Anisole 3-naphthol

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

When hypofluorous acid reacts with aromatic substrates 7 the isomeric distribution of phenols formed suggests the nature of the transformation is electrophilic, rather than radical 4-methoxy(2-2H)phenol (8) isolated from (4-2H)anisole shows a marked NIH effect (77% incorporation of deuterium).11 A similar reaction with naphthalene gives a mixture of up to three products in low yield (1-naphthol 2.9%, 2-naphthol 0.75% and 1.4-naphthoquinone 7.4%).9... 

C22H13N707, mw 487.38, N 20.12% dk crysts (from benz or acet+w), mp 265- 5 mod sol in benz or toluene si sol in anisole or acet diffc sol in ale insol in alkalies dissolves in in coned H2S04 giving a green color was prepd by treating 4-nitrobenzene-5 -nitro-l-naphthol in ale soln with 4-nitro-benzene-l-diazoniumchloride. Its expl props were not investigated... 

Regioselective chlorination of aromatics. Phenol undergoes regioselective chlorination at the orf/io-position with 1, but selectivepara-chlorinationwith2. Chlorination of anisole by either reagent results exclusively in para-chlorination, because of steric effects.2 Chlorination of naphthol with 1 and 2 is more regioselective than that of phenol.1... 

The alkyl ethers of phenols, naphthols and hydroxyanthraquinones can be prepared, in many cases, by treatment of the halogen compounds with alcoholates at high temperature under pressure (e.g., anisole, page 97). Of course, the phenols themselves can be etherified (cf., page 148), and the cheaper method is used in each case. The dialkyl sulfates serve as active alkylating reagents in certain instances, as in the preparation of Caledon jade green (dimethoxydibenzanthrone). 

In the absence of hydrogen fluoride catalysis, anisole. phenol, 2-naphthol, 1,2-dimethoxybenzene, 1,2-dihydroxybenzene and 1,3-dihydroxybcnzene react with xenon difluoride to give monosubstituted products in fair to good yield (Table 15). ... 

The para positions of A,A-dimethylanihne, diphenylamine, phenol, and anisole are electron-rich and accordingly attack 2-alkylthio-l,3-dithiolium cations at C-2, yielding various 2-aryl-1,3-dithiolium cations. A similar reaction occurs with 2,6-bis(/er/-butyl)phenol and with 2-naphthol, and by subsequent deprotonation ketones such as 174 and 175 are obtained. ... 

The acetylation of alcohols and phenols with acetic anhydride and HSZ-360 zeolite at 60oC used no solvent. The acetate of 1-dodecanol was obtained in 98% yield, and the acetate from 1 naphthol in 100% yield.183 The acylation of anisole with acetic anhydride at 100oC without solvent using zeolite H-/8 gave 4-methoxyacetophenone (6.30) in 98%yield.184 The catalyst could be recovered, regenerated, and reused with no decrease in yield. These reactions show that not all zeolites are used at high temperatures in the vapor phase. 

Phenol Ethers. The phenol ethers are prepared similarly to the aliphatic ethers. An alkyl halide, a sodium alkyl sulfate, dialkyl sulfate, or alkyl toluenesulfonate is treated with a phenol in an alkaline medium (sodium ethylate) or in the presence of metal halides (cf. Anisole, Acetophenetidine, and vanillin). Naphthols alkylated more easily than phenols, heating of naphthol with methanol in the presence of sulfuric acid or alumina being sufficient to give satisfactory yields. 

Other phenols and phenol ethers were examined to assess the breadth of activity of this catalyst. Anisole was selected as an electron rich aromatic system though less so than phenol. A cleaner reaction at lower conversion was expected. Under similar conditions employed for phenol hydroxylation, a 20% conversion of anisole was measured with selectivity to 4-methoxy phenol of 15% and to guiacol of 42%. 1-naphthol was also assessed. No conversion was seen, presumably due to the bulky nature of the molecule. These findings are consistent with a mechanism involving an electrophilic oxidant species. 

Setting Up As accurately as possible, calibrate several Pasteur pipets to contain 1.5 mL. In separate labeled test tubes, place 1.5 mL of a 0.2 M stock solution of each of fhe following substrates in 15 M(90%) acetic acid (a) phenol, (b) anisole, (c) diphenyl ether, (d) acetanilide, (e) 4-bromophenol, and (f) 1-naphthol. Use special care to ensure that one stock solution is not contaminated by another during any transfer operations you perform. 

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