3583-02-6Relevant articles and documents
The Acceptor Properties of some Organophosphorus(V) Bromides
Deng, Robert M. K.,Dillon, Keith B.
, p. 1917 - 1920 (1984)
The acceptor properties of the organophosphorous(V) bromides PBr3(cat) (cat = benzene-1,2-diolate), PBr(cat)2, and PBr4Ph, and of the PBr3Ph(1+) cation, towards Lewis bases such as halide ions and uni- or bi-dentate pyridines have been investigated, mainl
Experiments towards the formation of 1,6-dehydroquadricyclane and density functional calculations on this and related molecules
Glueck-Walther, Susanne,Jarosch, Oliver,Szeimies, Guenter
, p. 493 - 500 (2007/10/03)
1,6-Dibromoquadricyclane (6) was obtained from norbornadiene (11) by hydroboration, oxidation of the diol 12 to the diketone 14 and its conversion into 2,6-dibromonorbornadiene (20) using tribromodioxaphosphole 16b followed by treatment of the mixture 17/18 with potassium tert-butoxide in DMSO and photocyclization of 20. Reaction of 6 with tBuLi (2 equiv.) led to the formation of 1-bromo-6-lithioquadricyclane 7, the NMR spectra of which were observed up to 0°C. 7 did not lose LiBr to give 4, but could be trapped with H2O and chlorotrimethylsilane to give 21e (53%) and 21f (64%). Reaction of 6 with fBuLi (> 4 equiv.) gave rise to 1,6-dilithioquadricyclane (21c), whose NMR spectra could also be recorded. 21c was converted into the corresponding 1,6-disubstituted quadricyclanes with D2O (87%), chlorotrimethylsilane (92%), dimethyl sulfate (55%), methyl chloroformate (45%), iodine monochloride (62%), and p-toluenesulfonyl chloride (48%). - Density functional calculations using the B3LYP/6-31G* level of theory showed that 1,6-dehydroquadricyclane (4) is a local energy minimum in its singlet electronic state. 4 contains a unique structure with 4 condensed cyclopropane units. The parent hydrocarbons 27 and 28, hitherto unknown, are also local energy minima in their singlet electronic states.
2-(2,2,3,3-TETRAFLUOROPROPOXY)-1,3,2-BENZODIOXAPHOSPHOLE IN REACTION WITH BROMINE
Ofitserov, E. N.,Mironov, V. F.,Sinyashina, T. N.,Gol'dfarb, E. I.,Konovalova, I. V.,Pudovik, A. N.
, p. 671 - 680 (2007/10/02)
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