('3 N I ll \ l .THS BENZYLATI ax: (3F c «CHLOROPHENCL THESE FEB THE DEGREE 0F 13:. Glenn W’. \X/arrm 1931 31293 0172144 5'. THE BENZYLATION OF o-CHLOROPHENOL A Thesis Submitted to the Faculty of Michigan State College In Partial Fulfillment of the Requirements for the Degree of Master of Sciencé by Glenn W. Warren {arch 1931 \ #ch- 53’“ ACKHOWLEDSEMEN The author wishes to eXpress his gratitude to Dr. R. C. Huston for his kindly advice and counsel. 33.1671 taitn 1.3.3.7 0» J. .. CONTENTS The Alkylation of Phenols The Chlorination of Phenols The Work of Claisen The Use of Aluminum Chloride as a Condensing Agent Statement of the Problem EXperimental Summary Graphic Summary 13 15 31 32 1. Historical The Alkylation Of Phenols Many investigators have studied the alkyl- ation of phenols and a vast number of compounds have been prepared by them. The purpose of this historical sketch is to give a list of the more important investigators, what their work was, and when it appeared in the literature. E. Paterno in 1972 (Gazz. chim. ital. l, 166, 1872) heated a mixture of benzyl Chloride and phenol with metallic zinc. He obtained a benzylated phenol which crystallized in small, silky crystals and had a melting point of 84°. E. Paterno and.Fileti (Gazz. chim. ital. 3, 121— 129 and 251-254, 1874) reported a nnmber of derivatives of this benzylated phenol among them the acetate (B. p. 317°) and the benzoate (M. p. 86°). Two years later in 1876 the same two workers found (Gazz. chim. ital. 5, 381-383- 876) that benzyl alcohol with phenol in a mix- ture of sulphuric and acetic acids yielded the same benzylated phenol and also some oil which seemed to be an isomeric compound. Later in 1882 Rennie (J. Chem. Soc. 1&1, 220, 1882) proved the benzylated compound which melted at 84° to be para benzylphenol and in 1886 (J. Chem. Soc. 49 , 406, 1886) he isolated and proved the structure of ortho benzylphenol which was formed in Paterno and Fileti’s eXperiment. Paterno and Mazzaro (Gazz. chim. ital. 8, 303-305, 1879) condensed benzyl chloride and paracresol by using zinc turnings to form a mono- benzyl paracresol, which boiled at 240° under 40 mm. of pressure. Two years later Mazzaro pro— duced a monobenzyl thymol, boiling at 255° under 8 mm. of pressure by the same reaction (Gazz. chim. ital. 10, 346-352, 1881). By using magnesium chloride the same eXperimenter condensed prOpyl and iso-prOpyl alcohol with meta cresol and formed, prOpyl, iso—prOpyl, diiso—prOpyl and diprOpyl meta cresol (Gazz. chim. ital. 12, 505-511, 1883): In 1881 Liebeman (Ber. 14, 1842-44. 1881) reported that higher homologues of phenols cannot be obtained by the action of chlorine derivatives of the hydrocarbons on the phenols, but that their preparation can be affected by the action of zinc chloride on a mixture of the phenols and alcohols. Heat was also necessary for this reaction. He prepared butyl phenol, m. p. 98°, amyl phenol, m. p. 92°, and benzyl phenol b.-p. 314-316° in this way. Ethyl phenol was produced J .II.. V '..5vp.‘o'l1~illlvulvvl’~l I 3. in 1884 by Auer (Ber. 17, 669-673, 1884) using zinc chloride as a condensing agent. Four years later Herzig and Zeisel (Monatsch. 9, 217-226, 1888) treated phloroglucinol in aqueous alkaline solution with methyl iodide and obtained the hexa- and penta-methyl derivatives of it. Bakunin (Gazz. chim. ital. 33, 495-5, 1903) produced the benzyl derivatives of alpha and beta naphthol in the presence of zinc. Johnson and Hodges (J. Am. Chem. Soc. 35, 1014, 1913) found that mixed ketones containing the hydroxyl or alkyloxy radicals in the benzene nucleous are readily reduced by zinc amalgam and hydrochloric acid to the sorreSponding alkyl substituted phenols or ethers. In 1910 Braun (Ber. 43, 1350-52, 1910) produced ethers by boiling such compounds as benzyl bromide and o-xylyl bromide with dilute suphuric acid and alcohol. They made benzyl- methyl ether, b. p. 189°, benzylallyl ether, b. p. 204—205o, and o-xylylethyl ether, b. p. 208-2io°. In the same year Halban (Ber. 43, 2071, 1910) reported that benzyl halegenoids react with phenols and carboxylic acids to firm ethers. In 1920 Powecl and Adams (J. Am. Chem. Soc. . 1r: 4‘ n....PFUp1l-.!u. .DE’I’ I Inf»... 42, 646-58, 1920) prepared p-bromOphenyl benzyl ether by refluxing benzyl chloride, p-bromOphenol and potassium carbonate in acetone solution. Dibenzyl ether and amylbenzyl ether were prepared by heating benzyl chloride with the alcohol in sulphuric acid by Senderens in 1924 (Compt. rend. 178, 1412-15, 1924). Baw used leucotrOpe (C6H5CH2C6H5(CH3)2N01) to benzylate a number of phenols (Quart. J. Ind. Chem. Soc. 3, 101-4, 1926). Among them were 0-, m-, and p-chlorOphenol. He produced the benzyl ethers of these phenols, and reported the boil- ing point of o-chlorOphenyl benzyl ether as 296°. The Chlorination of Phenols In 1898, Peratoner (Gazz. chim. ital. 281, 197-240, 1898) prepared a benzyl chlorOphenol by chlorinating para benzylphenol with sulfuryl chloride. This monochlorOphenol boiled at 318-321°. Richter’s Lixikon reports it as benzyl meta-chlorOphenol while Beilsteins hand- book gives it the structure of alpha-chloro- 4 hydroxy diphenyl methane. 5. The Work of Claisen L. Claisen published a paper in 1923 (Z. angew. chem. 36, 478-9, 1923) describing an eXperiment in which he treated an alkali phenbl- ate with an alkyl halide in a solution of benzene or toluene. The product was largly alkyl sub- stituted phenol (substituted in the ring) ahd a smaller portion of alkyl phenyl ether which was removed with petroleum ether after the phenols had been changed to the potassium salts in methyl alcohol solution. Claisen states that while oxygen alkylation would be eXpected carbon alkylation does take place to a very large extent. The entering alkyl group always goes to the ortho position. Claisen eXplains this by Michaels theory (J. pr. 31, 486; 46, 189) of the reaction between silver cyanide and methyl iodide. When this is applied to the reaction between alkyl halide and alkali phenolate it can be illustrated as follows, -1 _ 0Na 1:1 O\i a/C,1./}R NaCl .0 = c - + RC1 = - c - c- = H R 9 H\? § / .. C - C - : .. = C - Claisen says that unsaturatbd alkyl halides substitute in the ring more easily than saturated 6. alkyl halides and that alkyl phenols are carbon alkylated more readily than unsubstituted phenols. However, the most important single [actor is the solvent. The use of alcohol yields entirely the alkyl phenyl ethers while non- dissociating media such as benzene or toluene give to a large exyent carbon alkylated deriva- tives. Two years later in 1925 M. Busch (Z. angew. chem. 38, 1145-6, 1925) states that the tendency of benzyl radicals toward carbon alkylation in phenols increases with the increasing sub— stitution on the methane carbon atom. He gives as proof that it is possible to obtain ethers with benzyl chloride in a non-dissociating media, but that diphenyl chloromethane gives only the carbon alkylated derivatives. Busch and Knoll (Ber. 60B, 2243-57, 1927) state that the introduction of electro negative groups in phenols favor the ether formation, and substantiates Claisens claim that alkyl group on the phenol nucleous diminish ether formation. In an article in 1925 Claisen (Ann. 442, 210-45, 1925) gives the results of several condensations which were similar to those described in his first paper. One of them is that of allyl bromide with paracresol. In methyl alcohol Isolution 90% of the p-cresol allyl ether was form- ed. While in benzene there was 20% cresol allyl ether, 40% monoallyl cresol and 15% diallyl cresol formed. Several workers have found that alkyl phenol ethers rearrange to form substituted phenols. Claisen (Ann. 418, 69-120, 1901) rearranged allyl phenyl ether to o-allyl phenol. Schorigen (Ber. 58B, 2028, 1929 found that benzyl ethers rearrange to form carbinols. van Alphen (Rec. trav. chim. 46, 799-812) found that benzyl phenyl ether rearranges when heated with zinc chloride, to form 4 hydroxy diphenyl methane. Short (J. Chem. Soc. 137 , 528, 1928) isolated from the same reaction 0- and p- . flyyxflxf benzyl phenol, phenol and some high boiling products. However, although allyl and benzyl phenyl ethers are readily rearranged, evidence seems to show that carbon alkylation Qfl’pnenols does not take place by the formation of the ether and the subsequent migration of the alkyl radicals; but that it takes place as Claisen first eXplained it by simple addition, splitting off of sodium chloride and the formation of the enol. (Ann. 442, 212, 1925) .'n f. 6 w»: |.Il...I.9n .tuliu‘ The Use of Aluminum Chloride as a Condensing Agent Kuhlman was the firstobservor to use aluminum chloride as a condensing agent. He used it in 1840 (Ann. 33134, 97—204, 1840) tp prepare ethers from mixtures of alcohols. It was 37 years after this, in 1877, when Friedel and Crafts published their paper on the catalytic action of aluminum chloride. (Bull. Soc. Chim. 27, 48, 1877; Compt. rend. 84, 1392-5, 1877). They found that amyl chloride reacted with aluminum chloride with a stronge evolution of hydrochloric acid gas. They then applied this metal chloride to aromatic hydrocarbons and were able to synthesize homologues of benzene. However, when they attempted to use alcohols or phenols in this reaction, decomposition took place. They came to the conclusion that in general compounds with an OH or an OR underwent decomposition when treated with aluminum chloride. In 1881, Merz and Weith (Ber. 14, 187-202, 1881) reported that when zinc chloride acted upon phenol, diphenyl ether was formed, but when aluminum chloride was substituted for zinc chloride benzene, diphenyl ether and methylene-diphenyl oxide resulted, 9. Gatterman, Erhardt and Maisch found (Ber. 23, 1199-1210, 1890) that acid chlorides react with phenols in the presence of aluminum chloride in Just the same way as with aromatic hydrocarbons. G. Perrier (Compt. rend. 122, 195-198, 1896) isolated an addition product of o-chlorOphenol and aluminum chloride. 2 mols of o-chlorOphenol reacted with one mol of aluminum chloride with the elimination of 2 mols of hydrogen chloride. The product was A13014(OCSH.61)3 which was a white crystalline powder, melting at 207-210°. It was readily soluble in alcohol and slightly soluble in carbon bisulfide. Kohn and Muller (Monatsch. 30, 407-9, 1909) found that bromobenzene and phenol were formed by the action of aluminum chloride on a solution of tribromOphenol in benzene but trichlorOphenol under similar conditions remained unattacked. Annie Homer (Proc. Camb. Phil. Soc. 16, 65-6, 1911) treated dry benzene with 25% of its weight of aluminum chloride and heated it to 100° for 10-14 days. She obtained a low boiling fraction consisting of phenol and naphthalene and a higher boiling one (160-200°) 10mm) which was colorless but turned to a purple oil in the air. 10. Frankfurter and POppe (Orig. Com. 8th Intern. Congr. Appl. Chem. 25, 361, 1913) reported that aluminum chloride reacted vigorously at ordinary temperatures with phenol ethers in the presence of chloral and bromal and that the same products were formed as when concentrated sulphuric acid was used. In 1914, Frankfurter and Kritchivosky (J. Am. Chem. Soc. 36, 1511-29, 1914) used aluminum chloride to condense aliphatic and aromatic compounds with chloral, chloral hydrate, and bromal. In 1916 Huston started an investigation with Friedeman upon the dehydration prOperties of alum- inum chloride upon mixtures of aromatic alcohols and aromatic compounds.(J. Am. Chem. Soc. 38, 2527, 1916) This paper described the condensation of benzyl alcohol and benzene. In 1918 the same workers studied the action of secondary alcohols on benzene (J. Am. Chem. Soc. 40, 783, 1918). They used benzhydrol, methyl phenyl carbinol, and ethyl phenyl carbinol, from which they obtanned triphenyl methane, diphenyl ethane, and diphenyl prOpane respectively. They foundthat benzhydrol gave the largest yield and ehhyl phenyl carbinol the smallest, so they concluded that the longer the paraffin chain the more difficultly it reacts 11. with benzene under the influence of aluminum chloride. In 1924 Huston (J. Am. Chem. Soc. 46, 2775—9, 1924) found that benzyl alcohol would react with phenol at relatively low temperatures when treated with aluminum chloride. The product was para benzyl phenol. Huston and Sager (J. Am. Chem. Soc. 48, 1955, 1926) attempted to condense saturated and unsaturat- ed aliphatic and aromatic alcohols with benzene under the influence of aluminum chloride, and came to the following conclusions, (1) That saturated aliphatic alcohols up to and including amyl alcohol do not react. (2) That unsaturate aliphatic; alcohols such as allyl do react. (3) That of the alcohol derivatives of the aromatic hydrocarbons, only those having the hydroxyl group on the carbon atom adjacent to the ring react. In 1927 Huston with Lewis and Grotemut (J. Am. Chem. Soc. 49, 1365-8, 1927) condensed methyl phenyl carbinol and phenol with aluminum chloride to form p-hydroxy-l,1-diphenylethane and ethyl- phenyl carbinol to form p-hydroxy-1,1-diphenyl- prOpane. Diphenyl carbinol was also condensed with phenol to form p-hydroxy triphenylmethane. I draw.“ ‘Ii'l 12. This gave a yield of 40%, which was a 10% increase over the other two. They gave this as additional evidence of the effect of unsaturation of the alpha carbon atom on the reactivity of the alcoholic hydroxyl. Huston, Swartout and Wardwell (J. Am. Chem. Soc. 52, 4484, 1930) condensed o-cresol with benzyl alcohol in the presence of aluminum chlor- ide, forming for the most part 2 methyl-6 benzyl- phenol and smaller amounts of 2 methyl-6 benzyl- phenol and 2 methyl-4,6 dibenzyl phenol. The exact office of the aluminum chloride in all of these condensations is not definitely known. The possibilities may be one or a combin- ation of the following, (1) catalytic action (2) intermediate compounds (3) dehydration. There is evidence to show that it acts in some condensations as a simple catalyst, and in other cases intermediate compounds have been isolated. However, for this problem it may be thought of as a dehydrating agent and the aluminum hydroxide thus formed as forming an addition product with the phenols. J .71" 'l‘ -III'I’I.-|~ V A . 13. Statement of the Problem 1. To study the condensation of o-chloro- phenol with benzyl alcohol under the influence of aluminum chloride. 2. To isolate the products of this condensa- tion and to determine some of their physical prOperties. The products of this reaction should according to the previous work be, primarily, 4 benzyl-6 chlorOphenol, 0H C1 OH; with the formation of some, 2 benzyl-6 chloro- phenol, 0H and some 2,4 dibenzyl-6 chlorOphenol, OH c1 CH2 C> CH3 is. , ,i .I ulna ‘l’liil. I'll!!! \ 14. To destinguish between the two monobenzyl o—chlorol phenols it will be necessary to condense benzyl chloride with sodium o-chlorOphenolate by Claisens method, which will give only one mono- benzylphenol, namely, 2 benzyl-6 chlorOphenol and some o-chlorOphenyl benzyl ether. 3. To determine the position that chlorine takes when introduced into the two compounds, OH OH c1 -CH. O (:1 cs, 4. To prepare the benzoyl, benzenqbulfonyl, and toluene sulphonyl derivatives of the two monobenzyl chlorOphenols. 15. Experimental One half mol of benzyl alcohol and 3/2 mols of o-chlorOphenol was dissolved in 2000c. of petroleum ether which was placed in a tall condensation flask, fitted with a mechanical stirrer. To this mixture was slowly added 1/4 mol of pulverized aluminum chloride, the addition taking about one hour. The stirring was kept up vigorously throughout. Ifter about one third 0; the aluminum chloride had been added, gydrochloric acid fumes began to be given off and the color of the mixture changed to a deep red. The temperature, however, remained constant, between 25 and 30°. The stirring was continued for one hour after all of the aluminum chloride had been added and the mixture was allowed to stand overnight. While standing the reaction products changed into a gel like mass. This mass was taken out of the cylinder and poured on to cracked ice. It then changed into an oil and was strongly acidified with concentrated hydrochloric acid. The ice decomposes the addition products of the aluminum and the phenols and the acid prevents the aluminum from precipitating as aluminum hydroxide. The oil was extracted from the water with diethyl ether. .7371} ..I 1.-.... I..cniulvulllllrallvllul1‘ \ .. . {Or 16. After the ether had been evaporated the residue was fractionally distilled. After the fourth, fractionation the fractions collected were as given below. 4th Fractionation at 5mm. 1. up to 90° 85.0g 2. 90-130° 9.4g 3. 130-145° 5.3g 4. 145-147° 21.5 g 5. 147—160° 18.4g 6. 160—2oo° 11.55 7. zoo-270° 14.5g Fractions 1 and 2 were unreacted o-chloro- phenol, 4 and 5 were thought to be monobenzyl substituted o-chlorOphenol, however, repeated fractionations were not successful in obtaining two or even one fraction with definite boiling points within their ranges. Fraction 7 was thought to be a dibenzyl compound and after several more distillations a heavy yellow oil was obtained boiling at 203-205° at 3mm. of pressure. This oil must have the formula, OH Cl CH. CD 17. In order to obtain a larger amount of the monobenzyl substituted o-chlorOphenol, seven other condensations were made. In all of them the amounts and the conditions were like the first and the results were also very similar. The fractions of all eight condensations were combined and the oil boiling from l30-175° at 5mm. of mercury pressure was subjected to a great many fractionations. A fractionating column was used, it was of the dented glass tube type and was two feet long. It was made in this laboratory. The fractions were all collected over a range of fifteen degrees, from 140° to 155° at 4mm. After many distillations the lowest boiling fraction, 140-142° partially solidfied when' placed in: an ice and saly mixture. The crystals were filtered out, amounting to only a small fraction of a gram and the oil fractionated again. This was repeated until no more crystals could be filtered off. The total weight 0: these crystals from the eight condensations only amounted to 20 grams. They were recrystallized 4 times from h1:h test gasoline, coming down as soft, snow white needles and gave a constant melting point of 40.5-41.5°. We will call these crystals compound I. 18. The oil remaining after the removal of these crystals could not be purified further by distill- ation. The boiling point was 145-148° at 3mm. We will call it compound II. The yield of monobenzyl substituted o-chloro- phenol in these condensations, when calculated from the standpoint of the benzyl alcohol used amounted to about 40%. The Preparation of 2 Chloro-6 Benzyl Phenol by Claisens Method 23 grams of sodium was placed in a long necked round bottom dlask with 250cc. of dry toluene. The toluene was then heated until the sodium melted and then shaken vigorously to break the sodium up into pieces abnut the size of bird shot. The flask was fitted with a reflux condenser and one mol of o-chlorOphenol was slowly added. Hydrogen was evolved ahd a white cheesy mass was formed. The mixture was allowed to stand overnight. It was then heated on amater bath for one hour in order to make sure that 811 of the Sodium had reacted with the o-chlorOphnaol. The mixture was then codled and one mol of 19. redistilled benzyl chloride was added. No visible I reaction took place so an oil bath was placed under the flask and heated from 150 to 160° for eight hours. The thermometer was in the oil bath. During the heating the white sodium phenolate gradually disappeared and a red oil took its place. A precipitate of sodium chloride was formed. After the heating the sodium chloride was washed out with water and the toluene distilled from the oil. The oil residue was dissolved in 500cc. of Claisens alcoholic potash solution (Ann. 442,224). The alcoholic potash dissolved the phenols and the ethers were then extracted with petroleum ether, 4000c. was used in 100cc. portions. The residue after the extraction with petrol- eum ether was acidified with hydrochloric acid and extracted with diethyl ether. The ether was evaporated and the phenols fractionally distilled. After two fractionations, 59g. of the oil boiling at 140-145° under 3mm. of pressure crystallized. These crystals were pressed between filter papers and recrystallized from high test gasoline. After 3 crystallizations they gave a constant melting point of 40.5-41.5°. These crystals were identical in appearence and in melting point with 20. the crystals formed in the aluminum chloride condensation, that is compound I. Therfore they must be, because of their preparation by Claisens method, 2 chloro-6 benzyl phenol, 0H and the oil formed in the aluminum chloride cond- ensation, compound II, must be its para isomer, 0H Cl CH3 which is 2 chloro-4 benzyl phenol. The 2 chloro-6 benzyl phenol when analyzed for chlorine by the Parr bomb method gave the following result. Substance Chlorine % Chlorine % Gale. 1. 0.2361 0.0372 15.76 16.24 2. 0.1429 0.02289 16.019 16.24 The 2 chloro-4 benzyl phenol when analyzed for chlorine by the same method gave the follow- ing results, 21. Substance Chlorine % Chlorine % Gale. 1. .1444 .023075 15.98 16.24 2. .1381 .022365 16.19 16.24 fidfficulty was had in making this determination. Because of the compound being an oil. it was hard to make a uniform mixture of it in the fusion, thus causing erratic results. This phenol, 2 chloro—4 benzylphenol, boiled at 319-321° under atmospheric pressure, in a stream of carbon dioxide. It will be noticed that this is the boiling point of the chloro- para benzylphenol prepared by Peratoner, by chlorinating p-benzylphenol with sulfuryl chloride. (page 4) Thinking that perhaps his compound and the one whose preparation is described above were the same, p-benzylphenol in chloroform so- ution was mixed with a molecular quantity of sulfuryl chloride and allowed to stand for several days. The chloroform was then evaporated off and the oil distilled. Its boiling point under vaccuum also checked with the boiling point of 2 chloro- 4 benzylphenol. More evidence that these two compounds are identical will be given under some of the derivatives of this substituted chloro- phenO]. o 22. The Petroleum Ether Extract of the Claisen Condensation The petroleum ether was evaporated off and the remaining oil was fractionally distilled. After 3 fractionations at 3mm the following fractions were obtained, 1. up to 110° 98 2. 110-150° 8g 3. ISO-165° 16.5g 4. 165-230° 10.0g The third fraction after further purification became a clear yellow oil boiling at 147-150° under 6mm of pressure and 138-140° under 3mm. This is o-chlorOphenyl benzyl ether, 0 CH2C> Cl This structure was proveh by the fact that when sodium o-cglorOphenolate was treated with benzyl chloride in methyl alcohol solution an ether was nearly quantitatively obtained, which had the same boiling point. The same difficulty was found here in analysis that was encountered in the case of 2 chloro-4 23, benzyl phenol. 0f the many determinations that were made, the one following was the best. Substance Chlorine % Chlorine % Gale. .0591 .015028 15.75 16.24 This compound was prepared as was given in the historical part of this thesis by Baw (Quart. J. Ind. Chem. Soc. 3, lOl-4),1926) who obtained a boiling point for it of 296° under atmospheric pressure. When checking the compound described above with this, difficulty was had in obtaining a definite boiling point because of decpmposition. However, it seemed to start to boil in the near proximity of 296°. In this Claisen reaction there was 27% of 2 chloro-6 benzylphenol, 7.5% of o-chloro- phenyl benzyl ether and 4.5% of 2 chloro—6 benzylphenyl benzyl ether produced. 24. Chlorine Derivatives of 2 Chloro-6benzylphenol and 2 Chloro-4 benzylphenol The following two dichlorobenzylphenols, 0H 0H 01 c1 0 CH. C) CH; 01 were reported by Eldridge in his thesis for a Masters Degree. He prepared them by benzylating 2-6 dichlorOphenol and 2-4 dcchlorOphenol reSpect- ively. The first had a melting point q£'58-58.5° and the second multed at 77-77.5°. In making these compounds from 2 chloro- 4 benzyl and 6 benzylphenol, the method of chlorinating described in Houben (Vol. 3, 799) was used. The source of chlorine was hydrochloric acid, which was allowed to drOp slowly from a drOpping funnel on to solid potassium permanganate. The permanganate oxidized the hydrochloric acid to chlorine which was led through a tube into a solution of the phenol in chloroform. When the last of the hydrochloric acid had 25. been added the flask containing the permanganate was gently heated and the last of the chlorine driven into the chloroform solution with carbon dioxide. The amounts used were based on the information given in Houben, that 11.2g 0; chlorine was obtained from 10g of potassium permanganate and 60-65cc. of hydrochloric acid (Sp,gr. 1.17) Ten grams of each phenol was chlorinated. The chlorination took place smoothly, with a slight evolution of heat. When necessary the flask containing the phenol was codled. After all of the chlorine had been added the chloroform was driven off. The oil residue from each phenol solidfiied when seeded with some of the crystals prepared by Eldfldge. The product from the 2-chloroi4 benzylphenol after 4 crystallizations from high test gasoline gave a melting point of 58-59°. It crystallized in short yellow needles. It was analyzed for chlorine by the Parr bomb method. Substance Chlorine % Chlorine % Gale. 1. .2380 .06569 27.604 28.063 2. .2227 .06215 27.91 428.063 The product from the 2 chloro-6 benzylphenol after 4 crystallizations from high test gasoline melted at 77-77.5°. It came down as a floccul- ent mass with no definite crystalline form. It was also analyzed for chlorine by the Parr bomb method. Substance Chlorine % Chlorine % Calc. 1. .2187 .05984 27.52 28.063 2. .2677 .07511 27.85 28.063 Esters from 2 Chloro-4 benzylphenol 2 grams of 2 chloro-4 benzylphenol was dissolved in 5 grams of pyridine. An equivalent quantity of benzoyl chloride was added and the mixture well shaken. Heat was evolved and after stand- ing for some time crystals began to separate out. The mixture was allowed to stang overnight. An equal volume of water was added and shaken until the odor of benzoyl chloride had disappeared, and then poured into cold dilute sulphuric acid. The ester was extracted from this with ether and the etheral solution washed with dilute sodium carbonate solution. The ether was then evaportted off, leaving a heavy, viscous oil. After atand- ing some time the oil crystallized and was recrystallized from alcohol; obtaining after the 27. third crystallization crystals which gave a constant melting point of 71-73°. The crystals were small thin flakes. Its structural formula is OCOQ Cl Ch. Analysis by the Parr bomb method gave the follow- ing results, Substance Chlorine % Chlorine % Gale. 1. .2602 .02842 10.925 11.007 2. ..2886 .03197 11.07 11.007 The benzene sulfonyl ester was made in the same way excepting that benzene sulfonyl chloride was substituted for benzoyl chloride. This gave an ester of the following structure, OH; This ester was recrystallized from alcohol 28. in small granular crystals. After 3 crystallizations they gave a constant melting point of 65—68°. Analysis was by the Parr bomb method. ~ Substance fihlorine % Chlorine % Gale. 1. .2024 .01973 9.705 9.902 2. .2131 .02055 9.649 9.902 Para toluene sulfonyl chloride was used to form the following ester, 0 so. CH3 c1 O OH; This compound melted at 51.53° after 4 cry- stallizations from alcohol. It also came down as small granular crystals. Chlorine analysis was by the Parr bomb method. Substance Chlorine % Chlorine % Gale. 1. .2453 .02318 9.45 9.530 2. .2057 .01936 9.37 9.530 Benzoyl and benzene sulfonyl esters were also made from the chloro-benzylphenol made by Peratoners method, that is, by chlorinating p-benzylphenol with sulfuryl chloride. This produced two esters that were identical in appear- 29. ence and in melting point with the same two described above. The benzoyl ester melted at 71-73° and the benzene sulfonyl ester from 65-68°. Mixed melting points were taken of both, however, no drOp in melting point took place. Therefore the evidence, that the boiling points of these two phenols are the same and that they form identical esters seems to prove that the chloro- benzylphenol prepared by Peratoner is not benzyl- meta-chlorOphenol as reported by Richters Lexikon or as Beilstein names it alpha-chloro-4 hydroxy diphenyl methane but rather 2 chloro-4 benzyl- phenol. Esters from 2 Chloro-6 benzylphenol The same three esters were made from 2 chlam- 6 benzylphenol and in the same way as given above. That from benzoyl chloride, c co - CI CH2- crystallized from alcohol in large oblong crystals, and gave a constant melting point of 69-71° after 3 crystallizations. Chlorine analysis was by the Parr method. 30. Substance Chlorine % Chlorine % Calc. l. .2119 .02523 10.78 11.007 2. .2340 .02834 11.57 11.007 The ester from benzene sulfonyl chloride, 050,- ’31 CH, - melted at 62-64° after 4 crystallizations from alcohol. It crystallized in coarse, white needles. Chlorine analysis was by the Parr method. Substance Chlorine % Chlorine % Gale. 1. .3162 . 03135 9.916 9.902 2. .2111 .02099 9.930 9.902 The ester from p-toluene sulfonyl chloride, crystallized from alcohol in small white needles. After 3 crystallizations they melted at 81.5-83.5°. Analysis was by the Parr method. Substance Chlorine % Chlorine % Gale. 1. .4116 .03887 9.444 9.530 2. .2834 .02704 9.543 9.530 31. Summary 1. o-ChlorOphenol was condensed with benzyl alcohol in the presence of aluminum chloride. The products were 2 chloro-4 benzylphenol, 2 chloro- 6 benzylphenol and 2 chloro-4—6 dibenzylphenol. The Claisen condensation was used to differentiate between the two chloro-monobenzyl phenols. The mono benzyl substituted o-chlorOphenols produced in the aluminum chloride condensation amounted to 40% of the theoretical amount. This was calculated from the standpoint of the amount of benzyl alcohol that was used. 2. The 2 chloro-4 benzylphenol was shown to be the same as the compound that was produced when p-benzylphenol was chlorinated with sulfuryl chloride. 3. Chlorine derivatives were prepared from the two benzyl chlorOphenols, namely, 2-6 dichloro- 4 benzyl phenol and 2-4 dichloro-6 benzylphenol. 4. The benzoyl, benzene sulfonyl and toluene sulfonyl derivatives were made of the 2 chloro- 4 benzylphenol and also of the 2 chloro-6 benzyl- phenol. 32. _ n S.» .35: \u 9:» 1Q X l it“ *1 3.33 «IQ 2m~xtt\3 N Kmq>N2m® v- A . HICHIGRN STRTE UNIV. LIBRRRIES llll ll 1 312930172 4457