Alkyl compounds, general

RTIX2 derivatives are covalent compounds, generally soluble in organic solvents. The aryl and vinyl derivatives are more stable than the corresponding alkyl compounds. This type of compound has been postulated to be an intermediate in many organic synthetic reactions involving thaUium(III) species. 

These compounds generally exist in carbonyl forms. The oxygen function can be converted into halogen by phosphorus halides. Reactions with electrophiles are quite complex. Thus urazole (511) reacts with diazomethane quickly to yield (512), which is more slowly converted into (513). 1-Phenylurazole gives (514) however, 4-phenylurazole yields (515). Oxadiazolinones of type (516) can be alkylated at both O- and N-atoms. 

This is intimately related to the nature of the solvent. If the solvent is nonpolar and lacks coordinating ability, then generally [known exceptions are the Pt(II) and Ir(III) complexes mentioned in Section B] the insertion will proceed via attack of L upon the alkyl compound ( 2 path), e.g.. Table I, reaction 6. 

The nitration of active methylene compounds generally proceeds via the reaction of carbanionic intermediates with an electrophilic nitrating agent such as alkyl nitrate (alkyl nitrate nitration). Details of this process are well documented in the reviews.38 The alkyl nitrate nitration method has been used extensively for the preparation of arylnitromethanes. The toluene derivatives, which have electron-withdrawing groups are nitrated with alkyl nitrates in the presence of KNH2 in liquid ammonia (Eqs. 2.19 and 2.20).39... 

In terms of their chemical behavior, dialkylzinc compounds generally react to transfer alkyl groups to other metals. Dialkyls of cadmium are usually prepared by the reaction of a Grignard reagent with a cadmium halide. 

Stability of Cyclic Nitronates For steric reasons, fragmentation of five-and six-membered cyclic nitronates cannot follow pathways presented in Scheme 3.72. Hence, stability of these compounds can be substantially higher than that of alkyl nitronates. These compounds generally exist in the crystalline state and can be purified by recrystallization or liquid chromatography. Selected melting points of nitronates are given in Table 3.8. 

The D. pulchra furanone compounds generally consist of a furan ring structure with a substituted alkyl chain at the C-3 position and a bromine substitution at the C-4 position (Fig. 5). The substituent at the C-5 position may vary in terms of side chain structure. The natural furanones are halogenated at various positions by bromine, iodine, or chlorine [128]. D. pulchra produces at least 30 different halogenated furanones which are stored in specialized vesicles and are released at the surface of the thallus at concentrations ranging from 1 to 100 ng/cm2 [132]. Field experiments have demonstrated that the surface concentration of furanones is inversely correlated with the degree of colonization by marine bacteria [133]. 

Diazo compounds generally do not undergo [3 + 2] cycloaddition with unactivated nitriles under purely thermal, noncatalyzed conditions. The formation of 4-R-5-trimethylsilyl-l//-l,2,3-triazoles from the reaction of diazo(trimethylsilyl)-methyl lithium and a broad range of nitriles [RCN R = alkyl, aryl, SEt, OPh, PO(OEt)2] appears to be an exception, but this reaction most likely occurs in a stepwise manner with initial nucleophilic attack at the nitrile (275). 

When enolates 11 (R 4= H) were alkylated, compounds 12 and 13 containing a quaternary center were created. The diastereoselectivities are generally lower in these cases than with /i-hydroxy esters, but occur in the same direction, i.e., the anti-alkylation product 12 is favored by a factor of about 4-954. 

Analytical data on the soluble products isolated from chloroform are in excellent agreement with the composition 1 Ni+2 1 monoalkylated ligand 1 I or Br. The magnetic moment of this methylated complex was found to be 1.89 Bohr magnetons per nickel (II). The molar conductivities of the methylated and benzylated complexes in methanol at 25° C. are 75.4 and 68.4 ohm-1, respectively. These values approximate those expected for uni-univalent electrolytes in this solvent. The formulation of these alkylated compounds as dimeric electrolytes (structure VII) does not appear to be totally consistent with their physical properties. One or both halide ions may be bound to the metal ion. These results lead to the easily understood generalization that terminal sulfur atoms alkylate more readily than bridged mercaptide groups. 

Amphipathic substances such as we have discussed throughout this chapter are used as collectors. Alkyl compounds with C8 to C18 chains are widely used with carboxylate, sulfate, or amine polar heads. For sulfide minerals, sulfur-containing compounds such as mercaptans, monothiocarbonates, and dithiophosphates are used as collectors. The most important collectors for sulfides are xanthates, the general formula for which is... 

Naphthalene and other fused ring compounds generally give poor yields in Friedel-Crafts alkylation, because they are so reactive that they react with the catalyst. Heterocyclic rings are usually also poor substrates for the reaction. Although some furans and thiophenes have been alkylated, a true alkylation of a pyridine or a quinoline has never been described.21,0 However, alkylation of pyridine and other nitrogen heterocycles can be accomplished by a free radical (4-23) and by a nucleophilic method (3-17). 

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