Oxaphospholane oxides

The reaction of diacetone alcohol 1 with alkyldichlorophosphines afforded 3-chloro-l,2-oxaphospholane-2-oxide 2. The latter undergo isomerization followed by dehydrochlorination to the corresponding 1,2-oxaphosphole derivatives 3 (Scheme 1) [29],... 

Secondary phosphines with a /3-hydroxyethyl substituent, obtained by addition of primary phosphines to a-oxides, easily undergo a reaction with ketones and aldehydes, giving 1,3-oxaphospholanes (6) [Eq. (4)] (72T2587). 

Die Reaktion wurde besonders auf 2-Organo-5-oxo-1,2A5-oxaphospholan-2-oxide ange-wendet. So erhalt man aus dem 2-Ethyl-Derivat und 180-markiertem Wasser (2-Carboxy-ethyl)-ethyl-phosphinsdure107 ... 

Phosphinsaure Ethyl-[2-(3-nitro-anilinocarbonyl)-ethyl]- E2, 141 (aus 5-Oxo-l, 2-oxaphospholan-2-oxid-Der. + Amin)... 

A /l -phosphane oxide was also obtained when oxaphospholane 1 rearranged to ylide 2 in the presence of a ketone and afforded an alkene. ... 

The interaction of a dialkyl hydrogenphosphonate with a 3-hydroxyalkanal to afford mixtures of diastereoisomers of the linear dialkyl (l,3-dihydroxyalkyl)phosphonate and derived 1,2-oxaphospholane 2-oxides has already been discussed. Lack of protection at appropriately sited hydroxy groups in carbohydrate molecules allows a similar reaction to occur. With D-erythrose, the 1 1 adduct is obtained as a mixture of epimers 324 (R, R = H, or OH) on acid-catalysed cyclization, these yield the phosphorus epimeric analogues of D-ribo and D-arabino-furanosides with phosphorus in the epimeric position 324 (R = H, R = OH) affords 325 as a mixture of the 2R, 35,4R, 5R and 25, 35,4R, 5R, forms in the ratio 2 1, and 324 (R = OH, R = H) also yields the phosphorus epimeric 321 in the same ratio ... 

Novel synthesis ofP-chiral 1,3-oxaphospholane 309 starting from optically pure propylene oxide was described. The structure was defined by X-ray crystallographic analysis (Scheme 104) [203]. 

Huang K, Emge TJ, Zhang X (2014) Synthesis of a novel F-chiral 1,3-oxaphospholane from optically pure propylene oxide. Heteroatom Chem 25 131-134... 

In 2003, Mitsubishi Chemical Corporation found that the cyclic phosphate 2-ethoxy-l,2-oxaphospholane 2-oxide (71) can be used as an additive in small quantities [98],... 

Phostonic acid (2-hydroxy-1,2 oxaphospholane 2-oxide), can be made from the ethyl ester which is obtained by heating diethyl-3-bromopropyl phosphonate (6.950). The six-membered ring oxy-phosphinane analogue (also called phostonic acid), can be made by a similar route commencing with diethyl bromobutylphosphonate. 

Polymer with the prevailing stmcture of poly(phosphine oxide) (poly-49 Mn = 3.9 x 10 ) was obtained in the cationic polymerization of 2-phenyl-1,2-oxaphospholane (49). Poly-49 was next reduced to the corresponding polyphosphine to confirm its stmcture. Stmcture 49 was also polymerized with chloro-and/or iodomethylated polystyrene, giving graft copolymers. 

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