I-Bromonaphthalene

These selection rules can be related to spin-orbit coupling with the help of the Fermi golden ride. (Cf. Section 5.2.3.) The values k j 10 s for naphthalene and kgj 10 s " for I-bromonaphthalene (Birks, 1970), the difference of which can be explained through the heavy atom effect, also indicate clearly the influence of spin-orbit coupling. The fact that the rate... 

Branching space, 183, 217.316-17,339 Bridging. 87. 175. also Perturbation, hierarchy of Brillouin s theorem, 54 I-Bromonaphthalene. 255, 264 Brookerdyes, 135... 

I Bromonaphthalene reacts slowly with piperidine at 230 °C to give compound I. The addition of sodium amide accelerates the reaction, which then occurs at 100 °C to give compounds I and II. (a) Explain the difference in the two reaction conditions, (b) Explain the product distribution. 

I -Bromonaphthalene Trichlorobiphenyl Perfluoromethylcyclohexane Perfluorodimethylcyclohexane Perfluoro-n-heptane... 

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

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. 

Bromonaphthalene has been reduced to naphthalene in good yield by hydrogenation over Raney nickel in methanolic potassium hydroxide, by triphenyltin hydride in benzene, by magnesium in isopropyl alcohol, by sodium hydrazide and hydrazine in ether, and by copper(I) acetate in pyridine. ... 

In a dry 200-cc. flask fitted with a ground-in reflux condenser and protected from moisture with a calcium chloride tube are placed 66 g. (0.32 mole) of a-bromonaphthalene (Note 1), 35 g. (0.39 mole) of dry powdered cuprous cyanide (Note 2), and 30 cc. of pyridine (Note 3) in the order mentioned. This mixture is heated in a Wood s metal bath (Note 4) at 215-225° for fifteen hours. The resulting dark brown solution is poured while still hot (about ioo°) into a flask containing 150 cc. of aqueous ammonia (sp. gr. 0.90) and 150 cc. of water. About 140 cc. of benzene is added, and the flask is stoppered and shaken until all the lumps have disintegrated. After the mixture has cooled to room temperature, 100 cc. of ether is added and the mixture filtered (Note 5). The filtrate is transferred to a i-l. separatory funnel and the aqueous layer separated (Note 6). The ether-benzene layer is washed successively with (a) four 100-cc. portions of dilute aqueous ammonia (Note 7), (b) two 100-cc. portions of 6 N hydrochloric acid (Note 8), (c) two 100-cc. portions of water, and (d) two 100-cc. portions of saturated sodium chloride solution. The ether and benzene are removed by distillation from a water bath, and the residue is distilled under reduced pressure from a 125-cc. modified Claisen flask. The temperature rises rapidly, and the yield of colorless a-naphthonitrile, b.p. i73-i74°/27 mm. (i66-i69°/i8 mm.) is 40-44 g. (82-90 per cent of the theoretical amount) (Notes 9 tnd 10). 

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... 

In addition to bromonaphthalene, bromobenzophenone (see earlier) or 4-bromoben-zonitrile may be used as a substrate (Pinson Saveant 1978). The latter two compounds carry not only bromine but also other electrochemically active groups, i.e., C=0 or C=N. Along with the thiophenyl, the thiomethyl or thio-tert-butyl groups can be introduced as substituting fragments. The yields of the substitution products are high (from 60 to 95%), and one electron is consumed per 20-30 molecules of substrate. The reactions proceed at ambient temperature and do not proceed at all when a potential difference is not set up. 

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