31238-54-7

Upstream product

• 1263914-08-4 N-(tert-butoxycarbonyl)-2-aminophenylphosphonic acid diethyl ester 

Downstream Products

• 31238-66-1 2-phenyl-2,3-dihydro-1H-benzo[1,3]azaphosphole 
• 126741-50-2 Bis(trimethylsilyl)-<2-bis(trimethylsilyl)amino>phenylphosphin 
• 130090-57-2 C₁₀H₁₉N₃P₂ 
• 130090-56-1 1,2,3-benzazadiphosphole 
• 124-40-3 dimethyl amine 
• 524745-31-1 Os(CO)11(2-aminophenylphosphine) 
• 524745-32-2 1,2-Os(CO)10(2-aminophenylphosphine)2 
• 126741-51-3 <2-Bis(trimethylsilyl)amino>phenyl-bis(trimethylsilylanilino)-methylen-phosphin 
• 126741-52-4 C₂₈H₄₂N₃PSi₃ 
• 126779-24-6 2-Anilino-1,3-benzazaphosphol 
• 31238-68-3 2-methyl-2-phenyl-2,3-dihydro-1H-benzo[1,3]azaphosphole 
• 67405-20-3 2-phenyl-1H-1,3-benzazaphosphole 

Relevant academic research and scientific papers

PC-N-Heterocycles: Synthesis of biaryl-type 1,3-benzazaphospholes with ortho-substituted phenyl or 2-heteroaryl groups

A facile synthesis of functionally substituted 2-(hetero)aryl 1,3-benzazaphospholes via nickel- or palladium-catalyzed phosphonylation of N-acyl-2-bromoanilides 1a-k with triethyl phosphite is presented. Anilidophosphonates 2a-g with naphthoyl-, o-substituted phenyl, furoyl- or thenoyl groups allow direct reductive cyclization with LiAlH4 to benzazaphospholes 3. The reaction of the o-bromoderivative 2d proceeds with concomitant replacement of bromine by hydrogen, whereas the electron-withdrawing pyridyl group of 2h prevents the synthesis of 3h by this short route. An alternative synthesis of 2-pyridylbenzazaphosphole 3hvia anilidophosphonates succeeded starting from Fmoc-anilinophosphonate 2kvia selective cleavage of the N-protecting group, reduction of the resulting phosphonoaniline to phosphinoaniline and cyclization with pyridine-2-carboxaldehyde via a dihydrobenzazaphosphole 8. N-Substituted pyridylmethylbenzazaphosphole 9 was detected as a side product. The structure elucidation of the new compounds is based on multinuclear NMR data and X-ray crystal structure analyses of a phosphonoanilide, underlining the dominance of N-H...OP hydrogen bonds over N-H...OC type hydrogen bonds, of 3h and a supramolecular associate of 3b and its unprecedented air oxidation product 10.

1H-1,3-benzazaphospholes: The organometallic route and a new three-step synthesis with reductive ring closure

Primary and N-secondary 2-phosphanylanilines were synthesized via metallation of 2-bromoanilines, coupling with CIP(NMe2)2, alcoholysis and reduction with LiAlH4, and subsequently reacted with formimidoester hydrochloride to give 1,3-benzazaphospholes. For 1H-1,3-benzazaphospholes, a shorter alternative three-step synthesis was developed, based on N-acylation of 2-bromoaniline, NiCl2-catalyzed arylation of triethyl phosphite and a new reductive cyclization of amidophosphonic acid ester with excess LiAlH4.