Lugh wouldn't it be possible to have an alcoholic solution of Methylamine.HCl in one beaker and an alcoholic solution of NaOH in a separate beaker, and simply combine the 2 solutions with stirring to create the imine?

It's easier to utilize methylamine hydrochloride using the Al-Hg:

http://www.erowid.org/archive/rhodium/chemistry/brightstar.mdma.html

for many reasons which can bee found using the search engines    Methods that work well have been posted for over a decade but there's always someone looking for new ways to waste precious reagents trying to find short cuts that seldom exist    If you want to test your hypothesis it would best to do it on very small scale    Let us know how it works out  

  

You've got me wrong. I thought this was already a valid path. I'm not chasing a new way of doing anything nor trying to pose a hypothesis. I'm not qualified to do that. I simply saw the "wet NaBH4 reductive alkylation" text, and the method appeared to be transferable to MDP2P, and with this thread I'm trying to ask if it can be done---that's all. I'm being told that the water is the problem, and I'm saying fine, fucq the water, I don't care about water I care about being able to reduce using NaBH4 and methylamine salt instead of gas,if possible, can I do that? All I need is a yes or no to that question (and if no, why not), and then I can move to figuring out how to get it done.

It's possible to generate methylamine gas easily from methylamine hydrochloride, the basic procedure has been posted in this thread already    More details are available from various online resources, perhaps you should spend more time studying organic chemistry    As far as your question, it's impossible form an imine directly from an amine salt and a methyl ketone (carbonyl group):

h**ps://secure.wikimedia.org/wikipedia/en/wiki/Imine

The end results from the effort applied 

You would be better to attempt an "isolation" of the imine prior to reduction with borohydrides. Single pot such as can be performed using an amalgum could lead to head and heartaches in this case.

The end results from the effort applied

I get the feeling you're trying to paint me as a lazy guy who doesn't want to put out any effort. If you knew my history, you'd know I spent many months trying to improve the nitro Al-Hg and sharing the results with the community.

I'm not pissed; I just don't want you to misunderstand me.

My method is to do a bunch of net research first (yes, including pumping others for what they are willing to share) and then when I have information sufficient to warrant real-world activity, I dive in and meticulously detail all of my many observations and then SHARE them with everyone. I'm not trying to get a free ride here. I'm actually trying to avoid going down a dead end and wasting time, just like anyone else. When/if I finally put another writeup out there, it will give back even more than I was given.

I guess the thread itself has run its course. If anyone is willing to PM me any info regarding NaBH4 reductions, I would appreciate it. Links to net articles are always appreciated, but what I'm really looking for is reports of actual experience.

cheers
MM

There are no carbon or chlorine atoms in sodium borohydride, so it's hard to understand how anyone versed in basic inorganic chemistry would post such a question  Roll Eyes

Well that's the thing... I'm not, and never claimed to be, versed in basic inorganic or organic chemistry, so it is unsurprising that I wouldn't know. But I do what I do, and enjoy it. I learn as I go. Is it still okay with you if I hang around?

Back in the Hive days we had a real interesting array of members with a whole range of knowledge levels, and it was fun. I'm hoping it's a similar sentiment behind things here. Maybe you could think of me as kind of like an overly enthusiastic bat boy in baseball, if it helps you tolerate me.

Anyway I certainly don't want to annoy you or anyone else here, that's the last thing I want. I gave it a good shot and learned some good info, so thanks. I'll pursue it some more in different channels now and put this thread out of its misery.

Thanks again, everybody.   

OK, I for one am happy with the effort being put forth here so lets back track and start from the beginning.

Methylman,
Since you have admitted limited knowledge in this area of chemistry as far as how the reactions proceed could you do me a favor and explain in your own words what you feel takes place during a reductive amination. This will greatly push us in the right direction as to where to direct our attention to while aiding in further understanding.

Basicly I want to understand the steps that you feel take place when an amine is added to a ketone and further reduced.

Hopefully this will clear up any confusion and lead this thread onto a more productive path.

You're cheating yourself if you don't have these two.
Sixty Years of Hydride Reduction - a chapter from Reductions in Organic Synthesis
and
Reductions in Organic Chemistry

everyone should lighten up we are the fun kind of chemists after all!

MethylMan : a salt of an amine means something like R-NH3(+).Cl(-) which is a fancy way of writing RNH2.HCl (amine/hydrochloric acid salt).
The first equation i wrote represents the ions present. RNH3(+) is an ammonium ion. If you think about it graphically, you can think as if the lone pair of the nitrogen (which is essential for the formation of aldehyde/amine adduct) is busy bonding to the proton coming from the acid. What you have to do is to to neutralize it with a base. If you have methylamine.hcl its really quite easy to proceed, and ive wrote this above. ill write again -
take 74.27g of methylamine.hcl (1.1mol), dissolve in the minimum amount of water and write it down.
add toluene (5-10 times the amount of water) then drop in 1mol of NaOH flakes (40g), slowly while in an ice bath.
then add more NaOH, 6-8g per every ml of water present. So if you had to dissolve your amine in 50ml water, you must 300-400g dry NaOH. Then add 150g more NaOH to account for the water formed by the reaction between OH(-) and MeNH3(+). Shake well and let sit in the ice bath till everything settles down.
Decant or filter your toluene, add to it some methanol and 0.9mol of your ketone,stir 30 minutes, then add 10~17g NaBH4 (depending on quality of NaBH4) in small portions in the ice bath, let stir extra 2 hours @ r.t. after addition of NaBH4 is done, and workup as usual. This works and is easy!

No gassing needed. just some mixing and an ice bath. you can also add salt to the ice to make it even colder to ensure even less methylamine escapes. and either a hood or a well ventilated place if you dont cool it enough (methylamine will escape and stink up/carcinogen the place).

I apologize if posting old hive material is uncouth but unlike some of you I was not around "back in the day" so a lot of these experiments are news to me.  Argox does a dry NaBH4 using only 0.39 equiv of NaBH4 (much closer to the 0.25 theoretical than some other bees) and gets over 90% yield:

Summation:
1 mol PMK
0.39 mol NaBH4
1.19 mol CH3NH2
Methanol was 3 times weight PMK

 MeOH/MeNH2 solution was added to small RB via an overhead long column charged with MgSO4 in upper half and silicagel beads in lower half supported by cotton.  This resulted in dry solution. The MeOH/MeNH2 solution was followed with clean MeOH. [The use of a column charged with dessicant was a HUGE improvement over just adding the MGSO4 and/or silicagel to stinking MeOH/MeNH2 solution and then having to decant or filter and then wash the dessicant.  The solution came out of the column crystal clear, no need for filtration.  The dessicant was washed by following the initial MeOH/MeNH2 with clean MeOH.  Huge reduction in labor, time, hassle, stench, wear and tear, etc.  Column had a return connection just below the top, so that it would be impossible for it to overflow.]  The small RB and contents cooled with ice/water bath.

-5ºC PMK was dripped into 5ºC MeOH/MeNH2 solution.   Stirring 100 rpm. The solution turned a deep burgundy color.  Tubing leading directly to exhaust was attached to reactor.

NaBH4 was manually added over 5 hours.  Temperature of solution was never allowed to exceed 15ºC.  Boro was added every time temperature reached 8ºC.  The solution turned a pumpkin orange color.

Stirrer set at 200 rpm and small reactor allowed to slowly reach 20ºC, while the operator got some sleep.  Stirring maintained for 25 hours after final boro addition. Solution was a greenish lemonade yellow at end of 25 hours.

The RB was set up for atmospheric distillation.  MeOH was distilled off initially at 65º and up until temperature at stillhead reached 100ºC, then reduced pressure was applied (aspirator) thereby stripping off water and cooling the RB contents.  The RB was allowed to cool to room temperature and tap water was added to the contents (water was about 3 times volume of contents).  A white oil precipitate formed.  NaOH solution was added per operator judgement, exact quantity not recorded, but not very much.  White oil and water were stirred and allowed to settle.  Water was decanted.  More water was added and decanted.  All water washes (about 5 times volume of contents) were pooled and washed twice with DCM.  (The second DCM wash resulted in clear DCM, so no further washes were deemed needed.)  DCM was pooled and added into RB.  The contents of the RB were heated with stirring and atmospheric distillation.  DCM was recovered for re-use.  Water distillate was discarded.  RB subjected to reduced pressure to strip off remaining water.  Once all water deemed to have been removed, the aspirator was replaced with mechanical vacuum pump.  MDMA base came over at 145ºC and about 29.8" at the gauge.  Base was clear with slight tinge of yellow.  94.6% yield (mol/mol) of pure mdma.

edit:
He later clarifies that some of the supposed freebase did not crystallize and 0.47 molar ratio of NaBH4 is best (and conveniently works out to 1 gram of NaBH4 for every 10 grams of ketone)

Final product tally not in, but in case any bee is considering using less than about 0.50 moles of NaBH4, I would recommend against it.  In other words, I believe SWIA used too little boro this time.  A portion of what initially seemed to be mdma freebase may have been something else, who knows what?  But 10% of "freebase" will not form hydrochloride.  Even after several re-basings, re-distillations, and re-gassings in which a little more product was obtained each time.

Since all previous reductive aminations using 0.47 moles of boro per mole of ketone were stellar successes, (the 93.7% yield of freebase in previous post, resulted in almost stochiometric recovery of hydrochloride), I would recommend sticking with L/T's tried and true formula, and use 100 grams boro for every 1000 grams ketone.

Hey, thanks so much guys. What a nice surprise to find that this thread still goes on, with even more good stuff.

lugh: I will endeavor to understand it more deeply, I promise. In the meantime, however, I still need to gear up to do it. The order is going to have to be

(1) Do it (once having received good instructions, which I now appear to have)
(2) Understand how it works in more depth

If I try to understand it fully first, I may run out of time and become a broke homeless man, which doesn't do me or anyone else any good.

Sedit:  Regarding my understanding of what happens in reductive amination - I guess I understand it up to the point that one can without understanding the molecular theory behind it. In other words, not super deeply. Without the background of formal education in chemistry, I basically just get that molecules react to each other and undergo transition, that protons shift position, electrons dance, etc. I know essentially what happens, but not the fine details and theory. Throw in my math handicap, and the fact that these things happen on a molecular level and are thus not visible, and it makes it even more challenging. Over time I will learn more, but without serious classes in O-chem I will always be way behind most of you guys. But that's actually okay with me, because it's not a race, and I'm really just a hobbyist.

Think of it this way, and please pardon the "cooking" analogy, but with a good recipe and a little practice, a guy can learn to bake an excellent cake without knowing every last scientific aspect behind the flour, eggs, milk, butter, sugar, that go into it. Though it would help, he doesn't absolutely need to know all the exact properties* of those ingredients. It's kind of a lame analogy, but I'm just trying to illustrate that people can do chemistry without being knowledgable in chemistry theory/mechanics. They won't be on a sagacious level, but they will at least be on the field. (*of course in chemistry one has to learn the basic physical properties of things, for safety)

letters: THANK YOU! I'm grateful. That (#56) is what I've been trying to get. That is the kind of info that makes me feel confident enough to give it a try. Much the same as my attention to detail in my past writeups gave other guys the confidence to try something that previously had seemed prohibitively confusing. And I also really appreciate you throwing in the last part about old NaBH4, because that is exactly my case (10 years old, hardened into a lump in the jar, but apparently still usable).

akcom: thanks! New reading material! Love it.

Shake: thanks brother

Looks like I'm back on the borohydride track. I'll be reading all the above info, trying hard to absorb it into the gray matter...

cheers
MM