2- Bromonaphthalene preparation

Tin phthalocyanines can be prepared using tin(II)110 or -(IV)154 chlorides. The reaction can be performed in 1-chloro-1 10,1 37,1 55 or 1-bromonaphthalene,154 starting from phthalonitrile110137154,155 or phthalic anhydride. In the second case, urea and ammonium molyb-date(VI) arc added.137 The central tin atom can also be introduced into metal-free phthalocyanine by the reaction with tin(IV) chloride in dimethylformamide.141 Treatment of PcSnCl2 with disodium phthalocyanine in refluxing 1-chloronaphthalenc forms a sandwich-like bis-(phthalocyanine) Pc2Sn.154... 

Zinc phthalocyanine (PcZn) is prepared from phthalonitrile in solvents with a boiling point higher than 200 C, e.g. quinoline277,278 or 1-bromonaphthalene,137 or without solvent in a melt of phthalonitrile.83,116 The zinc compound normally used is zinc(ll) acetate or zinc powder. The reaction of zinc(II) acetate with phthalic acid anhydride, urea and ammonium mo-lybdate(VI) is also successful.262 The metal insertion into a metal-free phthalocyanine is carried out in an alcohol (e.g.. butan-l-ol).127,141,290 This reaction can be catalyzed by an alkali metal alkoxide.112,129... 

P-Bromonaphthalene. The preparation from p-naphthylamine, which has carcinogenic properties, is avoided by the use of 2-naphthylamine-1-sulphonic acid ( 2-amino-1-naphthalenesulphonic acid ) the latter is obtained commercially by cautious treatment of p-naphthol with sulphuric acid—the SOjH group first enters the 1-position—followed by the Bucherer reaction. Diazotisation and reaction with cuprous bromide yields 2-bromonaphthalene-l-sulphonic acid heating with sulphuric acid eliminates the sulphonic acid group to give 2-bromonaphthalene. 

Figure 27.1. Kinetic profiles for the coupling of 4-bromoanisole with phenylboronic acid to yield 4-bromonaphthalene, (a) using as-prepared BaCeo95Pdoo502 95 (open circles) or BaCeo9oPdoio02 9o (filled circles) as the catalyst and (b) using BaCeo95Pdoos02 95 as-prepared (small open circles) reduced (filled circles) and reoxidized (open squares) as the catalyst. Reagents and conditions 3.0 mg catalyst (0.05 mol % Pd, X = 0.05 0.10 mol % Pd, x = 0.10), 1.0 mmol 4-bromoanisole, 1.5 mmol PhB(OH)2, 4.0 mmol K2CO3, 12 mL IPA-H2O (1 1, v/v), 80°C. Lines are drawn only to guide the eye.

Phenylnaphthalene has been prepared by the reaction of a-halonaphthalenes with mercury diphenyl3 6 or with benzene in the presence of aluminum chloride,6 and by means of the Gri-gnard synthesis, starting with either bromobenzene, cyclohexyl chloride, and a-tetralone 7 or with a-bromonaphthalene and cyclohexanone.6 8 9 Dehydrogenation of the reduced naphthalene has been accomplished by the use of sulfur,6 bromine,8 platinum black, or selenium.7 The formation of the hydrocar-... 

Diathiadiphosphetane disulfides are probably the most studied and the most thermally and hydrolytically stable of all the phosphorus-chalcogen heterocycles. They contain a central four membered P2S2 ring and can be prepared from heating phosphorus pentasulfide with aromatic compounds. The most well-known of these is Lawesson s reagent (43), which is made from anisole and phosphorus pentasulfide,92 and is used extensively in organic synthesis procedures (see Section 5.4.1). Other dithiadiphosphetane disulfides of note are 44 and 45, formed from the reaction of phosphorus pentasulfide with ferrocene or 1 -bromonaphthalene respectively.93... 

The syntheses of 1 utilized the Ullmann ether synthesis.13 Reaction of 2 mol of 1-bromonaphthalene with 4,4-(hexafluoroisopropylidiene)diphenol afforded the desired product 1. The reaction was carried out in DM Ac at 160°C in the presence of potassium carbonate as the base and copper (I) iodine as the reaction catalyst to yield 1, as depicted in Scheme 1. The reaction proceeded slowly but in good yield with easy isolation of the desired compound. Acylation of 1 with 4-fluorobenzoyl chloride to prepare 2 was carried out under modified Friedel-Crafts reaction conditions14 using dimethyl-sulfone as catalyst moderator. Both 1 and 2 were easily recrystallized to yield high-purity monomers suitable for polymerizations. 

Since the presence of even 5-10% of unchanged 1-bromonaphthalene makes purification of the naphthalene difficult, it is important that the reduction be complete before the product is isolated. With reaction conditions described in this preparation [0.100 mole of ethylenediarnine, 0.0080 tnole of l-bromonaphthalono, 60 ml. (0.031 mole) of acpuious 0.519M... 

Diazotise 223 g. of 2-naphtliylamine-l-sulphonic acid as detailed under fi-Bromonaphthalene in Section IV,62. Prepare cuprous cyanide from 125 g. of cupric sulphate pentahydrate (Section IV,66) and dissolve it in a solution of 65 g. of potassium cyanide in 500 ml. of water contained in a 1-litre three-necked flask. Cool the potassium cuprocyanide solution in ice, stir mechanically, and add the damp cake of the diazonium compound in small portions whilst maintaining the temperature at 5-8°. Nitrogen is soon evolved and a red precipitate forms gradually. Continue the stirring for about 10 hours in the cold, heat slowly to the boiling point, add 250 g. of potassium chloride, stir, and allow to stand. Collect the orange crystals which separate by suction filtration recrystallise first from water and then from alcohol dry at 100°. The product is almost pure potassium 2-cyanonaphthalene-l-sulphonate. Transfer the product to a 2-litre round-bottomed flask, add a solution prepared from 400 ml. of concentrated sulphuric acid and 400 g. of crushed ice, and heat the mixture under reflux for 12 hours. Collect the -naphthoic acid formed (some of which sublimes from the reaction mixture) by suction filtration... 

Mercury di-/3-naphthyl has been prepared by the action of sodium amalgam on /3-bromonaphthalene,1 and by the action of alcoholic sodium iodide on /9-naphthylmercuric chloride.2... 

As methods of preparation, only the first three need be considered. It was decided not to try the direct action of bromine upon naphthalene, owing to the necessity of stirring the solid naphthalene and of collecting the hydrogen bromide gas the latter difficulty is also presented when carbon disulfide is used, and the objectionable properties of this solvent make its use further unfavorable. The third method, in which a suspension of naphthalene in alkaline hypobromite solution is treated with hydrochloric acid in aqueous solution, was found to give satisfactory results in so far as the yield of a-bromonaphthalene is concerned (though it was no better than with the method above described), but it presented considerable difficulties in the recovery of the hydrobromic acid. 

Naphthylamine is no longer manufactured and its laboratory preparation should never be attempted because of its potent carcinogenic properties. For many preparative purposes (e.g. see 2-bromonaphthalene, cognate preparation in Expt 6.72, and 2-naphthoic acid, Expt 6.154), 2-naphthylamine-l-sulphonic acid may be used. This is obtained commercially by cautious treatment of 2-naphthol with sulphuric acid - the sulphonic acid group entering the 1-position - followed by a Bucherer reaction. 

Diazotise 122g (0.5mol) of 2-naphthylamine-l-sulphonic acid (1) as detailed under 2-bromonaphthalene in Expt 6.72. Prepare copper(i) cyanide from... 

Mortellaro et al. prepared two (3-CD derivatives, which have a bromonaph-thalene unit at the primary (1) and secondary OH groups (2) of (3-CD [27], The phosphorescence of 2 at 530 nm is more than 100 times intense than that observed for an equimolar solution of 1. These results suggest that the bromonaphthalene moiety of 2 is protected from oxygen quenching, being located inside the CD cavity, whereas the bromonaphthalne moiety of 1 is not protected, being exposed into bulk solution. 

De Silva et al. [28] prepared a naphthalene derivative (3) with logic functions (Scheme 1). Here, the bromonaphthalene unit exhibits phosphorescence in the presence of both the calcium ion and (3-CD [28], However, without them, oxygen quenches the phosphorescence of 2-bromonaphthalene phosphor because the protection effect of (3-CD is absent and photoinduced electron transfer from the tetracarboxylate receptor to the 2-bromonaphthalene phosphor occurs. Thus, phosphorescence output occurs only when the calcium ion and (3-CD inputs are active. The operation of these two inputs with a phosphorescence output corresponds to the AND logic function. The input to the NOT gate is oxygen. In the presence of oxygen without either calcium or (3-CD, the AND gate is disabled. 

Diphenyl Naphthyl Telluronium Iodide1 10 g (28 mmol) of diphenyl tellurium dichloridc are dissolved in 250 ml of dry toluene. A solution of 1 -naphthyl magnesium bromide in diethyl ether is prepared from 17.4 g (84 mmol) of 1-bromonaphthalene. The solution of the tellurium compound is quickly poured into the freshly prepared Grignard solution, the mixture is shaken vigorously, and 20 ml of dilute hydrochloric acid are added immediately. The solution is decanted from the precipitate, the precipitate is dissolved in boiling water, silver chloride is added, and the mixture is heated. The mixture is then filtered, sodium sulfite is added to the filtrate, and the telluronium iodide is precipitated by the addition of potassium iodide yield 11.8 g (78%) m.p. 148° (from ethanol, ethanol/diethyl ether). 

Bromonaphthalene has been prepared from 2-aminonaphtha-lene by the reaction of mercuric bromide with the diazonaphtha-lene. The reaction described in this preparation appears to be fairly general and provides a useful alternative method for introducing bromine into the aromatic nucleus. Using conditions similar to those outlined, the following have been prepared from the corresponding aryl alcohols a-bromonaphthalene (72%), 3-bromopyridine (76%), 2-bromopyridine (61%), 8-bro-moquinoline (48)%, o-bromotoluene (72%), />-chlorobromo-benzene (90%), -nitrobromobenzene (60%), and />-methoxy-bromobenzene (59%). The use of the triphenylphosphine-halogen complex to convert alcohols to alkylhalides is described elsewhere in this series. ... 

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