84759-23-9

Basic information

• Product Name: Benzenamine, N-methyl-2-phosphino-
• CAS NO: 84759-23-9
• Molecular Formula: C7H10NP
• Molecular Weight: 139.137
• Mol File: 84759-23-9.mol

Chemical Properties

• CAS DataBase Reference: Benzenamine, N-methyl-2-phosphino-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzenamine, N-methyl-2-phosphino-(84759-23-9)
• EPA Substance Registry System: Benzenamine, N-methyl-2-phosphino-(84759-23-9)

Safety Data

• Hazardous Substances Data: 84759-23-9(Hazardous Substances Data)

Upstream product

• 10113-38-9 N-(2-bromophenyl)formamide 
• 615-36-1 2-bromoaniline 
• 84759-21-7 C₁₅H₃₁N₅P₂ 
• 344746-77-6 2-bromo-N-methylformanilide 
• 84759-22-8 N-methylaminobenzenephosphonous acid diethyl ester 

Downstream Products

• 1609396-91-9 N-methyl-2-isopropylphosphanylaniline 
• 1609397-01-4 N,P-diisopropyl-N-methyl-2-phosphanylaniline 

Relevant articles and documents

Syntheses of 2-unsubstituted 1h-1,3-benzazaphospholes from n-formyl-2-bromoanilides

The phosphonylation of 2-bromo-formylanilides 1 with triethyl phosphite in the presence of preformed Pd(0)(triethyl phosphite)n catalyst furnished 2-phosphono-formanilides 2 in good yields. Reduction with excess LiAlH4 provided mainl

Synthesis of 1H-1,3-benzazaphospholes: Substituent influence and mechanistical aspects

Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported.

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.

C-METALLIERUNG AN PHOSPHAAROMATEN-2-LITHIO-1-METHYL-1,3-BENZAAZAPHOSPHOL

1-Methyl-1,3-benzaazaphospholes are described; the 2H derivate and t-BuLi give the title compound, characterized by reaction with CO2 and Me3SiCl; NMR data confirm the results.