Anisole preparation

CioHi O. White leaflets, with a strong smell and sweet taste, m.p. 22 C, b.p. 235 C. The chief constituent of anise and fennel oils and other essential oils, from which it is manufactured. It can also be prepared from anisole (meihoxybenzene). It is widely used for flavouring pharmaceuticals and dentifrices, and in perfumery. 

In view of the high cost of methyl iodide in the above preparation of anisole, and the fact that, unless absolute methanol is used, the ready hydrolysis of the methyl iodide may cause a low yield of the ether, the preparation of anisole may be ad antageously replaced by that of phenetole. I he reaction is not of course a methylation, but is nevertheless of the same type as that used in the preparation of anisole. 

Dissolve 3-8 g. of sodium in 75 mi. of rectified spirit, using otherwise the same conditions as in the preparation of anisole. Then add 15 g. of phenol, and to the clear solution add 13 2 ml. (19-1 g., n mois.) of ethyl bromide. Continue precisely as in the preparation of anisole, shaking the ethereal extract with sodium hydroxide solution as before in order to eliminate any unchanged phenol. Finally collect the fraction boiling at 168-172°. Yield, 14 g. 

It was shown that in preparative experiments sulphuric acid markedly catalysed, and acetate ions markedly anticatalysed the nitration of anisole. ... 

Wnte equations showing how you could prepare each of the following from anisole and any necessary organic or inorganic reagents If an ortho para mixture is formed in any step of your synthesis assume that you can separate the two isomers... 

Two experiments are described in this paper. In the first experiment students determine the %w/w orange oil in a prepared sample by analyzing for d-limonene using anisole as an internal standard. Separations are accomplished using... 

Soluble analogues of these difunctional initiators have been prepared either by addition of small amounts of weakly basic additives such as triethylamine (73) or anisole (74) which have relatively minor effects on diene microstmcture (37). Another method to solubilize these initiators is to use a seeding technique, whereby small amounts of diene monomer are added to form a hydrocarbon-soluble, oligomeric dilithium-initiating species (69,75). 

Ciesol and xylenol can be prepared by the methylation of phenol with methanol over both acid and base catalysts. It is postulated that phenol methylation on acid catalysts proceeds through the initial formation of anisole (methoxybenzene [100-66-3]) followed by intramolecular rearrangement of... 

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). 

Picolyl ethers are prepared from their chlorides by a Williamson ether synthesis (68-83% yield). Some selectivity for primary versus secondary alcohols can be achieved (ratios = 4.3-4.6 1). They are cleaved electrolytically ( — 1.4 V, 0.5 M HBF4, MeOH, 70% yield). Since picolyl chlorides are unstable as the free base, they must be generated from the hydrochloride prior to use. These derivatives are relatively stable to acid (CF3CO2H, HF/anisole). Cleavage can also be effected by hydrogenolysis in acetic acid. ... 

Benzylsulfonamides, prepared in 40-70% yield, are cleaved by reduction (Na, NH3, 75% yield H2, Raney Ni, 65-85% yield, but not by H2, Pt02) and by acid hydrolysis (HBr or HI, slow). They are also cleaved by photolysis (2-4 h, 40-90% yield). The similar p-methylbenzylsulfonamide (PMS—NR2) has been prepared to protect the e-amino group in lysine it is quantitatively cleaved by anhydrous hydrogen fluoride/anisole (—20°, 60 min). Another example of this seldom used group is illustrated below... 

The checkers distilled the anisole from calcium sulfate before use. This reagent functions not only as a reactant, but also as solvent. In some similar preparations the intermediate trichloride is rather insoluble, as in the case of bis(3-methyl-4-methoxyphenyl)tellurium dichloride. The addition of co-solvents such as bis-(2-methoxyethyl) ether is beneficial. ... 

The cinnamyl ester can be prepared from an activated carboxylic acid derivative and cinnamyl alcohol or by transesterification with cinnamyl alcohol in the presence of the H-Beta Zeolite (toluene, reflux, 8 h, 59-96% yield). It is cleaved under nearly neutral conditions [Hg(OAc)2, MeOH, 23°, 2-A h KSCN, H2O, 23°, 12-16 h, 90% yield]or by treatment with Sulfated-Sn02, toluene, anisole, reflux. The latter conditions also cleave crotyl and prenyl esters. 

Brown et al. were not able to prepare 3-(prop-2-ynyl)indole [i.e., 3-propargylindole (49)] by the Grignard reaction however, Williamson and later Zenitz readily obtained 49 in satisfactory yield by the action of propargyl bromide on indole magnesium bromide in anisole. 

Zenitz obtained the analogous compounds 237 and 238 by the action of the corresponding a-cyano-w-bromo-w-alkanes on 2-methylindolyl magnesium bromide in ether. Eiter and Svierak prepared a-(3-indolyl)propionitrile (239) by the action of a-bromopropionitrile on indole magnesium iodide in anisole. ... 

Majiina and Kotake prepared 2,2-di(3-indolyl)propane (336) by the action of acetone on indole magnesium iodide in other or anisole. Recently 1 -indolyl derivatives have been o btained as primary products by interaction of ketones with indole Grignard reagents for example acetone gave a 75% yield of 2-(l-indolyl)propan-2-ol (337). 

The nitration of 6-methoxyquinoxaline in concentrated sulfuric acid at 0°C gives 6-methoxy-5-nitroquinoxaline. The position of the nitro group is confirmed by reduction of the product to 5-amino-6-methoxy-quinoxaline identical with a sample prepared from 2,3,4-triamino-anisole and glyoxal ... 

This ether, CgHj. O. CHg, known as anisole, is a mobile oil of very fragrant odour. It is used to some extent in synthetic perfumery. It is prepared by the action of methyl iodide on sodium-phenol, according to the following equation —... 

Ethers can be prepared by reaction of an alkoxide or phenoxide ion with a primary alkyl halide. Anisole, for instance, results from reaction of sodium phenoxide with iodomethane. What kind of reaction is occurring Show the mechanism. 

Anhydrides, preparation with phosgene and tnethylamine, 47, 91 Anisole, chlorination with sulfuiyl chloride, 47, 23... 

Whereas the production of arylnitrenes by the deoxygenation of nitrosobenzenes or nitro-benzenes by trivalent phosphorus reagents and their subsequent intramolecular ring expansion to 3//-azepines are well-known processes, the corresponding intermolecular reactions to form 1//-azepines have been exploited only on rare occasions and appear to be of little preparative value. For example, the highly electrophilic pentafluorophenylnitrene, obtained by deoxygenation of pentafluoronitrosobenzene with triethyl phosphite in benzene solution, produced a low yield (2-10%) of l-(pentafluorophenyl)-l//-azepine, which was isolated as its [4 + 2] cycloadduct with ethenetetracarbonitrile.169 With anisole as the substrate l-(pentafluorophenyl)-l//-azepin-2(3//)-one (16% bp 128 —130 C/0.4 Torr) was obtained. 

Dichlorodibenzo-p-dioxin was prepared from isotopic potassium 2,4-dichlorophenate uniformly labeled with Ullman conditions gave a 20.5% yield. Small amounts of dichlorophenoxy chlorophenol were removed from the product by extraction with sodium hydroxide before purification by fractional sublimation and recrystallization from anisole. Chlorination of 2,7-dichlorodibenzo-p-dioxin in chloroform solution containing trace amounts of FeCls and 12 yielded a mixture of tri-, tetra-, and pentachloro substitution products. Purification by digestion in boiling chloroform, fractional sublimation, and recrystallization from anisole was effective in refining this product to 92% 2,3,7,8-tetrachloro isomer, which also contained 7% of the tri- and 1% of the penta-substituted dibenzo-p-dioxin. Mass spectroscopy was used exclusively to monitor the quality of the products during the synthesis. 

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