Benzoyl chloride derivatives, analysis

Table 4.6 HPLC elution gradient program used for analysis of biogenic amine benzoyl chloride derivatives. Eluent A) 0.40 M sodium dodecyl sulfate aqueous solution buffered to pH 3.0 with 0.02M phosphate buffer, eluent B) acetonitrile.

Poly(methyl 3-(l-oxypyridinyl)siloxane) was synthesized and shown to have catalytic activity in transacylation reactions of carboxylic and phosphoric acid derivatives. 3-(Methyldichlorosilyl)pyridine (1) was made by metallation of 3-bromopyridine with n-BuLi followed by reaction with excess MeSiCl3. 1 was hydrolyzed in aqueous ammonia to give hydroxyl terminated poly(methyl 3-pyridinylsiloxane) (2) which was end-blocked to polymer 3 with (Me3Si)2NH and Me3SiCl. Polymer 3 was N-oxidized with m-ClC6H4C03H to give 4. Species 1-4 were characterized by IR and H NMR spectra. MS of 1 and thermal analysis (DSC and TGA) of 2-4 are discussed. 3-(Trimethylsilyl)-pyridine 1-oxide (6), l,3-dimethyl-l,3-bis-3-(l-oxypyridinyl) disiloxane (7) and 4 were effective catalysts for conversion of benzoyl chloride to benzoic anhydride in CH2Cl2/aqueous NaHCC>3 suspensions and for hydrolysis of diphenyl phosphorochloridate in aqueous NaHCC>3. The latter had a ti/2 of less than 10 min at 23°C. 

Amination (11) and solution carbonation (8) reactions were carried out as described previously. For solid-state carbonations, a benzene solution of poly(styryl)lithium was freeze-dried on the vacuum line followed by introduction of high-purity, gaseous carbon dioxide (Air Products, 99.99% pure). Analysis and characterization of polymeric amines (11) and carboxylic acids (8) were performed as described previously. Benzoyl derivatives of the aminated polystyrenes were prepared in toluene/pyridine (2/1. v/v) mixtures with benzoyl chloride (Aldrich, 99%). 

Benzoyl chlorides, like other acyl chlorides, react readily with alcohols to form the corresponding esters (259). The reaction requires 19 h to be completed, and it has been studied in the analysis of carbohydrates, aminosugars, and glycosides (260). Because the preparation of acyl derivatives of monosaccharides is difficult, phenyldimethylsilyl chloride has been also investigated as an alternative label (261). After dissolving the analytes in dimethylformamide and addition of... 

The properties and reactions of amino-alcohols, obtained largely by hydrolysis of naturally occurring alkaloids, were investigated primarily for the purposes of structural analysis and the preparation of physiologically active derivatives. Many authors have described acylation of pyrrolizidine alcohols with benzoyl chloride and acetic anhydride (see, e.g., refs. 83 and 101). Trachelanthamidine benzoate and p-aminobenzoate were prepared especially for testing of their physiological activity.102 The p-aminobenzoate was obtained by treatment of trachelanthamidine with p-nitrobenzoyl chloride and subsequent reduction of the nitro group with iron in 20% acetic acid. The compound exhibited an anesthetic activity close to that of cocaine. 

Hwang et al. developed a rapid and sensitive HPLC-UV method for the analysis of nine derivatized BAs, with benzoyl chloride as the derivatization agent. The reaction is faster than with tosyl chloride and leads to stable products with shorter elution times than do dansyl derivatives. The amines were previously extracted after acidification with TCA. The method was applied to detect BAs in fried marlin fillet, implicated in a food poisoning incident (in Taipei City in 1996) and indicated that a high level of His (84.1 mg/100 g) was present in the sample (80). 

Borate complexes have been utilized by Brigl and Griiner47 to effect partial esterification. Anhydrous D-glucose and metaboric acid dissolved in acetone give a complex which exhibits the analysis of a diborate. Reaction of the latter with an excess of benzoyl chloride gives 2,6-di-O-benzoyl-D-glucose (XL). D-Mannitol likewise forms a diborate, which produces the 1,6-di-O-benzoyl derivative (XLI) upon benzoylation. In the presence of boric acid, D-glucose diethyl thioacetal yields the 6-benzoate (XLII). In the non-aqueous medium the formation of complexes... 

A quantitative HPLC method for the analysis of sphingolipids as their perbenzoyl derivatives was first developed for ceramides (5). Ceramides can be conveniently derivatized with benzoic anhydride in pyridine (3 hrs at 110°C) and the products formed have been utilized for the quantitative analysis of NFA and HFA ceramides in normal and Farber s disease tissue. Iwamori and Moser also utilized this procedure for the analysis of ceramides in Farber s disease urine (6). More recently Iwamori and Moser (7) established that the ceramide derivatives formed by reaction with benzoyl chloride or benzoic anhydride are analogous to those formed with cerebrosides. They also characterized the behavior... 

Treatment of aromatic carboxaldehyde (diaminomethylene)hydrazones (105) with hot acetic anhydride or benzoyl chloride affords l,4-diacyl-3-acylamino-5-ary 1-4,5-dihydro- 1H-1,2,4-traizoles (106) in 75-95% yields. In contrast, when the 4-pyridine analog of 105 was employed, the unusual hemianimal triazole derivative (107) was obtained. The structures of the novel compounds were determined by spectral methods and in several cases by x-ray structural analysis. Mechanistic considerations are discussed [95M733]. The oxazole-1,2,4-triazole (108) was prepared by cyclization of the corresponding oxazolecarbonyl-thiosemicarbazide with bicarbonate, alkylation at the sulfur and oxidation to the sulfoxide with MCPBA [95JHC1235]. 

Parameters such as solvent, basic medium and reaction time, affecting the derivatization of alcohols and phenols with benzoyl chloride, were investigated. End analysis was by GC with UVD . a sensitive method proposed for trace determination of phenols in water consists of preconcentration by SPE with a commercial styrene-divinylbenzene copolymer, acylation with pentafluorobenzoyl chloride in the presence of tetrabutylammonium bromide and end analysis by GC with either ECD or ITD-MS. LOD was 3 to 20 ngL for ECD and 10 to 60 ngL for ITD-MS, with 500 mL samples . Acylation with the fluorinated glutaric acid derivative 43 was proposed for determination of urinary phenols, as indicative of exposure to benzene and other aromatic hydrocarbons. End analysis by GC-MS shows strong molecular ions of the derivatives by electron ionization. The proto-nated ions are the base peaks obtained by chemical ionization. LOD was 0.5 mgL and the linearity range 0-100 mg L for phenol . 

In the case of peraksine [RP-5 (27)] it was shown to have the formula C19H22N2O2, a fact not readily derived from combustion analysis since the free base crystallized from alcohol in a hydrated form (27). It has also been observed that this water of solvation could be displaced by chloroform (20). Peraksine has UV-absorption typical of a 2,3-disub-stituted indole and reacted with benzoyl chloride to form an 0-benzoyl derivative. The second oxygen was apparently present as a cyclic ether when it was found that although peraksine did not react with hydrazine derivatives, it was reducible with sodium borohydride to furnish a diol (mp 290°-291° [a]j) - -41° in Py diacetate, mp 103°-105°). This diol readily lost the elements of water upon acid treatment to afford a new ether, deoxyperaksine, 230° change in crystalline form (mp 255°-257°). Because of these properties peraksine was considered to possess a cyclic hemiacetal moiety. 

Recently, m our laboratories, an improved method for quantitative analysis of amino acids has been developed (Yeung, Baker, and Courts, manuscript in preparation). The carboxylic acid moiety IS derivahzed quantitatively by adding one drop of concentrated HCl to an isobutanol solution of the amino acids, rather than bubbling HCl gas in the conventional manner, prior to heating. Benzoyl chloride is known to be more reactive chemically than acid anhydrides, and pentafluorobenzoyl derivatives are highly sensitive to electron-capture detection (Moffat et al., 1972, Matin and Rowland, 1972, McCallum and Armstrong, 1973 Midha et al., 1979 Cristofoli et al, 1982, Nazarali et al., 1983). Pentafluorobenzoyl chloride (PFBC), therefore, was chosen to derivatize the other reactive groups of the amino acid isobutyl esters. Pentafluorobenzoylation (Fig. 7) was conducted at room temperature in aqueous conditions. 

Pyridine has also been used as the basic catalyst and chloride acceptor for benzoylation reactions. In one procedure, amines, volatile alcohols or thiols isolated by benzene extraction, are benzoylated with pyridine (1 ml) and benzoyl chloride (0.5 ml) by shaking intermittently at room temperature for several hours. The pyridine phase is extracted with 2 M HCl and the excess benzoyl chloride is hydrolysed with water for 12 hours. After shaking with 2 M sodium carbonate to remove benzoic acid, the benzene solution is dried and concentrated for analysis [144]. Aminoglycoside antibiotics are derivatized to the benzoyl derivatives in a similar reaction using 90 fi of pyridine and 10 /il of benzoyl chloride at 80 °C for 30 minutes. The pyridine is evaporated in a stream of nitrogen and excess benzoyl chloride is converted to methyl benzoate with methanol, again at 80°C, for 10 minutes. The product is cleaned up for analysis by a rather involved solvent extraction procedure [145]. 

In these studies, the analysis of off-gas products was also found to provide insight into the chemistry of this ROP process. The breakdown products of benzoic acid found in the off-gas included benzoyl chloride and benzonitrile. At low polymer yields, the only additional species found was HCl, formed from the acidic proton and chlorine liberated from the trimer. In this study, the relative amounts of each constituent were not obtained due to low concentrations however, the authors observed that the benzoic acid was consumed relatively early in the polymerization. The small difference in the rates of catalysis for both the acid and the sodium salt also supported a quick reaction to some derivative compound however, no structure was proposed for this compound. 

The N-benzoyl methyl ester of Gly has been analysed on QF-1 [242] and N-benzyl-oxycarbonyl methyl and ethyl esters and N-palmitoyl ethyl esters of Leu on SE-30 [243]. N-Propionyl isoamyl derivatives of fourteen amino acids were prepared by allowing isoamyl esters to react with propionyl chloride and were also analysed on QF-1 and applied to the analysis of amino acids in bacterial cultures [244]. 

The concept utilised was based on a retrosynthetic analysis comprising a nicotinic acid derivative (41) and a dihydroxychromone. The nicotinic acid moiety was prepared by lithiation of nicotinaldehyde followed by treatment with trimethyltin chloride. After benzoylation of the chromone noreugenin to protect the free phenolic group the compound was brominated to yield (42) and the two compounds formed were reacted with the nicotinic derivative to give a C-C bond with either the 6 or 8 of the chromone to give a compound such as (43) from which isoschumanniophytine or schumanniophytine respectively could be easily obtained by debenzoylation and lactonisation. 

Benzoyl and benzenesulphonyl derivatives have not been widely applied for chromatographic analyses, but because they can be detected in the ultraviolet they have found some use in HPLC. They are also used to make derivatives from volatile compounds as a means avoiding evaporative losses. They are readily made under Schotten-Baumann conditions. Thus, an amine solution (3 ml) is made alkaline with an equal volume of 7.5 M NaOH, and 50 fi of benzoyl choride is vigorously shaken with this solution until consumed. The product is extracted twice with 2 ml of diisopropyl ether, and the ether extracts are blown dry with nitrogen before being taken up in the ether for analysis [142]. A similar procedure was used for amines by Terashi et at. but using benzenesulphonyl chloride [143]. 

Acyl chlorides react readily with amino groups to form amides. The reactions (Figure 1) are carried out in an alkaline medium (Schotten-Baumann conditions). The use of amide derivatives for the HPLC analysis of amines has been widely studied. Clark and Wells [9] described several acyl chlorides such as p-nitrobenzoyl, p-methoxy-benzoyL p-methylbenzoyl and p-chlorobenzoyl chlorides. The spectrophotometric properties of their benzamides were investigated. The methoxybenzamides showed the most intense absorption at 252 nm, and therefore most fixed-wavelength (254 nm) UV detectors can conveniently be used for detection. The reaction of p-methoxybenzoyl chloride with some amines and the molar absorptivities of the derivatives are shown in Table I. 

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