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Author: Subject: nitrosobenzene
Fery
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[*] posted on 27-7-2021 at 03:35
nitrosobenzene


I would like to prepare nitrosobenzene:
nitrobenzene + Zn + NH4Cl -> phenylhydroxylamine
phenylhydroxylamine + Na2Cr2O7 + H2SO4 -> nitrosobenzene

http://www.orgsyn.org/demo.aspx?prep=CV3P0668

this synthesis requires efficient cooling so I will postpone it to winter time when I can grab some snow outside (much better cooling material than crushed ice)
this compound is not stable so I will quickly use it for other syntheses:

[0]
Nitroso Diels Alder reaction with dienes (I will use sorbic acid, alternatively dicyclopentadiene which above 150 °C undergoes a retro-Diels–Alder reaction to cyclopentadiene), I found enough info here, they used cyclohexa-1,3-diene and similar derivates:
https://www.mdpi.com/1420-3049/25/3/563/htm
https://www.mdpi.com/1420-3049/25/3/563/pdf
https://www.mdpi.com/molecules/molecules-25-00563/article_de...

molecules-25-00563-sch001_sm.png - 16kB

[1]
Condensation with active methylene group (malonic acid ester, benzycyanide) - I did not find any useful info other than this abstract:
https://doi.org/10.1039/B503212C
I was unable to access the full article.
Did anyone perform such a condensation? Do you have any idea of the products of these condensations? Reaction conditions (solvent, catalyst etc)? I have dimethylmalonate, diethylmalonate, benzylcyanide in stock. Maybe there is no useful product of the condensation? Only guessing as I did not find anything although I tried to search for a long time. I found only something else where they condensed nitro group (not nitroso), but used sulfur as a reducing agent and the sulfur seemed to kick off also the CN group (maybe via production of -SCN ?), catalyzed by Fe3+
https://sci-hub.st/10.1002/ejoc.201701607
But the above article is something else than the condensation of nitrosobenzene with benzylcyanide.
Does anyone have any helpful info, any helpful idea? Producing nitrosobenzene itself as a last step could be only a curiosity, it is unstable. I would like to synthesize something else from it before it decomposes. It is still plenty of time untill winter comes here and brings the snow :)
edit: with malonic acid esters this article seems to be useful
https://www2.chemistry.msu.edu/faculty/wulff/myweb26/Literat...
I have also a lot of aldehydes upto C8, there are some reactions in the above article
I have also few kg of L-proline which is able to enantioselectively catalyze condensations
then also various ketones to condense with nitrosobenzene mentioned in the article :)
here article about nitrosobenzene + diethylmalonate:
https://www.journal.csj.jp/doi/pdf/10.1246/bcsj.36.870
but still nothing found about nitrosobenzene + benzylcyanide :(

[2]
I also found that nitrosobenzene+triphenylphosphine (1:1) could be used for Mitsunobu Esterification Reaction, but I do not expect to perform such esterifications:
https://sci-hub.st/10.1021/acsomega.8b03551

[Edited on 27-7-2021 by Fery]




If there is a heaven, it seems not to be materially based. Does chemistry exist there and if yes, how does it look like? Are there good souls well supplied with laboratory equipment, glass, chemicals and information?
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Triflic Acid
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[*] posted on 27-7-2021 at 06:15


For the condensation reaction, you seem to be talking about the ehrlich-sachs reaction. I've never done it before, but I've heard of it. The solvent is methanol and the base catalyst is generally potassium carbonate. Attached is a pdf for a prep.

Attachment: ehrlich-sachs.pdf (172kB)
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Fery
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[*] posted on 27-7-2021 at 07:32


Triflic Acid - thank you very much, that's it !!! :)



If there is a heaven, it seems not to be materially based. Does chemistry exist there and if yes, how does it look like? Are there good souls well supplied with laboratory equipment, glass, chemicals and information?
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