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Formula409
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Thank you manimal. I also found this procedure which calls for the imine to be formed before adding the reducing agent. It doesn't need nitrogen,
however and still gets quite a good yield.
http://www.erowid.org/archive/rhodium/chemistry/redamin.aque...
| Quote: |
To a solution of 1-(2,4-dimethoxyphenyl)-2-propanone (48.56g, 250 mmol) in 300 ml IPA was added a solution of methylamine hydrochloride (25.3g, 375
mmol) in 30 ml water followed by dropwise addition of a solution of NaOH (15g, 375 mmol) in 40 ml water during 10 minutes while stirring the mixture
violently. When the addition was complete the mixture was stirred for another hour at room temperature.
A solution of sodium borohydride (5.5g, 145 mmol) in 20 ml water containing 25 mg NaOH (to prevent decomposition) was then added dropwise over 30
minutes while the mixture was stirred violently. When addition was complete the stirring was continued for two hours. The residual borohydride was
destroyed by addition of 2M hydrochloric acid (1:5 37% HCl:H2O) until gas evolution ceased and pH 3 was reached. The alcohol was removed by
distillation in a rotovap and the aqueous solution diluted with 100 ml water, extracted once with 50 ml toluene, made strongly alkaline with 25% aq.
NaOH and then extracted with 2x50 ml toluene. The combined alkaline extracts was dried over MgSO4 and the solvent removed by distillation. The
residual oil was dissolved in 200 ml EtOAc and 5N HCl/IPA was added in portions until pH 5 was reached. Several times the acid addition had to be
stopped and the formed crystals removed by filtration. The salt was then recrystallised in IPA.
Yield: 48.5g 2,4-Dimethoxymethamphetamine HCl (79%).
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One would imagine that one would just substitute in an equivalent molar amount of TUD to test it.
What would be an easy substrate to test this on? I was thinking along the lines of Fructose, as it is quite a readily available ketone.
Formula409.
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497
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I don't know if TUD could directly replace NaBH4 in that writeup. TUD requires a strongly basic environment to work, while NaBH4 does not AFAIK. So I
would add more NaOH..
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UnintentionalChaos
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| Quote: |
What would be an easy substrate to test this on? I was thinking along the lines of Fructose, as it is quite a readily available ketone.
Formula409. |
Cyclohexanone? MEK?
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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kclo4
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Would fructose even work in that reaction as the ketone? It would fascinate me if it did.
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smuv
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Fructose is a ketone...at least something like 1% of the time. Fructose exists as an equilibrium between a linear ketone and a cyclic hemiketal.
This is why fructose is considered a ketose.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Formula409
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| Quote: | Originally posted by smuv
Fructose is a ketone...at least something like 1% of the time. Fructose exists as an equilibrium between a linear ketone and a cyclic hemiketal.
This is why fructose is considered a ketose. |
Damn. Looks like I'll try my hand at the amination with MEK unless anyone can think of a suitable substrate that isn't going to turn into a
phenethylamine/amphetamine and get me vanned 
Formula409.
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Aubrey
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"...A solution is made by stirring 73.5 grams (0.5 mole) of finely powdered
phthalimide with 250 ce. water and 125 grams of ice and then
adding 55 cc. sodium hydroxide solution (40° Be)."
rom Dye chemstry. There is an accent over the Be, what does this mean?
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sparkgap
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@Aubrey: see this.
sparky (~_~)
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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smuv
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Under strongly basic conditions, imines don't form, except with really nucleophilic amines such as hydroxylamine and hydrazine (draw out the
mechanism, see for yourself; the hemiaminal needs to be dehydrated, and in basic conditions this is not favorable).
To do this, with thiourea dioxide (which I am not familiar enough with to say if it would even work) you would need to generate the imine then treat
it with base and reducing agent; you can't just substitute it directly into those borohydride procedures.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Formula409
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| Quote: | Originally posted by smuv
Under strongly basic conditions, imines don't form
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Are they stable in strongly basic conditions (pH 13.5-14), however?
| Quote: |
To do this, with thiourea dioxide (which I am not familiar enough with to say if it would even work) you would need to generate the imine then treat
it with base and reducing agent; you can't just substitute it directly into those borohydride procedures. |
Understood. A solution of pH 13.82 (0.66M) seems to be used in this reference (http://www.sciencemadness.org/talk/viewthread.php?action=att...).
Formula409.
[Edited on 21-2-2009 by Formula409]
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not_important
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| Quote: | Originally posted by Formula409
... Looks like I'll try my hand at the amination with MEK unless anyone can think of a suitable substrate that isn't going to turn into a
phenethylamine/amphetamine and get me vanned
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Carvone (caraway), camphor, methyl isobutyl ketone (much less water soluble than MEK and used in some OTC products).
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manimal
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What is a kewl?
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Formula409
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| Quote: | Originally posted by manimal
What is a kewl? |
In what context was the term used? Normally in chemistry/pyro circles it refers to one who comes onto a forum with a primary interest in creating a
drug/explosion in the easiest way possible with no concern for the reaction mechanism or safety consideration.
Formula409.
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sparkgap
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@manimal: This may be enlightening.
sparky (~_~)
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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Aubrey
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If i want to preprepare specific concentrations of NaOH / dH20, will these keep or do they decompose? Its the kind of thing that seems pretty useful
for lots of experiments and it can be a pain when you spill litle granules o it and it make the newspaper orange. noob question i know 
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smuv
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@Formula: Imines will hydrolyze under strongly basic conditions, how quickly is hard for me to say; for that matter they hydrolize under acidic
conditions as well. To avoid hydrolysis one could add the imine dropwisely to a solution of thioureadioxide and the base; hopefully this would reduce
the bulk of the imine faster than it hydrolized. Also if you could acomplish this reaction in an appreciably dry solvent (say methanol) hydrolysis
would be minimal.
@Aubrey: Sodium Hydroxide solutions are stable so long as they are tightly capped. If they are not tightly capped they absorb CO2 from the air to
contaminate the solution with a lot of carbonates. Store concentrated NaOH solutions in HDPE or PMP plastic bottles as concentrated solutions will
(slowly) attack glass.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Ebao-lu
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I'd like to add, never use usual plastic bottles (like coca cola, sprite, soda water etc) for alkaline solutions storage(and ammonia solution). The
bottom will be destroyer after some time, and the solution will leave the bottle
As for imines reduction with TUD, there is a problem of solubility also. If you want to do this in water, then imine should be stable there, and
soluble(i'm not sure the base is a good catalyst fot hydrolysis, but it will surely proceed without any catalyst if the imine is not stanle enough).
And if it is some fatty-like alkylarylketone, i.m sure its solubility in water is an issue.
Carying out the reduction in organic solvents is also problematic because TUD is having a slight or a poor solubility in most organic solvents, and
its deprotonated form - even worse. (still, maybe it is possible, but should take much time, or a special method to evelate the deprotonated TUD
solubility there). And if the imine is comperatively stable in water and alkaline, but not enough soluble, you can try to use a kind of biphasal
system - IPA layer with imine and water layer with NaOH/TUD. The main problem is the eqiulibrium concentration of a ketone in comparison to the rate
of reduction by TUD - you can get only alcohol if the imine is unstable.
[Edited on 22-2-2009 by Ebao-lu]
[Edited on 22-2-2009 by Ebao-lu]
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hellfire23
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I am planning on doing a nitric acid synth using the KN03 and H2SO4 route, but I have recently acquired 2lbs of sodium bisulfate I was wondering if I
could use a sodium bisulfate solution as a substitute for the sulfuric acid, as that acid is somewhat precious to me.
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DJF90
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I'm pretty sure this has been covered before here. I'm not 100% but I think you can heat the solid bisulfate with the nitrate to yield nitric acid.
UTFSE.
http://www.sciencemadness.org/talk/viewthread.php?tid=2823&a...
Edited to add link.
[Edited on 23-2-2009 by DJF90]
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pantone159
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Disposal of sodium sulfide
I have a bottle of sodium sulfide, that I got about 2 years ago. I did not open it until now, and it seems the bottle was not well sealed - there is a
solution inside, along with some crystals.
I figure the stuff is no good now, and I plan to dispose of it. Is there a convenient way to react it into something less hazardous?
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Nicodem
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| Quote: | Originally posted by pantone159
I have a bottle of sodium sulfide, that I got about 2 years ago. I did not open it until now, and it seems the bottle was not well sealed - there is a
solution inside, along with some crystals.
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That is a quite normal situation for sodium sulfide nonahydrate. It is still useful for most things you would want to use it, just use the solid and
decant the liquid.
You can destroy the sulfide with most oxidants or you can form an insoluble sulfide, but pouring small amounts into the sink will do no harm to the
ambient. There are plenty of organisms feeding on H2S and sulfides and none of those who would be harmed by it live in the sewage system.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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dann2
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Hello,
Can anyone direct me in the direction of a graph or table showing saturated Sodium Chloride solution densities, or a table/graph telling me grams or
moles per liter of saturated solutions. (I have lots of info. grams/moles per 100grams water).
I obtained a paper on Sodium Chloride densities (thanks to noe_c) but I never realized something as simple as NaCl solutions could be made so
complicated!!!!
I could work it out with pencil (like the constipated Accountant) but a table would be nice.
TIA,
Dann2
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pantone159
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| Quote: | | Originally posted by NicodemYou can destroy the sulfide with most oxidants |
Bleach (5-6% NaOCl) would be fine, presumably? Since you say that it is still good, I'll keep the Na2S-9H2O, but I do want to know how it might be
treated, I might practice with some of it. There actually seems to be some mold growing in there, maybe I'll scrape it out, pour off the liquid, and
treat that with bleach as practice. Nice point about the sewer system - that is kind of where sulfides go normally, so a little Na2S will fit right
in!
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Formula409
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Could someone please provide me with some data regarding n-methylcamphoramine/n-methylcamphorimine (BP, solubility, etc). Google is turning up
nothing, so my naming nomenclature must be incorrect.
Thanks!
Formula409.
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sparkgap
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"my naming nomenclature must be incorrect"
Apparently; your "n", if it does imply that it's attached to the nitrogen atom should be capitalized. Anyway, how about drawing the structure so we
all have a better idea of what to look for?
sparky (~_~)
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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