4-Chloro-2-nitroanisole

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. 

Prisms or plates from EtOH. Plates from AcOEt. M.p. 56°. B.p. 267°. Sol. Et 0, CS. CHCI3, CgHg, hot EtOH Volatile in steam. DJ 1-4390. Zn 4- HCl —> 2 5-dichloroanil-ine. Alo. NH3 —> 4-chloro-2-nitroaniline. NaOH + MeOH —> 4-chloro-2-nitroanisole. Crauw, Rec. trav. chim., 1931, 50, 766. HoUeman, den Hollander, van Haeften, Rec. trav. chim., 1921, 40, 325. Eiprianow, Mikhail iko, Chem. Abstracts, 1931, 25, 5033. 

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). 

Chemicals. Antipyrine, carbon monoxide (Matheson, Coleman and Bell, Los Angeles, CA), and 1 CH3-N-antipyrine (11.1 mCi/mM, ICN, Irvine, CA) were purchased. Aldrin (1,8,9,10,11,11-hexa-chloro-2,3-7,6-endo-2,1-7,8-exo-tetracyclo (6.2.1.13,6.02 7) dodeca-A,9-diene) and its epoxide, dieldrin were gifts of Shell Development Co. (Modesto, CA). Each was recrystallized from methanol-water solutions and was greater than 99% pure as determined by gas chromatography. l CH30-p-Nitroanisole (1.9 mCi/mmole) was synthesized (1A) and 3H-benzo(a)pyrene (8.3 Ci/ mmole) was purchased (Amersham-Searle Co., Arlington Heights,... 

Already, with one of the first nucleophilic aromatic photosubstitutions encountered, curious behaviour was found when studying the rate of reaction as a function of pH. m-Nitrophenyl sulphate shows no increase in the quantum yield of photohydrolysis with increase of hydroxide ion concentration up to values as high as 0-1 M. This behaviour, also found with one other compound (5-chloro-3-nitroanisole), is in clear contradistinction to what is... 

Ch1oromethyl)toluene, AM91 L-(Ch1oromethyl)toluene, AM92 5-Chloro-2-nitroaniline, AG24 2-Chloro-L-nitroanisole, AJ56... 

Chloro-5 -methylphenylhydroxylamine, 2792 3,4-Dichlorophenylhydroxylamine, 2236 2-Nitroanisole, Hydrogen, 2764 1,1,1 -Tris(azidomethyl)ethane, 1931 Tris(hydroxymethyl)nitromethane, 1658... 

In a Japanese factory at Maizuru a two stage process was used for the manufacture of trinitroanisole, namely alcoholysis of l-chloro-2,4-dinitroberuene to 2,4-dinitroanisole and subsequently nitration of di- to tri-nitroanisole. 

C7H7N03 3-nitroanisole 555-03-3 531.15 46.885 1.2 10763 C7H8CIN03S 6-amino-4-chloro-m-toluenesulfonic acid 88-51-7 436.15 37.785 1,2... 

Alcoholysis of l chloro 2,4 dinitrobcnzene to2,4-dinitroanizok Nitration of di- to tri>nitroanisole Purirication of trinitroanisole Tetranitroanisole Trinit ropheneiole... 

Amino-6-chloro-m-benzene- Calcium Cyanamide 3,S-Dimethyl-2-nitroanisole... 

Aiylphenylamines required for the synthesis of novel dopamine antagmiists, containing the 1,3-benzodiazepine fragment [136], have been prepared from 5-chloro -methoxy-2-nitrophenylacetonitrile, derived from the reaction of 2-chloro-5-nitroanisole with cyanomethyl dimethyldithiocarbamate, proceeding via typical VNS procedure (Scheme 42) [15]. 

The use of liquid ammonia as a solvent for Ar reactions has been explored. With 4-fluoronitrobenzene and chloropyrimidines, solvolysis occurs although substitution by added nucleophiles such as phenoxide or triazolate ions can compete successfully. Kinetic studies of the reactions of 2-chloro- and 2-ethoxy-3,5-dinitropyridine with substituted anilines in DMSO in the presence of DABCO indicate a base-catalysed pathway, which is likely to involve rate-limiting proton transfer from the zwitterionic intermediate to base." ° In the reaction of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole, (26), with substituted anilines in DMSO/methanol mixtures, nucleophilic attack is rate-limiting. Rate constants have higher values in DMSO than in methanol, and in DMSO-rich mixtures, there is evidence, from changes in slope of Brpnsted and Hammett plots, that formation of the zwitterionic intermediate involves an SET process." ... 

Wubbels et al. reported the temperature dependent nucleophilic aromatic photosubstitution of the Sn2 Ar type. Irradiation of 2-chloro-4-nitroanisole (122) at 25 °C in aqueous NaOH gave three substitution products 2-methoxy-5-nitrophenol (123), 2-chloro-4-nitrophenol (124), and... 

Only the 4-chloro group is replaced because the negative charge of the intermediate formed by addition of methoxide ion can be delocalized to the oxygen atoms of the nitro group. No such stabilization is possible if attack occurs at the meta position. Thus, the 3-chloro group cannot be displaced in an addition-elimination mechanism. The product is 2-chloro-4-nitroanisole. 

To study the substrate specificity of the hydroxylaminolyases, a set of substituted hydroxylaminoaromatic compounds was synthesized (Fig. 9). In initial experiments, the substrate-dependent oxygen uptake by 4-nitrobenzoate-grown cell suspensions was investigated (Table 2). The synthesized hydroxylaminoaromatic compounds and the corresponding nitroaromatic compounds were used as substrates. It is clear from Table 2 that 4-nitrobenzoate and 4-hydroxylaminobenzoate showed the highest oxygen uptake rate. However, 1-chloro-4-nitrobenzene, 4-nitrobenzonitrile, 4-nitroanisole and, to a... 

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