And in the recipe above, Vogel want's to get rid of a secondary alcohol just like the one on MD-P2Pol and replace it with a bromine. "Wait a minute!" you may say, "That isn't a double bond like
AMPHETAMINES & METH AMPHETAMINES FROM BROMOSAFROLE & PHENYLISOPROPYLBROMIDE
With bromo or iodo compound in hand it is time to quit and turn one's self over to the proper authorities. Wait! There are a few who would continue. Most likely in the following manner.
METHOD #1: The bromine on the safrole or allylbenzene is in what is called a secondary position. To chemists this means that if one were to try and screw around with that bromine where it is and replace it with something like ammonia (which would give MDA right off the bat) then more bad things than good would occur. Ammonia is a so-so nucleophile and if it tries to muscle the bromine from its spot then the most likely thing that would happen is that an elimination reaction will occur and the double bond will reform (giving safrole and isosafrole as products) or unwanted inappropriate additions may occur (please don't ask). As it so happens, an azide (N3) is as good a nucleophile as bromine and will fill its position quite nicely. Having a nitrogen where it's supposed to be on the safrole or allylbenzene molecule is certainly a step in the right direction even though it happens to have a couple of extra nitrogens attached to it. This is not going to be too big an obstacle as you will see.
The best azide to use these days is sodium azide (NaN3). It is inexpensive and unwatched. All azides have the potential to explode upon degradation and are toxic to breathe. The methods
given here are designed to insure that this will not occur. Even handled carelessly the potential for harm is not as dire as it may seem. Nevertheless, these procedures should be done in the hood and, if possible, performed behind a clear pane of acrylic that the chemist can find down at the home improvement store. Relax. Trust in the science and read the articles provided [62-67],
The setup used is the one pictured in fig. 9 except there is no ice bath tray. In the reaction flask is stirred a solution of 30g NaN3 in 400ml_ ethanol (Everclear is perfectly ok) or propanol (chemist's choice) and 80mL dH20. 120g of bromo-safrole or 80g bromo-allylbenzene is dripped into the solution from the separa-tory funnel over a period of 20 minutes. After addition the thermometer and separatory funnel are removed, a condenser is attached and the solution slowly brought to reflux over an hour's time. The solution is refluxed for 24 hours, cooled, 100mL ether is added and the entire solution slowly poured into 1000mL of dH20. The upper ether layer is separated, the bottom water layer extracted once with 100mL more ether and the two ether fractions combined and dried through Na2S04. The chemist now vacuum distills the ether/azide fraction to get what is now safrole-azide (yield=50%).
A much greater yield can be had if the chemist uses carbitol as a solvent instead of propanol , Carbitol is a really hazardous solvent and should not be breathed or placed on one's skin. The reaction proceeds exactly as before except that after 24 hours of reflux and cooling the mixture is slowly poured into 1500ml_ ice cold dH20. The upper solvent layer is separated and the aqueous layer extracted with 200mL ether which is then combined with that upper solvent layer. The combined solvent portions are vacuum distilled to afford safrole-azide (or phenylisopropyl-azide for amphetamine) with the yield rising to 70%.
A newer and equally effective way of swapping azides with halides (bromines or iodines) is in the use of phase transfer catalysts , Strike wouldn't expect an underground chemist to purchase the exotic catalyst Aliquat 336 which the investigators in this reference used to get yields approaching 100% but an alternative catalyst of
butylamine is offered as an effective alternate with yields approaching 75%. The figure 9 set up is again used with 100g bromo-safrole (80g phenylisopropyl-bromide), 30mL dH20 and 50g sodium azide are stirred in the reaction flask. 5g of butylamine is dripped in, a condenser is attached, the solution slowly brought to reflux and kept there for 6 hours. After cooling, the solution is extracted with ether, dried through Na2S04 and distilled to provide the azide product. The chemist should keep In mind that here, as with the previous two azide procedures, will be a significant amount of salvageable isosafrole formed as a byproduct.
One of the ways that this azide method is going to make it resistant to intervention by law enforcement is that the azide species comes in so many forms aside of plain old sodium azide such as potassium azide, phenyl azide, trimethylsilyl azide  etc. However, what makes this method so stellar is the number of ways this azide can be reduced to the final amine of MDA or amphetamine. When most underground methods introduce that precious nitrogen there is always a catch. Usually there is a formyl or acetyl group attached that has to removed in sloppy, destructive ways. Sometimes the amino group is introduced through expensive high-pressure catalysts and equipment usually using that hyper-watched chemical called methylamine. The chemists using azides are in a unique position because the mechanism by which those two extra nitrogens can be flicked off and replaced with hydrogen are varied, easy and successful in producing almost 100% yields.
The chemist can use older methods to reduce such as pressure reactions using Raney-nickle, Pt02 and Na amalgam. Until recently the most popular way was to use LiAIH4 , To do this, the chemist mixes 50g of safrole-azide with 200mL anhydrous ether and slowly drips this solution into a stirring mix of 40g LiAIH4 in 200ml_ anhydrous ether. After addition, the solution is refluxed for 4 hours, during which time the chemist will notice profuse bubbling which is harmless nitrogen gas (N2) being evolved. After 4 hours and cooling, 100mL dH20 is added to destroy the catalyst, the ether layer separated and distilled to give MDA at yields of 70%.
The following two reductions are, hands down, the ways to go for reducing azides [71, 72], 200g safrole-azide or 160g phenyliso-propyl-azide and 1000mL methanol are chilled in a well-stocked ice bath with stirring. All the chemist needs now is 34g magnesium (Mg) powder or 60g calcium (Ca), which can be purchased in pure form down at the pharmacy or in the vitamin section of the local hippie health food store (you know, Strike thinks Strike should stop bad mouthing the hippie health food stores). This powder is scraped into the cold solution in small increments. Almost immediately, heavy bubbling and heat will evolve. The bubbling is released N2 gas which lets the chemist know that things are working. The solution stirs in the ice bath for 15 minutes more and that's it. The methanol is removed by vacuum distillation, cooled and 500mL ice cold dH20 added to the residual oil left in the flask. The solution's pH is adjusted to between 9-10 with dilute NaOH solution and saturated with NaCI. This solution is extracted with ether, the ether washed with dilute NaCI solution then dried through Na2S04 . Removal of the solvent by distillation will give MDA or amphetamine in yields of 98%!
A cousin to this reduction is one using stannous chloride (a.k.a. SnCI2, a.k.a. Tin chloride) which is done exactly as the calcium one except that about 100g of SnCI2 is used in place of the Mg or Ca and the addition occurs at room temperature and the solution is stirred for one hour rather than 15 minutes. Some very good reductions that operate almost exclusively at room temperature with no pressure and give almost 100% yields are to follow. The only reason Strike did not detail these methods is that some of the chemicals involved are a little less common than Strike is used to but all are available to the public. These alternatives include: acetlylacetone and triethylamine , propanedithiol and trieth-ylamine , triphenylphosphine , NaBH4 with phase transfer catalyst , H2S and pyridine , and palladium hydroxide/carbon with hydrazine , stannous chloride dihydrate .
Recently, a nice bee named Quirks submitted an article from our new, favorite patron researcher: Rajender S. Varma. This time the good doctor is tackling our azide problem with another novel use of his clay phase transfer catalyst system. This is just going to be
quote from the journal article , If you like the looks of this experimental, then go and read the entire article for more detail.
"Alkvl Azides from Alkyl Bromides and Sodium Azide : General procedure for the synthesis of alkyl azides. In a typical experiment, benzyl bromide (360 mg, 2.1 mmol) in petroleum ether (3 mL) and sodium azide (180 mg, 2.76 mmol) in water (3 mL) are admixed in a round-bottomed flask. To this stirred solution, pillared clay (100 mg) is added and the reaction mixture is refluxed with constant stirring at 90-100 'C until all the starting material is consumed, as observed by thin layer chromatography using pure hexane as solvent. The reaction is quenched with water and the product extracted into ether. The ether extracts are washed with water and the organic layer dried over sodium sulfate. The removal of solvent under reduced pressure affords the pure alkyl azides as confirmed by the spectral analysis."
METHOD #2: This method is a backup use for all that bromo-safrole or phenylisopropyl-bromide that the chemist made. It is the simplest method in the entire book, uses the cheapest most basic ingredients and happens to be the first method that Strike ever 'studied' . Strike does not have many fond reminiscences about this method because it kind of sucks but the chemistry is so basic that it may well serve the most pathetic chemist. The reaction proceeds as follows which uses ammonia to replace the bromine giving MDA or amphetamine directly:
All this business of swapping out bromine would be a lot easier if that bromine were at the end of that aliphatic chain which would make it a primary bromine (don't ask). As it so happens, the bromine in bromo-safrole is at a secondary position which means that - 156-
one is going to need a good nucleophile (like N3) to swap out at such a position. Ammonia is not a very good nucleophile, so in order to do this the chemist is going to need a lot of it. Strike is talking a lot of it! This will not only push the reaction towards substitution, but will help prevent elimination and competing reactions (don't ask). The most basic ammonia available to the chemist is ammonium hydroxide which is ammonia (NH4) dissolved in water. What the chemist needs is as concentrated a solution of ammonium hydroxide as possible. A desirous term for a good solution would be one that has a specific gravity of 0.9. An even better option would be to buy a solution of ammonia in methanol or ethanol. A good concentration of ammonia in such a solution would be 18-25%. Using methanol or alcohol means that the bromo-safrole or phenylisopropyl-bromide oils can dissolve into the medium so that they can come in greater contact with the ammonia. What may prove to be the best choice for the chemist would be that of going down to the specialty gas cannister company and buying a tank of ammonia gas. The chemist will bubble that gas into ice cold methanol or ethanol until that solution can gain no more weight in ammonia. All of this work with ammonia is going to stink like crazy so good ventilation is a must.
Now, contrary to popular opinions, this method need not be conducted in a sealed pipe bomb. Secondary amination by substitution is as much a reaction of opportunity as it is of brute force and heat. In fact, heating can tend to cause the reformation of safrole and isosafrole. So the simplest way to do this would be to use 500ml_ of ammonium hydroxide or alcoholic ammonia or, for those wishing to make MDMA or meth, 40% aqueous methylamine or alcoholic methylamine (to tell you the truth, methylamine is preferable in this method because it is more reactive that ammonia so yield will increase). This 500ml_ is placed in a flask and into it is poured a solution of 35g bromosafrole (30g phenylisopropyl-bromide) mixed with 50ml_ methanol. The flask is stoppered and stirred at room temperature for anywhere from 3 to 7 days. The chemist could also reflux the same mixture for 6-12 hours or she could throw the whole mix into a sealed pipe bomb (see How to Make section) and cook it for 5 hours in a 120-130°C oil bath.
When whichever reaction is complete, the excess ammonia and alcohol is distilled off. The exhaust coming from the vacuum or distillation apparatus must be channeled to the out of doors or bubbled into a container of NaOH solution because all that ammonia discharge will become devastating. The remaining liquid is acidified with 500ml 10% HCI solution and extracted with 100mL ether. By now you readers realize that the MDA product will remain in that acid water and extracting with ether will remove valuable unreacted safrole, isosafrole and bromo compound. The ether is separated and the water layer, which is normally brownish gray at this point, is basified with concentrated NaOH solution and then, will appear dark brown droplets of you-know-what. You-know-what is extracted from the solution with ether or some other solvent, dried through Na2S04 and removed of solvent by distillation to afford you-know-what.
Right about now the chemist is probably screaming, "Hey, where the hell is my big yield of you-know-what?!". Sorry, Charlie. This way of aminating is easy but chemically it's a crap shoot with yields anywhere from 10-50%. The theoretical odds are against the reaction but if it is done as outlined here, the chances of success are better. Actually, Strike thinks the yields could be higher because half the problem was probably caused by low bromosa-frole yield which we have hopefully corrected in the preceding section!
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