Naphthalene benzoylation

Aluminium chloride has to be introduced gradually in the naphthalene/benzoyl chloride mixture and the mixture of these two reagents has to be brought to a temperature that is high enough so that it is in the molten state. Crystallised naphthalene residues are enough to cause the medium to detonate. 

Copolymers of diallyl itaconate [2767-99-9] with AJ-vinylpyrrolidinone and styrene have been proposed as oxygen-permeable contact lenses (qv) (77). Reactivity ratios have been studied ia the copolymerization of diallyl tartrate (78). A lens of a high refractive iadex n- = 1.63) and a heat distortion above 280°C has been reported for diallyl 2,6-naphthalene dicarboxylate [51223-57-5] (79). Diallyl chlorendate [3232-62-0] polymerized ia the presence of di-/-butyl peroxide gives a lens with a refractive iadex of n = 1.57 (80). Hardness as high as Rockwell 150 is obtained by polymerization of triaHyl trimeUitate [2694-54-4] initiated by benzoyl peroxide (81). 

The greater steric hindrance to acetylation was also shown by a comparison of the rate of (103At2) of acetylation of toluene (0.763), ethylbenzene (0.660), i-propylbenzene (0.606) and f-butylbenzene (0.462) with those (determined by the competition method) for benzoylation both sets of data (Table 112) were obtained with dichloroethane as solvent at 25 °C, all reagent concentrations being 0.1 A/421. Relative rates of acylation other aromatics under the same conditions have also been obtained and are given in Table 113422. The different steric requirements for acetylation and benzoylation are further shown by the following respective relative rates for acylation of naphthalene derivatives in chloroform at 0 °C naphthalene (1 position) 1.00,1.00, (2 position) 0.31,0.04 2,3-dimethylnaphthalene (1 position) 1.59, 172, (5 position) 7.14, 38.2, (6 position) 3.68, 7.7422a. 

Most of the substrates that give both types of cycloaurated complexes are limited to pyridine derivatives, although recently a few exceptions have been reported with thiazoles and imidazoles. The reaction of substituted pyridine ligands such as phpy,1 49,1924 2-benzoyl pyridine,1924 2-anili-nopyridine,1925,1926 l-(2-pyridylamino and 2-pyrimidinylamino)naphthalene, 7 2-phenoxypyri-dine,1811 2-(phenylsulfanyl)pyridine,1925 2-(2-thienyl)pyridine, 8 2-(3-thienyl)pyridine,1928 2-(alkylsulfanyl)pyridine,1929 or papavorine1930 at room temperature yields the nonmetallated compounds which, upon heating, are transformed into the metallated complexes [Au(N,C)Cl2], The process with phpy is illustrated in Scheme 21. 

During preparation of 1,5-dibenzoylnaphthalene, addition of aluminium chloride to a mixture of benzoyl chloride and naphthalene must be effected above the m.p. of the mixture to avoid a violent reaction. 

Aluminium chloride, Naphthalene See Aluminium chloride Benzoyl chloride, etc. 

Methyl methacrylate 4-Methylnitrobenzene 2- Methylpyridine Methylsodium Molybdenum trioxide Naphthalene 2-Naphthol Air, benzoyl peroxide Sulfuric acid, tetranitromethane Hydrogen peroxide, iron(II) sulfate, sulfuric acid 4-Chloronitrobenzene Chlorine trifluoride, interhalogens, metals Chromium trioxide, dinitrogen pentaoxide Antipyrine, camphor, phenol, iron(III) salts, menthol, oxidizing materials, permanganates, urethane... 

The benzanthrone system is susceptible to both electrophilic and nucleophilic attack. The most reactive sites towards electrophiles are the 3- and 9-positions, which can be compared with the 4,4 -positions in biphenyl. The 9-position is somewhat deactivated by the carbonyl group, however. Thus, for example, monobromination takes place at the 3-position and further substitution gives 3,9-dibromobenzanthrone. Nitration and benzoylation similarly give rise to the 3-substituted product. The 3-position is in fact peri-hindered (compare naphthalene) so that sulphonation yields the 9-sulphonic acid. Electron withdrawal by the carbonyl group activates the 4- and 6-positions towards nucleophilic attack for example, hydroxylation occurs at these sites. 

Primary and secondary amines are acylated by acid chlorides and anhydrides, in particular also by the chloride of benzene sulphonic add (p. 192). The preparation of acetanilide has already been described (pp. 125, 128). The acetyl- and benzoyl-derivatives of all the simpler primary amines of the benzene and naphthalene series are known, so that these derivatives can always serve for purposes of identification. 

N-Ethyl-N-benzoylnaphthylamme-l-dioxonium Hydroxide. See 4-[(N-Benzoyl-N-etbyl)-amino)-naphthalene-l-diazonium Hydroxide in Vol 2, p B90-L... 

Methoxy-7-methoxycarbonyl-1,2,3,4-tetrahydronaphthalene 2-Naphthalene-carboxylic acid, 5,6,7,8-tetrahydro-3-methoxy-, methyl ester (78112-34-2), 65, 98 Methyl acrylate (96-33-3), 66, 54, 59 dimerization by Pd(II), 66, 52 Methylamine, N-benzylidene-, 65, 140 METHYL 4-0-BENZOYL-6-BROMO-6-DEOXY-a-0-GLUCOPYRANOSIDE ... 

N-Benzoyl-N-ethyl)-amino]-naphthalene-l-diazonium hydroxide 2 B90... 

The IR spectrum of thieno [ 2,3-A]thiophene (1) was first reported by Godart192 in 1937 in work devoted to the UV and IR spectral analysis of thiophene, thienothiophene 1, and benzo[A]thiophene. Comparison of spectral features in the 4000-11,000 cm 1 region of thiophene and benzene, tfiieno[2,3-6]thiophene (1) and naphthalene, and benzoyl-thiophene, benzene, and naphthalene demonstrated, in Godart s opinion, the similarity of IR spectra (in this region) of thiophene, thienothiophene 1, and benzo[A]thiophene, on the one hand, and benzene, thienothiophene 1, and naphthalene, on the other hand. The molecular absorption coefficients of benzene and thiophene, as well as of naphthalene and thienothiophene 1, were also similar. 

The importance of the steric effect accounts for the spread of the data for lf-N in the substitution reactions. Nitration and non-catalytic chlorination, reactions of modest steric requirements, define points which fall above the arbitrary reference line. Bromination, a reaction of somewhat greater steric requirements, is not accelerated to the extent anticipated on the basis of the results for nitration or chlorination. The benzoylation reaction with large steric requirements is two orders of magnitude slower than the equally selective chlorination reaction. The unusually small ratio for lf-N/2f-N for the acylation reaction is a further indication of the steric effects. Apparently, the direct substitution reactions of naphthalene respond to the retarding steric influence of the peri hydrogen in much the same way as for other ortho substituents. 

Naphthyl-plienyl-ketone is obtained from naphthalene and benzoyl chloride, in the presence of zinc 7... 

Benzoyl Chloride and Naphthalene. A violent reaction occurs if aluminum chloride is added below the melting point of the mixture.4... 

Jacob et al/12] found that o-xylene can be benzoylated selectively to 3,4-dimethyl-benzophenone using zeolites as catalysts and benzoyl chloride as benzoylating agent. As shown in Scheme 4.2, zeolite H-BEA exhibits higher activity and selectivity for 3,4-dimethylbenzophenone (3,4-DMBP) than that of the other zeolite catalysts (H-ZSM-5, H-Y and H-MOR), due on the one hand to its stronger acid sites compared with the other zeolite catalysts and on the other hand to smaller pore openings (7.6 x 6.4 A and 5.5 x 5.5 A) than H-Y (7.4 x 7.4 A) zeolite, leading to a shape selectivity. In another article on benzoylation of toluene and naphthalene/101... 

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