Easier Grignard to ----

tina_craig · Mon May 30, 2005 8:39 pm

Ok, WD keeps going up and down and switc is trying to get some input on this, so she figured she would post here and see what anybee might think about this. Ning from WD and the Hive has been helping switc tremendously, so here it is:

"The secret word is "N-acyliminium ion".

Basically, it means that, by attaching an electron-withdrawing group to the amine, and having a removeable group alpha to it, one can make a very efficient synthesis of ----.

What does this mean?

The new reaction would look like this:

Ph-CH-M.Cl + CH3-N(COR)-CH(OR)-CH3 + MCl(n) --> ----.

Where M is some metal, and R is some alkyl group derived from an alcohol (methyl, ethyl, isopropyl, etc.)

MCl(n) is some lewis acid, like AlCl3, ZnCl2, FeCl3, BF3, SnCl4, TiCl4, etc.

Basically, the electron withdrawing group makes the alpha-position of the amide very activated, so it can be attacked even by weak organometallics. The purpose of the lewis acid is to remove the alpha-group and produce the highly reactive N-acyliminium ion, which then reacts with the organometallic.

So how does one go about making the precursors?
As far as I(ning) can tell, like this:

C2H2 + ROH + acid & catalysts --> CH3-CH(OR)2

this is "hydration" of acetylene. Also, acetaldehyde + alcohol will produce an acetal in presence of acid.

H2N-CO-CH3 + NaOCl + NaOH + ROH --> ROOC-NH-CH3

The hoffmann rearrangement of acetamide, in presence of alcohol, produces a good yield of N-methyl carbamate.

CH3-NH(COOR) + (RO)2CH-CH3 --> CH3-N(COOR)-CH(OR)-CH3 + ROH

heating (he thinks) acetal with N-methyl carbamate produces the precursor compound.

Benzyl zinc chloride or some other organometal compound is produced, and reacted with the precursor and a lewis acid, and N-alkylcarboxyl ---- is produced.
when heated with aqueous acid or base, it hydrolyzes and decarboxylates to racemic ----.

List of precursors:

benzyl chloride
metal
lewis acid
acetamide
bleach
acetylene or CaC2
alcohol
Metal Catalysts for hydration (Hg or Cu salts, some iron)"

So, what does everyone think about this?

Also, if anyone can help switc out, she searched for the proper terms we are suppose to use for certain words and couldn't find them, so in order to get rid of the dashes could someone point her into the right direction?

MiNdBaBY · Sat Aug 06, 2005 4:58 am

TC, MiNd doesn't see what's easier about this compared to Grignard Reagent; Ethanal; & Methylamine equalling ----.

Yes, one must produce each of the precursors, the BzCl, the Ethanal, & the Methylamine but it is all entirely OTC and very inexpensive, the secret is more in the equipment and setup used than the synths.

Ethanal easily made in an electro cell (getting ready now to research possibilities for other synth routes from OH and maybe Acetic Acid also).

Metylamine very easily made for pennies via OTC products when done in bombs and in custom high temp oven as previously publicly outlined in detail by MiNd at the old WD.

But MiNd can't disagree with you on having multiple options or routes..

Regarding Ethanal, it's restriction is IMPOSSIBLE as it can be produced from the OH, and the OH can be made from (MiNd does this in large qtys in 50gal custom drums being modified electric hot water heaters) just bakers yeast, tap/well water, & dextrose (sugar used in baking; otc <$20 per 50lb bag).

As for Methylamine, MeOH is virtually unrestrictable as well, Nh4Cl (yeah, OTC ammonia & HCl), H2O oh yeah, reall restrictable, and FeCl (water & metal, hmm, rust & HCl). MiNds point is this method of producing Methylamine will always be possible though MiNd yet knows of no other alive utilizing such route, even after MiNd mistakening publicly promoting and detailing how to easily setup a process for doing such.

Hopefully, this lil input might be of use to you TC and help you on your path.

MiNdBaBY · Sat Aug 06, 2005 5:00 am

Adding emphasize to MiNds point in equipment setups..

It is well worth the time to build/construct custom equipment and setups to make the tasks of certain synths almost effortless, this is where alot of chemists go wrong or could use improvement on. Additionally, it is also easier to do things in much larger scales. Please save yourself much trouble & effort by applying such concepts.. Smile