Dinitronaphthalenes nitration

In the nitration of benzene, wj-dinilro- and sym-trinitrobenzenes are obtained under more vigorous conditions. With naphthalene, 1-nitronaphthalene is the first product and further nitration gives a mixture of 1,5- and 1,8-dinitronaphthalenes 2-nitronaphthalene is never obtained. 

Nitronaphthalene. 1-Nitronaphthalene is manufactured by nitrating naphthalene with nitric and sulfuric acids at ca 40—50°C (37). The product is obtained in very high yield and contains ca 3—10 wt % 2-nitronaphthalene and traces of dinitronaphthalene the product can be purified by distillation or by recrystaUization from alcohol. 1-Nitronaphthalene is important for the manufacture of 1-naphthalenearnine. Photochemical nitration of naphthalene by tetranitromethane in dichioromethane and acetonitrile to give 1-nitronaphthalene has been described (38). 

Dinitronaphthalene ( Gamma-dinitronaph-thalene, 1,3-DNN), Bright yel needles from aq pyridine, mp 144°, bp subl (Refs 1 32) CA Registry No 606-37-1. It is prepd by the action of nitric ac/sulfuric ac on naphthalene at low temps (Refs 14 33) by the nitration of 1-MNN with a mixt of 17.3% nitric ac, 61.2% sulfuric ac, and 21.5% w, temp 59-75°, time 90min (Ref 52) by the action of powd Cu (Ref 18) or hydrazine (Ref 22) on l-chioro-2,4-dinitro-naphthalene by the diazotization of 2,4-dinitro-1-naphthylamine followed by redn of the dia-zonium salt with EtOH (Ref 25) or by the action of Br on 5,7-dinitro-l,2,3,4-tetrahydro-naphthalene followed by dehydrobromination (Ref 13). It is used to prep more highly nitrated naphthalenes... 

Dinitronaphthalene (Delta-dinitronaphtha-lenet 1,6-DNN). Crysts from acet ac, mp 166-67°, bp at 10mm 235°, 360° with decompn (Refs 2 31) CA Registry No 60746-5. It is prepd by the nitration of 2-nitronaphtha- ene with nitric ac/sulfuric ac in hot acet ac (Ref 21) by diazotization of 5-nitro-2-naphthyl-amine followed by treatment of the diazonium salt with Na cobaltinitrite, yield 40% (Ref 36) or by removal of the amino group from 1,6-dinitro-2-naphthylamine by diazotization followed by redn (Ref 17). The temp of expin is 492°(Refl7)... 

Dinitronaphthalene-2-sulfonic Acid. Solid which explds on heating prepd by nitration of 8-nitronaphthalene-2-sulfonic ac with mixed ac at 0-15° (Ref 2)... 

Mixtures of sodium (or its alloy with potassium) and nitromethane, trichloroni-tromethane, nitrobenzene, dinitrobenzene, dinitronaphthalene, ethyl nitrite, ethyl nitrate or glyceryl nitrate are shock-sensitive, the sensitivity increasing with the number of nitro groups. 

Nitration via diazotisation has been extensively used for the synthesis of isomeric dinitronaphthalenes. Ward and co-workers used nitration via diazotisation to prepare 3,3, 4,4 -tetranitrobiphenyl from 3,3 -dinitrobenzidine, and 3,4,5-trinitrotoluene from 3,5-dinitro-4-toluidine. Ward and Hardy " prepared 1,4,6-trinitronaphthalene from 4,7-dinitro-1-naphthylamine. Korner and Contardi used the nitrate salts of aryldiazonium compounds for the synthesis of polynitro derivatives of benzene " and toluene. " " Accordingly,... 

Am Nitrate Dinitronaphthalene Dinitrotoluene Trinitrotoluene Am Perchlorate K Perchlorate K Nitrate Woodflour OU... 

One of the most widely used mixtures comprised ammonium nitrate with dinitronaphthalene in a ratio giving complete decomposition with a zero oxygen balance ... 

Ammonium nitrate Sodium nitrate Nitronaphthalene Dinitronaphthalene... 

Schneiderite, for instance, consisting of a mixture of ammonium nitrate and dinitronaphthalene, is mixed in an edge runner in batches of 60 kg. The mixing... 

Abbreviations Amm Ammonium DNB Dinitrobenzene DNN Dinitronaphthalene DNDFhA Dinitrodiphenylamine GuN Guanidine nitrate HNDPhA Hexanitrodiphenylamine PETN Pentaerythritol Tetranitrate PH- olx Ethyl-enediamine Dinitrate RDX Cyclonite, or Hexogen TNT Trinitrotoluene TNX Trinitroxylene. 

Naphthalene nitrates more readily than benzene, the first nitro group taking the a-position which is ortho on one nucleus to the side chain which the other nucleus constitutes. The second nitro group takes one or another of the expected positions, either the position meta to the nitro group already present or one of the a-positions of the unsubstituted nucleus. The dinitration of naphthalene in actual practice thus produces a mixture which consists almost entirely of three isomers. Ten different isomeric dinitronaphthalenes are possible, seven of which are derived from a-nitronaphthalene, seven from /3-nitronaphthalene, and four... 

None of the nitrated naphthalenes is very sensitive to shock. a-Nitronaphthalene is not an explosive at all and cannot be detonated. Dinitronaphthalene begins to show a feeble capacity for explosion, and trinitronaphthalene stands between dinitrobenzene and dinitrotoluene in its explosive power. Tetranitro-naphthalene is about as powerful as TNT, and distinctly less sensitive to impact than that explosive. Vennin and Chesneau report that the nitrated naphthalenes, charged in a manometric bomb at a density of loading of 0.3, gave on firing the pressures indicated below.46... 

The Schneiderite (Explosif S or /Sc) which the French used during the first World War in small and medium-size high-explosive shells, especially in the 75 mm., was made by incorporating 7 parts of ammonium nitrate and 1 of dinitronaphthalene in a wheel mill, and was loaded by compression. Other mixtures, made in the same way, were used in place of Schneiderite or as a... 

MelMider nitrated naphthalene to a- dinitronaphthalene and other compounds to dinitro derivatives. When nitrating ordinary aromatic compounds (not containing heavier hydrogen isotopes) with a nitrating mixture containing water plus a... 

As for naphthalene, Pictet [56] found that nitration at temperatures from -50 to -60°C mostly resulted in the formation of 1,5-dinitronaphthalene with a certain amount of the 1,3-isomer, while at a temperature higher than room temperature 1,5-dinitronaphthalene is formed along with 1,8-isomer. 

Indeed Pascal [83] found that in the waste acid from the nitration of naphthalene to dinitronaphthalene, the NH3 content amounted to 0.001-0.002%, based on the naphthalene used for nitration. 

Donaldson [2] gives an example. In 1,8-dinitronaphthalene the 3- and 6-positions are the least deactivated and nitration leads to 1,3,6,8-tetranitronaphthalene. Where two positions remain open the a- position shows a greater activity because of the nature of the naphthalene ring. An anomalous and important case is that of 1,5 dinitronaphthalene, in which only positions 3 and 7 are not deactivated. The main product of nitration of 1,5-dinitronaphthalene is 1,4,5-trinitronaphthalene and not 1,3,5- as would be expected. This led Hodgson and Ward [3] to conclude that the predominant hybrid in 1,5-dinitronaphthalene is... 

Troost [12] obtained nitro- and dinitro-naphthalenes by successive nitration of naphthalene. Darmstadter and Wichelhaus [13] found that the dinitronaphthalene thus obtained was a mixture of the two isomers. 

SimilM experiments were carried out with the products of nitration of dinitronaphthalene. 

Later Sapozhnikov [20] used Patart s data [19] for his triangular diagram, representing nitration of naphthalene (Figs. 104). In Fig. 105 and 106 the nitration curves for naphthalene and dinitronaphthalene are shown (Pascal [21]). 

Fig. 106. Pascal s diagram of the nitration dinitronaphthalene-limits of formation ...

Patart [19] found that commercial grade dinitronaphthalene, being a mixture of isomers, could be obtained by the nitration of naphthalene or a- nitronaphthalene with a mixture of the composition ... 

Ward and Hawkins [27] nitrated 1-nitronaphthalene with a mixture of nitric (sp. gr. 1.42) and sulphuric (sp. gr. 1.84) acids, at a volume ratio 4 1 at 0°C and obtained a mixture of 1,8- and 1,5-dinitronaphthalenes, their ratio being about 70 30. 2-Nitronaphthalene, nitrated under similar conditions, gave a mixture of 1,6- and 1,7-dinitronaphthalenes along with 1,3,8-trinitronaphthalene, at a ratio of about 42 52 9. 

Application. A mixture of the dinitronaphthalene isomers is used in explosive compositions with picric acid and ammonium nitrate for military and mining explosives (Vol. III). The mixture is often referred to as Dinal . It is also designated by the symbols DN or DNN. It is an explosive very difficult to detonate. The highest rate of detonation of Dinal, when using a very powerful detonator, is about 5100 m/sec (Calvet [32]). 

As Pascal [20] found, in the nitration of 1,5-dinitronaphthalene a product of the following percentage of isomers can be obtained ... 

By the nitration of commercial dinitronaphthalene a product is obtained which consists of the 1,3,6,8-, 1,3,5,8- and 1,4,5,8-isomers. The existence of the a- isomer is not quite certain. It was reported by d Aguiar [14], who obtained it by the prolonged boiling of 1,5-dinitronaphthalene with nitric acid (sp. gr. 1.45). The exper-riments were repeated by Beilstein and Kuhlberg [15] with a mixture of nitric and sulphuric acids instead of the nitric acid alone. However, Will s investigations [17]... 

Starting from dinitronaphthalene more dilute nitrating mixtures may be applied ... 

The mixture is prepared from 600 kg of the spent acid from the dinitronaph-thalene manufacture and 550 kg of the spent acid from mononitration, which has been re-used for washing dinitronaphthalene. In consequence the spent acid contains some of the HN03 adsorbed by dinitronaphthalene. The composition and the quantity of the mixture should be so calculated as to contain 128 kg of HN03, required for complete nitration of 300 kg of naphthalene. 

The direct nitration of naphthalene to dinitronaphthalene by the method applied at I. G. Ludwigshafen is carried out in the following way ... 

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