Cocaine Extraction Ratios

DrugPhreak · Working Bee

How's the ratios in this extraction SWIDP put together? Is 130ml of 10% H2SO4 too much or too little? What about the other amounts?

910gm of coca leaves are finely ground and 155gm of sodium carbonate dissolved in just enough warm dH2O to cover them is added and this is stirred for two hours. 1300ml of kerosene is added and the stirring is continued for six hours. After stirring the solution is allowed to sit for 30 minutes and the kerosene is separated off and filtered. 130ml of 10% H2SO4 is added to the kerosene and the solution is stirred for 30 minutes and left to sit for 30 minutes. The acid is then separated off and an excess of sodium carbonate is added with stirring until no more coca paste precipitates. The solution is filtered and all the coca paste is scraped from the vessel and laid out to air dry. The coca paste is dissolved in 6% H2SO4 (10ml per gram of paste) and 10ml of aqueous 20% KMnO4 solution is added slowly (1ml every 10 minutes) with vigorous stirring to the acid (or until the solution is fairly colorless). This is left to sit for 1 hour (or until all the manganese dioxide comes out of solution) and then filtered. 10% NH4OH (about 10ml) is added to the filtrate with stirring until no more cocaine base precipitates. The cocaine base is filtered, washed with a little dH2O and laid out to air dry. The base is dissolved in 100ml of Et2O and filtered. 3ml of 37% HCl in 3ml of acetone is added with stirring (paying close attention to make sure the crystals don’t take on a yellow tint). Stirring is stopped and another 100ml of Et2O is added with some swirling. The cocaine HCl is allowed to precipitate in an undisturbed area for 3 hours. The cocaine HCl is vacuum filtered as the crystals are rinsed with a little Et2O and laid out to air dry.

Also, does anyone have these...

J. Prakt. Chem. 116, 285 (1927)

Boll. Chim. Farm. 88, 175 (1949)

Chem. Ztg. 54, 31 (1930)

Chemical Abstracts 24, 3322 (1930)

Tropenpflanzer 15, 684 (1911)

DrugPhreak · Working Bee

No south american bees? Don't be scared to order coca leaves... it gets through. Some insect somewhere in the universe ordered 1000gm and they had no problems. It's comes through as tea. The word "coca" is not present. Wink

This insect just doesn't want to waste any. Crying or Very sad

maj · Thu Apr 07, 2005 12:43 am

here are currently two general methods for processing coca leaves into coca paste, hereafter referred to as the solvent extraction technique and the acid extraction technique. The solvent technique (the traditional methodology) was directly derived from one of the original commercial processes developed in the early 20th century23, and remains the most commonly used method in Peru, Colombia, and Ecuador. The acid technique (a much more recently developed methodology) is a considerably more labor-intensive procedure also directly derived from yet another, even older commercial process59. It requires relatively little organic solvent (which is controlled in certain areas of South America), and is currently the most commonly used method in Bolivia. It should be noted that, to the authors' knowledge, all previous literature reports to date summarizing illicit cocaine processing have only detailed out versions of the solvent technique, i.e., this is the first detailed report of the acid technique.

a. The Solvent Extraction Technique (Scheme 1)

Scheme 1.
Illicit production of coca paste via the solvent
extraction technique (see text for details).

The coca leaves are macerated, dusted with an inorganic base (usually lime or a carbonate salt), dampened with a minimal amount of water, and placed in a maceration pit - typically either a 55-gallon drum or large plastic barrel, a large metal trough or a staked-out pit lined with heavy-duty plastic. Alternately, an aqueous solution of the inorganic base is pre-mixed, then poured over the macerated leaves. If fresh (i.e., not sun-dried) leaf is used, the operators may not add any water. The addition of the inorganic base ensures that the cocaine is in its free base form. A water-immiscible organic solvent (usually kerosene, less commonly diesel fuel or gasoline) is added to the dampened coca leaf slurry and the mixture is either vigorously mixed for several hours or left standing with occasional stirring for up to 3 days, thereby extracting the cocaine free base into the solvent. The efficiency of the extraction is highly dependent on how much time the leaves spend in contact with the solvent and how much effort the operators have put into macerating the leaves (the finer the leaves have been chopped up, the more efficient the transfer of cocaine base to the solvent). Mechanization of the maceration (e.g., with leaf mulchers) and extraction processes (e.g., with washing machines or cement mixers, etc.) is common. In addition, in certain operations the leaves are reportedly repeatedly extracted to ensure more quantitative recovery of cocaine.

After completion of the extraction procedure, the solvent is removed from the mixture either by pressing, filtering, draining from a plug, siphoning or other similar means. The resulting solution is usually completely organic, but may contain a small aqueous layer underlying the organic layer. If necessary, the liquid is re-filtered to remove any remaining vegetable matter and, if two layers remain, the lower (aqueous) layer (which is extremely basic due to dissolved lime or carbonate) is separated by pour-off and siphoning and discarded.

The large volume of organic solvent resulting from the leaf extraction(s) is then back-extracted with a much smaller volume of dilute sulfuric acid, which is added directly to the organic solvent, mixed vigorously for 2 to 10 minutes, then allowed to sit and re-separate. The acid converts the cocaine free base to cocaine sulfate, which dissolves in the aqueous layer. The organic solvent is then separated, leaving only the dilute sulfuric acid solution of cocaine sulfate. This latter yellowish-brown solution is commonly referred to as "agua rica" or "guarapo" (agua rica). The organic solvent is usually re-used indefinitely, with additions of fresh solvent to make up natural attrition due to handling and irrecoverable absorption into the leaf mulch.

In the final phase of coca paste isolation, an excess of base, usually lime, carbonate, or caustic soda, is slowly added to the agua rica solution with stirring. The base neutralizes the sulfuric acid and converts cocaine sulfate back to the free base, which precipitates out of the solution as a gummy, yellowish solid. This solid is coca paste, which is filtered, dried, packaged, and shipped to a base lab.

The cocaine content of coca paste generated by the solvent extraction technique varies from 30 to 80%. It contains numerous additional components other than cocaine, including other coca alkaloids and inorganics. However, most of the free carboxylic acids have been removed because of their limited solubility in dilute acid and solubility in dilute alkali solutions. The dried material usually has a "cakey" consistency and usually will not free-flow easily. Although kerosene and diesel fuel are the extraction solvents of choice, many other water-immiscible organic solvents or solvent mixtures may be substituted. Similarly, while any soluble inorganic base may be effectively used for the neutralization of the agua rica solution, carbonate salts are traditionally the most popular because they act as their own visual endpoint indicators. The addition of any carbonate salt to the acidic solution causes vigorous foaming from the release of carbon dioxide gas; thus, the neutralization endpoint is where the addition of carbonate no longer causes foaming of the reaction mixture. This visual endpoint indicator is very useful to operators without access to sophisticated equipment.

b. Bazuco

A variant of the solvent technique involves the production of bazuco, a crude preliminary run of coca paste with a low cocaine content. Bazuco is often given to paste laboratory workers as payment or co-payment. It is commonly mixed with tobacco and smoked by the user, and represents a very rapidly growing abuse and addiction problem throughout the cocaine-producing regions of South America2,24. In the most common variant, bazuco is obtained by mixing an insoluble diluent (e.g., flour or ground maize) into the dilute sulfuric acid solution prior to back-extraction of the organic solvent. Following extraction, the diluent-slurred aqueous layer is separated from the organic solvent in the previously described manner, and a base is added to the solution just to the point where some initial precipitation is observed. The solution is allowed to stand a few minutes and is then filtered to co-capture the diluent and this initial crude precipitate of coca paste, which is then air dried to give bazuco. Additional base is then added to the filtrate to precipitate the remainder of the coca paste in the usual manner. Chemically, the preparation of bazuco serves two purposes:

1. The diluent-slurred aqueous solution makes an excellent visual indicator of the interface boundary between the two layers; and
2. The first precipitate reportedly contains a relatively high content of the cinnamoylcocaines.

Thus, isolation of bazuco reduces the amount of oxidizing agent required in the next step for the production of coke base (vide infra). Coca paste obtained following preliminary isolation of bazuco is purer and usually whiter in appearance.

http://rhodium.moppy.net/www.rhodium.ws/chemistry/cocaine.illicit.production.html

maj · Thu Apr 07, 2005 12:45 am

c. The Acid Extraction Technique (Scheme 2)

Scheme 2.
Illicit production of coca paste via the acid
extraction technique (see text for details).

The coca leaves are placed directly in a maceration pit (almost always a staked-out pit lined with heavy-duty plastic, commonly referred to as a "pozo") containing just enough dilute sulfuric acid to cover the leaves. The leaf/dilute sulfuric acid mixture is vigorously macerated, typically by workers who get in the pit and forcefully stomp the leaves for 1 to 2 hours. The acid converts the cocaine free base in the leaves to cocaine sulfate, which dissolves in the aqueous solution. As with the solvent extraction technique, the efficiency of the extraction depends on how much time the leaves spend in contact with the dilute sulfuric acid solution and how much effort the workers put into stomping the leaves. After the stomping is complete, the acidic coca juice is removed (usually by bucketing) and poured through a coarse filter (to remove any remaining vegetable matter) into a separate decant pit (commonly referred to as a "chiquero"). At this point, an excess of lime or carbonate is added to the isolated dilute sulfuric acid solution with vigorous stirring, thus neutralizing the cocaine sulfate and any remaining sulfuric acid and precipitating a very crude curdled coca paste. The endpoint of the base addition is monitored via spot-testing of small aliquots of the solution with an ethanolic solution of phenolphthalein (called "punto"). The curdled coca paste in the solution is not collectable as such, but is rather back-extracted with a much smaller volume of kerosene, which is thoroughly mixed in for 2 to 10 minutes and allowed to re-separate. After isolation, the kerosene fraction is then handled exactly as in the solvent technique; i.e., the kerosene is back-extracted with a yet smaller volume of fresh dilute sulfuric acid, again generating an agua rica solution.

The acid technique always involves multiple (3 to 5) extractions of the leaves; i.e., the already stomped leaves are treated with another fresh solution of dilute sulfuric acid and re-stomped. Each pozo extract is handled identically in turn, except that the same agua rica solution is used to back-extract all of the kerosene extracts (thus continually enriching its cocaine content). Following processing of the final pozo extract, the isolated agua rica solution is again handled exactly as in the solvent technique; i.e., made basic via addition of an inorganic base, thereby precipitating coca paste.

Coca paste generated by the acid technique is essentially equivalent to that produced via the solvent method, and similarly contains from 30 to 80% cocaine. The advantage of the acid versus solvent technique is the use of a minimal volume of organic solvent; however, it is considerably more labor-intensive. This variant is used extensively throughout Bolivia, where personal possession of large volumes (more than 50 liters) of organic solvents (e.g., kerosene) in the coca-growing regions is illegal.

Chemically, coca paste from either extraction procedure has a gummy consistency and a limited shelf-life. If continuously exposed to excessive heat and humidity, it will slowly self-dissolve, turning into an oily liquid with a pungent, unpleasant odor. This drawback is well known to the clandestine operators; for this reason, coca paste is usually immediately processed to coke base. If this is not possible, it is usually stored as agua rica until further processing is possible.

http://rhodium.moppy.net/www.rhodium.ws/chemistry/cocaine.illicit.production.html

DrugPhreak · Working Bee

The extraction I posted is based on those jungle lab procedures. I have obtained one of the refs and I thought I would post it here also just incase someone that reads German too that doesn’t go to the other forums is interested in translating this article also. I'm somewhat busy at the present time, but I will translate it soon if nobody else does so first...

https://synthetikal.com/synthforum/viewtopic.php?t=405

I'm in the process of getting this... J. Prakt. Chem. 116, 285 (1927), but I'm sure most people can get the C.A article without any problems. What does it say? I think a few of these refs where actually about halogenated analogs though... I forget. Confused

hahas · Wed May 18, 2005 8:09 am

DrugPhreak · Working Bee

OK. It's translated, but most things are verbatim. Some things don't make sense and the chemistry seems sloppy. For instance... why would you wash cocaine base with ether or crystallize it in just acetone. Confused

I omitted a few things that made even less sense or seemed to be a waste of time. Translating this paper was a waste of time. SWIDP will just proceed on their own, which is what they normally do. Anyway, here it is for anyone that might get something from it... I highly doubt that though.

Production of Cocaine
By Dr. Duilius

Cocaine is common with other alkaloids in the leaves of the Erythroxylon Coca domestic to South America (Peru, Bolivia). The leaf is often used there by natives as a means of enjoyment. Also, on the islands of the Indian archipelago Coca is cultivated. However, in the American Erythroxylon types the alkaloid content is much lower. In the cultures of Java this is not the case. One also finds Tropacocaine in the latter leaves, on which during the processing is to be respected.

Cocainebase Production. Most important work course are: Production, separation, and cleaning of the raw bases. Since Coca leaf is very voluminous it suffers on transport and in return of its alkaloids. The extraction usually takes place on the spot; the raw cocaine is then brought as such into the trade. Standard practice designates raw cocaine as "Cocaine", which is not processed in sulfur-sour solution and oxidized with a 5°C permanganate solution. With the purchase of raw cocaine one has to take into consideration other things, such as raw cocaine contains other alkaloids like Hygrine, which make the work more difficult.

The production of the raw cocaine from the leaves of American origin goes as follows: The leaf is dampened with soda-solution then extracted with ether or benzene in the usual extraction equipment. After the extraction with ether it is shaken out and with sour water. The alkaloids thereby go as the appropriate salt into the watery solution. Here upon one adds ammonia or soda and filter the base. This is dried and further processed as needed. If acetic acid and ammonia were used with the isolation of the bases, then often Tropacocaine can be separated and collected after the separation of the ethers as colorless or yellowish oily fluid, which has a narcotic smell. In the further course of production, leaves of Javanese origin can produce pure Cocaine from raw cocaine if one separates the cocaine of its similar alkaloids Ecgonine, Cinnamylcocaine, and Isatropylcocaine. From these removed similar bases one can obtain pure cocaine from Ecgonine.

Determination. In order to be correct of the pure content of raw cocaine, one draws 50 g in 500 ccm 3% sulfur-sour solution up and cools this solution with ice to 3-4°C. Drop by drop a cold solution of permanganate is added on that until the red color no longer disappears. The temperature should not exceed 4°C. Finally ammonia is added to the solution followed by potash. After a short stand one vacuum filters the cocaine, washes with a little water each and dries it on plates in a an oven at 30-40°C. After drying one adds the cocaine to a glass flask and shakes with ether. The ether is distilled and the mud is weighed. Content 70-95%. One processes if possible a high-proof commodity.

The production of the pure cocaine follows for instance the course of the analysis. In a boiler of approximately 70 l one adds 7 kg raw cocaine in diluted sulfur sour (about 15 l water and 1.2 kg of sulfur sour). One adds large pieces of ice during the entire operation to keep the temperature under 4°C.

Over the boiler one sets up a container filled with 10% permanganate solution and drips it into the cocaine solution slowly the with good stirring. The temperature in the boiler should not go over 4°C (if the temperature becomes higher it’s easy for the cocaine to be oxidized/damaged). The addition rate of permanganate is reduced if the red colored foam in the boiler does not disappear in half an hour. Then it’s neutralized with ammonia or potash and the cocaine is filtered. Additional ammonia or potash is added until the solution no longer takes on a cloudy appearance. The cocaine separates quickly and is of a hard texture, which can decompose into a greasy mass if it’s not precipitated in crystalline form. The cocaine is usually clay-like now and is washed with water a few times and air dried. It is then dried on enamel plates at 60°C. Once it’s dried it may be somewhat colored because of manganese oxide contamination. If so, one fills a 12 l flask to about 1/4 of its contents with cocaine base. The flask is then filled with ether about halfway and it is shaken well. The ether is poured off through a fluted filter into a distilling flask. The ether is then distilled leaving the cocaine in the flask. The distillation can be interrupted once the solution is of an olive oil consistency. If so, the solution is then placed into a wide-necked bottle that is about 6 l. The solution is allowed to evaporate. Cocaine residue can be seen immediately and after about 12 hours the residue can be removed. The purified cocaine will form a firm crust on the walls of the bottle. This crust should be scraped out right away because if it’s left too long it will become dusty. This crust is placed in a Buchner funnel and washed twice ether. Then it is air dried. The cocaine is now sufficiently pure for preparing the salt.

Cocaine hydrochloride. This occurs in the trade as leaflet form and as a water solution. One adds the pure cocaine base to acetone and with the calculated quantity HCl.

0.5 kg of pure cocaine base is added to 2 l of acetone. This solution is then filtered into a 5 l wide-necked bottle. The acetone solution is stirred with a glass rod and neutralized quickly with a calculated quantity of 38% HCl. Most of the hydrochloride will precipitate as large leaflets immediately, but it allowed to sit for 12 hours. After 12 hours it is vacuum filtered on a Buchner funnel and washed carefully. The acetone is then evaporated in a dark area at 50° C

The hydrochloride as large crystals is dissolved in a fourfold quantity of 90% alcohol. After scratching the walls of the bottle with a glass rod the cocaine will start to recrystallize as short rough prisms. These will gather after some time and are placed into a glass funnel. It is then covered and dried at a low temperature. The crystals decompose easily. 2 M was obtained and this cocaine contained a crystallization of water.

DrugPhreak · Working Bee

OK... SWIDP has performed cocaine extractions since this post was made. They have been through many failures, but had enough success to keep them going. Every time an extraction was done a kilo of tea bags or whole leaves where used. The 1300ml of non-polar solvent stated above was way too little... 5000 to 7000ml is more like it with this amount of leaves. 155gm of sodium carbonate seems to be too much, but the pH of the water was ~9.75 when this amount was added to ~3l of dH2O and poured over the leaves so the pH is just where you want it for extracting into non-polar. 55gm for a kilo seems to work better, but the pH was not taken when that amount was used... it will be next time though. 3l of water makes the leaves from the tea bags able to be stirred, but that seems to be too much water... 1000ml of water per kilo is better, but an amount of water this small would have to be used with the whole leaves since the tea bag leaves takes up so much damn water. The cocaine goes into the non-polar much better when the leaves are just moist and not soaking wet. SWIDP poured like half a gallon on them and they where still kind of dry... they start looking like horse shit and when non-polar is added it starts to look like chick pea soup after they are stirred for a while and this crap is a bitch to filter. SWIDP tried filtering it many ways and adding them to a bucket with a fine screen at the bottom seemed to work best. One nice thing about working with with coca leaves is no emulsions form though. Stirring/working the leaves for at least 15 hours was necessary to extract the cocaine, but 2-3 days is best. Using whole leaves is definitely the way to go for many reasons... they act as a visual indicator since the they form grayish/brown spots as the cocaine (and other alkaloids) come out, they are much easier to filter, and their alkaloid content is normally higher since they are intact and the midrib of the leaf has not been severed... the area around the midrib has the highest concentration of alkaloids. Some whole leaves seem to respond differently, but the leaves from most of the tea bags are a lower grade (I forget the name of the line) and even smell somewhat different. I recommend using whole leaves though.

Extracting the non-polar into 10% H2SO4 is too strong... 2-5% is sufficient, but I'm still not exactly sure what the best amount to use is. SWIDP always uses a different amount depending on how the leaves respond. Last time they used 400ml, which is probably too much. Once it's added sometimes a whitish precipitate forms on the bottom, which of course isn't alkaloids, but I have no clue what this crap is. Adding 10% KMnO4 solution is better and using an ice bath is recommended. The rest of the procedure seemed to work ok, but it is being tweaked. This jungle lab procedure doesn't scale down well, but SWIDP will probably try it one more time. The times that SWIDP had success ~2-3.5gm where obtained. Since a small amount of leaves are being used a procedure that allows for minimal processing is in order. Going through all this work and sometimes not yielding anything sure gives you a sinking feeling... and then you have no pure uncut cocaine!! Twisted Evil

Actually, chewing 1-2gm of these leaves sure gives you a nice kick and your lips and gums get numb as hell! The high is much cleaner/smoother and there is no come down. Wink

SWIDP needs a steady supply of pharmaceutical cocaine though... arrggghh!!! Twisted Evil

One day SWIDP will be able to do some... it has to happen... SWIDP would kill someone to do it... lol. Shocked