The Vespiary

The Hive => Serious Chemistry => Topic started by: Rhodium on January 18, 2002, 04:25:00 PM

Title: Safrole to MDMA via isocyanates?
Post by: Rhodium on January 18, 2002, 04:25:00 PM
What if you made 3,4-methylenedioxyphenyl-2-isocyanato-propanone? That would be with a -NCO group on the middle carbon on the side chain.

When reducing an isocyanate, the N-methylamine should form (right?), in this case MDMA, this without having to use methylamine at all.

How would it be made? I don't know the best way, really. Either chloro- or bromosafrole would be reacted with potassium isocyanate (KNCO) in DMF or DMSO, or there may be a possibility that HNCO could be made by depolymerizing cyanuric acid by heating it to 330 deg C and then leading the gas through a solution of safrole, hoping that isocyanic acid is reactive enough to add across the double bond.

One problem is the formation of trialkyl isocyanurates when making alkyl isocyanates from KCNO, but is that a problem? What happens when a trialkyl isocyanurate is reduced? Is some strange triazine formed, or does it depolymerize in situ, forming the desired MDMA anyway?
Title: Re: Safrole to MDMA via isocyanates?
Post by: PrimoPyro on January 18, 2002, 08:25:00 PM
The entire procedure would obviously need to be carried out in grignard-similar conditions, as organoisocyanates hydrolyze to organoammonia derivatives and carbon dioxide.

Might be a really cool way to make MDA.

MDP-CH2(CHNCO)CH3 + H2O --> MDP-CH2(CHNH2)CH3 + CO2

                                                       PrimoPyro
Vivent Longtemps la Ruche!
Title: Re: Safrole to MDMA via isocyanates?
Post by: psychokitty on January 21, 2002, 11:34:00 AM
Another good one would be to react bromosafrole with guinidine (free base) and then hydrolize the intermediate to form the desired amine product. 

This reaction is definitely one for Ritter to tackle.
Title: Re: Safrole to MDMA via isocyanates?
Post by: terbium on February 17, 2002, 05:33:00 PM
When reducing an isocyanate, the N-methylamine should form (right?), in this case MDMA, this without having to use methylamine at all.
It would seem that the isocyanate could be converted to either MDA or a mixture of MDA and MDMA.

Reacting water with the isocyanate would produce MDA. There would also be a secondary reaction of the MDA with another molecule of the isocyanate to produce an MDA urea, presumably this could be hydrolyzed to two molecules of MDA.

If hydrogenation of the isocyanate produced MDMA then this MDMA should also react with another molecule of the isocyanate to produce the mixed MDA/MDMA urea.
Title: Re: Safrole to MDMA via isocyanates?
Post by: Greensnake on February 18, 2002, 04:41:00 AM
>to react bromosafrole with guinidine (free base) and then hydrolize

Probably will work very badly, guanidine is more basic and less nucleophilic than just NH3, so it should mostly eliminate HBr from bromosafrole, instead of making substitution product.

>If hydrogenation of the isocyanate produced MDMA then this MDMA should also react with another molecule of the isocyanate to produce the mixed MDA/MDMA urea.

I wonder, if it could be "prolonged action" form of X.
Title: Re: Safrole to MDMA via isocyanates?
Post by: cheeseboy on February 28, 2002, 07:31:00 PM
terbium : how does reacting water with the isocyante yield MDA, pls elaborate.
         May The Source Bee With You...Always.
Title: Re: Safrole to MDMA via isocyanates?
Post by: terbium on March 01, 2002, 08:46:00 AM
See towards the bottom of the page, under the section on Moisture-Cured Systems.

http://www.coatings.us.rhodia.com/chemistry.asp (http://www.coatings.us.rhodia.com/chemistry.asp)



or see here:

http://www.psrc.usm.edu/macrog/foamsyn.htm (http://www.psrc.usm.edu/macrog/foamsyn.htm)

Title: Re: Safrole to MDMA via isocyanates?
Post by: Ritter on March 18, 2002, 11:12:00 AM
I found two refs for producing phenethylamines from cyanates.  Someone PLEASE look these up and report the synthetic details!!!  SWIM has some bromosafrole which is just begging to be reacted with a cyanate and reduced to some lovely honey.  This would be a wonderful new route, hopefully these refs will bring this idea to fruition.

J. Chem. Soc. v.95, p.1127 (1909)
J. Am. Chem. Soc. v.55, p.3389 (1933)
Title: literature
Post by: Niels_Bohr on March 23, 2002, 02:59:00 PM
Ritter:  The articles deal with preparing p-hydroxyphenethylamine from p-hydroxyphenylacetonitrile, via Na reduction.
The other is obtaining OH-ß-phenethylamine from hydrogenation of the mandelonitrile using platinum oxide.

Is this what you were looking for?
Title: It Should Be Possible
Post by: PrimoPyro on March 25, 2002, 06:21:00 AM
"Isocyanates and Isothiocyanates are reduced to methylamines on treatment with LiAlH4."

March's, 5th Ed.

States no refs, no deeper investigation, just that sentence and a reaction picture. Makes no mention of water either.

                                                   PrimoPyro
Vivent Longtemps La Ruche!
Title: refs
Post by: lugh on March 26, 2002, 07:08:00 PM
Some references that may bee helpful as far as the reduction of isocyanates using LAH:

Monatsh 82 621 (1951)
Ber 85 470 (1952)
Abstracts of Papers 121st ACS Meeting, March 1952, p 41K  :)
Title: > See towards the bottom of the page, under ...
Post by: Osmium on April 02, 2002, 05:02:00 AM
> See towards the bottom of the page, under the section on
> Moisture-Cured Systems.
>

http://www.coatings.us.rhodia.com/chemistry.asp (http://www.coatings.us.rhodia.com/chemistry.asp)



That is overly simplified. Most one-component systems contain 'capped' isocyanates or amines. Isocyanates are usually derivatised with butanone oxime, amines used as aldimines or ketimines, which hydrolyse with moisture.
isocyanates aren't that moisture sensitive, you certainly don't need anhydrous conditions to work with them. Lots of the polyurethane-based coatings are made in water emulsion (solvent-free laquers), and there is no immediate reaction of the isocyanate with water.

Let's not get into too much detail, polyurethane chemistry is a vast area (during the first 30 or so years no real scientific research was done, there are not many refs, mostly patents from that time, it was mainly trial and error done by the industry)

I'm not fat just horizontally disproportionate.