1.6- Naphthalene diamine

Similarly, the isolated salt 39 reacts with naphthalene-1,8-diamine in dichloromethane at room temperature to afford the 2,3-dihydro-l//-perimidine 78 in 85% yield (92SC3141) (Scheme 24). 

Naphthalene-1,8-diamines 16 can be cyclized by reaction with nitrous acid, yielding l//-naphtho-[1,8-c/e]-l, 2,3-triazines 17.7,196... 

Di-2-hydroxy-3-o-naphthoquinoxalyldiphenyl diselenide is formed when the o-phenylenediamine is replaced by 1 2-naphthalene-diamine. It is an orange crystalline powder, M.pt. 352° to 355° C. 

The tetrazotization of m-phenylenediamine has been described also, under special conditions (nitrosylsulfuric acid in glacial acetic acid) a similar conversion of the ortho isomer has been accomplished. This procedure has been adaf>ted to the tetrazotization of certain naphthalene diamines. The simultaneous diazotization of two amino groups in the biphenyl series is illustrated by the synthesis of 4,4 -biphenylene-fejs-diazonium chloride and its 3,3 "dimethyl analog. ... 

In primary synthesis 2-perimidinamines (660) can be prepared from the naphthalene diamine with bromocyanogen or cyanamide (Scheme 106). 2-Anilino derivatives have been obtained in reactions with aryl isothiocyanates. 2-iV,7V-Dimethylamino derivatives (662) have been obtained via the alkylated amine (661) using dimethylamino(trichloro)methane. Nucleophilic substitution by amine readily occurs in the 2-position when carrying a halo, sulfenyl, or sulfonyl substituent <81RCR816>. 

Similar copolyimide was prepared using 3,7-diamino-2,8(6)-dimethyldibenzothiopheneS,5-dioxide (DDBT) instead of m-SED and its performance for olefin/paraffm separation was investigated [74]. Block copolymers of liquid crystalline polyamide and amorphous PI were prepared from a two-pot polycondensation reaetions [75]. Hydrocarbon (C-2 and C-3) separations in copolyimide dense membranes derived from 6FDA, DDA and 1,5-naphthalene diamine (NDA) was studied [76]. Gas transport properties of 6FDA, DDA and 3, 3 -diaminodiphenyl sulfone (DIDS) was reported [77]. 

Perylenes (70) are diimides of perylene-3,4,9,10-tetracarboxylic acid, and may be prepared by reaction of the bis-anhydride of this acid, 89 (1 mol) with the appropriate amine (2 mol) in a high-boiling solvent as illustrated in Scheme 4.11. The synthesis of perinones 71 and 72 involves condensation of naphthalene-1,4,5,8-tetracarboxylic acid with benzene-1,2-diamine in refluxing acetic acid. This affords a mixture of the two isomers, which may be separated by a variety of methods, generally involving their differential solubility in acids and alkalis. 

The simplest case for complete enforcement of the convergent conformation was provided by meta xylidine diamine 10. Condensation of two triacids with this amine in the melt gave excellent yields of the dicarboxylic acid 11 (Eq. (2)). The architectural cliche is easily repeated in the naphthalene series to provide 12 and in the acridine series to provide 13. The latter is derived from the commercially available acridine yellow at very low cost. 

This approach frequently leads to the most active metals as the relatively short reduction times at low temperatures leads to reduced sintering of the metal particles and hence higher reactivity. Fujita, et aL(62) have recently shown that lithium naphthalide in tqluepe can be prepared by sonicating lithium, naphthalene, and N, N, N, N-tetramethylethylene-diamine (TMEDA) in toluene. This allows reductions of metal salts in hydrocarbon solvents. This proved to be especially beneficial with cadmium(49). An extension of this approach is to use the solid dilithium salt of the dianion of naphthalene. Use of this reducing agent in a hydrocarbon solvent is essential in the preparation of highly reactive uranium(54). This will be discussed in detail below. 

Since the discovery of the exceptional basicity of l,8-bis(dimethylamino)-naphthalene (Alder et al., 1968) and its unusual kinetic behaviour (Hibbert, 1973, 1974, 1975) there has been considerable interest in the acid-base properties of hindered diaminonaphthalenes. 1,8-Bis(dimethylamino)naph-thalene (pK — 12.1 at 25°C and ionic strength 0.1 mol dm-3) (Alder et al., 1968 Hibbert, 1974 Chiang et al., 1980) is more basic than most aliphatic amines and the pAT-values of the partially methylated diamines [52] illustrate the dramatic effect of introducing the fourth methyl group (Alder et al., 1968). Reaction of protonated l,8-bis(dimethylamino)naphthalene with... 

Perinones are structurally similar to perylenes being made by condensing naphthalene tetracarboxylic dianhydride with amines, but in this case 1,2-diamines, e.g. Cl Pigment Orange 43 (2.71), or its cis isomer. The isomers can be separated by fractionation of their salts. They offer orange to bordeaux shades with similar properties to perylenes, but are less commercially important. 

Azetidines are often synthesized by reacting 1,3-dihalogenopropanes with an amine (ammonia gives poor yields), or from propane-1,3-diamines where one A-substituent can function as a leaving group. A reaction of the latter type is used to synthesize azetidine from A,A-bis(toluenesul-fonyl)-l,3-diaminopropane in two steps, the last being a reductive A-de-toluenesulfonation, caused by adding sodium to naphthalene in an inert solvent (Scheme 8.5). 

The oxidising agent usually employed is the nitro-compound corresponding to the amine, e.g., nitrobenzene when aniline is the base for p-toluidine, p-nitrotoluene serves, and so on. Arsenic acid, however, can be generally employed, and gives better results. The reaction is capable of very wide application nitro-, halogen-, hydroxy-, carboxy-quinolines can all be obtained from the corresponding amines the amino-naphthalenes also react. Diamines yield the so-called phen-anthrolines. (B., 16, 2519 23, 1016.)... 

In support of this view the p-amino-phenols themselves readily yield quinones. Also most p-substituted primary amines, e.g., p-diamines, p-alkylamines, such as p-toluidine, sulphanilic acid and its derivatives, behave similarly. In fact, the reaction can be used as a test for p-substi-tuted primary amines. p-Benzoquinone is usually made from aniline for the other p-quinones the p-amino-phenols, which are easily obtained by reduction of the p-nitroso-phenols and of azo-phenols, are employed. These reactions also apply, but not so widely, in the naphthalene series. 

Naphthoquinone has been prepared by the oxidation of naphthalene,1 1,4-aminonaphthol,2 1,4-naphthylene diamine,2 and 1,4-naphthylamine sulfonic acid.3 Recent work4 has shown that the oxidation of the 1,4-aminonaphthol is the most convenient method of preparation. 

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