It's so sweet of you
![Embarrassed :-[](https://thevespiary.org/talk/Smileys/default/embarrassed.gif)
...
And you did have me worried for a little while
since it seems the literature is scarce with examples of nitroalkane alpha-substitution (yay! ning learned more chemist jargon!)...
But then, ning found this:
Molecule:
What does this mean?? ("c1ccccc1CN(=O)=O.BrCCBr>>c1ccccc1C2(CC2)N(=O)=O")
Yield is only 18%, but still, it's something. And I can always handwave and say that poor yield is due to
ring strain...
Unfortunately, can't get the paper. Maybee someone else can?
Russian Journal of Organic Chemistry 1981, 1277
aka Zh. Org. Kh., p. 1435
And ning's hope was buoyed further by this paper:
JACS 1929, 2151, where they add a chloro compound to nitromethylbenzene with a yield of
82%.
Molecule:
Page 2151, NaOMe+NaOAc ("ClCCC(=O)c1ccccc1.c1ccccc1CN(=O)=O>>c1ccccc1C(N(=O)=O)CCC(=O)c1ccccc1")
A very wierd paper, actually. They ALSO perform a michael addition of the vinyl ketone version of that haloketone (like your idea), to give the exact same product.
Molecule:
Page 2151 ("C=CC(=O)c1ccccc1.c1ccccc1CN(=O)=O>>c1ccccc1C(N(=O)=O)CCC(=O)c1ccccc1")
Here is what they say:
"In the presence of alkaline reagents, phenylnitromethane combined with beta-chloropropiophenone to give the same saturated gamma-nitro-ketone as was obtained with phenyl vinyl ketone. Its structure was proved by formation of dibenzoylethane when a solution of the sodium derivative was decomposed with cold dilute hydrochloric acid.
...
The addition product with phenylnitromethane
gamma-nitro-gamma-phenylbutyrophenone:
Fifteen grams of beta-chloropropiophenone and 12 g. of fused potassium acetate were dissolved in 60 cc. of hot methyl alcohol. Then 12 g. of phenylnitromethane in 20 cc. of alcohol was added and the whole made faintly alkaline to litmus by admitting a 5% solution of sodium methylate(!), drop by drop. The reddish mixture was refluxed for 40 minutes, then acidified with acetic acid and poured into 120 cc. of cold water. After several hours, the precipitated addition product was filtered; the average yield of several precipitations was 82%--this was true only when the phenylnitromethane was redistilled.
...now the reaction with vinyl ketone...
To 3.8 g. of the ketone was add 10 cc. of absolute methyl alcohol; most of it immediately polymerized to a white, insoluble mass. The whole was warmed and the clear solution decanted from the polymer into a clean flask. Two grams of phenylnitromethane was added, then enough dilute sodium methylate to give an alkaline reaction to litmus, and the mixture warmed on the steam bath for fifteen minutes. It was next acidified with acetic acid; an oil separated and crystallized on cooling. This was purified as described above and identified as the same substance by a comparison of melting points, mixed melting points and solubilities."Two exciting points here: One, that it sounds like the substitution had a better yield than the Michael addition (that part about "decanting the liquid from polymers" didn't sound too good), and Two, that it is very likely that NaOMe is not necesary at all (enough was added to
give alkaline reaction to litmus??)--probably it was used because it was soluble in methanol, and they had lots of sodium lying around. Probably NaOH would do nicely.
Actually, upon reading in the org chem books, it seems that nitro and carbonyl groups are not so different. With carbonyls there is also a competition between attack on the carbonyl oxygen, and alpha substitution, right? How are they so different?
Anyway, if some bee could dig up that paper and post it, it would be real great.
Edit:
And of course, we should not ignore this fine post, made not many days ago, directly related to our topic, though going in reverse...
Post 475109
(Lego: "Amphetamines/PEAs w/o benzaldehyde or nitroethane", Novel Discourse) Lego, cool idea!