First post here so lets hope one's not breaking any etiquette;
Background - secondhand sources have implied that calamus oil (with an assay of 86% alpha-asarone fwiw) was subjected to a 2-phase nitrosation. Diluted HCl and H2SO4 apparently gave similarly gooey results, however the poor yeild (~20%) was made up for in a spectacularly clean nitropropene after subsequent digestion and multiple recrystalizations... Assuming that said nitropropene was indeed the product of interest, it was apparently subjected to reduction via a 12x molar excess via al/hg.
Here's where the problems come in - Upon completion, the (acidic) mixture was no longer yellow but a dark orangeish hue (multiple runs yeilded the same result). Upon basification with conc. NaOH, both phases were a deep purplish-black. Separation followed by acidification of the organic again yeilded a burgundy auaeous layer and a nearly colorless organic - Subsequent A/B led to similar results... When basified, the smell of an amine was apparent, however it was not the "amber" hue described by shulgin. Standing in air, the (regardless of separation or not of the aqueaous pahse) solution became slushy, assuming it was reacting with atmospheric CO2 to form the amine carbonate - addition of a small amount of NaOH and further mixing once again removed the "slush." This was seen in every attempt.
Now, one is left to assume that the reaction was incomplete - It would appear that the nitro function was reduced to the amine, while the double-bond was not. One would assume that this is the cause of the intense coloration - a conjugated double-bond, giving a pH dependant color change due to imine-enamine tautomerism...
...So, has anyone any experience with TMA-2 that they could share? Does this sound familiar at all? Should one ferry word of success or failure? The final expeiment is to be isolated as the HCl salt soon - will (hopefully) find out what the result is, but a bioassay is to be postponed until more information can be gathered...
Background - secondhand sources have implied that calamus oil (with an assay of 86% alpha-asarone fwiw) was subjected to a 2-phase nitrosation. Diluted HCl and H2SO4 apparently gave similarly gooey results, however the poor yeild (~20%) was made up for in a spectacularly clean nitropropene after subsequent digestion and multiple recrystalizations... Assuming that said nitropropene was indeed the product of interest, it was apparently subjected to reduction via a 12x molar excess via al/hg.
Here's where the problems come in - Upon completion, the (acidic) mixture was no longer yellow but a dark orangeish hue (multiple runs yeilded the same result). Upon basification with conc. NaOH, both phases were a deep purplish-black. Separation followed by acidification of the organic again yeilded a burgundy auaeous layer and a nearly colorless organic - Subsequent A/B led to similar results... When basified, the smell of an amine was apparent, however it was not the "amber" hue described by shulgin. Standing in air, the (regardless of separation or not of the aqueaous pahse) solution became slushy, assuming it was reacting with atmospheric CO2 to form the amine carbonate - addition of a small amount of NaOH and further mixing once again removed the "slush." This was seen in every attempt.
Now, one is left to assume that the reaction was incomplete - It would appear that the nitro function was reduced to the amine, while the double-bond was not. One would assume that this is the cause of the intense coloration - a conjugated double-bond, giving a pH dependant color change due to imine-enamine tautomerism...
...So, has anyone any experience with TMA-2 that they could share? Does this sound familiar at all? Should one ferry word of success or failure? The final expeiment is to be isolated as the HCl salt soon - will (hopefully) find out what the result is, but a bioassay is to be postponed until more information can be gathered...