The Hive > Tryptamine Chemistry

Indole Grignards

<< < (3/6) > >>

Ritter:
Diethylamine practically won't even react with the methyl ester, even when refluxed for 24 hours!

PolytheneSam:
Here's some interesting amide patents

Patent US6291712

In addition to the above processes, a process for producing a carboxylic acid amide has been proposed, in which the
carboxylic acid amide is produced from an ammonium carboxylate in the presence of a dehydration catalyst. In this process,
molybdenum oxide, an alkyltin catalyst, a mixture of silica gel and alumina or a titanium tetrachloride catalyst is used as the
dehydration catalyst.

In this process, the dehydration reaction can be carried out at relatively low temperatures, so that not only can the formation of
by-products such as nitrile compounds and carboxylic acid amide dimerization products be suppressed but also the reaction
time can be shortened. However, when the carboxylic acid amide is produced with the use of the catalyst, it is apprehended
that the catalyst be dissolved or otherwise contained in the obtained carboxylic acid amide and, hence, a step of separating or
otherwise removing the catalyst from the carboxylic acid amide after the completion of the reactions becomes requisite. If costs
of catalyst production and catalyst removal incurred by the use of the catalyst, etc. are taken into account, this process also
cannot be regarded as a satisfactory process.
--- End quote ---


Patent US4379928

Alkyl amides have been synthesized from cyclic anhydrides, carboxyl acids and their esters by contacting them with an amine carbamic acid salt.
--- End quote ---


The amine carbamic acid salts can be prepared by the interaction, e.g., of an alkylamine and carbon dioxide. A suitable
procedure is described in U.S. Pat. No. 2,927,128 by H. A. Lindahl et al. assignors to Pure Oil Co.

Alternately the amine carbamic acid salts can be generated in situ by the reaction of carbon dioxide with an amine. In the simple
case where the amine is dimethyl amine, the equation for the reaction is: ##STR7##
--- End quote ---


Patent US6313294

Many conventional synthetic pathways exist for preparing amide compounds. For instance, the reaction of an amine and an
ester in a solvent, a well-known basic organic reaction, can be used to form an amide. In particular, it is known that the
formation of an amide linkage by the reaction of a primary amine with an ester in a solvent under heating is possible. Moreover,
the formation of an amide by reacting a secondary amine and an ester, can require not only a solvent, but also a catalyst, such
as Lewis acid, strong base, or enzyme.
--- End quote ---


Patent US3763234 Lewis acid catalysts

Patent US2478114 hydrosulfite catalyst

Patent US1954433 carboxylic acid, amine and xylene or amylbenzene distilled

Patent US3288794 dimethylamides using alkali metals/alkoxide catalysts

Patent US4139557 dimethylacetamide, MoO3 catalyst

Patent US1582675 formamide


http://www.geocities.com/dritte123/PSPF.html

zed:
Zed has seen this reaction performed. It does produce a one pot DMT synthesis. And, yes, the yield is actually about 25%. I don't have the paperwork. But, as I recall, Ethyl Bromide or Iodide is added dropwise to Magnesium in Diethyl Ether, to form the Grignard reagent. Indole is then added slowly to to the reaction mixture to form a 1-Indole Magnesium complex, Which there after, is reacted with Dimethyl-Amino-Ethylchloride, to produce DMT. This Reaction, unlike many you find in Chemical Literature, actually works pretty well!

The Downside was, that at that time, Indole was a pretty tough acquisition. And, Dimethylaminoethylchloride wasn't easy either, seems folks were using it in some opioid synthesis. There were not as many Phychoactive substances, and the Feds could focus a lot of attention, on just a few precursers. So, the ones they did focus on, they could squeeze pretty tight.

That being said, the difficult part of this synthesis is in the execution. Ordinary stirring will not do for most proceedures. The additional solvents employed, and the cold temperatures we used, created a thick peanutbutter-like reaction mass. No ordinary stirrer can move this stuff. You must employ a powerful, explosion proof DC Motor to provide the required stirring. Also note, that a fair volume of ethane gas is released, don't be surprised.

Anyway, that was the old way, thanks for the great references, I'll cruise for improvements.

PolytheneSam:
In Patent US2692882 column 2 it says you can use Pd/C hydrogenation of an IAA amide at one atmosphere pressure.  I found an example of atmospheric pressure hydrogenation here. 
http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0586
It looks like you need very little Pd/C catalyst relative to the reactants and products.  Would 15-20 year old unopened Pd/C still be good for a reaction like this?

http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious

zed:
Saw patent. The Pd-C/H2..... Seemed it was being used to remove a 5-Benzyloxy-group.

They did make a claim, that the amide could be reduced to amine via Pt/H2. But, this is a pretty tough reduction. I haven't seen it done via Pt/H2. LAlH4...yes, NaBH4-AlCl3....yes, Pt/H2......? I would like to believe..........tell me more.

Navigation

[0] Message Index

[#] Next page

[*] Previous page