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Marc Brevoort

Why is the para product major in the nitrosation of phenol?

Cliff Curtis  Follow

Ortho and para positions are activated due to the +R effect of the $\ce{-OH}$ but the preference of the para product can be explained by the mechanism.

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The mechanism proceeds through a dienone. The ortho dienone intermediate will experience strain as $\ce{=O}$ annd$\ce{=NOH}$ lie in the same plane. Para nitrosated intermediate on the other hand is free from strain.


Reference: González-Mancebo S., Lacadena J., García-Alonso Y., Hernández-Benito J., Calle E., Casado J. Monatsh. Chem. 2002, 133 (2), 157-166. DOI: 10.1007/s706-002-8245-0.

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Guillaume Gaudin  Follow
-intermediate.More
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Iffat Ara Sharmeen  Follow
I feel this answer would be improved a lot by a drawing of the strained More
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Asif Makhdoomi  Follow

Due to steric hinderance and also there is some electronegativity of alcohol group due to induction it takes electron from sigma bond though not dominating therefore

These are the 2 reasons for more p- substitution

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Edward Njoro  Follow
Sources, please.More
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