Nitrocyclohexane Synthesis Via double displacement reaction

Hi
so i have kind of new to organic chemistry
i am using ChemSketch
considering mixing 1 moles of Sodium nitrite with 1 moles of sodium cyclohexyl Sulfate, could we obtain Nitrocyclohexane in any way








[Edited on 28-3-2015 by nelsonB]

[Edited on 28-3-2015 by nelsonB]

[Edited on 28-3-2015 by nelsonB]

Quote: Originally posted by Etaoin Shrdlu

Hmmmm, I'm not as sure as you are that this is bunk. I thought one could make nitroalkanes by reaction of nitrite salts with haloalkanes. Wikipedia is indicating it works with alkyl sulfates as well but the source is in German and I can't tell how well (or if) it supports the conclusion. Walden, P. (1907). "Zur Darstellung aliphatischer Sulfocyanide, Cyanide und Nitrokörper". Berichte der deutschen chemischen Gesellschaft 40 (3): 3214–3217. doi:10.1002/cber.19070400383 Ignore the above, I forgot sulfate sticks hard to carbon on the C-S bond and it's the sulfonate esters that will leave nicely. I know for sure nitroalkanes can be synthesized using silver nitrite and alkyl iodides/bromides, which isn't too terribly far off from what what's being proposed. I don't know what kind of yields are possible; it's one of the steps in the Victor Meyer test to distinguish primary/secondary/tertiary alcohols and I'm not very familiar with it. Also, I think alkyl nitrites are produced as well depending on substrate. Probably not impossible with a better leaving group. [Edited on 3-28-2015 by Etaoin Shrdlu]

Quote: Originally posted by Etaoin Shrdlu

Apparently, sodium nitrite in DMF works great for bromocyclopentane, and great for bromocycloheptane, annnnnnd bromocyclohexane just gives cyclohexane as a product. Table 2.3, it's a page further. On a similarly surprising note, silver nitrite seems to work the best for primary alkyl halides, but for secondary and tertiary it's terrible and sodium nitrite works fine. Chemistry Gods, what have you been smoking? EDIT: Looks like a couple of the listed reactions might be catalyzed by sodium iodide. Too bad I really don't want the desired product around, or I'd try it. [Edited on 3-28-2015 by Etaoin Shrdlu]

Quote: Originally posted by mnick12

How good of a nucleophile is nitrite? Again pretty darn bad Also where is the negative charge on nitirite? If it did work you would not get the N-C bond you are looking for.

The nitrite ion is actually a relatively good nucleophile in aprotic media. Like most poorly polarizable nucleophiles it is a poor nucleophile in protic media, but becomes much more reactive in aprotic solvents.
The formal position of the negative charge is not the only factor that dictates the O- vs. N-alkylation selectivity. The localization of the charge is just a formality, an oversimplified model, that does not always properly represents real systems. In the case of the nitrite anion, both the electron pairs on oxygen and the one on the nitrogen can participate in the S_N2 substitutions. In principle, softer electrophiles tend to give more N-alkylation, but a lot also depends on the counterion and the solvent.


Synthesis of nitromethane and nitroethane from methyl and ethyl sulfates and NaNO2 is discussed in many threads. At least one thread describes a detailed experimental.