8- Chloro-l-nitronaphthalene

The reactivities of 4- and 2-halo-l-nitronaphthalenes can usefully be compared with the behavior of azine analogs to aid in delineating any specific effects of the naphthalene 7r-electron system on nucleophilic substitution. With hydroxide ion (75°) as nucleophile (Table XII, lines 1 and 8), the 4-chloro compound reacts four times as fast as the 2-isomer, which has the higher and, with ethoxide ion (65°) (Table XII, lines 2 and 11), it reacts about 10 times as fast. With piperidine (Table XII, lines 5 and 17) the reactivity relation at 80° is reversed, the 2-bromo derivative reacts about 10 times as rapidly as the 4-isomer, presumably due to hydrogen bonding or to electrostatic attraction in the transition state, as postulated for benzene derivatives. 4-Chloro-l-nitronaphthalene reacts 6 times as fast with methanolic methoxide (60°) as does 4-chloroquinoline due to a considerably higher entropy of activation and in spite of a higher Ea (by 2 kcal). ... 

This method is essentially that described by Goldhahn. 4-Nitro-l-naphthylamine has also been prepared by the nitration of a-naphthylamine, acetyl-a-naphthylamine, and ethyl-1-naphthyloxamate, by the oxidation of 4-nitroso-l-naphthyl-amine, and by reaction of 4-chloro-l-nitronaphthalene with ammonia. ... 

Condensation of the dianion of 1,2-dimercaptobenzene (380) with 1-chloro-8-nitronaphthalene (483) in DMF provided 45% of benzo[2,3]naphthalene [5,6,7-/j][l,4]dithiepin (484) and a small amount of its 5-oxide 485 (Eq. 44) (89JHC667). Though the structure of 485 was adequately determined (NMR studies, X-ray crystallography), its formation was not definitely explained. 

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%... 

Di jiifro-2f2 osoRophthole ns (c ailed 2,2 -azobis [4-nitronaphthalene in CA) brn-red crysts, mp 315°. Prepd from the action of hydrazine in ale on l-chloro-2,4-dinitro-naphthalene, warmed 6 hrs on a w bath. The product was a mixt of the dinitro compd, the di-NH4 salt of 2,4-C10H6(NO2)2, m-nitro-naphthylazimidole and some 2,4-dimtro naphthalene. The reaction of anhyd hydrazine with l-chIoro-2.4-dinitronaphthalene gave only the 4,4 -dinitro-2,2 -azonaphthaiene and 2,4-dinitronaphthalene (Refs 1 2)... 

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