So I'm back again and I have yet another problem.

I ordered some sassafras oil a wee while ago.

It came as a medium brown, translucent and thin oil. I distilled it under vacuum and all the oils came over at 120C through the still head. I don't have a manometer, so I'm not sure what pressure I was running it at, but I have a strong refrigeration vacuum pump.

I used a standard vacuum distillation setup with a 200mm liebig and a 1L distilling and 500ml receiving flask on a electric hotplate stirrer. I got the stirrer going and cranked up the hotplate to 370C (its a ceramic top and I'm using flat bottom flasks) and then switched on the vacuum pump. Note that I did not use a vigreux or fractionating column; I was struggling to get any oils to come over until everything got really hot and at a high vacuum, possibly because some of the glass joints were leaking air despite my best efforts to seal them with vaseline.

The seller had told me that the oil contained 85% safrole and 15% cineole, so I thought I could do a HCl acid wash to get rid of the cineole. I also tried with strong acetic acid, but I didn't get any precipitation of cineole products. After he sent me the GC report (attached, all I see is numbers though, except the 85% constituent, which I guess is safrole) I saw that it was not just cineole, but multitudes of other oils that make up the other 15%. Which worries me a little bit, I really dont want any anethole in my safrole.

So half way through the distillation, I get about 400ml of a clear liquid with a light yellow/tan tinge to it. Very light, almost unnoticeable, with a density of 1.06g/ml. There was a slightly unpleasant smell to it; I could not smell sweet shop anywhere. Upon testing with conc h2so4 and anhydrous methanol, I got a dark red/purple wine coloured precipitate, consistent with high safrole % (http://www.unodc.org/documents/scientific/SCITEC21_07fin.pdf).

The second fraction of about 450ml was yellower and just as thin, with a density of 1.081g/ml and a boiling point of 232.

I placed a small amount of either fraction in the freezer but did not observe any congealing or freezing. They certainly went under 0C which makes me very worried; shouldn't any oil above 80% be congealing above freezing point? Is it possible for other oils in the safrole mix to be overpowering the sweet shop smell? Or have I simply been cheated again?

Any thoughts or ideas will be very much appreciated. This is honestly driving me crazy and it's the third time I've ordered an oil that is meant to be safrole bearing.


I'm also thinking about getting a 24/40 vacuum distillation setup from ebay, should I fork out $230US for an american setup or get a chinese one for $100ish? Will the american one have more integral and air tight joints?

Some relevant pages from Ernest Guenther's Essential Oils are attached 

The presence of Pinene and Phellandrene (melting points -50ºC---- -65ºC) would inhibit the crystalization of Safrole. A small distillation setup without vacuum helps a lot checking the constituents of a new oil.

You're probably dealing with the same sort of business that caused this other thread to be posted:

http://127.0.0.1/talk/index.php/topic,2877

These guys always seem to open up shop once a precursor gets scarce due to government action    The formation of the pentabromide and the melting point of a derivative such as mdma would be a lot better tests than anything else    The absence of the overwhelming odor of sassafrass should settle the issue  You need to start looking into sources that you can harvest yourself since that eliminates the human element 

You're probably dealing with the same sort of business that caused this other thread to be posted:

http://127.0.0.1/talk/index.php/topic,2877

These guys always seem to open up shop once a precursor gets scarce due to government action    The formation of the pentabromide and the melting point of a derivative such as mdma would be a lot better tests than anything else    The absence of the overwhelming odor of sassafrass should settle the issue  You need to start looking into sources that you can harvest yourself since that eliminates the human element 

This is very difficult when you are in the N Z . There are no plants here that have safrole to the best of my knowledge.

I will try the hydroxide wash. Already tried the acetic wash, without a whole load of difference.

It seems strange, what with the density this oil has, the fact it stains wine red with conc h2so4, and that it sinks below water washes but doesn't smell of safrole...

Is anyone able to interpret that gas chromatography report?

"There are no plants here that have safrole to the best of my knowledge."

man knowing what the British were like with their botanical endeavours taking favored plants from all around the world and planting them in "the colonies" I would almost put money on there being HEAPS of 'Camphor' genus trees there.

The climate there is prime for them and they're very prolific once they take hold (which, if the case was probably over 100 years ago!

I could be wrong but...it's definitely worth checking out

Once you know what to look for they're easy to find...Big n smelly buggers!

I think a total synthesis using either catechol or methylenedioxybenzene and allyl chloride is my only other viable option. It is very hot here in the summer, but very cold in the winter, and camphor trees are not common in the south. I have never seen nor smelt them around here, only eucalyptus.

what about mercuric acetate?too expensive?

Yeah. Toxic and expensive. Just didn't look practical for large scale purification.

Although, I have had some developments. I did a glacial acetic acid wash on both fractions, then a 5% NaOH wash followed by a few water washes. Then I tested the boiling points of both fractions by pouring them both into large seperate beakers and heating them to their boiling points. With a bunsen.

Both boiled around 232/234, and now they both smell a lot more like safrole (possibly because impurities were boiled off?) with densities around 1.08g/ml. Gone a darker yellow/brown colour and slightly cloudy. Promising indeed.

There are ways to proceed directly from the mercury complex of allylbenzenes directly to amines so the process should never be ruled out by a competent chemist.

yes and in fact I would have thought they would be one of the preferred (tried and tested ) methods for the home chemist as well

Any Hg would be removed by the standard washes used.

fresh is interested in hearing of anywasp who has used HgAc, was it successful and particularly which solvent/s were used in the rxn

  PdAc is quite soluble in several solvents making 12hr pre-mixing unnecessary, AND would make recovery much easier (from a variety of methods to recover either as the acetate or with an alcohol to reduce it back to the metal

As PdAc reduces back into Pd metal in methanol, ethanol, propanol, isopropanol, tert-butanol, and the like

suitable solvents for PdAc are

 one of these solvents or a mixture of two or more kinds of solvents selected from acetonitrile, ethyl acetate, dioxane, methanol, benzene, toluene, pyridine, tetrahydrofurane, hexane and diethyl ether.

The acetates are fairly straightforward to prepare by boiling Palladium in a concentrated nitric acid/GAA mix...that's all I know just now?

And considering Pd is around $600 oz on the market collectable coins like the the Canadian $50 coin are pure Pd (0.995%) coin at $6-700 are good value when you do the math.


And Uchiacon this...

Both boiled around 232/234, and now they both smell a lot more like safrole (possibly because impurities were boiled off?) with densities around 1.08g/ml. Gone a darker yellow/brown colour and slightly cloudy. Promising indeed.

  Is good to hear      please keep us informed of your progress matey

Mistakes like these teach one a Lot, so sharing your experiences will hopefully help others

Ps. Good to have you and your (usually ) intelligent input back, sedit.  Your POV has been missed (at least by f1 )

There may be anethole present in the indian sassafras oil I received a while ago, will this be easily removed later on in the process? Or does it present a serious problem if not seperated?

no it wouldn't be removed by the 'process' but depending on the method used, most likely changed into something you probably dont want (i.e. like PMA aka Para-methoxyamphetamine) 

para-Methoxyamphetamine (PMA; "Death", "Dr. Death", "Chicken Powder", "Chicken Yellow"), also known as 4-methoxyamphetamine (4-MA), is a serotonergic drug of the amphetamine class. Unlike other similar drugs of this family, PMA does not produce stimulant, euphoriant, or entactogen effects, and behaves more like an antidepressant in comparison,[citation needed] though it does have some psychedelic properties.

PMA has been occasionally found in tablets labeled as MDMA (colloquially known as "ecstasy"), although its effects are markedly different compared to those of MDMA. PMA is commonly synthesized from anethole, the flavor compound of anise and fennel,

I'm not sure if you could 'freeze out' the saffy whilst leaving the anethole IDK  I guess it would depend a lot on the purity of the oil you have...

The chemical name for anethole is trans-1-methoxy-4-(prop-1-enyl)benzene (C10H12O). In its solid state, below 20° C, it forms white crystals. Its liquid state is clear and colorless. It has a boiling point of 234° C. Anethole can be made to crystalize out of the essential oil of fennel or anise by quickly cooling the oil.

http://en.wikipedia.org/wiki/Para-Methoxyamphetamine

 I guess fractional distillation with a good vacuum would most likely be the answer to your separation woes 

Here's the PIHKAL entry which also discusses what Sasha called the Ten Essential Amphetamines/Oils, which make up the basis for many of his substituted phenethylamines (PEA's)

Anethole is one of them

Have a browse through this article and pick up what info you can.  I have no doubt that if you're still working on your dreams in 2 years time, you WILL have come across and tried reading and understanding this article quite a few times (unless you have a eidetic (photographic ) memory!)

A final comment. But maybe a long one! Elsewhere, I have made comparisons between myristicin and MMDA, and between safrole and MDA. And here there is a similar parallel between elemicin and TMA. What are these relationships between the essential oils and the amphetamines? In a word, there are some ten essential oils that have a three carbon chain, and each lacks only a molecule of ammonia to become an amphetamine. So, maybe these essential oils, or "almost" amphetamines, can serve as an index for the corresponding real amphetamine counterparts. I had originally called this family the "natural" amphetamines, but my son suggested calling them the "essential" amphetamines, and I like that. At the time that I had synthesized TMA, back there in the '50s, I had the impulse to explore this body of Essential Amphetamines. As the old folk-wisdom says: "Nature is trying to tell us something.

http://www.erowid.org/library/books_online/pihkal/pihkal157.shtml

keep up the good work Uchiacon...and don't sweat the HgAl amalgums...they are very effective and treated with care no more 'dangerous' than crossing the road!  You will see this the more you read.

 If you want to be pointed in any particular direction just shoot me a pm and i'll try to 'f1' aka help