90929-07-0

Upstream product

• 113403-93-3 dimethyl 2-syn-phenyl-2-phosphabicyclo<2.2.2>oct-5-ene-7,8-dicarboxylate 
• 113403-96-6 2-phenyl-2-phosphabicyclo<2.2.2>octa-5,7-diene 

Downstream Products

• 118088-27-0 1,4,5-Trimethyl-1-phenyl-1,2,3,6-tetrahydro-phosphininium; iodide 
• 118088-29-2 4,5-Dimethyl-1-phenyl-1,2,3,6-tetrahydro-phosphinine 
• 118088-25-8 (1S,4R)-2-Phenyl-2-phospha-bicyclo[2.2.2]oct-5-ene 

Relevant academic research and scientific papers

Synthesis and NMR Spectral Properties of Phosphines in the 2-Phosphabicyclooct-5-ene and 2-Phosphabicycloocta-5,7-diene Systems

1,6-Dihydrophosphorin 1-oxides were synthesized by dehydration of 3-hydroxy-1,2,3,6-tetrahydrophosphorin 1-oxides; Diels-Alder reactions with maleic acid derivatives gave the 2-phosphabicyclooct-5-ene ring system, while reaction with dimethyl acetylenedicarboxylate gave the corresponding octa-5,7-diene system.The latter system was also approached by lead tetraacetate oxidation of a dicarboxylic acid in the oct-5-ene system.Removal of the phosphoryl oxygen required very gentle conditions with the dienes to prevent fragmentation.This was accomplished with trichlorosilane at -8 to 0 deg C.The dienic phosphines were stable at 0-25 deg C but lost the P-containing bridge at 30-50 deg C.The 31P NMR shifts of all compounds were normal and resembled monocyclic phosphorin models.This ring structure, either with one or two double bonds, therefore does not cause the strong deshielding so characteristicof the related 7-phosphanorbornene system.To interpret the 1H and 13C NMR spectra of the dienic phosphines, 2-D techniques were used.

THERMOLYSIS OF 2-PHOSPHABICYCLO(2.2.2)OCTA-5,7-DIENES: GENERATION AND TRAPPING OF P-METHYL- AND P-PHENYLPHOSPHAETHENE

P-Methyl- and P-phenylphosphaethene were generated in solution under very mild conditions in virtually quantitative yield by a thermally-induced extrusion of the phosphorus-containing bridge from appropriately substituted 2-phosphabicyclo(2.2.2)octa-5,7-dienes.The phosphaethenes so formed, the simplest yet produced by conventional methods, are trapped readily in (2+4) cycloadditions with conjugated dienes.

FRAGMENTATION REACTIONS OF BRIDGED HETEROCYCLIC PHOSPHORUS COMPOUNDS AS A SOURCE OF LOW-COORDINATION SPECIES

Several types of unsaturated, bridged structures have been prepared that can undergo retro-cycloaddition with the extrusion of phosphorus species having low coordination.By this technique, the species RO-PO2, R-PO2, R2N-P=S, RO-P=S, and R-P=CH2 have been