Mechanistic Investigations of Aluminum Nitrite Assisted Aryl Nitrile Synthesis through C(sp3)–C(sp2) Bond Cleavage of Aryl Ketones,The Journal of Physical Chemistry C

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Mechanistic Investigations of Aluminum Nitrite Assisted Aryl Nitrile Synthesis through C(sp3)–C(sp2) Bond Cleavage of Aryl Ketones
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2019-06-25 , DOI: 10.1021/acs.jpcc.9b02529
Dharitri Das ₁ , Pooja Jain ₁ , Sourav Pal _{1,

2} , Vidya Avasare ₃

Affiliation

The C(sp³)–C(sp²) bond activation reactions of 1-phenyl-2-propanone are facilitated by in situ generated Al(NO₂)₃ as an internal oxidant and the nitrogen source. The mechanistic investigations of formation of aryl nitrile from 1-phenyl-2-propanone are performed using density functional theory calculations at the CPCM/M06-2X/6-31G(d,p) level with the conductor-like polarizable continuum model. The mechanistic pathway involves C–H bond cleavage and Beckmann fragmentation as the key steps in the formation of phenyl nitrile, and it also supports that Al(NO₂)₃ is an active nitrite source instead of NaNO₂. The C–H bond cleavage is found to be the rate-determining step with a kinetic isotope effect of 1, which is also validated by the energetic span model. The computational investigations are in good agreement with experimental results.

中文翻译：

亚硝酸铝通过芳基酮的C（sp3）–C（sp2）键断裂裂解合成芳基腈的机理研究

原位生成的Al（NO ₂）₃作为内部氧化剂和氮源促进了1-苯基-2-丙酮的C（sp ³）–C（sp ²）键活化反应。使用密度泛函理论计算在CPCM / M06-2X / 6-31G（d，p）水平上使用类似导体的可极化连续体模型，对由1-苯基-2-丙酮形成芳基腈的机理进行了研究。机理途径涉及C–H键断裂和贝克曼断裂，这是形成苯腈的关键步骤，它也支持Al（NO ₂）₃是活性亚硝酸盐源而不是NaNO _2。。发现C–H键断裂是速率决定步骤，动力学同位素效应为1，这也通过高能跨度模型进行了验证。计算研究与实验结果非常吻合。

更新日期：2019-06-25

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