starlight (Hive Bee)
08-15-02 18:40
No 345681
      dmmda-2 related problems  Bookmark   

Hi everyone,

I have been having some problems with regard to dmmda-2 from dillapiole. These problems are really due to lack of experience.

I wondered if you might be kind enough to lend a bit of advice on the following imaginary situation:

250ml of dillapiole was placed under vacuum with 5g of KOH pellets (85%) and heated with stirring to 80C until the evolution of bubbles stopped (presuming all the water has evaporated). The vacuum was then removed and the temperature taken up to 150C for 12 hours. The flask which was now full of dark brown/black material (liquid) was then left to cool. On return, the flask had become full of tan/white crystals which filled the volume of the flask.

The flask full of crystals was warmed and transferred to another flask which was set up for distillation (simple distillation again due to lack of fractionating column). The result was a flask full of white crystals that were wet with an oily substance (presumably dillapiole or cis-isodillapiole). The distillate smelt different from the original compound, more "minty".

Recrystallization of the isodillapiole was the first stage that was found challenging (probably through not following or understanding directions properly).

AB2's writeup says to "recrystallize [the isodillapiole] from an equivalent volume of boiling petroleum ether". Well two attempts at this varying degrees of success. In the first attempt the crystals (about 200g) were completely dissolved in 200g of petroleum ether at just below 40C (40-60C boiling range petroleum ether). The solution was allowed to cool for a couple of hours and seed crystals were introduced, the glass were made with was scratched, but no crystallisation occured. The solution was then left for 12 hours. Unfortunately the vessel was not well sealed and the petroleum ether had evaporated in the morning. Therefore no purification resulted.

Another recrystallisation was therefore attempted, which went somewhat better, but not perfect. Around 200g of suspected isodillapiole was dissolved in 100ml of petroleum ether at around 40C. The solution was then left to stand in a tightly sealed container, whereupon a crop of crystals was evident after a couple of hours. The mother liquor was decanted from the crystals into another tightly sealed container and another crop of crystals formed. The mother liquor was decanted from this crop of crystals into a beaker, which was cooled in an ice bath and another crop of crystals was obtained. The remaining mother liquor was left in an open container (to evaporate the petroleum ether) and a yellow oil was the result (around 50 ml).

The crystals were needle-like prisms between 0.5-1cm in length in the first and last crop, and smaller in the middle crop. The crystals were however still somewhat oily to the extent that oil absorbed into paper when the crystals were placed upon them. THe middle crop was the worst. The impurity of the product was borne out in the melting points, with the first crop melting between 38-42C and the middle crop melting between 33-42C (such a wide melting point was presumed to indicate a substantially impure product).

Reading accounts of recrystallisation does not seem to help, as here we are dealing with a substance that melts at around the temperature of the recrystallisation solvent, so it is hard to select a volume of warm solvent that just dissolves the starting material.

So with regard to doing these stages of the preparation properly, I wondered whether you could clarify the following points:

With regard to isomerisation:

a) Do you think the crystals obtained from the distillation of the isomerisation reaction were mostly isodillapiole, or may there be crystals of dillapiole in there too (mp. of dillapiole is given as 29.5C in the Merck index and ambient temparature here is around 14-20C (depending upon the weather).

b) Do you think that not using the vacuum throughout the isomerisation is OK (just using it to remove water at the beginning), or is this asking for trouble?

c) Is it normal that the flask in which an isomerisation is carried out is very slightly marked (i.e. not entirely crystal clear on the inside even after cleaning with detergent, NaOH solution, acetone). The flask looks as if it has hard water  stains on the inside (although this is probably due to attack of the glass by KOH).

With regard to the recrystallisation:

a) Does equivalent volume mean around 200ml of petroleum ether for 200g of crystals?

b) How long does the solution need to be left, and to what temperature does it need to fall in order to recover the majority of the product?

c) Should the recrystallisation have removed the oily impurity?

d) would washing the crystals in cold petroleum ether get rid of the oily impurity, or would this dissolve too much of the crystals?

The crystals obtained were used in a modified performic reaction as follows:

154g of the crystals were dissolved in the appropriate volume of DCM and stirred with the appropriate amount of bicarb for 3 hours.

meanwhile performic acid was prepared by dripping 98% formic acid (amount adjusted due to different percentage than in AB2's writeup) into 30% H2O2 (no percentage specified in AB2's writeup but assumed it was 30%). This was conducted whilst cooling with an ice bath to avoid any temperature rise that could produce formic acid gas. The mixture was then left for an hour (still kept cool but not at 0C - maybe 5-10C).

The performic acid was then dripped into the iso-DCM-NaHCO3 with strong stirring over the course of an hour. The temparature rose gradually and reached 40C towards the end of the addition. Some slight refluxing occured as one drip every two seconds returned from the condensor.

As the performic acid was added, the stirred reaction mixture first went pink and then orange/red. The mixture was stirred for another 20 hours and allowed to settle. The aqueous (top layer) was deep orange, and the bottom organic layer was a dark red colour.

The organic layer was tapped off and the aqueous layer extracted with DCM. The extract was pooled with the organic layer to provide what was assumed to be a mixture of epoxide/glycol in DCM. This was stripped of solvent and then rearranged with H2S04 (15%) for 2 hrs at 80C

The organic layer was tapped off and the aqueous layer extracted with DCM. This left what was presumed to be crude ketone in DCM.

This was split into two portions which were taken forward in experiments that were failures. Both of these failures are somewhat embarassing but I will mention them anyway.

In the first experiment, a small amount of the presumed ketone was washed with NaHCO3 and the water wash was forgotten (reseracher was too tired and attempting to work at night).

The organic layer was isolated and stripped of solvent to leave around 30ml of presumed ketone (cloudy, viscous red oil). This was distilled under vacuum and came across at around 115C (iso came across around 100C - vacuum pump is rated at 0.01mbar but guage is not accurate enough to tell what the pressure actually was - researcher was using a dry ice/acetone cold trap). Only a simple distillation was attempted as no fractionating column was available. No insulation was used on the still head. The oil bath temperature was 140C whilst most of the distillate came across and was raised to 180 before stopping the distillation (nothing more came across even when the temperature was raised to 180C). The result was 15ml of light yellow oil. Left in the distillation flask was a substantial amount of red vitreous substance which was assumed to be polymerised ketone (this was soluble in acetone).

The yellow oil obtained was used to try and prepare an oxime, but in the morning there were no crystals - a yellow oil remained at the bottom of the flask. The researcher presumed that the lack of careful washing led to extensive polymerisation and that the yellow oil was only partly ketone and partly iso-dillapiole.

In the second experiment, the presumed ketone was shaken well with NaHCO3. The aqueous layer became brown. The organic layer was tapped off and washed twice with ion-exchange purified H2O and then once with brine (to remove the cloudiness from the organic layer). The DCM was then removed on a rotovap. The result was a clear, viscous red oil.

A small amount (~1ml) of this red oil was shaken with bisulfite reagent (~4ml). There was a definte white precipitate after about 25 mins although it was nowhere near crystals. So there must have been ketone in there (although it is not clear how much).

An attempt was made at distilling the remainder of the presumed ketone. Rightly or wrongly, the researcher tried to improvise a fractionating column from a claisen still head with a bit of knitted steel in it (had read about somebody else doing it on the hive). The column was insulated as was the still head and the very top of the flask with glass wool. The flask was clamped through the glass wool insulation.

When the temperature of the bath was 140C and still nothing was coming across, it was decided to go back to a simple distillation to avoid polymerisation of the ketone. Unfortunately what happened was even worse - the distillation rig was gradually dismantled. When the column was taken off the distillation flask, the flask fell into the oil bath and the presumed ketone mixed with the hot safflower oil. What a terrible end to the night!

The following questions arise from these experiences:

a) Would using the slightly oily crystals from the previous recrystallization (described earlier) affect the performic drastically (as opposed to having purer iso-dillapiole).

b) Accounts of the performic on iso-safrole talk about an orange organic layer. Is the red organic layer experienced with iso-dillapiole a sign of a problem or is it correct?

c) Should the formic / H2O2 be cooled during mixing or will this cause a problem?

d) Is it likely that the ketone was too impure in the first run to get crystals of the oxime? Or in fact non-existent?

e) How necessary is a column for ketone distillation if one is not worried about yields at this point but does want the production of the oxime to at least work?

f) When insulating a column, it seems dangerous to clamp the flask from outside the insulation - is it normal to leave the flask neck un-insulated?

I really would appreciate your views on the questions posed in this account. It seems hard to do this stuff when you don't know what you are doing - the researcher has been reading the Hive for a year but there is still no substitute for practical experience and advice from experts on specific points.

many thanks


(Synaptic Self-Mutilator)
08-15-02 19:30
No 345690
      Congrats  Bookmark   

Congratulations! You're one step ahead of where I am, to where I want to be. I love dmmda-2 and I ought to get off of my butt, get a good vacuum pump and pursue it.

I wouldn't have bothered recrystallizing your isodillapiole. It sounds fine. Vacuum is only necessary during the beginning of the isomerization. Once the water is removed, everything is a go. (there might even be other ways around this, such as using KOH in 99% IPA and distilling off the IPA... but why think about these methods as you have to use the vacuum anyways to do the reflux.

I'd always bisulfite test your ketone before you prepare your oxime. If you can't get the bisulfite to form crystals as I talked about in other posts, you haven't a chance with the oxime formation. It's a great priliminary test that involves almost no reagents (try 5ml sat K or Na (meta)bisulfite in water, and 0.2ml of ketone). The test tube should fill with white crystals. If you don't see white, that likely means there's a few impurities in the ketone. For example, the last run I did with mdp2p the bisulfite was yellowish orange. I went to prepare the oxime and it was a heavily viscious oil that did not crystallize when left to stand overnight in the freezer. In the past with tma-2, I just went on to reduce it and I got some yields! BUT... you can do better than me. No excuses. wink

>a) Would using the slightly oily crystals from the previous
>recrystallization (described earlier) affect the performic
>drastically (as opposed to having purer iso-dillapiole).

I doubt it. If it was relatively pure, the performic will go after the isodillapiole before the dillapiole.

>Is the red organic layer experienced with iso-dillapiole a sign
>of a problem or is it correct?

Color change to yellow or orange is common with epoxidation of propenylbenzenes, and I think is a sign of success.

>Should the formic / H2O2 be cooled during mixing or will this cause a problem?

Leave it for an hour like the writeup says, no cooling.

>Is it likely that the ketone was too impure in the first run to
>get crystals of the oxime?

Absolutely. With the tosic acid mdp2p I made (without further purification), I'd guestimate it was fairly pure. (my guess, and just a number from a hat, 80%+) But it wasn't pure enough to form the oxime. You really should distill it with a short fractionating column.

>Or in fact non-existent?

That I very much doubt. Use the bisulfite test to tell.

1) If your bisulfite fills with white crystals, it's likely quite pure. BRAVO!
2) If the crystals are off colored, then there's a small bit of impurity. Fine for amination, risky with oxime formation.
3) If the oil turns to small bits of chicken fat, then your ketone is pretty damn impure. Distill again!
4) If there's no reaction after 1-2 hours, then there's likely zero ketone.

>e) How necessary is a column for ketone distillation

I'd say it's pretty damn important, but if you collect relatively narrow fractions (5C range) with simple distillation I'd say you're going to get success.

>f) When insulating a column, it seems dangerous to clamp the flask from
>outside the insulation - is it normal to leave the flask neck un-insulated?

I insulate the necks with glasswool and clamp around the glasswool. Caveat emptor. I often don't know a normal intelligence quotient from Ally McBeal's dress size.
(Hive Bee)
08-16-02 03:42
No 345858
      Well what's the dill, Pickle?  Bookmark   

Hey, that's strange, swinl just recently started fucking with dillapiole as well.  For swinl, it's almost out of necessity as the Sass source has gotten fucked for swinl, meth is ...well its meth, it'll get you by, but ....and he's waiting for a new source to come through, but its been three weeks now swinl pulled out one of the jars of pickle juice(dillapiole) he had obtained months ago to go adventuring and experimenting. 

I've done lots of researching lately trying to gain whatever knowledge I can about this substance.  I'll share what I know, but I'm in the same boat as you, starlight.  Swinl is not as advanced as most of the bees he looks up to and respects, but hey, swinl's young and he's only been a bee for a year now I think.  Anyways, swinl did manage to get a good bit of experience down - two failed peracetic epoxidations (peracetic acid is hard to form), numerous successful benzo wackers (a la MM) and aminations via MeOH/Nitro/AlHg and AB's oxime.  Okay, I guess that's not that much experience as I can only imagine what some bees track list probably looks like ...

Okay, first some answers, to the first group of letters:

a)  Yes the crystals were more than likely isod.a.  Do a MP test if you're unsure.  (You probably know how, but feel free to ask if not).  Also, I think you can use cold anhydrous IPA (you know, red bottle next to yellow methanol everyone likes in auto store).  Not sure though, I'd recommend testing a very small portion of orignal iso xystals first to check for solubility at different temps in iso.  Perhaps cold dry acetone also would be a good candidate for washing iso xystals (recrys. or not). 

b) you have an answer for that, but swinl always left the vac. anyways.  I guess there's no real reason, just thought maybe reducing the atmosphere would help with the process - sort of catalytic like heat is (but then, swinl was using NaOH on safrole back then, now swinl's trying to whack dillapoile.) 

c) who knows if its normal or not, most peeps haven't fucked with this oil all that much when compared to miss sassy.  distill some DCM from stripper in that flask with a some added water to prevent gunking.  Empty flask while still at least warm and the stain will most likely be gone. 

Next group of questions:

a) I don't know, you want to use a minimal amount.  I don't like petroleum ether and I still think IPA is the way to go, but I'm guessing there.  At anyrate the solvent should dissolve the crsytals while hot (or warm), and when cold they should reform.  This allows impurites that were trapped in the formed crystals to escape and dissolve in the solvent(s) and stay there even once cold.  Usually crystals are crashed out with another solvent (ice cold)that it will not dissolve the product.  Acetone is what swinl's used, but that was for MDMA crystals, different I'm sure.  Either experiment or research.  Personally I think experimenting is more fun if you have time and interest.  Or just go with what you got, yields shouldn't suffer that much without rexystalization. 

b) just get it nice and cold - maybe twenty to thirty minutes in freezer.  Filter, rinse with cold solvent and move one.  You could probably then crash out more xystals with another solvent.

c)no not neccesarily all of it.  Its the rinse with the cold solvent after recry... that cleans off that oil you see on the outside. 

d) should be okay, use only what's necessary and again, test on small portions first to be sure. 

Last group of ques.

a)not drastically, but it technically makes a difference.  The oil represents impurity from the oil.  You probably just used it as is without vac. distilling it to purity before isomerizing.  I don't know, I could be wrong. 

b) yes blood red is usually cool beans (or cool dilly in this case!)  I wouldn't sweat it too much, but I just read through a post by kapten called "Overdone hydrolisis & orange/red 'ketone' ??"  You might read that.

c) ditto on Chromic's reply. 

d) ditto again.  yes the oxime sucks like that.  yeilds will drop through the floor unless you have (relatively)pure tone. 

e) fuck a column if you ask me.  just be patient turning up the heat.  what's close boiling anyways?  Dry the DCM with MgSO4 if its water you're worried about.  other than that, I don't see where a column is necessary.  They suck and take for-ev-er.  Last resort to swinl. 

f) put the clamp on the flask, that way you can pretty much be sure its safe.  Wrap HD reynolds wrap around everything, then wrap w/ plumbers insulation and again with foil.  Wait, that might be overkill with this shit though.  Remember AB said that polymerization would occur when the oil bath went over 185C.  so maybe just some foil would be alright - especially if you skip the column as I suggest. 


anyways, some other notes I hope helps.  Apparently this shit polymerizes easy as a mofo.  I'm sure certain things add to this unfortunate effect such as impurities, solids, high temp's, cyclization, etc.  As AB pointed out in a different post "dillapiole as well as many of its derivatives are unfortunately very subject to cyclization, specifically the 2-MeO group forming furan or pyran rings."  He noted that "aqueous acidic redxn conditions" resulted in no isolated product.  This could perhaps be just that cyclization.  The oxime is tricky to pull off with killer yields with MDP2P -> MDA/MDOH as is.  Then add to the problem the sensitivity of the OCH3's sticking out vulnerably from the benzene ring and it can be somewhat daunting (esp. to the clandestine chemist).  After a MP test on what may or may not be final product, I plan to make a post on DMMDA-2 soon myself.  Keep your fingers crossed, cause if it worked, its gonna be dank.  But something leads me to believe its too good to be true.  We'll see.  Keep trying. 

One mo' thing.  Fuck what people have said, aminate some DMMDMA-2 and take a large dose.  OR - be really different as swinl plans to and make DMMDEA-2 (substitue nitromethane with nitroethane in MM Nitro run).  That would be novel and I've NEVER heard of bioassay on that.  Who cares if its bunk, it'd be cool just to say you did it ...or, er, your screen name I mean.  Well whatever, you never know, it could be surprising active as TMA-2 was to Shulgin originally - never thinking the 2 position could increase potency so much ,..,.good luck, happy cooking.
(Bee without a Title)
08-25-02 00:28
No 348654
      did antibody omit to mention that it was 35% H202 ...  Bookmark   

did antibody omit to mention that it was 35% H202 that was used? no sweat, simply adjust to get the same molar quantity. a little extra H2O won't kill the rxn as long as you stirring is good.

the red color is normal (pre distillation)

the other thing that occurs to antibody is that nowhere in you write-up do you mention refrigeration or even cooling of the oxime, the oxime has a very low MP! summer temperatures apprach that MP, pop it in the freezer and you get a nice surprise.wink

reduction can still be attempted even if no crystals, but A/B after will be necessary

Loricran - 2,3MeO-4,5MD-Phenethylamine was inactive at 175mgs, waste of time IMO.
(Hive Bee)
08-25-02 01:51
No 348681
      Reply to 'did antibody omit to mention that it was  Bookmark   

Loricran - 2,3MeO-4,5MD-Phenethylamine was inactive at 175mgs, waste of time IMO.

No, I meant DMMDEA-2.  DiMethoxyMethyleneDioxyEthylAmphetamine-2.  Like the MDEA of the DiMethoxy world.  The ethyl-amphetamine.  There is nothing to prove that ethyl amphetamines will always be weak to inactive in all ring substituted amphetamines.  Who knows?