ISSN:
0009-2940
Keywords:
Phosphorus compounds, organic
;
Phosphorus heterocycles
;
Arbuzov rearrangement
;
Mechanism, SN2, SN1
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Addition Reactions of Phosphorus Nucleophiles to BenzothieteTrialkyl phosphites 4 add to the o-quinoid form 2 of benzothiete (1) to yield the phosphonates 6. An intermolecular migration of an alkyl group from oxygen to sulfur is the most important feature of this transformation. The rearrangement - related to the Arbuzov reaction - can be avoided in a two-step process by the subsequent action of PCl3 and alcohol; thus the phosphonates 10 are generated. Analogous to 2 → 6, dimethyl phenylphosphinate (11) furnishes 13. In contrast, the cyclic esters 14a-d form 2:1 adducts, namely the 12- to 15-membered heterocyclic compounds 17a - d. An intramolecular rearrangement in a 1:1 adduct is only observed for the 1,3,2-dioxaphosphepine 14e, a benzylic system which allows an SN1 process generating the 1,6,2-oxathiaphosphecine 18e. A similar rearrangement at a tertiary carbon center is prevented by the competitive addition of water (1 + 14f → 20).
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240221
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