Chloronitrobenzene

The reaction of substituted chloronitrobenzenes with arylamines to form substituted diphenyl amines is typified by 4-rutrodiphenylamine-2-sulfoiiic acid where 4-chloronitrobenzene-3-sulfonic acid (PN salt) is condensed with aniline ia an aqueous medium at 120°C and 200 kPa (2 atm) ia the presence of alkaline buffer at low pH to avoid the competing hydrolysis of the PN salt. 

In contrast to the nature of TBAF, tetrabutylammoniuin bifluoride converts benzyl bromide to its fluoride in 100% yield and 4-chloronitrobenzene to 4 fluoronitrobenzene in 70% yield 1-Bromodecane is transformed by tetrabutyl-atnmonium bifluoride to 1-fluorodecanein 88% yield, and Tchlorododecane forms 1-fluorododecane m 83% yield In neither case are significant amounts of the elimination products formed [25]... 

Cross-coupling of 5-ethynyl-4-chloro-l,3-dimethylpyrazole with 3-iodo-4-chloronitrobenzene was carried out in the presence of (PPh3)2PdCl2, Cul, and EtjN (66%) (96MC98) (Scheme 69). 

DTA shows that the reaction mixture from sulfonation of the nitro compound in 20% oleum, containing 35 wt% of 2-chloro-5-nitrobenzenesulfonic acid, exhibits 2 exothermic stages at 100 and 220° C, respectively, the latter being violently rapid. The adiabatic reaction mixture, initially at 89° attained 285°C with boiling after 17 h. At 180° the induction period was about 20 min [1], Sulfonation of 4-chloronitrobenzene with 65% oleum at 46°C led to a runaway decomposition... 

Methyl methacrylate 4-Methylnitrobenzene 2- Methylpyridine Methylsodium Molybdenum trioxide Naphthalene 2-Naphthol Air, benzoyl peroxide Sulfuric acid, tetranitromethane Hydrogen peroxide, iron(II) sulfate, sulfuric acid 4-Chloronitrobenzene Chlorine trifluoride, interhalogens, metals Chromium trioxide, dinitrogen pentaoxide Antipyrine, camphor, phenol, iron(III) salts, menthol, oxidizing materials, permanganates, urethane... 

The high-pressure reaction of A-methylpiperidine with 4-chloronitrobenzene yields A-(4-nitrophenyl)piperidine (equation 117) 2-chloronitrobenzene and chloro-2,4-dinitrobenzene behave analogously. A-Methylpyrrolidine and 4-chloronitrobenzene afford a mixture of A-(4-nitrophenyl)pyrrolidine and the product 342 of ring scission (equation 118)385. 

Chloronitrobenzene, 2141 4-Chloronitrobenzene, 2142 2-Chloro-5-nitrobenzenesulfonic acid, 2144 4-Chlorotrifluoromethylbenzene, 2646 1,2-Dichlorobenzene, 2156... 

Most mononitroaryl compounds do not deflagrate, but mixed with an excess of sodium or potassium hydroxide they deflagrate readily. Some rates (cm/min) for such mixtures are - 4-chloronitrobenzene + KOH (1 1.5 mol), 1.3 4-nitrobenzoic acid + KOH (1 2 mol), 5.1 4-nitrophenol + KOH (1 1.5 mol), 30 ... 

Ammonium dichromate, 4246 Azoformamide, 0816 Azoisobutyronitrile, 3011 Azoisobutyronitrile, 3011 f tert-Butyl peroxybenzoate, 3401 4-Chloronitrobenzene, 2142 f 1,1-Difluoroethylene, 0700 f Diketene, 1441... 

Figure 1 shows a plot of yield vs time for the reaction of 4-chloronitrobenzene with potassium cresoxide, catalyzed by Bu NBr, PEGM 5000 (polyethylene glycol monomethyl ether, avg. molecular weight = 5000) or PVP-X (crosslinked polyvinylpyrrolidone). 

Figure 1. Reaction forming 4-cresyl-4 -nitrophenyl ether from 4-chloronitrobenzene and potassium cresoxide in chlorobenzene at 125 catalyzed by PEGM 5000, PVP-X, or Bu NBr.

Table I. Effect of Cation on PVP Catalyzed Reaction of Sodium or Potassium Cresoxide with 4-Chloronitrobenzene ...

Figure 4. Preparation of the bis-(4-nitrophenyl) ether of bisphenol A via reaction of bisphenol A disodium salt with 4-chloronitrobenzene. Bis salt = biS (4 dihexylaminopyridinium) decane dibromide. Mono salt = N-(2-ethylhexyl) 4-dihexylaminopyridinium mesylate.

Table III. Reaction of 4-Chloronitrobenzene with 2,2,2-Trifluoroethoxide Ion under Neutral PTC Conditions ...

This transformation avoids problems with the change of polarity during the reaction, which occurred in the telomerization, because two aromatic compounds react with each other to form a new aromatic product. The synthesis of 4-nitrodiphenylamine via a Pd-catalyzed Buchwald-Hartwig-type amina-tion from 4-chloronitrobenzene and aniline was chosen as the next test reaction in a cooperation with Lanxess as industrial partner of the network (Scheme 5). 

The ONSH reaction of the carbanion of 2-phenylpropionitrile (45 c) with nitrobenzene in liquid ammonia at -70 °C involves rate-limiting Carom—H bond breaking, as evidenced by the 9.8 times faster rate than for reaction of the analogous substitution of deuterium in 4-<7-nitrobenzene and perdeuterionitrobenzene. Reactions of the carbanion derived from (45c) with 4-chloro-3-trifluoromethylnitrobenzene and 4-chloronitrobenzene in toluene under phase transfer catalysis has also been studied." ... 

The ratio of products (36) and (37) from VNS of hydrogen (Pe) and substimtion of halogen (Px), respectively (Scheme 4), will depend on the strength and concentration of base, provided that the elimination is a kinetically important step in the VNS reaction, namely Pr/Px = kikE[B]/k-ikx. The influence of base will decrease until a constant value Ph/Px = k /kx is reached as kslB] k i. This has been demonstrated for 4-chloronitrobenzene, which undergoes exclusive substimtion of chlorine unless strong base is present to favour the VNS process. The deuterium isotope effect for VNS hydroxylation by Bu OOH, determined as me ratio of H versus D substitution of l-deutero-2,4-dinitrobenzene, varied from 7.0 0.3 to 0.98 0.01 as the base in NH3 was changed from NaOH to Bu OK me former value is consistent with a rate determining E2 process. 

Biological. In an anaerobic medium, the bacteria of the Paracoccus sp. converted 4-chloroaniline to l,3-bis(/t-chlorophenyl)triazene and 4-chloroacetanilide with product yields of 80 and 5%, respectively (Minard et al., 1977). In a field experiment, [ C]4-chloroaniline was applied to a soil at a depth of 10 cm. After 20 wk, 32.4% of the applied amount was recovered in soil. Metabolites identified include 4-chloroformanilide, 4-chloroacetanilide, 4-chloronitrobenzene, 4-chloronitrosobenzene, 4,4 -dichloroazoxybenzene, and 4,4 -dichloroazobenzene (Freitag et al, 1984). 

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