Benzoyl chloride condensation

Benzoyl chloride condenses with benzonitrile or aryl cyanates in the presence of aluminum trichloride to give 1,3,5-oxadiazinium salts (Scheme 58) (67CB3736). 

Fig. 97. Preparation of DCl from heavy water and benzoyl chloride. /) Condensation trap A) reflux condenser m) open arm manometer r) reaction flask t) dropping fimnel with capillary stem.

Now distil the contents of C by heating carefully over a gauze. A small initial fraction of unchanged thionyl chloride boiling at 78-80° comes over, and the temperature then rises rapidly to 194°. Directly this happens, stop the distillation, allow the condenser to drain thoroughly, and then replace G by the duplicate receiver. Run the water out of the condenser so that it acts as an air-condenser, and then continue the distillation. Collect the benzoyl chloride as the fraction boiling at 194-198°. Yield, 19 g. 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

Method 2. Into a 500 ml. round-bottomed flask place 120 ml. of dry A.R. benzene, and 35 g. (29 ml.) of redistilled benzoyl chloride. Weigh out 30 g. of finely-powdered, anhydrous aluminium chloride into a dry corked test-tube, and add the solid, with frequent shaking, during 10 minutes to the contents of the flask. Fit a reflux condenser to the flask, and heat on a water bath for 3 hours or until hydrogen chloride is no longer evolved. Pour the contents of the flask wliile still warm into a mixture of 200 g. of crushed ice and 100 ml. of concentrated hydrochloric acid. Separate the upper benzene layer (filter first, if necessary), wash it with 50 ml. of 5 per cent, sodium hydroxide solution, then with water, and dry with anhydrous magnesium sulphate. Isolate the benzophenone as in Method 1. The yield is 30 g. 

The alkylphenylacetyi chloride 843 and benzoyl chloride undergo decarbo-nylative cross-condensation to give the enone 845 in the presence of EtiNf723]. The reaction is e.xplained by the insertion of the ketene 844 into the Pd-aryl bond and, 3-elimination. To support this mechanism, o, d-unsaturuted ketones are obtained by the reaction of ketenes with aroyl chlorides[724]. 

A round flask (250 c.c.) is fitted with an air-condenser. The phosphorous pentachlorlde is introduced from the bottle and weighed by difference. The operation must be conducted in the fume-cupboard. The benzoic acid is then added, and the air-condenser attached to the flask. The action begins almost immediately, and clouds of hydrochloric fumes are evolved. The whole contents become liquid and consist of benzoyl chloride (b. p. 200 ), phosphorous oxychloiide (b. p. 107°), and unchanged pentachloride. Most of the oxychloride may be removed by distilling in vacuo on the water-bath. The remainder is fractionated at the ordinary pressure and collected at 190-200°. Yield, 20 —25 giams. 

One such compound, bropirimine (112), is described as an agent which has both antineo-plastic and antiviral activity. The first step in the preparation involves formation of the dianion 108 from the half ester of malonic acid by treatment with butyllithium. Acylation of the anion with benzoyl chloride proceeds at the more nucleophilic carbon anion to give 109. This tricarbonyl compound decarboxylates on acidification to give the beta ketoester 110. Condensation with guanidine leads to the pyrimidone 111. Bromination with N-bromosuccinimide gives bropirimine (112) [24]. 

It is prepared artificially by the distillation of calcium benzoate, or by the condensation of benzene and benzoyl chloride in the presence of aluminium chloride. 

A solution of 0.1 mol of 1-cyclohexylamino-2-propanol in 30 grams of chloroform was saturated with dry hydrogen chloride gas, with cooling. A solution of 0.1 mol of benzoyl chloride in 30 grams of chloroform was added and the solution was heated in a bath at 50° to 55°C for four days under a reflux condenser protected from atmospheric moisture. Then the solvent was removed by vacuum distillation while the mixture was warmed on a water bath. Benzene was then added to the syrupy residue and the reaction product crystal lized out after the benzene was removed by vacuum distillation. 

Ethyl benzoylacetate has been prepared by the condensation (by means of sodium ethylate) of ethyl acetate with ethyl benzoate,1 acetophenone with ethyl carbonate,2 and acetophenone with ethyl oxalate, with subsequent heating 3 by treatment of ethyl phenylpropiolate4 or a-bromocinnamic acid 5 with concentrated sulfuric acid, and of ethyl diazoacetate with benzalde-hyde 6 by the condensation of benzene with the monoethyl ester of malonyl monoacid chloride and aluminum chloride,7 of benzoyl chloride with the product of the reaction of magnesium and ethyl chloroacetate in ether,8 of alcohol on benzoylacetimino ethyl... 

Yamato (1995) has given an extensive coverage of a variety of reactions such as alkylation of benzene, condensation of benzene/toluene with benzyl alcohol, and condensation of benzoyl chloride with benzene/toluene using Nafion resin. 

Condensation of 2,4-dihydroxypropiophenone (172) with benzoyl chloride and sodium benzoate goes to afford chromone 174, probably via ester 173. This procedure is known as the Kostanecki-Robinson reaction Methylation (175) of the remaining phenolic function by means of dimethyl sulfate, followed by reaction... 

Condensation of 2-bromoethylamine hydrobromide with benzoyl chloride in benzene in the presence of 5 equivalents of EtsN gave 2-phenyl-4,5-dihydrooxazole (1) in 67% yield [1]. Treatment of 1 with 3 equivalents of NBS in boiling CCL in the presence of AIBN led to 5-bromo-2-phenyloxazole (2). Presumably, sequential bromination and dehydrobromination of 1 led to 2-phenyloxazole, which underwent further bromination to afford 2. 

The benzoyl chloride is now distilled from a wire gauze or over a faintly luminous flame. A long air condenser with a receiver similar to that used for acetyl chloride is employed. The first portion of the distillate, which consists chiefly of thionyl chloride, is fairly large (this material also may be used again). Then the bulk passes over at 194°-199°. Pure benzoyl chloride boils at 194°. Yield 40-42 g. 

A wide variety of monomers, such as (3,5-dibromophenyl)boronic acid, 3,5-bis(trimethylsiloxy)benzoyl chloride, 3,5-diacetoxybenzoic acid, and 2,2-dimethylol propionic acid have been used for the synthesis of hyperbranched polymers. A selection of these polymers are described in Sect. 3. The majority of the polymers are synthesized via step-wise polymerizations where A B monomers are bulk-polymerized in the presence of a suitable catalyst, typically an acid or a transesterification reagent. To accomphsh a satisfactory conversion, the low molecular weight condensation product formed during the reaction has to be removed. This is most often achieved by a flow of argon or by reducing the pressure in the reaction flask. The resulting polymer is usually used without any purification or, in some cases, after precipitation of the dissolved reaction mixture into a non-solvent. 

Turner et al. [71, 72] also report on hyperbranched polyesters derived from 3,5-bis(trimethylsiloxy)benzoyl chloride and from 3,5-diacetoxybenzoic acid, which both yield phenolic polyesters after hydrolysis of the end groups. The same group investigated the hyperbranched polyesters obtained in the melt condensation of 5-acetoxyisophthalic acid and 5-(2-hydroxy)-ethoxyisophthalic acid respectively. The latter yields a soluble product while the former results in an insoluble polymer due to formation of anhydride bridges. 

The bicyclic tropane ring of cocaine of course presented serious synthetic difficulties. In one attempt to find an appropriate substitute for this structural unit, a piperidine was prepared that contained methyl groups at the point of attachment of the deleted ring. Condensation of acetone with ammonia affords the piperidone, 17. Isophorone (15) may well be an intermediate in this process conjugate addition of ammonia would then give the aminoketone, 16. Further aldol reaction followed by ammonolysis would afford the observed product. Hydrogenation of the piperidone (18) followed then by reaction with benzoyl chloride gives the ester, 19. Ethanolysis of the nitrile (20) affords alpha-eucaine (21), an effective, albeit somewhat toxic, local anesthetic. 

The Grohe-Heitzer sequence (Scheme 4.2) begins with acylation of malonate derivative 37 with benzoyl chloride 36 to give malonate 38 (Mitscher, 2005). Condensation of the malonate with an ortho-ester in the presence of a dehydrating agent such as acetic anhydride affords enol ether 39. The enol ether then undergoes an addition-elimination... 

Acylation of 2-pyrrolidinemethanol with benzoyl or substituted benzoyl chlorides gives chiral l-aroyl-2-pyrrolidinemethanols while condensation of 2-pyrrolidinecarboxylic acid with 2 H-3,l-benzoxazinc-2,4-(l 7/)-diones results in pyrrolobenzodiazepinediones25. 

HCA121). 3-Acetyl-4-hydroxy-l,5,5-trimethyl-2-pyrrolone 39a gives no acetylated products with either benzoyl chloride or benzoic anhydride, or acetic anhydride. By contrast phase-transfer catalysis (K2C03/CHC13 r.t.) affords a condensation product, formed from two molecules, 39a. This product does not bear a benzoyl group (87TH2). 

The aniline nitrogen is then converted to the para-toluenesulfonamide (4-3). Reaction of this intermediate with ethyl co-chlorobutyrate in the presence of potassium carbonate then gives the alkylation product (4-4). Potassium tert-butoxide-catalyzed Claisen condensation of this diester leads to azepinone (4-5) as a mixture of methyl and ethyl esters resulting from alternate cyclization routes. A strong acid leads to the transient keto-acid, which then decarboxylates the toluensulfonyl group is lost under reaction conditions as well as affording the benzazepinone (4-6). This last intermediate is then acylated with the benzoyl chloride (4-7) to afford amide (4-8). 

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