1.4.5- Tris naphthalenes nitration

Sulfonation. Sulfonation of naphthalene with sulfuric acid produces mono-, di-, tri-, and tetranaphthalenesulfonic acids (see Naphthalene derivatives), ah of the naphthalenesulfonic acids form salts with most bases. Naphthalenesulfonic acids are important starting materials in the manufacture of organic dyes (15) (see Azo dyes). They also are intermediates used in reactions, eg, caustic fusion to yield naphthols, nitration to yield nitronaphthalenesulfonic acids, etc. 

Tri nitro-1 -N aphthol (2,4,7 -Trinitro-1 -oxy-naphthalene). Yellow prisms from AcOH or benz, mp 145° (decompn). Sol in AcOH glac AcOH. Prepn from 2,4-dinitro-l-naphthol by mixed acid (nitric-sulfuric-acetic) nitration. The compound is extracted as the Na salt from... 

Other important expls obtd on nitration of products of distillation of coal tar were Di- and Tri nitrobenzene (Vol 2 of Encycl, pp B46ff and Nitronaphthalenes, which will be described under Naphthalene and Derivatives... 

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. 

Thermochemical data are available (Ref 2) on the heats of combustion and formation for all five isomers, on the heats of nitration from various Dinitrotoluenes for the 23,4-, 2,4,5-, and 2,3,6-isomers, and on the heats of crystn for the 2,3,4- and 2,4,5-isomers. Data are also available (Ref 1) on the shock sensitivities of all of the isomers except 2,3,6-, and on the rates of decompn at 140° of the 23,4-, 2,4,5-, and 23,5-isomers. The detonation pressure and the temp coefficient of decompn between 140 and 180° have been measured for the 2,4,5-isomer 2,3,4- and 2,4,5-TNT form addition compds ( 7r-complexes ) at 1 1 molar ratio with several polycyclic aromatic hydrocarbons (naphthalene, acenaphthene, fluorene, phenanthrene and anthracene) (Ref 2). 2,4,5-TNT forms complexes with 4-aminozaobenzene, 4-aminoacetophenone, bis (2 hydroxy ethyl) amine, and tris (2-hydroxy-ethyl) amine (Ref 1). The first two have a 1 1 molar ratio, the third 1 2, and the fourth 2 1. Upon heating, the two 4-amino compds react with replacement of the 5-nitro group, as discussed below... 

Nitration of naphthalene was first mentioned in description of experiments by Lament [9] between 1835 and 1842. On boiling naphthalene with nitric acid he obtained a mixture of mono-, di- and tri-nitronaphthalenes. 

The conditions under which mono-, di-, tri- and tetra-nitronaphthalenes Me formed were investigated in detail by Patart [19] in extensive experimental work. By applying similar conditions (temperature and time) for the nitration of naphthalene with various nitrating mixtures, Patart determined the compositions of the products (the number of nitro groups) from the pressures they produced in a manometric bomb. The pressures, produced by pure substMices were known, viz. ... 

Lantz [23 a] has studied the nitration of naphthalene sulphonic acids (mono-, di- and tri-sulphonic acids). He stated that no displacement of the sulphonic groups with nitro groups occurs. By using nitrating concentrated mixtures he was able to introduce nitro groups so that the number of both S03H and N02 groups reached a maximum of four. 

In contrast to the 4-nitro derivative 108, its tetraethyl counterpart 164 could be mononitrated to form a mixture of compounds 166 and 167 (Scheme 28)164. Probably, in this case, owing to higher basicity of the tetraethyl sponge (Table 16), both dinitro derivatives in sulfuric acid are present mainly in the form of cations and their further nitration occurs relatively slowly. The nitration of 4-bromo-l,8-bis(dimethylamino)- (117)52 and l,4,5-tris(dimethylamino)naphthalenes (64)44 in H2SO4 led to compounds 169, 170 and 171. 

If the graphic formula of benzene be represented thus (No. 1), then the positions 1 and 2 represent the ortho, 1 and 3 the meta, and 1 and 4 the para compounds. When the body phenol, C 6 H 5. OH, is nitrated, a compound is formed known as tri-nitro-phenol, or picric acid, C 6 H 2 (NO 2 ) 3 OH, which is used very extensively as an explosive, both as picric acid and in the form of picrates. Another nitro body that is used as an explosive is nitro-naphthalene, C 10 H 6 (NO 2 ) 2, in roburite, securite, and other explosives of this class. The hexa-nitro-maimite, C 6 H 8 (ONO 2 ) 6, is formed... 

Securite eonsists of 26 parts of meta-di-nitro-benzol and 74 parts of ammonimn nitrate. It is a yellow powder, with an odour of nitro-benzol. It was licensed in 1886. It sometimes contains tri-nitro-benzol, and tri-nitro-naphthalene. The equation of its combustion is given as... 

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