Originally I had the idea of making this information into a website. But after reading articles about certain people being arrested for information they had posted on their websites in America by the way , I decided a text file would be better suited for information such as what you are about to read. My main reason for choosing to put this information in a text file is because I am pretty much allowed to say whatever I want. A website draws too much unwanted attention from very unrespectable American Bureaus. Let me cut to the chase. Basicly, this is a handbook that will explain to you exactly how to manufacture illegal drugs.
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I am a huge fan of the show and frequently watch it while working in the lab late at night. But season after season my thirst for technical analysis was left unquenched; I found a few articles that touched on the clandestine chemistry, but none were comprehensive.
After dedicating the last seven years of my life to organic chemistry, it felt like a natural departure from writing my dissertation to examine this matter more closely. Nagai Nagayoshi N-methylphenylpropanamine or methamphetamine was first synthesized from the naturally occurring alkaloid ephedrine by Japanese chemist Nagai Nagayoshi in while researching the structure of ephedrine . By the s stimulants became a regular part of the American routine, and a flourishing black-market in diverted pharmaceuticals soon developed.
This supply began to wither in the s as law enforcement prosecuted over-prescribing doctors and placed pressure on pharmaceutical companies to withdraw certain products. Many believe the first clandestine labs originated in the California bay area from this environment around . When it comes to making meth, the difference between cooking and synthesis should be acknowledged.
In the same manner anyone can learn how to cook a fancy meal, anyone can be taught to cook meth regardless of chemistry education—cooking meth may be just a little more explosive.
In fact, cooking meth can be extremely dangerous because a lack of chemical knowledge puts the cook and anyone else nearby at serious risk of injury. How would you even know? A skilled chemist like Walt understands the chemistry allowing him to alter or adapt the synthesis as necessary. In early episodes, Walt and Jessie produce methamphetamine using the Nagai method—the same synthetic route used by Nagai Nagayoshi in the first recorded methamphetamine synthesis. The Nagai method employs pseudoephedrine as a precursor, which is reduced with hydroiodic acid HI to yield methamphetamine.
The Nagai method is portrayed twice in the pilot episode S. As may now be obvious, the popularity of the Nagai method stems from the ease of obtaining the necessary chemicals. Pseudoephedrine is extracted via water or alcohol and coffee filters from OTC cold medicine. Red phosphorus needed to reduce elemental iodine I2 to HI and to recycle reformed I2 , is collected from matchbook striker pads or road flares.
Walt and Jessie use both as phosphorus sources at different times. I2 crystals can be extracted from readily accessible disinfectants. Once readied, pseudoephedrine, I2, and red phosphorus are placed in a boiling flask along with water and heated for varying lengths of time. The resulting deep purple solution, a result of I2, is a telltale sign of this reaction. Once complete the reaction is worked up.
How to prepare l2 from Iodine tinctures. In the pilot episode, Walt does this by making the solution basic and then extracting it with an organic solvent. His use of a plastic syringe to remove the organic solvent layer is typical of clandestine cooks—an easier alternative favored by legitimate chemists is a separatory funnel. By bubbling the HCI gas into the solution, the resulting d-methamphetamine is then precipitated as the HCl salt. A nucleophilic substitution reaction then occurs with an iodide anion.
Water is lost to give iodoephedrine, which then undergoes reductive dehalogenation by liberated H2 producing methamphetamine . To circumvent this, Walt decides on an alternate synthesis—reductive amination using P2P phenylacetone and methylamine. Obtaining methylamine required for this reaction—which is on the DEA watch list, a list of chemicals the DEA has classified as having use in drug manufacture—becomes a major plot line throughout the seasons.
In reductive amination, a ketone or aldehyde is condensed with an amine to form an imine or Schiff base intermediate, which is then reduced to an amine. In this case, P2P and methylamine are condensed forming the imine; this is then reduced by adding hydrogen to methamphetamine.
The steps can be performed in separate reactions or together one-pot. Although H2 is generated, the reduction actually involves an internal electrolytic process involving electron transfer from the metal that forms a radical carbon and subsequent hydrogen abstractions from solvent. Once complete, the reaction is worked up and product-obtained by vacuum distillation. A clandestine meth chemist using the pseudonym Loius Feech writes of his own experience with PtO2 spontaneously exploding in his lab  in his guide Large Scale Methamphetamine Manufacture.
PtO2 is a perfectly good reducing agent and was at one point common in clandestine methamphetamine labs . One of the listed items Jessie gets for Walt is hydrogen gas. Meanwhile clandestine operations became more complex, dangerous, and environmentally hazardous.
The resourceful clandestine chemists adopted several well-known methods to synthesize P2P . Thorium nitrate is used to generate thorium dioxide ThO2 , a radioactive metal oxide catalyst used in the relatively complex—though high yielding—gas phase reaction in a heated tube furnace.
In dehydrocarboxylation, two carboxylic acids are vaporized—in this case PAA and acetic acid—and passed through a catalyst bed enclosed by a heated tube furnace. These form the desired asymmetric ketone P2P , some undesirable symmetric ketones, acetone, dibenzylketone, and the side products CO2 and water.
The resulting crude brownish oil is collected. After separation from the aqueous water layer, the P2P is purified via vacuum distillation.
From the s to the mids, reductive amination was the method of choice for clandestine methamphetamine production. Enterprising biker gangs who dominated the trade at this time mostly ran these operations. Reductive amination is less common today. While ephedrine was the initial choice, additional controls led to greater use of pseudoephedrine.
Aside from limited short-term impacts, these legislative efforts failed to reduce availability of methamphetamine—the DEA Domestic Drug Seizure Statistics indicate meth availability may have even increased in recent years with 3, kgs confiscated in from 2, in While domestic large-scale clandestine labs have been impacted, small-scale less than two ounces labs have become increasingly common, representing 81 percent of seized domestic laboratories in .
These small-scale domestic labs only provide a minor portion of the current US meth supply—the majority originating in Mexican cartel operated super-labs [2,3]. Showing the scale of these operations, one bust of a Guadalajara based super-lab allegedly confiscated 15 tons of high purity methamphetamine . Phenylacetic acid.
The potency difference is due to a chemical phenomenon called chirality, not purity. On the other, reductive amination produces a racemic or mixture of d- and l-methamphetamine. This is because the planar P2P-methylamine imine is not chiral and hydrogen addition occurs equally from either side of the planar imine bond.
Enantiomers often have distinct biological effects. Despite being a common pedagogical illustration, the enantiomers of thalidomide interconvert in the body because of the acidic hydrogen at the chiral center. The enantiomers do not easily interconvert, because the chiral center of methamphetamine does not have acidic hydrogen. Crystallography is relatively easy and high yielding, and the resolving agent can be recycled, making it a green option.
We also know that Walt has professional experience in crystallography, further pointing to this method. In a crystallographic resolution, a diasteromeric crystal or complex is formed between a chiral acid like D-tartaric acid and the compound so they can be separated.
Unlike enantiomers, diastereomers have distinct physical properties that allow cooks to separate them using physical means like solubility. One chiral acid used to resolve methamphetamine is Di-p-toluoyl-tartaric acid . As the pure HCl salt, methamphetamine is a colorless-white crystalline solid.
Illicit methamphetamine exists in a number of colors, although colorless, white, and yellow are most common.
In the early days of clandestine production, a brown waxy product called peanut butter crank was common. Identity and quantity of impurities vary by synthesis. Profiling the impurities, an analytical chemist can often determine the method used to produce a sample. However, the analytical chemist should take care—P2P is actually produced as a side product in the Nagai reduction of pseudoephedrine .
A quick search of posts from the last few years of various online drug discussion forums shows that there has been many encounters of high quality crystalline blue meth. Surprisingly many of the law enforcement personal and reporters in Kansas City failed to make the connection to Breaking Bad.
Two news reports speculated the blue color might have been an ineffective attempt to fool the chemical reagent field tests, which give a blue color when tested positive for methamphetamine. It seems very unlikely that highly successful criminals would think dying their product blue would be sufficient to fool police detection efforts.
Another explanation was the blue color was a marketing technique—drug dealers do use a variety of methods to brand their products and colored drugs are not new. Similarly pink strawberry flavored cocaine has been encountered by the DEA , and methamphetamine has been available in a rainbow of colors and flavors .
The nature of the blue color was unfortunately not determined but speculated to be an additive dye. Attesting to the power of entertainment, Mexican drug cartels are believed to be responsible for these samples . From pronunciation of complex chemicals to the appearance of specific reactions, they get it right—Bryan Cranston pronounces chemical names better than some graduate students I know. Donna Nelson from University of Oklahoma. Details are sometimes overlooked, like condensers not being connected to a water source and the order of synthesis steps sometimes being wrong.
The industrial scale crystallization technique shown is unfamiliar to me, but my synthesis experiences are on the relatively small scale. With the final episodes starting, I hope that Breaking Bad continues to set a new standard in narco-entertainment.
Sources 1. Nagai N. Studies on the components of Ephedraceae in herb medicine. Yakugaku Zasshi ;— 2. Owen F. National Drug Threat Assessment. Journal of Organometallic Chemistry. Ogata A. Uncle Fester. Secrets of Methamphetamine Manufacture 7th Edition.
Loompanics Unlimited. Freeh L. Large-Scale Methamphetamine Manufacture. Allen A.
The Clandestine Chemist's Notebook
I am a huge fan of the show and frequently watch it while working in the lab late at night. But season after season my thirst for technical analysis was left unquenched; I found a few articles that touched on the clandestine chemistry, but none were comprehensive. After dedicating the last seven years of my life to organic chemistry, it felt like a natural departure from writing my dissertation to examine this matter more closely. Nagai Nagayoshi N-methylphenylpropanamine or methamphetamine was first synthesized from the naturally occurring alkaloid ephedrine by Japanese chemist Nagai Nagayoshi in while researching the structure of ephedrine . By the s stimulants became a regular part of the American routine, and a flourishing black-market in diverted pharmaceuticals soon developed. This supply began to wither in the s as law enforcement prosecuted over-prescribing doctors and placed pressure on pharmaceutical companies to withdraw certain products.
A Comprehensive Guide to the Clandestine Chemistry of 'Breaking Bad'
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