FROM ALKYL AND ARYL HALIDES OR SULFONATES

N3CH2SPh/KOH or HCOjH (R = aryl only) r1C(N3)=CHR2 (M = Li R = aryl, benzylic) TSN3/UAIH4 

N3CH2SPh / KOH or HCCfeH (R = aryl only) R C(N3)=CHR2 (M=Li R=aryl, benzylic) TsN3/LiAlH  

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Another general process involves the reaction of Pd(0) species with halides or sulfonates by oxidative addition, generating reactive intermediates having the organic group attached to Pd(II) by a ct bond. The oxidative addition reaction is very useful for aryl and alkenyl halides, but the products from saturated alkyl halides often decompose by (3-elimination. The a-bonded species formed by oxidative addition can react with alkenes and other unsaturated compounds to form new carbon-carbon bonds. The... 

Salts of sulfinic acids ace converted to sulfones by the action of pri-lary/ secondary, and benzyl halides, alkyl sulfates, and aryl halides in which the halogen atoms are activated by nitro groups in the ortbo or para positions. The reaction fails with t-amyl halide. The yields vary widely, depending upon the nature of the reactants. From salts of benzenesulfinic acid and simple alkylating agents, sulfones are produced in 50-90% yields. Satisfactory results have been obtained when the aryl sulfinic acid contains nitro, cyano, and acetamido groups. Keto sulfones are made in 48-62% yields by alkylation with a-halo ketones. ... 

Chlorobenzene is employed in the synthesis of certain amino-containing vat dye intermediates. When reacted with phthalic anhydride, the product is 2-chloroanthraquinone, which, with ammonia, is converted readily into 2-aminoanthraquinone (61). Other routes include replacement of halogen by amino groups, with ammonia or ammonium salts of urea, and alkyl- and aryl amines to afford secondary amines. Modification of the amino group by alkylation, with dimethyl sulfate, alkyl halides or esters of toluenesul-fonic acids, is of synthetic value. Arylation of the amino groups is of importance only in the reaction between aminoanthraquinones and nitro- or chloroanthraquinones to yield dianthraquinonylamines, or anthrimides48. For example, the reaction between 62 and 63 yields 64, which can then be converted into carbazole 65, Cl Vat Brown R (Scheme 14). Amination of haloanthraquinones such as l-amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) (66), prepared from 1-aminoanthraquinone, is of industrial use. 

This section lists examples of the hydrogenolysis of esters, R COOR — RH. For the conversion R COOR — R R" or RR" (R"=alkyl) see section 68 (Alkyls and Aryls from Esters). The reduction of esters of sulfonic acids (e.g. ROTs — RH) is included in section 160 (Hydrides from Halides and Sulfonates)... 

Cobalt has attracted attention in recent years as a cost-effective and sustainable alternative to palladium or nickel. As indicated earlier, functionalized arylzinc reagents can be prepared from aryl halides and sulfonates by zinc insertion in the presence of catalytic amounts of CoBtj [50, 51, 210). Interestingly, the presence of this cobalt salt suffices to catalyze in situ the cross-coupling of the arylzincs thus produced with aryl, alkyl, and heteroaryl electrophiles such as organic halides [211-214] or thioethers, as exemplified with the formation of 286 [214] (Scheme 4.63). 

Sodium mercaptides are prepared from the mercaptans and aqueous or alcoholic solutions of sodium hydroxide or alcoholic sodium eth-oxide. The sodium mercaptide reacts with halides, chlorohydrins, esters of sulfonic acid, or alkyl sulfonates [6] to give sulfides in yields of 70% or more. A recent report describes a general procedure for synthesizing aryl thioesters by a nucleophilic displacement of aryl halide with thiolate ion in amide solvents. No copper catalysis is necessary as in an Ullmann-type reaction. 

Alkyl halides are often used as substrates instead of alcohols. In such cases the salt of the inorganic acid is usually used and the mechanism is nucleophilic substitution at the carbon atom. An important example is the treatment of alkyl halides with silver nitrate to form alkyl nitrates. This is used as a test for alkyl halides. In some cases there is competition from the central atom. Thus nitrite ion is an ambident nucleophile that can give nitrites or nitro compounds (see 0-60).731 Dialkyl or aryl alkyl ethers can be cleaved with anhydrous sulfonic acids.732... 

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