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The acid catalyzed isomerization and dimerization of styrene oxide

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The acid catalyzed isomerization and dimerization of styrene oxide

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Content THE ACID CATALYZED ISOMERIZATION AND DIMERIZATION OF STYRENE OXIDE A Thesis Presented to the Faoulty of the Department of Chemistry University of Southern California In Partial Fulfillment of the Requirements for the Degree Master of Science hy Levonna Herzog July 19-49 UMI Number: EP41574 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI EP41574 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQ uest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 -1 3 4 6 This thesis, written by under the guidance of h.Q.T... Faculty Committee, and approved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill ment of the requirements for the degree of . M a . a . t . e . r . . . . . o X . . . S . c ± e n c . e . Embry"Si^BQgai?lus ■ ' Dean D ate July 21. 1949 Faculty Com m ittee Chairman . ACKNOWLEDGMENT I The author wishes to express her appreciation and gratitude to Dr. Gyrus 0. Guss for the counsel and guidance rendered during the course of this investigation. t TABIE OF CONTENTS ‘ *0 I CHAPTER PACE I INTRODUCTION............. . . . . . ................. X H HISTORICAL ................................3 III DISCUSSION . . . . ,................................ 5 IF EXPERIMENTAL ........ ... .. .. . XO A. Preparation of Styrene Oxide................. 10 B. Reaction of Styrene Oxide with Concentrated Sulfuric Acid ....................10 G, Preparation of 2,5-Dichlorodioxane . . . . . . . 15 D. Preparation of 2,5-DIphenyldioxane....................15 E. Attempted Preparation of Cyanomethyl Ether .... 16 F. Preparation of Ethyl Phenyl-a-Bromoacetate .... 17 G. Preparation of Diethyl Dimandelate . . . . . . . IS H. Preparation of a -Phenyl--hydroxyethyl Ether . . * 18 I. Attempted Preparation of 2,6-0iphenyldioxane from a -Phenyl-£ -hydroxyethyl Ether . . . . . . . . 20 J. Reaction of a -Phenyl- ^-hydroxyethyl Ether with Phosphorus Trlbromide . . . . . « . . . . . 21 K. Preparation of a, ft -Dicbloroethyl Ether . . . . . 22 L. Reaction of a,$-Dicbloroethyl Ether with Phenylmagnesium Bromide ..............22 M. Preparation of p-Bromostyrene Bromohydrin . . . . . 26 f N. Preparation of p-Bromostyrene Oxide .................. 26 V SUMMARY .................................... 28 VI BIBLIOGRAPHY............................................. 29 CHAPTER I INTRODUCTION Olefin oxides, three-membered hetero-systems containing oxygen, are readily attacked by many electron rich molecules. The ring opening reaction results in relief of strain, allowing both the ring carbon and oxygen atoms to return to their normal configurations. The reactive center of the entering group may be oxygen, as in phenols, alcohols, and aelds, nitrogen, as in amines, or carbon, as in carbanione from acetoaeetic ester, malonic ester, and similarly activated species. Many of the reactions of olefin oxides are catalysed both by acids and bases. Acid catalysis often has been found to yield significant amounts of high boiling by-products whose formation is sometimes at tributed to reaction of the oxide with itself* It has been supposed by several authors, without adequate evidence, that these by-products are substituted dioxanes that result from dimerlzation of the oxide* Knowledge of the nature of the by-products is Important from a theo retical point of view, because the reaction mechanism .possibly may be better understood thereby, and from a synthetic point of view, since increased yields might be attained if the formation of the undesirable compounds can be prevented* Styrene oxide is a readily available and reactive compound which should prove very useful as a synthetic intermediate, and with which relatively little work has been done. It was therefore selected for the present study of the reaction of an oxide in the presence of Sul furic acid. When and if the effect of mineral acids on styrene oxide 2 is ascertained, the knowledge should be of help in the general study of the add-catalysed reactions of olefin oxides with other organic com pounds. CHAPTER II HISTORICAL Olefin oxides in general are very reactive compounds. Naphthyl- ethylene oxides were found by Winstein and coworkers (1$) to be so sensitive that they isomerized when distilled at 0.5-1.0 mm.» or in the presence of traces of acid, so that all equipment for handling these oxides had first to be washed with ammonia, and distillation had to be carried out at 5 x 10“ ^ mm. This is an extreme example and many olefin oxides may be distilled at atmospheric pressure. In many cases an isomerization can be made to go in almost quan- titative yield and has proved useful for the synthesis of some aldehydes and ketones. Cohen, Marshall, and Woodman (8) found that by long boiling of 1-phenyl-l-methylethylene oxide with dilute hydro chloric acid a 9056 yield of phenylmethylacetaldehyde could be obtained. Similarly, Barnes and Budde (23) converted 1-methyl-l-isopropylethylene oxide in 61% yield into 2,3-dimethylbutanal by refluxing the oxide for five hours with 1($ hydrochloric acid. By boiling 1,1,2-trimethyl- ethylene oxide with dilute sulfuric acid for two hours, Read and Reid (3) obtained methyl isopropyl ketone. Stall and Commarmont (4) were able to prepare cyclohexadecanone in 75% yield by the action of mag nesium bromide on cyclohexadecene oxide; this isomerization also occurred when toe cyclohexadecene oxide was distilled from silica gel. The isomerization of olefin oxides to aldehydes or ketones is quite a general reaction and many more examples could be cited. Tiffenau and Foumeau (l) were the first to study the reactions of styrene oxide. They found that styrene oxide wee isomerized to phenyl aeetaldehyd© when heated above 20G°C. and that this isomerization was catalyzed by acid. Unfortunately no experimental details accompanied this early work. The only other study of this isomerization was done more recently by Tiffenau (2) who investigated the action of an ether solution of magnesium bromide on styrene oxide. When styrene oxide f t i was treated with a cold ether solution of magnesium bromide, styrene bromobydrin resulted; but if the ether was warmed and evaporated,.,,, phenylacetaldehyde was obtained. Styrene oxide reacts with alcohols in the presence of sulfuric or phosphoric acid to form an alkyl ether of phenyiethylene glycol. Ac cording to Emerson (9) a by-product, "probably 2,6-diphenyldioxane contaminated with some of the 2,5-isomer" was obtained from these reactions in 12-27$ yield, Thomas and Hochwalt (10) have likewise described material obtained as a by-product in this reaction as 2,6-dlphenyldloxane, In neither of these papers was a structure proof or treason for so identifying the material described. CHAPTER III DISCUSSION When a catalytic amount of concentrated sulfuric acid m s added to styrene oxide an immediate, violent, and exothermic reaction Occurred. The resulting mixture was worked up and a variety of components sepa rated. The overall reaction may be represented as follows1 C ^ - C ^ H g C6H5-CH2-CH0 + (C^Hj-CHgCHO)* +• + " , 0 ^ L IX. III. h^ - Q - c^ + residue IV. V. Phenylacetaldehyde (I) was obtained in 15-20$ yield. Its refrac tive Index agreed with the literature value and two derivatives were prepared which corresponded in physical properties to those reported in the literature. 1 Phenylacetaldehyde polymer (II) decomposed on distillation at atmospheric pressure into phenylacetaldehyde and non-distillable resi due. The yield of this material was 25-30$. The melting point of III agreed with the reported melting point of 2.5-diphenyldioxane and a mixed point with an authentic sample of 2.5-dlphenyldioxane prepared from 2,5-dichlorodioxane (12) showed no depression. The yield of 2,5-diphenyldioxane was about 3-6$. This diphenyldioxane (IV) was obtained in about 3-6$ yield and was the same compound to which Baker, Cornell, and Cron (13) have tentatively assigned the structure of cis-2,5-diphenyldioxane. This diphenyldioxane could also be a 2,6-isomer which has never been pre pared by an unequivocal method. Several attempts were made to synthesize 2,6-dlphanyldioxane (hereafter referred to as 2,6-DFD) ac cording to the schemes listed below, but none was successful. > * ■ CuGH § (1) (C1CH2)2Q + <*• (NCCH2)20 (C6H5CCH2)20 KCN LiAlH^ (C^H^CHOHCH^gO -H20 2,6-DPD • ‘ The first reaction could not be made to yield the desired product. ONa <jJ00a2H$ (?) Cg^CHBrCOOCgHj + C^H^HCOOG^ ' )20 ^ O H LiAlH^ (C^HrCH- JjjO -H20 2,6-DFD a-Phenyl-yS -hydroxyethyl ether was prepared, but the removal of water by use of anhydrous hydrogen chloride, 85% phosphoric acid, phosphort|| pentoxide, concentrated sulfuric acid, and 60% sulfuric acid was unsuccessful. CH20H GHgBr V (3) (C^HjCH^G + PBr3 ( C ^ H ) 20 (0H~) ^ 2,6-DPD The reaction of phosphorSi tribromide and a -phenyl- $- hydroxyethyl ether was not successful. (4) (CH2=CH)20 + C l2 * (CHjClGHClJjgO C6H5MgBr > GHjjGl (Gfcg^H^O (QHr j 2.6-DFD The product obtained from the reaction of pheny Imagneslum bromide and a,)9 -dichloroethyl ether was not converted to the desired product after long refluMng with aqueous potassium hydroxide. The residue (V) which was obtained in 30-50% yield was not investigated. The isolation of phenylacetaldehyde in this reaction was not un expected since a large variety of oxides as well as styrene oxide have been shown to isomerize to aldehydes or ketones in the presence of acid. The polymeric phenylacetaldehyde (II) resembled eloseily in boiling point and refractive index that which Emerson (9) and Thomas and Hochwalt (10) obtained as by-products from the add catalyzed reactions of styrene oxide and alcohols in 12-27% yield, and which has been designated by them as 2,6-diphenyldioxane or 2,6-diphenyldioxane con taminated with some of the 2,5-isomer. When a sample of II was sub jected to distillation at atmospheric pressure, the distillate had the identical refractive index reported by Emerson for 2,6-diphenyldioxane. The presence of phenylacetaldehyde in this distillate was unmistakable axid it could not possibly have arisen from a 2,6-diphenyldioxane, or for that matter from any diphenyldioxane since the diphenyldioxanes Isolated in the present work distill at atmospheric pressure without any trace of decomposition* Furthermore, polymeric phenylacetaldehyde would have been expected from any acid catalyzed reaction of styrene oxide since the production of phenylacetaldehyde apparently is in evitable, and phenylacetaldehyde polymerizes in the presence of afeid (6). Therefore, it is believed that the material, described by Emerson (9) and Thomas and Hochwalt (10) is not a diphenyldioxane of any sort, but rather polymeric phenylacetaldehyde, The work of Baker, Cornell, and Cron (13) also supports this point of view. When the authors subjected to hydrogenolysis a sample of material supplied by Emerson and designated by him as 2,6-diphenyldioxane, none of the expected /3-phonylethy1 ether was obtained; however, ft-phenylethanol was isolated, the expected product If the material were polymeric phenylacetaldehyde. Furthermore, the known 2,5-diphenyldioxane, m.p. 172°C. and 2,3-diphenyldioxane, m.p. 50°C., are both solids and 2,6-diphenyldioxane would also be expected to be a solid. The material isolated by Emerson and Thomas and Hochwalt was a liquid. Several authors (5,8,15) have suggested that 2,5-substituted di oxane s are formed when olefin oxides are isomerized by heat or with acid. For instance Wiastoin and coworkers (15) believed that whan 4-methoxynaphtbylethylene oxide decomposed on distillation at 0.5-1.0 aan., part of the material formed had the configuration of 2,5-bls(4- methoxynaphthyl) dioxane. The evidence for this structure rested mainly on a correct analysis. Hence, the identification of 2,5- diphenyldioxane as a product in the acid catalyzed reaction of styrene oxide lends credence to the assigned structures of the other dioxanes. It was originally planned to do some work with p-bromos tyrene oxide. This compound was prepared by the reduction of p-bromophenacyl bromide to p-bromostyrene bromohydrin with aluminum isopropoxide, and then removal of hydrogen bromide to form the oxide, in a manner analogous to that used by Wlnstein and coworkers (15) for the prepara tion of various Substituted naphthylethylene oxides. This compound has also been reported recently by Bergkviet (16) who prepared it in 36# yield via the reaction of p-bromophenylmagnesium bromide and chloro- acetaldehyde. The synthesis from p-bromophenacyl bromide on one trial resulted in a 74.5# overall yield of purified p-bromostyrene oxide. The proof of structure consisted of analysis of the intermediate bromohydrtn and hydrolysis of the oxide to the known p-broxnostyrane glycol. The properties of the oxide agree with those found by Bergkviet. CHAPTER 17 KXmiMENTAL# PyQp^frfetoa of fftyrene Oxide Styrene oxide was prepared by the method of Alquist and Guss (14) , b.p. 61?0./3 »»., a20® 1*5350. B, Reaction of Styrene Oxide with Concentrated Sulfuric Add 1. General Method of Reaction.— In a three-necked flask fitted with a stirrer, thermometer* and a condenser with a calcium chloride tube* was placed a quantity of freshly distilled styrene oxide (20 g,, 0.17 M»). The styrene oxide was cooled to about -10°C,, and one or two drops of concentrated sulfuric acid (0.05-0*10 ce.) were introduced. An immediate* violent, and exothermic reaction occurred. This caused a small amount of charring* but on continued stirring most of the char- s ring seemed to disappear and the solution became yellow. The extremely sweet odor of phenylacetaldehyde was noticeable immediately. When the cooling bath was removed, the heat of reaction esused the temperature of the reaction mixture to rise slowly and to remain at 30°C. for one or two hours. After the reaction mixture had cooled to room tempera ture, it was dissolved in ether and washed with a saturated aqueous solution of sodium bicarbonate, and with water. The ether was removed under vacuum, A colorless solid precipitated. This solid was filtered from an oil and found to malt at about 160-165°G. This material was shown to consist of 2,5-diphenyldioxane (m.p. 171°C.) and a diphenyl- * Analyses were performed by analyst at California Institute of Tech nology. All melting points and boiling points are uncorrected. 11 dioxane (m.p. 122°C.). Since* not all of the two diphenyl&ioxanes would crystallize out of the solution, in most oases they were not removed at this stage. The residue was then distilled from a Claisen < § * flask, and the following fractions were taken: Fraction # Vapor Temp. °c. Bath Temp. . Pressure mm. Percentage sield 1 35-50 160-180 3^2, 15-20 2 80-140(120-140) 180-210 1-2 20-30 3 ^(residue) 150-180 210-300 1-2 0-8 30—62 Since the fractions were not sharp the percentages given are actually only rough, approximations. Furthermore, fraction 1 distilled slowly as long as the bath temperature was held below 180°C.; as soon as the bath temperature was allowed to go above 180°C., a higher boiling fraction could be obtained. Hence the amount of low boiling material obtained depended somewhat on the length of time the bath tem perature was held below 180°C. Xn some oases the bath temperature was not taken above 200°C. which accounts for the 0$ of fraction 3 and the s large residue. The figures do not represent averages, but rather the * * * • « * » widest range over Which the results varied when the conditions under which the reaction, was run and worked up were substantially the same. 2. Identification of the Components of the Reaction.— a) Frac tion 1. This material was a liquid with a strong, sweet odor. When T shakbn with fuchsin-aldehyde reagent (Sehiff test), it gave a positive aldehyde test immediately. Styrene oxide also gives a positive Schiff test, but only after several minutes. 12 The 2,4-dirdLtrophenylhydrazone of fraction 1 was prepared by the method given by Shrinfir and Fuson (11, p. 143) j golden leaflets m.p. 119-120°C. Were obtained after one crystallisation from ethanol. The reported melting point for phenylacetaldehyde-2,4-dinitrophenyl- hydrasone is 121°C. (11), Styrene oodde was made to react in the same manner with 2,4-dinitrophenylhydrazine. The procedure calls for the addition of hydrochloric acid to the mixture of sample and 2,4-di- nitrophenylhydrazine in ethanol solution. With styrene oxide vigorous boiling occurred. This was not observed in the reaction with fraction 1. When the solution with styrene oxide was boiled the prescribed length of time, it became dark red whereas with fraction 1 the color was yellow. Upon cooling, red crystals separated, m.p. 174°C. The m.p. of pure 2,4-dinitrophenylhydrasine is 194°C♦ From the filtrate a mixture of two types of crystals was obtained, heavy red crystals described above and yellow light crystals which were separated manually and found to melt at 118-119°C.; mixed melting point with the 2,4-di- nitrophenylhydraeone of fraction 1 showed no depression. Apparently the hydrochloric acid caused some of the styrene oxide to isomerlze to phenylacetaldehyde which reacts with the 2,4-dinitrophenylhydrazine, If fraction 1 was immediately redistilled at 1-2 mm., the boiling point was found to be the same (ca. 45-50°C.) but it distilled rapidly when the bath temperature was held at about 85°G. instead of 160°C. necessary for the first distillation. The refractive index of the re distilled liquid was 1.5248 at 25°C.j the refractive index reported for phenylacetaldehyde (25) at 19*6°C. was 1.52546. Fraction 1, therefore, was composed of phenylacetaldehyde. It was 13 believed that before the initial distillation very little phenyl- aoetaldehyde was present as the monomer and that the high temperature necessary for the first distillation was actually necessary In de- polymerlzatlon of some of the phenylacetaldehyde polymer. a) Fraction 2. This fraction was partially solid. The crystals were filtered and washed with ethanol, m.p. ca. 110-120°C. After all of the crystals were removed (about 2% of the fraction), a yellowish oil remained which waa redistilled and from 5 g. of material two fractions were taken: Fraction Vapor Temp. Bath Temp. n g . _ 3 u __ 3b«_ 1 _ 1 36*48 100*120 1.5490 0.2 2 130-145 180*190 1.5715 2.5 The first fraction gave an Immediate Schiff test and smelled strongly of phenylacetaldehyde. The second fraction smelled only faintly of phenylacetaldehyde and gave a positive Schiff test only after several minutes. It was then subjected to distillation at atmospheric pressure, b.p. 250*270°C., n^p 1.5558. (The material reported by Emerson (9) as 2,6-diphenyldioxane boiled at 207.5*210,5/18 xtei,, n2^) 1.5553#) The distillate smelled strongly of phenylacetaldehyde and gave an immediate Schiff test. Upon reaction with 2,4-dinitro- phenylhydrazine, a small amount of golden leaflets m.p. 118-120°C. were obtained which had to be separated manually from the heavier red crystals as in the case of the styrene oxide reaction. Only about half of the sample of fraction 2 that was subjected to atmospheric distilla tion would distill, even on very strong heating. The residue consisted u of very dark viscous material. A mixture of 2,5-dIphenyldI oxane and the diphenyldioxane of unknown structure, m.p. 122°G. was distilled at atmospheric pressure without any trace of decomposition. e) Fraction 3. fhis fraction was partially crystalline. It con sisted of about !C$ of the same solid as was obtained from the second fraction, The nature of this solid is discussed below. The remainder of the fraction was yellow oil which was not investigated but is prob ably of the same nature as the oil of fraction 2. d) Residue. The residue was vary dark and very viscous, ho work was done with this material except an attempt to crystallize it. In cases where the distillation had not been taken tip to a very high tem perature (not above 180 or 190°C.), crystalline material could be ob- tained from an alcohol-ether solution of the residue. Crystallisation ? was very slow and only a small amount of crystals were obtained each time the residue was dissolved and then cooled. The crystalline material was the same found in fraction 2 and 3, and, in fact, as the first crystal obtained from the 'evaporation of the ether solution before distillation. i e) Crystalline Material* The solid materials separated in the • / . ' . t ways mentioned above were obtained in 6-12% combined yield, and melted above 10G°C. bat below 165°c., usually over a 5-10° range* By frac tional crystallisation from ethanol or isopropyl ether two varieties of crystals were finally separated. The higher melting and less soluble compound, m.p. 171-171.5°C., crystallised in leaflets. The reported melting point for 2,5-diphenyldloxan© Is 172-173°C. (12), 4 mixed 15 melting point with an authentic sample of 2,5-diphenyldicxane showed no depression. Tito more soluble compound, m.p. 120-120.5°C., crystallized in needles. A mixed melting point with the compound, m.p. 121-121,5°C., obtained from the preparation of 2,5-diphenyldioxane by the reaction of phenylmagneslum bromide and 2,5-dichlorodioxane showed no depression. The 2,5-dichlorodioxane was prepared by the low temperature chlorina tion of dioxane and could contain some of the 2,6-isomer or the cis 2,5- isomer; hence the exact nature of this compound is as yet unknown. Anal- Calcd. for Cl6Hl602i C, 79.97; H, 6.71; mol. vt., 240. Found; C, 79.74; H, 6.93; mol. wt.# 230. C. Preparation of 2,5-Dichlorodloxane This compound was prepared according to the directions of Smedley (12), m.p. H8°C. The melting point reported by Smedley (12) was 117— 118°C, D. Preparation of 2,5-diphenyldloxane To the Grignard reagent, freshly prepared from magnesium (0.81 g., 0.034- M.), bromobenzene (6.3 g., 0.40 M.), and about 50 cc. of dry ether in a pear-shaped three-necked flask fitted with a mercury seal stirrer, dropping fennel, and condenser with a drying tube, was added 2,5-dichlorodioxane (0.2 g,, 0.014 H.) dissolved in about 100 cc, of dry ether, A white precipitate formed immediately. After the addition was complete, the mixture was stirred for an hour and was then decom posed with water and dilute hydrochloric acid. The ether layer was separated; the aqueous layer was extracted with ether and the extracts added to the main ether solution. The ether was then evaporated to 16 about 50 co, and allowed to stand overnight. The crystals which had separated were filtered and recrystallized from ethanol, m.p. 169°G.j after another crystallization from ethanol, m.p. 171-172°C»j the melting point reported by Smedley (12) is 173.5°C. The original ether filtrate was concentrated and, after cooling, yielded more crystals, m.p. 109-H2°C. After several crystallizations from ethanol, crystals were obtained which did not change their melting point on further crystallization, m.p. 121-121.5°G♦ A recent publica tion by Baker, Cornell, and Cron (13) mentioned the isolation of two isomeric compounds from this reaction, a 172° isomer and a 122° isomer. The original anther (12) made no mention of a second compound, although ' the low melting point of his crude product indicated a mixture. 1. Reaction of Chloromethyi Ether with Potassium Cyanide*— In a flask fitted with a stirrer and dropping funnel was placed a solution of potassium cyanide (6,4. g., 0.99 M.) dissolved in water (15 cc.)* Eastman Kodak white label grade chloromethyi ether (5.0 g*, 0.45 H.) dissolved in ethanol (15 cc.) was added to the potassium cyanide slowly from the dropping funnel. After a few cc. of the ethanol solution had been added, the reaction mixture became yellow and warm. Stirring was continued for twelve hours after the addition was complete, by which time the solution had turned black. The solution was extracted with ether; the ether was evaporated leaving a small amount of residue. The residue was boiled for eight hours with aqueous sodium hydroxide. No diglycollic acid could be isolated from this reaction, the expected product if the residue had contained eyanomethyl ether. 2. Reaction of Chloromethyl Ether with Copper Cyanide.— To a flask fitted with a mercury-sealed stirrer, dropping funnel, and conden ser with a drying tube was added cuprous cyanide (22 g., 0*12 M.) and dry ether (60 cc,). While this mixture was vigorously stirred, chloro methyl ether (10,1 g., 0,88 M.) was added from the dropping funnel. The addition did not cause any noticeable change. The mixture was then * * A - warmed so that the ether refluxed. Stirring and reflux were continued for five hours after the addition was complete. After standing over night, the ether solution was filtered; the precipitate was washed with / more etherj and the ether filtrates combined. After the ether was removed, 6 g. of material, b.p, 100-105°C,, was obtained, which was obviously the starting material, b.p. 101-109°C. The remainder of the product consisted of dark solid resinous material which could not be crystallized. A similar reaction was carried out in refluxing benzene, with the same results except that very little of the starting material was recovered and a large amount of resinous material insoluble in benzene was formed. P. Pgegaratlon-Of Etbgl_Pfag^3^_-§ggig?aoetatg This compound was prepared by the action of phosphorus and bromine on phenylacetic acid according to the directions of Anschutz (24), and by the action of i0> hydrogen bromide on mandelonitrile, in a manner analogous to the reaction of 48$ hydrogen bromide and lactonitrile to produce a-bromopropionie acid (22, p. 131). The former procedure proved most satisfactory since fewer operations were involved and the yields were higher. Since phenylacetic acid was not available at the 18 time this material was first needed, the latter preparation was devised. Mandelonltrile was prepared according to the directions of Fieaer (20, p. 94) from a solution of sodium bisulfite (32 g., 0.3 M.) dissolved in water (80 cc,), benzaldehyde (30 g,, 0,28 M.), and potassium cyanide (20 g., 0.31 M.). The mandelonltrile was immediately treated with 48$ hydrogen bromide (120 cc.). This mixture was allowed to stand at room temperature for one hour, after which it was reflux®d for two hours. The water and hydrogen bromide were removed by distillation until the bumping caused by the precipitated salt became too severe. The residue was dissolved in carbon tetrachloride, decanted from the ammonium bromide, and filtered, The carbon tetrachloride was evaporated, and the residue ref luxed with absolute ethanol (250 co.) and p-toluene- sulfonic acid (l g.). Most of the excess ethanol was then removed by distillation. The cooled residue was dissolved in ether and washed with aqueous sodium bicarbonate solution. The ether was removed by distillation and the product distilled at 95-115°C./l mm. A total of 27.5 g., 41.8$ of -theory (based on .benzaldehyde) of slightly yellow product was collected, n2^ 1.5385; literature value 1.5375 (26). This compound was prepared from sodium ethyl mandelate and ethyl phenyl- a-bromoacetate according to the directions of Hurd and Raternick (19). The product used for further preparations was collected at 180-190°C./3 mm., n22’5D 1.5350. H. Preparation of a -Phenyl- -hydroxyethyl Ether To a three-necked flask fitted with a dropping funnel, mercury- sealed stirrer, and condenser with a drying tube was added dry ether 19 (200 cc*) and lithium aluminohydride (A g., 0.1 M.), All of the lithium aluminohydride did not dissolve in the ether. Prom the dropping funnel diethyl dlmandelate (27 g., 0.08 M.) was added during one hour. Stir ring was continued for two additional hours. The product was worked up in the manner suggested by Nystrom and Brown (17). The ether was removed under vacuum leaving 18 g. of almost colorless, very viscous, material that could not be obtained In crystalline form. A small amount r of material was distilled with decomposition, b.p. 185-200°C./l mm. The distillate was yellow and could not be crystallised. The trttyl derivative was prepared according to the directions of Seikel and Huntress (18). A mixture of the glycol (1.42 g., 0.0055 M,), triphenylchloromethane (2.95 g.» 0.0105 M.), and pyridine (3 cc.) were placed in a test tube protected froia moisture and heated in a boiling water bath for four hours. The mixture was washed several times with water and then dissolved in acetone. A volume of about 75 cc. of solution produced crystals after standing overnight in the refrigerator. The amount of solution seemed to be critical since an oil precipitated when less solvent was used and nothing precipitated when a larger volume was used. The crystals which had separated were filtered, m.p. 222- 226°C., after two crystallizations from acetone, m.p. 228-228.5°C. Anal. Calcd. for C : c» 87*32} H, 6.U. Pounds C, 88.7} H, 6.5. It was believed that the compound was contaminated with a small amount of triphenylmethane, since this was about the only possible com pound having a considerably higher carbon and hydrogen content (93.5 and 6.66 reap.). 20 I. Attempted Preparation of 2,6-Dlphenyldloxane from a-Phenyl- -hydroxyetfayl Ether ♦ 1. Reaction with Anhydrous Hydrogen Chloride.— A solution of a -*phenyl-/3 -hydroxyethyl ether (2*8 g., 0.01 M,) in benzene (50 ce.) was placed in a gas washing chamber protected from moisture* Hydrogen chloride was bubbled through the solution for twenty minutes. After about one minute, the solution turned cloudy and gradually became pink. The benzene solution was washed with cold aqueous sodium hydroxide and then with water. The benzene solution gave a negative halide test when treated with alcoholic silver nitrate. The benzene was removed by distillation and the residue distilled at 185-19 5°C ./l mm. The distillate was slightly colored and could not be crystallized. It was apparently unchanged starting material. The experiment was repeated, except that the hydrogen chloride was bubbled through the solution for eight hours; the starting material was again recovered unchanged. 2. Reaction with 85% Phosphoric Acid.— To a -phenyl-/3 -hydroxy ethyl ether (1*2 g,, 0*005 M.) was added 85% phosphoric acid (15 cc.) with stirring. After standing at room temperature overnight, the mixture had become orange. The mixture was poured into water and ex tracted with ether. The ether solution was washed with dilute aqueous sodium hydroxide and with water. The ether was removed and the residue distilled at ca. 18Q~205°C ,/l-2 mm. A viscous yellow distillate was obtained which could not be crystallized* 3. Reaction with Phosphoric Anhydride.— To a solution of the glycol (1.4 g., 0,005 M.) dissolved in 10 cc. of ether was added 21 phosphoric ashy dr id© (0,8 g., 0.005 H.). The mixture was refluxed for about three hours. It was then diluted with water and the ether layer separated. The ether was removed and an attempt was made to crystallize the residue from ethanol, ethanol and water, ethanol and petroleum solvent, and isopropyl ether. When this was not successful the residue was distilled with decomposition above l65°C,/l-2 mm, (the 'distillate was too small to get the boiling range), A. Reaction with Concentrated Sulfuric Acid.— To a solution of the glycol (2 g., 0,008 M.) dissolved in ether (5 ce.) was added concentra ted sulfuric acid (1 cc»). The solution was warmed gently until all of the ether was evaporated. The residue became quite dark; it was cooled, diluted with ether, and washed with dilute aqueous sodium hydroxide and with water. Attempts to crystallize the viscous material obtained after the ether was removed were unsuccessful. Steam distillation of this residue produced no organic material insoluble in water. 5. Reaction with 60% Sulfuric Acid,— A mixture of the glycol - (0.8 g,, 0*003 M.) and 60% sulfuric acid (3 eo.) was allowed to stand for three days. By this time the mixture was dark. It was worked up in the usual manner and a dark viscous material resulted. This was treated with decolorizing charcoal and crystallization attempted; however no crystalline material was obtained. J. Reaction of a -Phenyl-# ~hydroxyethyl Ether with Phosphorus Tribromi&e To a cooled solution of the glycol (0,98 g., 0.004 M.) dissolved in pyridine (3 g») was added phosphorus /trlbromid© (2.5 g., 0.009 M#), The mixture was allowed to stand overnight and was then warmed for an 22 bow on the a team hath, and finally heated to 150°0* for ten minutes. The mixture was cooled and diluted with water. A dark resinous material appeared. The aqueous layer was decanted; the resinous material was washed with more water and removed. This resinous material would not dissolve in benzene, ether, petroleum solvent, or ethanol, and dissolved only to a very small extent in acetone. The aqueous layer was ex tracted with ether, and the ether was evaporated, leaving no residue, K. Preparation of a.ft-PIohloroethyl Ether A solution of vinyl ether (53.5 g,, 0,81 M., Merck nVinethineu containing 3.5% ethanol) and chloroform (395 g*) was placed in a gas washing bottle which was protected from moisture by calcium chloride tubes. The gas washing bottle was placed in an acetone-dry Ice ba,th maintained at -20°C. Chlorine gas was bubbled through the sintered- glass inlet tube until the yellow Color of chlorine was no longer discharged immediately,, The solution gained 108.5 g., corresponding to . 91.7% of the theory. The chloroform was removed under vacuum, and the residue distilled at 45-107°G./8 mm., n^p 1.4890; 102 g, of product / corresponding to 60% of theory was obtained in this manner. In one v • case this material was distilled slowly from a Cl§isen flask and an • vv > Attempt made to get fractions having a constant toiling point. It was found that the refractive Index rose with the boiling point from 1.4620 to 1.5008 and no constant value was obtained for the boiling point or refractive index. L. Reaction of g , -Pi chlor oe thy I Ether with Phenylmagnesium Bromide In a three-neck flask fitted with mercury-sealed stirrer, dropping % funnel, and a condenser with a drying tube was placed a,$-diohloro- ethyl ether (63.5 g«, 0*3 M., b.p. 55-70°C./2 mm.). A solution of phenylmagnesium bromide, freshly prepared from magnesium turnings (17 g., 0*7 M.) and bromobenssene (130 g., 0.7 M.) in about 350 ce. of dry ether was filtered and added to the a, ft -dichloroethyl ether during two hours. A slight precipitation appeared immediately. Whan about 10 ce, of the Grignard solution had been added, the reaction mixture became very cloudy and a crystalline precipitate appeared, the heat of reaction caused the ether to reflux when the reagent was added at about two drops/sec, The mixture was allowed to stir for two days; the Grignard reagent was decomposed with a saturated ammonium ohloride solution. The ether layer was separated, the aqueous layer, extracted with ether, and the extracts added to the main fraction. The ether was removed under vacuum and the residue distilled at 1-2 mm. The follow ing fractions were collected! Vapor Temp, °G. n2% 1 42-64(56) 70-81 12 1.5246 2 65-87(86) 81-122 52 solid 3 90-135(118) 130-175 21.6 1.5574 Fraction 1 was believed to be tmreacted starting material. Frac- "tion 2 was biphenyl; a mixed melting point with an authentic sample of biphenyl showed no depression. Since it was hoped that fraction 3 was the desired a-phenyl-£ -chioroethyl ether it was redistilled at 1-2 mm. The product from the first distillation was quite yellow. Most of the color distilled with the first fraction listed below; however, each of the fractions had a faint yellow cast. 24 Fraction IsmLlmu-ZSu. nZJp 1 80-92 124-127 1.5600 2 93-100 130 1.5557 3 103-105 127 1.5570 4 105-307 127 1.5572 5 107-108 127-133 1.5578 6 1 1 0 133-140 1.5590 Fraction 5 was found to give a negative halide test when treated with alcoholic silver nitrate; but after sodium fusion a positive halide test was obtained. Fraction 4 was analyzed. Anal. Galcd. for C1 4H1 6 QCI2 * 0, 65.09; H, 5.47. Found* C, 71.44; H, 6*30# Although the analytical data were very poor, (this might be due to ’ contamination with biphenyl), a reaction was run with a mixture of 3 g. from fractions 2 , 3, and 4 and 5 0 cc. of 1 0$ potassium hydroxide, and 10 ec. of dioxane. After this mixture had been refluxed for five days, It was extracted with ether, the ether evaporated and the residue distilled at 110-113oC./2 mm., 1.5570. The colorless liquid ob- < tained in this manner was redistilled and a center fraction b.p. H 2 °C* / 2 mm., n2^ 1 . 5 5 6 4 analyzed. ' f Anal. Caled. for Cl6Hl6 02: G, 79.97, H, 6.93. Found* C, 74.79; H, 6,78. Another reaction of phenylmagnesium bromide and a, # -dichloroethyl ether (b.p. 75-85°C./2 mm.) was carried out in the same manner; except that the a -dlchloroethyl ether used was a slightly higher boiling fraction, and the reaction mixture was cooled with an ice water bath 25 while the Grignard reagent waa_ added. In this ease there was no evi dence that reaction was talcing place until all of the Grignard reagent had been added, when an oil precipitated out. Stirring of the reaction was continued for three,days during which time there was no observable change. The reaction was worked up in the same manner as previously described. When the ether was evaporated, a solid precipitated which was filtered and found to be biphenyl) the filtrate was then distilled and the following fractions taken at 1-2 ram.s im^Usm Mm*,. , °Qa„ . Steagu ° c, n 2 2 o 1 .4-5-70 70-85 3.5 1.5400 2 60-75 85-95 6 1.5660 3 75-90 95-100 17 solid(m.p. 62°C.) 4 90-130 130-150 5.5 5 130-165 150-245 8 aolid(m.p. 205°G.) Fraction 3 was found by mixed malting point to be biphenyl. Frac tion 4 was redistilled: 1 87-102 125-142 1.4 1.5570 2 120-140 155-180 1.9 1.5542 Fraction 5 was found to melt at 205°C. after two crystallisations from ethanol. This material gave a negative halide test when treated with alcoholic silver nitrate and also after sodium fusion. Since it was not of use in this work it was not Identified. It is possible that this compound was also present in the residue from the distillation of the previously described reaction of phenylmagneslum bromide and -dichloroethyl ether. However, no Investigation was made of the residue. 26 M. Preparation of p-Bromostyrene Bromohy&rln To a reflusdng solution of aluminum ieopropoad.de (108 g„, 0,5 M.) (21) and 350 cc. of anhydrous isopropyl alcohol was added a solution of freshly prepared p-bromophenaeyl bromide (25) (27 g,« 0,1 M.) and anhydrous isopropyl alcohol (50 cc.) which had been brought to its boiling point just previous to the addition. This mixture was refluxed for exactly eighteen minutes; after the flask was cooled, a slush of concentrated hydrochloric add (80 cc.) and ice (ca. 200 g.) was added to the solution. The solution was cooled in an ice bath and stirred mechanically for about an hour; more water was then added until fur ther dilution produced no more cloudiness (total volume about three liters). The precipitate was filtered and dried, and 25 C«> correspond* ing to 92$ of theory (based on p-bromophenacyl bromide), of slightly yellow crystals were collected, m.p. 63-65°C. After one crystalliza tion from petroleum solvent, colorless crystals, m.p. 66-66,5°C. were obtained. Anal. Calcd. for CgHgOBr2f C, 34*.31; H, 2,86. Found* C, 34.32; H, 3.03. N. Preparation of p-Bromostyrene Oxide To a well stirred solution of 20$ sodium hydroxide (23 cc.) which had been warmed to 65°C. was added crude p-bromostyrene bromohydrin. The mixture was stirred for fifteen minutes while the bath temperature was kept at 65-75°C. The mixture was cooled and then extracted several times with benzene. The benzene was removed under vacuum and the prod uct distilled at 85-89°C./2 mm,; 11.5 g. of colorless liquid, which solidified on cooling was collected, corresponding to 81$ of theory, m.p, 26-27°G. 27 « Hydrolysis of p-bronsostyrene to the glycol was effected by refloat ing 1 g. of the oxide with about 35 cc. of water and one drop of hydrochloric acid for about fifteen hours. The water was evaporated and the glyeol crystallized from a solution of benzene and petroleum solvent* m*p« 101-102°G. The reported sup. of p-bromostyrene glycol is 102^0. (7). CHAPTER V SUMMARY Styrene oxide has been shewn to form phony lac©taldehyde, a polymer of phenylacotaldehyde, 2t5-diphanyldioxane, and an unknown diphenyl- dioxane in the presence of a catalytic amount of concentrated sulfuric acid. Attempts to synthesize the unknown diphenyldioxane were unsuccessful. A material previously described as 2,6-diphenyldioxane has been shown to be a polymer of phenylacetaldehyde. p-Bromostyrene oxide has been prepared in good yield by a new method. ; CHAPTER VI BIBLIOGRAPHY 1. Tlffenau and Fouraeau; Compt. rend. 146. 697 (1908) 2. Tiff ©nanj Ibid 2Q£, 918 (1938) 3*. Read and Reid? J. Chem. Soc. 122, 1487 (1928) 4. Stall and Commarmont; Helv. Chisu Acta 21, 1077 (1948) L * 5. Danilov and Venus-Danilovaj Ber. 6Q, 1050 (1927) 6. Stobbe and Lipoid; J. prakt, Chem, (2) J2Q, 285 7. Schramm? Ber, 2L» 1335 (1891) 8. Cohen, Marshall, and Woodman? J, Chem, Soc. 107f 898 (1915) 9# Emerson? J. Amer, Cham, Soc. &l, 516 (1945) 10. Thomas and Hocbwalt? U.S. 2,372,615 Mar. 1945 11. Shriner and Fuson, "Identification of Organic Compounds," 2nd ed. John Wiley and Sons Publishing Co., New York, N. Y, 1940 12. Sxnedley? D.S. 2,4X4,982 Jan. 1947 13. Baker, Cornell, and Cron? J. Amer. Chem. See. 70r 1490 (1948) r ' ri 14. Alquist and Guss? U.S. 2,237,289 Apr. 1941 15. V I ins to in et al; J. Org. Chem. 11. 157 (1946) 16. Bergkvist? Svensk. Kem, Tid. 22, 205? C. A. 2584 (1948) 17. Nystrom and Brown? J. Amer. Chem. Soc. jgg, 1197 (1947) 18. Seikel and Huntress? Ibid 6J, 593 (1941) 19. Hurd and Raternick; Ibid £2, 1541 (1933) 20. Fieaer, "Experiments in Organic Chemistry," 2nd ed,., D. C. Heath Publishing Co., New York, N. Y. 1941 21. Wilds, "Organic Reactions" Vol.xII, John Wiley and Sons Publishing Co., New York, H. Y. 1944* P* 198 t 30 » 22, BGrganie Synthesis" Coll, Vol. I., 2nd ed., John Wiley and Sons Publishing Co., Hew York, N. Y. p. 709 23, Barnes and Budde; J. Amer. Chem. Soe. £>§» 2339 (1946) 24, Anschuta; Ann, 127 (1907) 25, Awers and Eisenlohrj J. Prakt. Chem. (2) 82. 123 26, Marvel et alj J. Amer. Chem. Boo. J$, 52 (1947) su n iv ersftv of S o u th e r n £aSl?©m (a L lS iH ?

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Creator Herzog, Levonna (author)

Core Title The acid catalyzed isomerization and dimerization of styrene oxide

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