1 -Bromonaphthalene

The oil is then fractionally distilled under reduced pressure, and the main fraction which passes over at 132-135° at 12 mm. (145-148° at 20 mm.) is collected separately. The fore-runs on chilling yield naphthalene, which is filtered off and the filtrate is again distilled. The higher boiling portions on chilling yield dibromonaphthalene and the filtrate is again fractionated. 

The united water solutions are distilled and 48 per cent hydrobromic acid boiling at 125-126° is collected. The yield of pure a-bromonaphthalene varies from 2000 to 2200 g. and in certain cases reaches 2450 g., the yield of hydrobromic acid amounting to about 2650 g. 

It is essential that the stirring should be efficient. A glass stirrer of the tube or propeller type answers satisfactorily, provided that the naphthalene flakes are not too coarse. As the reaction proceeds the product becomes oily, rendering the stirring more efficient. 

The necessity of introducing the bromine at the bottom of the mixture should be emphasized. If this is not done, local overheating is almost certain to occur, with consequent loss of both bromine and hydrobromic acid. 

If the distillation of a-bromonaphthalene is carried on at atmospheric pressure, the product darkens on standing, but it does not do so if distilled under reduced pressure. 

A mixture of 50 g. (0.35 mole) of 2-naphthylamine, 670 ml. of water, and 140 ml. of concentrated hydrochloric acid is diazotized at 0-10° in the usual manner by the addition of 20% aqueous sodium nitrite solution. To the resulting solution of the diazonium salt is added with stirring a cold suspension of mercuric bromide formed by treating 57 g. (0.175 mole) of mercuric nitrate with 83 g. (0.80 mole) of sodium bromide in a total volume of 250 ml. of water. The precipitated yellow complex is removed by filtration, washed with water and acetone, and air-dried. It weighs 137-149 g. The solid is mixed well with 300 g. of powdered sodium bromide, and the mixture is added in several portions to a reflux apparatus heated to 90° in an oil bath. Vigorous evolution of gas follows the addition of each portion. After decomposition is complete, the reaction mixture is extracted with benzene and the benzene solution is washed with dilute acid and alkali. Removal of the solvent followed by two distillations of the residual oil gives a product boiling at 103-104°/4 mm. After one recrystallization from a mixture of 110 ml. of hot ethanol and 4 ml. of water, 38-43 g. (53-59%) of colorless plates of 2-bromonaphthalene, m.p. 55-56.4°, is obtained. 

A solution of 80 g. (0.50 mole) of bromine in 100 ml. of acetic acid is added dropwise with water-bath cooling to a solution of 72 g. (0.50 mole) of /J-naphthol in 350 ml. of acetic acid. The resulting solution is poured into 2 1. of water, and the precipitated solid product is removed by filtration. The product weighs 108 g. (97%) and melts at 80-81°. 

Submitted by J. P. Schaefer, Jerry Higgins, and P. K. Shenoy Checked by James P. Nelson, Wayland E. Noland, and WiLLLAU E. Parham 

A 500 ml., three-necked, round-bottomed flask is equipped with a Trubore stirrer, a pressure-compensating dropping funnel, and a reflux condenser with drying tube. The flask is charged with 144 g. of triphenylphosphine (0.55 mole) (Note 1) and 125 

Triphenylphosphine was obtained from M and T Chemicals Inc. and was used without further purification. 

The acetonitrile was cautiously distilled from phosphorus )cntoxide. Phe solid phosphorus pentoxide may cause bumping 

The temperature is kept below 40° and the reaction mixture thoroughly stirred during this addition. 

---

Bromonaphthalene [90-11-9] M 207.1, b 118 /6mm, d 1.489. Purified by passage through activated alumina, and three vacuum distns. 

Certain halides, notably fluorides, are comparatively inert under these reaction conditions. In such cases the entrainment method, can be used, and reduction can be accomplished in the presence of a reactive halide such as 1-bromonaphthalene or 1-bromobutane. Also with certain halides, such as chlorocyclo-hexane, the tendency for dehydrohalogenation is diminished by the use of such entraining agents. 

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... 

Subsequently577b, the naphthalene values were changed to 30,000 and 600, other values (lO7 ) being 1-nitronaphthalene, 0.7 falling to 0.6 1-cyano-naphthalene, 6 falling to 0.8 2-naphthoic acid, 0.9 falling to 0.6 1-chloronaph-thalene, 850 and 1-bromonaphthalene, 700, though little can be deduced from these results. 

Rapid aminations of 1-bromonaphthalenes with piperidine under microwave irradiation were reported by Hamann using Pd2(dba)3/rac. PPFA (N,N-dimethyl-1-[2-(diphenylphosphanyl)ferrocenyl]ethylamine) precatalyst in combination with NaO-t-Bu in toluene at 120 °C (Scheme 92) [97]. Typically, reactions performed under conventional heating at 120 °C (oil bath) were still progressing after 16 h and were essentially complete by 24 h, whereas the microwave reactions appeared to be finished after 10 min. The same reaction conditions were also useful to functionalize 5- and 8-bromoquinolines with anilines and aliphatic amines (Schemes 93 and 94). Remarkably, no product formation was observed with 5-bromo-8-cyanoquinoline and 5-bromo-8-methoxyquinoline under conventional heating for 24 h at the same temperature, while the desired 5-aminoquinolines were smoothly obtained under microwave irradiation in a reaction time of only 10 min. 

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... 

Common Name 1-Bromonaphthalene Synonym a-bromonaphthalene Chemical Name 1-bromonaphthalene CAS Registry No 90-11-9 Molecular Formula C10H7Br Molecular Weight 207.067 Melting Point (°C) ... 

Reported vapor pressures of 1-bromonaphthalene at various temperatures and the coefficients for the vapor pressure equations... 

FIGURE 4.1.4.1.1 Logarithm of vapor pressure versus reciprocal temperature for 1 -bromonaphthalene. 

N,N-Dimethylacetamide (DMAc), 4-fluorobenzoic acid, 4-fluorobenzoyl chloride, aluminum chloride, 1 -bromonaphthalene, nitrobenzene, ferric chloride, dimethyl sulfone, 4,4 -dihydroxybiphenyl (DHB), and potassium carbonate were obtained from Aldrich and used without purification. 4,4-(Hexafluoroiso-propylidiene)-diphenol (6F-BPA), 9,9-bis(4-hydroxyphenyl)fluorene (HPF), and l,l-bis(4-hydroxyphenyl)-l-phenylethane (Bisphenol AP) were obtained from Ken Seika Corporation and used without purification. 4,4 -Dihydroxydiphenyl sulfone (DHDS) was obtained from Nachem Incorporated and used without purification. 

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. 

Hydrogen-deuterium exchange in diazoalkanes, 53, 43 HYDROGENOLYSIS OF CARBON-HALO-GEN BONDS WITH CHROMIUM (II)-EN PERCHLORATE NAPHTHALENE FROM 1—BROMONAPHTHALENE, 52, 62... 

---