Methoxybenzenes

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... 

Displacement of a tertiary amine from a quaternary (eq. lb) iavolves the attack of a nucleophile on the a-carbon of a quaternary and usually competes with the Hoffman elimination (173). The counterion greatiy iafluences the course of this reaction. For example, the reaction of propyltrimethylammonium ion with hydroxide ion yields 19% methanol and 81% propylene, whereas the reaction with phenoxide ion yields 65% methoxybenzene and 15% propylene (174). 

Contrary to the findings of Cox and Ghosh, methanesulfonyl cyanide may be distilled without decomposition. Samples of benzene-, p-methoxybenzene-, and p-chlorobenzenesulfonyl cyanides were kept for over a year without loss in purity. 

The o- and />-intermediates are therefore stabilized relative to the intermediate formed from benzene but the ffi-intermediate is not, as is illustrated in Fig. 4.7. As a result, methoxybenzene reacts faster than benzene, and the products are mainly the ortho- and nara-isomers. 

Bromination has been shown not to exhibit a primary kinetic isotope effect in the case of benzene, bromobenzene, toluene, or methoxybenzene. There are several examples of substrates which do show significant isotope effects, including substituted anisoles, JV,iV-dimethylanilines, and 1,3,5-trialkylbenzenes. The observation of isotope effects in highly substituted systems seems to be the result of steric factors that can operate in two ways. There may be resistance to the bromine taking up a position coplanar with adjacent substituents in the aromatization step. This would favor return of the ff-complex to reactants. In addition, the steric bulk of several substituents may hinder solvent or other base from assisting in the proton removal. Either factor would allow deprotonation to become rate-controlling. 

The Y appendage of 2-cyclohexenone 191 cannot be directly disconnected by an alkylation transform. (y-Extended enolates derived from 2-cyclohexenones undergo alkylation a- rather than y- to the carbonyl group). However, 191 can be converted to 192 by application of the retro-Michael transform. The synthesis of 192 from methoxybenzene by way of the Birch reduction product 193 is straightforward. Another synthesis of 191 (free acid) is outlined in... 

For the Birch reduction of mono-substituted aromatic substrates the substituents generally influence the course of the reduction process. Electron-donating substituents (e.g. alkyl or alkoxyl groups) lead to products with the substituent located at a double bond carbon center. The reduction of methoxybenzene (anisole) 7 yields 1-methoxycyclohexa-1,4-diene 8 ... 

Figure 2.21 A gas cluomatogram of a sample of river water (2.25 ml) spiked at 5 ppb levels with 1, toluene 2, ethylbenzene 3, methoxybenzene 4, p-dichlorobenzene 5, dimethylphe-nol 6, dimethylaniline 7, chloroaniline 8, indole 9, dichlorobenzonitrile 10, tiichlorophe-nol 11, dinitrobenzene 12, tiifluranil 13, atrazine 14, phenantlnene. Reprinted from Journal of High Resolution Chromatography, 16, H. G. J. Mol et al., Use of open-tubular tapping columns for on-line extraction-capillary gas cluomatography of aqueous samples , pp. 413-418, 1993, with permission from Wiley-VCH.

Chemical Name 1,1, 1 "-(1-chloro-1-ethenyl-2-ylidene)tris[4-methoxybenzene] Common Name Tri-p-anisylchloroethylene Structural Formula ... 

Chemical Name 4-[2-(Diethylamino)-2-oxoethoxyl -3-methoxybenzene-acetic acid propyl ester... 

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