Benzoyl chloride reagent

Derivatives of higher melting point may be obtained withp-nitrobenzoyl chloride the experimental details are similar to those given above for benzoyl chloride. 3 5-Dinitrobenzoyl chloride (Section 111,27,7) may also be used glycerol gives unsatisfactory results with this reagent. 

Benzoates. Benzoyl chloride has a very limited application as a reagent in the sugar series, but it is useful for the preparation of a crystal line derivative of glucose and of fructose. 

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 ... 

Dissolve 5 g. of phenol in 75 ml. of 10 per cent, sodium hydroxide solution contained in a wide-mouthed reagent bottle or conical flask of about 200 ml. capacity. Add 11 g. (9 ml.) of redistilled benzoyl chloride, cork the vessel securely, and shake the mixture vigorously for 15-20 minutes. At the end of this period the reaction is usually practically complete and a sohd product is obtained. Filter oflf the soUd ester with suction, break up any lumps on the filter, wash thoroughly with water and drain well. RecrystaUise the crude ester from rectified (or methylated) spirit use a quantity of hot solvent approximately twice the minimum volume required for complete solution in order to ensure that the ester does not separate until the temperature of the solution has fallen below the melting point of phenyl benzoate. Filter the hot solution, if necessary, through a hot water funnel or through a Buchner funnel preheated by the filtration of some boiling solvent. Colourless crystals of phenyl benzoate, m.p. 69°, are thus obtained. The yield is 8 g. 

Bemoyl chloride may replace acetyl chloride as a class reagent it possesses the advantage that it is only very slowly decomposed by cold water and consequently may be employed for detecting alcohols even in aqueous solution. The reaction is usually carried out in aqueous solution containing sufficient caustic alkali to decompose any excess of benzoyl chloride into the water-soluble alkali benzoate (Schotten - Baumann reaction compare Section IV,52). The benzoyl esters formed are insoluble in water ... 

Nitration using this reagent was first investigated, by Francis. He showed that benzene and some of its homologues bromobenzene, benzonitrile, benzoyl chloride, benzaldehyde and some related compounds, and phenol were mono-nitrated in solutions of benzoyl nitrate in carbon tetrachloride anilines would not react cleanly and a series of naphthols yielded dinitro compounds. Further work on the orientation of substitution associated this reagent with higher proportions of o-substitution than that brought about by nitric acid this point is discussed below ( 5.3.4). 

The dienone 858 is synthesized by coupling of the alkenyl copper reagent 856 with crotyl chloride (857) in the presence or absence of ZnCl2[731], Tetrabutyllead (859) reacts with benzoyl chloride to afford butyl phenyl ketone[732]. 

The acylstannanes 874 and 875 are prepared by the reaction of acyl chlorides with (MciSnl - The symmetrical 1,2-diketones 877 can be prepared by the reaction of an excess of benzoyl chloride with (EtjSn) . Half of the benzoyl chloride is converted into the benzoyltin reagent 876, which is then coupled with the remaining benzoyl chloride under a CO atmosphere to afford the a-diketone 877[748], Triethyl phosphite is used as a ligand. 

BzCl or BZ2O, Pyr, 0°. Benzoyl chloride is the most common reagent for the introduction of the benzoate group. Reaction conditions vaiy depending on the nature of the alcohol to be protected. Cosolvents such as CH2CI2 are often used with pyridine. Benzoylation in a polyhydroxylated system is much more selective than acetylation. A primary alcohol is selectively... 

This material in pyridine (120 ml) is benzoylated by addition of benzoyl chloride (12 ml). After 2 hr, water (20 ml) is added to destroy excess reagent, and the product is precipitated after a further 2 hr by addition of more water (200 ml). Addition of boiling methanol (135 ml) to a solution of the substance in boiling chloroform (45 ml) gives 11-ketotigogenin benzoate as lances (11.5g), mp 228-232° [aJo, —32°. A further 1.05 g is obtained from the mother liquors by evaporation and repeated crystallization. The total yield is 12.6 g, 83%. 

When written in this way it is clear what is happening. The mechanisms of these reactions are probably similar, despite the different p values. The distinction is that in Reaction 10 the substituent X is on the substrate, its usual location but in Reaction 15 the substituent changes have been made on the reagent. Thus, electron-withdrawing substituents on the benzoyl chloride render the carbonyl carbon more positive and more susceptible to nucleophilic attack, whereas electron-donating substituents on the aniline increase the electron density on nitrogen, also facilitating nucleophilic attack. The mechanism may be an addition-elimination via a tetrahedral intermediate ... 

Dibenzoyl-2,2 -biindole (295) was obtained by the action of benzoyl chloride on the 2,2 -biindole Grignard reagent. ... 

Brown and Young410,411 studied the benzoylation of benzene and toluene by benzoyl chloride catalysed by aluminium chloride at 25 °C in nitrobenzene as solvent. For a given concentration of reagents, the rate equation was... 

Although the submitters report that this reagent is stable at 0° i.e., still reactive toward benzoyl chloride) for periods of at least one hour under a nitrogen atmosphere,4 the checkers repeatedly observed evidence of thermal decomposition when the solution was allowed to warm above —40°. This decomposition was indicated by the appearance of a red-brown coloration as the reagent was warmed to —40° as the... 

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. 

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