4-Chloro-1,2-dinitrobenzene → Phenol, 5-chloro-2-nitro-
反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([N+]([O-])=O)[CH:3]=1.[N+](C1C=CC(N)=CC=1O)([O-])=[O:15]>[Cu]Cl>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=1[OH:15])([O-:10])=[O:9]参加物
4
実験手順
It is known that the fluorine compound mentioned may be prepared over long reaction times (32 hours) in ethers such as dioxane, using phase transfer catalysis at low temperatures (30° C.) (JP 63310851 A2). Working in water produces an isomeric ratio of about 7:1. Nothing is known from this source about the separation of the isomers. Furthermore, it is known that the chlorine compound may also be prepared in solvent/water mixtures in yields of about 90% (DE 29 39 056). In an earlier known process (DE 29 35 629) aqueous alkali metal hydroxide solutions are used in polar aprotic solvents and emulsifiers (20 hours, 60° C., 81%) for this reaction. Finally it is known that in general 2-nitrohalophenols may be prepared by the reaction of the corresponding nitrohalobenzenes at high temperatures (155° C., 2 hours) in anhydrous media. 4,5-dichloro-2-nitrophenol may be obtained in 77% yield in this way (DE 26 14 264). 2-nitro-5-chlorophenol may be obtained by reacting 4-chloronitrobenzene with KOH at 50° C. in the presence of glass bodies (FR 1 581 400). The same oxidation may be performed in 85-87% yield in solvents, for example 1,2-dimethoxyethane, using phase transfer catalysis (18-crown-6) (Izv. Akad. Nauk. SSSR, Ser. Khim., (11) 2635-2636). Yields of about 90% may be obtained in tertiary alcohols when using aqueous potassium hydroxide solution (6 hours, 60° C.) (JP 52142031). Nitration of 3-chlorophenol has long been known (Uhlemann, Chem. Ber. (1878), 1161; De Kiewiet, Stephen, J. Chem. Soc. (1931), 84). This nitration may also be performed in acetic acid at 0° C. (Roberts, Rhys, J. Chem. Soc. (1937), 39, 41) or using sodium nitrate and dilute sulfuric acid (Hodgson, Moore, J. Chem. Soc. 127 (1925), 1600). A variant is the reaction of 3-chloroaniline with dilute nitric acid (Uhlemann, loc. cit.) or gases containing nitrogen oxides (NOx); however, isomers are produced besides the desired product (v. Auwers, Deines, Fortschr. Ch. Phys. 18, 59; Chem. Zentralblatt, 1924 (II) 2268). In addition, reactions of 4-chloro-1,2-dinitrobenzene with aqueous alkali metal hydroxide solution (Laubenheimer, Chem. Ber. 9 (1876), 768) and of 2-nitro-5-aminophenol with copper(I) chloride in the sense of a Sandmeyer reaction (Phillips, J. Chem. Soc. (1930), 1910, 1913) are known, 2-nitro-5-chlorophenol being obtained.