Organic Chemistry Reactions

The Baker-Venkataraman rearrangement transforms aromatic ortho-acyloxyketones to beta-diketones by basic treatment (catalysis). Beta-diketones are of great interest in the synthesis of chromones, flavones and coumarins. The most commonly used bases in the reaction are: KOH, potassium tert-butoxide, sodium in toluene, potassium hydride.

baker venkataraman 01

The Barton reaction produces 4-nitrosoalcohols [2] from nitrites [1] by irradiation with ultraviolet light.

 
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The Schiemann reaction consists of the thermal decomposition of aromatic diazonium tetrafluoroborates to yield the corresponding fluorinated derivative. Although diazonium salts are intestable, diazonium tetrafluoroborates have significant stability and can be prepared in good yield. Diazonium tetrafluoroborate is prepared from aromatic amines by the diazotization reaction.

 Balz Shiemann 01

Aldehydes and ketones [1] react with a,b -unsaturated [2] in the presence of tertiary amines that act as catalysts, to form a- hydroxyalkylated [3] .

 
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Tosylhydrazones [2] of aliphatic aldehydes or ketones [1] react with strong bases to give alkenes [3].

Bamford Stevens reaction

The Beckmann reaction produces the rearrangement of an oxime into an amide. This reaction is carried out in an acid medium.

beckmann transposition 01

The Barbier reaction makes it possible to obtain unstable organometallic reagents in the reaction medium. Initially it was carried out with Magnesium metal, generating magnesium in situ. Later it was extended to other metals: Sn, Zn..., being able to work in aqueous media, without requiring the protection of acid groups (hydroxyls).

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The Blanc reaction allows the chloromethylation of aromatic compounds.

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It uses as reagents methane with gaseous hydrogen chloride in the presence of a Lewis acid. The result is the introduction of a hydroxymethyl group on the aromatic ring (benzene) whose hydroxyl is replaced by chlorine in the presence of hydrogen chloride.

In 1989, G. Bartoli described the reaction of substituted nitroarenes with Grignard vinyl organometallics at low temperature, yielding substituted indoles after aqueous work-up. Three equivalents of magnesium are necessary, added to a cold nitroarene solution, which is stirred for twenty minutes, followed by the addition of saturated ammonium chloride solution and final extraction with ether. Better performance is obtained with indoles substituted in the ortho position to the nitro.
 
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Aldehydes, without alpha hydrogens, give the Cannizzaro reaction on treatment with a strong base (NaOH)

cannizzaro

In this reaction one molecule is reduced to alcohol, while the other is oxidized to carboxylic acid.