Sauron
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CC and DMF - Two Distinct Adducts
Many of us are familiar with the equimolar solid adduct of cyanuric chloride and DMF that forms at ambient temperature and is so useful for near
quantitative, rapid chlorinations of alcohols.
This reaction was actually disovered by H.Gold in 1960 and published in Angew.Chem 72, 956.
The article goes on to describe Gold's Reagent, formed by reaction of CC with 6 mols DMF at higher temperature.
As is clear from structure, the product is formed from two mols of DMG and one of the repeating units of CC which is a trimer. Thus one mol CC * 6
mols DMF -> 3 mols product + some CO2. Yield is very high.
Translated Abstract:
Cyanuric chloride reacts at room temprature with dimethylformamide to form an addition compound of the Vilsmeier Haak type. In the course of further
reaction with dimethylformamide this addition compound forms 3 moles of the hither to unknown 3-methyl-amino-2-azaprop-2-en-1-ylidenedimethylammonium
chloride ,3moles Co2being eliminated and the triazine ring being split. The compound formed is to be interpreted as an azaisolog of the
N-methyl-2[-dimethylaminovinyl]-formiminemetho-jodide first prepared by W.T. Simpson. It was possible to secure the constitution of this salt by
means of splitting reactions and independent syntheses as well as by UV and IR spectra. Cyanuric chloride reacts with other formyl compounds of
secondary amines in an analogous way.
The aminoazapropenylidene ammonium salts obtained in this way are suitable intermediate products for synthesizing triazoles or triazines from
monosubstituted hydrazines or amidines by means of combination with ;e.g. 2-phenyl-1,3,5-triazine from benzamidine.
.
I have requested this article, but while we are waiting here is a followon from J.Org.Chem, in English, which sheds some light on the preparation and
chemistry of this second, higher MW product.
[Edited on 16-4-2007 by Sauron]
Attachment: jo01310a058[1].pdf (412kB)
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Sauron
International Hazard
Posts: 5351
Registered: 22-12-2006
Location: Barad-Dur, Mordor
Member Is Offline
Mood: metastable
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STRUCTURE:
Apologies for double post all around.
[Edited on 17-4-2007 by Sauron]
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