Sciencemadness Discussion Board

Eugenol

Maja - 14-10-2008 at 11:00

Maybe someone knows some cheap source for Clove oil or Eugenol ? I have found a source for cheap, pure eugenol, but shipping costs a lot. 1l of pure Eugenol costs 50$ and shipping - 40$. This is to europe. That's too much. Some people from europe willing to share a source or trade ? ;] Thanks.

Sauron - 14-10-2008 at 11:23

I used to buy eugenol at the corner pharmacy, it is a toothache remedy.

Is it no longer sold that way in EU?

You can of course obtain is from cloves.

Or you can synthesize it.

If you check around you will find there are companies in Europe that sell bulk herbs abd also essential oils.

Acros Organics (chemicals not herbs) sells eugenol for $25/100 g or $98/500 g and they are in Belgium.

I'm quite sure that Panreac (Spain), Merck (Germany), Fluka (Switzerland) and Carlo Erba (Italy) also sell eugenol.

[Edited on 15-10-2008 by Sauron]

chemrox - 14-10-2008 at 20:15

Pure Eugenol is packed under N2. I have some that's still in a bottle in an envelope. I'm guessing that there's a problem with oxidation? Maybe someone here knows for sure. I would take a look at OTC Eugenol on the IR and see what else might be there. As an aside, a DEA guy told me you have to have an importer's license to but reagents from off shore. I'm still struggling with this one and have my Sen.'s staff looking for clarification. The DEA license has a high tag, $1100!

Sauron - 14-10-2008 at 21:37

What I purchased at a US pharmacy was labeled Eugenol. Perhaps USP. I do not recall. But it was not oil of cloves which is surely a mixture. Merck cites a reference from Annalen for isolation of eugenol from oil of cloves.

I used to use oil of cloves for cleaning and preserving antique Japanese swords, a traditional application for many centuries in Japan. A very pleasant fragrance.

I don't know what your DEA contact is talking about, chemrox. I am pretty sure that a DEA import license is not required for ALL reagent imports, most likely he is talking about scheduled controlled substances and perhaps the very limited number of substances on the List One and List Two mandating record keeping. Is eugenol on any of those? Anyway the thread author is talking about importing into Europe not into USA if I read him correctly.

Given that it's a 3,4-catechol (4-allylguiacol) and is not exactly unknown as a starting point for various naughtier things described in PIHKAL, I would not be amazed if eugenol is a DEA chemical of interest. But I have not taken the effort to find out because frankly I do not care.

jarynth - 14-10-2008 at 22:06

Check out this eBay seller of essential oils:

wf-medical

Sauron - 14-10-2008 at 23:29

I repeat, eugenol is not same as oil of cloves. You can if competent isolate eugenol from oil of cloves. Citation for details on how to do are to be found in Merck Index. The paper cited in in German and available via References.

Nicodem - 15-10-2008 at 00:02

Oil of clove practically always contains more than 80% eugenol. Actually, it is quite common for it to contain up to 95% eugenol while the rest being a couple of % of O-methyleugenol and O-acetyleugenol. I think for the average amateur this is not such a bad purity and can be considered technical quality eugenol.

Sauron - 15-10-2008 at 03:14

100 g for $25 for pure eugenol, who needs technical?

$5.59/oz. for the essential oil. I'd hold out for the pure.

[Edited on 15-10-2008 by Sauron]

Maja - 15-10-2008 at 03:22

http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&item=17023... Pretty reasonable price ! But shipping ... Thank you jarynth for that link ! Very helpful.

Ephoton - 15-10-2008 at 03:48

that's a ripoff I pay around $60 us for a liter of oil.

fractionation is far from requiring competence just the right equipment and patience.

jarynth - 15-10-2008 at 04:00

The offer Maja posted is comparable to yours. And $60/L IS not a ripoff. Shipping will probably double the cost, but it'll still be very affordable compared to European prices.

Sauron - 15-10-2008 at 18:28

I'm more than a little disappointed and chagrined that on a forum of sois-dissant chemists, no one, not one, has had anything to say about the synthesis of eugenol.

Why is that?

Where are all the guys who always insist on making their own reagents, for the love of chemistry, even when the stuff is readily obtainable?

It is not a very complex compound. It is true that the prep does not exactly leap from the pages of the chemical literature. Org.Syn. has only o-Eugenol which is useless. Merck only cites the isolation from clove oil. The ACS search engine is also unhelpful. Still, I haven't despaired. I can think of several entry points, such as allylbenzene, or guiacol, or catechol.

For me it's just a five finger exercise. I have no use for eugenol.

bfesser - 15-10-2008 at 19:55

Not sure how much you need, or the purity, but I'd recommend isolation from whole cloves. The following is summarized from notes in an old lab notebook of mine:

Crush whole cloves in mortar/pestle and steam distill until the distillate comes over clear. Extract with t-butyl methyl ether. Extract the ether phase with 10% NaOH(aq.). Acidify the aqueous phase with dil. HCl to pH 1, then extract again with t-butyl methyl ether. To ensure good separation and to aid in drying, shake the ether phase with saturated aqueous NaCl before drying over anhydrous CaCl<sub>2</sub> (MgSO<sub>4</sub> is also suitable). Filter out the desiccant and evaporate the ether solvent.

20.1% yield based on an expected 15% by mass 'essential oils' content of the cloves, but the distillation was cut short due to time constraints. The <sup>1</sup>H NMR of the eugenol was very clean--I would estimate at least 99% purity.

[Edited on 10/15/08 by bfesser]

Sauron - 15-10-2008 at 20:06

I suppose the whole matter of eugenol synthesis has been done to death by the usual suspects on Rhodium/Hive. Org.Syn. has got catechol prep from salicaldehyde, that suggests the aspirin squeezers are on right track.

Rhodium has got propenylbenzenes from propiophenones via Friedel-Crafts acylation with propionyl chloride.

So it seems there are no new worlds to conquer at least in this neighborhood. I should have known.

Case closed.

kalacrow - 16-10-2008 at 08:13

I suppose the whole "eugenol synthesis" thing has no interest because it is not only easily obtainable and cheap, but as a starting material it isn't particularly amazing, since the side chain is subject to polymerization if you breathe on it too hard. The routes to get TO eugenol, as well, involve things which are more interesting THAN eugenol, generally speaking.

One thing I intend on playing with, though, is using the old method to oxidize eugenol to vanillin. Kind of a neat synth, even though it is ancient. Are there any public refs for it? I have spent a little time looking, but so far no procedural details.. only oblique references.

This is interesting as I am guessing the reagents are cheap, and the end product I can use to make cookies :) Not only that, but vanillin in pure form is (NOT extract), for some odd reason, expensive retail. A lot more than clove oil.

FYI essentialoil.com has clove bud oil for $232US/10lbs (4.535 Liters.. 153 oz) for those folks in the US. That works out to $51/liter sans shipping. I wonder how much it would cost to get enough clovebuds in bulk to extract that much?

Sauron - 16-10-2008 at 08:47

If I recall that old vanillin prep is from isoeugenol, and that not being a terminal alkene, is not so much of a polymerization hassle. While you can make isoeugenol via isomerization of eugenol, it is not necessary, as it is available in essential oils in high concentrations as well.

The Flavors & Fragrances section of Ullmans, particularly the subsection on Phenolics, has a good overview on the whole family of these compounds.

[Edited on 16-10-2008 by Sauron]

zed - 16-10-2008 at 22:09

Permit to import Eugenol? It isn't listed!

It is common for government agents to lie when making oral statements.

Few, are willing to put those lies down on paper.

A probing registered letter, demanding a quote of current import regulations will put this question to rest.

I read the regulations recently, and I found no prohibition that requires a permit to import unlisted chemicals.

Sauron - 17-10-2008 at 02:03

My o my, you are a paranoiac. You think search ing Aldrich online "creates a record" and you think all federal agents are liars. More likely the guy was simply mistaken, or that chemrox misquotes or misunderstood him.

As to Aldrich, well, what a burdensome and useless data mine that would be if you were correct. How incriminating. "So and so looked at a page in a publicly available catalog on a website." Bring out the leg irons. Give the rack a turn. Fetch the comfy chair. No one expects the Spanish Inquisition!

zed - 17-10-2008 at 08:18

Sauron,

So, a lot of law enforcement guys are liars, as are government officials in general. You should know that.

In the jurisdiction where I reside, there are many officers that are permanently restricted to desk duty. They are not permitted to make arrests, because they cannot testify in court. The local judges will not permit them to testify, because it has been proven that they are not credible witnesses.

You should also know from reading the regulations, that acquiring an importers permit
isn't the end of the story. In obtaining one, you may give up some of your civil rights. Especially so, if you import any listed chemical. You become subject to "inspections". These may be unannounced inspections. They could be walk throughs, paperwork inspections, or full blown searches. Nagging phonecalls are also commonplace. Better off not to get the permit, and not just because it costs $1100.00! Truth is, they make you suffer.

I once worked at a small college where they drove us positively berzerk with such shit.

An ATF agent came regularly, to measure the useage of our one gallon of tax-free 100% grain alcohol. We had 300-600 students, but we actually used very little ethanol. None-the- less his verdict was always the same.....He was suspicious, "AND WE WERE USING TOO MUCH ALCOHOL".

We finally gave up using this product all together. We were willing to pay the tax, so we wouldn't be screwed with, but our suppliers were not willing to collect it. That meant we had to use heavily denatured ethyl-alcohol instead.

Our chromatography experiments no longer worked properly. Change the polarity of your solvent mix, and your rates of elution are altered.

Diversion control agents, or chemical company employees working at their behest, made our school's purchasing agent cry. They made groundless accusation, after groundless accusation. It was one thing after another. Everything was suspect.
We couldn't replenish needed lab supplies, and our students suffered.

Our instructors were harassed and fearful of arrest or termination. They were stressed out of their minds.

Yet remarkably, we hadn't done a single thing improperly...we were completely legit.

So yes, Sauron....Perhaps I am a little paranoiac. I don't like to be messed with.
Do you blame me?

As for data mining. Yes, federal agents are very through. For those that must be concerned about such things, that attention to detail is a concern.

They have a lot of information they never act on, and rightly so. Conversely, when they do decide to act, they usually have mountains of information, that collectively can look pretty damning, even if you really haven't done much.

Some of the guys see a drop of pine sap on the pavement, and they are pretty sure that it is evidence, that a gang of black islamo-terrorists has just gang raped a baby Christian girl at the site.

The paranoia of law enforcement personnel is what fuels my paranoia. Here in the U.S., it's a good idea to do yourself a favor, and make yourself a small target.

PS. This is really kind of fun. Just a few hours ago somebody U2Ued me, and accused me of being a cop. Not so! I'm a bored, over-weight, middle-aged, ex-housewife. Are you Married?

[Edited on 17-10-2008 by zed]

Sauron - 17-10-2008 at 08:57

Yes. And divorced, and remarried for twenty years.

Since an importer's license is not required for anything but listed or scheduled stuff, which eugenol is not, it's irrelevant and off topic, isn't it?

zed - 17-10-2008 at 14:55

It came up in the thread. A poster complained. Said an agent had informed him he needed an importer's license to import. No qualifiers. Eugenol, and every other chemical, would be effected, if true.

I've heard such reports elsewhere. Not a problem, for those of you outside the U.S..
But, possibly a problem for those of us here that have a hobby, or envision starting a fledgling business.

The agent may be over-reaching. The regs don't read that way. If you study them.....They actually seem pretty reasonable.

But, are the regs still the same? The problem is that the rules may be changed at anytime with very little public notice. And, that the DEA may read the regs differently than we do. You really don't want to spend the next few years of your life either battling in court, or rotting in prison.

Chemrox seems to be saying, that the true situation is so murky, that he has asked for help from his Senator to obtain clarification.

Sauron - 17-10-2008 at 19:17

Read the forum. Lots of US members import chemicals, China is a popular source. Not one of those members has ever posted anything about Customs demanding a DEA (or DHS) import permit/license/clearance.

Now if they had been importing red P and I2 that might be different.

Anyway this IS OT and so please do not seek to perpetuate the tangent or you are likely to hear from the Mod Squad.

chemrox - 17-10-2008 at 23:36

@Sauron- I think the DEA guy is full of shit too. I'm trying to resolve the question though since I was told directly. Only seems prudent and I passed on the information in case the caution is apt. Eugenol is not on any list I know of ... yet. Maybe all the essential alcohols and aldehydes will be in the future. Anyway, I probably shouldn't have rocked that boat.

Sauron - 18-10-2008 at 01:54

I think vanilline and safrole are the only ones that are listed, IIRC, but I haven't really made a close study, as I don't live there and don't really give a damn. Vanillin is off the shelf here, though I have never even priced it. It's simply on the list of what the local suppliers keep ex stock.

kalacrow - 18-10-2008 at 18:09

Vanillin isnt listed.

http://www.deadiversion.usdoj.gov/21cfr/cfr/1310/1310_02.htm...

Sauron - 18-10-2008 at 19:44

You are right. But safrole, isosafrole and piperonal are listed. I appreciate your posting the link so I could refresh my memory.

Piperonal(dehyde) = 3,4-methylenedioxybenzaldehyde while the safrole/isosafrole system are the isomeric propenyl compounds. As such it is obvious why DEA wants then under wraps.

Vanillin and eugenol are the 3-methoxy phenols of same series, i.e., vanillin is the aldehyde and eugenol the allyl compound.

ALL of these can be synthesized from phenol to catechol to guiacol and so on. For a speed course (no pun intended!) on why chemrox says all of these might be listed in the future, just see Rhodium, and its ilk.

Of course I am epistomologically certain that all those threads about these are due to innocent fascination with fragrance and flavor chemistry. Well, it is a fascinating subject.



[Edited on 19-10-2008 by Sauron]

flavors.jpg - 62kB

kalacrow - 19-10-2008 at 00:35

Academic interest, yes :) It is frustrating though, that such useful precursors to so many legal, interesting things are listed. What really gets me is the restriction on Iodine. Man! So many useful compounds are unavailable, and nowadays you cant easily buy any chemicals as an individual.

I have my doubts that Vanillin will be listed, as well as Eugenol. They are both traded in HUGE quantities in the food service industries, and are (were) definitely not anything like as rare in use as safrole and piperonal. Besides, you'd have to be an actual Chemist to turn Vanillin or Eugenol into the MDxx or other drugs.. I think it would be a very rare cook who could do it. And anyone who is an actual chemist could get there from any one of numerous routes... you cant list ALL of them, or you'd break whole economies.

Even benzaldehyde is restricted. Eesh. I see its a meth precursor, but it smells so good!!

Sauron - 19-10-2008 at 00:55

Oh? Are they traded more than toluene, MEK, acetone, or MIBK? Because they are all listed and you coulkd put the trade in vanillin and eugenol (forget the others) into a pimple on the left buttock of any one of those.

Does it take a real chemist? If so there are lots of bent real chemists aren't there?

zed - 19-10-2008 at 03:07

Many of the listings are meant to target the International Heroin and Cocaine cartels.
The listed chemicals are completely easy to obtain inside the U.S.. I can buy most of them at my local hardware store.

Others listings are aimed specifically at illegal, drug production in the U.S..
Those chemicals may be difficult to obtain here.

To a certain extent, listing is based on threat assessment.

In recent times, those drugs deemed most harmful get the most attention, and the chemicals from which those drugs can most easily be made, get listed.

Coke/Crack....Heroin.....Meth.....PCP....? And then, a bunch of stuff that probably isn't a threat to end civilization as we know it.

Ecstasy and Mescaline are illegal, but making them from Eugenol or Vanillin, isn't exactly easy. And, at this point, Eugenol and Vanillin, are not listed. If sanity prevails, they will not be. X isn't really that big a problem, and Mescaline is a rare substance.

From some perspectives it appears that the DEA is actually becoming less-reactionary, rather than more-reactionary. Recently, they have been fairly slow to outlaw materials just because they appear to be somewhat psychedelic. And remarkably, in some cases they have chosen against prohibition.

The Feds have plenty of bigger problems to deal with.

Sauron - 19-10-2008 at 03:48

You are pretty new here, so you may not be aware that the management strongly discourages precisely this sort of discussion. I am not part of The Management. Just a friendly bit of advice.

I would be really curious as to why KMnO4 and NaMnO4 are all of a sudden listed.

But don't post a reply. PM me or email me.

jarynth - 19-10-2008 at 04:33

Quote:
Originally posted by zed
I'm a bored, over-weight, middle-aged, ex-housewife.

You don't sound like a woman. You also purport yearlong experience in chemistry-related activities, but your posts reveal your naivete.
Quote:
Originally posted by zed
From some perspectives it appears that the DEA is actually becoming less-reactionary, rather than more-reactionary. Recently, they have been fairly slow to outlaw materials just because they appear to be somewhat psychedelic. And remarkably, in some cases they have chosen against prohibition.


The DEA has no decisional power on the legislative processes that lead to the regulation of chemicals. It merely enforces the appropriate policies, although it does have some leeway in choosing which paths to pursue and which to ignore. Due to the mass of information continually gathered during its operations, it understandably has some influence on the legislators as well.

You seem to have a grasp of drug-related issues in chemistry but apparently don't see the difference in tenor between the various lists of precursors, or within one list. I highly doubt your local hardware store sells methylenedioxyphenyl derivatives by the pound, or even just acetic anhydride (same list as acetone).

[Edited on 19-10-2008 by jarynth]

Sauron - 19-10-2008 at 06:47

jarynth, please see my last post above. Polverone does not want drugs-policy debates, period. Not even civil ones. He has closed perfectly couteous threads containing exchanges just like this. Please, if you want to discuss this with zed, take it private. I would encourage you to delete this last post and I will do same. I don't want to see this thread locked. I doubt you want to either, but that's where it is headed if you don't cease and desist.

smuv - 19-10-2008 at 19:33

KMnO4 b/c of 2-[methylamino]-1-phenylpropan-1-one; I cant remember the trivial name for this.

It is also used in the processing of cocaine.

IIRC some time ago, people were very worried about how easily ephedrines can be oxidized into fairly powerful stimulants.

Bah, mdma from vanillan and eugenol I'll pass! You can probably make piperonal from catechol with higher yields than you can make it from vanillan. But it doesn't matter, where there's money and guns precursors will always be diverted.

Polverone - 20-10-2008 at 12:18

Please do not use this thread, or any other thread really, for broad discussions of drug policy. If you're not here to discuss eugenol, this is the wrong thread.

chemrox - 20-10-2008 at 13:38

@Sauron, nice images how did you make them? what sw?

Sauron - 20-10-2008 at 15:01

MDL ISIS, then Export as jpg. That actually generates a wmf. Then Photoshop to reduce the image size, and convert to jpg. In the course of that the image gets nice and bold. Dunno why. It is normal, thin faint lines on screen in ISIS and as a wmf.

Just renaming the wmf as a jpg of course works but as I have to reduce size, better to do both in PS and be done with it.

ISISDraw is free, always has been, though MDL no longer gives away the AutoNom plugin like they used to.

I like this a lot better than ChemDraw, Chemsketch etc.

It also had a plugin to interface directly with AccuModel but now AccuModel is dead and out of business. Oh well. They had an undisclosed 5 yr limit on my academic license, I guess they don't approve of perpetual students.

[Edited on 21-10-2008 by Sauron]

bfesser - 6-11-2008 at 16:39

I recently purchased a 1 Ounce bottle of "Eugenol, U.S.P." from an online source. The bottle is obviously old, and is from Magnus, Mabee & Reynard Inc. The bottle contained a dark brown viscous liquid, but it reeks of eugenol. Unfortunately, because the bottle had a linerless cap, it leaked during shipment. I have two questions.

First, what type of liner should the cap of the new bottle have? Would polypropylene or polyethylene be suitable? (I noticed that the foam packing materials surrounding the bottle had partially dissolved.)

Second, what should I do to purify this (preferably in high yield)? It should be a clear to faintly yellow viscous liquid, correct? I'm guessing that what I have is basically an unpurified clove extract. I'm considering steam distillation, but is there a better method or anything I should do in addition to the distillation? Column chromatography, pelletized Norrit, liquid-liquid extraction (for me, ethers are not an option as solvents)? I am concerned that following steam distillation, I will be unable to get a high-yield extraction of the eugenol without an ether solvent.

[Edited on 11/6/08 by bfesser]

pantone159 - 6-11-2008 at 20:32

I would think steam distillation. Eugenol is soluble in DCM, do you have that?

bfesser - 7-11-2008 at 10:45

No, I don't have DCM.