Safrole

Dark oil of camphor consists very largely of safrole. 

Safrole is the 1 starting material for making X today. As a pure chemical it is a schedule 1 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 safroie molecule. Commercially, there are two kinds of sassafras... 

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. ... 

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 [6]. 

It will be a little tricky but one can also try to purify by freezing I 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... 

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-... 

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). 

Wash with rectified spirits (azeotrope of Ethanol + water, also known as "grain alcohol") to dissolve the Safrole, leaving the Phellandrene 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. 

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 ... 

Added 100 grams denatured alcohol, no layer formed as the oily product is miscible in ethanol. Added 20 grams of C//-/2O. 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 boll and maintained 234 C. Product ui/as 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 ivas left behind, no participate formed. 

At this point the chemist has what can be loosely considered as pure safrole. She can use this for some methods or can convert it to isosafrole for others. Isosafrole is the runner-up precursor for making X. It cannot be found in nature but rather is made from almost exclusively safrole. 

Strike had previously written that about the best recipe for making isosafrole was from boiling safrole with concentrated KOH (Potassium Hydroxide) in ethanol. This was actually the only... 

What happens when isomerization is performed is that the double bond of the allylbenzene safrole migrates to the more energetically favorable position between the alpha and beta carbons of the propyl side chain. Thus isosafrole, a propenylbenzene, is born. 

To isomerize safrole to isosafrole one would like to have pure safrole to start with. This, usually, is not the case. Quasi-pure safrole from sassafras oil is ok. Straight-up sassafras oil is probably ok too, though not recommended. The safrole is then refluxed (boiled under a condenser) in a saturated KOHyethanoI solution for about a day and that s it. The temperature of reflux is about 120-140°C owing to the fact that the ethanol (usually boiling around 65-70°C) is saturated with the halide salt. 

So now that we have all the reagents out of the way let s see how the reaction proceeds. There s the clear- yellow "safrole" sitting in the bottom if the flask and the clear saturated KOH solution is dumped in. The solution is heated to reflux etc. and yes, some brown byproducts and destruction artifacts will appear. Especially if the safrole is not pure. These byproducts should be expected to some extent because concentrated basic (OH) solutions can be as nasty as concentrated acidic solutions. One is mindful that KOH is less intrusive towards the delicate methylenedioxy ring structure of the safrole/isosafrole molecule. 

GENERAL PROCEDURE The Alcoholic alkaline solution is prepared by prolonged stirring of 8.8g (or 4.4g) of KOH pellets in 30mL of alcohol. The alkaline solution is placed in a round-bottom flask provided with a reflux condenser (microwave or conventional systems). Then 4.0g of Safrole (or eugenol) is added and the solution heated."... 

Gee, that all sounds fine and dandy. But Strike saved the best for last. Without a doubt, the cleanest, fastest and easiest method for isomerizing safrole and other allylbenzenes is to use CaOH. Someone who is Not Tim (Strike s name for her) emailed Strike the Chemical Abstracts entry for the procedure ... 

Strike can t believe Strike can actually quote Strike s own book. That is so freaky )]. Most of these things will make amphetamines that are much more potent than X. It is also possible to play around with some of the little side groups on these to eventually make X or some other interesting psychotomimetics. With few exceptions these precursors are all substituted allylbenzenes just like safrole. They are all found in the same kind of legal oils and sold in the same kinds of places as sassafras. Finally, these precursors are turned into their own respective amphetamines using the exact same conversion recipes used for safrole. 

So let s say, for instance, that some deranged lunatic did the exact opposite of what this book says, and went ahead and got some equipment, a couple of chemicals and some safrole, isosafrole and/or the precursor of their choice. They may very well decide to do something to it to get it farther along the path to final product. Well, currently on the place called Earth, the most widely made precursor for X and amphetamine production is the phenylace-tone. For crystal meth the precursor is called just that phen-ylacetone (a.k.a. phenyl-2-propanone, a.k.a. P2P). For X the precursor would be called 3,4-Methylenedioxyphenylacetone (a.k.a 3,4-Methylenedioxy-phenyl-2-propanone, a.k.a. MD-P2P). Strike knows it should technically be written as MDP-2-P, but Strike has always written it incorrectly as MD-P2P and that is just how stupid-ass Strike is always gonna refer to it. 

METHOD 2 Without a doubt, this is the current world favorite for making P2Ps. This method is known as the Wacker oxidation and involves mixing safrole (or any other allylbenzene), palladium chloride, cuprous chloride and dimethylformamide in an oxygen atmosphere to get MD-P2P very quickly and in a totally clean manner [11, 12]. There s also a very nice review in ref. 13. 

The idea is to have everything in place before the oxygen is applied. So, lOOg of safrole is in the addition funnel and stirring around in the reaction flask are 10.6g of PdCU, 60g CuCI and 500mL of aqueous dimethylformamide (made by mixing 62.5mL dH20 and 437,5mL DMF). Dimethylformamide (DMF) is not the same as the watched chemical known as N-methylformamide. 

The above reagents (ok the safrole and H2O aren t reagent) are weighed or measured accordingly. The flask is securely clamped into place on the magnetic stirrer. Add the DMF and H2O. Start stirring, and then slowly add the palladium chloride and cuprous chloride. If you add the powders first then the liquids you ll have problems with the stir bar finding a place to spin. 

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