Journal
ORGANIC PROCESS RESEARCH & DEVELOPMENT
Volume 22, Issue 11, Pages 1570-1577Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.oprd.8b00295
Keywords
Cl-2 Gas; DOPO-Cl; chlorination reaction; industrial upscaling; phosphonamidates; phosphonates
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Funding
- Swiss Science Foundation (SNF) [150638]
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Herein, we report the industrial synthesis procedure of phosphonamidate and phosphonate derivatives via an efficient and simple chlorination of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (DOPO) with Cl-2 gas. The key step in the synthesis is the conversion of the P-H bond to P-Cl of DOPO by flowing Cl-2 gas into a solution of DOPO in dichloromethane, affording the key intermediate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-chloride (DOPO-Cl) compound which is industrially not available. DOPO-Cl was isolated, characterized, and used for this synthesis of DOPO-based phosphonamidates and phosphonates in relatively high yield by reaction with the corresponding amines and alcohols, respectively. The experimental results show that the chlorination reaction occurs in equimolar ratios of Cl-2 gas to DOPO compound. Subsequently, the procedure developed in laboratory scale was industrially applied for synthesis of the 6,6'-(ethane-1,2-diylbis(azanediyl))bis(dibenzo [c,e] [1,2]oxaphosphinine-6-oxide) (EDA-DOPO) compound and 6-((1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octan-4-yl)methoxy)dibenzo [c,e][1,2]oxaphosphinine-6-oxide (DOPO-PEPA). All synthetic compounds thus obtained were characterized and found to be identical to the authentic laboratory scale products.
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