it would'nt procedd for numerous reasons amine adjacent to electron withdrawing group, zwitterionic, lone pairs of nitrogen are protonated by said zwitterion, no go.
just bubble some methylamine into alcohol need advice as there are some details in the technique of obtaining concentrated solution 20+ % of methylamine in alcohol, pm me i'll give you the lowdown.

You make a good point there Jon and thats the responce I have been looking for for some time now, however as such the sodium salt of glycine being already deprotanated should not show zwitterionic properties and proceed as long as it does not attempt to react with the bromo grouping.

Regardless of all of this last resort could be to reflux the mixture in a 50/50 Acetone/MeOH solution to effect decarboxylation yeilding insitu methylamine in an easy to control LARGE excess.

http://www.erowid.org/archive/rhodium/pdf/sodium.triacetoxyborohydride.pdf
Table 1 #38 standard procedure II
Procedure II - Only DCE and the hydride in 30 to 60% excess
"Procedures. 1. Direct Reductive Amination Methods.
General Notes. (a) The amine and the carbonyl compound
are mixed in 1,2-dichloroethane and treated with NaBH(OAc)3.
THF, CH2Cl2, or CH3CN may also be used as solvents.
(b) Acetic acid (1-2 mol equiv) may be used in reactions of
ketones but is not necessary with most aldehydes.
(c) Reactions are normally carried out using the free amines;
however, the amine salt may be used. In this case, 1-2 equiv
of Et3N is added to the reaction mixture. The Et3N must be
removed from basified product prior to salt formation."
and
"Method I. This procedure is used for most ketone reactions.
A representative example is the reductive amination of cyclopentanone
with hexamethyleneimine (Table 1: entry 4):
Hexamethyleneimine (1.0 g, 10 mmol) and cyclopentanone
(0.84 g, 10 mmol) were mixed in 1,2-dichloroethane (35 mL)
and then treated with sodium triacetoxyborohydride (3.0 g,
14 mmol) and AcOH (0.6 g, 10 mmol). The mixture was stirred
at rt under a N2 atmosphere for 24 h until the reactants were
consumed as determined by GC analysis."

I get the dry players going into this fight and being under dry n2 but not a mention of imine formation drying, in fact quite the opposite with all the "direct" not "stepwise indirect" written in the ref.

From looking at the tables one would infer that methylamine will be faster than #38 by quite a bit, as would additional acetic acid. You say this is a bad assumption and they are not mentioning parts of the tech?

So are these Docs liars? Or white lie tellers?

http://www.rohmhaas.com/assets/attachments/business/process_chemicals/reducing_agents/reductive_aminations.pdf
says that it is even better to generate STAB in situ. Researchers were all geared up to to have NaBH4 pulverized under N2, add correct amount of AcOH with the excess for catalyzing, then add the methylamine gassed DCE and ketone, and stir like hell for a day under n2 even though it should be done in hours from the looks of the tables and the read.

Just a good read? That sucks.

So how about titanium salts?

I guess back to a-teaming the PtCl6/NaBH4 and hydrogenation rig. At least nitromethane to methylamine runs in the same rig and solvent, so that scratches that nightmare off the list. What does the peanut gallery think of waiting for the cat to settle then dropping a mesh bag of silica gel in to get the water produced after the nitro reduction? How sensitive is the hydrogenation to water from the imine formation?

There is a thing on Rhodiums back up about using aq. 40% methylamine and p2p, hydrogenating  in denatured ethanol, that seems like a pile of water from where I'm sitting.

Sorry this isn't really short questions now, but it follows the last. It will probably only receive short answers. Move/delete/deathray at your leisure. Also sorry if this is too methy. These things are applicable to all the forbidden flavors and a bit beyond the shake and baker or whatever the matchbook scrapers are doing these days.

Probably because the gas molecules are losing energy between the time they leave the liquid and the time they condense on your thermometer.  As the liquid gets hotter, the particles leaving are more energetic and don't cool off as quickly or could even become hotter than the true boiling point if the top portion of the glassware is hot.  Just my guess.


I have a question:  Why does the terminal carbon not get brominated as well when forming bromosafrole from safrole?

I know secondary carbons are generally more reactive than primary carbons in most reactions, so is it just that it's easier for a bromine to attach to another secondary carbon on another safrole molecule than to continue and brominate the primary on the first molecule?

All right, not to sure how found this chemistry is, or if it has already been mentioned, but lets see if this would happen.

It is well known that acetate electrolysis produces ethane - this is from the methyl radicals combining. I believe this works with other carboxylates as well. So what would happen if you electrolyzed the salt of phenylalanine with an excess of acetate?

It would make sense to me, assuming that the amine didn't interfere, that the methyl radical, and the    2-Amino-3-phenylpropanyl radical would combine to form amphetamine...


I'm guessing it would probably have very low yields since I doubt you could ever get the phenylalanine to effectively ionize? Unless in a really basic solution, which then may cause problems with the amine to some degree.. I don't know.

But anyways - whats wrong with this idea? has it already been discussed? I'd be interested in seeing more info on it.

Vesp I never heard of it.

so you worked it out?

does it work ?

Anyone know what's up with blacklight?

The potential of a LARGE excess of Acetate ions to Phenylalanine could mean more then just some low yeilds. Mostly ethane would be formed but every now and then a Phenylalanine mol would be in the right place at the right time in order to condense with the acetate releasing 2CO₂ and yeilding amphetamine. We are using the sodium salts of these as well which means as Amphetamines formed from the dimmerization one could possibly extract it right away into a Non polar solvent on the top to prevent it from reacting further with anything else.

Hmmmmm........



BTW
Also food for thought

BnCH2CH2(NH2)COO-  + OH-  = BnCH2CH2(NH2)OH.

View Shrooms thread on the uses of DMSO to turn that OH into a methyl.

Here is the mechanism for Kolbe electrolysis from the paper above, generating the radical intermediate which is the procedure for producing dimers. The dimer is the major product but there is some of the required compound formed as a by-product even when the reaction has been tweaked to produce as much dimer as possible.

does anyone know how to remove a methyl group of the nitrogen in an indole ?

thanx vesp thats what I thought too.
makes it pritty easy if it works.