Where to begin! Where to begin! Well, starting with this chapter is a good idea! Every amphetamine is a chemical. And since your government doesn't allow one to own or buy the chemical itself, one has to go about making the amphetamine from legal (or sometimes illegal) chemicals that are as close to the final drug as possible. For ecstasy, that starting chemical is almost always Safrole.
Safrole is the #1 starting material for making X today. As a pure chemical it is a schedule I controlled substance and, obviously, is illegal to own or buy without a permit. But, safrole is the major component of the essential oil of sassafras which is still quite legal to obtain. Sassafras oil has a strong licorice smell which is imparted to it from the safrole molecule. Commercially, there are two kinds of sassafras oil being sold today: American sassafras (Sassafras albidum) and Brazilian sassafras (Ocotea cymbarum). Plain old American sassafras contains about 80% safrole but the Brazilian sassafras oil is almost 90-95% safrole and can pretty much be used as is.
So where does one go to get sassafras oil? Well, if one were to go down to one of those sickening hippie health food stores or incense shops there, on the shelves, will be small bottles of 80-90% ecstacy starting material labeled as sassafras oil. Larger quantities are ordered rather cheaply from fragrance or perfume supply companies that one can find in any big city yellow pages. Now the people at these companies aren't stupid. They have a general idea of what some of their essential oils can be used for so they might ask. But they still have no legal reason not to sell these things to the chemist. After all, the same stuff is being sold over the counter to hippies just down the street. Just to make every--30-
thing easier for all involved the chemist informs the company of the fake name of her business and that she makes soaps, incense, potpourri or is an aromatherapist (no kidding). Other places to order essential oils would be home care products houses, toiletry base companies, soap companies, flavoring companies, aromatherapy stores and organic foodstuff companies.
As of the year 1998, small quantities of sassafras oil are still being sold on retail shelves without any scrutiny. Usually in 1-4oz sizes. Anything larger is usually sold only through distributors and manufacturers. And as of 1998, the DEA has informed most of these distributors that they (the DEA) want lists kept or sales reported of most, if not all, sassafras oil purchases. Mind you it is not illegal to buy the oil. It's just that you will be put on a list if you do. The operative term here is 'Watched Substance'. Solution: have someone else buy it for you.
Strike has also been poking around the DEA and is getting the distinct impression that they will very soon reschedule sassafras oil as schedule I. Then one won't be able to get it at all without a permit or some serious deception.
All of the above safrole/sassafras oil sources are the more standard avenues to get these commodities. There are some rather exotic sources of safrole for the desperate, governmen-tally-challenged citizens of the future. Certain kinds of Asian camphor oils, especially brown camphor oil, can contain 40-90% safrole (another term to look for is 'Camphor 1070'). Sources selling 'artificial sassafras oil' are actually selling a mix of 50% camphor and 50% safrole, which can of course be used. Appreciable amounts of safrole can be found in star anise oil, and smaller amounts can found in the oils of cinnamon, mace, betel leaf and nutmeg (lots of fun things in nutmeg). Also, there is a spice bush that grows in India called Betel. Betel leaf oil can be found commercially and can contain up to 40% safrole depending on the region it was cultivated in.
The sassafras tree itself grows like a weed in the wilds and along disturbed fence lines throughout the south, southeast, eastern
seaboard, and Appalachian mountain regions of the United States. The trunk and root bark of older, mature sassafras trees can be steam distilled to afford the safrole-containing oil. Another source of safrole would have to the be leaf oil of a little shrub that grows down in the low woods and swamps throughout the coastal plains from Florida to Georgia. The oil is more than 90% safrole . The plant is known as lllicium parviflorum michx and Strike has no idea what the hell it looks like.
A new source of safrole that Strike has just stumbled upon is in Strike's back yard. Momma comes home from the local nursery with two plants that have these enormous leaves. They are succulents and grow like crazy. Strike: "What ya got there Momma?" Momma: "Don't think I haven't noticed those filthy drug books you write, you sick little monkey!" Strike: "Aw c'mon, Mom. Let's not get into this again. Strike doesn't..." Momma: "Well I needed some new ground cover plants, and...sigh...I know you're into this twisted licorice thing...so I bought these weeds that are called 'Licorice Plants'."
Strike breaks off a piece of the plant and smells it. Oh Yeah! That's the bomb! The plant Is called Piper auritum. Its common name is Hojo Santa. Strike loves Strike's mother.
Suffice to say that anything that remotely smells like sassafras oil or licorice or any of those strong rustic spices is going to have some amphetamine precursor, maybe not safrole exactly, but definitely something. There is just no other substitute in nature for the aroma these unique compounds give.
The sassafras oil that one gets these days is not only going to have the safrole but is usually going to have some amount of each of the compounds seen in Table 1 .
Usual Components of Sassafras Oil Component range of content [email protected](oC)
No matter what the safrole content is, even that of the Brazilian sassafras oil, it Is always a good idea to try to get rid of as much of the other components as possible. The most basic way to do this is to throw all of the crude sassafras oil into a PP container and stir it with an equal amount of 3-5% sodium hydroxide (NaOH) solution. Little white crystals of eugenol anion will form in the water layer. The water layer is poured off and saved. That eugenol is valuable. Eugenol is usually the main contaminant in safrole in more ways than one. It is the only molecule in sassafras oil that will react the same way as safrole so if it hangs around with the safrole it will compete with safrole in the conversion reactions. Also, eugenol is about the closest to safrole in both structure and boiling point so that trying to get rid of it by fractional distillation will be very tough indeed. Anyway, after the eugenol/water is poured off the oil that remains is stirred with 3 washings of clean water. The cleaned oil will look a little cloudy now. Strike still does not know why. But it never seems to hurt anything. After the third washing is poured away from the oil, the oil is transferred to an ordinary cooking pot and boiled at 100°C for a few minutes to boil off all the water. What would you think of french fries cooked in that oil, huh?
Strike wrote the above paragraph relying on the few accounts of sassafras oil content that Strike had at the time. Since then, Strike has come across more substantial data showing that Brazilian sassafras has NO eugenol in it. This agrees with the claims of many bees who have stated that no appreciable recovery of
eugenol is observed when washed with the dilute NaOH. Strike has also had commercial samples of both sassafras and brown camphor analyzed for components and the results showed that there was no eugenol in either. So give it a shot with NaOH or don't. Strike no longer feels that it matters.
The above procedure was a good step towards purity and may be all that one can hope for without a distillation apparatus. For those that have a distillation kit its time to get rid of the rest of the stuff by fractional distillation. This still isn't going to be easy because even with a packed Claisen adapter or Vigreux column the entire mass of oil is going to distill over with barely a 5 degree difference between the first drop of oil to come over to the last (this usually occurs at around 170-180°C under normal vacuum). The best strategy is to distill the oil at least 2 times; discarding the first few mLs (milliliters) of distillate and leaving the darker last few mLs behind in the reaction flask (discarding them as well).
It will be a little tricky but one can also try to purify by freezing! The sassafras oil is thrown into the freezer to chill. Safrole itself freezes at -14°C so anything that starts to freeze prior to that can be cold filtered in a prechilled vacuum filtration setup. The filtrate goes back in the freezer until -14°C is reached and the mother lode of safrole freezes up. This again is filtered cold but this time the frozen mass of safrole crystals are washed with some ice cold methanol or ethanol (preferably at -14°C) to wash away the unfrozen high-boiling constituents.
If one is absolutely serious about ultra pure safrole then it can be separated from the eugenol-free sassafras oil by treatment with mercuric acetate [1,2,3,4] which likes that terminal double bond that only safrole has. The Hg(AcO)2 latches on to safrole at that double bond bringing it into solution as a solid; sort of like the way that eugenol was. The safrole can then be separated from its still oily buddies by vacuum filtration. Safrole is then regenerated to its normal oily form by treatment with hydrochloric acid (HCI) which flicks the Hg(AcO)2 off the safrole and the safrole double bond reforms. As it so happens, the mercuric acetate also reforms intact so that it can be reused again such as in one of those
top 10 recipes discussed later. The one problem with this method is that, having been disturbed, some of the safrole molecules' double bonds will tend to migrate or reform in the more energetically favorable position between the alpha and beta carbons. What was all that egghead shit Strike just said? Strike said that not only will safrole reform but there may also be a small amount of isosafrole that forms as well. Also, some very intuitive Bees have suggested that it may be possible to connect the isolating of the safrole with mercuric acetate and proceed directly with the complex into one of the oxidation reactions found later in this book. Could be. Could be.
After Strike wrote the first edition and started up the old web site, a lot of new theories came in. The most promising was a proposition from our founding father of cyber chemistry: Eleusis. This was his proposal:
Purification of Sassafras Oil v2.0
The Sassafras plant is an excellent source of Safrole, a highly useful compound. The plant yields up to 9% oil by weight, which is an exceptionally good yield. Sassafras is indigenous to Virginia, the Carolina's, Tennessee and parts of Canada. The preferred method of extracting oil out of the plant is by Steam Distillation. The most common method of obtaining Sassafras Oil, though, is by purchasing it;-).
According to the Merck, and "Essential Oils" by Guenther, Sassafras Oil is composed of the following:
80% Safrole 10% Phellandrene 7% Camphor
3% Eugenol & various Sesquiterpenes (Cadinene et al.)
I have derived a process for preferentially separating the Safrole out of Sassafras Oil. This process is based on the physical properties of the various components listed above combined with a little chemistry knowledge. The normal means of purifying Sassa-
fras Oil is through packed column vacuum fractional distillation. This is an expensive, messy, and difficult process - in short, impractical. My process that I am proposing takes advantage of differential solubility among the various oils in acetic acid to separate the mixture down to only two components. The two remaining oils have sufficiently different boiling points to make simple distillation, with or without vacuum, a feasible separation method. To wit: Sa-frole and Pheliandrene are left, Safrole boils at 232C while Phel-landrene boils at 171C. The difference of 61C is large enough to permit excellent separation of the two, though some texts feel that there should be 80C difference between distillants (see Vogel), it is generally accepted that fractional distillation is necessary only when the boiling points approach 25C of each other (see Zubrick). However, with information newly acquired, you now don't even have to do the distillation, since Safrole is soluble in ethanol, while pheliandrene isn't!
Enough of the arguments, let's take a look at what is going on here.
Materials —------Separatory funnel (2x volume to contain) Simple
Distillation setup or pot on stove ;-)
1) First wash with a volume of Glacial Acetic Acid equal to the amount of Sassafras Oil being processed. This will remove Euge-nol, Pinene and Camphor from the oil.
2) Wash with water to remove any salts made from other contaminants and to crash out any partially dissolved Safrole (it might emulsify from the shaking, if so, add common table salt to help it crash).
3) Wash with rectified spirits (azeotrope of Ethanol + water, also known as "grain alcohol") to dissolve the Safrole, leaving the Pheliandrene behind. Of course, one should use only the amount of alcohol necessary to dissolve the expected yield of Safrole. 1:1 seems to work, but could be an excessive amount.
4) Setup for simple distillation, on the water bath, or if you don't wish to recover the alcohol (shame on you) just heat gently with a double boiler setup (especially since this will take quite a while depending on how much you have to distill/evaporate).
5) After distillation terminates (Ethanol boils at 78.4C), test your Safrole using the physical properties data below to confirm purity. Theoretically, your product should be better than 99% pure now.
The entry for Safrole in Lange's indicates the following properties:
Safrole 3,4-methylenedioxyallylbenzene - Bielstein ref. #XIX-39
Molecular Weight: 162.19
Specific Gravity: [email protected]
Melting Point: 11C
Boiling Point: 233-234C
Insoluble in water, Soluble in Ethanol, Miscible with Ether and Chloroform
Note that this procedure has been modified from the earlier version in that we no longer distill off the Pheliandrene, rather, we target it's insolubility in ethanol as a means to separate it from safrole. I think we can all agree that this is a much better way, eh?
This procedure, Strike believes, was not tried by Eleusis. But his theory on the use of partial solubility is very old and founded. Taken, as we all are, by Eleusis' unique genius, our beloved Bee 'TDK' contracted a Philippine research laboratory to apply this proposal. Here is what they said:
Posted by TDK on December 28, 1997 at 01:28:34:
Sassafras Oil separation/purification
This was pretty simple and is well suited for someone without any distillation equipment!
Starting weight: 112 grams sassafras oil.
Placed 454 grams of 28% acetic acid in 2 liter separatory funnel.
Using 28% acetic acid allows the eugenol, d-camphor and pinene to form its own top layer. There was no separation using 99.5% acetic acid.
Added 112 grams sassafras oil. Shake for a couple of minutes. You get an orangish emulsion. Clears within 15 minutes forming two layers, bottom layer oil, top layer acetic acid, eugenol + the other solubles. Separated the oil from the others, washed the oil layer 2x with fresh dH20. Weight after acetic acid & water washes: 101.5 (-10.5 grams).
Added 100 grams denatured alcohol, no layer formed as the oily product is miscibte in ethanol. Added 20 grams of dH20. This pulled the ethanol and other product into the top layer, bottom layer containing some ethanol and safrole. Separated layers, placed the oily bottom layer into a 2-liter breaker. Took the temp right to 234 C. The ethanol and water came off <=100 C... The safrole started to boil @ 232C, then came to a full boil and maintained @ 234 C. Product was yellow orange in color, suitable for whatever purpose one has in mind! BTW, after the safrole cooled, she checked it with a 5% NaOH solution to see if any eugenol was left behind, no participate formed.
Beautiful, TDK! Beautiful. Strike suspects we will be seeing more from this gifted chemist later on in the book.
Continue reading here: Isosafrole
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