Tri nitro benzenes

It is obvious here to think of an interaction of the Debye type of the appreciable moment of the nitro or carbonyl group with the readily polarizable unsaturated C — C bond in the unsaturated hydrocarbons or with the likewise readily polarizable free electron pair in the amines, etc. Actually the stability increases with increasing polarizability, compare for example, the heat of formation of j-trinitrobenzene with, respectively, benzene, naphthalene and anthracene AH 0.6, 3.4 and 4.4 kcal. In the series mono-, di- and tri-nitro-benzene with acenaphthene AH also increases with increasing number of partial moments, namely AH — o, 1.35 and 2.45 kcal. Nevertheless this explanation is inadequate, nitromethane with a moment [x = 3.54 D gives very much less stable compounds than nitrobenzene with (X = 4,22 D, while nitrosobenzene with [x =3.2 D gives stronger colour effects than nitrobenzene. 

Tri-nitro Benzenes.—Of the three isomeric tri-nitro benzenes the symmetrical or 1-3-5 compound is the one formed by intense direct nitration of benzene. The 1-2-4 compound has been made by further nitration of para-di-nitro benzene. 

Tri-nitro Toluene. T.N.T.—One of the nitro toluenes is of especial interest and importance because of its use as a military high explosive. This is tri-nitro toluene, commonly known as T.N.T. Other names also used for the substance are, trotyly trinoly trilite and tritolo. The constitution of the compound is that of the symmetrical or 2-4-6-tri-nitro toluene. As a benzene derivative it is, therefore, i-methyl 2-4-6-tri-nitro benzene. 

Solubilities of Di-Nitro BENZENES and of Tri-Nitro BENZENES in Several Solvents. 

No Name Melting poinl, "C Boiling poinl C Pjcrale Slyphnate sym Tri nitro benzene derivative 2,4 7-Tn-nilrofluo-renone derivative Nitro derivative Phthalic anhy dride denva live 2 4Di niiro phenyl sulfenyl chloride denva live Miscellaneous... 

Explosives derived from Benzene—Toluene and Nitro-Benzene-Di- and Tri-nitro-Benzene-Roburite Properties and Manufacture-Bellite Properties, c.-Securite—Tonite No. 3.-Nitro-Toluene-Nitro-Naphthalene—Ammonite-Sprengel s Explosives-Picric Acid- Picrates-Picric Powders—Melinite-Abel s Mixture—Bmgere s Powders- The Fulminates-Composition, Formula, Preparation, Danger of, c.- Detonators Sizes, Composition, Manufacture—Fuses, c. 

Di-nitro-toluene is made in a similar manner. The tri-nitro-benzene can only be made by using a very large excess of the mixed acids. Nitro- benzene, when reduced with iron, zinc, or tin, and hydrochloric acids, forms aniline. 

Name Melting point c Boiling point c "d r Picrate Sulfon amide Nitro denvdtive Bromo derivative 135 Tri nitro benzene addition com pound 3 5- Dinitro- ben zoate... 

N. N -Dipicryl-ethylenedinitramine N,N -Bis(2,4,6 -trinitrophenyl-nitramino)- ethane N,N -Bis(2,4,6 -trinitrophenyl)- ethyl ene-dinitramine 2,4,6-T ri-nitro-1,3,5 tris(methylnitramino)- benzene 2,4,6,-2 , 4 6 -(B exanitrodiphenyD-ethylene-dinitramine Bitetryl or Ditetryl Its British name is Octyl [also called N,N>-Dinitro-N,N,-bis(2,4,6-trinitro-phenyl)-ethylenediamine Octanitroethylenedi-phenylamine and Bis-N(2, 4 ,6 -trinitropbenyl)... 

The addition of mercuric nitrate is here written as a 1,4-addition, but 1,2-addition would give the same final product, and there is no evidence in the facts concerning benzene which enables us to choose between the alternative hypotheses. Toluene yields tri-nitro-m-cresol by a similar series of reactions, and it is clear that the nitro group in the addition product of mercuric nitrate and toluene has taken either the 2-, the 4-, or the 6-position, that is, one or the other of the positions activated by the methyl group. In the addition of mercuric nitrate to naphthalene, the nitro group correspondingly may be supposed to go to the active a-position. If the addition is 1,2-, the product on oxidation will yield a derivative of /J-naphthol. If it is 1,4-, it will yield a derivative of a-naphthol. The two possibilities are indicated below. 

Resorcinol, 5-Methyl, 2,4,6-Trinitro (2,4,6-Tri-nitro-3,5-dioxy-l-methyl benzene or eso-Trinitro-Orcinol). (02N)3C6(OH)2.CH3 mw 259.15 ... 

The reaction occurs particularly readily with nitro groups that are in the 0-and p- position to each other, i.e. with mobile nitro groups . As to meta- nitro groups they react less readily and require a higher temperature. Nitro derivatives of higher homologues of benzene with two or three nitro groups (such as di- and tri-nitro derivatives of m- xylene also react less readily, and trinitromesitylene does not react with sodium sulphite [35a]. 

The so-called Janovsky reaction [53] is a very characteristic one for many higher nitrated benzene derivatives. It is probably also of nucleophilic character. It consists in treating a diluted di- or tri-nitro compound solution in acetone with a concentrated solution of potassium or sodium hydroxide (generally of 30% concentration). The acetone solution turns bright coloured. Red to violet colours may appear according to the nitro compound present. 

These groups direct electrophiles to the meta position and reduce reactivity. Nitration of tri-fluoromethyl benzene gives a nearly quantitative yield of meta nitro compound so there cannot be any significant ortho or para by-products. This reaction is important because reduction of the product (Chapter 24) gives the amine, also in very good yield. 

Di- and Tri-nitro Products.—By intensifying the action of nitration (by heat or fuming nitric acid) more than one nitro group is substituted in the ring, and di- and tri-mXxo derivatives of the hydrocarbons result. In the formation of the di-substitution products of benzene the second nitro group enters the meta position. 

One of the higher homologues of benzene yields a very interesting nitro product. When i-methyl 3-tertiary bulyl benzene is nitrated to a tri-nitro product the three nitro groups enter the 2-4-6 positions. 

The direct chlorination or bromination of aniline takes place more easily than that of benzene, the result being the symmetrical tri-chlor or tri-brom aniline, viz., i-amino 2-4-6-tri-chlor benzene, C6H2CI3-(NH2) and I-amino 2-4-6-tri-brom benzene, CeH2Br3(NH2). The mono-halogen anilines are prepared by reducing mono-chlor nitro benzenes, or by halogenating acetanilide and then hydrolyzing. 

Tri-nitro Phenol. Picric Acid.—When the nitration of phenol is effected with concentrated acid three nitro groups enter the benzene ring and a tri-nitro phenol results. The particular tri-nitro compound formed is the symmetrical one and is known as picric acid. 

Tri-nitro Tri-phenyl Methane.—When tri-phenyl methane is nitrated a tri-nitro tri-phenyl methane is obtained in which one nitro group enters each benzene ring. 

The simplest derivatives of this mixed character which yield dyes are the nitro naphthols, i.e., mixed nitro and hydroxyl substitution products. Recalling well-known compounds of the benzene series it will be remembered that whereas mono-nitro benzene has practically no color, and di-nitro-benzene only a faint yellow color, the mixed tri-nitro phenol or picric acid has an intense yellow color and was one of the first yellow dyes used. 

Other nitro-derivatives of hydrocarhons and of phenols are used in explosive mixtures. Among the former are dinitro-benzene, chlor-dinitro-benzene, dinitro-toluene, di- or tri-nitro-den-vatives of mesitylene, pseudocumene, and xylene, dinitro-naphthalene. Trinitro-naphthalene and tetra-nitro-naphthalene have also been proposed. Of the nitro-phenols, perhaps the most important is tri-nitro-cresol, known as Cresilite in France, where it is added to Melinite. Other nitro-derivatives of the aromatic series will be mentioned in the section on detonators. 

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