EXCHANGE 
 
THE PREPARATION OF SUBSTITUTED 
 
 ALPHA HALOGEN BENZYL BENZOATES, 
 
 AND A STUDY OF THE REACTIONS OF 
 
 THESE COMPOUNDS 
 
 BY 
 
 HERBERT EPHRAIM FRENCH 
 
 A. B. Morningside College, 1915 
 M. A. University of Illinois, 1917 
 
 THESIS 
 
 Submitted in Partial Fulfillment of the Requirements for the 
 
 Degree of 
 DOCTOR OF PHILOSOPHY 
 
 IN CHEMISTRY 
 
 IN 
 
 THE GRADUATE SCHOOL 
 OF THE 
 
 UNIVERSITY OF ILLINOIS 
 
 1920 
 
 (Reprinted from the Journal of the American Chemical Society, 
 Vol. XLIII No. 3 March, 1921) 
 
THE PREPARATION OF SUBSTITUTED 
 
 ALPHA HALOGEN BENZYL BENZOATES, 
 
 AND A STUDY OF THE REACTIONS OF 
 
 THESE COMPOUNDS 
 
 BY 
 
 HERBERT EPHRAIM FRENCH 
 
 A. B. Morningside College, 1915 
 M. A. University of Illinois, 1917 
 
 THESIS 
 
 * 
 Submitted in Partial Fulfillment of the Requirements for the 
 
 Degree of 
 DOCTOR OF PHILOSOPHY 
 
 IN CHEMISTRY 
 
 IN 
 
 THE GRADUATE SCHOOL 
 OF THE 
 
 UNIVERSITY OF ILLINOIS 
 1920 
 
 (Reprinted from the Journal of the American Chemical Society, 
 Vol. XLIII No. 3 March, 1921) 
 
ACKNOWLEDGMENT. 
 
 This investigation was undertaken at the suggestion and under 
 the direction of Professor Roger Adams. 
 
 The writer wishes to acknowledge his indebtedness to Professor 
 Adams for the interest he has shown, and for the many helpful 
 suggestions given during the course of this investigation. 
 
 444259 
 
VII. VITA 
 
 The writer of this thesis was born in Ireton, Iowa, November 13, 
 1889. He attended the grade schools at that place, but received his 
 high school education in Sioux City, Iowa. In September, 1910, he 
 entered Mforningside College, from which he graduated with the de- 
 gree of Bachelor of Arts, in June, 1915. During the summer of 
 1915, he attended the University of Chicago, taking work in the 
 Department of Chemistry, and in September of the same year, he 
 took up graduate work in Chemistry at the University of Illinois, 
 He received the degree of Master of Arts from that Institution in 
 June, 1917. During the time from February, 1916, to June, 1920, 
 he held the position of Assistant in Chemistry at the University 
 of Illinois. He is a member of Sigma Xi, Phi Lambda Upsilon, and 
 Alpha Chi Sigma. 
 
l&eprinted from the Journal of the AmericanChemical Society, 
 Vol. XLIII. No. 3. March, 1921.] 
 
 [CONTRIBUTION FROM THE CHEMICAL LABORATORY OF THE UNIVERSITY OF ILLINOIS.] 
 
 THE REACTION BETWEEN ACID HALIDES AND ALDEHYDES. II. 
 
 BY H. K. FRENCH WITH ROGER ADAMS. l 
 
 Received January 10, 1921. 
 
 In an earlier paper from this laboratory, 2 the fact was brought out that 
 many aromatic aldehydes and aromatic acid halides react readily to 
 form halogenated benzyl benzoates and a study of a number of the re- 
 actions of these condensation products was made. In the present com- 
 munication this work has been extended. 
 
 It has been shown that the reaction between aromatic acid halides and 
 the aromatic aldehydes is very general. The previous work indicated 
 that in a few instances perhaps, certain aromatic aldehydes would not 
 condense with certain aromatic acid halides to give the expected deriva- 
 tives. This conclusion resulted from the fact that solid products could not 
 be isolated although from the nature of the substituents solid products 
 might be expected. The oils which were produced always decomposed 
 when vacuum distillation was attempted so that it was impossible to 
 determine whether a definite substance existed or whether merely a 
 mechanical mixture. By treating these oily reaction mixtures with 
 pyridine, solid addition compounds of pyridine and the aldehyde-acid 
 halide products were formed and easily purified. Thus it was shown 
 that a reaction actually had taken place in these instances and the re- 
 sulting products were oils. Moreover the aldehyde-acid halide condensa- 
 tion products which were solids but too unstable to purify and analyze 
 could be isolated in the form of stable pyridine addition products. These 
 same pyridine addition products could be made also by first treating 
 pyridine with an acid-halide and then adding the aldehyde. 
 
 1 This communication is an abstract of work carried out by H. E. French in partial 
 fulfilment for the degree of Doctor of Philosophy at the University of Illinois. 
 
 2 THIS JOURNAL, 40, 1732 (1918). 
 
652 H. K. FRENCH WITH ROGER ADAMfe. 
 
 
 C 5 H 6 N\ 
 p 
 
 C 5 H 5 NXCOR + RCHO/ 
 Trimethylamine formed addition products in a similar manner to pyridine, 
 and presumably any other aliphatic tertiary amine would react similarly. 
 
 The large number of aromatic aldehydes and aromatic acid halide 
 compounds produced, allowed definite conclusions to be drawn in regard 
 to the ease of formation. In general the acid halides or aldehydes con- 
 taining a chlorine, bromine, iodine or nitro group reacted more slowly 
 to give addition products than those acid halides and aldehydes which 
 were unsubstituted or contained methyl or methoxy groups. On the 
 other hand the former class yielded much more stable products than were 
 formed in the latter class. If a methoxy or methyl group was present the 
 resulting halogenated esters, even though the phenyl groups contained a 
 halogen or nitro group in addition, were quite unstable substances. 
 Aromatic aldehydes did not react as rapidly with aromatic acid chlorides 
 as with the corresponding acid bromides. It appeared, moreover, that 
 with the acid chlorides the addition reactions did not run so nearly to 
 completion as with the acid bromides; in many cases, the acid chlorides 
 and aldehydes gave only semi-solid reaction masses even after several 
 days' standing. 
 
 It seems apparent that the reaction between the acid halides and 
 aldehydes to form the halogenated esters is an equilibrium reaction, the 
 equilibrium point depending on the nature of the initial substances and 
 of the product. Sometimes the reactions ran almost to completion, in 
 other cases only part way. The latter type was particularly noticeable 
 with the acid chlorides. Many of the pure halogenated esters, although 
 kept in a dry place changed within a few days to a semi-solid mass which 
 appeared similar to that formed by the addition of the acid halide to the 
 aldehyde. A trace of zinc chloride greatly speeded up the reactions and 
 caused the equilibrium point to be reached in a comparatively short time. 
 The tendency of these halogenated esters to dissociate accounts for a 
 number of their reactions, especially those which might be expected pro- 
 viding these compounds were merely mixtures of acid halide and aldehyde. 
 
 A preliminary study of the reactions of these addition compounds was 
 made by Adams and Vollweiler. 1 It was found that with water, the 
 addition compounds behaved as a simple mixture of acid halide and alde- 
 hyde producing hydrobromic acid, organic acid and aldehyde; with 
 alcohol, a similar reaction took place, with the formation of an ester, 
 aldehyde and hydrobromic acid; with ammonia in dry ether solution 
 there resulted an acid amide, aldehyde and ammonium bromide; with 
 1 Adams and Vollweiler, THIS JOURNAL, 40, 1732 (1918). 
 
REACTION BETWEEN ACID HAUDES AND ALDEHYDES. II. 653 
 
 aniline, the organic acid and phenyl-bromomethyl aniline in practically 
 quantitative yields formed according to the following equation: 
 CeHsCHBrOCOCeHs -f C 6 H 5 NH 2 > CeHsCHBrNHCeHg + C 6 H 5 COOH 
 
 | NaOH 
 
 C 6 H 5 CH : NC 6 H 5 + NaBr + H 2 O 
 
 In the present research, the action of different amines has been investi- 
 gated; o- and ^-chloro-anilines, o- and ^-toluidines all give analogous re- 
 sults to aniline itself. As a type of primary aliphatic amine, methyl 
 arnine was chosen. In dry ether solution, bromomethyl benzoate with 
 this amine yields methyl benzamide, methyl amine hydrobromide and 
 benzylidene methyl amine. 
 C6H 6 CHBrOCOC 6 H5 + 3CH 3 NH 2 > 
 
 C 6 H 5 CONHCH 3 + CH 3 NH 2 HBr -f C 6 H 5 CH = NCH 3 + H 2 O. 
 Secondary aliphatic amines, such as diethyl amine, give a mixture of 
 disubstituted acid amide, aldehyde and salt of the amine. 
 CeHsCHBrOCOCeHs + 2(C 2 H 5 ) 2 NH > 
 
 C 6 H 5 CON(C 2 H5) 2 + C 6 H 5 CHO + (C 2 H 5 ) 2 NH.HBr. 
 
 Tertiary aliphatic amines, such as trimethyl amine, give addition com- 
 pounds; pyridine acts in a similar manner as has already been mentioned. 
 With secondary and tertiary aromatic amines, complex substances be- 
 longing to the triphenyl methane series are produced. 
 
 These halogenated esters in dry ether react with zinc or copper powder 
 to give condensation products which are derivatives of the dibenzoate of 
 hydrobenzoin. 1 
 
 2C 6 H 6 CHBrOCOC 6 H5 + Zn ^ (CelfcCHOCOCeHs)* -f ZnBr 2 . 
 Many side reactions, however, take place, so that the yields seldom are 
 greater than 20%. 
 
 The addition compounds react with potassium cyanide, alkali salts of 
 organic acids or potassium hydroxide to give more or less complete hy- 
 drolysis. Definite compounds from these reactions have not been isolated. 
 
 Experimental. 
 
 To prepare the addition compounds, equimolecular amounts of the acid halide 
 and aldehyde were mixed and allowed to stand at room temperature in a tightly stop- 
 pered flask. More or less heat was invariably evolved and in the course of from a few 
 minutes up to several days, the mixtures became solid or semi-solid and did not change 
 on further standing. The products were washed with a little dry ether or petroleum 
 ether, powdered and then recrystallized. It was noticeable that the acid bromides 
 in most cases formed solids with the aldehydes while in general, the acid chlorides formed 
 semi-solids with the aldehydes. The times for the reactions given in the following 
 tables represent the maximum time necessary after which no further change in the mix- 
 ture was noticed. When a small amount of anhydrous zinc chloride was added, the 
 time required for reaching the end of the reaction was greatly diminished. 
 
 The compounds and their constants and analyses are given in the following table. 
 
 1 -Ber., 15, 1818 (1882); 17, 911 (1884). 
 
654 
 
 H. E. FRENCH WITH ROGER ADAMS. 
 
 So 8 
 
 00 -i 
 CO O3 
 
 3 cS 2 8 
 
 S S 
 
 o 
 
 g 
 
 o 
 
 S $ S3 
 
 
 <N (N CO T-I 
 
 4 d d i 
 
 S 
 35 
 
 9 S 
 
 ^}^ CO 
 
 t^* CD 
 
 0^ "5 
 
 ^H CM 
 
 1 I 
 
REACTION BETWEEN ACID HALIDES AND ALDEHYDES. II. 
 
 655 
 
 .9 
 
 8 S 
 
 CO 
 
656 H. E. FRENCH WITH ROGER ADAMS. 
 
 Phenyl Chloromethyl Benzoate, 
 
 Upon mixing benzoyl chloride and benzaldehyde together with a small piece of 
 fused zinc chloride, a reaction took place at once and heat was developed. No solid 
 formed, however, even after long standing and thorough chilling. The resulting oil 
 was fractionated as follows: 
 
 1st fraction, boiling 77-81 at 15 mm. 
 
 2nd fraction, boiling 84-86 at 15 mm. 
 
 3rd fraction, boiling 205-208 at 15 mtn. 
 
 The first and second fractions proved to be benzaldehyde and benzoyl chloride, respiv 
 tively. The third fraction which solidified proved to be benzoic anhydride. 
 
 In addition to the above chlorinated esters, (Nos. 22-28 in the table) 
 those produced from cinnamyl chloride and anisaldehyde as well as from 
 cinnamyl chloride and piperonal and methyl vanillin were- made. Both 
 were solids but unstable so that they were not purified for "analysis. 
 Compounds Formed from Pyridine and the Acid Halide-Aldehyde 
 
 Condensation Products. 
 
 Phenyl-bromomethyl Benzoate and Pyridine, C 6 H 5 XBrCH(CH 6 )OCOCH 6 .- 
 phenyl-bromomethyl benzoate was treated with excess of pyridine. It went into solution 
 slowly, but there was no evidence of a reaction. On standing, however, crystals began 
 to deposit and soon a heavy precipitate had formed. The solid material was tilUrrd 
 off and purified by dissolving in absolute alcohol and precipitating with dry ether. It 
 melted at 180 with decomposition, was very soluble in water and gave a neutral solu- 
 tion. This solution gave an immediate precipitate of silver bromide on the addition 
 of silver nitrate. 
 
 Analyses. Subs., 0.5954, 0.5934: 17.14, 17.14 cc. 0.0934 A' igNQ Calo. for 
 C 19 H 10 2 NBr: Br, 21.62. Found: 21.50, 21.58. 
 
 The same compound was also made by adding 1 mol of beuzoyl bromide to J .5 nu-U <- 
 of pyridine. The resulting solid addition compound was pulverized and to it 1 mol of 
 benzaldehyde was added. An immediate reaction took place and the solid suhstamv 
 just described above was produced. 
 
 Phenyl-chloromethyl Benzoate and Pyridine, CfiHoNClCHtCtHOOCOQH*. -On 
 mixing equimolecular amounts of benzoyl chloride and benzaldehyde, an immediate 
 reaction took place. When cold, the resulting oil was poured into one mol of pyridine 
 In about half an hour, the mixture had become a pasty solid. The solid material was 
 filtered off and purified by dissolving in absolute alcohol and precipitating with dry 
 ether. It then melted at 192 with decomposition. 
 
 Analyses. Subs., 0.6210, 0.5910: LS.67, 17.81 cc. of 0.1022 N AgNO s . Calc. for 
 C 19 H 16 O 2 NC1: Cl, 10.90. Found: 10.90, 10.93. 
 
 A mixture of 10 g. (one mol) of benzoyl chloride and 5.6 g. (one raol) of pyridine 
 was allowed to stand overnight. Only a few crystals had separated by that time. 
 When 7.5 g. (one mol) of benzaldehyde was added, a reaction took place at once with 
 the liberation of considerable heat. The solid product was purified as already men- 
 tioned by dissolving in absolute alcohol and precipitating with dry ether, and had the 
 same m. p., 192. 
 
 p - Methoxyphenyl-bromomethyl - p - Nitrobenzoate and Pyridine, CiH 5 NBrCH- 
 (CeH4OCH3)()OCOC6H 4 NO2().- />-Nitrobenzoyl bromide reacted with anisaldehyde to 
 give a solid product in about 2 minutes. This material was pulverized and'added in 
 small amounts to an excess of pyridine. Complete solution took place, followed in a 
 
 1 Compt. rend., 31, 113 (1850); Ann.. 154, 347 (1870). 
 
REACTION BETWEEN ACID HALIDES AND ALDEHYDES. II. 657 
 
 few minutes by the separation of a solid product. This was purified by dissolving in 
 absolute alcohol and precipitating with dry ether. After drying in vacuo over sulf uric 
 acid, the product melted at 126-128. 
 
 Analyses. Subs., 0.6097: 13.65 cc. of 0.1022 N AgNO,. Calc. for QHnO5N 2 Br: 
 Br, 17.97. Found: 18.17. 
 
 A semisolid product was obtained when the o-methylbenzoyl bromide and benzal- 
 dehyde were mixed and allowed to stand overnight. This was added to one mol of 
 pyridine, and the solid product thus obtained, after being purified by dissolving in 
 absolute alcohol and precipitating with dry ether, melted at 206 with decomposition. 
 
 Analyses. Subs., 0.6630, 0.7751: 17.08, 19.91 cc. 0.1022 N AgNO 3 . Calc. for 
 CwHigOaNBr: Br, 20.83. Found: 21.06, 21.00. 
 
 Reactions of Phenyl Bromomethyl Benzoate with Amines. 
 
 Phenyl Bromomethyl Benzoate and Methyl Amine. A heavy white precipitate 
 of methylamine hydrobromide began to form almost at once, when dry methylamiuc 
 was passed into a solution of the phenyl-bromo-methyl benzoate in dry ether. About 
 3 moles of the amine was added and the mixture then allowed to stand overnight. 
 After filtering off the precipitate, the ether was evaporated and the oil obtained was 
 separated into 2 fractions by distillation in vacuo. The lower boiling fraction was re- 
 distilled under ordinary pressures, and proved to be benzylidene methylamine, b. p. 
 180-181. The higher boiling fraction solidified and was methyl benzamide, CH 6 - 
 CONHCH 8 , m. p. 78-79. 
 
 Phenyl-bromomethyl Benzoate and Diethylamine. Phenyl-bromomethyl ben- 
 zqate when treated with diethylamine in the manner just described under methyl- 
 amine gave an oil, which, fractionated in vacuo, gave (1) boiling at 88 at 35 mm.; (II) 
 boiling at 160-175 at 35 mm. On redistillation under ordinary pressures, the 2 frac- 
 tions were found to be benzaldehyde, boiling at 179-182, and diethyl benzamide, boil- 
 ing at 278-282. 
 
 Phenyl-bromomethyl Benzoate and Trimethyl-amine, (CH 3 ) 8 NBrCH(CHo)- 
 OCOCH f . When dry trimethyl-amine was passed into an absolute ether solution of 
 phenyl-bromomethyl benzoate, a heavy white precipitate began to form at once. When 
 3 moles of the amine had been added, the thick mass resulting was filtered and the solid 
 recrystallized from alcohol. It melted at 136-137. 
 
 The white solid was completely soluble in water, and this solution when treated 
 with sodium hydroxide gave off trimethyl-amine. The odor of benzaldehyde could 
 also be detected. Acidification of the alkaline solution precipitated benzoic acid. 
 
 Analyses. Subs., 0.2632, 0.2042: AgBr, 0.1400, 0.1080. Calc. for CwHwOsNBr: 
 Br, 22.85. Found: 22.63, 22.50. 
 
 Phenyl-bromomethyl Benzoate and o-Chloro-aniline, CeHsCHBrNHCeH^Cl (<?). 
 Phenyl-bromomethyl benzoate and o-chloro-aniline reacted immediately and produced 
 a yellow solid. By treatment with several portions of dry ether, the benzoic acid pro- 
 duced as a by-product was extracted. The yellow solid remaining was analyzed. 
 
 Analyses. Subs., 0.5429: 17.84 cc. 0.1022 N AgNO 3 . Calc. for C u H u NBrCl: 
 Br, 26.98. Found: 26.86. 
 
 Some of this substance was treated with 20% sodium hydroxide solution, extracted 
 with ether, and the ether extract dried over calcium chloride and evaporated. The 
 solid remaining was found to melt at 54. A mixed melting point with some benzyl- 
 idene-0-chloroaniline (prepared from benzaldehyde and 0-chloro-aniline) was taken 
 and found to be 54. 
 
 It was found that the yellow solid was completely hydrolyzed by water, so that 
 if it were first dissolved in water and then sodium hydroxide solution added, o-chloro- 
 aniline was precipitated instead of benzylidene-o-chloro-amline. 
 
658 H. E. FRENCH WITH ROGER ADAMS. 
 
 Phenyl-bromomethyl Benzoate and />-Chloro-aniline, 
 Phenyl-bromomethyl benzoate and />-chloro-aniline were allowed to react, then treated 
 as described under the o-chloro-aniline. Phenyl-bromomethyl-p-chloro-aniline was 
 produced and yielded by treatment with 20% sodium hydroxide, benzylidene-p-chloro- 
 aniline, 1 m. p. 62. 
 
 Phenyl-bromomethyl Benzoate and -Toluidine, CeHsCHBrNHC^CH, (). 
 Phenyl-bromomethyl benzoate and />-toluidine reacted vigorously. After extraction 
 of the benzoic acid with dry ether, the solid proved to be phenyl-bromomethyl-/>-tolu- 
 idine. 
 
 Analyses. Subs., 0.5949: 21.26 cc. 0.1022 N AgNO,. Calc. for CuH 14 NBr: Br, 
 28.98. Found: 29.21. 
 
 Phenyl-bromomethyl Benzoate and Mono-ethylaniline. A dry ether solution of 
 phenyl-bromomethyl benzoate (one mol) was added to a dry ether solution of mono- 
 ethyl aniline (two mol) and enough heat was generated to cause the ether to boii. 
 After refluxing for 8 hours, the ether was decanted from the dark red viscous mass in 
 the flask. The ether was extracted successively with sodium carbonate and dilute 
 hydrochloric acid, which yielded benzoic acid and mono-ethylaniline respectively. 
 Evaporation of the ether furnished a small amount of benzaldehyde. 
 
 Oxidation of the red viscous material with lead dioxide and hydrochloric acid 
 yielded a green solution. An alcohol solution of the gummy material was red in direct 
 light and green in reflected light With mercuric chloride this solution produced a white 
 precipitate which turned blue on drying. These properties correspond to those expected 
 of the dye from diethyl-diamino-triphenyl carbinol.* 
 
 Phenyl-bromomethyl Benzoate and Diphenylamine. When a dry ether solution 
 of one mol of phenyl-bromo-methyl benzoate and a dry ether solution of two mols of 
 diphenylamine were mixed, a colorless precipitate began to form almost at once. After 
 standing for 1.5 hours a green gummy deposit formed. The solution was filtered, and 
 the residue washed with ether. By using the method of Meldola, 1 crystals of the dye 
 from diphenyl-diamino-triphenyl carbinol were obtained. 
 
 Phenyl-bromomethyl Benzoate and Dimethylaniline. A dry ether solution of 
 one mol of phenyl-bromomethyl benzoate and a dry ether solution of two mols of di- 
 methylaniline were mixed and refluxed for 9 hours. A considerable amount of a green 
 viscous mass separated. After evaporating the ether, the material was steam distilled. 
 As much water as possible was then distilled off from the residue and an attempt was 
 made to recrystallize the green mass remaining, but without success. The material 
 was then reduced with zinc and hydrochloric acid and the leuco base of malachite green 
 was obtained. On recrystallization from alcohol, this material melted at 92-93. 
 
 Reactions of Phenyl-Bromomethyl Benzoate and Substituted Benzoates 
 
 with Metals. 
 
 Phenyl-bromomethyl Benzoate and Zinc; Formation of Dibenzoyl-hydrobenzoin, 
 (CaHsCHOCOCeHeV To an absolute ether solution of phenyl-bromomethyl benzoate 
 (one mol) zinc dust (12 mol) was added in small portions. The flask was well shaken 
 during the addition. The solution was then filtered and the zinc extracted twice with 
 ether, then twice with hot benzene. Upon evaporation of the extraction liquors, the 
 product, dibenzoyl-hydrobenzoin in 20% yields was obtained. It melted at 246-247*, 
 after one crystallization from benzene. 
 
 On evaporation of the original ether solution, a tar was obtained which yielded 
 
 1 Ber., 34, 829 (1901). 
 
 8 Ann. Spl, 3, 363 (1865). 
 
 J. Chem. Soc., 41, 192 (1882). 
 
REACTION BETWEEN ACID HAUDES AND ALDEHYDES. II. 659 
 
 benzole acid when extracted with 50% alcohol. Attempts to recrystallize the resin 
 remaining were unsuccessful. 
 
 ^-Bromophenyl-bromomethyl Benzoate and Zinc; Formation of Dibenzoyl-/>,/?-di- 
 bromo-hydrobenzoin, ((/O-BrC^CHOCOCeHe^. An absolute ether solution of 
 -bromophenyl-bromomethyl benzoate was treated with a large excess of zinc dust in 
 the same way as the phenyl-bromomethyl benzoate. A 16.8% yield of the dibenzoate, 
 was obtained. After crystallization from benzene, the product melted at 225. 
 
 A nalyses. Subs., 0.0572 : AgBr, 0.0368. Calc. for C 28 H 2 oO 4 Br2 : Br, 27.58. Found : 
 27.37. 
 
 Phenyl-bromomethyl Benzoate and Copper Powder. The copper powder was 
 prepared by adding zinc dust to a solution of copper sulfate. It was filtered off and 
 digested with cone, hydrochloric acid, washed with water and dried in vacua over sul- 
 furic acid. 
 
 This reacted with the phenyl-bromomethyl benzoate in the same way as did the 
 zinc dust, producing a 20% yield of the dibenzoate of hydrobenzoin. 
 
 With sodium, magnesium or aluminum powders, only negative results were ob- 
 tained. 
 
 Phenyl-bromomethyl Benzoate and Alkalies or Alkali Cyanide. The reaction 
 between phenyl-bromomethyl benzoate and potassium hydroxide or potassium cyanide, 
 although carried out under widely varying conditions, always produced complete hy- 
 drolysis. 
 
 Summary. 
 
 1. The reaction between aromatic acid halides and aromatic aldehydes 
 is a general one. Benzoyl bromide, benzoyl chloride, and a number of 
 their substitution products have been condensed with various aromatic 
 aldehydes. 
 
 2. Halogen and nitro groups in either aromatic nucleus tend to retard 
 the speed of reaction, and usually produce more stable substances. Methyl 
 and methoxy groups tend to hasten the speed of the reaction, with the 
 formation of less stable products. 
 
 3. The acid halide-aldehyde compounds react with pyridine or tertiary 
 aliphatic amines to give stable addition products. These same products 
 are produced by allowing the acid halide to react with pyridine and then 
 adding the aldehyde. 
 
 4. The acid halide-aldehyde compounds react with primary and sec- 
 ondary aliphatic amines to give substituted benzamides, benzaldehyde, 
 and the amine hydrobromides. With primary aromatic amines, the hydro- 
 bromides of benzylidene or substituted benzylidene anilines together with 
 the aromatic acid are produced. Secondary and tertiary aromatic amines 
 produce complex compounds in the triphenyl methane series. 
 
 5. The acid halide-aldehyde compounds react with zinc or copper to 
 give esters of hydrobenzoin or substituted hydrobenzoin. 
 
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