Reactions of p-nitrobenzyl halides with dialkyl phosphite anions in dimethyl sulfoxide
✍ Scribed by Glen A. Russell; Jong Uk Rhee; Woonphil Baik
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 173 KB
- Volume
- 9
- Category
- Article
- ISSN
- 1042-7163
No coin nor oath required. For personal study only.
✦ Synopsis
The reactions of p-O 2 NC 6 H 4 CH 2 Cl with (RO) 2 PO מ in Me 2 SO with R ס Me, Et, Pr, Bu, CF 3 CH 2 , i-Pr or Ph involve the formation of p-O 2 NC 6 H 4 CH 2 P(O)(OR) 2 by S N 2 substitution followed by a further S RN 1 p-nitrobenzylation of p-O 2 NC 6 H 4 CH[P(O)(OR) 2 ] מ and p-O 2 NC 6 H 4 C(CH 2 C 6 H 4 NO 2 -p)[P(O)(OR) 2 ] מ . With p-O 2 NC 6 H 4 CH 2 Br, the reactions proceed mainly to form , which undergoes reaction with p-מ p-O NC H CH 2 6 4 2 O 2 NC 6 H 4 CH 2 Br to form p-O 2 NC 6 H 4 CH 2 CH 2 C 6 H 4 NO 2p. Halophilic reaction of (RO) 2 PO מ with p-O 2 NC 6 H 4 CH(CH 3 )X (X ס Cl, Br) leading to the bibenzyl is the preferred reaction course. Reactions of (RO) 2 PO מ or p-O 2 NC 6 H 4 CH[P(O)(OR) 2 ] מ with p-O 2 NC 6 H 4 CH 2 X in Me 2 SO do not form significant amounts of p-O 2 NC 6 H 4 CHX מ that would yield p-O 2 NC 6 H 4 CHסCHC 6 H 4 NO 2 -p. However, p-Cl-C 6 H 4 CH[P(O)(OEt) 2 ] מ readily abstracts the benzylic proton from p-O 2 NC 6 H 4 CH 2 X to form the stilbene, although p-O 2 NC 6 H 4 CH 2 Br reacts with p-O 2 NC 6 H 4 -CH[P(O)(OR) 2 ] מ to form p-O 2 NC 6 H 4 CH(CH 2 C 6 -Dedicated to Prof. William McEwen on the occasion of his seventy-fifth birthday.