M-Methoxy-toluene

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. 

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. 

Bis[4-methylphenyl] Tellurium Bis[2-(4 -methylbenzylidenamino)phenoxide]" A solution of sodium methoxi-de in 30 w/absolute methanol, prepared by the addition of 0.95 g (40 mmol) sodium to methanol, is added to a stirred solution of 9.40 g (20 mmol) of bis [4-methylphenyl] tellurium dibromide in 50 m/ dry toluene. Methanol is distilled from the reaction mixture until the temperature of the vapors reach 110°, Sodium bromide is removed by filtration. The filtrate, containing his 4-methylphenyl] tellurium dimethoxide, is added to a stirred solution of 8.44 g (40 mmol) of 2-(4-methylbenzylidenamino)phenol in 50 ml dry toluene. Most of the toluene is distilled under vacuum from the reaction mixture. The concentrate ( 30 ml) is mixed with an equal volume of absolute diethyl ether. The mixture is cooled to — 5°. The crystals are collected by filtration and recrystallized from hexane m.p. 135°. 

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

Ammoxidation of p-methoxytoluene (protection of the OH group in the p-cresol feed by methylation) over vanadium-titanium oxide catalysts gives p-methoxy-benzonitrile in 65 % yield [81,82]. Because of the greater reactivity of p-methoxy-toluene compared with the m isomer the ammoxidation of m,p-methoxytoluene mixtures results in the formation of only p-methoxybenzonitrile and the m isomer remains mainly unreacted. This presents the possibility of reactive separation of differently substituted toluenes [82]. 

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

Catalytic asymmetric methylation of 6,7-dichloro-5-methoxy-2-phenyl-l-indanone with methyl chloride in 50% sodium hydroxide/toluene using M-(p-trifluoro-methylbenzyDcinchoninium bromide as chiral phase transfer catalyst produces (S)-(+)-6,7-dichloro-5-methoxy-2-methyl-2--phenyl-l-indanone in 94% ee and 95% yield. Under similar conditions, via an asymmetric modification of the Robinson annulation enqploying 1,3-dichloro-2-butene (Wichterle reagent) as a methyl vinyl ketone surrogate, 6,7 dichloro-5-methoxy 2-propyl-l-indanone is alkylated to (S)-(+)-6,7-dichloro-2-(3-chloro-2-butenyl)-2,3 dihydroxy-5-methoxy-2-propyl-l-inden-l-one in 92% ee and 99% yield. Kinetic and mechanistic studies provide evidence for an intermediate dimeric catalyst species and subsequent formation of a tight ion pair between catalyst and substrate. 

M = Solvent Pyrene Paraffin oil 1-Methyl-naphthalene Ethanol 2-Methyl- naphthalene Ethanol 1,6-Dimethyl-naphthalene Ethanol 1-Methoxy- naphthalene Toluene 2-Methoxy- naphthalene Toluene... 

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