β-Nitrostyrenes can be used for many things. Such as making speed, meth and ectsasy. Yup, this one is for you, dear reader who came here via Google. Rougly 40 % of you search for “how to make speed” or something very similar, say my Analtyics data. So, feel most welcome, dear underground Sirs and Madams. (I give you what you want, not necessarily what you need.)

The most common route to β-nitrostyrenes has to be the Henry reaction, which is a classic variation of the Knoevenagel condensation, using aldehydes and nitroalkanes. Nitroethane and unsubstituted benzaldehyde give an intermediate that upon reduction yields amphetamine. Fans of PIHKAL and half-decent organic chemists know this story by heart already.

Correct me if I am wrong, but I do not think anybody in the community knows yet how to add straight ammonia to unactivated double bonds, which is why we have to resort to tricks like this to stitch carbons and nitogens together.

A curious reagent big-dog Alexander Shulgin sometimes used (uses?) to directly nitrate double bonds was tetranitromethane. A lovely little molecule that contains more oxygen per volume than liquid oxygen itself. It is known to go KA-BA-DANG if used improperly. I bet most of us would not touch it even for big chunks of cash. The byproduct, if everything goes according to plans, is nitroform, whose anion is aromatic (sic!), and whose salts are more or less unstable. Avoid.

Considering everything, my immediate thought as I saw this recent paper…

Nitration with ferric nitrate and TEMPO
J. Org. Chem. 2013, 78, 5949-5954 (DOI: 10.1021/jo400598p)

… was: “I wonder if Jesse Pinkman reads the primary literature?” Check out for instance compound 4r in the following table… mhmm. There you go. The E:Z ratio is pretty irrelevant if your plan is to later hydrogenate the hell of out it.

Nitrostyrenes

You know what I think? I think the underground has a new toy. Ferric nitrate.

P.S. It should be noted that a very similar reaction was reported simultaneously by the same group in a different journal. (Go h-index!)

Nitration with TEMPO and t-BuONO
Org. Lett. 2013, Article ASAP (DOI: 10.1021/ol401426p)

The funny thing herein is that the nitrating agent is instead tert-butylnitrite, better known to gays and non-scholars as poppers. Peace out.

 

8 Responses to The price for ferric nitrate just went up a bit

  1. DangerousBill says:

    Oh, great. I use ferric nitrate for etching silver, and now I’ll have the DEA on my butt whenever I drop around to the chemical supplier. (Who might stop selling it, for all I know.) Or I’ll have to compete with crank crafters for every resupply. Or the cartels will come after me for my half-pound stock of Fe nitrate. Is nothing sacred, not even silversmithing?

  2. Jordan says:

    Correction: Isobutyl nitrite is used in poppers

    • drfreddy says:

      Not necessarily. It could be almost any small and volatile alkyl nitrite. They all get the job done. If one is banned, then another one is soon commercially available. And I’m not talking about stuff from the Sigma-Aldrich catalog.

  3. Acme Rocket says:

    It would appear those who read the chemical synthesis literature fall into two categories. One group searches the literature to understand the latest advances in the field and further their own research interests. The other group always asks the question, “Does this reaction lower my start-up costs and/or reduce my legal risk for a clandestine pilot plant?”

    I’m glad I’m not alone. Now if someone could just take it all the way from styrene in one pot I might just a new career.

  4. Winston says:

    Look into the loading of this salt into various clays, then Microwave.

  5. Jesse says:

    Nice post! How come the E/Z ratio doesn’t matter if you’re going to hydrogenate it? Doesn’t that yield 7:1 D:L?

    Another question: hypothetically, if you were to reduce only the C=C with NaBH4 and subsequently use Al/Hg for the NO2, would this yield different D:L ratio?

    Sorry my english not so good

    • drfreddy says:

      The ratio does not matter since both E and Z are achiral starting materials. You can not get a chiral product out of achiral starting materials. You would have to employ a chiral ligand or something during say a hydrogenation. Chirality can not pop out of nowhere.

      The answer to your second question is the same, for the same reason: racemic product.

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