posted 09-15-98 12:15 PM         

The only problem (other than the oxidation of piperic acid) being the LAH reduction.

I couldnt find any mention of another way to reduce the nitropropene untill today when I decided to take a looksee in Deja News on the subject of TMA-2.

I found the following :

Zn-Hg

ref. - CPB [Chemical and Pharmaceutical Bulletin] 16,217(1968).

"Suspend 0.2 M [of the nitropropene] and Zn-Hg from 200g Zn and 20g HgCl2 in 2 L ethanol and add
with vigorous stirring portions of concentrated HCl until the yellow color disappears. Continue stirring one-half hour, filter, evaporate in vacuum to get about 0.14 M of the amine."

Electrolytic

refs: J. Prakt. Chem. 137,345,138,271(1933), and JACS 54,273(1932).

"[illustrated for TMA-2, the nitropropene being 2,4,5-trimethoxy-phenyl-2-nitropropene I take it] Add 4g crystals [here, the nitropropene recrystallized from methanol] to 100ml ethanol and 50ml glacial
acetic acid; then add 10ml concentrated HCl or 50ml concentrated sulfuric acid for the catholyte in a 40 cm^2 Hg-cathode in a porous cell surrounded by 3N sulfuric acid anolyte with a water cooled lead anode and reduce at 4 amps (about 0.07 amps/cm^2 cathode surface) at 30-40 degrees for twenty hours or until solution is colorless. Evaporate in vacuum to about 20ml; cool with ice, basify with NaOH and extract with ether. Wash, dry and dilute the ether (or dry, evaporate in vacuum) to get [the amphetamine]." P.C. doesn't mention any yields. No, I have no idea how to build such a cell."

Refs are also given for a bomb reduction :

AP 270,340,410(1932), AP 273,481(1935), and JOC 37,1861(1972).

Also mentioned was a method for preparation of the nitropropene -

"The nitropropene is prepared by adding a saturated soln of 40g sodium nitrite to 10g asarone in 90ml ether, and then adding to this dropwise over 4h 75ml 20% H2SO4. It stands 8h, then the ppt. is filtered out, washed, dried, and dissolved in 8% potassium carbonate in ethanol w/ gentle heating (10g ppt. to 60ml 8% KCO3). Ice, then dilute HCl is added (150g ice, 100ml dilute HCl for 10g ppt.), it stands 30min @ 0 degrees, then the nitropropene is filtered out, washed and dried (7g from 10g ppt)."

I dont know about you but this gets me a little moist.

posted 09-15-98 12:15 PM         

The only problem (other than the oxidation of piperic acid) being the LAH reduction.

I couldnt find any mention of another way to reduce the nitropropene untill today when I decided to take a looksee in Deja News on the subject of TMA-2.

I found the following :

Zn-Hg

ref. - CPB [Chemical and Pharmaceutical Bulletin] 16,217(1968).

"Suspend 0.2 M [of the nitropropene] and Zn-Hg from 200g Zn and 20g HgCl2 in 2 L ethanol and add
with vigorous stirring portions of concentrated HCl until the yellow color disappears. Continue stirring one-half hour, filter, evaporate in vacuum to get about 0.14 M of the amine."

Electrolytic

refs: J. Prakt. Chem. 137,345,138,271(1933), and JACS 54,273(1932).

"[illustrated for TMA-2, the nitropropene being 2,4,5-trimethoxy-phenyl-2-nitropropene I take it] Add 4g crystals [here, the nitropropene recrystallized from methanol] to 100ml ethanol and 50ml glacial
acetic acid; then add 10ml concentrated HCl or 50ml concentrated sulfuric acid for the catholyte in a 40 cm^2 Hg-cathode in a porous cell surrounded by 3N sulfuric acid anolyte with a water cooled lead anode and reduce at 4 amps (about 0.07 amps/cm^2 cathode surface) at 30-40 degrees for twenty hours or until solution is colorless. Evaporate in vacuum to about 20ml; cool with ice, basify with NaOH and extract with ether. Wash, dry and dilute the ether (or dry, evaporate in vacuum) to get [the amphetamine]." P.C. doesn't mention any yields. No, I have no idea how to build such a cell."

Refs are also given for a bomb reduction :

AP 270,340,410(1932), AP 273,481(1935), and JOC 37,1861(1972).

Also mentioned was a method for preparation of the nitropropene -

"The nitropropene is prepared by adding a saturated soln of 40g sodium nitrite to 10g asarone in 90ml ether, and then adding to this dropwise over 4h 75ml 20% H2SO4. It stands 8h, then the ppt. is filtered out, washed, dried, and dissolved in 8% potassium carbonate in ethanol w/ gentle heating (10g ppt. to 60ml 8% KCO3). Ice, then dilute HCl is added (150g ice, 100ml dilute HCl for 10g ppt.), it stands 30min @ 0 degrees, then the nitropropene is filtered out, washed and dried (7g from 10g ppt)."

I dont know about you but this gets me a little moist.

posted 09-15-98 02:07 PM         

In "tale of pseudonitrosite" Sparky and Muki use the Zn-Hg method but substituting Al for Zn and using only 1/5th of the amount of Al compared to Zn, and only 1/50th the amount of HgCl2 mentioned in the above ref.

Yeild was apparently 3g of TMA-2 from 5g beta nitroasarone

This shit is looking really good

Oh no, I think I've wet myself.

posted 09-15-98 02:07 PM         

In "tale of pseudonitrosite" Sparky and Muki use the Zn-Hg method but substituting Al for Zn and using only 1/5th of the amount of Al compared to Zn, and only 1/50th the amount of HgCl2 mentioned in the above ref.

Yeild was apparently 3g of TMA-2 from 5g beta nitroasarone

This shit is looking really good

Oh no, I think I've wet myself.

posted 10-13-98 05:05 PM         

Anyway, sorry, AP = Archiv der Pharmazie.

The refs originally come from Psychedelic Chemistry by M.V. Smith.

posted 10-13-98 05:05 PM         

Anyway, sorry, AP = Archiv der Pharmazie.

The refs originally come from Psychedelic Chemistry by M.V. Smith.

posted 10-14-98 07:05 AM         

Piglet

posted 10-14-98 07:05 AM         

Piglet

posted 10-19-98 01:46 PM         

this message was brought to you by the letters B and O and M and of course B...

posted 10-19-98 01:46 PM         

this message was brought to you by the letters B and O and M and of course B...

posted 12-14-98 02:45 AM         

what can you share about 'TMA from nothing'??
(I presume 'from' calamus root???

posted 12-16-98 03:27 PM         

Sorry, but I made a few mistakes above.

1. The authors name is Jiro TSUJI.

2. The article describes the synthesis of 1-ketones from 1,2-halohydrins synthesized from internal alkenes -- in the case of isosafrole, the yield was quantitative when using NBS (N-bromosuccinimide), DMSO (dimethylsulfoxide), isosafrole, and a little water, I think.

3. The diagram is on page four of the article, not page two.

Aside from those three errors, the details are accurate as formerly described.

posted 12-16-98 03:37 PM         

That is an interesting article that you mention, but have you checked out the price of the catalyst that they used? If memory serves, they used a mixture of tri-o-toluyl-palladium and some other palladium catalyst. Its rather expensive, and my experience is that the rxn does not tolerate a reduction in catalyst level well.

posted 12-17-98 06:59 PM         

Simple as pie:

In place of safrole used in Strike's #2 MD-P2P synthesis use asarone.

Yes, that's what I said. Use asarone, a propenylbenzene, in place of safrole, an allylbenzene in the Wacker oxidation. All other variables stay the same. I say again, all other variables: PdCl2, CuCl, O2, H2O, DMF -- they all stay the same. Won't work you say? Go look up the reference I posted earlier. Yes, it's about rearranging the 1,2-halohydrin to the ketone. But that's not the part of the article I wanted people to pay particular attention to. As an alternative reaction to achieve the same goal, the experimental information found in this post was used.

Again I say, use Strike's #2 ketone synthesis -- keep everything the same -- exept the use of safrole (use asarone instead) and you'll get the respective 2-ketone.

Yes, terminal alkenes are typically used in the wacker oxidation. But this article proves that at least in regard to isosafrole, a propenylbenzene can be used to effect the same transformation!