Toluene 4-methoxy

The electrosynthesis of 4-methoxybenzaldehyde (anisaldehyde) from 4-methoxy-toluene by means of direct anodic oxidation is performed on an industrial scale [69]. Via an intermediate methyl ether derivative, the corresponding diacetal is obtained, which can be hydrolyzed to the target product. The different types of products - ether, diacetal, aldehyde - correspond to three distinct single oxidation steps. 

Typical primary amines which undergo such nitrosation are m-toluidine, p-xylidine, m-anisidine, 2-amino-4-methoxytoluene, 3-amino-4-methoxy-toluene, m-aminophenol, a-naphthylamine, l-naphthylamine-2-, -6-, -7-, and -8-monosulfonic acids, and l-naphthylamine-4-monosulfonic acid (which reacts with displacement of the sulfonic acid group). The secondary amines derived from these primary amines also can be nitrosated directly (i.e., without the intermediate formation of an JV-nitroso compound which needs to be subjected to the Fischer-Hepp rearrangement). The entering nitroso group appears to substitute exclusively in the para position. 

Toluene has been oxidized by the silver ion catalysed reaction with peroxy-disulfate. The reaction produces a mixture of bibenzyl, benzaldehyde and benzoic acids.299 Russian workers have described the conversion of 4-methoxy-toluene to the benzaldehyde by oxidation with peroxydisulfate in the presence of silver or copper ions and oxalic acid.300 The presence of copper salts in iron or copper catalysed peroxydisulfate oxidation is believed to suppress side-reactions.301 Phillips have patented a palladium(II)/tin(IV)/persulfate system for the oxidation of toluene derivatives.302 The reactions are carried out in carboxylic acid solvents (Figure 3.78). 

Poly isobutylene. 9. A, 3-bromo-4-methoxy toluene B, < -methoxy benzyl bromide C, < -bromophenetole. 15. M, (CH2=CH)20 N, CICH2CHOHCH2OCH3, retention ... 

Methoxylation of 3-bromo-4-methoxy toluene to 3,4-dimethoxy-toluene... 

Liquid phase oxidation of 4-methoxy toluene to anisaldehyde at 60 bar/115°C in acetic acid containing heavy metal salts is violent, and must be controlled by the rate of addition of oxygen gas. 

A striking feature in the nitration of 4-substituted toluenes is the change in the preference of 1,2- versus 1,4-adduct formation as a function of the 4-substituent. Thus, nitration of 4-acetamido-,4-chloro-, and 4-methoxy-toluene in acetic anhydride gives in each case a cis-1,2-nitronium acetate adduct (103) in addition to the nitro substitution product(s) (Scheme 171). Nitration of 4-fluorotoluene gives a pair of diastereoisomeric 1,4-nitronium acetate adducts (104) and the cis-1,2-adduct. 

Methyl-o-anisidine (2-methoxy-5-methyl benzenamine, p-cresidine, 2-methoxy-5-methylaniline, 3 - amino -4-methoxy toluene) [120-71-8]... 

Me ether 6-Methoxy-3-methyl-l,2,4-benzenetriol. 2,3,6-Trihydroxy-4-methoxy toluene C8H10O4 M 170.165... 

Fora (4-Methyl anisole, p-Cresyl methyl ether, p-Methoxy toluene or Methyl-p-Cresol), colorl... 

Electrochemical Oxidations of Arylmethanes Investigated in Micro Reactors Organic synthesis 85 [OS 85] Oxidation of4-methoxy toluene to 4-methoxy benzaldehyde... 

M m-methoxy-toluene (or analog), 30 ml HCI, 30 ml benzene cool to 0° and with cooling and stirring saturate with HCI. Add 0.15 M formaldehyde and then more HCI for fifteen minutes. Stir at room temperature for two hours and dry, evaporate in vacuum the benzene layer to get about 30% 2-methyl-4-methoxy-benzyl-CI (or analog). 0.5 M (l), 0.8 M NaCn, 5 g Nal or K1 in 250 ml dry acetone stir and boil twenty hours. Filter, wash precipitate with 100 ml acetone and dissolve precipitate with 75 ml benzene. Wash with 100 ml water and dry, evaporate in vacuum to get about 80% yield 2-methyl-4-methoxy-benzyl-CN (II). 0.1 M (ID in 60 ml 10N NH3 in methanol 4 g Ni-Cr20 and shake in autoclave at 70-100 atmospheres H2 and 120° to get about 80% yield of the phenethylamine. 

H3CC6H(N02)3(NHOH) mw 258.15, N 21.71%, OB -62% dark yellow crystals (from aq ale), mp 99° (decomp) sol in alkalis or aq ammonia. Prepd by heating 2,4,6-Trinitro-3-methoxy-toluene with an ale soln of hydroxylamine. 

N 20.73% yel crysrs, mp 98° Prepd from echylamine and 2,4,6-rtrinitro-3 methoxy-toluene in ale... 

T rinitro-5-( tert-hutyl)-2-methoxy- toluene, yel ndls, having an odor of musk, mp 69 70° was prepd from the Ag salt of butyltrinitro-ortho -cresol as described in Ref 2, or by nitrating butyl-ortho-methoxytoluene(Ref 2). The expl props of these trinitro-derivs were not detd Refs l)Beil 6,[507-8] 2)A.Baur, Ber 27,... 

The Dinitro Methoxy Toluenes. See in Vol 3, C556-R to C557-L under Nitro Derivatives of Cresol . The CA Registry No for these compds is [50741-92-9]... 

Side-chain substitution of aromatics is best rationalized by an ECrECn me" chanism via a radical cation 30 in Eq. (101) as intermediate 106-226-241-243. Yet side products of typical radical origin, e.g., bibenzyl in acetoxylation of toluene, have been accounted in favor of a radical chain mechanism (Eq.(99) ) 230, 244,24 5) An ECE-mechanism however has been clearly demonstrated by cyclic voltammetry for side-chain substitution of pentamethylanisole and p-methoxy-toluene 241 Eberson has proposed a modified ECrECn mechanism to account for the formation of radical coupling products 242 (Eq. (101) ) The radical cation 30, the first intermediate, can escape from the electrode surface and loose a proton to form a benzyl radical in the bulk of the solution. This benzyl radical can couple to bibenzyl or abstract hydrogen to form starting material. 

For a series of methylbenzenes, the rates decreased in the order toluene > xylenes > mesitylene > durene > hexamethylbenzene. This order of reactivity is the reverse of that expected for a mechanism involving electrophilic substitution or electron transfer. However, Bushweller598 found that electron-releasing groups facilitate the benzylic oxidation of substituted toluenes by Pd(OAc)2 in acetic acid. p-Methoxy toluene gave a 96% yield of p-methoxybenzyl acetate, and p-nitrotoluene gave only 2% p-nitrobenzyl acetate, in agreement with either an electrophilic substitution or electron transfer mechanism. More mechanistic studies are necessary to clear up these anomalies. Steric effects may play an important role in these reactions. 

SYNS p-CRESOL methyl ether p-cresyl METHYL ETHER FEMANo. 2681 p-METHOXY-TOLUENE 4-METHOXYTOLUENE 4-METHYL-l-METHOXYBENZENE 4-METHYLPHENOL METHYL ETHER METHYL-p-TOLYL ETHER p-TOLYL METHYL ETHER... 

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