The Complete Book of Ecstacy

The Complete Book Of Ecstacy

Second Edition by U. P. Yourspigs (c) 1992, 1995 Synthesis Books HTML conversion by Rhodium 1999

Introduction Chapter 1 - Chemistry Basics Chapter 2 - Laboratory Techniques Chapter 3 - Miscellaneous Chemicals Chapter 4 - Alkyl Halides Chapter 5 - The Main Precursors Chapter 6 - Simple Aliphatic Amines Chapter 7 - MDA Chapter 8 - Ecstacy and Eve Chapter 9 - Tidbits on Other Highs References

Introduction

This book was written for the enlightenment of the general public or at least the open minded and curious percentage. It is to be used for informational purposes only. It is not meant to be a production manual. All the syntheses are geared to demonstrate how the underground chemist might proceed in "secretly" manufacturing MDMA. Some o these methods are in fact being used to feed the growing underground market right now.

Many of the syntheses contained in this book are dangerous. An effort has been made to point out those dangers,

but the reader is referred to any manual on laboratory safety for more detailed coverage.

Many of the syntheses given in this book would never have been used by the professional chemist, because he would have the chemicals readily available from chemical supply houses. Many chemicals are also available to the average person, but the DEA uses open purchasing to entrap many unsuspecting customers. For this reason, a underground chemist's best move is to produce as many of his own precursors as possible. There are quite a number of possibilities to be had from normal household, garden, paint, sealant and OTC medical products. Routinely reading labels of these products will provide most of the information one needs. Cross-checking the ingredients on the labels with a dictionary of chemical synonyms or trade name index will help clear up any ambiguity in naming schemes. The reader can always obtain more information by referring to the original article cited and general references given at the end of chapter one. Reading through chapters one and two first will help make the terminology in the rest of the book much clearer.

Many professional people are pursuing legal routes in an effort to legalize this wonderful substance. MAPS, The Multidisciplinary Society for Psychedelic Studies, founded by Rick Doblin is a non-profit organization dedicated to MDMA research. MAPS associated psychiatrists petitioned the FDA for approval to administer MDMA to research subjects. They have already won some ground and conducted research, but the fight goes on. The proces and research is very expensive and all membership dues go to the effort. If you would like to join ($30) and recieve their newsletter or make a tax deductible contribution, contact MAPS at 23-A Shalter Lane, Cambridge, MA, 02138. The spelling of the name Ecstacy has been questioned by some who prefer the dictionary spelling of Ecstasy which means intense joy or delight. I use Ecstacy because we are not talking about manufacturing intense joy or delight, but instead, a drug whose slang name is Ecstacy and may produce intense joy or delight.

Chapter 3 - Miscellaneous Chemicals

Ether [60-29-7] (aka,ethyl ether,diethyl ether)

Ether is hot on the DEA's list of suspect chemicals and is officially illegal to possess. It is relatively easy to produce if one has the proper work area to do it safely. Good ventilation (a fume hood) is a must to prevent dangerous concentrations of ether from building up in the air.

[1]Place 2 pounds of concentrated sulfuric acid in a 3 neck round bottom flask. Place a thermometer through a stopper (or glass thermometer holder) and into one of the flask's holes. Be sure the thermometer reaches into the sulfuric acid. Into a separatory funnel place 3 pounds of ethanol (190 proof). If your separatory funnel will not hold all of the ethanol just keep the funnel filles as the reaction proceeds. Use the final neck to set up a simple distillation apparatus. In the collection flask place ice to help condense the ether. Heat the sulfuric acid to 280°F (or 138°C). When this temperature is reached open the stopcock on the separatory funnel and allow a slow steady stream in. Do not allow the temperature to exceed 286°F (141°C) or ethene will begin to be produced instead of ether.

Separate the ether from the ice water with a separatory funnel,wash with 10% sodium hydroxide solution, dry over calcium chloride for 24 hours, and redistill the ether. Ether boils at 35C, density at 30°C--.7019, at 20°C--.7134. Anhydrous Ether

Dry ether can be prepared by letting ether dry over thin slices of sodum metal (or sodium wire) for 24 hours. Use 5g of sodium for every 100g of ether. Distill the ether over fresh sodium metal under inert atmosphere. To generally see how to set up your apparatus for inert atmosphere look under methylenation of 4-allyl catechol in chapter five. Instead of leading the nitrogen to the top of a reflux apparatus as shown, you would lead it into a distillation apparatus where the thermometer normally goes. You will also need to lead the nitrogen through a flask containing calcium chloride or other drying agent to remove moisture from the nitrogen before it enters the

distillation apparatus. This all serves to keep the ether from reabsorbing moisture from the air. Stopper the receiving flask for storage of this dry ether. Peroxide Formation in Ether

In addition to the danger of explosions from the build up of ether vapors. Explosive peroxides that form from prolonged contact with oxygen in the air pose a significant risk to the chemist. Even air trapped inside the bottle will form significant amounts of peroxides in time; therefore, before using ether that has been stored over a perio of time one should first test for peroxides and then treat the ether if necessary. TEST A: .1g of sodium iodide is dissolved in 1 ml of glacial acetic acid and this solution added to 10ml of the ether to be tested. Formation of a red color due to free iodine formed indicates the presence of peroxides.

TEST B: 5ml of a 1% ferrous ammonium sulfate solution, .5ml of 1 N sulfuric acid, and .5 ml of .1 N ammonium thiocyanate are mixed. If color is present in the solution, it is decolorized by adding a trace of zinc powder. This added to an equal amount of ether to be tested. If a red color develops peroxides are present. REMOVING PEROXIDES: To 1 liter of ether, add 40g of a 30% aqueous ferrous sulfate solutions (12g of ferrous sulfate in 28g water). The reaction can be vigorous if appreciable amounts of peroxides are present. Separate the ether and dry it over calcium chloride or magnesium sulfate and distill. OTC Ether

For those who don't care to synthesize ether, there is a readily available source in the automotive section of your local department store. Most people know it as starting fluid. The main component is diethyl ether. The current leading K-mart brand contains heptane(bp 98°), dimethyl propyl methane (2-methyl pentane, bp 60°), and diethy methyl methane (3-methyl pentane, bp 63°) as added ingredients. The other ingredients all boil significantly higher than ether so the ether can be removed by distillation. To collect the ether for distillation, spray the contents of the can into a flask that is nestled in crushed ice (in a well ventilated area or outside). Once can use one of the "straws" tha comes with a can of WD-40 to spray the starting fluid contents well into the flask. Distill the liquid collecting the portion boiling up to 35°C. Chloroform [67-66-3]

In a 1000ml flask, mix 300g of calcium hypoclorite (swimming pool chlorine) and 300ml of water.Mix thoroughly so that no chunks are left. To the separatory funnel add 50g (63.5ml) of acetone. Acetone can be purchased in teh paint section of any store that sells paint.. Run water through the jacket of the condenser and set the receiving flask in an ice bath. Allow the acetone to slowly run into the reaction flask so that the tempereature does not rise above 45°C. Cool with a water bath if necessary. When all the acetone is added, heat the flask with water bath to distill over the chloroform. It will distill over in the range of about 56-66°C. Wash the chloroform that distills over with an equal volume of water and then dry it overnight with calcium chloride. Finally, distill th chloroform (bp 61-62°C, density 1.48)

Chloroform can also be prepared by the following method. [2] Mix 2 pounds of calcium hypochlorite (swimming pool chlorine), 12 pounds of water and 12 fluid ounces of ethanol in a suitable sized flask. Place this flask in a reflux apparatus. Heat with a water bath until no more chloroform is produced (chloroform will collect as a separate layer in the flask). Use a separatory funnel to separate the water from chloroform and redistill the chloroform. Decomposition in Chloroform

Chlorform decomposes under the influence of light, air, and moisture. After storage, it therefore contains phosgene (carbonyl dichloride, COCl2), HCl, chlorine and other chlorinated methane products. For this reason most purchased chloroform contains from 0.5 - 1.0% ethanol as a stabilizer. The ethanol will react first before an chloroform decomposes. The formation of phosgene and HCl can be represented as follows: CHCl3 + H2O + O2 --> COCl2 + H2O2 + HCl CHCl3 + H2O2 --> COCl2 + H2O Formic Acid[64-18-6] (CHOOH)

[3] Mix an equal amount of glycerine and oxalic acid and place in a flask. Heat this mixture at 75-90°C. Continu heating until no more CO2 bubbles out. Fresh oxalic acid is added and the process continued. When enough acid is made, distill it over using the proper apparatus and raising the temperature with an oil bath. 90% formic acid is collected. Alternatively, you can place the mixture in a distillation apparatus with a vacuum connection. Read the temperature with the thermometer placed into the mixture. Heat the mixture to ~90°C, but while under reduced pressure. As the reaction proceeds the formic acid will distill over. This takes about 4 to 5 hours for 500g of glycerine and 500g of oxalic acid. Allyl Alcohol[107-18-6]

(based on 500g of glycerine and 500g of oxalic acid) [4] Continue heating the mixture from the formic acid synthesis with an oil bath or Bunsen burner (if using a Bunsen burner heat the flask through wire mesh to spread the heat). Some liquid should come over before the temperature reaches 210°C. This liquid can be discarded since it contains mostly water and formic acid. When th temperature of the liquid reaches 220-225°C carbon dioxide is rapidly evolved and allyl alcohol and allyl formate distill over in approximately equal amounts. Collect this distillate in a flask containing a few cubes of ice. Stop reactin when the temperature reaches 240°C. Heating beyond this temperature produces acrolein. Add 50g of sodium hydroxide in 1L of water to the distillate. Let the mixture sit at room temperature for 12 hours. This will hydrolyze the allyl formate to allyl alcohol. Distill this mixture collecting the first 300ml which come over. This contains the whole of the allyl alcohol. By careful fractional distillation a constant boiling mixture can be obtaine which boils at 87-88°C. This solution contains 27-28% water. As an alternative to fractional distillation, 50grams of anhydrous potassium carbonate can be added to the 300ml and the heavier layer which forms is discarded.

Pure Allyl Alcohol

To the aqueous allyl alcohol solution is added 10g portions of anhydrous potassium carbonate. The heavier aqueous layer is removed with a separatory funnel. Continue this procedure until no layer separates and the potassium carbonate remains solid. Allow time to be sure no separate layer will form. Filter off the solid and collect all that distills between 94-97°C. The alcohol obtained is 90-98% pure. Toluene

Toluene in its commercial grade is known as Toluol and is sold by the gallon and pint sizes in hardware stores as a paint thinner. Methylene Chloride[75-09-2]

Methylene chloride is the main component of paint strippers. These strippers also contains a reasonable amount o methanol that can be saved. They caome as a gelatinous substances because of a thickening agent present. If one distills the stripper, methylene chloride will be the first component to distill over, followed by methanol. The remaining residue is the thickening agent which will cling to the glassware. The thickener left can be scraped out with a coat hanger (methylene chloride bp 40°C/ methanol bp 65°C) Ethanol

Ethanol is the common alcohol that we drink. Any alcoholic beverage could be distilled to produce this alcohol i a maximum concentration of 95% (vol/vol). To get any higher concentration you have to resort to other means. There is no need to distill alcoholic beverages, though, since 190 proof grain alcohol (95%) is available at the liquor store. Anhydrous Ethanol[64-17-5]

To 1 liter of 190 proof grain alcohol is added 200g of calcium oxide. Calcium oxide is commonly called lime, bu it should not be confused with the lime sold for agriculture which is calcium anbd magnesium carbonate. The mixture is refluxed for 24 hours in a reflux apparatus fitted with a calcium chloride tube to keep out atmospheric moisture. The alcohol is then distilled off. This results in 99% ethanol which is treated again with 35g of calcium oxide to yield 99.7% ethanol. For laboratory preparation of calcium oxide form calcium carbonate see Handbook of Preparative Inorganic Chemistry. Hydrobromic Acid(48%) [5]

Hydrobromic acid is not as commonly available as the components it can be made from, namely sodium bromide and sulfuric acid. It's preparation is straight forward and a good quality constant boiling 48% solution can be obtained. H2SO4 + KBr --> KHSO4 + HBr

220g of KBr (potassium bromide) or 190g of NaBr (sodium bromide) is dissolved in 200ml of distilled water and chilled in an ice bath. 90 ml of concentrated H2SO4 is chilled in the ice bath and then slowly added to the chilled bromide solution being sure not to allow the temperature to rise above 75°C, in order not to form any free bromine. The solution is cooled to room temperature and the K2SO4 that was formed is filtered out. The solution is then placed in a 1000ml boiling flask in a simple distillation apparatus. Add a few boiling chips. Start a flow o water through the condenser and heat with flame through a wire gauze. Water will distill over first, but when the temperature reaches 125°C replace the receiving flask with a clean flask. Monitor the temperature as it will continue to rise to 126°C and remain there steadily until the constant boiling solution has distilled over. When th temperature begins to drop stop the distillation. [It is important to know the correct temperature in order to collec the proper fraction. To calibrate the thermometer first boil water in the apparatus and note the temparature. If it reads 100C, then the thermometer reads correctly. If it reads say 101°C, you should substract one degree when reading your thermometer. If it reads say 99C, you should add one degree when reading your thermometer.] Even purer HBr can be obtained by redistilling and collecting the portion boiling at 126C. The acid obtained is approximately 47.5% HBr with a density of 1.49g/ml. Hydrogen Chloride Gas [6]

HCl gas can be easily generated with the apparatus shown. The still head (bent adapter) is stoppered with a one hole #2 rubber stopper with a glass tubing fitted in the hole. Vinyl or rubber tubing is then fitted to the glass tubing and finally to a longer piece of glass tubing (or pipette) that will reach into the receiving containter (not shown). The separatory funnel is filled with concentrated sulfuric acid and left unstoppered. The reaction flask is filled 1/4 of the way with table salt (sodium chloride) and made to a thick slurry by addition of water or if handy muriatic acid. Use less salt if only a small amount of gas is needed for the reaction. Be sure that the separatory funnel is clean so that any unused sulfuric acid can be returned to its container. Place the glass tube into the flask to receive the HCl. To start the gas generation, open the stopcock partway and allow a stream of sulfuric acid into the flask. Tilt the apparatus if necessary to prevent the sulfuric acid from entering the side-arm of the still head. Slow the flow of the sulfuric acid to a fast drip. The HCl first generated will flush out the air present before coming out full strength. Pressure will build up in the apparatus in proportion to the depth the glass tube is submersed in the flask receiving the HCl. Keeping this in mind, adjust the flow of the sulfuric acid so that a stead steam of bubbles exit the glass tube. If sulfuric acid is added too fast, gas will bubble up through the separatory funnel. As long as the solution that you are feeding HCl is not saturated with HCl it will continue to absorb gas and very little will actually escape. Without proper ventilation, it will become quite obvious when the reaction with HCl is complete and the solution saturated. At this point, stop the flow of sulfuric acid and lead the gas into lye solution (sodium hydroxide). When no more gas is produced, carefully dilute the contents of the reaction flas and discard down the drain with the faucet flushing behind it. (to lessen the fumes even more dilute with sodium hydroxide solution) Hydrogen Iodide(57%) [7]

Hydrogen iodide can be prepared by the reaction of hydrogen sulfide gas on iodine. The hydrogen sulfide (H2S) generated by reaction of dilute HCl solution on iron sulfide (fools gold, pyrite) in a gas generator. Hydrogen sulfide is what we commonly know as rotten egg gas and the smell of stove gas since it found in both. This is what will kill most people. Don't let its familiarity disguise it's hazards. It is extremey poisonous and exposure to small quantities numbs ones perception of increasing concentrations; although, it will remain

unmistakably present. To generate the H2S dilute muriatic acid with an equal volume of water and fill the separatory funnel. Fill the reaction flask with powdered iron sulfide. Run in the HCl solutioan at such a rate as to keep steady bubbling in the receiving flask. The H2S can be bubbled through a flask containing water to remove HCl(not shown) before entering the receiving flask. The receiving flask should contain a constantly stirred (magnetic stirrer) suspension of 120g I2 (iodine, solid not tincture) and 150 ml water. The H2S that is not absorbed in the iodine suspension is bubbled through a lye solution(not shown) and then out through the fume hood. The solution will become clear(from red) and sulfur will accumulate in the flask when the reaction is complete. The sulfur is filtered out and the solution boiled in a hood to drive out dissolved H2S gas. The boiling continued until no black precipitate(copper sulfide) forms when 1ml of the solution is added to a cupric nitrate solution (1g in 10ml of water). The solution is then distilled being sure to add boiling chips. The fraction boiling from 125°C to 127°C is collected. This is the acetropic 57% solution, bp 126°C(@760mmHg), density 1.70. Stor the acid in a dark bottle and use soon after preparation to avoid considerable decomposition. The yield is 90% based on iodine consumed. Chlorine [8]

Chlorine can be simply prepared using the same gas generator as used for HCl and H2S. Fill the separatory funne with muriatic acid (hydrochloric acid from the hardware store). Fill the reaction flask 1/4 full with calcium hypochlorite (swimming pool chlorine). Slowly add the acid solution to the flask and lead the gas formed through the tubing to the solution receiving the gas. Be warned that chlorine gas is much more overpowering and destructive to mucous membranes than HCl and ammonia. Excellent exhaust is a must. Chlorine gas can also be prepared by adding sulfuric acid to a mixture of table salt and manganese dioxide. The HCl that is formed from NaCl and sulfuric acid is immediately oxidized to chlorine. Some info on the preparation of the other halogens, bromine and iodine, can be found in Comprehensive Inorganic Chemistry Vol III such as isolation iodine from kelp ash. Acetic Anhydride(from acteone and acetic acid) [9][108-24-7]

Acetic Anhydride is hot on the DEA's list due to its use in the manufacture of phenylacetone for methamphetamine production. It is conveniently produced from glacial acetic acid by bubbling ketene through it Even diluted solutions of acetic acid could be used since the keten would react with water to produce acetic acid and water would react with acetic acid anhydride to produce acetic acid. In time, all of the water would be consumed and only acetic acid left to react with the ketene. All that is needed for formation of ketene is acetone and some glass blowing skills. See the reference cited for details. In place of chromel A, one could probably use nichrome wire(also a nickel-chromium alloy) from a toaster and the toaster's own plug to run it from. Acetic Anhydride is a combustible liquid with a flash point of 130°F, boiling point of 139°C, and density of 1.080. Acetic Acid

Acetic acid is also referred to as glacial acetic acid in its pure form since it freezes in cool weather(16.7°C) and forms chunks(glaciers) that float in the unsoldified portion. It boils at 118°C and has a liquid density of 1.053. Acetic aid in solution is what we commonly know as vinegar. The vinegar purchased in the store is quite dilute, but could be concentrated. Refer to Dicks's Encyclopiedia of Practical Reciepts and Processes for simple method of doing so. Dick's Encyclopedia has been reprinted as a part of Granddad's Wonderful Book of Chemistry by Kurt Saxon. The sodium acetate mentioned in some of the methods can be made by addition of sodium hydroxid

solution to vinegar until the smell of vinegar is barely perceptible and then distilling off the water. Ammonia

Ammonia gas is easily prepared with the gas generator apparatus used for HCl, etc. Add an equal volume of red devil lye or other quality lye(sodium hydroxide) to water. Stir until it is dissolved. A large amount of heat will be evolved in forming the solution. (At 50% concentration sodium carbonate will settle out and on exposure air, CO reacts with the sodium hydroxide to form sodium carbonate, so keep stoppered). Pour the solution into the separatory funnel in the apparatus. The reaction flask is filled with ammonium nitrate fertilizer which is about ha ammonium nitrate and half ammonium chloride. The sodium hydroxide will release ammonia and form sodium chloride(table salt) and sodium nitrate. Lead the ammonia through the tubing and into the solution requiring the ammonia. Determining Concentration

Scale weight Place a flask or beaker containing a known volume of liquid(alcohol, water, etc.) on a scale. Calculate the liquid' weight by multiplying it's volume by it's density.(density of water is 1, density of methanol is 0.79g/ml). Calcula the weight of ammonia needed to produce the desired concentration by multiplying the concentration needed(decimal form i.e. 50%=.50) by the liquid's weight and dividing this by 1 minus the concentration(decima form). weight of liquid * concentration -------------------------------- = weight of ammonia needed 1 - concentration When the scale shows this increase in weight, you have the desired concentration. Since weight in the tens or hundreds og grams will be weighed, an inexpensive school balance can be used with 0.5-1g accuracy. Density/volume

Another way to determine concentration is to first determine the density of the solution. Sine beam scales that can't hold a whole beaker full of liquid can support a weight from the beam(with a thread). This weight can first be weighed in the air and then weighed while suspended in the solution. The difference in this weight divided by the volume of the weight is the density of the solution. The volume of the weight is easily found by submerging the weight in water in a graduated cylinder and measuring the volume change. Now all you need to know is the original volume of the solution and it's density and the final volume of the solution and its density you calculated. From this you know the weight of the original solution(volume * density) and the weight of the ammonia added(original weight - final weight) and you can calculate concentration(weight of ammonia divided by the total weight of the solution). Saturated solution

Since nearly all of the ammonia will be absorbed by the solution before it is concentrated, one can easily tell whe it has reached this point(when the smell of ammonia becomes quite strong). The concentration is then just a function the particular solvent's temperature. In general, the lower the temperature the more ammonia will

dissolve. Following are the saturation concentrations of solvents at various temperatures.

temp water 0C

47%

15C

38%

20C

34%

25C

31%

30C

28%

50C

18%

190 proof ethanol

Absolute Ethanol

Methanol

20%

15%

10% 16%

11%

Hydrogen

Although hydrogen is not used in any of the syntheses in this book it's simple preparation is worth mentioning. In the spearatory funnel of the HCl gas generator, put a lye solution made from equal volumes of red devil lye(sodium hydroxide) and water. Fill the reaction flask half way with folded or rolled up pieces of aluminum fo Feed in the lye solution at a rate to meet desired production. Feeding the gas from the generator through a flask containing calcium chloride will remove water vapor. Both the dissolution of the lye in water and the reaction with aluminum generate a lot of heat so be careful handling your apparatus. (Try filling plastic bags with hydrogen) Sulfur Trioxide

Sulfur trioxide when combined with water forms H2SO4, sulfuric acid. Although sulfuric acid can be bought wit relative ease, fuming sulfuric acid cannot. Fuming sulfuric is 100% sulfuric acid with sulfur trioxide dissolved in it. It is also called oleum. This is not called for in any particular synthesis in this book, but its application can be very useful for the outgoing chemist. Adding carbon tetrachloride to it in the gas generator apparatus will produc phosgene(a deadly war gas and highly reactive intermediate compound). Reacting it with methyl alcohol gives dimethyl sulfate(a mehtylating agent)(Guyot and Simon, Chemical Abstracts, 539, 1920.) To produce sulfur trioxide, sodium bisulfate is first dried in a thin layer on a pan in an oven set at 300°F. Let it dry for at least an hour. The sodium bisulfate is swimming pool pH minus adjuster. The sodium bisulfate is then placed in a flask s for distillation. Heat this under a gas flame. The bisulfate will melt and convert to sodium pyrosulfate and water. Try to control the heat to where water is just being produced. Collect the water and discard. When no more water is produced heat the flask more vigorously and the sodium pyrosulfate that was previously formed will

decompose into sulfur trioxide and sodium sulfate. Collect this gas in a cooled flask. It will liquify and then solidify if the temperature is low enough. If fuming sulfuric acid is the goal, collect the gas in chilled concentrate sulfuric acid. One could collect the gas in water and form the sulfuric acid first but that would take more time and sodium bisulfate. Sulfur trioxide can be produced in a similar fashion by heating ferrous sulfate(copperas, iron sulfate for gardens) or ferric sulfate to a read heat after first being dried in an oven for several hours. This is the method employed for sulfuric acid manufacture before the chamber process for burning sulfur was developed. Iron oxide, rust, is left afterward. Heating it hot enough is the trick. White Phosphorus

White phosphorus is another starting point for many compounds such as phosphorus trichloride, phosphorus tribromide, phosphoric acid, and phosphorus pentoxide. One must be careful in handling phosphorus. Forceps an other instruments must be used in handling it since the heat from ones body would ignite it in air. It will ignite in moist air at 30°C. It can be melted under water at 44.1°C. 50-100mg is fatal when taken internally. External exposures can lead to nechrosis of the bone which was an industrial disease known as phossy jaw when matches were still manufactured from white phosphorus. The red form of phosphorus is the one people are more familiar with since it can be handled more easily. It only burns in air when heated to 260°C and it is relatively non-toxic a long as it does not contain the white form as an impurity. Phosphorus' preparation was kept secret by the first alchemists who discovered it. Luckily for us, its preparation is now well known. Make a clay retort with a lid fro modeling clay and bake it in an oven or kiln. Fill the retort 1/3 of the way with a mixture of Triple siper phospha from the local nursery and 1/4 of the phosphate's weight of sand and 1/4 of the phosphate's weight of charcoal. The mixture should be as finely powdered and well mixed as possible. A high quality charcoal or activated charcoal from the fish section of a pet store should be used for charcoal. Place the lid on the retort and seal with clay or cement. With the neck of the retort dipping in a container of water, begin heating the retort. The temperature must eventually rise to 1450°C. This can be accomplished by heating the retort with coal or an acetylene torch. It can be preheated with a propane or natural gas flame, but they are not hot enough themselves. Building a brick enclosure around the retort with an opening for the neck and flame will help maintain the temperature. White phosphorus and carbon monoxide will distill over into the water where the phosphorus will condense and the carbon monoxide bubble out. The reaction can be summarized by the following equations. 2 Ca3(PO4)2 + 6 SiO2 --> 6 CaSiO3 + P4O10

P4O10 + 10 C --> P4 + 10 CO Acetamide [10]

Acetamide is used to later synthesize methylamine. Acetamide itself is easily prepared from ethyl acetate and saturated ammonia solution. The ethyl acetate needed can be obtained by distilling denatured alcohol(ethyl aceta is the major component) purchased at the hardware store and collection the portion boiling around from 70-78°C Wash this fraction with sodium carbonate solution, then water, dry over calcium chloride and redistill collection the portion boiling at 77°C. The best thing about this route to methylamine is that every component is commonly available. 200 grams of ethyl acetate are placed in a flask followed by 300ml of 28% commercial ammonia (or 195ml H2O). Cool this mixture in an ice salt bath to -8 to -10C. Bubble in dry ammonia gas by running ammonia gas from the generator through a flask containing calcium chloride and then into the mixture. When the solution

saturated(smell of ammonia is strong from undissolved gas) stopper the flask tightly and let it sit in a cool place for 3 days. Within a day or so the layers will merge into one. After 3 days, distill the contents of the flask under reduced pressure on a boiling water bath. Distill the residue on an oil bath under reduced pressure collecting the distillate in a cooled receiving flask. This is acetamide. Acetamide melts at 81°C, bp 222°C, @100mmHg bp 158°C, @40mmHg bp 136°C. Mercury Chloride[7487-94-7]

Mercury chloride(HgCl2, mercuric chloride) is prepared from mercury by the action of aqua regia or chlorine water. It is also prepared by first forming the sulfate with concentrated sulfuric acid and then subliming it with manganese dioxide and table salt. (see Thorpe's Dictionary of Applied Chemistry). Mercuric chloride is a white crystalline solid that melts at 227°C and sublimes at 300°C. Adding a small amount of sodium hydroxide solutio forms a yellow precipitate of HgO. Mercurous chloride, calomel, forms a black precipitate with soidum hydroxid solution. Aqua regia is prepared by mixing strong nitric acid (1 volume) and muriatic acid (4 volmues). The nitri acid acts to dissolve some of the mercury where it is then acted upon by free chlorine(Cl2). The chlorine is forme in aqua regia according to the folowing equation. HNO3 + 3 HCl --> NOCl + Cl2 + 2 H2O Acetone

Acetone is soluble in water and in 70% strength it is sold as finger nail polish remover. Alongside other solvents, acetone is sold in the pint, gallong and 5 gallon sizes in the paint section of hardware stores. In this form, it is ful strength. Water content in this commercial form is low since it does not form an azeotrope with water, but drying overnight with calcium chloride or potassium carbonate and distilling the solvent will remove much of the water that is present. Addition of phosporus pentoxide to this dry acetone and distilling will reduce the water content to approximately 0.01-0.02%. Acetone has a boiling point of 56.5°C and a density of 0.788 g/ml

Chapter 4 - Alkyl Halides

Alkyl halides in chemistry are powerful tools as intermediates and as end products in varied chemical industries. For our purpose in this book, we will consider them for intermediates in the formation of amines and in the case of the allyl halides for the synthesis of safrole.

The name Alkyl is just generic for a carbon chain and Halide is generic for any one of the four halogens: Fluorin (F), Chlorine (Cl), Bromine (Br), and Iodine (I). The halide derivatives of safrole will be discussed in the chapter on Safrole. There are several choices of functional groups to form alkyl halides from. The ones that will be encountered in this book are ethers, alkenes, and most importantly here and elsewhere --alcohols. We will use alcohols for the lower alkyl halides discussed in this chapter since they are the most practical and readily availab materials. Mechanism

The two general reagents that will be discussed for transforming alcohol groups to halides are: Phosphorus halide and Hydrogen halides, Hydrogen halides are just the corresponding acid of each halide such as hydrochloric acid or hydrobromic acid. The acids can be purchased as such or be generated in the reaction mixture from halide salt ice. sodium bromide or potassium bromide, and another acid.

The acids replace the alcoholic -OH by first protonating the group. OH is a very poor leaving group but H20 is a very good leaving group and the Bromine ion, acting as the nucleophile, replaces the H20. There are two ways in which the bromine replaces the H2O. First is that the H2O leaves first, leaving behind a positive charge on the carbon and the second is that the bromine directly displaces the H20 as illustrated in figure 4.1. These are examples of SI and Sn2 substitution, respectively. Which route is taken depends mainly on the number of other carbons the affected carbon is bonded to. Tertiary carbons (bonded to three other carbons) undergo Sn l substitution. Primary (bonded to one other carbon) and methyl groups (single carbons) undergo Sn2 substitution. Secondary carbons (bonded to two other carbons) can go either way, only experimentation will tell. Depending o which substitution occurs, reaction conditions can be altered to increase the rate and yield. These conditions and why are discussed in any Organic Chemistry text from the local college bookstore. Check it out!

The Phosphorus halides have good yields for primary and secondary alcohols, but next to nil for tertiary. Their mechanism is somewhat similar to the acids in that a good leaving group is formed first and then is displaced wit an Sn2 attack. Halide Salts As Reagents

The preparation of three alkyl halides will be discussed here (methyl, ethyl, and allyl). Of these, the iodides and bromides will be produced using the appropriate salts. The alcohols, methanol & ethanol, that will be used as starting materials can be easily obtained at the local hardware store in the section containing paint thinners, etc. The alcohols are also known by many common names which one should be familiar with: Methanol = methyl alcohol, wood alcohol Ethanol = ethyl alcohol, grain alcohol

A simple preparation for allyl alcohol is given in the miscellaneous chemicals chapter. The salts, sodium iodide, sodium bromide, potassium iodide, or potassium bromide, would have to be purchased from a chemical supplier. These salts are relatively common and are available in bulk from industrial chemical supply houses as is sulfuric and phosphoric acid. Halide Salts With Sulfuric Acid

The procedure below was originally written for Ethyl bromide, but is easily modified for the corresponding Methyl arid Allyl halides. Ethyl bromide

Alfred E. Holt published a paper in 1916 in the Journal of the Chemical Society for the best preparation of ethyl bromide from his practical experience.

In a 5 L flask, 300ml of water are added to 500ml (920g, 9.0 moles) of concentrated (96%) sulfuric acid. After cooling, 500ml (395g) of absolute alcohol are run in (or 429g of 190 proof). Leave the flask in an ice bath to prevent the temperature from rising too much, When cold, slowly add 380g of potassium bromide to the solution Be sure to keep the solution cold to prevent the evolution of HBr gas. Place the flask in a simple distillation set up and gently heat on a water bath at the lowest temperature that the ethyl bromide will distill over (slowly i.e. 2-3 hrs; pure ethyl bromide distills at 38.4 C). The ethyl bromide is collected in cool water and washed by repeated shakings with water then dried with calcium chloride ( it's dry when the calcium chloride no longer cakes up). Holt reports that yields as high as 96% have been achieved and rarely fall below 90%. Those that did were attributed to temperature irregularity during distillation. The dilution of the sulfuric acid is necessary to prevent the formation of diethyl ether to any great degree (see ether synthesis in miscellaneous chemicals chapter). If 93% sulfuric acid is used, add 270ml H2O and 518ml (959.5g, 9.0 moles) of sulfuric acid. The large excess of ethanol is used to achieve the highest yield of product based on the bromide salt. In other words, the ethanol is cheap but the bromide salts are expensive and can't be wasted.

The following table lists the information needed to substitute potassium bromide with sodium bromide. Substituting the bromide salt for the iodide will not work well here for producing the corresponding iodide since sulfuric acid easily oxidizes the hydrogen iodide as is produced, yielding SO, and free iodine (1,). Substituting methanol for ethanol yields the corresponding methyl halide. All other chemicals retain their proportion. Physica constants and other data are included for comparison and any calculations one would want to do. Compound

m.w. (g/mole)

moles Amount for Ethyl Halide Amount for Methyl Halide Formula

Potassium bromide 119.0

3.2

380g

1380g

KBr

Sodium bromide

102.9

3.2

329g

329g

NaBr

Potassium iodide

166.0

KI

Sodium iodide

149.9

Nal

Compound

m.w. (g/mole)

moles

density(g/ml)

Boiling Point of the pure liquid

Amount for Ethyl Amount for Formula Halide Methyl Halide

Methyl alcohol

32.0

8.6

0.791

65

---

348ml (275g)

CH3OH

Ethyl alcohol 46.0

8.6

0.789

78.5

Allyl alcohol 58.08

0.8540

97.1

CH2=CHCH2OH

Allyl chloride 76.53

0.9376

45

CH2=CHCH2CI

Allyl bromide

120.98

1.398

70

CH2=CHCH2Br

Allyl iodide

167.98

1.8

102(744mm)

CH2=CHCH2I

Ethyl chloride

64.51

0.8978

12.3

CH3CH2Cl

Ethyl bromide

108.97

1.4604

38.4

CH3CH2Br

Ethyl iodide 155.97

1.9435

72.3

CH3CH2I

Methyl bromide

94.94

1.6755

3.6

CH3Br

Methyl iodide

141.94

2.279 42.4

CH3I

500ml(394.5g)

---

CH3CH2O

Methyl bromide

Producing methyl bromide requires some special treatment due to the fact that it boils well below room temperature. The collection flask would have to be cooled well below zero with an acetone/dry ice bath. A regula ice bath would not be cool enough to condense all of the product quickly enough or prevent rapid evaporation. The washing water would have to have some salt added and be cooled in the bath also. The salt keeps the water from freezing and the cooling keeps the bromide from boiling away. Once the product is washed it should be dissolved in alcohol and placed in the freezer. This would be more cost effective than methyl iodide for methylating MDA, but worrisome for making methylamine since there are better methods for its production. Allyl bromide

In the case of allyl alcohol where the alcohol is prepared by the chemist, the great excess of alcohol in the preceding procedure and the savings of halide salts may not be justified. By using a mole ratio where the halides are in excess would save on having to recover unreacted allyl alcohol at the expense of using about 50% more halide salt.

In a 2000m! beaker add 602g of concentrated sulfuric acid to 495.9 water (always add acid to water, not water to acid). Cool solution in an ice bath and add 607g (5.9 moles) of sodium bromide (or 702g potassium bromide) wit stirring. Keep the solution cool and stir for a few minutes. Filter off any solid material.

Pour solution into a 3000m1 boiling flask and place in the following apparatus. Add 324g of 72% allyl alcohol to the flask. Then slowly add 300g of concentrated sulfuric acid through the separatory funnel with stirring from a magnetic stirrer. The allyl bromide will completely distill over in about 1 hour (add your sulfuric acid at approximately this rate). Wash the crude bromide with dilute sodium carbonate solution, dry with calcium chloride (dry when no more calcium chloride clumps together), filter out calcium chloride, and then redistill. The product boils from 69-72 degrees C. Yield 92-96%. For 93% commercial sulfuric acid use 622g sulfuric acid and 477 g water. Use 310g of 93% in the separatory funnel. Iodide Salts With Phosphoric Acid

(Herman Stone and Harold Shechter, A new method for the preparation of organic iodides, Journal of Organic Chemistry, 1950, vol. 15, pg 491-495) Phosphoric Acid has been used with the iodides to generate HI (as oppose to using sulfuric acid) in the preparation of alkyl iodides from ethers and alcohols. 95% phosphoric acid gave better yields than 85% phosphoric acid, but the 85% yields were still good. If for some reason ethers are more available, the preceding reference can be examined. Only the use of alcohols are described here. Consult the original reference for the 95% procedure keeping in mind that phosphoric anhydride is P2O5, phosphorus pentoxide. 2 moles of H3PO4 are formed for every 3 moles H2O and 1 mole P205. From Alcohols

The general procedure is basically a mole ratio for the alcohol, iodide salt, and phosphoric acid (85%) of 1 : 2 : 2.1, respectively. Then refluxing and purification.

For ethyl iodide; To 142.5 ml ( 242 g, 2.1 mole) of 85% phosphoric acid add 332g (2 moles) of potassium iodide being sure to keep the mixture cool to avoid evolution of Hydrogen iodide. Then add 58.3 ml (46g, 1 mole) of ethanol. Reflux for 6 hours. (use of a stirrer would aid the reaction) The mixture will separate into two layers during the reaction. The mixture is cooled and 150 ml of water is added followed by extracting the mixture with 250 ml of diethyl ether. The ether layer is separated and decolorized with a sodium thiosulfate solution (25g in 100 ml, use only as much as needed). This removes any iodine that is formed during the reaction. It is then washed with a saturated sodium chloride solution (as much table salt as you can dissolve in water). The ether solution is then distilled on a water bath with ether coming over first at approximately 35 C and then the ethyl iodide at 72.3°C (collect each separately). For sodium iodide use 300g in place of potassium iodide. For allyl iodide use 80.7g of 72% (1 mole) allyl alcohol in place of ethanol. All other proportions remain. For methyl iodide use 40.5 ml (32 g, 1 mole) of methanol. All other proportions remain the same. Since ethyl ether has a boiling point so close to that of methyl iodide do not extract with this solvent. Instead separate the layers with a separatory funnel and continue with the procedure. The chemist would only have methyl iodide to

distill from any impurities. Phosphorus Halides as Reagents

Organic Syntheses Collective Vols. contain great methods for preparing halide derivatives. In vol. l, pg 399-403, is given a synthesis for methyl iodide using phosphorus triiodide which is generated in the reaction mixture with iodine, red phosphorus, and white phosphorus. They give the best directions and should be referred to. Keep in mind that white phosphorus, aka yellow phosphorus, burns in moist air at approximately 30 degrees C and at slightly higher temperatures in dry air. Phosphorus tribromide

Organic Syntheses Collective Vol. II, page 358, gives a procedure for the production of isobutyl bromide using the alcohol and phosphorus tribromide. This procedure can be easily modified for ethyl and allyl bromide. Phosphorus tribromide decomposes in water so absolute (anhydrous) alcohols are use to avoid wasting this reagent. Ethyl bromide

In a 2L flask is placed 322g (407.6m1, 7 moles) of absolute ethyl alcohol. Cool the alcohol in an ice-salt bath to 10 degrees C an place in the following apparatus. Slip a gym clip over the claisen adapter joint to break the seal between it and the thermometer adapter. This prevents having a closed system. 695g (244ml, 2.56 moles) of phosphorus tribromide is placed in the separatory funnel and added slowly to the cooled alcohol without allowing the temperature rise above 0 degrees C (about 4 hours). When the addition is complete the ice bath is removed an stirring continued until it reaches room temperature. Allow to stand overnight. Place the flask in a fractional distillation set-up (30 cm column). Distill under mildly reduced pressure. The ethyl bromide will be first to come over. Place ice in the collection flask to help condense the ethyl bromide. Separate the ethyl bromide from the water/ice and redistill in a simple distillation apparatus. The chemist can substitute allyl alcohol (100%, 420g) in this procedure to obtain allyl bromide. High yields can be expected with this procedure. Halogen Acids as Reagents

Concentrated aqueous acids can be used to generate alkyl halides. This is generally the same as using the halides salts, but with the salts the halogen acid is generated in the reaction mixture. Hydrochloric acid

Hydrochloric acid reacts so slowly with alcohols it is generally impractical for producing chlorides. With lower alcohols (short carbon chain) it can be helped by the Lewis acid, ZnCl2 (zinc chloride), to give reasonable yields Ethyl Chloride

Atherton M. Whaley and J. E. Copenhaver Preparation of Some Lower Alkyl Chlorides... , Journal of the

American Chemical Society, vol. 60, pg 2497-8, 1938

Cool 117g Hydrochloric acid, 31.25% muriatic acid, (1 mole) in a 500m1 or larger boiling flask with an ice bath. Add to this 136.4g (1 mole) of Zinc Chloride and stir to dissolve completely. To this solution add 25g (.5 mole) o 95% (190 proof) ethyl alcohol. Place in the following apparatus and heat in an oil bath. Maintain the oil bath temperature at -P125 degrees C. Maintain water flow in the up right condenser so that the thermometer doesn't read over room temperature. Ethyl chloride boils at 12.3 C so place ice in the collection flask to help it to condense along with an external ice bath so ice can be added.. When the production of chloride ceases (30-60 min) stop heating, remove collection flask, and separate the layers with a separatory funnel that has been chilled the freezer. Use directly. Expect yields of at least 70%+. Hydrobromic acid

Constant boiling 48% hydrobromic acid is the commonly available strength for this acid. Constant boiling generally means that it can't be concentrated further by distillation. This along with sulfuric acid to speed things along can be used analogously to the halide salt method to generate alkyl bromides. Following are procedures from Organic Syntheses collective vol. I. Ethyl bromide

To 1037g (6.15 moles) of 48% Hydrobromic acid and 300g (162m1) of concentrated sulfuric acid in a 3000ml flask is added 250g (311m1, 5 moles) of 95% (190 proof) ethyl alcohol. This alcohol is added through the top of the claisen adapter where the separatory funnel is located (see following apparatus). Place ice in collection flask help condense the ethyl bromide. 500g (272m1) of concentrated sulfuric acid is added to the separatory funnel an fed at a moderate drip into the flask. The flask is gently heated, if necessary, with a water bath to slowly distill over the ethyl bromide as it forms. (Bp. 38.5-39.5) When no more ethyl bromide distills over, stop the reaction, wash bromide with an equal volume of water, and then sodium bicarbonate solution. Redistill using an ice water bath around the collection flask instead of ice in flask. Stopper and store in a cool place. (yield ~90-95%) Allyl bromide

In a 300 L round bottom flask, add 1 Ing (5.9 moles) of 48% hydrobromic acid and 300g of concentrated sulfuric acid. To this is added 323g of 72% allyl alcohol (3.9 moles). Place in the same apparatus as above. Use a magnetic stirrer. 300g of concentrated sulfuric acid is placed in the separatory funnel and added gradually. The allyl bromide distills over in about 1 hr. Wash the crude bromide with dilute sodium carbonate solution and dry with calcium chloride (dry when calcium chloride no longer clumps together) and redistill. The product distills from 69-72°C. Yield 92-96%. Hydrogen iodide

This acid is a watched chemical and not generally available anyway but it can be prepared by the chemist (see miscellaneous chemicals chapter). It can be employed in a modification of the above procedure. Sulfuric acid wil

not be added since it would oxidize the HI in solution to Iodine. It is the most reactive of the three acids and should give good yields of iodides. A mole ratio of alcohol to acid of 1:2 is used. Methyl iodide

Add 99.2 g (3.1 moles, 125.6m1) methyl alcohol to 1392g HI (57%, 6.2 moles) in a 3 L flask. Place flask in simple distillation apparatus and gently heat with a water bath. Methyl iodide distills over at 42.4 C as it is formed. Use an ice bath around collection flask. Wash with a saturated sodium chloride solution and redistill. Ethyl iodide

Add 142.6 g (3.1 moles) of 95% ethyl alcohol to 1392g HI (57%, 6.2 moles) in a 3L flask. Place in a simple distillation apparatus and heat with a water bath. Ethyl iodide boils at 72.3 degrees C. Use an ice bath around collection flask. Finish as above. Allyl iodide

Add 246g (2.95 moles) of 72% allyl alcohol to 1324g HI (57%, 5.9) in a 3L flask. Place in a reflux setup and hea with an oil bath. Reflux for six hours (the chemist can play with this time) Finish as in the iodide salts from phosphoric acid method. Allyl iodide boils at 102 C at 744 mm Hg. (760mmHg is atmospheric pressure) Miscellaneous Methods Dichlorocarbene Chlorination

Dichlorocarbene formed from sodium hydroxide and chloroform can be used to chlorinate alcohols (Tabushi, et. al., Journal of the American Chemical Society, vol. 93, pg 1820, 1971). This method cannot be used with allyl alcohol since this reagent adds a dichloromethylene group to double bonds. This method is more economical for large alcohol molecules (where the previously given chlorination method wouldn't work) due to the large amoun of chloroform used per mole of alcohol. It is an interesting method though. The dichlorocarbene radical is also used to introduce a carbonyl group (aldehyde) to aromatic rings. This use of a dichlorocarbene radical is known a the Reimer-Tiemann reaction. A modification of this reaction is presented under piperonal in Chapter 5.

Chapter 5 - The Main Precursors

Safrole, piperonal, and isosafrole are generally the first step for any of the syntheses outlined in this book for the preparation of MDA, MDMA, and MDEA. They are all found to some extent as essentials oils in many botanical species. This affords a last resort means of obtaining any or all of them, forever. That is assuming that the DEA and their puppets around the world don't wage war on most of the plant kingdom.

These compounds have pleasant although potent aromas and as such have been used in perfumery for countless years. That makes obtaining them that much easier. The DEA knows this too and is keeping an increasingly close watch on their distribution as well as taking action to make them illegal to possess in these forms. Each of them

individually are already listed precursors which makes their possession illegal. Legal manipulation may extend this listing to include perfumery products if one were caught with them and it were alleged that drugs were going to be produced. No sweat for our just and caring legal system. Syntheses for these compounds have existed in the scientific literature for decades due to their importance in perfumery. The bulk of this chapter will focus on those syntheses. Safrole [94-59-71] 1,3-benzodioxole, -5-(2-propenyl); Safrole; 1-allyl-3,4-methylenedioxybenzene

Safrole is the most common and easily obtainable of any of the necessary precursors. It can also be used to make isosafrole and piperonal. Safrole is the main constituent of sassafras oil (70-80%)[11] and Ocotea cymbarum oil[12] (90%, aka-- Brazilian oil of sassafras). The oil of massoria bark[13], Cinnamomum massoia, contains 79% phenols which is mainly eugenol. The oil after being freed of phenols by washing with alkali solution contains a lower boiling fraction of mostly terpenes (7% of oil) and a high boiling fraction of mainly safrole (14% of oil). Camphor oil from the camphor tree[14] is another source of safrole as a by product in the manufacture of camphor. Safrole is contained in the high boiling fraction of the oil mainly between 228-235°C. The percentage o safrole in the oil depends mainly on the source tree variety. Safrole is also found in much smaller amounts in countless other plant oils around the world.

Sassafras oil is derived from the root of the sassafras tree which grows in the mid to eastern United States as wel as other sassafras species elsewhere in the world. The dried root bark contains up to 10% oil by weight and the rest of the root 1%. Many botanical companies sell sassafras root bark by the pound at a 1994 price of around $15/lb. Bigger companies sell larger quantities for much less per pound. Local herb/naturalist/health food type stores usually sell this in there herb section; though, not for consumption due to safrole's listing as a suspected carcinogen. In these same stores, one can usually find essential oils by the ounce or larger size. Sassafras oil is on of these essential oils. If a store has such a section, but does not have sassafras oil, do not hesitate to ask them to order it for you (just not in large quantities). It makes a nice gift. Aroma therapy is a large consumer of essential oils today. They are also used as adulterants in massage oils in connection with aroma therapy.

Ocotea cymbarum oil is derived from the wood of Ocotea pretiosa which grows in South America (more specifically Brazil, Paraguay, and Columbia). The wood contains 1% oil by weight which may not sound like much until one considers easily cutting down a thousand pounds worth of tree. Carefully steam distilled wood chips yield oil containing not less than 90% safrole. You may not find this by name in the herb shops, but it is sometimes substituted for sassafras oil since without analysis you can not tell the difference. The large distributo of perfumery and flavoring chemicals may have Ocotea cymbarum by name. Many of these companies sell as small as pound quantities. In pound and kilogram quantities, Their prices can't be beat. The ounce bottles sold by health food stores have greatly inflated prices. Check the OPD directory for essential oil and botanicals companies. Small herb shops nationwide that sell by mail order can be found in The Catalog of Catalogs ($2 at Books a Million) also check your local phone book. Extraction Extracting sassafras oil from root bark is easy. The hard part is learning to identify the tree and then digging up the roots. The easiest way to learn to identify the tree is to visit an arboretum. The leaves alternate on the stem and are of three

shapes. Often all three shaped leaves are on the same tree. They are 3" long and 1 1/2-4" wide. When a tree is located, d up the roots. Wash them and scrape off all of the bark. The oil can now be steam distilled from the root bark scrapings. A steam passes through the roots, it extracts oil through azeotropic distillation and the oil and water condense in the condenser. The oil and water are then collected in suitable sized containers. The oil can be seen as tiny droplets in the condensing water. When no more droplets are see all of the oil has been extracted.

Separate the oil from the water by pouring off the excess water and then pouring the rest into a separatory funnel to separate oil from the remaining water. The oil is heavier than water. Dry the oil with calcium chloride or other drying agent and place in a boiling flask for distillation. Collect the portion boiling from ~228-235°C, this is safrole. The main other fraction will pass at lower temps and consist mainly of pinene. Using reduced pressure is highly recommended since it is hard to maintain an oil bath at this high a temperature. The yield will also be decreased at higher temperatures due to destruction of the safrole. At 10-11 mmHg safrole bolls at 100-101°C. Isolate safrole from commercial oils by similar distillation of the oil. Safrole from Pyrocatechol

Pyrocatechol, catechol, forms a monoallyl ether with allylbromide that undergoes Claisen rearrangement to 3-and 4allylpyrocatechol (1,2-dihydroxy-3-allylbenzene and 1,2-dihydroxy-4-allylbenzene). This mixture can be fractionally distille to isolate the 4-allyl product and then methylenated to safrole. This method was first reported by Perkin and Trikojus[15] and later by Gerchuk and Ivanova[16]. The yield of allyl catechols from the monoallyl ether is 90% but only 44% of the product is 4 allyl catechol. The yield of safrole after methylenation is only about 20% from 4-allyl catechol as reported by Perkin. Bonthrone and Conforth[17] reported on an improved method of methylenation giving yields from 69-94% for various alkyl catechols. 4-allyl catechol via the monoallyl ether of catechol 132g of catechol and 144g of pure allyl bromide are dissolved in 220ml of pure dry acetone, finely powdered anhydrous potassium carbonate (170g) is gradually added with shaking of the mixture to prevent caking. The mixture is refluxed 6-8 hrs on a water bath with the condenser fitted with a calcium chloride tube to absorb moisture from the air.

The acetone is distilled off. Add ~50ml water and dilute sulfuric acid until acidic (blue litmus paper turns red).

This is then extracted with an equal portion ether. The ether is separated and washed with dilute sodium hydroxid solution to remove unreacted catechol and the monoallyl ether from the ether (the diallyl ether remains in the ether). The aqueous layer is acidified with dilute sulfuric acid and the oil which precipitates is removed from the water by dissolving in chloroform and separating the layers in a separatory funnel. The chloroform is removed by distillation and the oil distilled under reduced pressure. This sequence of purification takes advantage of the fact that hydroxy groups on benzene rings are reasonably acidic, but the diallyl compound has both of it's hydroxy groups converted to allyl ethers.

92 g of the monoallyl ether are heated in a reflux apparatus with an oil bath to 170-180°C. The contents of the flask will rise in temperature suddenly to 265°C and the color will change to red. Fractionally distill the contents under reduced pressure (15-16mm Hg) at one or two drops per second. Collect the first portion from 142-152°C (66g) and the second from 152-160°C (17g) a residue of about 9g will be left. Clean the flask and refractionate the first portion collecting at the same temperatures as before. Continue this process until a good separation is achieved. Do the same for the second fraction as well. Pure 4-allyl catechol boils at 156-158°C at 16 mmHg and has a melting point of 48°C. 4-allyl catechol from eugenol A better method by far for producing 4-allyl catechol is to remove a methyl group from eugenol. Eugenol like the main precursors is found in essential oils. Clove oil is mostly eugenol (95%). Allspice oil from the pimenta berry and cinnamon leaf oil also contain a high percentage of eugenol. Many other oils contain reasonable quantities of eugenol.

Imoto and Ono, Journal of the Chemical Society of Japan, vol 55, pg 275-9 (1934) (Chemical Abstracts 4048' vo 28) report on cleaving methylene ethers of several compounds by refluxing the compound with AlCl3 in chlorobenzene as solvent. This method should be perfectly applicable to cleaving eugenol's methyl ether (experiment is king). Yields were as high 96% (for piperonylic acid) with chlorobenzene as solvent. 1,2dicloroethane as solvent gave yields of 90% for demethylenation of piperonylic acid, chloroform 70%, and nitrobenzene 3%. Generally the chemist would reflux (with stirring) 164g dried eugenol (1 mole) in 1000g of chlorobenzene and add in several portions AlCl3 (totaling 500g) over 2.5 hours in a reflux apparatus fitted with a calcium chloride tube. After refluxing add dilute hydrochloric acid (15-20%) to the warm solution with stirring until the mixture is definitely acidic to congo red indicator. Extract the aqueous layer with several portions of ether. Extract the ether with portions of dilute 5% sodium hydroxide solution. Acidify the aqueous solution and extract with ether. Separate the layers and distill off the ether and collect the product. The original article will have to be consulted for their exact method and purification scheme. See under piperonal for other demethylation procedures that can be applied. Methylenation of 4 allyl catechol Bonthrone and Cornforth strictly exclude moisture and air in their methylenation procedure as well as employing a polar aprotic solvent. They do this under an inert atmosphere of nitrogen and introduce the reactants through a special apparatus of their own design. Similar yields should be obtained without their special introduction of reactants.

A mixture of 100ml methylene chloride and 500ml dimethylsulphoxide is stirred and heated to 125-130°C in a reflux setup on an oil bath. The top of the reflux condenser is fitted with a one hole stopper with a short glass tub in the hole. To the glass tube is connected rubber or vinyl tubing which is connected to a T. One end of the T is connected to cylinder of nitrogen with tubing and the other to a glass tube in a two holed stopper. The stopper is

placed in a test tube containing oil (1/4 to 1/3 full). The other hole of the stopper is left open. This setup feeds a stream of nitrogen into the apparatus while allowing a pressure release through the test tube. If the nitrogen purchased is not dry it will need to be run through a flask containing calcium chloride. Lift the condenser up out of the flask to allow nitrogen to flush through the condenser. Allow the nitrogen to blow into the flask at the sam time so it is flushed out too. Any leak in the apparatus will only allow nitrogen to escape as opposed to air and moisture entering. Add 7.55g 4-allyl-catechol and 4.15g sodium hydroxide simultaneously through the top of the condenser with a powder funnel. Repeat this addition every 5 min. (19 times) for a total of 151g (1 mole) 4-allyl catechol and 83g sodium hydroxide. After an additional 20 min. add 20ml methylene chloride and 3g sodium hydroxide. Continue stirring for 70 min.

Alternate to adding the reagents in portions, the entire amount can be added at once with about a 10-15% decreas in yield. 4-allyl catechol is added in small amounts above to keep a low concentration of the dianion so that side reactions are minimized. Still add the additional methylene chloride and sodium hydroxide at the 1.5 hr mark. Steam distill the final solution in the same manner as safrole is steam distilled from root bark (using glassware setup). Separate the oil from the distillate water, dry with calcium chloride or sodium sulfate, and redistill under reduced pressure. Safrole from benzodioxole Feugaes[18] reports an 87% yield of safrole (abbreviated R-CH2=CHCH2) from benzodioxole (3,4methylenedioxybenzene, designated R) by the Grignard reaction of RMgBr with allyl bromide (CH2=CHCH2Br). The reagents in Grignard reactions must be absolutely dry and the glassware flame dried prior to use. The author here uses tetrahydrofuran as solvent which even when purchased dry usually has to be dried by distilling with sodium metal under an atmosphere of dry nitrogen.

L. Bert[19] gives a synthesis of safrole by the Friedel-Crafts reaction of benzodioxole and 3-chloro-allylchloride (CH2ClCH=CHCl2) then reducing the chloride compound formed to safrole with sodium. This journal is not in English so I can not give you the details. Benzodioxole can be synthesize from catechol by methylenating it by th same procedure as safrole and substituting 4-allyl-catechol with 110g of catechol. Similar to the above method, allyl chloride and benzodioxole can be reacted in the presence of copper to form safrole in 30% yield[20]. Catechol Catechol like it's isomer hydroquinone has been used in black and white photography as a fine grain reducing agent. Hydroquinone is more common in this role, but ready mix solutions have replaced almost all intelligence in photographic development today. Catechol has a long history in the chemical literature such as it's isolation from waste liquor in the manufacture of wood pulp and other ligninous materials. All woods contain phenols such as catechol in there complex lignin structures and these are freed when the wood is processed. Much work has been done in isolating these materials economically. The other most common citations for catechol is it's preparation from phenol by hydroxylation with hydrogen peroxide yielding a mixture of catechol and hydroquinone. Many catalysts have been recommended for this process. o-Chlorophenol has also been hydroxylated to catechol. Organic Syntheses Collective Vol 1. (pg 149-153) gives two procedures for catechol's preparation. The first is from hydrogen peroxide and salicyaldehyde and the other from guaiacol and HBr. Halogen Derivatives of Safrole

The use of halogen derivatives of safrole to arrive at MDMA is probably the simplest method of all even though it is the least commonly used in the chemical literature. There are two general ways the halogen derivatives are formed: 1) The hydrogen halide gas is passed directly into the safrole or safrole in solvent 2) Concentrated halogen acid added to the safrole. Both can be used simultaneously. (Hydrogen halide gas into a mixture of safrole and halogen acid.) The two concerns here in terms of side products are polymerization and demethylenation.

Bromosafrole This is the intermediate used in the first synthesis of MDMA by Merck[21] and later repeated by Biniecki and Krajewski[22]. The authors used 70% Hydrobromic acid which is not the commonly available strength (48%) since at normal temperatures it's solubility in water is 48%. The reaction was run at 0°C where side products are minimized and th solubility of HBr is greater. Running HBr gas into the 48% strength can raise the concentration at this temperature. Sakakibara[23] added safrole to hydrobromic acid with a density of 1.8 (47% is d 1.49) at 0°C. Mueller[24] bubbled HBr ga through safrole and 42% HBr at 0°C.

(from Biniecki) 5.3g of safrole are cooled and added dropwise to 21g of HBr at 0°C. The mixture is left at 0°C fo 14 hours. (Keep in an ice salt bath on a magnetic stirrer) The mixture is poured on crushed ice and extracted with two 30ml portions of ether. The ether is dried with anhydrous potassium carbonate, distilled off, and the residue distilled in vacuum, bp 154-158°C/13-14mmHg (reported yield 97%). with HBr and acetic acid[25]

This procedure was preformed with allylbenzene and should work equally well for safrole. 200g of glacial acetic acid containing 150g of HBr gas is placed in a 500 ml flask and chilled in an ice bath (Uncle Fester modifies this to 200 ml of acetic acid (chill) and then add 300g (200ml) of chilled 48% HBr slowly keeping the temperature down). 100g of safrole is added slowly to keep the temperature down. Stopper the flask. Leave in the ice bath an allow it to come to room temperature as the ice melts with occasional shaking. In 10-12 hours the two layers merge into one clear red solution. In 24 hours, the reaction is complete and the solution is poured onto 500g of crushed ice in a 1000ml container. The smaller red layer is seperated in a separatory funnel and the water layer extracted with a small portion of ether (100ml) or methylene chloride. The extract is combined with the red bromosafrole layer and washed with several portions of water and calcium bicarbonate solution to remove acid present. Remove the ether or methylene chloride by distillation and use the bromosafrole as is.

lodosafrole Use of 57% hydriodic (see misc. chemicals chapter) in the above procedure would yield iodosafrole with a similar yield an faster reaction time. The boiling point would be higher than that of bromosafrole.

Chlorosafrole Use of chlorosafrole would be the most attractive derivative in terms of availability since HCl is easily generated from salt and sulfuric acid. The downside to this is an extended reaction time from that of the more reactive HBr. The yield would almost surely be lower. With the extended reaction time polymerization would play a greater role, but could be overcom

by dissolving the safrole in benzene or ligroin (VM&P naptha paint thinner). These solvents were shown to eliminate polymerization in the reaction of HCl with isosafrole. (Chemical Abstracts 3774c (1947) (isosafrole gives the halogen in the wrong position) Chlorosafrole's boiling point would lie between that of safrole and bromosafrole. Piperonal

[120-57-01] 1,3-benzodioxole-5-carboxaldehyde; Piperonal; Heliotrope; 3,4-methylenedioxybenzaldehyde

Piperonal otherwise known in the perfumery world as heliotrope is derived naturally from the flower hyacynth. I is also available through perfume suppliers and herb type stores as hyacynth or heliotrope (sometimes dissolved i alcohol). The chemist might procure a sample of piperonal and then scout out all the cheap perfumes that they ca find for a match. That is about the end of the reasonable procurement of this compound, but much work has been done on it's synthesis over the years. Piperonal from isosafrole The most common citation for piperonal's synthesis is by oxidation of isosafrole with O3 (ozone). One of the more interesting papers[26] reports a yield of 96% of piperonal from isosafrole. See Handbook of Preparative Inorganic Chemistry for how to construct an ozone generator.

Another oxidation reports yields from isosafrole of 47% by potassium dichromate (K2Cr2O7) and H2SO4 oxidation[27]. In the same paper, potassium permanganate was also utilized with a yield of 8% (Most the isosafrole being oxidized to piperonylic acid).

Solvent extracts of black pepper contain compounds that can be treated with the above methods to yield piperona Refer to Guenther, The Essential Oils Vol, 5. pg. 144-147 for details on the extraction and contents. The three main components are shown below. Each would split at each double bond and form an aldehyde group at those carbons.

Piperonal from catechol

Via piperonyl chloride Shorygin et.al., Journal of the Chemical Society of the USSR, vol. 8, 975-80 (1938); Chemical Abstracts 3777 (1939) report synthesis of piperonal from pyrocatechol in the following steps: catechol → benzodioxole → piperonyl chloride → piperonal. The reported yield for methylenating catechol is low so the method previously reported in this book could be used. The interesting thing is his use of chloromethylation (see Organic Reactions, Chloromethylation of Aromatic Compounds) and then reacting this with hexamine (hexamethylenetetramine, uropine) to give piperonal. The piperonyl chloride could also be reacted with copper nitrate or copper chloride, CuCl2 to give piperonal as in the method reported b Professor Buzz in Recreational Drugs for benzaldehyde (pg. 116) (real easy).

Photo-Reimer-Tiemann[28] Since dihydroxybenzenes are sensitive to air, especially in alkaline solution, the Reimer-Tiemann reaction is not generally applicable to catechol; however, the photo reaction is and gives yields of approximately 29% for the desired isomer. Using the normal Reimer-Tiemann reaction Graebe and Mantz[29] report a yield of 11% for the desired isomer.

The precise route to piperonal is catechol → protocatechualdehyde → piperonal. A carbonyl (aldehyde) group is added to catechol with the photo-Reimer-Tiemann reaction and then it is methylenated with the same procedure a 4-allyl catechol. Protocatechualdehyde is also know as 3,4 dihydroxy benzaldehyde, 3,4 dihydroxybenzenecarboxaldehyde and protocatechuic aldehyde.

The authors dissolved the reagents in an incredible excess of solvent and separated the products with preparative TLC. The following is a suggested modification allowing a reasonable purity. Dissolve 33 g of catechol in 100m of 90% aqueous methanol and 20 g of chloroform in an erlenmeyer flask.. While stirring, irradiate with three 70 watt mercury vapor lamps (those sold for flood lighting) placed symmetrically around the the flask for 5-10 hrs. Remove the solvent in vacuum and then add 40ml of nearly boiling water and stir momentarily. Let the layers separate while keeping the whole hot on a hot plate. Decant the water from any organic material not dissolved while still very hot and then cool the aqueous layer with an ice bath. Filter the crystals that form. Wash the crystals with very small amounts of ice cold water.

Methylenate the protocatechualdehyde with the procedure in the safrole section replacing the 4-allyl catechol wit 138 g of protocatechualdehyde.

Gattermann Synthesis of Aldehydes In the normal Gattermann synthesis, hydrogen cyanide is introduced to an etheral solution of the phenol and anhydrous aluminum chloride. In a modification to this this procedure, hydrogen cyanide and zinc chloride are generated in the reaction mixture. Zinc chloride has been demonstrated to be a good condensing agent in these reactions in place of aluminum chloride. Water must be carefully omitted in the Gattermann reaction by using anhydrous reagents and solvents. Although no specific example for catechol is cited, much experimentation has been done on dihydric phenols an their ethers with the Gattermann reaction showing that the aldehyde group enters para to the hydroxy group when available and in good yields (normally 80-100%) for these phenols. Consult Organic reactions under the heading Gattermann Synthesis of Aldehydes for details on the reaction. For substitution of hydrogen cyanide gas with zinc cyanide see: Adams and Montgomery, Journal of the American Chemical Society, vol 46, pg 1518, 1924. and Adams and Levine, I vol. 45, 2373, 1923.

The Gattermann synthesis can be used to introduce the aldehyde group to catechol and then methylenate it to piperonal (as in the procedure in the safrole section replacing the 4-allyl catechol with 138 g of protocatechualdehyde.) or methylenate catechol to benzodioxole and then add the aldehyde group.

Hydrogen cyanide is extremely dangerous and if the chemist values his life he will heed all precautions. 1) Place the entire apparatus in a fume hood. 2) Check all connections for leaks. 3) Wear rubber gloves. 4) Consult texts on handling dangerous substances and first aid for cyanide poisoning. 5) Wearing a gas mask with filters for hydrogen cyanide is also highly recommended.

Anhydrous hydrogen cyanide can be purchased in cylinders; although it is not sold to just anyone. The acid can also be prepared by reaction of sodium cyanide with sulfuric acid (Ziegler, Organic Syntheses, Collective Vol. 1, 2nd ed., pg 314, John Whiley and Sons, 1941.). It is also prepared from potassium ferrocyanide in the following procedure.

400 g of potassium ferrocyanide are heated in a 2L flask with a mixture of 320g of concentrated sulfuric acid and 560ml of water (dilute the acid by adding it to the water, cool, then add to the potassium ferrocyanide). Place a condenser in the flask with a one hole stopper fitted with a glass tube on the other end. To the tube, fit tubing and lead through consecutive flasks containing calcium chloride and then an empty flask to dry the gas. (The flasks will need to be kept warm (35-40°C, heating pad) since hydrogen cyanide condenses at 26 C. Mix the calcium chloride with some glass wool to allow the gas to more freely pass through.)

Piperonal from Benzodioxole Feugeas (see safrole from benzodioxole) also gives a synthesis for piperonal (RCHO) in 65% yield from RMgBr and HCONHMe (methyl formamide).

Piperonal From Vanillin Vanillin can be used to synthesize piperonal. The route is vanillin → protocatechualdehyde → piperonal. Vanillin's methyl ether is cleaved and then the protocatechualdehyde is methylenated to piperonal. Vanillin is the flavor of vanilla. The extracts from the store are quite watered down and normally expensive. Sometimes one can find large bottles of extract cheap. Large flavoring companies would probably be glad to sell you a heap of the pure stuff.

Vanillin's methyl ether is difficult to cleave under the conditions normally employed for demethylation according to Robert Lange[30]. Lange cites references to this fact referring to their low yields (less than 50%) when using such reagents as dilute HCl, HBr, phosphorus pentachloride, aluminum chloride in benzene. N mention of the use of aluminum chloride in chlorobenzene was given as is cited for possible use with demethylation of eugenol. That method may be worthy and should be tested. Reference was given to the first hig yielding method by using aluminum bromide in nitrobenzene to yield 93% of protocatechualdehyde from vanillin Lange goes on to present his demethylation procedure of vanillin with aluminum chloride, and pyridine in methylene chloride as solvent. Pyridine is a very hot chemical and is best avoided so I refer you to the original reference for the details. The procedure given there is easy enough to follow. Pearl and Beyer[31] report on the method of aluminum bromide in nitrobenzene for demethylation of vanilla as follows:

In a fume hood. A solution of 15.2 g (0.1 mole) of vanilla in 45 ml of nitrobenzene at 15°C is treated with a solution of 53.4 g of anhydrous aluminum bromide in 60ml of nitrobenzene. 125 ml of nitrobenzene are added to the gel which forms with stirring. (do not breath nitrobenzene vapors or let contact with skin. If contact occurs flush area with water for 15 min.) Heat solution to 95°C and then let cool to room temperature. Allow to stand at room temperature for 30 minutes. The dark mixture is cooled and added to IL of water containing a little HCl. Th mixture is extracted with ether and the ether is then extracted with 5% sodium hydroxide solution. The hydroxide solution is washed with ether and then acidified with dilute sulfuric acid. The acidic solution is extracted with ether, dried, and then distilled off to leave 12.8 g of protocatechualdehyde. Methylenate this with the procedure listed in the safrole section replacing the 4-allyl catechol with 138 g of protocatechualdehyde. Hayashi and Namura[32] discuss demethylation during the pulping process and conducted experiments on individual components under such conditions. Eugenol and vanillin were both demethylated by cooking with either 5% NaOH or 5% Na2SO4, 1% NaHCO3 and H2O. The degree of demethylation is not given in the abstract but it is in the paper which luckily is in English if one cares to look it up. The reaction does proceed slowly. Isosafrole

[120-58-1] 1,3-benzodioxole, 5-(1-propenyl); Isosafrole

Isosafrole is not found in any large amount in essential oils; although it is present in quite a few. That makes its

preparation a must since obtaining it from chemical suppliers is extremely risky or impossible. Thankfully it is a pretty straight forward procedure to isomerize safrole to isosafrole.

Waterman and Preister[33] report on isomerizing safrole to isosafrole by refluxing 1 kg of safrole, 2.5kg 96% alcohol (presumably ethanol), and 450g potassium hydroxide for 25 hrs to obtain 55% isosafrole and 45% unchanged safrole. The authors removed safrole by dissolving it with aqueous mercury acetate solution (Hg(OAc)2). Alternate to this is to remove the alcohol with reduced pressure (to speed the distillation up), filter out the KOH and fractionally distill the mixture under reduced pressure. Safrole boils lower so when you get two fractions with distinct boiling points the higher is isosafrole. Using anhydrous ethanol will more than likely increase the yield of isosafrole. Similar to this but using 2.2 times as much potassium hydroxide, a higher concentration alcohol, and autoclaving for 2 hrs. 90% conversion has been achieved Chemical Abstracts, Brazilian oil of sassafras, vol 45, 3618i. Two Japanese patents, Japan 5331 (1951) and Japan 5987 (1951), report on heating safrole with calcium oxide and potassium hydroxide to obtain safrole in 90 and 95% yields. Add 15g calcium oxide and 1g potassium hydroxide to 100g safrole in a flask and place in a reflux apparatus. Heat with a flame to reflux for 15 min. Filter out the CaO and KOH and distill under reduced pressure. Calcium oxide is common known as lime, but do not confuse this with limestone, CaCO3, commonly sold as lime at garden shops. Riezebos, et. al., Rec. Trav. Chim. Pays-Bas, vol 86, pg 31-32 (1967) (in English), report on isomerizing 500g safrole with 2.5g Fe(CO)5(iron pentacarbonyl) and 1.6g KOH to obtain 97% isosafrole.

Nagai, Journal of the Society of the Chemical Industry of Japan, vol. 29, 364-70 (1924); Chemical Abstracts vol. 21 pg 72, reports an 85-90% yield of isosafrole by heating 100g safrole, 5g KOH (potassium hydroxide), and 150g anhydrous ethanol. This is then heated under 6-8 atmospheres of pressure for 5-6 hours.

Hirao, Journal of the Society of the Chemical Industry of Japan, vol. 29, pg 241-7 (1926), Chemical Abstracts pg 379 (1927), reports on using minimal amounts of alcoholic potassium hydroxide to convert safrole to isosafrole. The presence of even very small quantities of water greatly hinders the reaction in this procedure. This has been unsuccessfully repeated by other investigators. Isosafrole from Benzodioxole Feugeas (see safrole from benzodioxole) also gives a synthesis for isosafrole (RCH=CHMe) from RMgBr by first reacting with propanaldehyde (EtCHO) with an 81% yield and then with para-tolulenesulfonic acid to give isosafrole in 79% yield. The reported boiling point at 17 mmHg is 131°C. Piperonylacetone 2-propanone, 1-(1,3-benzodioxol-5-yl); 2-propanone, 1-(3,4-methylenedioxybenzene); 3,4methylenedioxyphenylacetone; methyl piperonyl ketone; MDP2P Boiling point 2 mmHg/108-12°C, 11 mmHg/154-6°C, 22mmHg/166-7°C (also reported 168°C @ 17 mmHg); Molecular weight 179 g/mole

Piperonylacetone, a listed precursor, is used in some of the higher yielding and more common methods for MDMA and it's structurally similar compounds. Several methods are given in the chemical literature for preparation of piperonylacetone with varying yields and staring materials. Phenylacetone which is structurally closely related to piperonylacetone is prepared by these same methods and many others which could be applied t piperonylacetone's synthesis.

Piperonylacetone from Isosafrole Isosafrole can be oxidized by peracids to it's diol derivative (or more specifically it's hydroxy formate in the case of performic acid--not depicted) and subsequently heated with sulfuric acid to form piperonylacetone in moderate yields.

For in depth coverage of this reaction, see Organic Reactions, Epoxidation and Hydroxylation of Ethylenic Bond with Organic Peracids. This reference also contains instructions for generating perbenzoic acid from benzaldehyd and air by photochemical means (real easy) (benzaldehyde is the major component of bitter almond oil). See Milas, Kurz, and Anzlow, The Photochemical Addition of Hydrogen Peroxide to Double Bonds. Journal of the American Chemical Society, vol. 59, pg 543, (1937) for another good reference. Performic Acid Oxidation Fugisawa and Deguchi[34] report on oxidizing isosafrole with performic acid by generating the performic acid in the reaction mixture.

A solution 34g 30% H2O2 (hydrogen peroxide) and 150g of 80% HCO2H (formic acid) is stirred. To this is added dropwise 32.4g of isosafrole in 120ml of acetone. Add slowly enough to keep the temperature from rising above 40°C (about I hr). Continue stirring for 16 hrs while keeping the temperature below 40°C. Remove the solvent an formic acid with distillation under reduced pressure. A deep red residue will be left amounting to about 60g. Dissolve this residue in 60ml of methanol and 360g of 15% sulfuric acid. Heat on a water bath (boiling) for 3hrs in a reflux apparatus. Cool the solution and extract with 3x75ml portions of ether. Combine the ether extracts and wash first with water and then 5% sodium hydroxide. Remove the solvent in vacuum and distill the residue to yield approximately 20.6 g piperonylacetone (58% yield).

Kojima, et. al., Japan. Kokia 74 100,044; Chemical Abstracts vol. 82, 72640z (1974), report a similar method as above, but they used somewhat higher concentrations of reactants (not as commonly available) and dichloroethan as solvent. The reported yield is 73%.

Peracetic Acid Oxidation Hoffsommer[35] report on converting isosafrole to piperonylacetone by using peracetic acid in ethylacetate. The authors used prepared peracetic acid as opposed to generating it in situ. It can be generated, though, with acetic acid and hydrogen peroxide by using a slight excess of hydrogen peroxide over isosafrole and excess acetic acid as solvent. A secon oxidation using pertrifluoroacetic acid is also given. No yield is given. Permanganate Oxidation Potassium permanganate as a cold 2% solution in water (4258ml water + 86.9g KMnO4 (0.55moles)) will oxidize double bonds to a diol with the precipitation of manganese dioxide. This is commonly used as test for double bonds. Warm, slightly acidic, or concentrated solutions will cause further oxidation resulting in cleavage of the double bond. Add the above purple solution to 89.5g (0.5 moles) of isosafrole with stirring in an ice bath. As the reaction proceeds, manganese dioxide will precipitate as a brown-black solid and the purple permanganate color of the aqueous layer will gradually disappeared. When the color no longer lightens, stop stirring and pour off the excess aqueous layer. Filter the remaining aqueous and organic layers to remove the manganese dioxide and wash the precipitate with water. Extract the filtrate with ether (or toluene, benzene, etc). Remove the solvent in vacuum and treat the residue as in the performic oxidation above. (where it is dissolved in methanol and sulfuric acid). Alternative to beginning with a dilute solution of permanganate, a more concentrated solution could be added to the compound and a small amount of dilute solution. In

this way, the permanganate is consumed as it is added so it remains diluted in the reaction flask.

Piperonylacetone from Beta-nitroisosafrole The nitrostyrene formed from the condensation of piperonal with nitroethane can be converted to the ketone, piperonyl acetone, by reaction with elemental iron in acetic acid[36].

A stirred suspension of 32g iron fillings in 140 glacial acetic acid is gradually warmed on a steam bath. When quite hot but no white salts apparent, add dropwise a solution of beta-nitroisosafrole in 75ml acetic acid. (see MDA for the nitrostyrene, beta-nitroisosafrole, synthesis) Add the solution quickly enough to allow the reaction proceed vigorously without excessive frothing. The orange color of the reaction mixture will turn reddish with white salts and a dark crust. The product will appear as a black oil on the sides of the flask. The mixture is added to 2L of water (use some of the water to wash the product free from the flask). This is then extracted with three 100ml portions of CH2Cl2 (methylene chloride). The extracts are combined and washed with several portions of 5% NaOH (sodium hydroxide). After removal of the methylene chloride under reduced pressure the residue is distilled under reduced pressure to yield approximately 8g of piperonylacetone. Piperonylacetone from the Dichloro Derivative of Isosafrole Yuki[37] reports on piperonylacetone from 1-(3,4-methylenedioxyphenyl)dichloropropane and KOH.

Chlorine and the other halogens react readily with double bonds (like the one of isosafrole's) to form dichloro compounds in solvents inert to the halogens. The most commonly used solvents are CH2Cl2 (methylene chloride) CHCl3 (chloroform), and CCl4 (carbon tetrachloride). Running a stream of chlorine in a solution of isosafrole in one of these solvents from a cylinder or chlorine generator (see misc. chemicals chapter) will produce the appropriate dichloro compound. Use of bromine will generate the dibromo compound which could be used in place of the dichloro compound. Bromine reacts quickly in carbon tetrachloride. It is bromine in carbon tetrachloride that is used as a test for double bonds since the solution is clear red and the red color disappears as the bromine reacts. Chlorine will react slower. If water is present, a chlorohydrin will be formed which would probably react similarly to give the ketone. Experiment is king.

23.2 g (0.1 mole) of 1-(3,4-methylenedioxyphenyl)-1,2-dichloropropane is refluxed for 10hrs with 75g of 15% KOH (potassium hydroxide) solution. The mixture is cooled extracted with benzene. The benzene is removed in vacuum and the residue distilled to yield approximately 15.2 g of piperonylacetone (bp 149-151°C/10 mmHg). 85% yield from the dichloro compound.

Piperonylacetone from Glycidic Esters Elks and Hey[38] report on preparation of the appropriate glycidic ester and it's hydroxylation and decarboxylation to piperonylacetone in 21% overall yield. Hinkley and Budavari[39] report on a similar method of preparing piperonylaceton through the glycidic ester.

The method involves condensation of piperonal with ethyl alpha-bromopropionate (sodium methoxide as catalys to give the glycidic ester. Hydroxylation with sodium hydroxide, purification, and distillation in the presence copper powder.

Other Methods Hashimoto, et.al., Heterocycles, vol. 15, 975-9 (1981); Chemical Abstracts vol. 95, 41756f (1981), report piperonylacetone as a side product in the reaction of piperonal and Me3SiCHN2 in the presence of Et3N.

Meguro, Japan. Kokai 77 77,063; Chemical Abstracts vol 87, 184480g (1977), report an 85% yield of piperonylacetone from D-5-methyl-5-(3,4-methylenedioxybenzyl)hydantoin.

Phenylacetone Methods With appropriate substitution many phenylacetone methods can be used to synthesize piperonylacetone. Yields will vary Phenylacetone itself when used with the MDA methods yields amphetamine and with MDMA methods yields methamphetamine (equal mole substitution of piperonylacetone for phenylacetone).

Hydramine splitting Refluxing ephedrine with phosphoric acid yields phenylacetone. There is no available equivalent to ephedrine that would yield piperonylacetone. No time of reaction or yield is given. Auterhoff and Roth[40].

Methods with phenylacetic acid Phenyl acetic acid (listed precursor) could probably be most easily be obtained by oxidizing phenethyl alcohol (phenylethy alcohol) which is the major constituent of concrete and absolute rose oil (oil obtained by extraction with solvents). Phenethyl alcohol is a minor constituent of oils obtained by steam distillation of the oil from the flowers. Uncle Fester in Secrets of Methamphetamine Manufacture covers several phenylacetone methods in detail. Following is a survey of methods employed for phenylacetone preparation to demonstrate their diversity.

Phenylacetic acid and diazomethane. (68% yield) Bacchetti, Chimica e industia (Milan), vol. 35, 619-21 (1953); Chemical Abstracts 162d (1955) Phenylacetic acid, acetic acid, and catalyst. (55-65% yield) Organic Syntheses Vol. 16, 47-50 (1936); Chemical Abstracts vol. 30, 3807.

Phenylacetic acid and acetic anhydride. (87% yield) Magidson and Garkusha, Journal of General Chemistry of th USSR (in English), vol. 11, 339-43 (1941); Chemical Abstracts vol. 35,58685, Phenylacetic acid, acetic acid, and catalyst. (70% yield) Zettlemoyer, et. al., U.S. 2,612,524 (1952); Chemical Abstracts 7534g (1953).

Phenylacetic acid, acetic acid, and catalyst. (74% yield) Martello and Ceccotti, Chimica e industia (Milan), vol 3 289-92 (1956); Chemical Abstracts 15454e (1956).

Sodium phenylacetate and Isopropylmagnesiumchloride and then react the product with ethyl acetate. (62% yield Ivanov, et. al., Rev. Chim. Acad. Rep. Populaire Roumanine, Vol. 7, 985-92 (1962); Chemical Abstracts 4254e (1964).

Phenylacetic acid, acetone, and catalyst. No yield given in abstract. Le Cryberg, et. al., Ger. Offen. 2,737,511 (1978); US application 716,142 Aug 1976; Chemical Abstracts vol. 88, 152248s (1978).

Method with Benzyl Chloride Benzyl chloride (PhCH2Cl) and sodium give benzyl sodium. This reacted with ethyl acetate gives phenylacetone. No yield is given in the abstract. Tsuruta, Bull. Inst. Chem. Research, Kyoto Univ., vol. 31, 190-200 (1953) (in English); Chemical Abstracts vol 49, 6183b. Method from Glycidates

The glycidate from benzaldehyde and ethyl alpha-chloropropionate. Dullaghan and Nord, Journal of Organic Chemistry, vol 17, 1183 (1952).

The glycidate and HCl. (15 to 30% yield) Dullaghan and Nord, Journal of the American Chemical Society, vol 7 1764 (1953).

Method using Diethyl Acylmalonates Phenylacetyl chloride (acid chloride of phenyl acetic acid --- phenyl acetic acid + thionyl chloride) and the magnesium ethoxy derivative of diethyl malonate (diethyl malonate + magnesium-- directions given). (71% yield) Walker and Hauser, Journal of the American Chemical Society, vol. 68, 1386-8 (1946); Chemical Abstracts vol. 40, 571271. Friedel-Crafts Method Benzene and chloroacetone with aluminum chloride catalyst. (yield 32%); Mason and Terry, Journal of the American Chemical Society, vol. 62, 1622 (1940); Chemical Abstracts vol. 34, 624821. Grignard Method Benzyl chloride + magnesium to yield the grignard reagent. The grignard reagent + acetic anhydride to yield phenylacetone. (52% yield) Newman and Booth, Journal of the American Chemical Society, vol. 67, 154 (1945); Chemical Abstracts vol 39, 11318,

Grignard reagent from bromobenzene (watched) with chloroacetone. (22% yield) Kuriaki, J. Pharm. Soc. Japan, vol. 64, 128-9 (1944); Chemical Abstracts 2898i (1951).

Etard Reaction Propylbenzene (1-phenylpropane) and chromyl chloride. (15% yield) Wiberg, Tetrahedron Letters, 345-8 (1962); Chemica Abstracts vol 57, 9724b. Cyanide Compound Hydrolysis Hydrolysis of PhCH(CN)Ac with H2SO4. (77-86% yield) Julian and Oliver, Organic Syntheses Vol. 18, 54-5 (1938).

Modified method of above. (85% yield) Zaputryaev, et. al., Med. Prom. SSSR, vol. 14 no. 1, 48-51 (1960); Chemical Abstracts 7154d (1962). From alpha-methyl styrene Alpha-methyl styrene (1-phenyl-1-propene; Benzene, 1-propenyl) and Bromine in 15% sulfuric acid. (51.5% yield). Inoi,

Japan 69 09,892 (1969); Chemical Abstracts vol 71, 61016x (1969).

Chapter 6 - Simple Aliphatic Amines

Some simple aliphatic amines are employed in the final synthesis steps of some of the syntheses covered in this book. Amines can be considered derivatives of ammonia (NH3) with one or more of the hydrogens replaced by a alkyl group (carbon chain). Aliphatic means that no aromatic stuctures are present such as a benzene ring and by simple is meant that the alkyl groups are relatively small. Here we will be concerned with primary amines (only one hydrogen replaced) and alkyl groups no longer than two carbons. In short, ethylamine and methylamine. Ethylamine and methylamine are listed compounds so they are illegal to possess. They are very closely watched, particularly methylamine due to its notorious use in methamphetamine manufacture (X too). Since I know of no common means of obtaining these chemicals only synthetic routes will be discussed.

Hexamethylenetetramine Method Hexamethylenetetramine, also known as urotropine, hexamine and methenamine, is used to form primary amines from alkyl halides in the Delepine reaction. Urotropine reacts at a much higher rate with alkyl iodides than with bromides or chlorides. In the reaction, a quaternary ammonium complex is formed first which is hydrolyzed under acidic conditions to the salt of the primary amine.

Galat and Eliot, Journal of the American Chemical Society, vol 61, 3585 (1939), give a procedure where alkyl chlorides or bromides are converted to the iodide in the reaction mixture by sodium iodide and the complex hydrolyzed without isolating it first. By their procedure, 72% methylamine was obtained with a reaction time of one week, 82% ethylamine in days, and 54% phenethylamine in three weeks. This is not bad considering the time spent is mainly just in waiting. Dissolve 140g (1 mole) of urotropine and 157.5 (1.05 moles) sodium iodide (or 174g/1.05moles potassium iodide) in 1.0 liters of hot 95% ethyl alcohol. 109 g of ethyl bromide is then added and the solution is allowed to stand until no more precipitation occurs (~8 days). A stream of HCl gas is then run into the mixture where the precipitate is hydrolyzed and dissolves, and ammonium chloride precipitates. The ammonium chloride is filtered off and the alcohol in the filtrate removed by distillation under reduced pressure. The authors purified the crude amine by distilling with excess sodium hydroxide (45g in ~135ml water). Use of an ice-salt bath or acetone-dry ice bath is necessary to condense the amines coming over (methylamine bp -6.3°C, ethylamine 16.6°C). The amines are then dissolved in ether (or toluene, methylene chloride etc) and reconverted to the HCl salts with a stream of HCl gas. Filter the crystals formed from the ether. For methyl iodide (142g) and ethyl iodide (156g) in place of ethyl bromide, omit the iodide salt above. When substituting ethyl chloride, use 65 g of ethyl chloride.

Formaldehyde and Ammonium Chloride Method This is probably the best method next to buying methylamine to be had. The method is also covered in exceptional detail in Organic Syntheses Collective Vol. 1, p 347-350. This book can be found in university libraries everywhere, so I will only cover the method in general.

37% technical formaldehyde and ammonium chloride are placed in a distillation apparatus and heated on a steam bath. The distillate that comes over is discarded. As the reaction mixture cools, crystals of crude methylamine hydrochloride ar formed and filtered. The filtrate liquid is then heated to reduce the volume of liquid and then cooled again to crystallize out more crude methylamine hydrochloride. This process is continued. The successive crystallizations produce progressively less pure methylamine hydrochloride. Purification through recrystallization and washing is discussed. Hofmann Rearrangement[41] Amides react with chlorine and bromine under basic conditions to yield an amine of one less carbon. Reacting acetamide with calcium hypochlorite, the source of chlorine, and subsequently with sodium hydroxide we get methylamine. The methylamine formed is bubbled through HCl in the two receiving flasks and are there converted to methylamine hydrochloride. Refer to the miscellaneous chemicals chapter for the synthesis of acetamide. Propanamide would undergo a similar reaction to yield ethylamine.

Set up the apparatus as shown and fill the two receiving flasks with 300ml muriatic acid each. A #4 rubber stopper will fit a 24/40 joint. Using a two-hole stopper, place a glass tube and a thermometer through the holes and into the solution. Greasing the glass with joint grease will help sliding them in.

In an erlenmeyer flask, place 164 g of HTH swimming pool chlorine or other similar source of calcium hypochlorite. 500 m of water are added and the flask stirred to dissolve as much as possible. The contents are then chilled in an ice bath. 100 of crushed ice are then added.

The reaction flask (2000ml) is disconnected from the apparatus and a chilled solution of 100g acetamide in 200 ml water added. The flask is placed in an ice bath and 100g of ice is added followed by one third of the HTH solution. The flask is shaken and chilled. The remaining HTH solution is added in two portions each time followed by shaking and cooling. If the temperature rises above 10°C, start over. It is OK to add more ice if necessary (One could clamp a separatory funnel in place and let it drip feed the solution while the reaction flask remains immersed in the ice bath and is stirred with a magnetic stirrer). Once the addition is complete, the flask is allowed to sit in the ice bath for 10 more minutes. The flask i then placed back in the distillation apparatus and a solution of 24g sodium hydroxide in 40 ml water at room temperature is added through the top of the still head. The top is immediately restoppered and air passed into the solution through th glass tube by an aquarium air pump.

The temperature is raised to 60°C and then more carefully up to 65°C where the heat is removed. Decomposition of the N chloroacetamide takes place between 65°C and 75°C. This decomposition should be controlled in order to prevent the contents from boiling over into the receiver. If the temperature rises to 80°C, cool the flask with an ice bath. When heat is no longer spontaneously generated in 5-10 min, the contents are heated to a boil until 400-500ml of distillate are collected. The contents of the two receiving flasks are then combined and poured into an evaporating dish which is heate

over a wire gauze until only about 150 ml remain. It is then heated over a water bath to dryness (or oven set on 200°F). The residue consists of methylamine hydrochloride along with ammonium chloride. Recrystallizing with absolute ethyl alcohol will remove most of the ammonium chloride. The authors also relate another purification method.

Ammonolysis Reacting ammonia with the corresponding alkyl halide would be an ideal way to produce methylamine and ethylamine if wasn't for the significant amounts of di- and tri-amines being produced from overreacting. These impurities would be troublesome to remove completely due to their close solubilities and boiling points to the desired compounds. Purificatio of the hydrochloride salts with some of the procedures as in the above methylamine article could lead to reasonable enough purities. The remaining impurities would just produce the corresponding analogue in the final reaction for MDMA or MDEA. These analogues are inactive and would only dilute the final product. Methylamine The higher the concentration of the products in this reaction the faster the rate. Alkyl iodides also react faster than alkyl bromides which react faster than alkyl chlorides.

To 142 grams (1 mole) of methyl iodide add 5 moles (85g) of ammonia in methanol. The amount of solution this is depend on the concentration of your solution (see mischellaneous chapter for its preparation). To find this amount divide 85 by the concentration of your ammonia solution. For example if your solution is 20% then divide 85 by 0.20, which is 425 g of ammonia solution. Place this in a flask, stopper, and let sit for a week. If the solution is very discolored, add some sodium thiosulfate to clear it up. Acidify the solution with a stream of HCl gas (see misc chapter). Filter the crystals that form. This contains a lot of ammonium chloride formed from the excess ammonia in the solutuion. Purify further with methods in th above cited article.

To replace methyl iodide use the following amounts of other alkyl halides: ethyl iodide (156g, 1 mole), ethyl bromide (109g, 1 mole), ethyl chloride (65g, 1 mole). When substituting slower reacting alkyl halides, the reaction times should be increased significantly (2-3 weeks). Industrial Methods As a side note for the curious, methylamine is produced industrially by reacting methanol directly with ammonia and a catalyst at elevated temperatures. This may not be very practical for any clandestine operation, but the following are articles describing the method:

Davis and Elderfield, The Catalytic Preparation of Methylamine, Journal of the American Chemical Society, vol 50, p 1786 1789 (1928) Turner and Howard, Methylamines from Methanol and Ammonium Chloride, Journal of the American Chemical Society, vol 42, p 2663-2665 (1920)

Chapter 7 - MDA MDA is slightly more simple to make than MDMA and still quite rewarding. It is a psychedelic in true spirit. It has been

described as a "stoning intoxication" with a full dose. The appearance of smoke rings as visual hallucinations has been ascribed to this drug. Anorexia and pupil dilation accompany MDA as with other psychedelics and overall it is a pleasant trip. As closely related to MDMA as it is, though; MDA lacks the wonderful empathogenic qualities that makes MDMA so special. We now turn our attention to the synthesis for ecstacy of which there are several choices. A simple modification in most these will yield Eve (100-200 mg/dose, 3-5 hour duration).

MDA

Dosage: 80160 mg Duration: 812 hours

Hexamethylenetetramine Method This method is analogous to the one used in the previous chapter. To produce MDA, we simply substitute bromosafrole o the like as the alkyl halide. This method hasn't been reported in the scientific literature that I know of for MDA. A long reaction time (1 month) is reccommended based on the yield reported for phenethylamine (54% after 3 weeks) in the article previously cited. This is not too bad considering all you are doing is setting the reaction flask to the side for a while

Dissolve 140g (1 mole) of hexamethylenetetramine (urotropine, hexamine) and 157.5g (1.05 moles) sodium iodide (or 174g (1.05 moles) potassium iodide) in 1000ml of hot 95% ethyl alcohol (190 proof grain alcohol). 243g of bromosafrole ( mole) is then added and the solution is allowed to stand until no precipitation occurs. A stream of HCl gas is then run into the mixture where the precipitate is hydrolyzed, dissolves and ammonium chloride precipitates. The ammonium chloride filtered off and the alcohol of the filtrate is removed through distillation under reduced pressure. Purify the crude amine left by releasing the free base with NaOH solution (45g NaOH in 135 ml water). Extract the oil with ether (or toluene, methylene chloride etc.) and reconvert to the HCl salt with a stream of HCl gas. Filter the crystals formed from the ether. To substitute iodosafrole use 290 grams (1 mole) or chlorosafrole 199g (1 mole). When substituting iodosafrole omit the sodium iodide (or potassium iodide). Reductive Amination

This general method utilizes piperonylacetone and ammonium chloride as the starting materials. These two compounds react in an equilibrium to form an imine. The imine is then reduced to MDA. Two methods of reducing the imine are given. Sodium Borohydride Reduction[42] In the following reaction, 10 times the theoretical amount of ammonium chloride is used to push the equilibrium of the reaction to the right in the formation of the intermediate imine compound. When the imine is formed it is reduced by the hydride to the amine, MDA. To a solution of 20 grams of ammonium chloride in 110 ml of methanol are added 6.6 grams of piperonylacetone (0.037 mole) and then 3 grams of sodium cyanoborohydride. The mixture is stirred at ambient temperature, and concentrated (12 M) HCl is added with a dropper or pipet as required to maintain pH at neutrality (pH 7 as determined by universal pH paper); 31.5% muriatic acid will suffice even though it is less concentrated.

The reaction is complete 36 hours folowing the addition of 1000ml water containing 5ml concentrated HCl (6ml of muriat acid). The reaction mixture is extracted twice with 150 ml of methylene chloride (discard these extractions). The reaction made basic with 25% sodium hydroxide (red litmus turns blue), and extracted with 3x150ml methylene chloride, the extracts are pooled together and the methylene chloride is distilled out. The oil that remains is distilled at reduced pressure (0.2 mmHg; bp 85-95°C) and the recovered oil is dissolved in 60 ml of isopropyl alcohol (100%) and acidified with concentrated HCl (blue litmus turns red). An equal volume of ether is added and the crystals should spontaneously form. They are filtered out, washed with a 50/50 isopropyl alcohol/ether solution and then ether alone.

The author of the article cited likes this final method of crystallization. This is not necessary. After distillation of the oil, dissolve the oil in ether (or toluene or methylene chloride) and pass HCl gas into the solution until no more crystals form. Filter out the crystals and let dry.

Aluminum Amalgam Reduction[43] 72.5g of aluminum foil is cut into one inch squares and placed into a 3000ml erlenmeyer flask or other suitable glass container. A solution of 1.8 grams of mercuric chloride (HgCl2) in 2530 ml water is added, and the mixture is stirred occasionally over 30 minutes to amalgamate the aluminum. The solution is poured off and the foil is washed with four on liter portions of water. To the amalgam is added, in sequence, 80g of ammonium chloride in 101ml of water, 302ml of isopropyl alcohol (100%), 244ml of 25% NaOH solution, 89g (0.5 moles) of piperonylacetone, and then 588ml of isopropyl alcohol. The mixture is swirled occasionally for two hours, and kept below 60°C by cooling with an ice bath as necessary.

The mixture is then filtered through Celite (a diatomaceous silicate powder which is placed in a layer over the filter paper

before filtering, it is sold by chemical companies as Celite), and the filter cake is washed thoroughly with methanol. Combine the liquid filtrates and distill off the methanol (65°C), isopropyl alcohol (82°C) and the water (100°C).

Dissolve the oil in 200ml of ether, and extract the MDA into two 500 ml portions of 3N HCl. The acid solution is washed with three portions of methylene chloride equal in volume to the acid solution (you will probably have to wash portions o the solution at a time unless you have a huge separatory funnel). The acid solution is basified with excess 25% sodium hydroxide solution (red litmus turns blue) and the liberated oil is extracted into three 500ml portions of methylene chloride.

The methylene chloride solution is dried with magnesium sulfate. The drying agent is filtered out and the methylene chloride distilled out. The residual oil is distilled under reduced pressure and the distilled oil then dissolved in ether (or toluene or methylene chloride). HCl gas is bubbled through the solution until no more precipitate is formed. The precipitate is filtered off and allowed to dry (~70% yield can be expected).

Nitrostyrene Method This method utilizes piperonal as the starting material and condenses it with nitroethane. The nitrostyrene compound the formed is reduced to MDA. Reduction with lithium aluminium hydride (LAH) and with an electrochemical cell are covered but it is possible that reduction with metals such as zinc powder and acetic acid, tin powder and hydrochloric acid, or iron powder and hydrochloric acid may work. The general method of using these reagents is covered in Robert L. Augustine, Reduction: Techniques and Application in Organic Synthesis under the chapter Dissolving Metal Reductions.

Nitrostyrene Preparation[44] To a solution of 15 grams of piperonal in 80 ml glacial acetic acid, add 15 ml nitroethane followed by 10g of cyclohexylamine. The mixture is heated with a boiling water bath for 6 hours. Remove from heat, dilute with 10ml water and cool in an ice bath overnight (place ice bath and reaction mixture in the refrigerator to keep the ice from melting too quick). Bright yellow crystals should precipitate. These are filtered from the cold solution and allowed to dry. Yield ~10g.

A general procedure described by Gairaud and Lappin[45] uses ammonium acetate as the base catalyst for the condensation. It is as follows: 5g of piperonal, 5ml of nitroethane ans 2g of ammonium acetate are added to 20 ml of glacial acetic acid. The resulting solution is refluxed for two hours and then poured into ice-water. The solution is cooled in an ice-bath overnight and the crystals filtered out and allowed to dry. LAH for Reduction A suspension of 20g LAH in 250 ml of anhydrous THF (tetrahydrofuran - this solvent eagerly sucks water out of the air so don't leave it exposed to the air for long) is placed under a nitrogen atmosphere and stirred with a magnetic stirrer (see

chapter 5 under safrole synthesis for a nitrogen atmosphere apparatus). There is added, dropwise, 18 grams of the nitrostyrene dissolved in THF and the reaction mixture is refluxed for 36 hours. After being brought back to room temperature, the excess hydride is destroyed with 15 ml isopropyl alcohol, followed by 15 ml of 15% NaOH. An additiona 50 ml of water is added to complete the conversion of the aluminum salts to a loose, white, easily filtered solid. This is removed by filtration and the filter cake washed with additional THF. The combined filtrate and washings are distilled to remove the solvents. The residue is dissolved in dilute sulfuric acid (15%) and washed with three 75ml portions of CH2Cl2 (methylene chloride). Make the aqueous solution basic with 25% NaOH and extract it with three 100ml portions of methylene chloride. Distill off the solvent and then distill over the residual oil inder reduced pressure. Dissolve the distille oil in ether (or toluene or methylene chloride) and run a stream of HCl gas through it until no more precipitation occurs. Filter the crystals and allow to dry.

Electrochemical Cell For Reduction Although I have seen many references to the use of electrochemical cells, the construction of them I have yet to see thoroughly described or for that matter where they can be purchased. This doesn't mean they are impractical, because fo clandestine chemistry where the most reliable reduction reagents are watched like a hawk, electrochemical reductions could be the next breakthrough. The cells are basically a container divided by some material which will allow charged ions to pass and therefore allow electricity to flow. The membrane also halts the flow (or reduces it considerably) of the material being reduced. This is necessary because if the membrane wasn't there, the reduced product could travel to the other electrode and become oxidized. The membranes are made of such materials as sintered glass, cellophane, porous ceramic plates etc.

This procedure was written for the analogous nitrostyrene which would lead to amphetamine. It should work equally wel for MDA[46]. 207g (1 mole) of the nitrostyrene is dissolved with a solvent prepared by mixing one liter of ethanol with 500ml of acetic acid and 500ml of 12N sulfuric acid. The solution is placed in the cathode compartment of a divided electrolytic cell containing a mercury, copper or metal of similar nature as the cathode electrode. The anode can be made of lead. 3N sulfuric acid is placed in the anode compartment. Current is passed equaling ~0.2 amperes/cm2 of cathode surface. The temperature is kept between 30-40°C during the electrolysis until at least 8 Faradays of electricity have passed through the solution.

The number of square centimeters of your cathode surface (count both sides if both sides are in contact with the solution times 0.2 is the amount of current you need flowing through your cell. 1 Faraday is equal to 96485.309 coulombs/mole of electrons and 1 Ampere is equal to 1 coulomb/second. The amount of time in hours the reaction should be run is then 771882.5 divided by the number of Amperes divided by 3600. If you have a total cathode electrode area of 40 cm2 then you need 8 Amperes running through your cell for 26.8 hours.

Remove the ethanol and ethyl acetate present through distillation (quit distilling when the temperature approaches 100°C). Basify the remaining solution with 25% NaOH and extract the MDA from the solution with 3 portions of ether (or toluene or methylene chloride). Wash the extract with several portions of calcium carbonate solution, water and then dry with magnesium sulfate. Filter out the drying agent. Pass HCl gas through the solution until no more precipitate is formed

Filter the crystals and wash with ether and allow to dry. Leuckart Reaction This is a beauty of a reaction to get around the need for difficult to obtain reducing agents. The piperonylacetone and ammonia reacts to form the intermediate imine and formic acid reduces it to the amine, MDA. With excess formic acid present, the amine, MDA, forms an amide which is hydrolyzed back to the amine with acid or alkali (acid usually gives better yields).

This method is tagen from an Austran patent[47]. 4 parts piperonylacetone (40g), 11 parts formamide (110g), 0.2 parts glacial acetic acid (2g) and 2 parts water (20 ml) are heated on an oil bath in a distillation apparatus with the thermomete reaching into the reaction mixture. The temperature is raised to 100°C and then more slowly after that. Watch for bubble of carbon dioxide forming to gauge the rate of the reaction. When they slow down to nearly stopping, raise the temperature a few degrees. Continue this until the temperature has been raised to 150°C. Water will distill over as the temperature rises. Let the reaction cool to about 100°C and add a vacuum adapter to the apparatus. Distill out the excess formamide under vacuum. Boiling points of formamide at various pressures are: 1°C@1mmHg, 109.5°C@10mmHg, 122.5°C@20mmHg and 147°C@60mmHg. The remaining meterial is refluxed 20 minutes with 6 parts KOH (potassium hydroxide, 60g) in 160ml ethanol and 50ml water. The excess ethanol is evaporated on a water bath and the residue diluted with water and filtered over activated charcoal. Basify with 25% NaOH and extract the oil with ether. Run a stream of HCl gas ino the ether until no more precipitate forms. The author claims 70% yield.

A general procedure for the Leuckart reaction is given by Crossley and Moore[48] using formic acid, ammonia solution an the ketone. It is as follows:

To a three-necked flask equipped with a dropping funnel, thermometer (into the reaction mixture), and down directed condenser (simple distillation apparatus) is added with 105g (1.72 moles) of 28% ammonia solution and 88g (1.72 moles) of 90% formic acid. The temperature is raised to 160°C by distilling out water, and 59.4 grams (0.334 moles) of piperonylacetone is added at one time. The following apparatus can be substituted for a three-neck flask and the piperonylacetone added by momentarily replacing the thermometer with a funnel. The mixture is maintained at 160-170 for 7 hours and any ketone which distills over is periodically returned to the flask. The formyl derivative is hydrolyzed in the reaction mixture by refluxing for eight hours with 120 ml of concentrated HCl (145ml 31.5% muriatic acid). The mixtur is diluted with 200 ml of water and extracted with benzene (or ether etc.) to remove water insoluble material. The aqueous solution is treated with a little charcoal, Norit (or filtered through activated charcoal from pet stores). The solution is made alkaline with ammonia (or alternatively 25% NaOH) and the oil thus produced is extracted with benzene (or ether etc.). The benzene is washed three times with water and dried with sodium sulfate or other drying agent. A stream of HCl gas is fed through the solution until no more precipitate is formed. The precipitate is filtered out and allowe to dry. Elks and Hey[49] describes a similar procedure as above, but using already prepared ammonium formate instead of

ammonia and formic acid. Their reported yield was about 20% after purification.

Ritter Reaction[50] This reaction utilizes safrole to directly form the formamide (or acetamide) of MDA which is then hydrolyzed to MDA. The following procedures are adapted from procedures used to produce amphetamine from allylbenzene and other amines from their corresponding tertiary alcohol or alkene. A fume hood is required for this procedure due to use of cyanide which can easily be released from acidic solutions as a gas. A mixture of 25ml acetic acid, 34.2g safrole (0.2 moles, 29.5 ml), and 11g (0.2 moles) of 90% sodium cyanide is placed in the flask of the apparatus shown in the picture.

To the separatory funnel is added a mixture of 50g (27.2 ml) of concentrated sulfuric acid and 25 ml of acetic acid. This is dripped into the flask over 30 minutes. Shake the reaction mixture occasionally or stir the solution with a magnetic stirring bar. Remove the separatory funnel and still head and allow the mixture to sit overnight. Add a solution of 120g of NaOH in 250 ml water to the mixture. The mixture will heat up and neutralize the acid. A few boiling chips are added and a condenser is fitted into the top of the flask for refluxing. The mixture is refluxed for five hours. The mixture is allowed to cool and the amine and unreacted amide are extracted with ether (or toluene etc). The ether is washed three times with water and the MDA is precipitated by a stream of HCl gas. Filter and let dry. Acetonitrile can be used in place of sodium cyanide to form the acetamide. The acetamide would need to be hydrolyzed with hydrochloric acid though. Refer to Ritter's article under N-(benzylmethylcarbinyl)-acetamide. Substitute the allylbenzene for 32.4g of safrole.

Halosafrole Method This method is adapted from the procedure written by Biniecki and Krajewski[51]. 49g (0.2 moles) of bromosafrole are added to methanol containing 34g (2 moles) of ammonia (see chapter 3). This is placed in an adequate sized pipe "bomb" This pipe "bomb" should be made of stailess steel and have fine threads on each end. The treads can be wrapped with teflon tape to ensure a good seal. Tighten the pipe ends securely and place the pipe bomb in cooking oil and heat at 130° for 3-4 hours. The temperature is monitored with a candy thermometer placed into the oil. When the pipe cools, pour the solution into the boiling flask of a simple distillation apparatus and remove the methanol and excess ammonia through distillation. Acidify the residue with hydrochloric acid (muriatic acid) with shaking until a pH of 3 is reached. Extract the solution with ether (or toluene or methylene chloride etc.) to remove unreacted bromosafrole. Basify the aqueous solutio with 25% NaOH and extract the oil released with ether (or toluene etc). Place the ether extract in a vacuum distillation apparatus and remove the ether. Apply a vacuum and distill over the MDA. Dissolve the distilled oil in toluene and run a stream of HCl gas in to precipitate the MDA. Filter and allow to dry. The solvent from the bromosafrole extract can be removed and the recovered bromosafrole reused. When substituting

iodosafrole use 58g (0.2 moles). After acidifying the residue with hydrochloric acid, decolorize the solution with a little sodium thiosulfate. When substituting chlorosafrole use 40g (0.2 moles) and extend the reaction time to 6-8 hours.

Hofmann Rearrangement The Hofmann rearrangement has also been used to produce MDA[52]. MDA was made as an intermediate to isoquinoline being studied. The amide used in the Hofmann rearrangement is also described from piperonal.

Chapter 8 - Ecstacy and Eve Ecstacy is one of the most interesting drugs to ever be discovered. It is most closely compared to psychedelic drugs in its general effects, but where there are many drugs that can reproduce the effects of the famed LSD, there is yet no substitution for ecstacy. A couple have come close, MDEA (Eve, N-ethyl-3,4-methylenedioxyphenylisopropylamine) and persons may find no significant difference and enjoy the lessened physical aspects.

Other books describe in detail the ecstacy experience so I refer you to them if it is unfamiliar. Ecstasy: The MDMA Story b Bruce Eisner has one of the best breakdowns of the "stages" of the experience as well as an in-depth look at its flip-flop legal status. E for Ecstasy by Nicholas Saunders covers the British perspective with thir largely "rave culture" use as well a the legal therapeutic use in Switzerland. Both give practical considerations for ecstacy's use. PiHKAL - A Chemical Love Story by Ann and Alexander Shulgin give comments at various dosages for ecstacy and 178 other psychedelic amphetamines as well as their synthesis. We now turn our attention to the synthesis for ecstacy of which there are several choices. A simple modification in most these will yield Eve (100-200 mg/dose, 3-5 hour duration). MDMA, 3,4-Methylenedioxymethamphetamine, ecstacy, N-methyl-3,4-methylenedioxyphenylisopropylamine, N,alpha-dimethyl-1,3-benzodioxole-5-ethanamine. CAS No: [42542-10-9] Dosage: 80-150 mg Duration: 4-6 hours N-Alkylation of MDA MDA can be used to synthesize MDMA simply by adding a methyl group. Two of the general methods for doing this are covered below. The one utilizing methyl sulfate is only referred to due to methyl sulfate's nasty properties.

The Method of Decker and Becker[53] 179 g (1 mole) of MDA as the free base and 106 g (1 mole) of benzaldehyde are dissolved in 95% ethanol (as much it take to dissolve them). This solution is refluxed for 30 minutes forming the Shiff base (imine) intermediate of these two compounds. The ethanol is removed by distilling under reduced pressure leaving an oil. This oil is added to 142 g (1 mole) of methyl iodide and placed in a pipe "bomb". Use a pipe with fine threads and wrap

these with teflon tape to form a good seal. Tighten down the caps well and place the pipe "bomb" in boiling water for five hours. The material in the "bomb" is then washed out with a solution of 80ml methanol and 10 ml water and placed in a boiling flask to be refluxed. Only enough solution to rinse out the pipe is required. Reflux the mixture for 30 minutes. Add an equal volume of water and reflux the mixture until the odor of benzaldehyde has disappeared. Acidify the mixture with hydrochloric acid (shake well) and the extract with three portions of ether. The solution is made basic with 25% NaOH solution and the liberated amine is extracted with ether (or methylene chloride etc.). The ether is washed with water, dried with MgSO4 and HCl gas is run into the solution to precipitate the amine. Filter and allow to dry.

The MDMA may contain some MDA but this should be acceptable. Replacing methyl iodide with 156g (1 mole) ethyl iodid and boiling the pipe for 10-15 hours will give Eve.

Methyl Sulfate Methylation Kiefer[54] describes the use of methyl sulfate to methylate substituted phenethylamines. Be cautioned that methyl sulfat (dimethyl sulfate) causes severe damage to tissue it comes in contact with and lethal poisoning is possible. Wear gloves and wash after handling this material. The reader is referred to cited journal article for the details. Reduction of the Formamide of MDA The formamide used here can be obtained from the reaction mixture of the Ritter Reaction for MDA by extracting with ether (or toluene etc.) the oil formed after the addition of NaOH solution.

A solution of 7.7 grams of the formamide in 25 ml anhydrous THF (Tetrahydrofuran) is added with stirring (magnetic) to a solution of 7.4 g LAH in 600ml anhydrous THF under inert atmosphere. See under safrole synthesis in chapter 5 for inert atmosphere apparatus. The reaction mixture is brought to reflux and held there for 4 days. The solution is then cooled to room temperature and 7.4 ml water in 7.4 ml THF are added to the solution followed by 7.4 ml 15% NaOH and 22 ml water. The solids are filtered out and washed with THF. The filtrate is removed of solvent and the residue dissolved in 200ml of methylene chloride. The methylene chloride solution is then extracted with three 100ml portions of dilite HCl. These extracts are made basic with 25% NaOH solution and the oil released is extracted with methylene chloride. The methylene chloride is distilled off and the MDMA remaining is distilled under reduced pressure. The distilled oil is dissolved in ether (or toluene etc.) and HCl gas is run in to precipitate the MDMA. Filter and allow to dry. Similar reduction of the acetamide formed by using acetonitrile in the Ritter Reaction will give Eve. Reductive Amination This general method utilizes piperonyl acetone and methylamine hydrochloride as the starting materials. These two compounds react in an equilibrium to form an imine. The imine is then reduced to MDMA. Two methods of reducing the imine are given. This is analogous to the methods used for MDA. Sodium Borohydride Reduction[55] In the following reaction, 10 times the theoretical amount of methylamine

hydrochloride is used to push the equilibrium of the reaction to the right in the formation of the intermediate imine compound. When the imine is formed it is reduced by the hydride to the amine, MDMA. To a solution of 26 grams of methylamine hydrochloride in 110 ml of methanol are added 6.6 grams of piperonylacetone (0.037 mole) and then 3g of sodium cyanoborohydride. The mixture is stirred at ambient temperature, and 12 N HCl is added with a dropper or pipet as required to maintain the pH at neutrality (pH 7 as determined by universal pH paper; 31.5% muriatic acid will suffice even though it is less concentrated). The reaction is complete after 36 hours following the addition of 1L of water containing 5ml of 12N HCl (6 ml of muriatic acid). The reaction mixture is extracted twice with 150 ml of methylene chloride (discard these extractions). The reaction made basic with 25% NaOH solution (red litmus turns blue), and extracted with three 150ml portions of methylene chloride. The extracts are pooled together and the methylene chloride is distilled out.

The oil that remains is distilled at reduced pressure (0.2 mmHg; bp 85-95°C) and the recovered oil is dissolved in 60 ml of isopropyl alcohol (100%) and acidified with 12N HCl (blue litmus turns red). An equal volume of ether is added and the crystals should spontaneously form. They are filtered out, washed with a 50/50 isopropyl alcohol/ether solution and then ether alone.

The author of this article cited likes this final method for crystallization. This is not necessary. After distillation of the oil, dissolve the oil in ether (or toluene or methylene chloride) and pass HCl gas into the solution until no more crystals form. Filter out the crystals and let dry. Aluminum Amalgam Reduction[56] 72.5 grams of aluminum foil is cut into one inch squares and placed in a 3000ml erlenmeyer flask or other suitable glass container. A solution of 1.8g of mercury chloride (HgCl2, mercuric chloride) in 2530ml (2.53 L) if water is added, and the mixture is stirred occasionally over 30 minutes or until there is evolution of fine bubbles, the formation of a light grey precipitate, and the occasional appearance of silvery spots on the surface of the aluminum. This amalgamates the aluminum. The solution is poured off and the foil is washed with four 1000ml portions of water.

To the amalgam is added, in sequence, 101 grams of methylamine hydrochloride in 101 ml of water, 302 ml of isopropyl alcohol (100%), 244ml of 25% sodium hydroxide solution, 89g (0.5 moles) of piperonylacetone and then 588 ml of isopropyl alcohol. The mixture is swirled occasionally for 2 hours and kept below 60°C by cooling with an ice water bath a necessary. When the temperature no longer rises, sit on the benchtop and allow to cool to room temperature. If 40% methylamine in water is used the following substitutions can be made. In sequence add 128g aqueous methylamine, 302 ml isopropyl alcohol (100%), a suspension of 84g NaCl (table salt) in 42 ml 25% NaOH that has been diluted to 235 ml with water, 89g (0.5 moles) of piperonylacetone, and finally 588ml isopropyl alcohol (100%).

The mixture is then filtered through Celite (a diatomaceous silicate powder which is placed in a layer over the filter paper before filtering, it is sold by chemical companies as Celite) and the filter cake is washed thoroughly with methanol. Compine the liquid filtrates and distill off the methanol (65°C) the isopropyl alcohol (82°C) and the water (100°C).

Dissolve the oil in 200 ml of ether and extract the MDMA into two 500 ml portions of 3N HCl. The acid solution is washed with three portions of methylene chloride equal in volume to the acid solution (you will probably have to wash portions o the solution at a time unless you have a huge separatory funnel. The acid solution is basified with excess 25% sodium hydroxide solution (red litmus turns blue) and the liberated oil is extracted into three 500 ml portions of methylene chloride The methylene chloride solution is dried with magnesium sulfate. The drying agent is filtered out and the methylene chloride distilled out. The residual oil is distilled under reduced pressure and the distilled oil then dissolved in ether (or toluene or methylene chloride). HCl gas is bubbled through the solution until no more precipitate is formed. The precipitate is filtered off and allowed to dry (~70% yield can be expected). To produce Eve, substitute 122g ethylamine hydrochloride for methylamine hydrochloride.

Leuckart Reaction Methylamine is substituted in the Leuckart reaction for MDA to produce MDMA[57]. This is elaborated below. Uncle Fester[58] describes generating high purity N-methyl formamide[59] and then carefully reacting this with phenylacetone for highest yield of methamphetamine. Substituting piperonylacetone for phenylacetone would give MDMA. Fester gives long "idiot proof" directions so I refer you to his book for his directions.

To a three-necked flask equipped with a dropping funnel, thermometer (into the reaction mixture), and down directed condenser (simple distillation apparatus) is added with 133g (1.72 moles) of 40% methylamine solution and 88g (1.72 moles) of 90% formic acid. The temperature is raised to 160°C by distilling out water, and 59.4 grams (0.334 moles) of piperonylacetone is added at one time. The following apparatus can be substituted for a three-neck flask and the piperonylacetone added by momentarily replacing the thermometer with a funnel. The mixture is maintained at 160-170 for 7 hours and any ketone which distills over is periodically returned to the flask. The formyl derivative is hydrolyzed in the reaction mixture by refluxing for eight hours with 120 ml of concentrated HCl (145ml 31.5% muriatic acid). The mixtur is diluted with 200 ml of water and extracted with benzene (or ether etc.) to remove water insoluble material. The aqueous solution is treated with a little charcoal, Norit (or filtered through activated charcoal from pet stores). The solution is made alkaline with ammonia (or alternatively 25% NaOH) and the oil thus produced is extracted with benzene (or ether etc.). The benzene is washed three times with water and dried with sodium sulfate or other drying agent. A stream of HCl gas is fed through the solution until no more precipitate is formed. The precipitate is filtered out and allowe to dry.

40% methylamine is the commonly available form along with methylamine hydrochloride. Basifying 116g of methylamine hydrochloride with 68.5g of NaOH in 80 ml of water will approximate the 40% solution called for. Slowly add the methylamine hydrochloride to the NaOH solution after it cools. Keep the solution cool to maximize the solubility of the methylamine. Substituting ethylamine will give Eve. HaloSafrole Method This method is identical to the halosafrole

method used for MDA with the exception that methylamine (or ethylamine) is substituted for ammonia.

49 g (0.2 moles) of bromosafrole are added to methanol containing 62g (2 moles) of methylamine (155g of 40% methylamine in water can be used. The bromosafrole and methylamine layers are joined by adding the minimum amount of methanol that brings both layers into solution). This is placed in an adequate size pipe "bomb". This pipe "bomb" shoul be made of stainless steel and have fine threads on each end. The threads can be wrapped with teflon tape to ensure a good seal. Tighten the pipe ends securely and place the pipe bomb in cooking oil and heat at 130°C for 3-4 hours. The temperature is monitored by a candy thermometer placed ino the oil. When the pipe cool, pour the solution into the boiling flask of a simple distillation apparatus and remove the excess methanol and ammonia through distillation. Acidify the residue with hydrochloric acid (muriatic acid) with shaking until a pH of 3 is reached. Extract the solution with ether (o toluene or methylene chloride etc.) to remove unreacted bromosafrole. Basify the aqueous solution with 25% NaOH solution and extract the oil released with ether (or toluene etc.). Place the ether extract in a vacuum distillation apparatu and remove the ether. Apply a vacuum and distil over the MDMA. Dissolve the distilled oil into toluene and run in a strea of HCl gas to precipitate the MDMA. Filter and allow to dry. The solvent from the bromosafrole extract can be removed and the recovered bromosafrole reused. For Eve use 90g (2 moles) of ethylamine in methanol. 40 g of chlorosafrole or 58g of iodosafrole can be substituted for bromosafrole. Extend the heating for 6-8 hours when substituting chlorosafrole.

Chapter 9 - Tidbits On Other Highs

LSD

LSD is also known as Lysergic Acid Diethylamide, LSD-25, Acid, and a variety of street names. It is so far the most potent psychedelic with a threshold dose weighing ~50 micrograms (0.00050 grams) in the tartrate salt form. A saturation dose is reached at 500 micrograms (0.5 mg) in most users where the effects reach a maximum. Many people become uncomfortable at 250 micrograms where temporary loss of ego or identity occurs.

There are two basic routes to LSD. Those beginning with lysergic acid and those beginning with an amide of lysergic acid (total synthesis leading to lysergic acid is not considered basic). There are several sources of naturally occurring lysergic acid amides which can be used to produce LSD. I believe this is a point of confusion for most laymen. Lysergic acid amides are not LSD. They are just that, an amide of lysergic acid. An amide is generally a compound formed from a carboxylic acid (which lysergic acid is) and an amine (one of whic is diethylamine). LSD is not naturally occurring. Lysergic acid is naturally occurring but in the form of amides. Many of these naturally occurring amides are biologically active. Extracts from the ergot fungus growing on rye grass have been used by midwives since the middle ages. This is because the ergotoxine and ergotamine group of alkaloids present act to stimulate contraction of the uterus and reduce hemorrhaging after childbirth. Ergonovine is even more selective in this action. Another effect of prolonged exposure to these amides is gangrene and convulsions. This is because they cause constriction of the blood vessels and as a result reduce or halt bloodflow. It is this effect upon blood vessels that warranted their use in migraine headache treatments. Sleepy Grass (Stipa Robusta) contains lysergic acid amides produced by symbiotic fungus in the plant. This fungus is also in the seeds so its continuation is assured. These amides knock out livestock that eats the grass. It is said that indians give one seed to quiet babies. Rivea (Turbina) corymbosa which is the source of the Mexican Indians ololiqui contains psychoactive lysergic acid amides. Hawaiian woodrose seeds and morning glory seeds contain similar lysergic acid amides. Although these have been described by others as psychedelic, I would not consider them as anything close to the grand effect of LSD and becoming nauseous is very likely. There are also "Alpha-adrenergic blockers used in the treatment of impaired mental functioning in the elderly"[60] that are amides of lysergic acid. Some of these are used as so-called "smart drugs".

Three books that I know of describe the making of LSD for underground chemists. The Book of Acid available as one of the 1 pamphlets in the Underground Psychedelic Library, Recreational

Drugs by Professor Buzz, and Psychedelic Chemistry by Michael Valentine Smith. All three give syntheses for LSD with The Book of Acid containing the least (but in my opinion all you need), Recreational Drugs more, and Psychedelic Chemistry the most. Psychedelic Chemistry gives details on extracting amides from woodrose seeds and obtaining Lysergic acid amides from Aspergillus clavatus ("which grows on Roquefort cheese and long store foods"), ergot, morning glory and baby Hawaiian woodrose seeds.

The hydrazine method discussed in these books gives the versatility of not isolating lysergic acid from the amide The problem here is that anhydrous hydrazine (N2H4) is not found everywhere and when it is it sounds alarms to the DEA.The other requirement for this and the other syntheses is diethylamine. It too makes you a marked man. Clandestine chemistry to the rescue. Diethylamine is a side product in the synthesis of ethylamine from ammonia and ethyl iodide which can be maximized with with a mole ratio of 1 to 2 respectively. It can be freed from the other two hydrochlorides (ethylamine, bp 16°C and triethylamine, bp 89°C) by basifying with excess 25% NaOH followed by fractional distillation (diethylamine, bp 55.5°C). Anhydrous hydrazine can be made from hydrazine sulfate and NaOH[61]. Hydrazine sulfate can be prepared from calcium hypochlorite (swimming pool chlorine), ammonia and gelatin[62]. Now the only problem is doing the work! (Can't you just see people mowing their sleepy grass lawns and loving it!).

Essential Amphetamines Safrole is a component of the essential oil of Sassafras. Essential comes from essence and the oil is thus the essence of th smell of Sassafras. There are many other essential oils which contain compounds with allylic double bonds like safrole. These compounds can be used in the syntheses in this book to produce other psychedelic amphetamines. The term amphetamine is used because their structure contain the amphetamine molecule with a few extra substituents. So we have the essential amphetamines. The term was originally coined by Dr. Alexander Shulgin in his book Pihkal. Most of these compounds have been assayed in his book as to dosage, duration, and effects. Elemicin Elemicin is found in Elemi oil from the Philippines and its use in place of safrole yields TMA (100-250 mg/dose), 6-8 hrs duration). An analogue of mescaline where mescaline's apprpximate dosage is 180-260 mg in the HCl salt form.

Asarone Asarone is the major component of calamus oil (~80%). It is analogous to isosafrole. Replacement of isosafrole with asarone would yield TMA-2 (20-40 mg/dose, 8-12h).

Apiole Apiole is a major component of parsley seed oil. It is also a component in parsley and fennel oil. These oils are all readily commercially available.

Dillapiole Dillapiole is a component of most every variety of dill oil from 0-25%. Substituting for safrole would lead to DMMDA2 by Shulgin's nomenclature (30-75 mg/dose, 6-8 hrs).

Myristicin This oil is a component of nutmeg oil. The myristicin fraction along with elemicin constitute ~7% (85% of this is myristicin) of the oil. Myristicin has also been found in the seed oil of several plants[63]. The substitution of safrole with myristicin would lead to MMDA, 3-Methoxy-4,5-methylenedioxyamphetamine (100-250 mg/dose). This compound was made illegal with the first list of controlled substances. Eugenol

Eugenol is present in many oils. Clove oil is mostly eugenol (~95%). Allspice oil from the pimenta berry and cinnamon leaf oil also contain a high percentage of eugenol. Many other oils contain reasonable quantities of eugenol. The aminated form has not been tested as far as I know.

Vanillin Vanillin as one might expect is the taste and odor of vanilla extract. Substituting for piperonal would lead to the same compound as eugenol does. A better use for vanillin and eugenol may be to convert them to elemicin or myristicin[64]. Anethole Anethole is the chief constituent of anise oil (~90%), star anise (~95%) and fennel oils. The substitution for isosafrole would lead to 4-Methoxyamphetamine. The dosage appears to be ~50-80mg and its effects not strongly psychedelic, although it has appeared on the street enough to be listed as a controlled substance. Tetramethoxyallylbenzene This compound has been repotred as having been prepared from parsley seed oil[65]. This has all the makings of a winner. It has been tested up to 35mg with some intoxication. Shulgin in Pihkal anticipates a possible treshold of ~50mg.

2,5-Disubstitution Pattern The 2,5-dimethoxy pattern is the parent of 2C-B which has come into limited view in recent years as Nexus or Erox. Nexus is the name given to 5mg tablets sold by the German pharmaceutical company Drittwelle for alleviating impotence. They refer to 2C-B as cathabromide and claim it is a drivative of a phenylethylamine from the african plant Catha Edulis. Catha Edulis is the source for cathinone, a relative of amphetamine with similar effects, but I haven't seen reference anywhere else of such a phenethylamine. If it is there it is probably in small amounts (?). This pattern is also the start of the Aleph and 2C-T series of Shulgin in Pihkal. These series have brought forth some very interesting compounds.

A starting material for this series could be as innoculus as salicylaldehyde. Reaction of this in the Elbs Persulfate Oxidation [66] would lead to the 2,5-dihydroxybenzaldehyde. Methylation with methyl iodide and potassium hydroxide as base catalyst would give 2,5-dimethoxybenzaldehyde. This gets you to Shulgin's starting point for all the compounds mentione

Tryptamines The tryptamine psilocybin and psilocin, from muschrooms, are two of the most easily produced psychedelics today. High times magazine is always filled with advertisers of mushroom spores and kits. The best I have seen is by Psylocybe Fanaticus (PF). They sell sterile spore syringes and very clear instructions for their use. The spore syringes eliminates having a sterile work area to transfer spores because you use a medium in canning jars sterilized in a pressure cooker and introduce the spores with the syringe. It works great and all the materials you need can be easily purchased with absolutely no suspicion. Others are copying this technique with PF's medium formula. Stay away from anything other than spore syringes if possible. They're not worth th hassle.

These methods are great for you and your friends, but those interested in stockpiling for th future, liquid culturing is probably the way to go[67]. This entails growing the mycelia in liquid culture and extracting psilocybin from it. Mass production is easier this way. It is interesting to note how the structure for phenethylamine (XTC is a substituted phenethylamine) overlaps the tryptamine and how the tryptamine molecule overlaps LSD.

Barbiturates Barbituric acid is the condensation product of urea and diethyl malonate (the diethyl ester of malonic acid) Barbiturates are formed from condensing urea and a derivative of diethylmalonate or by condensing barbituric acid with the appropriate alkylhalides with a base catalyst (claisen condensation)

Condensation of Urea with Diethylmalonate to Give Barbituric Acid

Phenobarbital, Pentobarbital and Sodium Pentobarbital Cocaine

Cocaine, like the opiates and other narcotics, present significant threat in the way of addiction and physical harm. I don't like addiction and hence one reason for my choosing psychedelics instead. I am lucky not have faced addiction to these substances unlike others I have known. I try not to be a hypocrite either so for Cocaine Syntheses see the following:

Robert Robertson, A Synthesis of Tropinone, Journal of the Chemical Society 762-769 and 876 (1917). Paquette and Himaste, Journal of the American Chemical Society 763-768 (1966). Tufariello et al, Pseudotropine and dl-Cocaine, Journal of the American Chemical Society 2435-2442 (1979). Hayakawa, Journal of the American Chemical Society 1786-1791 (1978). Tufariello et al, A Stereospecific Synthesis of Cocaine, Tetrahedron Letters 20, 1733-1736 (1978).

Opium See Opium for the Masses by Jim Hogshire for some interesting reading. I wouldn't take opium addiction as lightly as he seems to though. One thing to mention here is that dried Papaver (Opium Poppies) can be bought in bundles from craft stores along with other dried flowers. The poppy heads contain all the seeds one should ever need with the added bonus of providing the ingredients for a little poppy tea. The poppy seeds bought in the spice section of your local grocer have many viable seeds too.

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