Double Perkow reaction. 1,3-Butadiene-2,3-diol bis(dialkyl phosphate)

Abstract

Notes net, was difficult. Only by repeated recrystallizations from alcohol under nitrogen ivas an analytically pure sample obtained. The oxazine was stable in the solid state, but was unstable in certain solutions (e.g., benzene or hexane), particularly in the presence of oxygen. No pure compounds have been isolated from this decomposition.Compound 2 wTas unreactive tow-ard NaBH4 and reacted only partially with LiAlH4 in pyridine or boiling alcoholic KOH. As expected, reaction with acid occurred readily. However, acid hydrolysis did not result in the expected regeneration of starting material. Instead, under a variety of conditions, the only substance isolated was a high molecular weight compound of complex structure.The evidence at hand does not allow a definite structure for this compound or a mechanism for its formation. However, the compound wras shown not to arise from diphenacylaniline, since, under the same conditions in which 2 was hydrolyzed (boiling acetic acid), diphenacylaniline reacted only partially and did not produce any of the hydrolysis product. The reactions of 2 will be the subject of future investigations.A Double Perkow Reaction. l,

The Chemistry of α-Haloketones and Their Utility in Heterocyclic Synthesis

“…Trialkyl phosphites (RO) 3 P are known to react with α-haloketones to yield 318 (Arbusov reaction) (Eq 11) [ 610 , 611 , 612 , 613 , 614 , 615 , 616 , 617 , 618 , 619 , 620 , 621 , 622 , 623 , 624 ]. …”

The Chemistry of α‐Haloketones and Their Utility in Heterocyclic Synthesis

“…Trialkyl phosphites (RO) 3 P are known to react with α-haloketones to yield 318 (Arbusov reaction) (Eq 11)[610][611][612][613][614][615][616][617][618][619][620][621][622][623][624].In general, the attack of phosphites can take place at four positions: (1) attack on the carbon atom carrying the halogen giving rise to an enol phosphate 319 or to a β-ketophosphonate 320; (2) attack on the carbonyl oxygen; (3) attack on the carbonyl carbon, giving rise to an epoxyphosphonate 321 or a vinyl phosphate 319; (4) attack on the halogen, furnishing the enol phosphate 319 (Scheme 92).…”