Author Topic: Methylamine.HCl red. amin. questions  (Read 4562 times)

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nitrous351

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Methylamine.HCl red. amin. questions
« on: October 20, 2003, 07:06:00 PM »
SWIN has been researching MeAm.HCl synthing on the Hive for the last few days. SWIN got his start with MDMA by reading the Dr. Drool synth on Rhod's page. SWIN never attempted the Os/BS reductive amination because Dr. Drool said he failed to successfully make MeAm.HCl in his four attempts. But, after reading what he has read the past few days, SWIN has decided that maybee it's not so hard to make MeAm.HCl from hexamine. He plans to follow RB's/Chromic's writeup to the letter, but he has a few questions regarding MeAm.HCl in general:
1. What would bee the advantages of aminating with MeAm.HCl as opposed to using nitromethane in situ? (SWIN's assumptions are that it's less violent, and a person doesn't need as big glassware as with a MM Al/Hg)
2. What are the storage options for a successful crop of MeAm.HCl? (should he store it in a dessicator, or will an acetone-cleaned-hair-dryer-dried-tightly-sealed mason jar bee enough to keep purity acceptable?)
3. How long can one store MeAm.HCl crystals, and in what environment should they bee stored in (dark, dry, cool, etc???)
4. If reductively aminating a 50g batch of ketone in a 1 litre flask, how long of a condenser does swim need?

SWIN thanks everyone in advance for any help. He wouldn't even bee asking these questions if it weren't for the damn dog that broke both of his 400mm condensers... else he would stick with what he "knows" best (the MM Al/Hg).


RoundBottom

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welcome to the school of MeAm
« Reply #1 on: October 21, 2003, 03:19:00 AM »
... where all the girls wear plaid miniskirts and white knee socks.  enjoy your stay.

1. advantages: i believe it's a 5-fold decreace in volume for a given amount of ketone.  if you are using ground thin Al foil, it WILL run as violently as a MeNO2 reaction, especially if you dump all your ketone in at once.  in a 3000mL flask, SWIM will drip 160g ketone, and with clean, pure ketone and MeAm, will get back between 150g and 170g salt.  addition rate is a factor with thin foil.

2. storage in a ziplock bag which, in turn, is kept in a tupperware container has worked perfectly for SWIM.  this is kept on a shelf in SWIM's workspace, with no further precautions.  if you're feeling cautious, throw in a couple dessicator sachets from your last pair of shoes.

3. see above.  if the container is airtight, SWIM hasn't seen any further storage requirements.  it cannot hurt to keep is cool and dark.

4. in a 1000mL flask at the 300mmol (53.4g) level, SWIM has always used a 400mm, 6 bulb allihn with no problems.

SWIM has never gone back to MeNO2 after using MeAM.  it's just not worth it.  and sWIM has never had a failure with a hexamine reaction.  even dirty, impure MeAm (when vac pump broke in the middle of filtration) returned 44g salt from 54 ketone.

good luck.


nitrous351

  • Guest
WOW!!!
« Reply #2 on: October 21, 2003, 08:06:00 AM »
the girls at the MeAm school really DO wear plaid miniskirts with white kneehigh socks (and some of them don't wear panties!)... Thanks, RB, for such a quick reply. Since you are the Master of the MeAm, what type of foil would you recommend for SWIN? He wants to aminate 40-50g of ketone in a 1000mL flask and his condenser options are 2 x 200mm Liebigs. He apologizes for asking such a specific question, but SWIN, while he has a building collection of glassware, is still limited in options. Also, his access to precursors are very limited, so he hates to make stupid mistakes, especially with rxns that he's never run beefore. Are 2 x 200mm Liebigs stacked on top of each other good enough to just dump in the ketone wholesale, or do you advise him to drip? Again, thanks in advance for any help you give him.


RoundBottom

  • Guest
mmmm... socks....
« Reply #3 on: October 21, 2003, 03:11:00 PM »
> you are the Master of the MeAm

HA!  hardly... i'm just a well trained monkey... besides, you mean SWIM is the Master of the MeAm,

> 2 x 200mm Liebigs stacked on top of each other good enough to just
> dump in the ketone wholesale

probably not.  you might be able to if you're using REALLY cold cooling fluid, and run the pump in PARALLEL not SERIAL (ie, DO NOT connect the outlet of the first condenser to the input of the second, have 2 independant lines to the inputs from a Y or T splitter).

> do you advise him to drip?

always.  when you're trying a reaction for the first time, always take it SLOW... you have no idea what is going to happen, so why chance it?    basically, treat it as a MeNO2, and keep a few ice cubes on hand in case it gets out of hand (to rub on the outside of the flask to cool it).

good luck.


nitrous351

  • Guest
do people really do that?
« Reply #4 on: October 21, 2003, 10:46:00 PM »
Are some people really posting saying a really bad thing happened when they tried to stack 2 condensers and didn't run 2 sets of cooling line? Seems  like common sense to me that you can't run 2 separate condensers just by running water in one and expecting it to come out of the other one...
EDIT: After re-reading your last post I see now what you meant by running in parallel. I have never thought to do that before, but if I did think of it, I probably wouldn't have suggested it to SWIN. (SWIN has 2 5 gallon buckets and 2 aquarium pumps already)


evoh_1

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a y splitter is a good investment as it can...
« Reply #5 on: October 22, 2003, 08:12:00 AM »
a y splitter is a good investment as it can turn your less expensive and more easily available 1 neck flask into a 2 neck flask.


RoundBottom

  • Guest
not what i meant
« Reply #6 on: October 22, 2003, 01:45:00 PM »
evoh, i wasn't referring to a splitter that fit in the flask.  what you are thinking of is a claissen adapter.  i was referring to a plastic Y or T splitter for the cooling line when using multiple stacked condensers. 

what this does is provide the coldest water at 2 points in your condensor stack; the bottom, and the middle.  i'm sure the home audience can figure out what that means.

nitrous also has a good idea... 2 condensors, 2 pumps.  they are cheap, about $30-$40, so why not.


scram

  • Guest
You shouldn't have a problem doing that scale...
« Reply #7 on: October 23, 2003, 12:02:00 PM »
You shouldn't have a problem doing that scale in a 1000ml flask with meam even using hd reynolds foil. For that scale aim your drip time for 25 minutes and no longer than 35 minutes (reynolds hd foil only for these times). RB is definately telling you right about it. It will heat up ~75% as vigorously as nitro but it can be handled much easier. The best part about meam is that you can reduce your al by 2/3. No exagerating here either. It make cleanup so much less of a pain. You won't ever want to switch back to nitro once you lose your virginity to meam.

RoundBottom

  • Guest
the numbers
« Reply #8 on: October 23, 2003, 02:07:00 PM »
here's a quick writeup to follow... these numbers are what SWIM follows, and are scalable.  make a spreadsheet to save your brain.

17.8g MDP-2-P (100mmol)

20.3g MeAm (300mmol, 3x excess) mixed in 20.3g dH2O, then chilled

12.0g NaOH (300mmol, 1x ratio to MeAm, 25% solution) mixed in 36g dH2O, then chilled

SLOWLY drip the cold NaOH solution into the MeAm solution, chill.

110.7g MeOH, mixed with ~50mg HgCl2

7.6g Al Foil (280mmol, 2.8x excess) HD Reynolds

put into a 500mL RBF with condensor in this order:

stir bar
Al foil
MeOH and HgCl2 solution, swirl occasionaly until amalgamation started, then add...

basifed MeAm solution
then drip in Ketone.

if stirring cannot be acheived, swirl every 5 minutes during addition, and every 10 minutes until stirring gets going.

let react for 210-240 minutes.

premake 125mL 30% NaOH solution (37.8g NaOH, 88.1g dH2O), and let cool.
premake 250mL 5% NaOH solution (12.5g NaOH, 237.5g dH2O), and let cool.

slowly basify reaction with 30% NaOH solution.

extract basified reaction with 1x 200mL toluene, 1x 50mL toluene, combine.

perform A/B wash, titrate, dry, recrystalize.


scram

  • Guest
If that were me, I would use be using between...
« Reply #9 on: October 26, 2003, 12:19:00 PM »
If that were me, I would use be using between 4 and no more than 4.5g hd reynold foil in that reaction. But that's me and that's him. Don't use any more foil than what he is suggesting above, it may be harder to get the product out. All I can say is in the past, that without having distillation equipment, this has been the best numbers for me:
75ml undistlled oil (sg ~1.18 to 1.198) / 11.2g al hd reynold/65mg hgcl2 amalgamated @ 25-30c for 12-17 minutes. 32 mls 40% meam, 16ml mixed into 50ml Meoh buffer along with the 75ml oil 1 hour prior to additon. Ketone warms up within a minute of adding the meam. Dump the other 16ml in prior to drip. set drip for 25 minutes.
I'm not suggesting anything here, but merely explaining what has worked best over here.

RoundBottom

  • Guest
leftover foil
« Reply #10 on: October 26, 2003, 05:55:00 PM »
the above procedure has worked flawlessly for a number of runs.  yield has always run between 90% and 110% w/w (10g ketone in, 9g to 11g salt out, AFTER recrystalization).

the reaction has always been strained through a metal sieve to remove any unreacted foil.  there has been between 0g and 3g-4g remaining.  if you make a spreadsheet out of the above, you can adjust the ratios accordingly.  SWIM started out with 3x ratio of Al foil, and has moved to 2.8x. 

> 75ml undistlled oil

by oil, you're refering to ketone?


nitrous351

  • Guest
titrattion and NaOH solution questions
« Reply #11 on: October 27, 2003, 07:47:00 AM »
RB,
  Please clarify this for me... in the above post, what does SWIY use the 5% NaOH solution for? The A/B? Your post says to premake 2 NaOH solutions (30% and 5%) but only says what the 30% is used for. Also, SWIN has never titrated before, but wants to try. After he distills his freebase, does he use a solvent, or does he just drip into the freebase? One more question, what is the target pH? 4.8? Thanks for your help...you have helped SWIN more than you know... peace


scram

  • Guest
Yes, a matrix of oils including ketone in it,...
« Reply #12 on: October 27, 2003, 11:08:00 AM »
Yes, a matrix of oils including ketone in it, assumed 50-60%
.............!Activate Flame Shield!.............

RoundBottom

  • Guest
wash
« Reply #13 on: October 27, 2003, 11:59:00 AM »
the 5% NaOH is for washing the toluene.  if you do an A/B then you don't need to wash it.  my mistake.


RoundBottom

  • Guest
titration
« Reply #14 on: October 27, 2003, 12:02:00 PM »
this is something i PM'd someone who wanted a titration procedure.  i don't have time right now to proof it.

premix some 10% HCl, and some 10% NaOH...  SWIM just makes a litre of each and have them already cooled on the shelf.  measure out 100ml of 10% HCl, and 20mL of 10% NaOH.  the amount you'll need is determined by the amount of toluene and freebase... this is for a 300mmol size batch, same as in the writeup.  you'll need two glass eye droppers, don't use plastic ones.  you'll also need some pH strips.

with your freebase in the toluene, put the toluene in a beaker with lots of room.  add a stir bar, and start stirring vigorously.  you want a good vortex forming, as these two liquids don't want to mix easily.

slowly add 10% HCl (i find about 70mL is about what you'll need) in 5mL squirts.  start measuring the pH after about 40mL, until you get the hang of it.  you're shooting for about pH 4, but it worked as low as pH 2.  if you overshoot the pH, and the solution turns salmon-y red.  if this happens, slowly add a few drops of 10% NaOH until it disappears, then check the pH again to see where you're at.

the difference between the right pH and too low is very finicky.  we're talking just a few drops.  the pH will hang at about 10 for a while, then drop rapidly (like 5mL will drop it to 3 or 2).  that's why it's important to do everything slowly.  you'll notice the reddish hue when it's too acidic, then just add a couple drops of NaOH and it will clear up.

once you have it at the right pH, put it in a sep funnel, and drain off the water, then put the water into a pyrex pan, and let evaporate overnight.  i put a fan blowing across it, not a heater.  also, make note of how much 10% HCl you used (before the pH corrections started) and you can use that as a starting point next time.  just subtract what's left from the 100mL you started with.

you don't need too many pH strips, only 3 or 4.  just reuse one until you see it drop, then use another to get an accurate reading.  you'll figure it out.

and there you go.


OcoteaCymbarum

  • Guest
Is my conception of an A/B wrong?
« Reply #15 on: October 27, 2003, 03:48:00 PM »
Rb, Here's an A/B to me.

Extract in np. Wash with 5% NaOH. Extract with 10% HCl. Wash with fresh np. Basify. Extract.
What about you?

Oh and by the way, Nymphomania doesnt apply to guys, only to women. The proper word for a man is satyriasis, which is a state of permanent sexual excitation.

nitrous351

  • Guest
question on solutions
« Reply #16 on: October 28, 2003, 05:55:00 AM »
this may be the newbee-ist question I have ever asked, but I get confused here at the Hive. Every chem lab I've had, solutions have been given in molarity. Here, everything is given in percents... are these percents by w/w or v/v? thanks, I swear that is my last question in this thread. peace


cublium

  • Guest
w/w if not said otherwise
« Reply #17 on: October 28, 2003, 06:08:00 AM »
w/w if not said otherwise

RoundBottom

  • Guest
w/w is weight for weight, and v/v is volume...
« Reply #18 on: October 28, 2003, 09:17:00 AM »
w/w is weight for weight, and v/v is volume for volume.  so 90% w/w means, eg. from 100g ketone, 90g salt was returned.  no molarity calculations, just read off the scale.  i know professionals prefer m/m, but SWIM has a hard enough time calculating sales tax and figuring out daylight savings.


RoundBottom

  • Guest
oooops
« Reply #19 on: October 28, 2003, 09:29:00 AM »
this is why i don't post (or drink) until the sun is over the yard arm.  sorry about that... yes, w/w (at least everone know's what w/w means now  ;) ).


nitrous351

  • Guest
thanks for clarification
« Reply #20 on: October 28, 2003, 11:38:00 AM »
SWIN has been using w/w calculations, but he wanted to make sure he was doing it correctly. He kinda assumed it wasn't v/v since it's difficult to measure the volume of a solid when compared to a liquid (i.e. try to make a 10% NaOH solution using v/v measurements). I think that one weakness of the Hive is the need to use molarities when making stock solutions instead of w/w.... or at least state in your writeup that your solutions are w/w. peace


hypo

  • Guest
nope
« Reply #21 on: October 28, 2003, 11:45:00 AM »
it's your weakness. % is always w/w, we even learned that in highschool.
(well, maybe in backwards america things are different...)


killerbeezzz

  • Guest
Water and MDMA?
« Reply #22 on: October 09, 2004, 12:04:00 AM »
So when you tittrate the salts it ends up in the water layer and then you just evap the water to get the crystals?  Could a rotovap be used to help evap the water?

DoctorFeelgood

  • Guest
Forget evaporating.
« Reply #23 on: October 09, 2004, 09:53:00 AM »
I agree with OC. evaporate the HCL water ??? This is nonsens. Pour HCL/np into clean sepfunnel and sep off the bottom HCL layer, which contains the base in its saltform. Then pour the HCL back into you cleaned sepfunnel and slowly add enough e.g. 20% NaOH to bring the PH up (>12). The solution will turn milkywhite and you will see the base falling out, it settles to the bottom of your sepfunnel.
Sep off base, extract remaining waterlayer once with DCM to get everything out. Combine DCM with base and strip off DCM on waterbath.
Now you have 2 options:
1)You can distill the base under reduced pressure (bp 150-155 C in my case), to get a waterwhite and clean base (higherboiling impurities removed, dark redish trash remains in flask). Then you can dissolve the clean base in e.g. xylene and gas it. This is how i do it. If you want maximum yield you can skip the distillation.
2) Dissolve it like it is in e.g. xylene and gas.

killerbeezzz

  • Guest
If the salt is there
« Reply #24 on: October 16, 2004, 08:57:00 AM »
If the salt is there why go threw all the extra steps?  SWIM would think that it would be easier just to evorate the water and get the MDMA out.  Does it give you a cleaner product to redisolve it in the NP then gass?

DoctorFeelgood

  • Guest
this is no 'extra' work
« Reply #25 on: October 19, 2004, 01:18:00 AM »
this is no extra work, this is the normal labcycle. if you skip these steps you will get a 'product' which i sure do not want to eat. you should go for purity, because these chemicals are not edible and therefore you must do these steps. some like to exclude the distilling of the freebase, but an A/B is a must. 8)

ranxerox

  • Guest
Color change
« Reply #26 on: October 20, 2004, 04:33:00 AM »
If you try to reduce the volume of water by evaporation, the heat will cause the flask contents to turn a beautiful violet color, then darken to a very deep purple, almost black. Then after crystalization the formed crystals will have the same purple color. The color can be removed by recrystalization.

Recrystalization is almost always necessary with titrated products. Gassing is a bad nightmare compared to titration.

psychokitty

  • Guest
Cinnamaldehyde?
« Reply #27 on: October 20, 2004, 05:30:00 AM »
Has anyone considered using cinnamaldehyde in the Al-Hg reductive amination to see if it works equally well at creating the same reaction conditions that using MD ketone does?

My thought is that cinnamaldehyde could be appied to a practice run. This could eliminate the risk of wasting valuable chems during a standard newbee Al-Hg reductive-amination familiarization process.