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A straightforward catalytic approach to obtain deuterated chloroform at room temperature
Magnetic Resonance in Chemistry ( IF 1.9 ) Pub Date : 2020-07-06 , DOI: 10.1002/mrc.5066
Angel Ruben Higuera-Padilla 1 , Flávio Vinícius Crizóstomo Kock 2, 3 , Alzir Azevedo Batista 3 , Luiz Alberto Colnago 1
Affiliation  

We report the catalytic activity for the complexes - cis-[RuCl2 (dppb)(bipy)] (A), and [η6 -(p-cymene)Ru (dppb)Cl]PF6 (B), wherein dppb = 1,4-bis (diphenylphosphine)butane, and bipy = 2,2'-bipyridine - for the synthesis of CDCl3 from CHCl3 using D2 O as deuterium source. H/D exchange reactions were performed using a chloroform/D2 O, 1:2 molar ratio, vigorously stirred, at room temperature. 1 mol of KOH was dissolved in D2 O fraction and catalytic complexes from 0.002 to 0.05 mmol were dissolved in chloroform. The H/D exchange reactions were monitored using 13 C NMR sequences without proton decoupling. The reaction using 0.01 mmol of compound A reached approximately 55% of H/D conversion in one hour. In the same time, the reactions with 0.002 mmol of compound A and without catalyst, show approximately 28% and 3% H/D exchange, respectively. Without the catalysts, the H/D exchange was only 12.0% in 5 hours. For compound B, 55% H/D conversion was observed in 1 hour, only when 0.05 mmol was used, which is much higher catalyst concentration. After the isolation of the chloroform fraction and two more addition of D2 O it was possible to obtain 95.0% H/D exchange in approximately 3 hours, using 0.01 mmol of the compound A. Therefore, compound A is an efficient catalyst for a rapid and straightforward synthesis of CDCl3 from CHCl3 at room temperature and using D2 O as deuterium source.

中文翻译:

在室温下获得氘代氯仿的直接催化方法

我们报告了复合物的催化活性 - cis-[RuCl2 (dppb)(bipy)] (A) 和 [η6 -(p-cymene)Ru (dppb)Cl]PF6 (B),其中 dppb = 1,4 -双(二苯基膦)丁烷和 bipy = 2,2'-联吡啶 - 用于使用 D2 O 作为氘源从 CHCl3 合成 CDCl3。H/D 交换反应使用氯仿/D2 O,1:2 摩尔比,剧烈搅拌,在室温下进行。将 1 mol KOH 溶解在 D2 O 馏分中,并将 0.002 至 0.05 mmol 的催化配合物溶解在氯仿中。使用 13 C NMR 序列监测 H/D 交换反应,无需质子去偶联。使用0.01 mmol化合物A的反应在一小时内达到约55%的H/D转化率。同时,与 0.002 mmol 化合物 A 和无催化剂的反应分别显示约 28% 和 3% 的 H/D 交换。在没有催化剂的情况下,H/D 交换在 5 小时内仅为 12.0%。对于化合物 B,在 1 小时内观察到 55% 的 H/D 转化率,仅当使用 0.05 毫摩尔时,这是更高的催化剂浓度。在分离氯仿馏分并再加入两次 D2 O 后,使用 0.01 mmol 化合物 A 可以在大约 3 小时内获得 95.0% 的 H/D 交换。因此,化合物 A 是一种有效的催化剂,可用于快速和在室温下从 CHCl3 直接合成 CDCl3,并使用 D2O 作为氘源。
更新日期:2020-07-06
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