downwardsfromzero
Boundary condition
So my neighbour's crazy friend has been at it again! There's one part of the report I've not seen mentioned in any way anywhere else before - using basic, wet IPA to pull from limonene.
Apologies for the length of this post - I've put a summary of important points at the end of the post.
Here is a report in brief of his latest story:
"*oxidised solid DMT collected from on top of 3yr old MRHB/STB.
*dissolved in dH2O/ascorbic acid solution forming a deep orange solution. Simmer 5mins. Add a suitable amount of NaOH.
*cool and extract with light naphtha - but do not remove naphtha from the surface of the liquid. Stopper well - but not completely airtight - and refrigerate for a total of about 3 years.
*less than halfway through the refrigeration period, all the naphtha has evaporated, leaving a suspension of curdy precipitate resembling mould/yeast infection.
*place in a water bath and bring the temperature up to 100degC. The curdy precipitate redissolves and the orange colour of the solution becomes more of a deep yellow.
*allow to cool, then place back in the refrigerator. Subsequent observation shows return of the curdy precipitate, plus small crystals have formed in the same area/volume. This indicates it wasn't mould - not so surprising at pH >10.
*maybe repeat the heating step a year later.
*temperature cycling between 4degC and room temperature produces enlargement of the crystals to a maximum of about 2mm x 1mm.
*at some point when the time seems right, add a couple more spoonfuls of NaOH and a requisite amount of NaCl. Place in a separatory funnel and extract with 6 portions of limonene. The limonene turns cloudy, but the insolubles soon settle out to form a layer between the limonene and the aqueous phase leaving only a slight haze in the limonene.
*drain off the cloudy material and put to one side in a tall, thin container, e.g. a large test tube. More limonene will float off from the insolubles, and more aqueous solution will drain beneath. Use a pipette to transfer the limonene in with all the rest of the limonene. Use another pipette to transfer the aqueous phase into the bulk of the same - which was kept (haven't you??)
*back-extract the combined limonene pulls with 5 portions of 5% acetic acid.
*put all the acetic acid pulls into a a broad pyrex dish of a suitable size and evaporate to dryness using standard methods, e.g. computer fan and reptile heating mat works well. It stinks of vinegar while this is taking place.
*scrape up acetates and marvel at how little there seems to be. Now look back at the limonene and see how orange it still looks. Hmmm....
*going back to the tube of curdy gunk, an amount of isopropanol was added and the tube was swirled to mix. This caused the limonene to float to the top, in between was a layer of IPA and at the bottom was the aqueous phase, with the gunk floating between the water and the IPA.
*both the limonene and the IPA were virtually crystal clear - all the cloudiness had been pulled down to the aqueous part - but... virtually all the orange coloration had been transferred to the IPA phase!! The limonene had only a very slight yellow tinge remaining.
*this was scaled up in order to wash the limonene: the vinegar extracted limonene was washed with saturated sodium carbonate solution (3 to 4 potions making a volume about half that of the limonene). The washes were kept. Isopropanol was mixed with the saturated sodium carbonate washes. Further anhydrous Na2CO3 was added. Two layers formed and the upper, IPA-rich layer was added to the limonene in the separatory funnel.
*lo and behold! Three layers formed - the limonene clear and pale yellow, the IPA now a deep orange and the water cloudy and only a very faint yellow. The layers were separated and placed into stoppered flasks.
*presumptive testing of the IPA showed a result corresponding to that which might be expected from DMT.
*the IPA was dried with anhydrous sodium carbonate powder, then carefully decanted into a test tube to settle thoroughly. After settling, the IPA was removed by pipette and placed into a suitably sized Erlenmeyer flask.
*FASA was added. A thick white precipitate immediately formed. At some point a further test drop of FASA to the solution did not produce any further turbidity.
*the flask was allowed to stand for a couple of days, during which time the precipitate clumped together in bigger lumps but refused to settle out or become crystalline."
The question here is how to procede and separate the precipitate from the liquid?
Filtration is considered too tedious (ironically!!) and risks yield reduction. Perhaps temperature cycling may help to grow the crystals, e.g. hot water bath, slow cooling, fridge, then freezer, repeat if necessary.
Decanting into a test tube may also help, although the crystals are then stuck at the bottom of a tube.
Any other suggestions?
Summary:
* Ascorbate appears to reduce oxidised DMT under alkaline conditions.
* There is a byproduct which seems to be insoluble in water, limonene, IPA and acetone.
* Basic (Na2CO3) wet IPA extracts DMT and orange coloration from acetic acid washed limonene, forming three phases.
* The IPA extract after drying produces abundant precipitate with FASA.
* Refrigerating for 3 years is probably unnecessary
Apologies for the length of this post - I've put a summary of important points at the end of the post.
Here is a report in brief of his latest story:
"*oxidised solid DMT collected from on top of 3yr old MRHB/STB.
*dissolved in dH2O/ascorbic acid solution forming a deep orange solution. Simmer 5mins. Add a suitable amount of NaOH.
*cool and extract with light naphtha - but do not remove naphtha from the surface of the liquid. Stopper well - but not completely airtight - and refrigerate for a total of about 3 years.
*less than halfway through the refrigeration period, all the naphtha has evaporated, leaving a suspension of curdy precipitate resembling mould/yeast infection.
*place in a water bath and bring the temperature up to 100degC. The curdy precipitate redissolves and the orange colour of the solution becomes more of a deep yellow.
*allow to cool, then place back in the refrigerator. Subsequent observation shows return of the curdy precipitate, plus small crystals have formed in the same area/volume. This indicates it wasn't mould - not so surprising at pH >10.
*maybe repeat the heating step a year later.
*temperature cycling between 4degC and room temperature produces enlargement of the crystals to a maximum of about 2mm x 1mm.
*at some point when the time seems right, add a couple more spoonfuls of NaOH and a requisite amount of NaCl. Place in a separatory funnel and extract with 6 portions of limonene. The limonene turns cloudy, but the insolubles soon settle out to form a layer between the limonene and the aqueous phase leaving only a slight haze in the limonene.
*drain off the cloudy material and put to one side in a tall, thin container, e.g. a large test tube. More limonene will float off from the insolubles, and more aqueous solution will drain beneath. Use a pipette to transfer the limonene in with all the rest of the limonene. Use another pipette to transfer the aqueous phase into the bulk of the same - which was kept (haven't you??)
*back-extract the combined limonene pulls with 5 portions of 5% acetic acid.
*put all the acetic acid pulls into a a broad pyrex dish of a suitable size and evaporate to dryness using standard methods, e.g. computer fan and reptile heating mat works well. It stinks of vinegar while this is taking place.
*scrape up acetates and marvel at how little there seems to be. Now look back at the limonene and see how orange it still looks. Hmmm....
*going back to the tube of curdy gunk, an amount of isopropanol was added and the tube was swirled to mix. This caused the limonene to float to the top, in between was a layer of IPA and at the bottom was the aqueous phase, with the gunk floating between the water and the IPA.
*both the limonene and the IPA were virtually crystal clear - all the cloudiness had been pulled down to the aqueous part - but... virtually all the orange coloration had been transferred to the IPA phase!! The limonene had only a very slight yellow tinge remaining.
*this was scaled up in order to wash the limonene: the vinegar extracted limonene was washed with saturated sodium carbonate solution (3 to 4 potions making a volume about half that of the limonene). The washes were kept. Isopropanol was mixed with the saturated sodium carbonate washes. Further anhydrous Na2CO3 was added. Two layers formed and the upper, IPA-rich layer was added to the limonene in the separatory funnel.
*lo and behold! Three layers formed - the limonene clear and pale yellow, the IPA now a deep orange and the water cloudy and only a very faint yellow. The layers were separated and placed into stoppered flasks.
*presumptive testing of the IPA showed a result corresponding to that which might be expected from DMT.
*the IPA was dried with anhydrous sodium carbonate powder, then carefully decanted into a test tube to settle thoroughly. After settling, the IPA was removed by pipette and placed into a suitably sized Erlenmeyer flask.
*FASA was added. A thick white precipitate immediately formed. At some point a further test drop of FASA to the solution did not produce any further turbidity.
*the flask was allowed to stand for a couple of days, during which time the precipitate clumped together in bigger lumps but refused to settle out or become crystalline."
The question here is how to procede and separate the precipitate from the liquid?
Filtration is considered too tedious (ironically!!) and risks yield reduction. Perhaps temperature cycling may help to grow the crystals, e.g. hot water bath, slow cooling, fridge, then freezer, repeat if necessary.
Decanting into a test tube may also help, although the crystals are then stuck at the bottom of a tube.
Any other suggestions?
Summary:
* Ascorbate appears to reduce oxidised DMT under alkaline conditions.
* There is a byproduct which seems to be insoluble in water, limonene, IPA and acetone.
* Basic (Na2CO3) wet IPA extracts DMT and orange coloration from acetic acid washed limonene, forming three phases.
* The IPA extract after drying produces abundant precipitate with FASA.
* Refrigerating for 3 years is probably unnecessary
