Amines benzoyl chloride

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.

The experimental technique is similar to that given under Aromatic Amines, Section IV,100,2. The following alternative method may also be used. Mix together 0 -5-0 - 8 ml. of the polyhydroxy compound, 5 ml. of pyridine and 2 -5 ml. of redistilled benzoyl chloride in a 50 ml. flask. 

In general, benzoylation of aromatic amines finds less application than acetylation in preparative work, but the process is often employed for the identification and characterisation of aromatic amines (and also of hydroxy compounds). Benzoyl chloride (Section IV, 185) is the reagent commonly used. This reagent is so slowly hydrolysed by water that benzoylation can be carried out in an aqueous medium. In the Schotten-Baumann method of benzoylation the amino compound or its salt is dissolved or suspended in a slight excess of 8-15 per cent, sodium hydroxide solution, a small excess (about 10-15 per cent, more than the theoretical quantity) of benzoyl chloride is then added and the mixture vigorously shaken in a stoppered vessel (or else the mixture is stirred mechanically). Benzoylation proceeds smoothly and the sparingly soluble benzoyl derivative usually separates as a solid. The sodium hydroxide hydrolyses the excess of benzoyl chloride, yielding sodium benzoate and sodium chloride, which remain in solution ... 

The following alternative procedure is sometimes useful. Heat the amine with the theoretical quantity of benzoyl chloride (if the molecular weight is unknown, use an equal weight of benzoyl chloride in the preliminary experiment) to 100° for 20-30 minutes. Allow to cool, add excess of 5 per cent, sodium hydroxide solution and shake, if necessary,... 

The Schotten - Baumann method of benzoylation with benzoyl chloride in the presence of aqueous sodium hydroxide may be used. Full details are given under Amines Section IV.lOO, 2. 

Benzoyl chloride test (for primary and secondary amines). Place 0-5 ml. (or 0 5 g.) of the compound, 10 ml. of 5 per cent, sodium hydroxide solution and 1 ml. of benzoyl chloride (CAUTION) in a test-tube, stopper the tube and shake until the odour of benzoyl chloride disappears. Examine the properties of the substance formed. 

Benzenesulphonyl chloride test. Proceed as in the benzoyl chloride test, but use 15-20 ml. of 5 per cent, sodium hydroxide solution. Examine the product when the odour of the sulphonyl chloride has disappeared. (If no reaction has occurred, the substance is probably a tertiary amine.) If a precipitate appears in the alkaline solution, dilute with about 10 ml. of water and shake if the precipitate does not dissolve, a secondary amine is indicated. If the solution is clear, acidify it cautioiosly to Congo red with dilute hydrochloric acid a precipitate is indicative of a primary amine. 

Benzoyl chloride is an important benzoylating agent. In this use the benzoyl radical is introduced into alcohols, phenols, amines, and other compounds through the Friedel-Crafts reaction and the Schotten-Baumaim reaction. Other significant uses are in the production of benzoyl peroxide [94-56-0], benzophenone [119-61-9], and in derivatives employed in the fields of dyes, resins, perfumes, pharmaceuticals, and as polymerization catalysts. 

Benzoyl Chloride.—The formation of esters by ibe action of benzoyl chloride or othei acid chloride on an alcohol or ]ohcnol in presence of caustic soda is known as the Schotten- 13riumann reaction. The reaction may also be employed in the preparation of deri ati es of the aromatic amines containing i.n acid radical, like benzanilide, CjjH NH.CO... 

Incorporation of extensive branching in the side chain similarly does not decrease pharmacologic activity. Reductive alkylation of aminoalcohol, 42, with isobutyraldehyde affords the amine, 43. Acylation of the amine with benzoyl chloride probably goes initially to the amide (44). The acid catalysis used in the reaction leads to an N to 0 acyl migration to afford iso-bucaine (45). ... 

In an analogous sequence, reductive alkylation of aminoalcohol, 46, with cyclohexanone affords the secondary amine (47). Acylation with benzoyl chloride affords hexylcaine (48) in a reaction that may again involve acyl migration. 

A wide array of aliphatic and aromatic amines has been converted to amides in very high yields by the particularly reactive tetrazolides. The reaction temperature was 10 °C to 20 °C. Higher temperatures (refluxing THF) should be avoided because of instability of the tetrazolide, which in this case was prepared from benzoyl chloride and phenyltetrazole in 68% yield.[99],[100]... 

Method of Preparation Dissolve 1 mL of benzoyl chloride in 5 mL of pure benzene and treat slowly with 1 mL of aniline dissolved in benzene until the odour of the benzoyl chloride was no longer detectable. After vigorous stirring, treat the mixture with dilute HC1. Evaporate to remove excess of amine and the benzene from the solution and recrystallise the product in aqueous alcohol. 

Similarly, a solid-supported imide has been reported to serve as an acylating reagent under microwave conditions by Nicewonger and coworkers [130], The starting imide was immobilized on aminomethyl polystyrene and in this case benzoyl chloride was chosen to prepare the acylating reagent (Scheme 7.111). Primary amines and piperazines were smoothly acylated at room temperature, but more hindered secondary amines required more time and higher temperatures, and anilines... 

Ti(OPr1)4-mediated nucleophilic ring opening of 2,3-epoxy-alcohol with primary amine requires more rigorous conditions, and the product is a complex mixture. Lin and Zeng22 found that this problem could be overcome and moderate to good yields could be obtained under weak base conditions by in situ /V-acylation of the aminolysis product with benzoyl chloride. 

Benzoylation of )V-(2,2-diethoxycarbonylvinyl)-/3-D-galactopyranosy-lamine and -/3-D-gluco analogue in pyridine with benzoyl chloride afforded mixtures of di-, tri-, and tetra-O-benzoyl derivatives. From 2,3,6-tri-O-benzoyl-N-(2,2-ethoxycarbonylvinyl)-j8-D-galatopyranosylamine and -/3-D-glucopyranosylamine the amines were liberated with bromine or chlorine in chloroform or methylene chloride (89MI4). 

The reaction of tertiary amines such as trimethylamine or triethylamine, with acetyl or benzoyl chloride, followed by anion exchange with sodium tetraphenylborate gives stable... 

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%). 

The starting material was prepared with the modification on the epibatidine bicychc ring system by repositioning the nitrogen atom to a methylene group. We carried out the Hetero-Diels Alder reaction of cyclopentadiene and iminium ion generated from ammonium chloride and formaldehyde in the aqueous medium and protected resulted unstable secondary amine with benzoyl chloride to provide (3) in good yields [5] (Scheme 38.1). 

A kinetic smdy of the acylation of ethylenediamine with benzoyl chloride (110) in water-dioxane mixtures at pH 5-7 showed that the reaction involves mainly benzoylation of the monoprotonated form of ethylenediamine. Stopped-flow FT-IR spectroscopy has been used to study the amine-catalysed reactions of benzoyl chloride (110) with either butanol or phenol in dichloromethane at 0 °C. A large isotope effect was observed for butanol versus butanol-O-d, which is consistent with a general-base-catalysed mechanism. An overall reaction order of three and a negligible isotope effect for phenol versus phenol- /6 were observed and are consistent with either a base- or nucleophilic-catalysed mechanism. Mechanistic studies of the aminolysis of substituted phenylacetyl chlorides (111) in acetonitrile at —15 °C have revealed that reactions with anilines point to an associative iSN2 pathway. ... 

Amines also react with benzoyl chloride (CgHgCOCl). This reaction is known as benzoylatlon. 

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