Extraction of opioids from painkiller products
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In this extraction, the undesirable products are removed from opioid containing pills through taking advantage of solubility differences. Using near freezing water as a solvent and the opioid containing pill as a solute, the opioids will dissolve into the solution while the unwanted additives of the pill will precipitate out of the water. The remaining cold water solvent will contain the desired dissolved opioids. Though this is generally true for all types of opioid containing pills, each substance contained within the pill may react differently.
Pill contents
Opioids
Opioid salts are very soluble, especially in near-freezing water, allowing for its dissolution into water and subsequent extraction from pressed tablets and capsules. The solubility of codeine is 9000 mg/L at 20 °C. This means that codeine will readily dissolve in room temperature and cold water. Codeine will begin to decompose at temperatures above 60°C[1], so hot or boiling water should not be used in this extraction. Other opioids have different breakdown temperatures so every extraction should be preformed with the specific opioid one is working with in mind.
Paracetamol
Paracetamol is soluble in water at room temperature, but much less soluble in water that is close to 0°C. Paracetamol has a solubility of 14,000 mg/L at 25 °C[2]. This high solubility level allows paracetamol to dissolve readily in room temperature water along with the desired codeine in the pills. With refrigeration and subsequent lowering of the water temperature to the near freezing temperature of ~0°C, the paracetamol waste product is then removed by filtration.
Ibuprofen
Ibuprofen is practically insoluble in water at room temperature, which allows for a very simple extraction process. Ibuprofen has a solubility of 21 mg/L at 25 °C[3]. This low solubility makes ibuprofen much less able to dissolve in water than codeine. The product is simply dissolved in warm water, mixed thoroughly with the codeine containing pills, then the aqueous layer containing the extracted codeine or other opioid/opiate is harvested. The ibuprofen waste product is then removed by filtration.
Toxicity of non-opioid painkiller products
Paracetamol
Paracetamol is also known as acetaminophen (and abbreviated as APAP) in the United States and is found in a variety of opioid and opiate-containing pills. It is known to be toxic to the liver at doses exceeding 4 grams per day.[4] It is accepted that overuse of paracetamol can result in liver failure and possible death. For this reason, it is essential that the paracetamol portion of the opioid/opiate containing product be removed before ingestion of recreational doses of opioids with high amounts of any over-the-counter or prescription painkiller products.
Ibuprofen
Ibuprofen is not as toxic to the liver as paracetamol and can be tolerated below 6g per day in healthy individuals; however, even at the commonly used perscription doses of 2,400mg - 3,200mg per day it can still cause gastrointestinal, renal, and liver toxicity in otherwise healthy adults [5]. Some individuals are susceptible to allergic-like reactions to low, moderate, and high doses of ibuprofen that can appear within days after taking it [6] Because of the risks, it is beneficial to remove the ibuprofen fraction before consumption of recreational doses of over-the-counter or prescription painkillers.
Required materials
- Desired quantity and variety of opioid painkiller product - It is very important to note down the exact chemical contents of the pill so the correct extraction technique can be performed. The procedure may vary depending on the opioid/opiate content of the pills.
- Thin mesh filter material such as a paper towel or a thin shirt. Cheesecloth has a larger mesh and cannot be used for this extraction.
- Syringe or dropper - This is needed to remove the opioid-containing layer of liquid from the solution.
- Several large glasses or containers (if one wishes to dry the extract)
- Water (Ideally filtered or distilled/de-ionized) - This is the solvent that will carry the desired opioid product.
- Freezer - This is needed to get the water and pill mixture down to suitable temperatures for extraction.
- Scientific thermometer - This is needed to make sure that the solution does not freeze in the freezer. An ideal temperature of just above freezing (~2°C) is needed for the paracetamol extraction.
Procedure
Removal of paracetamol
In this example, the starting material is a generic box of 32 tablets, each containing 8mg codeine phosphate and 500mg paracetamol. The resulting solution should be mostly clear and contains up to 256mg codeine phosphate with very little paracetamol and pill binders.
- The tablets are removed from the packaging and dissolved in as little warm water as possible to cover the pills.
- Once thoroughly dissolved a little extra cold water is added to the solution to reduce the temperature and increase the total volume. Please be aware that the more water that is used in the extraction process, the more paracetamol will remain in the final product. However, using too little water will make it very difficult to filter without a vacuum.
- The solution is stirred and placed in a freezer for about 30 minutes, which should be enough time to reach close to freezing point and for the paracetamol to begin to precipitate out of the solution visibly. The solution should be periodically checked with a scientific alcohol thermometer when in the freezer to make sure an optimal temperature is reached.
- Once a suitable temperature of 2°C is reached, the solution is quickly stirred and removed from the freezer before being poured through the filter of choice. It is advisable when working with such a large number of tablets to use multiple cup and filter set ups as to avoid clogging and speed up the process.
- Once the solution has passed through the filter the precipitate should be washed with a small amount of cold water to dissolve and harvest any codeine caught by the filter.
- If one wants to consume the entire solution immediately after extraction, one will just drink the opiate containing water. If one wants to dry the solution, a pyrex or glass drying tray is needed.
- The drying process may take several days, but the resulting extract can be scraped off of the pan with a knife or razor blade and weighed out and dosed in a more consistant fashion than drinking the solution right after extraction.
Refrigeration and filtration can be repeated if a clearer solution is desired, but this is usually unnecessary and wasteful, as each successive filtration will reduce the opioid content as it is absorbed by the filter material.
Removal of ibuprofen
The process for extracting opioids from products which also contain ibuprofen is much easier than that of paracetamol, but the products are usually more expensive per mg of codeine. The starting material in this example is a box of the popular brand Nurofen+, using 32 tablets each containing 12.8mg codeine phosphate and 200mg ibuprofen. It is not essential to use a freezer to cool the mixture, but it will certainly speed up the separation process and ensure that a minimal amount of ibuprofen is left in the final extract.
- The tablets are removed from the package and dropped into a small amount of warm water. Once the tablets have absorbed the water, they will swell up and can now be easily mixed with a fork. At this point, the product is ready for extraction.
- Add a minimal amount of cold water to the mixture and agitate to help dissolve the codeine.
- Leave the mixture to settle for about 30 minutes in the freezer.
- After cooling the mixutre, remove it from the freezer. The insoluble ibuprofen and binders will be the bottom layer of the container, and the aqueous codeine solution will be at the top of the container. A white skin may form above the aqueous layer; this skin is not toxic but can be removed with a spoon if preferred.
- Using a syringe or dropper, the aqueous layer is filtered and harvested into another container for drying or immediate use. The resulting solution will contain very little if any ibuprofen and pill binders along with up to 409.6mg codeine phosphate.
- If one wants to consume the entire solution immediately after extraction, one will just drink the opiate containing water. If one wants to dry the solution, a pyrex or glass drying tray is needed.
- The drying process may take several days, but the resulting extract can be scraped off of the pan with a knife or razor blade and weighed out and dosed in a more consistant fashion than drinking the solution right after extraction.
Comparison of available products
In the UK there are two opioids available over-the-counter at pharmacies; codeine and dihydrocodeine. There are many branded and generic preparations of each, but UK law requires that over-the-counter opioid painkiller products must contain little opioid content in comparison to the larger fraction of the non-steroidal anti-inflammatory drug (NSAID).
In the United States and other countries, there are opioid pills available with a multitude of different opioids mixed in with NSAIDs. These include but are not limited to hydrocodone, codeine and oxycodone.
Codeine and paracetamol (co-codamol)
In the UK, the cheapest and most available preparation is the generic pack consisting of 32 tablets, each containing 8mg codeine phosphate and 500mg paracetamol, usually available from neighborhood pharmacies. A single box of 32 tablets will contain 256mg codeine phosphate and a massively toxic 16g of paracetamol in total. Doctors can offer co-codamol containing 15mg or 30mg of codeine phosphate per pill along with 500mg paracetamol.[7]
There are several popular brands available in the UK which are priced higher but contain no extra codeine than their generic counterparts. There are also effervescent forms of the product, which are not desirable for extraction purposes due to the increased solubility of the paracetamol, and other contaminants included in high quantity such as sodium. It is important to know the exact chemical contents of the starting pills to use the correct extraction technique.
Codeine and ibuprofen
There are many preparations of codeine and ibuprofen available over the counter in the UK. Perhaps most well known is Nurofen+, which contains 12.8mg codeine phosphate and 200mg ibuprofen per tablet and comes in packs of 12, 24 and 32. The largest pack size can yield up to 409.6mg codeine phosphate and 6.4g ibuprofen.
There are generic versions available in some pharmacies, but these may have reduced codeine content and may not be much cheaper per mg.
Dihydrocodeine and paracetamol (co-dydramol)
Also available in the UK is the branded product Paramol in pack sizes of 12, 24 and 32 tablets, each containing 7.46mg dihydrocodeine tartrate and 500mg paracetamol. The largest pack size contains 238.72mg dihydrocodeine and 16g of paracetamol in total. Doctors can offer higher strengths; 10mg/20mg/30mg of dihydrocodeine, along with 500mg paracetamol.[8]
Oxycodone and various other NSAIDS
Oxycodone pills may be combined with ibuprofen[9], asprin, acetaminophen, or naltrexone under various brand names in the United States.
Legality
- United Kingdom: Please be aware that possession of codeine in its extracted form is illegal without a valid prescription. Pharmacies may only sell one box of any product containing codeine or dihydrocodeine per customer, and will likely question or refuse sale to any individual suspected of abusing the product.
- United States - All opioid containing pills are prescription only. Possession of prescription substances without a valid prescription is illegal.
See also
References
- ↑ Codeine, PubChem
- ↑ Acetaminophen, PubChem
- ↑ Ibuprofen, PubChem
- ↑ NIH, Liver Toxicity Sheet for Acetaminophen (Last updated 2018) | https://livertox.nih.gov/Acetaminophen.htm
- ↑ FDA Written submission to the NDAC meeting on risks of NSAIDs, August 2002 https://www.fda.gov/ohrms/dockets/ac/02/briefing/3882B2_06_International%20Ibuprofen%20Foundation.htm
- ↑ NIH Liver Toxicity Sheet for Ibuprofen https://livertox.nih.gov/Ibuprofen.htm
- ↑ Co-codamol for adults: painkiller containing paracetamol and codeine, 2018
- ↑ Co-dydramol: painkiller containing paracetamol and dihydrocodeine, 2018
- ↑ Sinatra, R. S., ed. (2009). Acute pain management. Cambridge University Press. ISBN 9780521874915.