5434-08-2

Upstream product

• 28272-96-0 2-vinylbenzaldehyde 
• 109-89-7 diethylamine 
• 1696-17-9 N,N-diethylbenzamide 
• 75-03-6 ethyl iodide 

Downstream Products

• 87768-49-8 C₁₃H₁₈⁽²⁾HNO 
• 139213-28-8 N,N-diethyl-2-[1-(trimethylsilyl)ethyl]benzamide 
• 721947-01-9 N,N-diethyl-2-formyl-6-(1-trimethylsilylethyl)benzamide 
• 721947-02-0 N,N,2-triethyl-6-formylbenzamide 
• 87768-45-4 N,N-diethyl-2-isopropylbenzamide 

Relevant academic research and scientific papers

Photochemistry of o-vinylbenzaldehyde: Formation of a ketene methide intermediate and its trapping with secondary amines

Irradiation of o-vinylbenzaldehyde (1) in the presence of primary and secondary amines results in N-H addition across the two chromophores of 1, to give o-ethylbenzamides 6. Photoreaction of deuterium-labeled aldehyde 15 with piperidine gave an amide (17)

(-)-Ephedrine as an auxiliary for the asymmetric synthesis of atropisomeric amides by dynamic resolution under thermodynamic control

N,N-Dialkyl-2-formylbenzamides and N,N-dialkyl-2-formyl-1-naphthamides condense with (-)-ephedrine in refluxing toluene to give oxazolidines both as single diastereoisomers with respect to the new stereogenic centre and as single conformers with respect t

Ortho-metalated aromatic tertiary amides: New synthetic applications

Ortho-lithio-cuprate species derived from aromatic tertiary amides exhibited a significantly larger field of application than the lithio precursor.

Photoreactivity of Conjugated Bichromophoric Molecules; Photoreaction of o-Vinylbenzaldehyde with Secondary Amines

Irradiation of o-vinylbenzaldehyde 8 in the presence of secondary amines 9 results in N-H addition across the two chromophores to give o-ethylbenzamides 6; photolysis of o-(2-dialkylaminoethyl)benzaldehydes 5a and 5b also affords 6 via photoexpulsion followed by recombination of the 8 and 9 which are formed.

The Tertiary Amide as an Effective Director of Ortho Lithiation

The tertiary amides N,N-diethylbenzamide (1) and N,N-diisopropylbenzamide (3) give the ortho-lithiated species 2 on treatment with sec-BuLi/TMEDA or n-BuLi/TMEDA, respectively, at -78 deg.Lithiation of 1 followed by rection with either methyl iodide, ethyl iodide, benzophenone, acetone, benzaldehyde, or trimethoxyborane-hydrogen peroxide gives the expected ortho substituted product.Intramolecular competition between the diethyloamido and chloro, methoxyl, sulfonamido, (dimethylamino)methyl, or oxazolino functions in ortho- and para-substituted benzamides establishes the tertiary amido group to be more effective in directing metalation than any noncarboxamide functional group under the prescribed conditions.Complimentarity of directing effects is observed with the chloro and methoxyl groups in the meta-substituted diethylbenzamides but not with the methyl group.The secondary amide is found to have a directing ability comparable to the tertiary amide with sec-BuLi/TMEDA at -78 deg in THF although the yields are low. 13C NMR chemical shifts are particularly useful for the structural assignments which are confirmed chemically by lactonization of some products.A labeling study with N,N-diisopropyl-2,6-dideuteriobenzamide suggests that lithiation of the ortho position of 3 is direct and not the result of rearrangement of an initially formed α-aza anion.Control of metalation at the ortho or benzylic position by proper selection of the organolithium base is illustrated for N,N-diisopropyl-p-toluamide.The value of the tertiary amide for control of ortho lithiations and regiospecific aromatic substitutions is noted.