109902-33-2

Upstream product

• 6298-19-7 2-chloro-3-aminopyridine 
• 3282-30-2 pivaloyl chloride 
• 24331-71-3 N,N-dimethylpivalamide 

Downstream Products

• 131653-73-1 2-chloro-4-phenyl-3-pivaloylaminopyridine 
• 142643-45-6 2-<2-(4-phenyl-3-pivaloylamino)pyridyl>quinoline 
• 143621-35-6 3-aminopyridine-2-carboxaldehyde thiosemicarbazone 
• 209798-44-7 2-styryl-3-pivaloylamidopyridine 

Relevant academic research and scientific papers

3H-1,3-Azaphospholo[4,5-b]pyridines-novel heterocyclic P,N-bridging or hybrid ligands: Synthesis and first d8-transition metal complexes

The first 3H-1,3-azaphospholo-pyridines 2a-c were synthesized as racemic mixtures in modest to medium yield by the reaction of N-(2-chloropyrid-3-yl)-trimethylacetimidoyl chloride 1 with RPLi2 (R = Ph, n-Bu, i-Bu), generated from RPH2/sub

Sulphuric acid immobilized on silica gel (H2SO4-SiO2) as an eco-friendly catalyst for transamidation

A novel method of transamidation of carboxamides with amines by using catalytic amounts of H2SO4-SiO2 has been developed under solvent free conditions. The transamidation is compatible with a wide range of aromatic, heteroaromatic, aliphatic, cyclic/acyclic primary or secondary amines. The metal/solvent-free conditions represent a significant improvement over other existing methods as the reaction can be performed in open air conditions and no column purification is required. The versatility of this methodology was further demonstrated by synthesizing the commercially available drug procainamide.

Synthesis of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP)

Palladium-catalyzed cross-coupling of methylboronic acid with 2-chloro- 3-nitropyridine produced 2-methyl-3-nitropyridine 4 in one step in high yield. Oxidation of 4 with selenium dioxide gave aldehyde 5. Alternatively, condensation of 4 with DMFDMA followed by oxidation gave 5 in a two step higher yielding conversion. Subsequent direct coupling of 5 with thiosemicarbazide followed by reduction of the nitro group using stannous chloride or sodium sulfide provided 3-AP (3). Reduction with sodium hydrosulfite gave 3-HAP (8). Finally a route which avoids the reduction of a nitro function was devised. Thus direct coupling of styrene with 2-chloro-3- aminopyridine 9 under Heck reaction conditions gave 16 which was converted to 17, oxidized to the aldehyde 18 and converted to 3-AP (3) with in situ deblocking of the t-Boc functionality.

Synthesis of ortho-substituted aminopyridines. Metalation of pivaloylamino derivatives

The three isomeric pivaloylaminopyridines were lithiated in more than 80% yields. Aminopyridine derivatives were treated by 2.5-3 equivalents of the complex BuLi-TMEDA at -10° in diethyl ether. Reaction of the lithiated species with various electrophiles afforded a number of ortho-substituted pivaloylaminopyridines in good yields. Secondary pyridine alcohols were oxidized to the corresponding aminopyridyl ketones. Pyridopyrimidines, benzonaphthyridines as well as an analogue of the natural antitumor alkaloid ellipticine has been synthesized showing the versatility of the method.