Dinitronaphthalenes

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). 

The reaction of the corresponding diamine of 1,5-dinitronaphthalene with phosgene produces 1,5-naphthalenediisocyanate/ 173-72-6] (41,42). 

Dimethyl sulfate, 57 Dimethyl sulfide, 57 Dimethyl sulfoxide, 57 Dimethyl terephthalate, 57 Dimetilan, 57 Dinitroanilines, 57 Dinitrobenzenes, 58 Dinitrolmide, 58 Dinitronaphthalenes, 58 Dinitro-o-Cresol, 58 Dinitrophenols, 58... 

Naphthalene-1,8-dicarboxylic add, its nitro-substituted derivatives, and naphthalene-1,4,5,8 tetracarboxylic acid, on treatment with sulfur tetrafluoride at 0 C, undergo dehydration to form quantitatively the corresponding anhydrides [218, 221] Unsubstituted and mononitrated monoanhydndes react further at 200-250 °C to give derivatives of 1,1,3,3-tetrafluoro-l// naphtho[I,8 c,d]pyran Dinitronaphthalene-l,8-di-carboxyhc acid anhydndes and naphthalene 1,4,5,8 tetracarboxylic acid dianhydnde give the respective tetra- and octafluoroethers only in the presence of an excess of anhydrous hydrogen fluoride [221] (equabons 113 and 114)... 

The following isomers are described by Beilstein. These compds are weaker expls than the corresponding dinitronaphthalenes (see under Naphthalene and its Derivatives in this Vol)... 

A zido-2t4-dinitronaphthalene (2,4-Dinitro-l-mphthyl azide). CioHsNgO mw 259.18, N 27.02%, OB to C02 —114% yel needles, mp 105° with decompn prepd by the action of Na azide in boiling abs EtOH on l-chloro-2,4-di-nitronaphthalene, yield 75%... 

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 (1,4-DNN). Long yel needles from MeOH, mp 134° (Refs 6 34) CA Registry No 6921-26-2. It is prepd by the diazotization of 4-nitro-l-naphthylamine followed by treatment of the diazonium salt with powd Cu and Na nitrite (Ref 45)... 

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 (2,6-DNN). Long yel needles from Ac20, mp 279° (Refs 9 30) ... 

Dinitronaphtkalene (2.7-DNNL Y el crysts from Ac20, mp 234° CA Registry No 24824-27-9. It is prepd by the decarboxylation of 3,6-dinitronaphthalene-l,8-dicarboxylic ac with powd Cu in boiling quinoline (Refs 10 26)... 

Dinitronaphthalene-1-sulfonic Acid. Needles from w, mp explds around 300 when heated on a Pt foil (Refs 1 5). It is prepd by the... 

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)... 

Capellos and Suryanarayanan (Ref 28) described a ruby laser nanosecond flash photolysis system to study the chemical reactivity of electrically excited state of aromatic nitrocompds. The system was capable of recording absorption spectra of transient species with half-lives in the range of 20 nanoseconds (20 x lO sec) to 1 millisecond (1 O 3sec). Kinetic data pertaining to the lifetime of electronically excited states could be recorded by following the transient absorption as a function of time. Preliminary data on the spectroscopic and kinetic behavior of 1,4-dinitronaphthalene triplet excited state were obtained with this equipment... 

Nanosecond flash photolysis of 1,4-dinitro-naphthalene in aerated and deaerated solvents showed a transient species with absorption maximum at 545nm. The maximum of the transient absorption was independent of solvent polarity and its lifetime seemed to be a function of the hydrogen donor efficiency of the solvent. The transient absorption was attributed to the lowest excited triplet state of 1,4-dinitronaphthalene. Based on spectroscopic and kinetic evidence, the triplet state of 1,4-dinitronaphthalene behaved as an n - Tt state in nonpolar solvents,... 

The most recent researches of Capellos and Suryanarayana on the triplet excited states of 1,2- and 1,8-dinitronaphthalenes, and those of Capellos and Lang on the triplet excited states of 4-nitronaphthalene and 4-nitro-N, N -dimethyl-naphthalene have been accepted for publication by the International Journal of Chemical Kinetics Refs 1) G. Schultz K.L. Ganguly, Ber 56,... 

Dinitro-o-phthalic Acid. Needles from eth, mp 200—202°. Easily sol in w, ale or eth. Can be prepd by heating 1,5-dinitronaphthalene with mixed nitric-sulfuric acid. Its barium salt (Refs 2 3) is expl... 

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