60170-00-5Relevant articles and documents
Selective Synthesis of (Z)-Diazadiphosphafulvalene from 2,2′-bis-Azaphosphindole
Huang, Haiyang,Luo, Huiying,Tao, Guanyu,Cai, Weihua,Cao, Jing,Duan, Zheng,Mathey, Fran?ois
, p. 1027 - 1030 (2018)
The unprecedented 2,2′-bis(azaphosphindole) has been synthesized via a new route. Reaction with NaH afforded a dianion derivative 5, which is easily transformed to alkylated bis(azaphosphindole) or (Z)-P,P,N,N-cisoid diazadiphosphafulvalene. The reaction features good regioselectivity and high steroselectivity. Relatively strong fluorescence is observed with diazadiphosphafulvalenes. The X-ray crystal structure analysis showed that dianion ligand 5 is bonded to two Na atoms in a bridging cis-fashion, which allows the synthesis of diazadiphosphafulvalene in a highly stereoselective approach.
Synthesis of 1H-1,3-benzazaphospholes: Substituent influence and mechanistical aspects
Heinicke, Joachim,Gupta, Nidhi,Surana, Anushka,Peulecke, Normen,Witt, Brigitte,Steinhauser, Kinga,Bansal, Raj K,Jones, Peter G
, p. 9963 - 9972 (2007/10/03)
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.
