Benzoyl deriv table

N-benzoyl derivatives of o -aminoacids give 2-phenyl-5-alkoxythiazoles (64). A list of the thiazoles prepared by this method is given in Table 11-32 (711). 

Ammodendrine, C jH oONj, HjO (No. 1, table, p. 116). The base has m.p. 73 °, becomes anhydrous at 70-80°, and then melts at 50-60°, Wd i 0°. The salts are amorphous and deliquescent except the hydriodide B. HI, which forms a crystalline precipitate, m.p. 218-20°, from alcohol, and the perchlorate, m.p. 199-200°. An amorphous A-benzoyl derivative was obtained. With methyl iodide ammodendrine behaves as a secondary base, yielding first A-methylammodendrine hydriodide (a crystalline precipitate, m.p. 183-5°, from a mixture of alcohol and acetone), and at the second stage iV-methylammodendrine methiodide, m.p. 163-5°. On hydrogenation ammodendrine furnishes a dihydro-base, which is hydrolysed into acetic acid and 2 3 -dipiperidyl, C oHjoNj, and must be dZ-A-acetyl-3-a-piperidylpiperidine. Ammodendrine should therefore be acetyltetrahydroanabasine and is of biological interest as the first recorded occurrence of this type of alkaloid in the Leguminoss. ... 

The benzoyl derivative, PhCOMn(CO)5 and related acyl derivatives have intrinsic interest because they can be prepared by alkyl group migration to coordinated CO, a formal internal nucleophilic attack. This reaction, which is often referred to as carbonyl insertion86), is reversible in certain instances to give the metal alkyl. The enthalpy of disruption for PhCOMn(CO)s (Table 13) can be divided up to give the b.e.c of the Mn-COPh bond if the values of T (Mn-CO) shown in Table 13 are used, then the Mn-COPh enthalpy lies in the range 105 10 kJ mol-1, the lower value being preferred as outlined earlier. 

Certain acetyl and benzoyl derivatives are surprisingly hydrolyzed in acidic media to the corresponding acid and the unsubstituted aza-pentalene (Table IV). This phenomenon appears to occur in compounds with an acyl group on a carbon atom where there is enhanced electron density. 280... 

The photochemical properties of 9-styrylanthracenes 70/71, all of them substituted by polar groups in the 10-position of the anthracene, closely resemble those of the parent compounds 68a/69a insofar as trans->cis isomerization is either nondetectable or inefficient in both cyclohexane and acetonitrile solution (see Table 11). The lack of photochemical trans-+cis isomerization of the 10-formyl and benzoyl derivatives 71b, 71c and 71d is of particular interest in view of the substituent effect which both the benzoyl and formyl groups exert on the photochemical trans- cis isomerization of 9-styrylanthracenes 69h and 69i (cf. Table 10). By introducing the formyl group into the 10-position of benzoyl-substituted 9-styrylanthracene 69h, trans-9-styrylanthracene 7ld becomes photochemically inert, even in acetonitrile solution. Conceivably, the anthraldehyde chromophore in 71c and 71d acts as an energy sink. 

Table 4. Estimation of relative reactivity of N-(p-substituted benzoyl) derivatives of 58 in the aminolysis with n-butylamine in dimethylformamide at 25 °C [66]...

The structural problem was finally cleared up by physical methods, including molar refraction,255-252 and ultraviolet263 and Raman254 spectroscopy. The 3-benzoyl derivative has also been submitted to X-ray analysis.233-235 All the evidence supports a planar fused system of six- and five-membered rings, although some of the earlier work was interpreted in terms of other structures. The proton NMR spectrum of anthranil has been analyzed 265 the parameters are listed in Table A. 

Nucleophilic Addition to Carboxylic Acid Derivatives Table 7 Comparison of Heterocuprate Reagents for Acylation with Benzoyl Chloride... 

Eighty-nine per cent of the variation in the biological data can be explained with the receptor model. On the other hand, a systematic deviation can be noticed. Some compounds (denoted by bold type in Table 24.1) are described by the model as being too weak by a constant factor of 1.0 or 1.5 orders of magnitude when compared with the experimental affinities. The inspection of the molecular formulae identifies those showing the larger deviation as fluorobenzoyl derivatives and those with the smaller deviation as benzoyl derivatives. In all cases, substances which are not optimally described by the model, possess an electron-deficient aromatic system. This leads to the hypothesis that for binding at the real receptor a type of interaction may be important which is... 

For the special case of substituted benzoyl derivatives, an empirical correlation of structure with the observed position of the primary absorption band has been developed (Table 7.12). It provides a means of estimating the position of the primary band for benzoyl derivatives within about 5 tun. 

The A-benzoyl derivative 45 afforded a mixture of both isomers when treated with tetrabutylammonium fluoride. In the mixture, the diaxial isomer 265 preponderated, but its abundance depended on the solvent and slightly on the amount of the reagent (Table VII). 

Table 2 shows that the derivation of the amine group of amino acids can improve chiral recognition, e.g., the enantioselectivity factors of alanine are 1.8 and 2.7 on teicoplanin and TAG CSPs they become 13 and 3.6, respectively, upon derivati-zation of the amine group forming A-benzoyl alanine (Table 2). Enantioselectivity enhancement is very often obtained by N-derivatization of amino acids [14, 16]. Such enantiorecognition enhancement is not an absolute rule as shown by iV-benzoyl phenylalanine in Table 2. The phenylalanine enantioselectivity factors jumps from 1.5 (native form, Rs = 3.1) to 4.4 (N-benzoylated form, Rs = 11.4) on teicoplanin CSP. It decreases from 3.7 (native form, Rs = 13.7) down to 1.5 Rs = 2.6) after N-benzoylation on the TAG CSP. There is a clear steric effect due to the attached benzoyl group very beneficial for enantiorecognition on teicoplanin CSP and detrimental when the TAG CSP is used.

Optimized reaction conditions are applied to other 1,3-dicarbonyl compounds 34b-j. Acetylacetone 34b exhibits higher reactivity than keto ester 34a to afford cycloadduct 33b quantitatively (Table 9.8, run 2). In the case of benzoy-lacetone 34c, the formation of the two regioisomers 33c and 33c is possible, of which 4-benzoyl derivative 33c is formed in preference to 4-acetyl one 33c (run 3). Other (3-keto esters 34d-i were subjected to the present cycloaddition under the... 

Can it promote vinyl polymerization initiated with Ce(IV) ion Dong et al. [37-39] for the first time reported that AAA and its derivatives such as o-acetoacetotolu-idine (AAT), o-acetoacetanisidide (AAN), and 2-benzoyl acetanilide (BAA) possess very high reactivity toward Ce(IV) ion in initiating the polymerization of vinyl monomer. The results are tabulated in Table 3. 

Yamase and Goto406 determined first- and second-order rate coefficients for the aluminium chloride-catalysed reaction of halide derivatives of benzoic acid (lO5 = F, 1.73 Cl, 4.49 Br, 4.35 I, 0.81) and phenylacetic acid (105fc2 = F, 12 Cl, 21 Br, 9 I, 6) with benzene. The maxima in the rates for the acid chloride are best accommodated by the assumption that a highly (but not completely) polarised complex takes part in the transition state. Polarisation of such a complex would be aided by electron supply, and consistently, the acetyl halides are about a hundred times as reactive as the benzoyl compounds (see p. 180, also Tables 105 and 108). 

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. 

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