Naphthyl chloride, conversion

Hydrolysis of chlorobenzene and the influence of silica gel catalysts on this reaction have been studied by Freidlin and co-workers (109). Pure silica gel gave up to 45% phenol from chlorobenzene at 600°C. When the silica gel was promoted with 2% cupric chloride, up to 75% phenol was obtained (381). A number of other salts were tested by Freidlin and co-workers as promoters, but they exerted an adverse effect on the activity or selectivity of the catalyst. With 0.2% cupric chloride and 6% metallic copper, the activity of silica-gel was doubled (389). At 500° under the above conditions, the halides were hydrolyzed at rates decreasing in the following order chloride, bromide, iodide, fluoride (110). The specific activation of aryl halides by cupric chloride was demonstrated by conversion of chlorobenzene to benzene and of naphthyl chloride to naphthalene when this catalyst was supported on oxides of titanium or tin (111). The silica promoted with cupric chloride was also found to be suitable for hydrolysis of chlorophenols and dichlorobenzenes however, side reactions were too prominent in these cases (112). 

Spencer and Brewer [111] have reviewed methods for the determination of nitrate in seawater. Classical methods for determining low concentrations of nitrate in seawater use reduction to nitrite with cadmium/copper [ 112,116,117] or zinc powder [113] followed by conversion to an azo dye using N- 1-naphthyl-ethylenediamine dihydrochloride and spectrophotometric evaluation. Malho-tra and Zanoni [114] and Lambert and Du Bois [115] have discussed the interference by chloride in reduction-azo dye methods for the determination of nitrate. 

Conversion of phenols into their methyl or ethyl ethers by reaction with the corresponding alkyl sulphates in the presence of aqueous sodium hydroxide affords a method which avoids the use of the more expensive alkyl halides (e.g. the synthesis of methyl 2-naphthyl ether and veratraldehyde, Expt 6.111). Also included in Expt 6.111 is a general procedure for the alkylation of phenols under PTC conditions.38,39 The method is suitable for 2,6-dialkylphenols, naphthols and various functionally substituted phenols. The alkylating agents include dimethyl sulphate, diethyl sulphate, methyl iodide, allyl bromide, epichlorohy-drin, butyl bromide and benzyl chloride. 

Apart from copper(I)-mediated reactions, few studies of the treatment of vinyliodonium salts with carbanions have appeared. The vinylations of the 2-phenyl- and 2- -hexyl-l,3-indandionate ions shown in equations 222 and 223 are the only reported examples of vinyliodonium-enolate reactions known to this author26,126. ( ,)-l-Dichloroiodo-2-chloroethene has been employed with aryl- and heteroarvllithium reagents for the synthesis of symmetrical diaryliodonium salts (equation 224)149,150. These transformations are thought to occur via the sequential displacement of both chloride ions with ArLi to give diaryl (/ -chlorovinyl)iodanes which then decompose with loss of acetylene (equation 225). That aryl(/ -chlorovinyl)iodonium chlorides are viable intermediates in such reactions has been shown by the conversion of ( )-(/ chlorovinyl)phenyliodonium chloride to diaryliodonium salts with 2-naphthyl- and 2-thienyllithium (equation 226)149,150. 

Alonsono and co-workers [146] have used substituted 1-naphthyl and phe-nylphosphonium chlorides as precursors for the generation of the corresponding arylmethyl radicals and cations in both nanosecond LFP and product studies. For instance, the salt 101 has a quantum yield for cation formation of 0.71 in methanol and the sole product observed was the corresponding methyl ether. No transient radical was observed in this solvent. In contrast, in 5% acetonitrile in dioxane, the radical was observed but now the cation was absent. No fluorescence was observed in either solvent suggesting that Si is very reactive. Redox potentials indicate that the conversion of the radical/radical ion pair to the cation/triphenyl-phosphine pair would be exothermic by some 25 kcal/mol. Therefore, both heterolytic cleavage from Si or homolytic cleavage followed by electron transfer were suggested as possible pathways for cation formation. 

As the reduced density is raised, competing formation of 2-naphthol and methanol from methoxy naphthalene, and catechol and methanol from guaiacol becomes apparent polycondensates are suppressed (e.g. at pr(H20) 1.36), charring products are reduced to 6% w/w equivalent of consumed naphthyl. This parallel hydrolysis pathway has been demonstrated also for other hetero-atom-containing organics [67]. The selectivity of hydrolysis increases with pressure and with the addition of salts to increase the polarity of the fluid [6]. Penninger and Kolmschate [65] used the secondary salt effect to test the mechanism of the hydrolytic reaction addition of 1.01% w/w sodium chloride enhanced rates and conversions to hydrolysis products compared with the water-only control at equal density. Protonic catalysis (cf. hydrolysis in liquid water) was also demonstrated, suggesting that the hydrolysis mechanism in SCF water is ionic. 

Having established an eflflcient catalytic system for the nickel catalyzed Heck reaction, a more in-depth study of the mechanistic details was desired. In order to investigate the role of the leaving group, aryl sulfonates with different electronic properties were prepared from 2-naphthol and various phenylsulfonyl chloride derivatives, using the same procedures as described in Chap. 5 (Table 6.3). Relying on the optimized reaction conditions, the coupling between 2-naphthyl benzene-sulfonate and n-butyl vinyl ether resulted in a 68 % conversion (entry 1). Mixtures of... 

---