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Phosphene

Three- and four-membered ring molecules of nitrogen and phosphorus are investigated (Scheme 32) [80]. The unsaturated four-membered ring molecule, tetracyclo-phosphene 79 is less strained than the saturated molecule, tetracyclophosphane 15... [Pg.286]

Note Added in Proof This is nicely illustrated by the landmark publication of Protasiewicz et al. [94] who describe derivative (122), the first conjugated polymers featuring phosphorus-phosphorus multiple bonds (Scheme 33). The di-phosphene-PPV (122) exhibits an extended 71-conjugated system as shown by the optical HOMO-LUMO gap that is close to that of related PPV [94]. [Pg.159]

Figure 10.3. d Arsonval and colleagues showing the apparatus used to induce visual phosphenes. This photo was taken in 1911. [Pg.177]

The overall reaction is reminiscent of the Wolff rearrangement of a-diazo carbonyl compounds which gives ketenes. Compounds 6 formally represent their phosphorus analogues and are sometimes also designated as phosphenes 11... [Pg.77]

As a proven technique for detecting reactive intermediates, flash pyrolysis seems to be the method of choice for direct detection or isolation of phosphenes. The result of thermal decomposition of (a-diazobenzyl)diphenylphosphine oxide (7) was nevertheless disappointing, since only triphenylmethane (75), fluorene (14), and benzophenone (75) but not the desired methyleneoxophosphorane 9 could be isolated 12). [Pg.77]

Table 1. Insertion reaction and phosphene rearrangement of diarylphosphorylcarbenes (8)... Table 1. Insertion reaction and phosphene rearrangement of diarylphosphorylcarbenes (8)...
Table 2. Insertion reaction, phosphene and ketene rearrangements of phosphorylacylcarbenes (37)... Table 2. Insertion reaction, phosphene and ketene rearrangements of phosphorylacylcarbenes (37)...
Photolysis of the first known cyclic a-diazo-p-oxophosphine oxide 49 is unsuccessful with regard to phosphene formation. There is no evidence for a P/C-phenyl shift, which should lead to 51, nor for a P/C-alkyl shift, which would afford 52 via ring contraction, since none of the expected phosphinic esters could be isolated in methanolM). [Pg.86]

Trapping reactions of benzoylmethyleneoxophosphorane 39 a with carbonyl compounds dispel any remaining doubts as to the existence of acylated phosphenes. Unlike the diphenylmethyleneoxophosphorane 9, whose P/C double bond participates in cycloadditions, compound 39 a acts as a hetero-1,3-diene and undergoes [4 + 2]-cycloaddition with aldehydes and ketones 10 I7,35> it may again be assumed that the reaction is a two-step process involving 55 as intermediate. [Pg.86]

If, on the other hand, unsymmetrically substituted carbonyl compounds such as monosubstituted benzophenones (X = OCH3, CH3, Cl), tert-butyl methyl ketone, acetophenone, acetaldehyde, or benzaldehyde are used for trapping 39a, diastere-omeric mixtures are formed in each case they could all be resolved except for the products obtained with p-methoxybenzophenone and acetophenone 33>. An X-ray structure analysis has been performed for the E-isomer 57g 36) which, in conjunction with H-NMR studies, permitted structural assignment in cases 56 and 57e, g and h35>. Additional chemical evidence for the structure of the six-membered heterocycles is provided by the thermolysis of 56 a considered in another context (see Sect. 3.1). In general the reaction 39a- 56 or 57 is accompanied by formation of phosphene dimers, presumably via [4 + 4]- and via [4 + 2]-cycloaddition 35). [Pg.86]

The recently synthesized phosphatriazolo[l,5- ]pyridines 4 can also participate in reactions involving the ring opening of the five-membered ring <1995ZNB558>. When the unsubstituted phospha-heterocycle is treated with aqueous acetonitrile, a hydrolysis occurs and the open-chained phosphenic amide 47 can be obtained in acceptable yield (Scheme 13). [Pg.652]

The experimental first-order decay rate for pentachlorobenzene in an aqueous solution containing a nonionic surfactant micelle (Brij 58, a polyoxyethylene cetyl ether) and illuminated by a photoreactor equipped with 253.7-nm monochromatic UV lamp is 1.47 x lO Vsec. The corresponding half-life is 47 sec. Photoproducts reported include all tetra-, tri-, and dichlorobenzenes, chlorobenzene, benzene, phenol, hydrogen, and chloride ions (Chu and Jafvert, 1994). Chemical/Physical. Emits toxic chlorinated acids and phosphene when incinerated (Sittig,... [Pg.915]

Various transition metal catalysts, including those based on Rh, Pt, Pd, Co, and Ti, have been bound to polymer supports—mainly through the phosphenation reaction described by Eq. 9-65 for polystyrene but also including other polymers, such as silica and cellulose, and also through other reactions (e.g., alkylation of titanocene by chloromethylated polystyrene). Transition-metal polymer catalysts have been studied in hydrogenation, hydroformylation, and hydrosilation reactions [Chauvin et al., 1977 Mathur et al., 1980]. [Pg.769]

An extensive theoretical investigation does not exist for the siloles, but PM3 calculations of formation enthalpies of 2 and its tautomers have indicated that the l//-silole is the most thermodynamically stable species200. The activation barrier for 11 — 2 isomerization was calculated to be 96 kJ moC1, comparable to that for cyclopentadiene2d 116. The (1H + 1H) dimer 1019 is isolated rather than the (2H + 1H) dimer as in the case of phosphole. This directly confirms the thermodynamic stability and the Diels-Alder kinetic instability of 2. The marked difference in the stability of the parent silole and phosphole was explained3 by the relative stabilities of the a bonds in silanes and phosphines (Si > P) and of the ji bonds in silenes and phosphenes (P > Si)117. [Pg.1998]

The same procedure, somewhat simplified, was then employed to study the effects of perceptual concentration over a longer period of time. Although many of the phenomena that resulted seemed readily explainable on the basis of afterimages, autokinetic movement, phosphenes, and the like, certain data did not seem adequately accounted for by reference to familiar perceptual phenomena or by the use of such theoretical explanatory concepts as are currently available, e.g., suggestion or projection. Additional hypotheses seem necessary, and it is the purpose of this paper to present these data and the postulates derived from them. [Pg.297]

The strategy was perfectly sound from the thermodynamic viewpoint, but the product is in fact a mixture of cyclic oligomers of the phosphene PPh ... [Pg.386]

I hosphazirconoccnc, preparation, 4, 819-820 Phosphenes, with tungsten carbonyls and isocyanides,... [Pg.168]

TABLE 4. 119Sn NMR data of stanna-alkenes, germanes and phosphenes... [Pg.413]


See other pages where Phosphene is mentioned: [Pg.364]    [Pg.45]    [Pg.554]    [Pg.176]    [Pg.178]    [Pg.29]    [Pg.298]    [Pg.83]    [Pg.84]    [Pg.84]    [Pg.85]    [Pg.122]    [Pg.82]    [Pg.851]    [Pg.195]    [Pg.54]    [Pg.301]    [Pg.67]    [Pg.78]    [Pg.131]    [Pg.170]    [Pg.174]    [Pg.155]    [Pg.169]    [Pg.214]    [Pg.79]   
See also in sourсe #XX -- [ Pg.3 , Pg.318 , Pg.321 ]




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Phosphene and Phosphyne Nomenclature

Phosphene intermediates

Phosphenes

Phosphenous acid

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