D alkylation

Nitrosation (Section 22 15) Nitrosation of amines occurs when sodium nitrite is added to a solution containing an amine and an acid Primary amines y e d alkyl diazonium salts Alkyl diazonium salts are very unstable and yield carbo cation derived products Aryl diazonium salts are exceedingly useful synthetic in termediates Their reactions are de scribed in Table 22 7... 

Fig. 11. Surface-active organosulfur compounds that form monolayers on gold (a) alkanethiol (b) dialkyl disulfide (c) dialkyl sulfide (d) alkyl xanthate ...

Gas-Phase Reaction of Cationic d° Alkyl Compounds of Group 4 Metals... 

M. Gallardo, L. Roblot-Treupel, J. Manhuteau, I. Genin, P. Couvreur, M. Plat, and F. Puisieux, Nanocapsules et nanospheres d alkyl-cyanoacrylate, interactions principe actif/polymere, in 1989 Proc. 5th Int. Conf. Pharm. Tech. pp. D36-D45. 

Class D Alkyl fluoroformates quaternary ammonium salts,... 

Fig. 6a-d. Alkyl-substituted naphthalene series (GC-MS key ions m/z 142,156,170, and 184) from a Red Sea sediment sample... 

Fig. 8a-d. Alkyl-substituted pyrene/fluoranthene series (key ions mlz 202,216,230, and 244) from a bottom ash sample from a coal fired power plant... 

There would appear to be two distinct modes of reactivity of early transition metal alkyls with O2. When the metal is not in its highest oxidation state, an O2 complex of variable stability may form, and its subsequent reactivity may or may not involve the metal-carbon bond. The formation of remarkable stable 0x0 alkyls is an example of this pathway. In contrast, d°-alkyls react with O2 by a radical chain mechanism that invariable leads to formation of alkoxide complexes labile alkylperoxo ligands are clearly imphcated as intermediates in these reactions. 

Leaving aside the autoxidations of d°-alkyls, which only formally yield O2 insertion products, there are a very few examples of reactions where migratory insertion of a coordinated O2 into a metal alkyl bond seems indicated. Thus, heating of Cp 2Ta( -02)Me (Sect. 2.1) in solution in the absence of any base results in its transformation into Cp 2Ta(0)0Me [1]. Lewis acids were noted to catalyze the reaction. While there is no direct evidence for the formation of an alkylperoxo intermediate, the final product could easily be rationaUzed as resulting from an a-alkoxide eUmination (Scheme 10). 

Figure 8.1. Relation of solubility parameters (solpars or Hildebrand 8 values) and carbon numbers in various homologous series of solvents. (4) Normal alkanes, (B) normal chloroalkanes, (C) methyl esters, (D) alkyl formates and acetates, (E) methyl ketones, (F) alkyl nitriles, ) normal alkanols, (H) alkyl benzenes, and (I) dialkyl phthalates.

Linford, M. R. and Chidsey, . E. D. Alkyl monolayers covalently bonded to silicon surfaces. Journal of the American Chemical Society 115, 12631 (1993). 

D. Alkylation of Compounds Having Acidic CH2 Groups with... 

Dihydrogen complexes may be intermediates in the oxidative addition of H2 to a metal14b (equation 1) and in the hydrogenolysis of d° alkyls. They will also need to be considered as possible species present in hydrogenases and nitrogenase.14f... 

Fig. 13. Universal building block 18, photo linker resin 19, and CSPOS sequence to the fully benzylated, resin-bound monosaccharide acceptors 21, 22, 23, and 24. Reactions (a) loading, (b) transesterification, (c) TBDPS cleavage, (d) alkylation, (e) ring opening [—> 6-OH], (f) ring opening [—> 4-OH], (g) acidic TBDPS cleavage, (h) neutral/acidic benzylation.

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