Anisole mixed

Solid phase amide synthesis is successful with all mentioned hnker types (Fig. 8, [149-165]) and several cleavage protocols (Scheme 20, [166-175]) have been developed to release primary amides 138 from these solid supports always depending on the cleavage conditions required for special hnker types 137. Rink amide (123) or PAL (124) resins are for example cleaved with TEA mixtures from 50-95% whereas MBHA resins (126) require HF/anisole mix-... 

Mix I gram of phenol with i c.c. of dimethyl sulphate and add 4 c.c. of a lo per cent, solution of caustic soda. Warm and shake. The odour of phenol is replaced by that of anisole, which can be extracted from the licjuid by ether (Ullmann s reaction). See Appendix. p. 294. 

Ethers are unaffected by sodium and by acetyl (or benzoyl) chloride. Both the purely aliphatic ethers e.g., di-n-butyl ether (C4H, )30 and the mixed aliphatic - aromatic ethers (e.g., anisole C3HSOCH3) are encountered in Solubility Group V the purely aromatic ethers e.g., diphenyl ether (C,Hj)20 are generally insoluble in concentrated sulphuric acid and are found in Solubility Group VI. The purely aliphatic ethers are very inert and their final identification may, of necessity, depend upon their physical properties (b.p., density and/or refractive index). Ethers do, however, suffer fission when heated with excess of 67 per cent, hydriodic acid, but the reaction is generally only of value for the characterisation of symmetrical ethers (R = R ) ... 

Electron-rich aromatic compounds such as durene, p-dimethoxybenzene, mesitylene, anisole, thiophene, and fluorene can be benzoylated or acetylated by the corresponding Af-acylimidazole in trifluoroacetic acid to give the corresponding benzophenone or acetophenone derivative in good yield (Method A). As the actual acylating agent, a mixed anhydride of trifluoroacetic acid and benzoic acid has been proposed 1973... 

Iodination versus chlorination. Three distinct classes of halogenation reactions are observed with various substituted methoxybenzenes and IC1 when carried out under an identical set of conditions, i.e., exclusive iodination, exclusive chlorination, and mixed chlorination and iodination. For example, equimolar mixtures of anisole, 2,5-dimethyl-1,4-dimethoxybenzene and 1,4-dimethoxybenzene and iodine monochloride (kept in the dark) yield p-iodoanisole, chloro-2,5-dimethyl- 1,4-dimethoxybenzene, and a (4 6) mixture of chloro- and iododimethoxybenzene, respectively, in nearly quantitative yields,225 i.e.,... 

When a colourless solution of Ar-nitro-4-carbomethoxypyridinium in acetonitrile is mixed with anisole at -40°C, it immediately turns orange and similarly, the addition of toluene spontaneously leads to a bright yellow... 

Isomeric product distributions. Isomeric product distributions obtained from toluene and anisole have been the subject of considerable mechanistic discussion in electrophilic aromatic nitration (Schofield, 1980 Olah et al., 1989). As applied to nitrations with iV-nitropyridinium ion, the yellow colour of the EDA complex immediately attendant upon the mixing of toluene and PyN02 in acetonitrile persists for about a day (in the dark), whereas the charge-transfer colour of toluene and Me2PyNOj is discharged within 10 min at 25°C. Both bleached solutions afford an identical product mixture (81), consisting of o- (62%), m- (4%) and p-nitrotoluenes (34%)... 

Mixed coupling between naphthalene and alkyl benzenes has also been demonstrated (Table 10, numbers 10-13). The relative yield of mixed coupling products increases with the basicity of the alkyl benzene with mesitylene 19%, with tetramethylbenzene 42%, and with pen-tamethylbenzene 64%. This suggests an electrophilic reaction between naphthalene cation radicals and alkylbenzenes. The mixed coupling reaction of phenan-threne with anisole has been studied kinetically [163]. 

Phenol ethers, like the parent phenols, are reactive substrates. Phenol ethers like anisole and phenetole are readily nitrated to their picryl ethers, 2,4,6-trinitroanisole and 2,4,6-trinitrophenetole respectively, on treatment with mixed acid composed of concentrated nitric and sulfuric acids at 0 °C. Such reactions are vigorous, prone to oxidative side-reactions, and pose a considerable safety risk. The direct nitration of 2,4-dinitrophenol ethers, obtained from the reaction of 2,4-dinitrochlorobenzene with alkoxides, provides a more practical route to picryl ethers on an industrial scale. ... 

Several studies have appeared (12,13,14) in which the propagation reactions involving styryllithium were examined in mixed solvent systems comprising benzene or toluene and ethers. The kinetics were examined under conditions where the ether concentration was held constant and the active center concentration varied. In most cases, the kinetic orders of the reactions were identical to those observed in the absence of the ether. Thus, in part, the conclusion was reached (13,14) that the ethers did not alter the dimeric association state of polystyryllithium. The ethers used were tetrahydrofuran, diphenyl ether, anisole, and the ortho and para isomers of ethylanisole. 

Although hole-catalyzed (cycloaddilions involving radical cation intermediates) and PET (photochemical electron transfer) mixed [2 -I- 2] cycloadditions have been reported from electron-rich alkenes, the only report of a cyclodimerization is that of (E)-4-(prop-l-enyl)anisole which gives stereoisomeric mixtures of the head-to-head dimers 1 and 2.12... 

Since they are similar structurally to the alcohols, phenols also form ethers. An example of an aromatic ether is mcthylphenyl elher (anisole) C(,Hs—O—CHi. There are lew ethers where both R and R are aryls The structure of thineihers is similar lo the other ethers, hut with a sitllur atom in the link instead of an oxygen amm. as R-S-R Examples of thioethers include diethyl sultide Cffly S-Cffls and methylethyl sulfide CHy—S—C Hs. which is a mixed ihioeihcr. 

CH3, It yel crysts, mp 88°. Can be prepd either by nitration of 5-(tert-butyl) 3-methyl-anisole with HN03 in Ac20 and then with mixed acid or by methylation of 5-(tert-butyl)-3-hydroxy-2,4,6 -trinitrotoluene with Me2S04(Refs 1, 2 3) and... 

A solution of 26.6 g 3,4-diethoxyphenol in 50 mL MeOH was mixed with another containing 9.6 g KOH pellets dissolved in 200 mL hot MeOH. There was then added 21.4 g methyl iodide, and the mixture was held at reflux for 2 h on the steam bath. This was then quenched in 3 volumes of water, made strongly basic with 25% NaOH, and extracted with 3x 150 mL CH2C12. Evaporation of the solvent from the pooled extracts gave 19.3 g of 1,2-diethoxy-4-methoxybenzene (3,4-diethoxy-anisole) as a clear, pale amber oil that solidified when cooled. The mp was 20-21 °C. 

Anisole (10 gms.) is mixed gradually with powdered anhydrous aluminium chloride (15 gms.). A vigorous reaction ensues, and crystals of aluminium double compound separate the flask is then heated in an oil-bath to 120° for three hours, when methyl chloride is steadily evolved. At the end of this time the aluminium phenolate is decomposed by cold water acidified with hydrochloric acid, and the phenol extracted with ether. 

Fig. 1. NMR spectra (00 MHz), showing ring-proton resonances, of 2,4,6-trinitro-anisole plus O 6 equivalents of sodium methoxide in dimethyl sulphoxide, (a) soon after mixing, (b) after 20 min.

Methoxyphenyl)-2-naphthyliodonium carboxylate (obtained from 3-iodosyl-2-naphthoic acid by coupling with anisole) (1 g, 2.47 mmol) and tetraphenylcyclo-pentadienone (2.85 g, 7.4 mmol) were mixed and heated, under argon, in an oil bath at 240-250°C for 20 min. The reaction mixture was extracted with dichloromethane and ether and the combined solutions were concentrated the residue was chromatographed on silica to give (after 4-iodoanisole) tetraphenylanthracene (0.66 g, 55%), m.p. 293-294°C. 

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