Premium
Synthesis of Symmetrical Bis‐(2‐chloro‐1,3,2‐benzodiazaphosphorinones) Hydrolysis and Fluorination of Selected Compounds
Author(s) -
Fei Zhaofu,
Thönnessen Holger,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 1999
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199910)625:10<1732::aid-zaac1732>3.0.co;2-o
Subject(s) - chemistry , triethylamine , amide , molecule , dichloromethane , crystal structure , diethyl ether , hydrolysis , chloroform , nuclear magnetic resonance spectroscopy , ether , medicinal chemistry , toluene , phosphorus trichloride , stereochemistry , crystallography , organic chemistry , solvent
The series of symmetrical bis‐amides 3 was formed by the reaction of N‐methylisatoic anhydride ( 1 ), with the diamines 2 . Reaction of 3 with phosphorus trichloride led to the formation of the symmetrical bis‐(1,3,2‐benzodiazaphosphorinones) ( 4 ). 4 c , 4 d and 4 e were easily hydrolyzed in moist air, leading to the formation of 5 c , 5 d and 5 e . In the presence of triethylamine, 4 c , 4 d and 4 e were allowed to react with Et 3 N · 3 HF to give the symmetrical bis‐P–F derivatives 6 c , 6 d and 6 e , which could be readily oxidized by (NH 2 ) 2 C(:O) · H 2 O 2 , leading to the formation of a series of P(:O)F compounds 7 c , 7 d and 7 e . All compounds were characterized unambiguously by 1 H, 13 C, 19 F, and 31 P‐NMR‐spectroscopy, mass spectrometry, and elemental analysis. All the bis‐amides and bis‐(1,3,2‐benzodiazaphosphorinones), except 4 b and 4 f , exist as single conformers in common solvents such as toluene, diethyl ether, dichloromethane or chloroform. For compound 6 c , a single crystal X‐ray structure analysis was conducted. The molecule displays crystallographic inversion symmetry.