You people won't believe the potential amphetamine precursors just sitting around in naturally occurring oils and essential oils [6, 7
(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.
ANETHOLE: Up to 90+% in anise seed oil, 70+% in fennel and star anise oils, and in varying amounts in betel leaf, dill seed, carrot seed and coriander oils.
ANISALDEHYDE: In small amounts (less than 5%) in anise cumin, fennel and star anise oils.
APIOLE: 23% of celery leaf oil, up to 30% in parsley leaf and seed oils, and in small amounts in cubeb, dill and fennel oils.
ASARONE: 70-80% of calamus oil. In trace amounts in Asian carrot seed and clove bud oils.
BENZALDEHYDE: The precursor for speed. It makes up nearly 100% of bitter almond oil. Not a very popular oil with the DEA. Some hints: Benzaldehyde is indispensable for the flavoring industry. It is the flavor in almond extract and synthetic benzaldehyde is used in all cherry flavorings. Also, there is currently a little loophole in the system when it comes to a product ^ ^CHO called 'Roasted Cassia Oil'. Apparently, some manufacturers take cassia oil and run it through some sort of industrial process to change it into benzaldehyde. No one wanted to tell Strike the particulars of how this was done. But one company chemist gave me some hints (You can get really chatty with some of these guys).
DILL APIOLE: Up to 60% in Indian dill seed oil and in varying amounts in other parts and other species of dill. In various small amounts in fennel and carrot seed oils.
ELEMICIN: In varying amounts in citronella, elemi, mace, nutmeg, parsley snakeroot and tarragon.
Apparently, these guys are taking regular old cassia oil and simply running it through a series of distillations. This even happens in the Asian fields when the oil is harvested so it obviously is not a complicated process. Cassia oil is made up almost exclusively of cinnamaldehyde. Any of you girls have any idea what these companies are doing to turn cheap cinnamaldehyde into benzaldehyde? Might be beneficial for you if you do. CHAVICOL: Up to 20% in West Indian bay oil.
EUGENOL: In very large amounts in bay, cinnamon, clove and pimento oils. In goodly amounts in basil, eucalyptus and tejpat. Lots of trace amounts in many other oils.
METHYLCHAVICOL: Up to 80+% in most basil, chervil and fennel oils. In small amounts in star anise and wormwood.
METHYLEUGENOL: Up to 60% in various parts of the basil plant. Around 45% in snakeroot oil. In decent amounts in calamus, cas-sie, myrtle, pimento, pistacia, pteronia and some forms of tarragon.
MYRISTICIN: In moderate amounts in dill, carrot, celery, fennel, mace and nutmeg (no more than 10% tops). Makes up about 40% of the oil of parsnip and can reach up to 50-60% of the oil of parsley leaves and seeds. Give nutmeg a rest folks! It just don't have it when compared to parsley and parsnip.
OSMORHIZOLE: Makes up 25% of the essential oil of chervil. Very hard to find this oil though.
PHENYLACETIC ACID: Very important fragrance chemical. Only recently was it banned by the DEA. Fragrance companies still can't believe they cannot openly sell it. It makes up 15% of jasmine oil (very expensive).
2,3,4,5-TETRAMETHOXYALLYLBENZENE: In varying amounts in some parsley oils (hell, just throw parsley oil in a pot to get a grab bag of psychedelic amphetamines!).
VANILLIN: In vanilla beans of course. But never more than 2%. This stuff is bought as a synthetic and is cheap and legal.
The standard way that scientists get these allylbenzenes and other goodies out of these oils is by careful, fractional distillation. You can see from above that some of the more desirable allylbenzenes do not occur in high concentrations in the oils they are found in. So that means there is a lot of crap one has to get rid of to isolate the goods. This is not as big of a concern as one might think.
Essential oils from plants are technically known as 'volatile' oils. This means, among other things, that most every component of them will eventually evaporate if left to stand. So there is a definite boiling range for these oils which, compared to other things in nature, is relatively low. Strike means to say that when these oils were extracted from the plants they come from, they were taken by steam distillation where steam was the carrier. This leaves you with compounds that have relatively low boiling points with 300°C being close to the max. And Strike can tell you right now that in oils that carry allylbenzenes, those same allylbenzenes are almost always going to be the highest boiling compounds. Usually the bulk of the oil is constituted with compounds that boil well below the allylbenzenes.
People with or without distillation apparatuses can take advantage of this fact. Just boil or distill off most of the oil up to the temperature of your preferred allylbenzene and stop. There is a very good chance that what is left will be a majority of what is wanted.
The above suggestion is, of course, rather broad. Most people would prefer a more specific solution. Unfortunately Strike has one. For over half a year preceding this second edition Strike was pouring money and time into the realization of making an isopropyl intermediate out of safrole using sulfuric acid (please don't ask). So Strike hires this Korean research lab to work out the synthesis. Well, things didn't work out for the isopropyl intermediate, but it did confirm the following procedure as a nifty way of isolating allylbenzenes (sort of) chemically.
The literature states that if one uses ice cold, concentrated sulfuric acid on a terminal alkene (a.k.a. allylbenzene) an alcohol (OH) intermediate will form 'Markovnikovly' on the secondary carbon (don't ask). What does this mean? Let's take an example. Say one has some elemi oil and wants that elemicin that is in it. What one can do is chill, say, 500mLs of the oil to freezing and do the same for about 100-200ml_s of concentrated sulfuric acid (at least 90% conc.). Next, one just mixes the two together for about 5 min. What will happen is that the cold H2S04 will make a hydrogen sulfate intermediate with the elemicin causing it to migrate out of the oil layer and go into the sulfuric acid layer. And since elemicin is going to be about the only thing in elemi oil that has a terminal alkene, it is going to be about the only thing that goes into the acid layer. Presto! Alkene isolated. Well, almost. What the chemist does next is separate the acid layer (still cold mind you!), place it in some vessel and pour in a big old excess of water. The temperature will go up and the hydrogen sulfate will be instantly hy-drolyzed by the water to form an OH. One can also heat for 5 minutes to insure conversion.
What happens during hydrolysis is that the OH forms and the 'elemicin propyl alcohol' drops out of solution and forms its own oil layer. Of course one won't see this because the solution is a big old brown mess, lousy with emulsion particles. Emulsions suck! But can be dealt with effectively by adding a little acid or base, or filtration and the like. Anyway, after a little work up one gets some really pure phenylpropyl compound. And if Strike had Strike's way, Strike would have that OH stuck right on the middle (beta) carbon of the species. Work could then progress on using that OH to get an amphetamine (Sob! Strike had so much about that subject that Strike was prepared to put in this book!).
But that is not the case. What the Korean lab found out was that when this procedure is performed, the OH stabilizes on the alpha carbon. That is the carbon right next to the phenyl ring. If one has any use for it as is then that is fine. But what is most preferable is to reduce the OH to get the propenylbenzene (say isoelemicin for our example). Using the simple potassium bisulfate reduction recipe, one can get rid of the OH with no problems at all.
Hey! That really wasn't a lot of work. Just a lot of talk on Strike's part. All one did was mix an oil with some acid, added water and isolated. One gets some pure propenylbenzene without distillation. Done on a massive scale, this is a cheap method for getting lots of small concentration allylbenzene compounds out of complex oil mixes. And since Strike blew so much dough on this glorified extraction protocol, someone better damn well use it! (In an academic lab of course).
A much more forgiving yet limited extraction method can be used to isolate phenol species such as eugenol and chavicol. You see farther back in this chapter where one can use dilute NaOH to remove eugenol from sassafras oil? Well, why not use it to isolate the damn things for further research. It works like a charm!
There are probably other methods for purifying the products one wants. But as this book makes clear, Strike is no chemist in the real sense of the word. Strike has no real idea of the true application of chemistry and takes a lot of guesses (why is Strike telling you this?). But on the Hive, Strike gave it a few stabs. Things like recrystallization (don't ask), partial solubilities like what our friend Eleusis proposed above, freezing, heating, freezing-and-heating in a two solvent system, solid phase extraction and alternative forms of chemical purification. Or one can use any of the above in combination. All of these are ways that an industrious chemist may wish to further study and apply. So hit the library, Bra'!
And now for the hardcore chemistry you've been waiting for...
Continue reading here: Phenylacetones
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