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Sauron
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[*] posted on 28-12-2006 at 05:44


Scientific inquiry should be free.

Maybe expensive but untrammelled.

The Nanny State should be resisted as much as Big Brother.

Lest we forget, how many public and university libraries are there? Many many yet not enough. Should censors be rifling through the journals and the books ripping out politically incorrect knowledge? As if there was such a thing!

Personally I find energetics chemistry fascinating but am not motivated to actually make any. Been there, done that.

Military chemistry, fascinating. That does not mean I want to make chemical weapons. The more you know about them the less you ever would want to be anywhere near them. There are quite a few Edgewood scientists whose vervous systems are a mess because of long term exposure to agents that were at levels that for many years were considered harmless. Turns out otherwise.

But on paper, quite fascinating.

The drugs thing, personally I am sick to death of it, and grit my teeth every time I see a post about an amphetamine precursor etc etc BUT I am not about to advocate telling another chemist what to investigate. Once upon a time heroin was a Bayer cold remedy, cocaine was a soft drink ingredient. The governments passed out amphetamiones to troops in wartime. Who's to say what perfectly respectable pharmaceutical of today might not be tomorrow's Schedule One abuse drug? PCP was developed as a therapeutic agent by Eli Lilly. Then the military spent years testing its potential for use as a chemical weapon (failed.) It didn't become a street drug till after that, maybe because of that.

What I REALLY hate is being told by some mindless Nanny State bureaucrat that I can't have a perfectly legitimate solvent or reagent or even certain elements. That's an insult to human ingenuity. And it's arbitrary and ineffectual. That is when I crack a reference book and start planning a preparation.
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[*] posted on 28-12-2006 at 12:04


interestng rant Sauron

if big brother is the USA who is the Nanny State? china?

not everyone can fit into the mold.... like Vincent van Gogh sometimes we have to drink absinthe, cut off our ear, and paint something that will go on beyond ourself....

yes cutting your ear off is foolish and absinthe probably aint good for ya either....
what should i do, work on my 401K and play golf when im sixy till i die a quite little death

shoot poor me some absinthe

not that there is anything wrong with golf mind you....
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Sauron
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[*] posted on 28-12-2006 at 13:01


Interesting that you would bring up absinthe. I'll get back to that in a moment.

Many governments are Big Brother not only the US. Many governments are Nanny States and treat their citizens like children in need of comprehensive protection. For example the EU tramples on free speech in certain areas (arguably with some justification) but much more so than does the US. The UK and its pervasive use of CCTV surveillance is definitely turning into Big Brother even down to the infamous telescreens of Orwell's nightmare dystopia.

Back to absinthe. I used to make absinthe, I used to drink absinthe, and I know something about the subject. I almost started making it commercially, formed a company to do it, then opted out. My former partner continued with the project and now rents one of the remaining two absinthe distilleries in France in Pontarlier near the Swiss Jura, that is the original home of absinthe. He makes Jade absinthe there, which is distributed by Liqueurs de France in the UK, to worldwide.

If you go to the Oxford University chemistry Dept. website you can find a page in the Molecule of the Month section called Absinthe & Thujone. I am the author of that page. I am told that it is their most popular webpage.

You may or may not know that absinthe is once again perfectly legal in the EU and also in Switzerland. Just about the only place that still bans it is USA and that is merely the US FDA being obstinate.

Thujone is the supposedly psychoactive component of wormwood. (Artemisia absinthium) and is a monoterpene closely related to camphor and menthol. The simple fact is that thujone does not drive anyone mad. It is the principle component of the culinary spice sage's essential oil. Sage does not make us crazy. It is the principle component of red and white cedar oil. Anyway there is not much thujone in absinthe and never was. The main herbal component of absinthe is anise while wormwood is a relatively minor part of the mix. There's more fennel in there than wormwood. Absinthe is made much in the same manner as gin, but the steep or maceration is done at high proof and the mixture is distilled with the herbs still in the pot. A delicate coloration step with more herbs balances the flavor and bouquet and provides the famous peridot green color. That is how authentic absinthe is made, from only herbs, grape alcohol and water.

The problem was that in the 19th and very early 20th century absinthe became so popular and so profitable that besides the 3-4 major distillers like Pernod and Berg who made real absinthe there arose scores of slipshod imitators who did not know or care how to make the real absinthe. They used chemicals to imitate the properties of genuine absinthe. For example they sometimes used aniline green dyes to color the drink or even Paris green rat poison (copper acetoarsenate.) They used antimony compounds to make the liquor cloud when diluted with water. Now what do you think the health effects were of that sort of chemical soup? And in a typical alcohol content of 72 degree -- 144 proof.

Old Vincent by the way was barking mad and had a pica for turpentine (a-pinene mostly)

Anyway politics reared its head. The wine industry, dormant since the phylloxera blight of the mid 1800s, had recovered and wanted their customers back, who by then had been drinking absinthe in place of wine for 50 years. They joined forces with the church based temperance movement and lobbied to ban absinthe and all other herbal liquors. They suborned the press, notably polemicist Emile Zola, to pamphleteer against absinthe. In the buildup to the World War the French military jumped on the bandwagon, they wanted to sober their cannon fodder up so they could go kill Germans with a clear head. By 1915 absinthe was banned in many countries. Not all. Spain never banned it. The UK never banned it. Pernod moved to Terragona, Spain and continued to make absinthe until 1957.

Much of the culture and artistic and literary history of the Belle Epoch is steeped in absinthe, For a highly ideaolized glimpse see Moulin Rouge (the recent musical film), or Johnny Depp's From Hell. Or the absinthe scene in Dracula. The real absinthe is a refined floral drink that is without peer. (Pastis is a pale imitator, mixed from oils and not distilled at all.)

Sadly I can no longer drink due to diabetes and hypertension but, I have my memories of la Fee Verte. (The Green Fairy.)
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[*] posted on 28-12-2006 at 15:07


Wow, I love when I accidentally mention the right word to the right person. Of all the people in the whole world to mention that word to.

See Ive started to still up alcohol for fuel purposes, but im working on a good whiskey recipe on the side. Ive wanted to make some absinthe mainly because its illegal is the USA. Hahaha go figure… I have a feeling it will just make me puke though, it appears that alcohol is the “effect” of the drink then…. Which makes me puke usually…

But after reading your page at oxford it appears the over all effect is the presentation and boutique. The act, the pomp, maybye a bit of circumstance…
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Sauron
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[*] posted on 28-12-2006 at 19:45


The main "active" component in absinthe is not thujone but anethole, q.v. Oil of anise.

The subject is OT in this thread, and except in general terms I am constrained by agreement with my former partner from giving his secrets away. He has spent years collecting unopened bottles of well preserved century old absinthe. He has reverse engineered the very best of them using GC-MS on aliquots taken by syringe through the cork and lead seal. About 9 years of research altogether. He is one of us, a chemist, also an envirnmental microbiologist working in remediation. He lives in New Orleans. If you Google on Jade absinthe you will read about his Edouard and Nouvelle Orleans labels. IMO the finest and by far most absolutely authentic absinthes the world has seen for at least 50 years since Pernod went out of business. (The modern conglomerate Pernod-Ricard bought the Pernod name a decade later but they know little about making absinthe. They are european Big Liquor.
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[*] posted on 1-1-2007 at 23:44
absinthe


Sauron, I thought you might enjoy hearing that your former partner and his absinthe distillery (Combier) were shown on the History channel tonight. His name was Breaux. He talked about the history of absinthe and his reverse engineering of the old recipes. He gave a plant tour showing how he makes Jade absinthe. He also showed how it is properly drunk using the double glass with the ice on top. Very nice presentation. ;)



The single most important condition for a successful synthesis is good mixing - Nicodem
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Sauron
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[*] posted on 2-1-2007 at 01:21


Thanks Magpie for calling that to my attention. I don't bother with cable TV in Thailand. It's available but boring.

Ted Breaux is a genius at publicity. He is also a vert personable fellow who strongly resembles Brad Pitt or Val Kilmer.

For which I hate him.

Just kidding.

BTW I am the one who named Jade Absinthe, while Ted picked the names of the specific variations, Edouard (after Edouard Pernod) and Nouvelle Orleans (for our mutual home town.)

I wish him all success.

[Edited on 2-1-2007 by Sauron]
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Sauron
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[*] posted on 2-1-2007 at 02:01


Back to the topic of politically incorrect chemistry:

I'd like to reiterate that there is no such thing as good chemistry vs evil chemistry, in the abstract. Just as explosives can be applied for good or ill, and almost all drugs of abuse have legitimate applications as well, if only in research in some instances, so also is it true that "chemical weapons" have their little publicized up side.

Cancer chemotherapy is an application of mustard vesicants to the selective destruction of tumors. Cancer chemo compounds are all or almost all derivatives of, or variations on nitrogen mustards (HN3 etc) not to be confused with hydrazoic acid. HN3 is the chlorinated form of triethanolamine.

DFP, an early nerve agent, is a standard tool in opthamology.

Esters of 3-quinuclidinol are important pharmacologic agents while BZ itself (renamed QCB) is a niche tool in psychopharmacology.

It's an ill wind indeed that blows no good.

The crimes against humanity associated with CW, and in some cases crimes against the environment and the very human genome, were committed not by individuals or by terrorists but by GOVERNMENTS who perverted science to their own ends.

So the proposition that the science itself is now beyond the Pale, is simply Thought Control and soon to be followed by the Thought Police.

What's next, Fahrenheit 451 and burning books?

Let me cite some examples of the utter absurdity this has already led us into:

The CWC bans pinacolyl alcohol and the Australia Group would like to extend that to pinacol and ponacolone.

Pinacolyl alcohol is the alcohol portion of the chemical agent GD (Soman).

Now, pinacolyl alcohol is prepared by the reduction of pinacolone, and pinacolone is the rearrangement product of pinacol and pinacol is prepared by the reduction, usually with Al-Hg (aluminum amalgam) in ethanol, of acetone.

The prep of pinacol and the conduct of the pinacolone rearrangement used to be very very ubiquitous instructional lab procedures. They are covered in Vogel.

Bear in mind that the other major nerve agents also have alcohol moieties. GA and VX have ethanol while Sarin (GB) has 2-propanol.

So why ban pinacolyl alcohol and not ban ethanol, or isopropanol?

Well, those have other uses while pinacolyl alcohol has few if any other uses. So it was easy for the member nations to agree on.

But pinacolyl alcohol is in and of itself HARMLESS in exactly the same way that rubbing alcohol (isopropyl) is harmless. The "business end" of the agents is the alkylphosphonate (or phosphorlamine) part.

What rubbish.

Furthermore, how do you effectively ban something that is facily prepared from nail varnish remover (acetone) by treatment with aluminum foil that has been brushed with a wee bit of HgCl2? Making pinacol>pinacolone>pinacolyl alcohol is child's play.

You see the absurdities?

There are many others.

Ever heard of the red tide? Off the pacific northwest coast, periodically there's a bloom of a specific dinoflagellate (algae) which produce a toxin called saxitoxin. The saxitoxin accululates in certain shellfish, and sometimes people who east the shellfish are poisoned. A certain well known alphabet soup agency had its technical services division study this toxin. They laboriously obtained it in pure form. AFAIK it was never used and it was banned by that agency's director in the 1970s.

Well, CWC has saxitoxin on its list.

There's a small company in Canada which developed a useful test kit to determine the presence of saxitoxin in mollusks in order to prevent any more outbreaks of shellfish poisoning in seafood restaurants.

The kits included an infinitesmal amount of saxitoxin to be used as an internal standard. The kits could have and would have saved who knows how many human lives?

CWC BANNED THE TEST KITS.
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[*] posted on 13-1-2007 at 07:18


Illegal drugs are just active substances with a pharmaceutical affect. What those evil connotations to illegal drugs do is make it harder for the pharmacists to do real research on basic active structures. Think about legal drugs like dihydroergotamine. By making the processes and the natural sources of these substances taboo, power is taken away from the individual researcher and given to the corporations. It says "Hey, you can play with whatever chemicals you want as long as you do it under the supervision of the pharmaceutical industry". Then, any new drug or chemical synthesized is then property of the company the chemist works for.

All chemical legislation targets home chemists, both drug makers and legitamite scientific researchers. I just don't understand why we can't just let people do drugs. They're usually only hurting themselves.




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Sauron
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[*] posted on 13-1-2007 at 07:30


Academic and pharmaceutical chemists have little or no trouble obtaining licenses to work with controlled substances. A good friend of mine is a professor of biochemistry at a medical school in Switzerland and he spends a fair amount of time filling out paperwork so that his department can buy for example piperidine to use as deprotecting reagent for Fmoc strategy peptide synthesis. They use maybe 50 liters a year. The Swiss govt does not say "no" they just want assurances that the material won't be diverted to making phencyclidine (for example.)

In the USA most every MD has a DEA number. So does every pharmacist. The pharm companies have them, academic labs have them if they need to buy reagents that are controlled, or study substances that are controlled.

Caught in the middle are the "home chemists" who can't qualify for lack of licensable facilities, credentials, or qualifications. You and I agree that this is a shame.
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[*] posted on 13-1-2007 at 07:38


One of the few researches in the US that has the DEA permit to work with schedule 1 drugs is David Nichols, so it is simply not true that it is easy to get the permit, for Strassman it took several painstaiking years to get the permit to work with DMT on adult volonteers. Admittedly I have no idea how it is with controlled substances that are not schedule 1, maybe it is easier but I doubt it is easy, at least if you are in the USA.

[Edited on 13-1-2007 by Sandmeyer]
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Sauron
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[*] posted on 13-1-2007 at 08:27


DEA does not regulate human trials of anything, that is an entirely different regulatory framework

And it applies to substances that are not and have never been DEA scheduled.

I am not in life sciences, I am not sure where that authority resides, whether it is at NIH Bethesda, or the NRC, NAS or what. I believe it is a committee. Anyone have the details?

ANYWAY there are myriads of sorts of research that do not involve human trials. There's in vitro. There's animal studies. There's development of novel analytical assays and protocols. The list could go on and on. The DEA is only involved in licensing the possession, or manufacture, of scheduled substances, their storage and secure transport, accounting, and counterdiversion. I doubt that any serious university or institutional or pharm compny R&D lab gets turned down.

After all, doesn't Merck still get all the ecgonine from Coca Cola Co. after it is extracted from the raw syrup? Merck processes that into pharm grade cocaine. The entire US end of the process under DEA control no doubt from import to processing to export. Or am I out of date on this?


[Edited on 13-1-2007 by Sauron]

[Edited on 13-1-2007 by Sauron]

[Edited on 13-1-2007 by Sauron]
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[*] posted on 13-1-2007 at 09:00


Coca-cola doesn't have anything to do with cocaine or cocao anymore, and hasn't since it stopped putting cocaine in it's products :)

[Edited on 13-1-2007 by tnhrbtnhb]

[Edited on 13-1-2007 by tnhrbtnhb]
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Sauron
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[*] posted on 13-1-2007 at 09:24


I think you are ill informed.

It is precisely when Coca Cola Co. stopped leaving the cocaine and its immediate precursors the ecgonines in their syrup, that they started removing it, and supplying it to E.Merck to be used to make medical and dental pharmaceutical cocaine. I believe it is still done that way today, because it is far cheaper than the total synthetic routes which suffer from vast inefficiencies due to multiple chiral centers and a largish number of undesirable isomers that must be removed with difficulty by special techniques.

And it is coca extract not cocoa.

Cocaine still has medical and dental uses and where do you think it comes from?
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[*] posted on 13-1-2007 at 10:56


I have seen cocaine containing antiseptic solution used in recent time as an anesthetizing wound cleaning irrigant and wash used immediately before suturing
gashes closed on conscious pediatric patients .

I know that is what it was because I read the bottle
label , and the doctor mentioned it also .....so cocaine most definitely has legitimate uses . It is possible too
that there may be tolerance for cocaine as a local in dental procedures for some patients that may have
difficulty with some of the synthetic analogues . Eye surgery is another legitimate use for cocaine .
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Sauron
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[*] posted on 13-1-2007 at 11:10


All that abour Merck was an aside, my point was that licensed (by DEA) legitimate uses do exist even for Schd 1 stuff. Some anyway. What schedule is Ketimine on? It's still a common veterinary anaethetic. I am not so sure about phencyclidine. Carfentanyl is used in Africa and Asia to take down rogue elephants. I know that for a fact because we have this problem sometimes, and a decade or so ago I was agent for the South African arms industry here, and the Thai Police wanted a nonlethal system because there was a huge public outcry when they shot a rogue elephant to death even though he had just killed several people. So I approached the RSA folks and they came up with the carfentanyl answer.

(And when the Russians used the same stuff against the Chechen rebels in the movie theatre I figured out what they were using about three days before CNN did.)
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[*] posted on 13-1-2007 at 21:56


@Sauron: The first few pages of your Alfa Aesar or Sigma Aldrich catalog will tell you what schedule it is. All of their ''listed'' products are in fact listed there as to which class they belong in.



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Sauron
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[*] posted on 13-1-2007 at 22:03


Thanks. My hardcopy Alfa Aesar and Aldrich are 12 years old and do not contain such a list. I generally search them online now, but, I will request current catalogs and retire the old ones to Chemical Heaven.

The DEA schedules are also online. So are the Canadian and the EU and the UN. All that used to be posted on Rhodium too.
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