2 -Aryl-2-methoxy

Aryl-2-methoxy- 2,5-Diaryl-2 -methoxy-azobenzole azobenzole... 

Mit Trifluoressigsaure protonierte Enaminone werden mit Natriumboranat in Isopropanol zu den entsprechenden a, /3-ungesattigten Ketonen reduziert9 und/3-Dialkylami-no-enone ergeben mit Natriumboranat/Eisen(III)-chlorid gesattigte Amino-alkohole10. Zur Reduktion von Aryl-, Methoxy- usw. Enamino-ketonen s.Lit.11. 

Chiralcel OJ Cellulose tris(4-methyl benzoate) Aryl methyl esters, aryl methoxy esters ... 

The same reaction has been developed that allows for in situ olefination in the synthesis of isoquinoline derivatives (Equation 11) <2003JOC980>. Although numerous examples were reported, it was found that the aryl methoxy substituent was necessary for the reaction to be successful. 

Indeed, it is known that very few or no methoxy groups are present in bituminous coals (34). In the lignite coal (Sample 1) aryl methoxy groups... 

Aryl(methoxy)carbenes, generated photolytically from 3-aryl-3-methoxy-3//-diazirines, underwent addition to 1,1-dimethylallene to give methylenecyclopropane derivatives 1 (no yields or physical properties of the products were reported). ... 

The aryl(methoxy)acrylonitrile (3) obtainable from benzylisovanillin and the sodium salt of methoxyacetonitrile can acylate amines in the presence of sodium benzylmer-captan e.g. benzylamine and the amine (5) are acylated to (4) and (6), respectively, the latter being useful as an intermediate in the synthesis of (7) or of 1-benzyltetrahydroisoquinolines. ... 

MeONa loses formaldehyde by reverse aldol reaction. Methylation of (119) with diazomethane yields a methyl ester, with concomitant appearance of an indolenine chromophore. N.m.r. and mass spectral data reveal the presence of the epoxide function, and determine the configuration at C-16. The remainder of the stereochemical details, and the position of the aryl methoxy-group, which rests at present solely on u.v. evidence, have yet to be established. 

Later, Saalfrank and Weiss (1984) showed that three ethenediazonium hexachloroan-timonates with aryl, methoxy, and piperidino substituents form cu,cu -di-lif-l,2,3-tri-azolylalkanes in the reaction with cu,cu -diaminoalkanes (H2N — (CH2) — NH2, n = 2,3,4 and 6). 

Fig. 5.4. The infrared spectra in the CH stretching region are illustrated for the aryl-methyl, the aryl-methoxy, and the aryl-methylamino groups. A triplet of bands at 3100-3000 cm are caused by aromatic CH stretching vibrations. The rest of the bands are caused by the CHa group.

Murrayastine (13), C16H17NO3 (M 271.1191) was isolated from the dried bark of Mur ray a euchrestifolia as a syrupy liquid by Furukawa et al 41). Its uv absorption spectrum 224, 247, 255, 298, 332 and 336 nm) and ir spectrum showed the presence of carbazole skeleton. NMR data showed the presence of one aryl methyl (8 2.47), and three aryl methoxy (83.95, 3.96 and 4.00) groups. The me/a-coupled H-4 (87.32) and H-2 (8 6.65) signals and their enhancements after irradiation of the aromatic C-methyl showed that C-2 and C-4 were unsubstituted and that the methyl occupied position 3. Presence of the ortho coupled signal of H-5 (/ = 8 Hz) showed that both C-5 and C-6 were unsubstituted. Hence murrayastine could be formulated as l,7,8-trimethoxy-3-methyl carbazole which has been confirmed by synthesis vide p. 97). 

Scheme 1-35. Indoline by intramolecular aryl/methoxy displacement.

The photo-NOCAS reaction with 2,6-dimethyl-l,6-heptadiene gave two major cyclic aryl-methoxy adducts (a cyclohexane and a cycloheptane) as well as an acyclic heptene adduct Variation in concentration of the nucleophile, methanol, and co-donor, biphenyl, has been shown to affect the product ratios. Further applications of the photo-NOCAS S 2Ar reactions with the aUeyl-4-enols, a-terpineol, limonene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, (3-myrcene, and 1,4-bis (methylene) cyclohexene have been reported.The aryl-methoxy adduct product ratios have been investigated and discussed in terms of the stability of radical intermediates and the factors controlling the regiochemistry of reaction with the nucleophiles alcohols, cyanide, and fluoride attempts to justify the results by ab initio molecular orbital calculations have been made. The photo-NOCAS reaction with 2-methylpropene in the absence of methanol and a donor molecule has shown that solvent acetonitrile can act as a nucleophile. Under these conditions a tetrahydroisoquinoline product is formed, prior to HCN elimination, in high yield as illustrated in Scheme 8. The adduct product formation was rationalized on the basis of the relatively high oxidation potential of the olefin. 

Goto et al. (386) have qualitatively studied the relationship between the structure and the ease of formation of some 2-aryl- and 2-heteroaryl-A-2-thiazolin-4-one derivatives. It is found that 2-pyridyI, 2-benzimidazoyl, and 2- 6 hydroxy-5 -methyl)-benzothiazolyl derivatives are too unstable to be isolated. 6 -Hydroxy-, 6 -methyl-, and unsubstituted 2-benzothiazoiyl derivatives, as well as naphtothiazolyl derivatives are unstable but isolable. On the other hand, 6 -methoxy-. 6 -acetoxy-. and 5, 7 -dimethyl-6 -hvdroxybenzothiazolyl derivatives as well as most of their 5-methyl substituted derivatives are stable and easily prepared. 

Isoxazole, 5-(p-anisyl)-3-phenyI-synthesis, 6, 63 Isoxazole, 4-aroyl-3,5-diaryI-synthesis, 6, 71 Isoxazole, aryl-UV spectra, 6, 4 Isoxazole, 3-aryl-5-unsubstituted ring cleavage, 6, 30 Isoxazole, 5-aryl-3-chloro-reactions, 5, 104 Isoxazole, 3-aryI-4-formyl-synthesis, 6, 84 Isoxazole, 3-aryl-5-methoxy-thermal isomerization, 6, 15 Isoxazole, 3-aryl-5-methyl-synthesis, 6, 63, 84 Isoxazole, 4-azorearrangement, 5, 719... 

Pyridinium salts, l-aryl-4-methoxy-2,6-dimethyl-synthesis, 3, 762 Pyridinium salts, N-aryloxy-rearrangements, 2, 354 Pyridinium salts, 1-benzyl-covalent amination, 2, 239 Pyridinium salts, N-benzyl-reactions... 

In the bromination of styrene, a po-+ plot is noticeably curved. If the extremes of the curves are taken to represent straight lines, the curve can be resolved into two Hammett relationships with p = —2.8 for electron-attracting substituents and p = —4.4 for electron-releasing substituents. When the corresponding -methylstyrenes are examined, a similarly curved ap plot is obtained. Furthermore, the stereospecificity of the reaction in the case of the -methylstyrenes varies with the aryl substituents. The reaction is a stereoespecific anti addition for strongly electron-attracting substituents but becomes only weakly stereoselective for electron-releasing substituents, e.g., 63% anti, 37% syn, forp-methoxy. Discuss the possible mechanistic basis for the Hammett plot curvature and its relationship to the stereochemical results. 

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