1-Chloro-4-nitro-benzene solution

Dichloro-6-nitroquinoxaline reacts with aziridine(ethyleneimine) in benzene solution at room temperature, in the presence of triethylamine as acid scavenger, to give the 2-aziridinyl derivative, the 6-nitro group thus selectively activating the 2-chloro substituent. Chlorine activation is also apparent in the substitution reactions of 2-chloroquinoxaline 1-oxide, which is converted into the 2-amino 1-oxide by treatment with aqueous or ethanolic ammonia at 60-80° and thus under much milder conditions than those used for the conversion of 2-chloroquinoxaline into 2-aminoquinoxaline. 

Solution What is an immediate precursor of the target Because the final step will involve introduction of one of three groups—chloro, nitro, or propyl—w-have to consider three possibilities. Of the three, we know that chlorinatioi. of o-nitropropylbenzene can t be used because the reaction would occur at the wrong position, Similarly, a Friedel-Crafts reaction can t be used as the final step because these reactions don t work on nitro-substituted (deactivated) benzenes, Thus, the immediate precursor of our desired product i> probably wt-chloropropylbenzene, which can be nitrated. This nitration gives a mixture of product isomers, which must then be separated (.Figure 16.24). 

Quite lately a patent has been taken out for a mixture of nitro- naphthalene or di-nitro-benzene with ammonium nitrate, and consists in using a solvent for one or other or both of the ingredients, effected in a wet state, and then evaporating off the solvent, care being taken not to melt the hydrocarbon. In this way a more intimate mixture is ensured between the particles of the components, and the explosive thus prepared can be fired by a small detonator, viz, by 0.54 grms. of fulminate. Favier s explosive also contains mono-nitro-naphthalene (8.5 parts), together with 91.5 parts of nitrate of ammonia. This explosive is made in England by the Miners Safety Explosive Co. A variety of roburite contains chloro-nitro-naphthalene. Romit consists of 100 parts ammonium nitrate and 7 parts potassium chlorate mixed with a solution of 1 part nitro-naphthalene and 2 parts rectified paraffin oil. 

Small hydrogen isotope effects have been found in a nucleophilic substitution of an aromatic heterocycle, the reaction of cyanuric chloride with aniline-N,N-d2 in benzene solution (Zollinger, 1961a). As the effects are small (5%), it is difficult to draw definite mechanistic conclusions. The reactions of cyanuric chloride and other halogenated triazine derivatives are subject to bifunctional catalysis (e.g. by carboxylic acids and by a -pyridone) and to catalysis by monofunctional bases like pyridine (Bitter and Zollinger, 1961). Reinheimer et al. (1962) measured the solvent isotope effect in the hydrolysis of 2-chloro-5-nitro-pyridine (A h,o/ d.o = 2 36). The result makes it probable, but... 

Metathiazanones (IX-88) are prepared by heating a benzene solution of thiosalicylic acid, 2-(or nd o-chloro-(or /n-nitro-)benzalde-... 

Diiron dodecacarbonyl has also been used as a reagent for the reduction of nitro-benzenes to anilines [47]. The two-phase reduction reaction which is believed to involve phase transfer of the HFe3(CO)ri anion occurs rapidly at room temperature and requires one half equivalent of Fe3(CO)i2. The reaction takes place as formulated in equation 9.18 and affords yields of 85%, 92%, 88%, and 60% with 4-methyl-, 4-methoxy-, 4-chloro- and 4-acetylnitrobenzenes. It is interesting that these reactions are so successful in benzene solution, a medium in which BTEAC is an ineffectual catalyst under other circumstances [48]. 

The electron affinities of halogenated aromatic and aliphatic compounds and nitro compounds have been evaluated. Additional electron affinities for halogenated benzene, freons, heterocyclic compounds, dibenzofuran, and the chloro- and fluoroben-zenes are reported from ECD data. The first positive Ea for the fluorochloroethanes were obtained from published ECD data. The Ea of halogenated aromatic radicals have been estimated from NIMS data. The AEa of all the halobenzenes have been calculated using CURES-EC. The Ea of chlorinated biphenyls and chlorinated napthalenes obtained from reduction potentials have been revised based on variable solution energy differences. 

According to Teppema and Sebrell [357], the preparation of benzo-thiazoline-2-thiones from aryl amines, sulfur and carbon disulfide is not generally applicable. This has been confirmed by several other authors. Another synthesis, method C, has been worked out starting with o-nitro chloro benzenes. On warming these products in a solution of sodium hydrogen sulfide with slow addition of hydrogen sulfide in the presence of carbon disulfide, near 90% yields of benzothiazoline-2-thiones are obtained. 

Unfortunately, a vast portion of the WO works reported in the literature deals with the non-catalyzed oxidation kinetics for single compounds. In a review by Matatov-Meytal and Sheintuch , it was found that pure compounds such as phenol, benzene, dichlorobenzene, and acetic acid obey a first-order rate law with respect to the substrates and mainly half order with respect to the oxygen concentration. A thorough kinetic investigation in an isothermal, differentially operated fixed bed reactor with the oxygen pre-saturated aqueous solutions has revealed that the catalytic oxidation of acetic acid, phenol, chloro-phenol, and nitro-phenol can be well expressed by means of the Langmuir-Hinshelwood kinetic formulation ° , namely... 

SOLUTION (a) The name and formula indicate a chloro-group. Cl, and a nitro-group, NO2, attached to a benzene ring. There are six positions in which to place these two groups. They can be ortho-, meta-, or... 

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