| Pages:
1
2 |
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Heh, easy everyone.
I see my interest in this similar to all my other interests. Recently I checked out the nucleararchives.org site, and was quite fascinated by it.
Doesn't mean I want to acquire fissible material or whatever, or that I intend to build one. Or, I looked up the molecular structure of Ricin, and
its mechanism of action, just because I thought it fascinating that a single proteinaceous molecule can have such a devastating effect on the
organism. Doesn't mean I want to poison someone or myself. Or I check historical facts, doesn't mean I use that as a basis for some fanatical
terrorist action in the future. Similarly, many a time I heard in the news of the use of rP and I2 in the Meth manufacture. Being a semi-chemist, but
really a biochemist in nature, I wonder of course how the reaction works. Doesn't mean I am planning to make 10 kg of the stuff to sell it for large
sums of money  The same goes for a little thermite here or there - it's small
scale harmless pyrotechnics, and as most of us here we are simply fascinated by the chemistry, and the effects it may or may not have. Without us
people wondering and questioning, the world would be a much poorer place. Without the ability to wonder, and to follow up experiments ourselves as in
amateur chem, physics and biology, science will undoubtedly decline. Already, in my research environment, I see this trend- most people simply don't
have a 'natural' interest in science. Instead, they study because they think it 'might' be interesting, then do a PhD because they think it might be
good for the career, and some end up to become professional scientists because they don't know what else to do, or maybe because at last they became
interested. This is quite in contrast to the great minds in the past, where they were free to pursue their interests, and where this was actively
encouraged, and where this interest could grow from childhood onwards, in an unregulated manner. Regulation has its price.
All this aside - the thread originator may well ask what he does, there were many similar threads to this, although not necessarily such a high
profile well-known example. Check the ppa thread for instance, I don't even know how ppa might be useful, but after some playing around with the
structures I might see how. The point is, they approach it from the chemistry, and not the cookbook angle, and this is what this forum is about. THe
particular use is not our concern, as people are responsible for themselves what they use it for. Also, the reactions described there may well apply
to other interesting examples. For that reason I have actually considered renaming this thread to 'Reduction of alcohols - a case study' or something
like that, to reduce the attention this seems to be getting, and also to make this thread somewhat more generic.
For example, I'd be interested to see on what other systems this type of reduction could be used. I.e. tartaric acid, getting succinic acid, which
could be used to make N-bromo succinimide for instance. Or, reduction of Tris, to get tertiary butylamine. Plenty of possibilities.
At last, what other methods are there for the reduction of alcohols?
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
len
Harmless
Posts: 35
Registered: 17-7-2006
Location: Australia
Member Is Offline
Mood: No Mood
|
|
chemoleo, my thoughts precisely. I see the same happening to science around where I am. But it was never so beaurocratically difficult to those
great minds of the past as it is now. Of course most of my colleagues at work don't give a damn, to them what they do is a tool to promote
themsleves. Plus I agree with Polverone, once somtheing is regulated, the beaurocrats want let it from their grasp. They will say in the future:
look no more cyberzed's, thats because iodine is regulated.
Thanks Organikum, everythings clear to me now.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
I think discussing other ways of reducing alcohols would be too much for this thread - please open a new one for this purpose. I agree though that we
should discuss here the scope of the HI system. It deserves it not at least for all the fog and pseudowisdom which lays like a fog over the topic.
So on topic:
HI is told to rip oxygen out of virtually any organic molecule - sometimes harsh conditions regarding temperature, concentration and pressure are
required.
Next to oxygen HI takes nitrogen.
An optimized (for the amateur scientist) HI reduction system would IMHO look like this:
- 85-95% H3PO4 as solvent/reagent
- NaI/KI as iodine source
- H3PO2 (or H3PO3) for recycling the formed iodine back to HI
The system is useful for most substrates it covers a temperature range up to about 150°C* without requirering specialised hardware the reagents are
even nowadays to get without to much hassle and it´s one-pot.
*thats of course deadly for some substrates
Depending on the substrate either a catalytic (with certain esters/ethers IIRC) or at least equimolar amount of iodine (as NaI or KI) is used.
Other systems which have been employed in the past (NOT ephedrine specific!)
- rP/I in H2O
- rP/I without solvent
- HI 57% to 72%
- HI + HCL (pressurized vessel)
- rP + I + acetic acid
- H3PO2 + I
- H3PO3 + I
and combinations thereof.
At the end of the 19th century the reduction of organic compounds by HI was an indutrial standard in Germany. And that was the only country which
counts at this time. The process was discontinued after the formation of the IG-Farben when the processes of synthesis where streamlined over all
german producers and these kind of reductions got obsolete because other substrates where availabe. There was also switch from batch to continous
processes, not to forget that iodine was never really cheap.
Thats just from memory. If there is interest I dig up some more stuff.
/ORG
edited one typo where I wrote H3PO4 instead of H3PO3
[Edited on 27-7-2006 by Organikum]
|
|
|
wa gwan
Harmless
Posts: 37
Registered: 15-4-2005
Member Is Offline
Mood: No Mood
|
|
You said twice H3PO4 recycles I2 to HI. Show me please.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
| Quote: | Originally posted by wa gwan
You said twice H3PO4 recycles I2 to HI. Show me please. |
Where?
|
|
|
hodges
National Hazard
Posts: 525
Registered: 17-12-2003
Location: Midwest
Member Is Offline
|
|
| Quote: | Originally posted by Organikum
I think discussing other ways of reducing alcohols would be too much for this thread - please open a new one for this purpose. I agree though that we
should discuss here the scope of the HI system.
HI is told to rip oxygen out of virtually any organic molecule - sometimes harsh conditions regarding temperature, concentration and pressure are
required.
Next to oxygen HI takes nitrogen.
An optimized (for the amateur scientist) HI reduction system would IMHO look like this:
- 85-95% H3PO4 as solvent/reagent
- NaI/KI as iodine source
- H3PO2 (or H3PO4) for recycling the formed iodine back to HI
The system is useful for most substrates it covers a temperature range up to about 150°C* without requirering specialised hardware the reagents are
even nowadays to get without to much hassle and it´s one-pot.
|
Okay, question. So this will reduce just about any alcohol? Lets say if for some odd reason I decided to mix H3PO4 and KI with isopropyl alochol.
Will I see propane gas start bubbling out of the system?
Hodges
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Probably not. The boiling point of IPA is to low, so the necessary reaction temperature cannot be reached without pressurisation (thats a guess, I
never tried to reduce this alcohol). The reaction should proceed but VERY VERY slowly.
ORG
|
|
|
wa gwan
Harmless
Posts: 37
Registered: 15-4-2005
Member Is Offline
Mood: No Mood
|
|
meth is a fucking shitty drug
| Quote: | Originally posted by Organikum
| Quote: | Originally posted by wa gwan
You said twice H3PO4 recycles I2 to HI. Show me please. |
Where? |
"- H3PO2 (or H3PO4) for recycling the formed iodine back to HI
I can't seem to find the first mention but I may have misread something.
It should also be said that the straight HI deoxygenation has been reported elsewhere to be very unproductive even with gross excess of HI.
H3PO3 is more optimal reactant for amateurs than H3PO2.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Was a typo - obviously. I edited it ok?
Now this thread really attracts the methheads, I suggest to close it.
Those interested in the specific reduction of (pseudo)ephedrine to the amine please go to:
http://www.wetdreams.ws
[Edited on 27-7-2006 by Organikum]
|
|
|
skippy
Harmless
Posts: 35
Registered: 10-4-2004
Member Is Offline
Mood: No Mood
|
|
http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/p...
They have an interesting phenylacetic acid synthesis from mandelic acid where the reaction is in a phosphoric acid solution with a greatly reduced (to
my cursory glance) need for red phosphorus. I guess at elevated temperatures the phosphoric acid establishes an initial HI concentration that reduces
the need for elemental iodine recycling.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
On the matter of phenylephrine, the pseudoephedrine substitute -- it doesn't work as a decongestant! Funnily enough I noticed precisely the same with
my recent cold!
Phenylephrine lacks the beta methyl, but has an extra OH on the phenyl group - interesting that it'd make such a difference!
| Quote: | Pharmacists Rap New Version of Decongestants
By Randy Dotinga
HealthDay ReporterFri Jul 28, 11:54 PM ET
FRIDAY, July 28 (HealthDay News) -- Starting in late September, Sudafed and similar cold medications will only be available from behind pharmacy
counters because their active ingredient can be used to make the street drug methamphetamine.
So, consumers may be tempted to try a new type of drug that will be easier to buy. But two pharmaceutical researchers contend there's a big problem
with the new nasal decongestants: They don't work.
In a peer-reviewed letter released this week to the editor of the Journal of Allergy and Clinical Immunology, University of Florida researchers argued
that there's little evidence to suggest that the active ingredient in the new Sudafed PE or similar medications will do anything to relieve a stuffy
nose.
But Pfizer, the maker of Sudafed PE, stands by its product and says it's effective. "We've seen some positive results with how consumers are
responding to it," said company spokeswoman Erica Johnson.
Under the USA Patriot Act, any drug containing pseudoephedrine must be kept under lock and key starting Sept. 30. That means consumers won't be able
to find the drugs on store shelves; instead, they'll have to ask a store employee for the drug, show identification, and sign a sales log. Some
states, such as Oregon, are adopting even tougher laws, requiring prescriptions for drugs containing pseudoephedrine.
The law is designed to make it more difficult for people to get their hands on pseudoephedrine to make methamphetamine.
But according to University of Florida pharmacist Dr. Leslie Hendeles, what the law really does "is perhaps provide the prosecutor with a trail if
you're caught, but it doesn't prevent anyone from getting a large quantity and making meth out of it."
If consumers want to avoid the hassle of speaking to a pharmacist and signing a logbook to buy a nasal decongestant like Sudafed or Claritin-D, they
have other options. One of those options is Sudafed PE, whose active ingredient -- phenylephrine -- can't be used to make methamphetamine. Sudafed PE
has been on the market since February 2005.
In their letter, Hendeles and colleague Dr. Randy Hatton contended that when the U.S. Food and Drug Administration approved the use of phenylephrine
in 1976, the agency was only able to find four studies that suggested it worked at a dose of 10 milligrams, the size of Sudafed PE pills. Two of those
studies were sponsored by drug companies, and all were unpublished and not reviewed by peers, Hendeles said.
Seven other studies, according to the authors, found that phenylephrine didn't work better than a placebo.
"It does nothing," Hendeles said. "Clearly the 10 milligram (dose) does not work."
According to Hendeles, it seems that phenylephrine is simply not absorbed well by the body when taken in pill form. In a nasal spray, by contrast,
phenylephrine works fine, he said.
Hendeles and Hatton wrote that it's unclear if larger oral doses of phenylephrine would work better.
Johnson, the Pfizer spokeswoman, said five studies showed that phenylephrine works in pill form. "We're pleased that people are recognizing there are
alternatives, they have a choice," she said.
So, what should you do if you have a cold and need to unstuff your nose?
There aren't many good answers, since there's actually little research suggesting that any cold remedies are effective, including the ingredient in
the original Sudafed, said Dr. Bruce Barrett, associate professor of family medicine, at the University of Wisconsin Medical School at Madison.
To make matters worse, "none of the approved cold treatments is clearly beneficial with benefits outweighing risks," he said.
Nasal steroids do work in people with allergies, Barrett said. Hendeles recommended decongestant nasal sprays for people with colds.
|
[Edited on 30-7-2006 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
JohnWW
International Hazard
Posts: 2849
Registered: 27-7-2004
Location: New Zealand
Member Is Offline
Mood: No Mood
|
|
Why are they so sure that phenylephrine cannot be made into methamphetamine, like ephredine and pseudoephredine? Judging by its molecular structure,
it very probably CAN be. Does anyone have any suggestions as to how that could be done?
|
|
|
Vitus_Verdegast
Hazard to Others
Posts: 297
Registered: 5-12-2004
Location: Ottoman Empire
Member Is Offline
Mood: tea time
|
|
Phenylephrine lacks the alpha-methyl group, so it cannot be made into methamphetamine.
compare:
phenylephrine
Suppose one could remove the beta-OH group from phenylephrine, the resulting compound 3-hydroxy-N-methylphenethylamine will certainly be inactive.
One reason for this is the fact that the alpha-methyl group is needed to block the amine from attack by the body's monoamine oxidase enzymes.
Another reason is that phenolic phenethylamines or amphetamines are not lipophylic enough to cross the blood-brain barrier.
The increased hydrophility is also why (pseudo)ephedrine is so much weaker than methamphetamine, due to the beta-OH group.
[Edited on 31-7-2006 by Vitus_Verdegast]
Sic transit gloria mundi
|
|
|
JohnWW
International Hazard
Posts: 2849
Registered: 27-7-2004
Location: New Zealand
Member Is Offline
Mood: No Mood
|
|
Do you mean alpha to the N atom? (The methyl group)? Chemoleo said "beta methyl".
BTW For a fair comparison, you would also need to remove the phenolic 3-OH from the benzene ring. I wonder whether this compound has been made, and
compared with ephedrine or pseudoephedrine as a decongestant? And whether the other OH (alpha to the benzene ring) has also been removed, to make
N-methylphenethylamine, and compared with methamphetamine as a narcotic? That would certainly reduce the hydrophility.
|
|
|
Vitus_Verdegast
Hazard to Others
Posts: 297
Registered: 5-12-2004
Location: Ottoman Empire
Member Is Offline
Mood: tea time
|
|
It's the alpha-methyl group, chemoleo made a mistake. Beta would be next to the ring.
amphetamine stands for alpha-methylphenethylamine.
N-methylphenethylamine would be completely inactive as it is a perfect substrate to be attacked by the body's MAO-enzymes. The alpha-methyl group is
necessary to block it from this attack.
This is also why in general, if you look at PiHKaL, you will see that the various substituted amphetamines are more active and/or more potent than
their phenethylamine counterparts.
Un-ringsubstituted PEA however, will be attacked. N-substitutions don't matter.
Have a look at http://www.erowid.org/library/books_online/pihkal/pihkal142....
Of course, when taken in combination with a MAO-inhibitor such as harmaline this is a different issue, but such a combination is highly discouraged
considering the effects on blood pressure and the cardiovascular system.
N-methyl-beta-hydroxy-phenethylamine is in the Merck Index under the name halostachine. According to this paper it has mild sympathomimetic properties.
It is not possible to remove the phenolic 3-OH group and leave the beta-OH group intact.
[Edited on 31-7-2006 by Vitus_Verdegast]
Sic transit gloria mundi
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
Hector, I truly think you don't have a clue what does the word stabilized mean in the context of phosphorous, but in any case I can assure you that no
chemical stabilization can prevent red phosphorous from reacting with iodine.
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
I doubt that Merck adulterates the red phosphorus - many professional chemists all over the world would be outraged. Not to forget that Merck is not a
primary source of methcooks - only few can order from them.
I suppose that the problem is somewhere else.
But thats easily tested: Just mix some red phosphorus with iodine and add some water, heat and you will see the HI forming.
|
|
|
Ozone
International Hazard
Posts: 1269
Registered: 28-7-2005
Location: Good Olde USA
Member Is Offline
Mood: Integrated
|
|
Please see Gattermann on this (via PI3)! Recycling via H2S might actually make industrial reduction financially do-able (if the feds can be convinced
that we are not releasing it ).
Cheers,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
Hector, how is that red phosphorous stabilized? Please check the package. It is usually written bellow the chemical name. Is it a chemical
stabilization at all or is it only a paraffin coating or other similar physical stabilization?
|
|
|
solo
International Hazard
Posts: 3967
Registered: 9-12-2002
Location: Estados Unidos de La Republica Mexicana
Member Is Offline
Mood: ....getting old and drowning in a sea of knowledge
|
|
Acidity is basically controlled by effective stabilization of the product. Stabilized Red Phosphorus keeps the pH neutral when dispersed in water for
longer time. On storage, Red Phosphorus gradually starts releasing toxic phosphine gas & also starts forming different types of phosphoric acids.
The phenomenon shown in the diagram below is accelerated in improperly stabilized Red Phosphorus.
If the properly stabilized Red phosphorus is not used then the Phosphoric acids, which are formed, will start eating away the striking surface &
thereby lower the life of matchboxes. The strike surface does not withstand the repeated impact of matchsticks & does not live up to the
expectation of lighting the number of matches it is expected to do.
Higher acidic Red phosphorus when used over a period of time will also badly affect the printing drums by eroding the surface. In view of this, it is
necessary to use red phosphorus with lower acidity levels.
............source.
http://www.starchemicals.com/app_rp.htm
It's better to die on your feet, than live on your knees....Emiliano Zapata.
|
|
|
Eclectic
National Hazard
Posts: 899
Registered: 14-11-2004
Member Is Offline
Mood: Obsessive
|
|
The stabilizer may be the dangerous and highly restricted compound NaHCO3 (baking soda).
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by hector2000
Mr Nicodem in the label wrote phosphorus (red)(stabilised) for synthesis
it is in metal can.(assay >=97)
no paraffin coating |
In such case, when on the label there is no mention of a chemical stabilizator, you can safely assume that they consider the words "red" and
"stabilized" as synonyms in the context of phosphorous (since you can consider the red allotropic modification of phosphorous as the stabilized form
of this element). Or perhaps it is just meant that it is stabilized by removing all traces of contaminants that speed up its deterioration (see Solo's
post above). In any case this is not the reason of your friend's failure in using Merck's red phosphorous for iodine reduction.
|
|
|
Matchheads
Harmless
Posts: 21
Registered: 19-4-2007
Member Is Offline
Mood: No Mood
|
|
you guys kind of sorted yourselves out. i don't know what it is. it may be alike to reading the reagent over the arrow, this thing i do of
transferrence of admiration for those with the most posts, like Organikum. you should read the sm and the product and come up w/ the rgt to pass the
test.
it is true that the chat room consists of typing only and not drugs.it should be protected due to the omnibus "Methamphetamine Anti-Proliferation Act
of 2000", seeing that that was struck down as unconstitutional through the efforts of the ACLU.
however, if you get busted the ACLU is nowhere around. The First Amendment is the sort of thing that it is worth the risk to exercise our First
Amendment rights. There's no guarantee. You have to be willing to fight for it.
Everyone would love to make meth w/ HI only. Can't be done. To know why, you'd have to do experiments to get rates, and from them mechanisms. You
don't just write it. The course I took was "Reaction Rates and Mechanisms" or YEAH: "Reactor Kinetics". chemical engineering. very enjoyable. Many
of us are starting to think a hydride mechanism may be implicated, because that is the nature of the H in HI. I minus has such a large diameter, a
diffuse charge. so does hydride ion, H minus.
P has so many valences it probably shifts around from 3 to 5-substituted. Organikum said "H3PO2 or H3PO3". I don't think so. Hypophosphite's the
anion of interest. It wouldn't be both of those. Uncle Fester says to use sodium hypophosphite or just plain electroless nickel solution, to help
those who can't get good phosphorous. I believe him. He works in electroplating.
I've bought sodium hypophosphite. The electroless nickel solution was too expensive. The proprietary formulation was too hard for me to match. You
have to put ammonia in there too. I now suspect the additives. The plating actually consists of a nickel-phosphorous alloy. At this point the
NaH2PO2 traffic is probably under scrutiny.
BTW, whoever said meth was easy I would disagree. Benzyl methyl ketone is harder to get to than phenyl ethyl ketone, IMHO.
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
