(2) The 3,4-dimethoxy pattern. The main actor here is methyleugenol, or 4-allyl-1,2-dimethoxybenzene. This is located in almost every item in the spice cabinet. It is in citronella, bay (which is laurel, which is myrtle), pimiento, allspice, pepper, tree-tea oil, and on and on. It has a faint smell of cloves, and when dilute is immediately mistaken for carnations. The propenyl analogue is, not unreasonably, methylisoeugenol, a bit more scarce, and seems to always be that little minor peak in any essential oil analysis. The compounds missing that methyl group on the 4-oxygen are famous. The allyl material is eugenol, 4-allylguaiacol, and it is in cinnamon, nutmeg, cloves, sassafras and myrrh. You taste it and it burns. You smell it and think immediately of cloves. And its property as an anesthetic, in the form of a clove, is well known in the folk-treatment of toothaches. Actually, flowers of clove (the gillyflower, like the carnation) are the small, pointy things that decorate baked hams and, when stuck into apples, make pomander balls. This anesthetic property has recently led to a drug abuse fad, called clove cigarettes. Very strong, very flavorful, and very corrosive things from Southeast Asia. The eugenol that is present numbs the throat, and allows many strong cigarettes to be smoked without pain. The propenyl analogue is isoeugenol, with a smell that is subtle but very long lasting, used more in soaps and perfumes than in foods. The amine addition to the methyleugenol world produces 3,4-dimethoxyamphetamine, or 3,4-DMA. The isomer with the other methyl group missing is chavibetol (3-hydroxy-4-methoxyallylbenzene) and is found in the pepper leaf that is used with betel nut. A couple of positional rearrangement isomers of methyleugenol are known in the plant world. The 2,4-isomer is called osmorrhizole, and the conjugated form is isoosmorrhizole or nothosmyrnol; both are found in carrot-like vegetables. They, with ammonia, would give 2,4-DMA. And the 3,5-dimethoxyallylbenzene isomer from artemisia (a pungent herb commonly called mugwort) and from sage, would give rise to 3,5-DMA. This is an unexplored isomer which would be both an antidote for opium as well as a stimulant, if the classical reputation of mugwort is transferred to the amphetamine.
(3) The 3,4-methylenedioxy pattern. One of the most famous essential oils is safrole, or 4-allyl-1,2-methylenedioxybenzene. This is the mainstay of sassafras oil, and it and its conjugated isomer isosafrole have a smell that is immediately familiar: root beer! These are among the most widely distributed essential oils, being present in most of the spices, including the heavies such as cinnamon and nutmeg. I am not aware of the 2,3-isomer ever having been found in nature. Adding ammonia to either would give MDA.
(4) The 3-methoxy-4,5-methylenedioxy pattern. The parent compound is myristicin, 5-allyl-1-methoxy-2,3-methylenedioxybenzene, and the source of this is nutmeg (or the botanically parallel material, mace). The nutmeg is the seed of the tree Myristica fragrans and mace is the fibrous covering of the seed. The two spices are virtually identical as to their chemical composition. Myristicin and the conjugated isomer isomyristicin are also found in parsley oil, and in dill. This was the oil that was actually shown to be converted to MMDA by the addition of ammonia by passage through an in vitro liver preparation. So here is the major justification for the equation between the essential oils and the Essential Amphetamines. Care must be taken to make an exact distinction between myristicin (this essential oil) and myristin (the fat) which is really trimyristin or glyceryl trimyristate from nutmeg and coconut. This is the fat from myristic acid, the C-14 fatty acid, and these two similar names are often interchanged even in the scientific literature.
(6) The 3,4,5-trimethoxy pattern. Elemicin is the well studied essential oil, 5-allyl-1,2,3-trimethoxybenzene, primarily from the oil of elemi. It is, like myristicin, a component of the Oil of Nutmeg, but it is also found in several of the Oils of Camphor, and in the resin of the Pili in the Philippines. This tree is the source of the Oil of Elemi. I had found a trace component in nutmeg many years ago that proved to be 5-methoxyeugenol, or elemicin without the 4-methyl group; it is also present in the magnolia plant. The aldehyde that corresponds to this is syringaldehyde, and its prefix has been spun into many natural products. Any natural product with a syring somewhere in it has a hydroxy between two methoxys. The amphetamine base from elemicin or isoelemicin would be TMA, the topic of this very recipe.
Shulgin ; TIHKAL
