3- Methyl-4-nitroanisole

Methyl-4-nitroanisole Anisole, 3-methyl-4-nitro- (8) Benzene, 4-methoxy-2-methyl-1-nitro- (9) (5367-32-8)... 

Sodium methoxide, 3-methyl-4-nitroanisole, diethyl oxalate, 30% hydrogen peroxide, 97% sodium hydride, methyl acetoacetate, sodium sulfate, 10% palladium on activated carbon, ammonium formate, and 2-nitrophenylacetic acid were purchased from Aldrich Chemical Company, Inc., and were used without further purification. 

Methyldopate hydrochloride 6-Methylhydrocortisone acetate 3-Methyl-4-nitroanisole 3-Methyl-3-pentanol carbamate 6-Methyl-prednisolone Methyl testosterone Metopirone Mikedimide... 

Muscogene 3/015181. See 3-Oxabicyclo [10.3.0] pentadec-6-en Muscovite mica. See Mica Mushul A-2404. See PPG-40 butyl ether Musk KS. See 2,6-Dibromo-3-methyl-4-nitroanisole... 

Citronellal acetone 2,6-Dibromo-3-methyl-4-nitroanisole 2-Ethylhexanal ethyleneglycol acetal Geraniol Isononanal diethyl acetal Isononanal dimethyl acetal Isononanal methylanthranilate Lilial methylanthranilate 4-Methyl-4-phenyl-2-pentyl isobutyrate Phenylacetaldehyde dicitronellyl acetal Thiogeraniol Tricyclodecane methylol acetate Trimethyl cyclohexyl acetate fragrance, synthetic beverages Benzaldehyde... 

Miscellaneous chemicals, such as dimetlylphihalate, methyl acrylate, methyl formate, sodium methylate, nitroanisole, dimethylaniline Other uses Solvent... 

The reaction of N bromosuccimmide with the following com pounds has been reported in the chemical literature Each compound yields a single product in 95% yield Identify the product formed from each starting material (a) p-tert Butyltoluene (b) 4 Methyl 3 nitroanisole... 

First of all, there are the two products of O-coupling addition of methoxide ion to the diazonium ion, the (Z)- and (jE)-diazo methyl ethers. As discussed in Section 6.2, they are formed in reversible reactions with half-lives of the order of a fraction of a second (Z) to a minute (E). The two diazo ethers are, however, decomposed rapidly to the final dediazoniation products. We show in Scheme 8-47 the products obtained by Broxton and McLeish (1983 b) in the dediazoniation of 4-chloro-3-nitrobenzenedi-azonium ion (8.64) with methoxide ion in CH3OH. The products are 4-chloro-3-nitro-anisole (8.65, 49 9o), 2-chloro-nitrobenzene (8.66, 449o), and 2-nitroanisole (8.67). 

The effect of an o-methyl substituent on the photosubstitution of o- and p-nitroanisole by hydroxide ions28 (equations 24-26) can be ascribed to both electronic and steric effects that determine the reactivity and selectivity. 

Dinitrotoluene, Sodium oxide, 2726 Lithium 4-nitrothiophenoxide, 2177 4-Methyl-2-nitrophenol, 2767 2-Nitroanisole, Sodium hydroxide, Zinc, 2768 Nitrobenzene, Alkali, 2262... 

The nitrophenyl radical can react with the iodide ion and solvent, methanol, as well. Transference of hydrogen radical from methyl alcohol to nitrophenyl radical gives rise to nitrobenzene and formaldehyde (CHjOH —> CH2O). Though carefully sought among the products of the reaction, 3-iodonitro-benzene and 4-nitroanisole were lacking. This completely rejects another possible mechanism of the reaction, cine-substitution, which involves the formation of dehydrobenzene as described earlier. 

Phenyl n-propyl et.her. Phenyl n-butyl ether o-Cresyl methyl ether (1) m-Cresyl methyl ether. p-Cresyl methyl ether. o-Cresyl ethyl ether m-Cresyl ethyl ether p-Cresyl ethyl ether Benzyl methyl ether Benzyl ethyl ether Methyl a-naphthyl ether Methyl p-naphthyl ether Ethyl a-naphthyl ether Ethyl p-naphthyl ether Benzyl a-naphthyl ether Benzyl P-naphthyl ether o-Methoxydiphenyl p-Methoxydiphenyl. o-Chloroanisole. m-Chloroanisole. p-Chloroanisolc o-Bromoanisole m-Bromoanisole. p-Bromoanisole. o-Iodoanisole m-Iodoanisole p-Iodoanisole o-Nitroanisole... 

Methyl myristate, m413 Methyl nicotinate, m404 4-Methyl-3-nitroanisole, m85... 

Solodovnikov (1976) studied the kinetics of the interaction of the 4-nitro-l-chlorobenzene with sodium methylate in dimethylsulfoxide in air via the method of spectrophotometry. Kinetic calculations were made in an assumption that all the anion radicals of 4-nitro-l-chlorobenzene are converted into 4-nitrophenolate. The calculations gave a sum of rate constants for formation of 4-nitroanisole and of the 4-nitro-l-chlorobenzene anion radicals close to the rate constant for the consumption of 4-nitro-l-chlorobenzene. Solodovnokov (1976) concluded that the anion radicals of 4-nitro-l-chlorobenzene are produced by a reaction parallel to substitution. Then it should be assumed that the reaction proceeds either by a nonradical mechanism or by a hidden radical mechanism, which implies that particles of a radical nature are produced and unite in a solvent cage without passing into a solvent pool. This conclusion generated objections (Shein 1983). The discussion deserves our consideration because it reveals features and limitations of the method for discerning the ion radical nature of a reaction. 

Methyl-4-nitroanisole (29.1 mmol) dissolved in 46 ml apiece glacial acetic acid and acetic anhydride at 0°C was treated dropwise with 6.9 ml 18 M sulfuric acid and Cr03 (80.8 mmol) portionwise over 60 minutes. The mixture was stirred an additional 15 minutes, then poured over ice, and a precipitate isolated. The solid was washed with cool water, then purified by flash chromatography with a solvent gradient of 15-50% EtOAc/hexanes, and the product isolated in 24% yield as a white solid. 

Technical Observations. A whole series of altyl and phenyl ethers in the benzene series (also in the naphthalene and anthraquinone series) can be prepared in an analogous manner. While anhydrous methylate gives satisfactory results in the case of nitroanisole, there are other cases (e.g., dinitroanisole from dinitrochloro-benzene) where it is betSr to use caustic potash, the small water content having no deleterious efFect. Moreover, better reswts are often obtained if onb 90 per cent of the calculated quantity of alkali is used. 

Remarks. Nitro-p-dichlorobenzene can be reduced to p-dicbloroaniline in tbe usual way with iron and a small amount of acid. Tbe chlorine ortbo to tbe nitro group is labile and can be replaced by various substituents, less easily, however, than the chlorine in 2,4-dinitrochlorobenzene, but more easity than that in o-nitrochloro-benzene. The replacement of the chlorine by hydrojyl by the action of aqueous sodium hydroxide is described in the following preparation. Reaction wiUi sodium methylate yields 4-chloro-2-nitroanisole, which is reduced to 4-chloro-2-am sidine (chloramsidine P, or fast red R base). With ammonia under pressure, 4-chloro-2-nitroaniline (fast red 3CL base) is formed. These bases are important starting materials for the preparation of azo dyes, especial pigment and lake coIots, as well as ice colors. 

The same authors also introduced a r scale of solvent dipolarity/polarizability [84a]. This n scale is so named because it is derived from solvent effects on the n n electronic transitions of a selection of seven positively solvatochromic nitroaromatics of the type D-C6H4-A, where D and A stand for electron-donor e.g. NMe2) and electron-acceptor e.g. NO2) groups, respectively 4-nitroanisole, A,A-diethyl-3-nitroaniline, 4-methoxy-/ -nitrostyrene, 1-ethyl-4-nitrobenzene, A-methyl-2-nitro-p-toluidine, N,N-diethyl-4-nitroaniline, and 4-(dimethylamino)benzophenone. Given a solvatochromic indicator compound, the n value for a solvent S was defined according to Eq. (7-32) ... 

SYNS l-METHOXY-2-NITROBENZENE 2-METHOXYNITROBENZENE NCI-C60388 2-NITROANISOLE o-NITROPHENYL METHYL ETHER... 

C8H9BrO 4-bromo-3,5-dimethyl phenol 7463-51-6 23 23 1,4369 2 13757 C8H9N03 3-methyl-2-nitroanisole 5345-42-6 38.00 1.1820 2... 

Problem 17.13 Predict the principal products of (a) bromination of p-methyl-anisole (b) nitration of m-nitroanisole (c) nitration ol benzyl phenyl ether. 

Properties Fused, crystalline mass. Crystallizing point57.2C (min), d 1.089 (55/55C), bp 242C. Soluble in alcohol and ether slightly soluble in water. Derivation (1) Reduction ofp-nitroanisole with iron filings and hydrochloric acid (2) methylation of p-aminophenol. 

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