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 Cl₂ gas. The key step in the synthesis is the conversion of the P–H bond to P–Cl of DOPO by flowing Cl₂ 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 Cl₂ 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 obtainedwere characterized and found to be identical to the authentic laboratory scale products.

中文翻译：

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使用Cl ₂气体作为氯化剂的DOPO基膦酰胺和膦酸酯衍生物的工业升级

在本文中，我们报告了通过Cl ₂气体对9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide（DOPO）进行有效而简单的氯化，从而合成了膦酰胺和膦酸酯衍生物的工业合成方法。合成中的关键步骤是通过使Cl ₂流动将P–H键转变为DOPO的P–Cl。将其通入DOPO的二氯甲烷溶液中，得到关键的中间体9,10-二氢-9-氧杂-10-磷菲基-10-氯化物（DOPO-Cl）化合物，该化合物在工业上无法获得。分离，表征DOPO-Cl，并通过分别与相应的胺和醇反应，以相对高的产率用于基于DOPO的膦酸酯和膦酸酯的合成。实验结果表明，氯化反应以Cl ₂气体与DOPO化合物的等摩尔比进行。随后，将实验室规模开发的方法工业化用于合成6,6'-（乙烷-1,2-二基双（氮杂二基））双（二苯并[ c，e] [1,2]氧杂膦-6-氧化物）（EDA-DOPO）化合物和6-（（1-氧化-2,6,7-三氧杂-1-磷酸双环[2.2.2]辛烷-4​​-基）甲氧基）二苯并[ c，e ] [1,2]氧杂膦-6氧化物（DOPO-PEPA）。对由此获得的所有合成化合物进行了表征，发现它们与真实的实验室规模的产品相同。