Anisole reagents

TfOH/TFA/ PhSMel MsOH/TFA/ anisole or MsOH/TFA/ anisole/PhSMe/o-cresolP MsOH/ anisole - reagent TFA/5% H20/3% anisole/1% ethane-1,2-dithioll reagent KP21]... 

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... 

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. ... 

Hg(OCOCF3)2, CF3COOH, anisole. The dimethoxybenzyl thioether is also cleaved with this reagent. ... 

The Fcm group can be removed with TFA, Ag(I), or Hg(II). The use of scavengers such as thiophenol and anisole is recommended. The Fcm group is stable to mild acid and base, but it is not stable to electrophilic reagents such as (SCN)2, VAcOH, or carboxymethylsulfenyl chloride (CmsCl). ... 

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). 

Oddo and Sessa claimed that 1-carboxyindole (375) was obtained on treatment of indole magnesium iodide with gaseous carbon dioxide. Majima and Kotake later reported that 3-carboxyindole (376) and not 375 was the main product obtained in this reaction improved yields of 376 were obtained when the reaction was carried out in anisole instead of ether.Subsequently, several workers have employed essentially this procedure, for the synthesis of 376. It has recently been shown, however, that both the acids 375 and 376 are formed in approximately equal amounts by the carbonation of the indole Grignard reagent (Kasparek and Hea-cook ). 

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. 

Scheme 11.2 shows some representative halogenation reactions. Entries 1 and 2 involve Lewis acid-catalyzed chlorination. Entry 3 is an acid-catalyzed chlorination using NCS as the reagent. Entry 4 shows a high-yield chlorination of acetanilide by i-butyl hypochlorite. This seems to be an especially facile reaction, since anisole is not chlorinated under these conditions, and may involve the A-chloroamide as an intermediate. Entry 5 describes a large-scale chlorination done with NCS. The product was used for the synthesis of sulamserod, a drug candidate. 

Tab. 7.6. G raphite-supported acylation of anisole (51) by use of a variety of acylating reagents (RCOX) under the action of MW irradiation3 [27, 66].

Diathiadiphosphetane disulfides are probably the most studied and the most thermally and hydrolytically stable of all the phosphorus-chalcogen heterocycles. They contain a central four membered P2S2 ring and can be prepared from heating phosphorus pentasulfide with aromatic compounds. The most well-known of these is Lawesson s reagent (43), which is made from anisole and phosphorus pentasulfide,92 and is used extensively in organic synthesis procedures (see Section 5.4.1). Other dithiadiphosphetane disulfides of note are 44 and 45, formed from the reaction of phosphorus pentasulfide with ferrocene or 1 -bromonaphthalene respectively.93... 

To the Grignard reagent prepared from 2.4 g Mg, 10 ml anisole and 16 g ethyl iodide, add 7.8 g indole in 10 ml anisole. Stir and cool to 0°. Slowly add dropwise 5.5 g Cl-acetonitrile in 40 ml anisole. Warm to room temperature and stir heat to 60-70° on water bath (a reddish precipitate forms over about twenty minutes). Cool and purify and convert to the dialkyltryptamine as described earlier. Tryptamines JOC 24,894(1959)... 

Anisole. The simultaneous (homolytic and nucleophilic) annihilations of AN+ as described by the time-resolved spectroscopic results lead to the distinctive mixtures of o- and p-nitroanisoles, in which the isomeric composition is strongly dependent on the nitrating reagent in the following way. 

Since the latter conditions pertain to aromatic nitration solely via the homolytic annihilation of the cation radical in Scheme 16, it follows from the isomeric distributions in (81) that the electrophilic nitrations of the less reactive aromatic donors (toluene, mesitylene, anisole, etc.) also proceed via Scheme 19. If so, why do the electrophilic and charge-transfer pathways diverge when the less reactive aromatic donors are treated with other /V-nitropyridinium reagents, particularly those derived from the electron-rich MeOPy and MePy The conundrum is cleanly resolved in Fig. 17, which shows the rate of homolytic annihilation of aromatic cation radicals by NO, (k2) to be singularly insensitive to cation-radical stability, as evaluated by x. By contrast, the rate of nucleophilic annihilation of ArH+- by pyridine (k2) shows a distinctive downward trend decreasing monotonically from toluene cation radical to anthracene cation radical. Indeed, the... 

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