check your local home brewery and wine places, sodium metabisulfite is very common in those places and substitutes for sodium bisulfite but you may know that already. one thing you can do without a thermometer is a very crude mp test on the oxime once it's finished drying. prepare a boiling water bath (you'll know it will be 100C) then put a tiny bit of oxime in a test tube or beaker or whatever and suspend it in the water bath, the contents in the test tube/beaker/etc should hopefully be just barely hot enough to watch the oxime melt. i'm not sure if it decomposes or melts at 86-87C but hopefully the water bath will be hot enough to get some type of indicator out of it

RoidRage · « **Reply #27 on:** October 23, 2010, 04:36:38 AM »

Sorry I remember I told me in your last post that you already tried it on an aldehyde lol. My short term memory absolutly sucks it seems

. That's already what I planned to do with the oxime, it's the best I can do. The problem with reagent test is that it's pretty unprobable I get a product without an MD bridge unless I destroy it for an unknown reason, which is also pretty unlikely with the reaction I'm using. Anyway I'm thinking this too much...

RoidRage · « **Reply #28 on:** October 23, 2010, 04:41:15 AM »

I'm still puzzled to know how I ended up with a bit of MDA lol. Aas far as I know, no other molecule could have gone through an acid-base extraction. Ph of toluene before adding Hcl was about 10-11. 1ml of 32% bringed the pH to 1-2, so I knew there wasn't a lot

. Powder also had the taste of MDMA and bioassay was successful, while only being sadly thresold.

NeilPatrickHarris · « **Reply #29 on:** October 23, 2010, 04:46:20 AM »

yeah your options are pretty limited without a thermometer but let us know how the mp test goes. that's really strange that your oxime dissolved in water, swim has no experience with this particular oxime but that's really weird that it dissolved in water because the oxime is created in alcohol (EtOH or MeOH, swim prefers 95% EtOH) and is precipitated out by flooding with water, so the oxime dissolving in water goes against it's solubility at the end of the oximation. i can't remember if i asked this already or not, but did the water have a neutral pH when the oxime dissolved in it or did it dissolve in an acidic AcOH solution? i'm not sure of the mdp2p oxime's solubility in AcOH or alcohols but the workup for the oximation states it should be insoluble in neutral and basic water (i get those assumptions because it precipitates out from basic water and because when the oxime is solidified it is washed with neutral cold water)

RoidRage · « **Reply #30 on:** October 23, 2010, 04:51:20 AM »

It dissolved in the water with the ''oxime'' I reduced, which I why I find weird I ended up with MDA. For your information, I didn't check pH of oximation reaction mixture.

Quote

In this example anethole ketone was used to form anethole ketoxime, but the amount of MDP2P is the given and in the end it will give a similar yield. Detailed notes on using isosafrole ketone aren't in my lab book as the procedure is straight forward and I never thought it necessary to take notes.
Added a 1" magnetic stirbar, 14ml dH2O and 6.7g Na2CO3 (126mmol base, 1.35 equiv) to a 250ml round bottom flask. Start stirring and add 9.6g (NH2OH)2.H2SO4 (116mmol hydroxylamine in the salt, 1.25 eq). Allow this to stir until uniform and add 72ml MeOH and 15.3g PMP2P (93mmol phenylacetone, 1 eq - or 16.6g MDP2P). Refluxed for 60 mins then added 37ml cold water. A white sludge settles to the bottom of the flask. This is not the oxime. Move this to the freezer for one hour. Remove and shake. Crunchy crystals of ketoxime should form. Do not confuse this with a thick sludge that always forms. Suction filter the solution and wash the crystals with 186ml of cold water. If you go to filter before the crystals form, you will see an oil form in the filter flask, this is your oxime that failed to crystallize. The yield of white anethole ketoxime in this example was 14.6g (87% yield). Expect a higher yield! I accidentally spilled some oil in transferring it... Isosafrole ketoxime has always been prepared in just as good yields, but has always turned out an off-white color. No purification was ever used before proceeding to the reduction. Make sure the oxime is bone dry--this can take days--before you take the yield and progress to the reduction. Also note that other substitutions for the hydroxylamine source, other alcohol solvents and other bases (baking soda, sodium acetate, etc) have worked just as well when in equimolar amounts.

What is underlined is actually the product I ''reduced'' the first time. I didn't flood the post-reaction mixture with water. The oxime I'm not drying is insoluble in water.

NeilPatrickHarris · « **Reply #31 on:** November 18, 2010, 01:06:31 PM »

when it comes to drying, this oxime is much more of a pain in the ass than [a different] oxime. here is the difference noted, the [other] oxime is easy to get to solidify from a paste to an amorphous crumbly solid over the course of a day. the mdp2p oxime seems to take exponentially longer, it's been a day and it's a little more dry but still more of a solid with a somewhat paste-like consistency than anything. posts on the old hive archives by madprosr state that it takes him anywhere from 1-7 days of leaving the oxime out and working it around periodically before it dries well enough to crumble apart, his average seemed to be around 5 days. other bees tried drying it under strong vacuum without much luck. another bee tried drying it with low heat and said his oxime kept melting even though it was nowhere near ~80C, but he was having problems with his oxime anyway i think it was a purity issue.

i believe reason for [the other] oxime solidifying so much faster and mdp2p's oxime taking much longer is due to purity as well. i think that presence of isosafrole is probably the problem here. does anyone have any tips on getting the oxime to dry faster? probably stay away from heat and just put a fan over it i'm guessing

RoidRage · « **Reply #32 on:** November 18, 2010, 04:28:23 PM »

Quote from: NeilPatrickHarris on November 18, 2010, 01:06:31 PM

does anyone have any tips on getting the oxime to dry faster?

I've ran more runs since last time, and dryness doesn't seems to affect yield, beside the fact it's a pain in the ass manipulating. In my case, it was still really sticky after 4-5 days.

RoidRage · « **Reply #33 on:** November 27, 2010, 01:47:41 AM »

Hey NeilPatrickHarris, any luck yet with the oxime reduction ? Did you find a way to dry the oxime faster...I'm interested to know how it wents out for you

NeilPatrickHarris · « **Reply #34 on:** December 01, 2010, 01:12:11 PM »

Quote from: RoidRage on November 27, 2010, 01:47:41 AM

Hey NeilPatrickHarris, any luck yet with the oxime reduction ? Did you find a way to dry the oxime faster...I'm interested to know how it wents out for you

yep, got just over 4g of the purified hcl salt from 9.4g still slightly-wet oxime. there is definitely room for improvement cuz those yields suck, i had to use some very mild external cooling briefly at the beginning as the reaction progressed more aggressively than i was expecting it to. i think next time i'll try to stay away from any external cooling and see if yields improve. i'll also gas next time without recrystallization because this time i over-titrated and had to recrystallize

NeilPatrickHarris · « **Reply #35 on:** December 19, 2010, 06:20:30 AM »

i posted this in a different forum but got no response, i'm hoping somebody might have some input on the reason for such low yields with this reaction. ran my first acidic al/hg a little while back and got low yields. approximate yield using this ketone in a MM nitro al/hg is usually ~60-65% w/w purified salt from vac distilled benzo wacker ketone, so it was surprising to see such a low yield with the oxime reduction. the oximation that was ran was with 10g ketone and yield was 9.4g ketoxime. not sure why there was such low yields. it was run it like chromic and madprossor ran it (see the first page of this thread for copy/paste details on their trials), their procedure was very similar to the MM nitro al/hg from a procedural standpoint.

but here's my question - any ideas as to why i got bad yields through this method? it's always small scale so i "kick off" amalgams with external heat, it causes the amalgamation to begin within 1-5 minutes everytime and works beautifully with great yields on the MM nitro al/hg so i did the same here. one thing i was unsure about is that i kept bouncing back and forth as to whether i should apply external heat or not after addition was complete. another thing i was unsure about was whether to add the oxime all at once and which to add first (oxime or AcOH), they were both added so close to each other i wouldn't think that would matter. i ended up adding all the oxime at once then all the AcOH immediately following the oxime. i did not do a mp test on the oxime but it is documented as having a low mp. since EtOH is the solvent used so perhaps the small amount of additional water or AcOH present allowed the solution's temperature to exceed the bp of EtOH or perhaps the EtOH superheated? that's an uneducated guess on my end, trying to look for an explanation, b/c if the solution's temperature was higher than the mp of the oxime then maybe some ketoxime reverted back to ketone? i'm really grasping at straws here.

Quote

ambient temp: 62F
   day 1:
   6:00am
after 3 days of sitting out, the white oxime looks dry/crumbly and only a few small parts are a little sticky/pasty still. the stickier the oxime is the more may be lost as it's not easy to scrape up and it gets stuck to everything. put a 1L 3-neck RBF in a water bath and added a large stirbar. charged the RBF with 0.06g HgCl2 (0.000224 moles), 145.8g/184.8ml 96% EtOH, and 17.7g/17.7ml H2O. stoppered all the necks. the HgCl2 dissolved immediately, let it continue to stir anyway b/c had to run errands.
   9:00am
weighed out 60ml ~85% EtOH Solution (42g/53ml EtOH + 7g/7ml H2O), swirled real well then divided the 60ml 85% EtOH solution equally between 3 jars, this is so that it can be used to dilute the reaction in 3 different additions later when it gets too thick. covered the jars with al foil to prevent evaporation. weighed out 24.8g/23.6ml Glacial Acetic Acid (0.41352 moles) in a jar, covered very tightly with al foil (pinched the edges) to prevent smell.
   9:30am
attached reflux condenser fed with cold water to RBF, turned heat to 4, turned stirring to 5
   10:00am
water bath temp is 121F, turned heat up to 5.5
   10:15am
water bath temp is 149F, added tons of ice to the water reservoir bucket to cool the condenser's recirculating water, turned off heat
   10:19am
added 11.3g Aluminum Foil (0.41790 moles) through the side neck, instant amalgamation which stopped the stirbar
   10:21am
added 9.4g MDP-2-P Oxime (0.04865 moles) then immediately added 24.8g/23.6ml Glacial Acetic Acid (0.41352 moles), the oxime just disappeared in the al foil and froth, never to be seen again =)
   10:22am
water bath temp is 150F, the solution began to bubble and froth like absolute crazy, it's running really hot right now and seems to be picking up even more momentum. the froth is nowhere near coming close to the neck of the flask, it's barely even at the halfway point at best, however the solution is getting VERY thick, so i added the first dilution of EtOH (20ml 85% EtOH). swirled the flask by hand as much as possible since stirring is stopped. added 5-6 ice cubes from the reservoir to the water bath to cool the reaction a little bit
   10:24am
water bath temp is 124F due to the ice cubes which are already melted, added 2nd dilution of EtOH (20ml 85% EtOH)
   10:25am
the reaction is calming down a little bit and stirring finally picked back up again
   10:27am
water bath temp went up to 134F due to the exothermia from the flask, there is still lots of foam in the flask and maybe close to half of the al is still there but it is all very dull gray
   10:31am
water bath temp is 139F, still lots of foam, refluxing at 1 drop per second
   10:35am
no change since the last update, the reaction seems to be at a constant plateau
   10:40am
water bath temp is 139F still, refluxing at 1 drop every 2 seconds, there's considerably less foil remaining compared to 10 min's ago. at no time during this reaction did the foam go anywhere near the neck of the flask, it made it to the halfway point at best, however the reaction does get crazy, frothy, hot, and very thick especially when you first add the oxime and AcOH. dilution with EtOH and some very mild cooling seem to do the trick, all of the craziness seemed to happen within the first couple min's of adding the Oxime and AcOH
   10:48am
water bath temp is 134F, refluxing at 1 drop every 4 seconds, the reaction is gradually slowing down, turned heat to its lowest setting
   10:55am
water bath temp is 130F, not much froth or al foil left, the solution is a murky dull gray throughout, still stirring with no problem
   11:02am
water bath temp is 130F, stopped stirring to check the consistency and about of al foil remaining. the consistency is like a thick gel but no problem stirring, went ahead and added the 3rd and final dilution of EtOH (20ml 85% EtOH), refluxing at 1 drop every 7 seconds, all the al foil appears to be gone, after adding the 20ml 85% EtOH it is a thinner consistency but still very gel-like. there's no problem stirring so i won't worry about it
   11:23am
water bath temp is 134F, there are little tiny bits of al foil left it seems but not much at all
   11:45am
water bath temp is 138F, went ahead and turned off heat because it seemed that Antibody2 and madprossor didn't apply external heat except for at the very beginning and they just let the reaction stir on its own until it slowly cools off enough to where it reaches room temperature. i was going to do a 3 hour reflux similar to BaalChemist but decided to do it the same as AB2 and madpro instead
   12:20pm
water bath temp is 109F, didn't expect it to cool off that quickly. went ahead and turned heat to 3. the solution appears much darker now.
   12:55pm
water bath temp is 129F, turned heat off
   1:25pm
water bath temp is 113F. upon reading notes by chromic, madprossor, etc, i don't believe external heat is necessary at all (except to kick off the al/hg if you choose to do so), i've been bouncing back and forth as to whether i should heat it after the rxn is done or not. going forward i'm not going to heat it afterwards unless there's a considerable amount of unreacted aluminum
   3:30pm
slowly basified by adding refrigerator chilled 336g/302ml 10% NaOH solution (302g/302ml h2o + 34g NaOH) over the course of 5 minutes, let it stir on high. the solution got incredibly thick at first due to all the sodium acetate created but thinned out after it was neutralized and the solution became basic with a greater volume of the aqueous layer being present.
   4:30pm
the pH was 14 and the solution was still a murky medium/dark gray, not nearly as dark as the black sludge from the MM nitro al/hg probably because of the NaOH solution used here was much lower concentation of NaOH compared to MM's write-up. extracted with toluene x 3 - 200ml, 60ml, 40ml. at a few points through the extraction it looked like there was 3 layers, a large top toluene layer, a tiny middle layer (must be "salted out" EtOH), and a large bottom sludge layer. i bet all the sodium acetate salt plus sludge salted out a small middle EtOH layer. the middle EtOH layer was kept with the toluene layer (in case any freebase was in it) but it would disappear depending on the amount of sludge layer present - as more sludge was added.
   5:35pm
the toluene is a cloudy creamy white/yellow color that looks a little dingy from residual sludge present suspending in the toluene. washed the toluene with 150ml distilled h2o x 3, this only noticeable difference this made was that it removed residual sludge during the first wash. then washed the toluene with 150ml saturated brine solution x 2, this removed the cloudiness from the toluene as the toluene was crudely dried via osmotic suction. the toluene is now a clear golden color. swim is used to seeing crystal clear toluene at this point as if the toluene/freebase was fresh out of the can, so after seeing this - swim is assuming that the oxime reduction produces a dirtier freebase in comparison to the MM nitro al/hg.

   day 2:
9:00am
did an a/b, distilled off the toluene to reveal the crude freebase. dissolved the undistilled freebase in equal volume IPA and titrated ala spice's method. removed the IPA with low heat until a gummy mass was present, this was to remove the 77% h2o from the 33% hcl azeotropically with the IPA. flooded the gummy mass with acetone and nice white crystals precipitated. washed with more acetone a few times and vac filtered over a #103. yield = 4.08g MDA HCl

swim later recrystallized from anhydrous EtOH per jon's recommendation and got absolutely stunning clusters of shardy crystals that looked a lot like DMT, crystal clear like glass.

RoidRage · « **Reply #36 on:** December 19, 2010, 07:24:54 AM »

As we already discussed, only difference between you and me is our solvent choice...The few times I ran the reaction, I've got the same yield as Chromic...No External heat either...I folloiw the procedure as is: Amalgamation--->Add Ketoxime then the acid...Same reaction time, same workup. ---> Great product

On a side note, I only added a LITTLE BIT bit of external heat once with a mini-reduction (4-5 grams oxime I think) maybe 1 hour into the reaction and I almost had a runaway reaction...Flask was correctly sise...I would be a bit nervous to try bigger reduction the first time, I find the reaction quite temperamental

TRY METHANOL

NeilPatrickHarris · « **Reply #37 on:** December 19, 2010, 06:24:58 PM »

that's right, thanks for the reminder. i delete pm's right after i read them and forgot your advice. i'll try MeOH next time as the solvent and won't preheat it. i can't help but wonder if the EtOH solvent system + preheating was too much heat and allowed some of the ketoxime to revert back, but i'm hardly educated enough to say anything for certain.

when i added the oxime to the preheated amalgam it reacted way too exothermically but only for the first couple minutes then it reached a steady plateau for quite some time. when i say it reacted too exothermically i mean it got so hot that even with good reflux the solution got incredibly thick (to the point where i was wondering it would solidify or smoke like the nitro al/hg does if you get too hasty with addition and the solvent gets too low, the al sludge will smoke if you don't keep enough MeOH covering it). oddly enough, there was never any risk of even coming close to rising out of the flask (1L RBF used), there was only a little of the "froth/foam" in comparison to nitro al/hg where the foam will actually fill up 1/2 the flask. so the solution never foamed up to the point of being in danger of it overflowing, not even close, but the first couple min's after addition of the oxime/AcOH it got incredibly hot to the point where too much of the EtOH stayed in vapor phase, even with a strong efficient reflux, making the solution too thick and in need of 85% EtOH dilution which was added through the reflux condenser and helped things a lot.

i noticed an intermittent triphasic system during washes due to the EtOH being salted out from all the base salt created upon basification (sodium acetate from AcOH + NaOH) which was a mild pain in the ass. i remember madprossor posts mentioning his problems with emulsions when using MeOH, did you have any problem with emulsion during the subsequent washes? i've never had emulsion problems from the nitro al/hg workup but i think the reason why madprossor (i'm just guessing here) is because madpro used not nearly as concentrated of an NaOH solution for basification, whereas if you use a fairly concentrated NaOH solution like MethylMan does in his nitro al/hg then that might allow for better separation since the aqueous layer will have a much higher density, plus there will be a larger aqueous layer so help keep the MeOH in the aqueous solution. so after all this rambling what i'm wondering is:
did you have any emulsion problems during washes?
did you use a stronger NaOH solution ala MM's nitro al/hg as opposed to madprossor's?
what was your yield w/w from oxime to final salt?
in the future i won't apply any external heat at any point (unless for some reason the rxn slows too earlier than it should), i don't think madpro or chromic used external heat at all

thanks for the help. this is a very well known route but there's a very limited amount of posts about it in the old hive archives, in fact i copy/pasted everything of value in the previous page in this thread, not much out there at all.

RoidRage · « **Reply #38 on:** December 20, 2010, 12:30:08 AM »

I agree there isn't enough information about this reaction. Anyway, not as far as I know...This reaction is probably the most over-the-counter/newbee-friendly route as far as I know.The 2 others ''Popular'' routes being the piperonal henry condensation and NaCNBH3 MDP2P reductive amination aren't exactly that. I don't know for you, but I have no idea where to get nitroethane (never searched though). As for the cyanoborohydride reaction, it's potentially dangerous for someone totally untrained/reckless

I remember seeing in school that ketoxime are fully reversible if I remember correctly but I don't remember under which conditions.

I never had a amalgam fumes or getting overly thick, but I do remember that last time the foaming had me worried. It was a 6.5g reduction so it was more or less 175ml of solvents. A bit more if you account for the aluminium but anyway igets eaten pretty fasty. Anyway, I was running the reaction in a 500ml RBF and I couldn't stop watching the reaction since the foam was actually touching the bottom of the flask's neck. I was lucky to see it, otherwise it wouldn't have been nice. Only thing that stopped the foam progression was adjusting the stirrer to the max (I normally don't bother running it at that setting). Never had the nitro al/hg foams excessively...I don't really find the reaction that violent. I ran it with 20g ketone in a 1L flask laSt time with a really fast-paced addition, and while It was quite challenging to fine-tune the addition, it wasn't worrying. Running it llike Methyl Man does isn't stressing at all. I though I had fucked up with something the first time I ran it since it wasn't violent at all...Yields sucks too...I'm pretty positive that the key to success with the Nitro Al/Hg is the addition rate since I'm CONSISTENLY getting a 100% w/w raw amine with that reaction since I started tuning the addition. Anyway sorry for rambling but I remember reading one of your post/thread on this(Or maybe another?) forum about the nitromethane reaction. That might helps ya in the future

So back to MDA lol...For the workup, I basify with 45% NaOH, extract with toluene, wash twice with 5% NaOH and finally once with brine. I followed those guidelines by Chromic from the start and it has served me well. Funnily, you're the one who gave me that procedure

As for emulsions, it's something I never had with methylamine or nitromethane reduction. I don't remember about washes, but it emulsions quite a bit with the solvent extraction. Adding water break it without much hassle. I'm not sure, bt it's probably because methanol is soluble in toluene. Anyway, water fixes the problem in no time. As I already said,, I don't remember if the washes form emulsions or not,·but I suppose that they doesn't since I don't remember

. Anyway it's a hassle-free workup as far as I'm concerned.

As for the yields, I only have the last lab session logged in my lab book (In reality I only ran the reaction 3 times IIRC). I obtained 4.5g raw MDA, so it's 69% w/w yield. I don't know why I said I got the same yields as Chromic in my last post, he got 5.9g from the same amount of oxime.

Sorry for being misleading lol

On a final note, just forget totally about external heat, the hive folks didn't use it, I don't either, and the reaction runs correctly. No idea if adding it negatively affect the reaction, but it's better not adding it since it's an additionnal variable in your problem. I used to think troubleshooting mechanical (car/atv/whatever) problems was challenging, especially electrical stuff. I now know that it's nothing compared to troubleshooting organic sythetics reactions

It's actually fun and quite rewarding as opposed to mechanic though (At least for me).

I'm on winter break from uni right now, so I have a lot of time for experimentation in the lab for about 3 weeks

Just received some new glassware and hardware, I can't wait! I'm gonna start working on MDA after christmas so let me know if you have any questions. I want to know how well this reaction scales...I'm pretty sure it sucks since it's already temperamental with small reactions. I shall report with my findings if you're interested. There is already quite a bit of informations in this thread, hopes it can be helpful to others aiming for MDA

While I was dissapointed with MDMA I was pleasantly surprised when I first tried MDA. IMHO, for people into that scene, it's definitly ''The club drug''. I don't understand when I read on forums that it sucks as opposed to it's cousin. Really nice substance, excepting it's not abusable (Which I suppose is a good thing). I seriously got my lesson last time when I ate too much in too little time

Anyway, hopes my rambling isn't too annoying haha

...Keep us updated!

NeilPatrickHarris · « **Reply #39 on:** December 20, 2010, 04:57:57 AM »

i've heard ppl say that nitroethane is OTC (just need to distill it out from other ingredients) and easy to find. i've looked for it for over 2 years and have only seen it in very small amounts, but even then it's difficult to order from those places due to certain restrictions because they're distributors. i'm looking for it for MDEA though

i'm not 100% on the factors that reverse the oxime back to hydroxylamine + ketone either. i've washed the oxime with AcOH before and it did not revert back, but that's the extent as to what i've done to the oxime i haven't done a mp test on it yet. i do remember reading that if you do a mp test on this ketoxime it will revert back to the ketone and hydroxylamine upon melting. i remember reading that from a post in the hive archives but can't remember who said it.

i've had a nitro al/hg smoke once before awhile back, i was tired and a bit careless. during the nitro al/hg i always have to add a little extra MeOH through the reflux condenser as needed. but this one time i had it going with an addition rate of over 3 drops per second with pauses every so often to keep it from overflowing, the scale was at around 10-12g ketone or so. i never added any MeOH like i normally do and the solvent got too low to the point where there wasn't enough to cover the al foil appropriately anymore. so the reaction was too dry as all the MeOH was vaporizing at an intense rate due to the exothermia from the ridiculous drip-rate, when it got dry it started to smoke, gray smoke fumes. added a considerable amount of MeOH through the condenser which put things back on track. oddly enough, yields were still decent that run but i was a bit more careful from there on out. with the nitro al/hg my 1L RBF maxes out at around ~15g ketone but that's with an aggressive drip-rate. 100% w/w yields ketone to raw amine is remarkable, something i only dream about. highest i ever got was 70% w/w but my vac pump is too strong, i can separate cis-isosafrole from ketone during vac fractional distillations but i can't fractionate trans-isosafrole from ketone, the pump's too strong so the bp's are too close together. what's your drip-rate and how is the ketone produced? i've heard before that the 100% w/w yields in the al/hg are only attainable from peracid ketone (being that it's more selective to producing our desired ketone) and not benzo wacker ketone (produces multiple ketones/aldehydes), but i don't know that i fully believe that. i recall seeing analytical results from benzo wacker ketone online and the non-mdp2p peaks were very minimal that i can't see them impacting yields on any significant level as long as you run the procedure under optimal conditions.

you have it right, the emulsions happen during the extraction not the washes, sorry about that. 69% w/w yields is excellent starting out and IMHO is satisfactory yield regardless. my crummy 42% w/w yields aren't satisfactory.

thanks again man, this time i copied off your pointers to my encrypted data to use your/Chromic's parameters next time. i won't be doing another run for a couple months though, trying to take care of something else first. but i'll definitely post back what results i get when i do another run.

yeah there really isn't very much info out there on this reaction in comparison to other procedures. i think this thread actually has all the useful information from the hive, as far as i know, so yeah there's not much at all. no your ramblings are not annoying at all and i don't find them to be rambling either, that's all good information. i do admit i prefer mdma to mda, the empathy and euphoria is what sells me. i've only had the opportunity to test out the mda made from this procedure twice, first time the night it was finished last month and the second time last night. mixed it with mdma, it was great. really nice psychedelic patterns as CEV's. i find the mdma alleviates mda's stimulating body load, not there's that much of a body load as it's pretty euphoric but there is a little bit of body load in there. mda stiffens my muscles whereas mdma loosens them. the mixture is great, i don't think my jaw has been that tight in years. i like the mental space that the mda put me in, mdma is so clear headed that the mda adds a nice layer of complexity. it took me away to my mind's eye just like mescaline does. i found mda to be something like a cross between mescaline and mdma. if you mix mescaline and mdma it's nothing like mda at all, but conceptually speaking mda is right in the middle.

Author Topic: Antibody2's Acidic Al/Hg - MDOH vs MDA (Read 2339 times)

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

RoidRage

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA

NeilPatrickHarris

Re: Antibody2's Acidic Al/Hg - MDOH vs MDA