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All 12 posts Subject: Will this route to TMA-2 work ok? Please login to post Down

sponsan
(Newbee)
07-22-03 00:45
No 448932
      Will this route to TMA-2 work ok?

Hello everyone!

Is the following route to TMA-2 feasable?

Calamus root oil ->
Asarone -> Sodium Nitrite/H2SO4 ->
Asarone pseudonitrosite -> Alcoholic KOH ->
Asarone nitropropene -> Fe/HCl ->
Asarone ketone -> (NH2OH)2.H2SO4/NaOAc.3H2O ->
Asarone ketoxime -> Al/Hg reduction in Acidic EtOH ->
TMA-2

Thanks,
Sponsan.

sYnThOmAtIc
(Hive Addict)
07-22-03 01:31
No 448937
User Picture       A duuh

Yea I believe everything there is covered on rhodiums too...I'm positive about that up to the ketoxime formation part

Yes, That pic really is me!

El_Zorro
(Hive Addict)
07-22-03 01:48
No 448940
      The only thing that would really hinder any...

The only thing that would really hinder any route taken from asarone, if I remember correctly, is that the methoxy groups on the molecule are exceptionally acid sensitive. That's what makes it hard to put asarone through a peracid oxidation. I'd bet a faster route would be just to use the oxone method on asarone, then rearrange the epoxide with LiI, or ZnI, or one of either bromides.

It is seductive, way too seductive.    -Eleusis

Rhodium
(Chief Bee)
07-22-03 02:10
No 448945
User Picture       From asarone/calamus to TMA-2
(Rated as: good read)

At my site, you can find the following descriptions of some of the transformations you mention:

Calamus oil -> Asarone -> Pseudonitrosite -> Nitropropene -> Asarone ketone (https://www.rhodium.ws/chemistry/tma2.html)
Calamus oil -> Asarone -> Pseudonitrosite (https://www.rhodium.ws/chemistry/asarone.html)
Asarone -> Pseudonitrosite -> Nitropropene (https://www.rhodium.ws/chemistry/pseudonitrosite.html)

The only part I'm a bit unsure of is the acidic Al/Hg reduction of the oxime, as I don't find that described in my notes on TMA-2 chemistry (but it might be posted somewhere at the Hive, can someone help finding it?). The oxime has been made in good yield using either Sonson's method (https://www.rhodium.ws/chemistry/mdaoxime.html) Chromic's modification (https://www.rhodium.ws/chemistry/alhg.oxime.html). The ketoxime is purified according to Post 365007 (Barium: "IPA is a good solvent for asarone ketoxime ...", Methods Discourse)

A more common way is probably reduce the nitropropene to TMA-2, directly or stepwise (https://www.rhodium.ws/chemistry/tmp2np-red.html), as you don't have to proceed through the ketone and ketoxime, which probably gives notably lower yields. In this document there is also a good procedure for the iron reduction of the nitropropene to asarone ketone, if you should decide to use that route in the end.

Anyhow, I suggest that you UTFSE for posts written by Antibody2, Dr_Sister, Chromic and Uemura to find good asarone chemistry discussions. I think that the pros and cons of all the methods you mention has been discussed here at the hive at one time or another during the years.

sponsan
(Hive Bee)
07-22-03 02:35
No 448951
      Thanks Rhodium! That direct nitropropeneš...

Thanks Rhodium!

That direct nitropropene reduction documented by Antibody2 looks much more straight forward than going via the oxime route. Will give it a go and see what comes out!

Thanks again,
Sponsan.

starlight
(Hive Bee)
07-22-03 10:29
No 449039
      experience

The pseudonitrosite works well on asarone. make sure you don't use too much H2SO4, or leave it too long or you will end up with red goo/tar and a ring nitrated product if I remember correctly. Little difference has been noted between dripping the acid into the top or bottom layers.

Stepwise reduction of the nitropropene also works well. A good route is reduction of the double bond with borohydride, followed by redution to the amine with Zn/NH4COOH in methanol.

have a look at Post 352269 (Barium: "Wow", Chemistry Discourse)

GC_MS
(Hive Addict)
07-22-03 11:17
No 449044
User Picture       nitrated impurity

make sure you don't use too much H2SO4, or leave it too long or you will end up with red goo/tar and a ring nitrated product if I remember correctly.

You remember correctly wink . Bruckner states that 2,4,5-trimethoxy-nitrobenzene is formed as impurity.

[...] Unterwirft man Asaron [...] in ätherischer oder ligroinischer Lösung der Einwirkung von nitrosen Gasen, so ist keine Ausscheidung eines Additionsproduktes zu bemerken. Auch im Falle sehr energischer Außenkühlung findet nur Oxydation oder Nitrierung statt, die zur Bildung von 2,4,5-trimethoxy-nitrobenzol führt und stets von starker Verharzung begleited wird. Diese merkwürdige Reaktion findet ihre Erklärung in der besonderen Sensibilität des Asarons, die wahrscheinlich mit der Stellung der Methoxylgruppen zur Propenylkette in Zusammenhange steht³.[...]

3. Eine ähnliche Erscheinung trafen beim Nitrierungsversuch der Asaronsäure (2,4,5-trimethoxy-benzoesäure) R Fabinyi und T Széki, Ber Deutsch chem Ges 39 (1906) 3681) an, indem in Eisessiglösung auf Einwirkung van 81 prozent. Salpetersäure die Carboxygruppe abspaltete und ebenfalls 2,4,5-trimethoxy-nitrobenzol entstand.

Bruckner also finds the nitrated impurity when he prepared the pseudonitrosite the traditional way. As Fabinyi and Széki found that 2,4,5-trimethoxybenzoic acid is converted to the same 2,4,5-trimethoxy-nitrobenzene when treated with HNO3, my guess is that asarone is partially oxidized to 2,4,5-trimethoxybenzoic acid (as a side reaction; atmospheric oxygen and an acidic environment can cause this cleavage), which in turn is nitrated.
For those interested in chemical history: Fabinyi and Széki have done quite some research in the asarone-field; for instance Post 431532 (GC_MS: "Characterization of asaraldehyde", Chemistry Discourse).

Reference of the Bruckner text: V Bruckner. Über das Pseudonitrosit des Asarons. J prakt Chem 138 (1933) 268-274. Also found on Rh's site.

Dirty old man

randolph_carter
(Hive Bee)
07-23-03 21:08
No 449327
User Picture       well hold the phone ethyl......

it looks like we have another acorus explorer!!!
yer synth route sounds well....sound...
read the post at rhod's site.....
it has been dreamed as posted by none other than this stumbling questor ......
and the high yields are in fact doable.....

i STRONGLY suggest that you hone yer org synth skills with some more simple quest prior to embarking on this adventure though......

it is infinitely more demanding than a rp/i bubble in the ice house........

but good luck and let us all know what YOU find in your adventures fellow questor.....

i hope ya have some open minded friends.....
the sexual potential is QUITE interesting!!!!

"remember little ones, love is real,not fade away, so pass some ammo on today......"

sponsan
(Hive Bee)
07-23-03 23:28
No 449351
      Hello Mr Carter :) I have read your previous...

Hello Mr Carter :)

I have read your previous adventures documented in Rhodium's archives - well done! The only part i was unsure about was your final reduction. Is the high yeild you reported really possible with leuckart on tma-2 ketone?

Rhodium pointed me at the alternative reduction with NaBH4 + Al/Hg, with ~ 55% yield, which i am tending to lean towards as it seems very simple. But, the oxime route claims ~80% yield for MDA, and if the asarone ketoxime reduces in such yield also, i am going to probably go via oxime route to get the extra 30%.

So far i've sucessfully completed mdma, mda and 2c-b synths, in decent yields. The organic synth skills have taken a big make-over over the last few sessions and seem to be improving. :)

Will keep you all posted!

Take care,
Sponsan.

gruns
(Newbee)
07-26-03 08:11
No 449894
      urushibara catalyst

In antibody2's urushibara catalyst reduction of tmp2np,
should the ethanol added be dry? Does anybody have
any caveats for this reaction?

over and under, then back to the start
this sidewalk's bottom is the same as its top

madprosr
(Hive Bee)
08-19-03 05:56
No 454475
      nitropropene -> ketone

why not use Al/AcOH to form the ketone from the nitropropene?
Rhodium posted an equivalent writeup for mdp2p giving 75% yeild...

gruns
(Hive Bee)
09-07-03 06:50
No 457558
      I like the idea of performing only two ...

I like the idea of performing only two reactions rather
than three, especially such relatively simple ones.

over and under, then back to the start
this sidewalk's bottom is the same as its top

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	All 12 posts		Subject: Will this route to TMA-2 work ok?		Please login to post		Down


		sponsan (Newbee) 07-22-03 00:45 No 448932				Will this route to TMA-2 work ok?
						Hello everyone! Is the following route to TMA-2 feasable? Calamus root oil -> Asarone -> Sodium Nitrite/H2SO4 -> Asarone pseudonitrosite -> Alcoholic KOH -> Asarone nitropropene -> Fe/HCl -> Asarone ketone -> (NH2OH)2.H2SO4/NaOAc.3H2O -> Asarone ketoxime -> Al/Hg reduction in Acidic EtOH -> TMA-2 Thanks, Sponsan.



		sYnThOmAtIc (Hive Addict) 07-22-03 01:31 No 448937				A duuh
						Yea I believe everything there is covered on rhodiums too...I'm positive about that up to the ketoxime formation part Yes, That pic really is me!



		El_Zorro (Hive Addict) 07-22-03 01:48 No 448940				The only thing that would really hinder any...
						The only thing that would really hinder any route taken from asarone, if I remember correctly, is that the methoxy groups on the molecule are exceptionally acid sensitive. That's what makes it hard to put asarone through a peracid oxidation. I'd bet a faster route would be just to use the oxone method on asarone, then rearrange the epoxide with LiI, or ZnI, or one of either bromides. It is seductive, way too seductive. -Eleusis



		Rhodium (Chief Bee) 07-22-03 02:10 No 448945				From asarone/calamus to TMA-2 (Rated as: good read)
						At my site, you can find the following descriptions of some of the transformations you mention: Calamus oil -> Asarone -> Pseudonitrosite -> Nitropropene -> Asarone ketone (https://www.rhodium.ws/chemistry/tma2.html) Calamus oil -> Asarone -> Pseudonitrosite (https://www.rhodium.ws/chemistry/asarone.html) Asarone -> Pseudonitrosite -> Nitropropene (https://www.rhodium.ws/chemistry/pseudonitrosite.html) The only part I'm a bit unsure of is the acidic Al/Hg reduction of the oxime, as I don't find that described in my notes on TMA-2 chemistry (but it might be posted somewhere at the Hive, can someone help finding it?). The oxime has been made in good yield using either Sonson's method (https://www.rhodium.ws/chemistry/mdaoxime.html) Chromic's modification (https://www.rhodium.ws/chemistry/alhg.oxime.html). The ketoxime is purified according to Post 365007 (Barium: "IPA is a good solvent for asarone ketoxime ...", Methods Discourse) A more common way is probably reduce the nitropropene to TMA-2, directly or stepwise (https://www.rhodium.ws/chemistry/tmp2np-red.html), as you don't have to proceed through the ketone and ketoxime, which probably gives notably lower yields. In this document there is also a good procedure for the iron reduction of the nitropropene to asarone ketone, if you should decide to use that route in the end. Anyhow, I suggest that you UTFSE for posts written by Antibody2, Dr_Sister, Chromic and Uemura to find good asarone chemistry discussions. I think that the pros and cons of all the methods you mention has been discussed here at the hive at one time or another during the years.



		sponsan (Hive Bee) 07-22-03 02:35 No 448951				Thanks Rhodium! That direct nitropropeneš...
						Thanks Rhodium! That direct nitropropene reduction documented by Antibody2 looks much more straight forward than going via the oxime route. Will give it a go and see what comes out! Thanks again, Sponsan.



		starlight (Hive Bee) 07-22-03 10:29 No 449039				experience
						The pseudonitrosite works well on asarone. make sure you don't use too much H2SO4, or leave it too long or you will end up with red goo/tar and a ring nitrated product if I remember correctly. Little difference has been noted between dripping the acid into the top or bottom layers. Stepwise reduction of the nitropropene also works well. A good route is reduction of the double bond with borohydride, followed by redution to the amine with Zn/NH4COOH in methanol. have a look at Post 352269 (Barium: "Wow", Chemistry Discourse)



		GC_MS (Hive Addict) 07-22-03 11:17 No 449044				nitrated impurity
						make sure you don't use too much H2SO4, or leave it too long or you will end up with red goo/tar and a ring nitrated product if I remember correctly. You remember correctly . Bruckner states that 2,4,5-trimethoxy-nitrobenzene is formed as impurity. [...] Unterwirft man Asaron [...] in ätherischer oder ligroinischer Lösung der Einwirkung von nitrosen Gasen, so ist keine Ausscheidung eines Additionsproduktes zu bemerken. Auch im Falle sehr energischer Außenkühlung findet nur Oxydation oder Nitrierung statt, die zur Bildung von 2,4,5-trimethoxy-nitrobenzol führt und stets von starker Verharzung begleited wird. Diese merkwürdige Reaktion findet ihre Erklärung in der besonderen Sensibilität des Asarons, die wahrscheinlich mit der Stellung der Methoxylgruppen zur Propenylkette in Zusammenhange steht³.[...] 3. Eine ähnliche Erscheinung trafen beim Nitrierungsversuch der Asaronsäure (2,4,5-trimethoxy-benzoesäure) R Fabinyi und T Széki, Ber Deutsch chem Ges 39 (1906) 3681) an, indem in Eisessiglösung auf Einwirkung van 81 prozent. Salpetersäure die Carboxygruppe abspaltete und ebenfalls 2,4,5-trimethoxy-nitrobenzol entstand. Bruckner also finds the nitrated impurity when he prepared the pseudonitrosite the traditional way. As Fabinyi and Széki found that 2,4,5-trimethoxybenzoic acid is converted to the same 2,4,5-trimethoxy-nitrobenzene when treated with HNO3, my guess is that asarone is partially oxidized to 2,4,5-trimethoxybenzoic acid (as a side reaction; atmospheric oxygen and an acidic environment can cause this cleavage), which in turn is nitrated. For those interested in chemical history: Fabinyi and Széki have done quite some research in the asarone-field; for instance Post 431532 (GC_MS: "Characterization of asaraldehyde", Chemistry Discourse). Reference of the Bruckner text: V Bruckner. Über das Pseudonitrosit des Asarons. J prakt Chem 138 (1933) 268-274. Also found on Rh's site. Dirty old man



		randolph_carter (Hive Bee) 07-23-03 21:08 No 449327				well hold the phone ethyl......
						it looks like we have another acorus explorer!!! yer synth route sounds well....sound... read the post at rhod's site..... it has been dreamed as posted by none other than this stumbling questor ...... and the high yields are in fact doable..... i STRONGLY suggest that you hone yer org synth skills with some more simple quest prior to embarking on this adventure though...... it is infinitely more demanding than a rp/i bubble in the ice house........ but good luck and let us all know what YOU find in your adventures fellow questor..... i hope ya have some open minded friends..... the sexual potential is QUITE interesting!!!! "remember little ones, love is real,not fade away, so pass some ammo on today......"



		sponsan (Hive Bee) 07-23-03 23:28 No 449351				Hello Mr Carter :) I have read your previous...
						Hello Mr Carter :) I have read your previous adventures documented in Rhodium's archives - well done! The only part i was unsure about was your final reduction. Is the high yeild you reported really possible with leuckart on tma-2 ketone? Rhodium pointed me at the alternative reduction with NaBH4 + Al/Hg, with ~ 55% yield, which i am tending to lean towards as it seems very simple. But, the oxime route claims ~80% yield for MDA, and if the asarone ketoxime reduces in such yield also, i am going to probably go via oxime route to get the extra 30%. So far i've sucessfully completed mdma, mda and 2c-b synths, in decent yields. The organic synth skills have taken a big make-over over the last few sessions and seem to be improving. :) Will keep you all posted! Take care, Sponsan.



		gruns (Newbee) 07-26-03 08:11 No 449894				urushibara catalyst
						In antibody2's urushibara catalyst reduction of tmp2np, should the ethanol added be dry? Does anybody have any caveats for this reaction? over and under, then back to the start this sidewalk's bottom is the same as its top



		madprosr (Hive Bee) 08-19-03 05:56 No 454475				nitropropene -> ketone
						why not use Al/AcOH to form the ketone from the nitropropene? Rhodium posted an equivalent writeup for mdp2p giving 75% yeild...



		gruns (Hive Bee) 09-07-03 06:50 No 457558				I like the idea of performing only two ...
						I like the idea of performing only two reactions rather than three, especially such relatively simple ones. over and under, then back to the start this sidewalk's bottom is the same as its top

All 12 posts	End of thread	Top