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Author: Subject: NO2 + alkene ?
Protium
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NO2 + alkene ?

If one bubbled NO2 gas through an ether solution of 2-hexene, would one get 2-nitro-2-hexene ?

It just depends on how you look at it...
JohnWW
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Where would the unpaired electron go? Frankly, I have an idea it might promote the polymerization of the 2-hexene, iof anything. Nitration requires the formation of the NO2+ cation, which can be supplied by N2O5 or NO2ClO4 or (NO2)2SO4, so for it to happen with NO2 the unpaired electron would have to be somehow lost first.
Turel
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Reduction

If you want a 2-nitro-2-ene you need to use a mixture of NO and NO2 to induce a pseudonitrosite reaction, followed by reducing the pseudonitrosite to the 2-nitro-2-ene.

-T
Marvin
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NO2 gas with alkenes forms a mixture of the dinitro, the nitro nitrite and the dinitrite as well as traces of nitrate products.
Axt
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I've uploaded references refering to NO2 reactions <a href=http://rogue.altlist.com/banners/nitrogen_tetroxide_reactions.pdf>here (3.1MB)</a> and <a href=http://rogue.altlist.com/banners/n-oxide_reactions.zip>here (1.5MB)</a>, The second link was all scanned and provided to me by Bromic Acid. These reenforce what Turel/Marvin just said.

I don't think hexene is mentioned, there is mention of cyclohexene:

Quote: Cyclohexene (176) with dry nitrogen tetroxide in cold petroleum ether gave about a 25 per cent yield of the bisnitrosonitro derivative and oily products.

The "bisnitrosonitro" being dimerised pseudonitrosite, with the oily products being dinitro/nitronitrate (check my "pseudonitrosite" thread for confirmation on this) which should also reduce to its mononitro. Also check "1.jpg" in the second link for reduction of dinitrocyclooctane to mononitro.

BTW: The pseudonitrosite structure in the first link shows no peroxide bonding, contrary to what I've posted in the other thread, though no reference gives it with certainty. So its structure is still open for debate.
JohnWW
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What are your references? I got 859 search results for the search string: "nitrogen dioxide" alkene OR alkenes reaction. These yielded contradictory results. http://www.meta-synthesis.com/webbook/14_radical/radical.htm... suggests that polymerization of alkenes is a likely outcome. http://scholar.lib.vt.edu/theses/available/etd-09052003-1009... and the associated PDF http://scholar.lib.vt.edu/theses/available/etd-09052003-1009... says an aldehyde is produced. Of the results that could be accessed, not one seems to point to a conventional nitration or nitrosation by NO2. If O2 is present with NO2 in the dark, NO3 is formed, which reacts with alkenes to form a covalent nitrate with the unpaired electron on a carbon atom, according to http://www.atmosphere.mpg.de/enid/24z.html .
solo
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REf: Nitrosation and comments on Pseudonitrosites and it's uses

Here is an article that discusses nitrosastion and the the synthesis of Pseudonitrosites.....solo
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Pseudonitrosite Synthesis
by Pugsley

Introduction

As a teaser, I will mention a preview on an upcoming article on the pseudonitrosite synthesis of propenyl benzene essential oils. Now this one can be scaled up to industrial sizes, and it has the advantage of using nothing that you can't buy at the local hardware store and herbal supply houses. I will first demonstrate 4-MA synthesis, which is like roller-coaster ride on your rocking chair. 2,4,5 TMA and MDA are next targets with the method. Secrets will be revealed on how to turn the most horrible carcinogenic goo into beautiful while dimer crystals.

As another interesting teaser, I will say (and you can confirm this at a very good university library) that the first person to ever synthesize MDA was an Italian chemist named Angelli. If you go back to the fin de siecle and earlier in the Gazette Italia Chemie you will find some articles where Angelli was nitrosating all types of essential oils and then reducing the b-nitropropane derivative so that he could try to glean the structure of the nitroso compounds. Unfortunately, he died soon thereafter, but not before synthesizing all sorts of neat nitroso dimers with just about every type of propenyl-benzene essential oil. Thus the MDA was never ingested, but just used as a tool in figuring out the nitroso compound.

The Pseudonitrosite MDA Synthesis

Someone had asked for a synthesis for MDMA that required no watched chemicals. I can deliver a synthesis for the n-amino derivatives of propenyl benzene compounds that requires no chemicals beyond those that can be bought in hardware stores and herbal supply houses. Examples of such amines are MDA, TMA-2, and PMA (4-MA).

The synthesis is along the lines of the work done by late19th and early 20th century chemists such as Angeli, H. Wieland, V. Bruckner, and O Wallach. Angeli's work can be found in Italia Chemica Gazetta. However, most of the other articles are in J. Prakt. Chem. See Chemical Abstracts in the 1910-1940 era for specifics. Angeli's papers are referenced in the later articles. (Chem Berichte and Annallen Justes Liebigs contain some of the other authors' works)

By the way, Angelli was the first person to synthesize MDA using the pseudonitrosite method, way back in the 1890's, although he did not ingest the substance. (I believe that the credit is sometimes incorrectly given to Gordon Alles and other times to some German in the early part of the 20th century)

The synthesis depends on the remarkable properties of the magical PSEUDONITROSITES. These pseudonitronitrosites were studied for decades to discern their true structure, but you need only understand their properties and under what conditions they are formed. They can be more formerly referred to as nitroso-nitrite dimers.

Pseudonitrosites are formed when propenyl benzene compounds in aprotic solvents such as diethyl ether or ligroin react with N2O3 gas(NO and NO2 in equimolar amts) or nitrous acid. The nitrous acid reaction is carried out in a two phase stirred mixture, while the N203 is simply bubbled in.

Now, the first remarkable property of the pseudonitrosites is that they are insoluble in water, alcohol, and ether. That means that it is possible to take a bulk essential oil such as anise or calamus, and nitrosate it directly without first purifying it. The insolubility of the pseudonitrosite allows it to be easily washed of impurities and filtered out. Other ally benzene oils such as sassafras, nutmet, etc will have to be isomerized by refluxing or bomb with NaOH in alcohol to turn them into the propenyl benzene compounds.

(another reaction that was used at the turn of the century was the formation of blue-green nitroso-chloro dimers from essential oils by reaction with nitrosyl chloride in solvents. Again the dimers were insoluble, so they could be conveniently used to characterize essential oils)

The second property is that on treatment with Na2CO3 in alcohol, the pseudonitrosites turn from an insoluble white powder into the beautiful fluorescent yellow-green beta-nitro-propane derivatives. You only need then reduce the nitro group to get the n-amino end product.

The other secret to the synthesis is that the beta-nitro group can be reduced with aluminum foil like you find at the grocery store.

Finally, copius amounts of N2O3 can be formed by dipping steel wool in dilute nitric acid, made by common hardware store products.

Nitrosation

N2O3 Generation:

As I said, there are two major ways of nitrosating the essential oils. I will first describe the N2O3 method since it uses common hardware store chemicals.

First you need to find a reaction container. A jar capable of holding 16oz with a rubber stopper is suitable. The stopper has two holes: a small hole for sliding a straight length of coat-hanger (hook on end) up and down; and a larger hold for fitting a 1/4inch wide aluminum tubing. The tubing is several feet long and is used to deliver N2O3 to another reaction container. Prepare the reaction mixture by adding one pound of NaNO3 (stump remover from garden section of store) to a half gallon of water in a glass orange juice container. Will probably take a day to dissolve. When you are ready to make N2O3, put a half piece of "00" grade steel wool on the hooked end of the hanger. Add 4-8oz of NaNO3 solution to the reaction jar and pour a small amount of conc H2SO4 (drain cleaner) into the solution. Probably less than 1/2 oz is needed- be careful!!! Then pull the hanger up to the stopper and put the stopper on the reaction jar, being very careful that the steel wool doesn't touch the solution. Then when you are ready to create the N2O3, just gradually lower the hanger in to the solution, a little at a time.

Always carry this operation under some sort of hood or exhaust fan. NO2 is a very dangerous poison, causing chemical pneumonia in a few hours or more.

The Reaction:

The main reaction container is a large pyrex punch container that can be found in most stores. The aluminum tube from the N2O3 generator should be long enough to reach the bottom of the main reaction container. First a quantity of ether-hexane (starting fluid) needs to be chilled in a well sealed container in a freezer to well below 0C. Enough should be chilled to fill the main reaction container to an inch in depth. Then add 30g or so of essential oil. Then N203 is added from the generator in a ste ady fashion. Be careful- the first NO formed in the container reacts with O2, creating a vacuum that can suck ether-hexane-oil back into the generator. Thus wait until you are sure that gas is exiting the aluminum tube before you dip it down into the solution.

Then swirl the main reaction container as the gas is bubbling in, simultaneously lowering the hanger as neccessary to generate more gas as the steel wool is dissolved. In several minutes you will start to see a white to green-white precipitate or goo. Don't worry if all you get is goo. Next I show how to turn goo into nice crystals. After it appears the reaction is finished, either filter out the crystals, or if all you get is goo, drain out the unwanted solution as the goo will stick to the sides of the container, and then wash with water . If you get nice crystals, wash with water and then cool alcohol.

The Ungoo-ing:

Make certain the main reaction container has been rid of any ether and place it in a boiling water bath. Remember ether and nearby flames will be your death sentence. After a short period it will turn blue or green and start to bubble. Continue heating for several minutes after the bubbling starts. Some brown NO2 may be formed and is a good sign. Evidently this step increases yield by turning unreacted monomers in to the pseudonitrosite dimer. While its hot, add 4 oz or so of ethanol. White crystals of the pseudonitrosite dimer seperate out. Filter the hot mixture and wash the crystals with more ethanol.

The Nitrous Acid method:

If you can get NaNO2, you can add 50g to 16oz of water, and then pour the afformentioned ether-hexane-oil mixture in also to create a two phase mixture. Then gradually pour in small amounts of dilute H2SO4 (calculate the exact amount needed to react with the NaNO2 and don't add any more) while swirling the container. Alternatively, you can drop the H2SO4 in over several hours while stirring with a magnetic stirrer. Its not really clear whether either method has better yields overall, but it appears the N2O3 method works better with calamus oil/herb.

B-Nitro Conversion:

For sassafrass and anise oil process:

In a quart jar, add several grams of Na2Co3 (washing soda) and the absolute minimum amount of water to fully dissolve it. Then add enough ethanol to fill container to within inch of top. Then add 5-10g of the pseudonitrosite crystals. Let sit for several days. The pseudonitrosite crystals should slowly be digested with the solution becoming yellow. Then filter solution and add ice to chill to within freezing. Then add just enough HCl to make the solution slightly acidic. It should turn Day-glo yellow-green under a fluorescent light. If you're lucky, the beta-nitro compound will just crystalize out- then just filter and wash it. More than likely though, you will have to extract it with 1,1,1 trichloroethane (flux remover for electronics) and then let the solvent evaporate to get crystals. Recrystalization can be done in the minimum volume of boiling methanol ("Heat" auto gas treatment) that will dissolve the product. Then cool to get pure well formed crystals that can be filtered out.

For calamus:

Calamus is much easier to convert to the beta-nitro compound. Just take the crystals and add them to a dilute solution of NaOH (lye) in water. They instantly will turn bright yellow. Then filter and wash (possibly in dilute HCl).

Reduction:

Small pieces of foil are stuffed into a bottle with a few grams of mercury liquid. The bottle is then shaken for about 10 minutes and the aluminum will amalgamate with the mercury forming a greyish black mass with the more liquid portion coating the bottle like a mirror. (get mercury from electrical relays or from mineralogical supply store) Take 5g or so of the beta-nitro compound and add to 8oz of ethanol. Then add 1oz of HCl. Dump the amalgalm contents into the HCl-alcohol mixture. It should start bubbling and after 20 minutes to 1 hour the solution will go from yellow to clear. If it doesn't by the time the amalgalm is used up you need to make more. If the solution overheats, add an icecube. When the step is complete decant the solution from the jar, leaving the now liquid (again) mercury. The mercury can be reused by leaving it or a few days with conc HCl over top it in a bottle. When its needed again simply wash away the HCl and dry the mercury off with tissue paper. Take the solution and slowly add NaOH in water beyond the neutral point until the aluminum hydroxide gel that is formed breaks up. Then filter the solution and add water until the solution becomes cloudy. Extract with 1,1,1 TCE. You can also extract the filtrate. Evaporate the TCE-amine solution to get an oil which is then added to 2oz of acetone. Conc H2SO4 is added drop by drop to precipitate out the amine sulfate. Note that if you are storing the product, you will want to recrystalize it with methanol, since small amounts of H2SO4 remaining will ruin the product in a few weeks unless this is done.

I have not intentionally left out any steps or info, but some things may be missing since I recreated this from memory.

I hope this synthesis sheds more light on the sillyness of the war on drugs, considering that only ordinary hardware store chemicals and Aromatherapy type essential oils are used as reagents.

Taken along with the knowledge of trippy tryptamines being found in grass in most peoples backyards, I hope it is one more small tack to nail the coffin eventually some day.

I suggest the beginning alchemist try making PMA from anise oil. Anise oil is cheap ($18/16oz) and readily available. The end product will be PMA. Consult PIKHAL by Alexander Shulgin for dosage and effects. PMA has been described as toxic, but there is no conclusive evidence. It is suspected mainly to elevate blood pressure levels. I suggest making this compound only to perfect your skill with the synthesis. I would then try to make 2,4,5 TMA out of calamus oil. TMA has also successfully been made from a solution of calamus bulk root in ether-hexane (starting fluid). Calamus oil is much more expensive ($120 per 8oz)than anise oil but then you get a neat ultra trippy powerful product.

MDA, MMDA, or DMMDA (from parsley oil) would be the penultimate goal. However, the isomerization is a pain, and usually cheap essential oils (esp. sassafras) contain adulterants that will turn the alkali-alcohol-oil mixture into red-brown intractible gue while isomerizing. But with high quality oil it is definitely possible to directly isomerize sassafras oil without first distilling out the safrole. The isosafrole containing oil can then be handled like any of the other propenyl benzene type oils.

NOTE: Because these experiments were performed a decade ago, I can only give an approximate or qualitative description of the procedures. Still the competant chemist will have all the info he needs.

Have fun, Pugsley. (Wednesday contributed soapbox comments)

It's better to die on your feet, than live on your knees....Emiliano Zapata.

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