Graham reaction

Diazirines are popular precursors for the formation of carbenes and a review of their synthesis and use has addressed the Graham reaction, the diazirine exchange reaction, and radical-initiated exchange in addition to mechanistic details of the diazirine exchange.1... 

Oxidation of diaziridines, a widely used method for preparing diazirines, has been described above. In an important alternative approach, the three-membered ring is generated by oxidation of an amidine in a hypochlorite or hypobromite solution containing the respective halide ion (Graham reaction).Chlorotrifluoromethyl-3//-diazirine (258) was synthesized in this way from trifluoroacetamidine (257). The reaction is believed to proceed via intermediates 259-261 chloride ion attack on 261 in Sn2 fashion completes the transformation to diazirine 258. 

Graham reaction—additive oxidation Hoch-Campbell aziridine synthesis Payne rearrangement Wenker synthesis Aziridine synthesis... 

Though illustrated here by the Scott and Dullien flux relations, this is an example of a general principle which is often overlooked namely, an isobaric set of flux relations cannot, in general, be used to represent diffusion in the presence of chemical reactions. The reason for this is the existence of a relation between the species fluxes in isobaric systems (the Graham relation in the case of a binary mixture, or its extension (6.2) for multicomponent mixtures) which is inconsistent with the demands of stoichiometry. If the fluxes are to meet the constraints of stoichiometry, the pressure gradient must be left free to adjust itself accordingly. We shall return to this point in more detail in Chapter 11. 

Phthalic anhydride. Naphthalene is oxidized by air to phthalic anhydride in a Bubbling flmdized reaclor. Even though the naphthalene feed is in liquid form, the reaction is highly exothermic. Temperature control is achieved by removing heat through vertical tubes in the bed to raise steam [Graham and Way, Chem. Eng. Prog., 58, 96 (Januaiy 1962)]. 

The IR bands of carbenes [2], [5], and [6] have also been observed in the spectrum after vacuum UV photolysis of matrix-isolated methylacetylene (Huang and Graham, 1990). It was found that a fourth carbene -propendiylidene [8] - was formed in this reaction as well. In accord with ab initio calculations, the first of two absorptions (3292 cm and 1960 cm ) has been assigned to V2 ( ) of cw-[8] and the second one to (a ) of trans-[8]. 

The insertion reaction of 16e -complexes into the Si-H bond has been investigated by Graham... 

Stevenson F.J., Fitch A. Reactions with organic matter . In Copper in Soils and Plants, J.F. Loneragan, A.D. Robson, R.D. Graham, eds. Sydney Academic Press. 1981. 

Ma, W.P., Jacobs, G., Sparks, D.E., Spicer, R.L., Graham, U.M., and Davis, B. H. 2008. Comparison of the kinetics of the Fischer-Tropsch synthesis reaction between structured alumina supported cobalt catalysts with different pore size. Prepr. Am. Chem. Soc. Div. Petro. Chem. 53 99-102. (see Chapter 8 of this book.)... 

Bunluesin, T., Gorte, R.J., and Graham, G.W. 1998. Studies of the water-gas-shift reaction on ceria-supported Pt, Pd, and Rh Implications for oxygen-storage properties. Appl. Catal. B Environ. 15 107-14. 

Jacobs, G., Williams, L., Graham, U., Sparks, D., Thomas, G., and Davis, B.H. 2003. Low temperature water-gas shift In situ DRIFTS-reaction study of ceria surface area on the evolution of formates on Pt/Ce02 fuel processing catalysts for fuel cell applications. Appl. Catal. A Gen. 252 107. 

Jacobs, G., Patterson, P.M., Graham, U.M., Crawford, A.C., Dozier, A., and Davis, B.H. 2005. Catalytic links among the water-gas shift, water-assisted formic acid decomposition, and methanol steam reforming reactions over Pt-promoted thoria. J. Catal. 235 79. 

The chemical structure of 2,5-hexanedione suggested that it could react with lysine side-chain amino groups in proteins to form pyrroles (see Figure 2-7). In vitro experiments showed that this was, in fact, the case, and that the modified proteins can undergo secondary reactions to yield oxidized and polymeric products (DeCaprio et al. 1982 Graham et al. 1982). Oral administration of 2,5-hexanedione produced evidence that this process can take place in vivo as demonstrated by the detection of 2,5-dimethylpyrrole adducts in serum and axonal cytoskeletal proteins (DeCaprio and O Neill 1985). When a series of... 

Exposure. The presence of the -hexane metabolite 2,5-hexanedione in the urine is a reasonably reliable marker for exposure to -hexane and has been correlated with air concentrations in the workplace. This is not a specific marker since 2-hexanone is also metabolized to 2,5-hexanedione. The levels of this metabolite in the urine associated with neurotoxicity are not known. A more sensitive marker for exposure may be the presence of pyrolidated proteins in the blood or hair, a result of the reaction of 2,5-hexanedione with the side-chain amino group of lysine (Graham et al. 1995 Johnson et al. 1995). These methods have only been tested after oral exposure to 2,5-hexanedione in the rat model. It would be very useful to know if measurement of pyrrole adducts or cross-linked proteins is also feasible after inhalation exposure to u-hexane in the rat model. Further development and validation of this method in an occupationally exposed population may then be useful. 

Weaver, R., Graham, K.S., Beattie, I.G. and Riley, R.J. (2003) Cytochrome P450 inhibition using recombinant proteins and mass spectrometry/multiple reaction monitoring technology in a... 

These findings have stimulated enormously the search for intermolecular activation of C-H bonds, in particular those of unsubstituted arenes and alkanes. In 1982 Bergman [2] and Graham [3] reported on the reaction of well-defined complexes with alkanes and arenes in a controlled manner. It was realised that the oxidative addition of alkanes to electron-rich metal complexes could be thermodynamically forbidden as the loss of a ligand and rupture of the C-H bond might be as much as 480 kl.mol, and the gain in M-H and M-C... 

The reversible absorption was observed to proceed in presence of either metallic palladium or in palladium-silver alloys much less hydrogen was absorbed in Cu sponge (1 vol. Cu 0.6 vol. H.), and not at all in Os-Ir. The reaction of hydrogen with palladium, so being described by Graham, was ... 

Slagle, I. R., J. R. Gilbert, R. E. Graham, and D. Gutman. Direct identification of reactive channels in the reactions of hydroxyl radicals with allene, propylene and 2-butene. Int. J. Chem. Kinet. Symp. 1 (Chemical Kinetics Data for the Lower and Upper Atmosphere) 317-328, 1975. 

Figure 3. Effect of partition coefficient (P) on availance within a multilaminate septum in which detoxifying reactions occur with rate constants (k) = 1 and (k) = 0.04. Redrawn from Hartley and Graham-Bryce (13).

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