University of Southern California Dissertations and Theses

The reaction of phenylmagnesium bromide with methyl B-benzoylpropionate and with diethyl succinate

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The reaction of phenylmagnesium bromide with methyl B-benzoylpropionate and with diethyl succinate

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Content THE REACTION OF PHENYLMAGNESIUM BROMIDE WITH METHYL 0-BENZOYLPROPIONATE AND WITH DIETHYL SUCCINATE A Thesis Presented to the Faculty of the Department of Chemistry The University of Southern California In Partial Fulfillment of the Requirements for the Degree Master of Science in Chemistry hy William,J. Wasserman June 1950 UMI Number: EP41583 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. UMI EP41583 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. UMI* Dissertation Publishing Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 81 0 6 -1 3 4 6 t so This thesis, written by William_jJ. Wasserman under the guidance of hF a cu lty Committee, and approved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fu lfill ment of the requirements fo r the degree of Master of Science in Chemistry D ate.... Faculty Committee DEDICATION I would like to dedicate this thesis in the memory of my late wife, Dorothy Alice Wasserman, whose last xvish was for the completion of this work, even in the event of her death. ACKNOWLEDGEMENT The author is indebted to Dr. M. C. KLoetzel for his invaluable assistance during the course of this investigation. TABLE OF CONTENTS PAGE INTRODUCTION ....................... 1 DISCUSSION............................... 4 EXPERIMENTAL..........................'............ 14 Preparation of l,l,4>4-Tetraphenyl-l,4-butanediol and 1,4~Diphenyl-1,4-butanedione from Methyl £ -Benzoylpropionate . ..................... . 14 Conversion of 1,1,4 *4-Tetraphenyl-1,4-butanediol to 2,2,5,5-Tetraphenyltetrahydrofuran ...... 15 (a) With Acetic A c i d .......................... 15 (b) With Bromine ...................... 16 (c) With Anhydrous Hydrogen Chloride.......... 17 Preparation of l,l,4>4-Tetraphenyl-l,3-butadiene from 2,2,5*5-Tetraphenyltetrahydrofuran ... .......... 18 Reaction of Diethyl Succinate with Phenylmagnesium Bromide....................... 19 (a) Preparation of l,l,4,4-Tetraphenyl-l,4- butanediol and 1,1,4,4-Tetraphenyl- 3-butene-l-ol......................... 19 (b) Preparation of 1,1,4,4-Tetraphenyl-1,4“ butanediol and 1,4-Diphenyl-1,4- butanedione........................... 24 (c) Preparation of 1,1,4,4-Tetrap^henyl-1,4- but anediol, 1,4-Diphenyl-1,4-butanedione vi PAGE and 1, l^^-Tetraphenyl-^** butene-l-ol............... 2b (d) Preparation of 2,2, 5,5«Tetraphenyl-^ tetrahydrofuran and 1,1,^-,^- Tetraphenyl~l,3-butadiene ............ - 25 The Zerewitinoff Apparatus « Description and Operation....................................... 27 Diagram - The Zerewitinoff Apparatus................. 31 Summary . ......................................... 32 Bibliography. ............... 3^ INTRODUCTION An addition reaction between alkyl substituted tetrahydrofurans and methylmagnesium iodide has been ob served during Zerewitinoff determinations for active hydro gen (1). In order to study the reaction of the tetrahydro- furan nucleus with Grignard reagents, it seemed appropriate to prepare first a symmetrically-substituted tetrahydrofuran, and to investigate its behavior upon treatment with methyl- magnesium iodide and other Grignard reagents. T,h® first compound selected for investigation was 2,2,5,5-tetraphenyltetrahydrofuran (I). A literature survey yielded three reports concerning the preparation of this' compound. I Valeur (2) treated l^^^-tetraphenyl-lj^-butanediol (II) with boiling glacial acetic acid for five minutes, and obtained a compound, melting at 182°, which gave a carbon and hydrogen analysis corresponding closely to that calcu lated for I. (Calculated: C, 89.32; H, 6.^2. Observed: C, 89.37.; H, 6.57.) If a small amount of either hydrochloric or sulfuric acid was employed with the acetic acid, the 2 resulting product was found to be l,l,4>4-tetraphenyl-l,3- butadiene (III), melting at 202°. Valeur found I to be difficult to oxidize, and also difficult to reduce with ; nascent hydrogen, but gave no other structure proof. II III The same method.of preparation of I was employed by Salkind and Teterin (3), who also used a second method. This consisted of adding a bromine solution in chloroform dropwise to a chloroform solution of II, and allowing the resulting solution to remain at room temperature for six or seven hours. The main product was I. However, III was also obtained; and, if the temperature was raised above room temperature, the yield of III was increased. While the two preceding reports were in agreement concerning the assignment of the tetrahydrofuran structure to the compound melting at 182°, a paper by Acree (4) intro duced a certain degree of confusion by designating the tetrahydrofuran structure as one of the two possibilities for another compound, melting at 163-165°. Acree had obtained this compound as a by-product in the preparation of the diol 3 (II) from diethyl succinate through a Grignard reaction with . phenylmagnesium bromide in refluxing diethyl ether. He also reported having obtained the compound by treating the diol with either boiling glacial acetic acid or acetyl chloride. The material slowly decolorized a chloroform solution of bromine, and was found to have a carbon and hydrogen analy sis indicative of a monodehydration product of II (Calculated: C, 89.32; H, 6.42. Observed: C, 89.54; H, 6.36). Acree be lieved the material to be either I or l,l,4,4-tetraphenyl-3- butene-l-ol (IV), but did no further work on the problem. IV In view of the uncertainty regarding the assignment of the tetraphenyltetrahydrofuran structure, it appeared 'necessary to investigate the reaction between diethyl succi nate and phenylmagnesium bromide, and, also, to attempt to determine the structure of the compound melting at 182°. DISCUSSION The preparation of the compound melting at 182°, called 2,2, 53 5-tetraphenyltetrahydrofuran (I) by Valeur (2) and Salkind and Teterin (3) required the prior synthesis of 1,1 j^j^-tetraphenyl-l^-butanediol (III). Kloetzel (5) had (V) with phenylmagnesium bromide for the preparation of II in 5^% yield at room temperature. In our attempts to improve the yield of diol from this Grignard reaction, we employed two reaction temperatures, namely 0°, and the temperature of re- fluxing ether. Hydrolysis of the reaction mixture was ac complished with ice and ammonium chloride. A U-9% yield of diol was obtained from the reaction at the higher tempera ture, and a ^1.5% yield from reaction at 0°. A compound melting at li +5-lL f ' 60 was also obtained in the latter instance, and was found to be identical, by mixed melting point, with authentic 1,4—diphenyl-1,^-butanedione (VI), prepared as de scribed by Fritz (6, 7). ported by Borsche and co-workers (8) as being one of three products formed from a Friedel-Crafts reaction between previously employed the reaction of - methyl ^-benzoylpropionate CHoCHoCOOCH V VI l.^-Diphenyl-l,*+-butanedione (VI) had also been re- benzene and succinyl chloride (VII). The other products were 0«benzoylpropionic acid and ^ ’ S-diphenyl-li-butyrolactone (VIII). Ij^-Diphenyl-lj^-butanedione (VI) was reported as melting at lMf-lM^0, and VIII was hydrolyzed to give -diphenyl-6-hydroxybutyric acid (IX), melting at 135°.^ Q Q CH2G-C1 ch2cn Ah_</ ^ CH„CH„COOH IX VII VIII Using the methods of Valeur (2), and Salkind and Teterin (3), we were able to obtain the compound, which they designated as 2,2,5,5-tetraphenyltetrahydrofuran (I), melt ing at 180.5-l8l.5°. The compound showed the proper analysis for a monodehydration product of diol II. A Zerewitinoff determination showed that this product contained no active hydrogen. The material did not react with cold aqueous potassium permanganate solution. When dehydrated with 1 Auger (9) had previously studied the same reaction, and had reported obtaining VI, melting at 13*+°> and after hydrolysis, IX, melting at l*+5°. Since the diketone, as pre pared through different routes, by both Fritz and ourselves,, had the same melting point as the diketone prepared by Borsche, it seems that Auger had confused the melting points of VI and IX. 6 anhydrous formic acid 1,1,4*4-tetraphenyl-l,3-butadiene (III) was obtained. These results definitely identified the com pound as 2,2,5,5-tetraphenyltetrahydrofuran (I). A third method of dehydrating II was used in an attempt to find a milder method of accomplishing the con version of II to I. KLoetzel (5) had used anhydrous hydrogen chloride to prepare several tetrahydrofurans from the corre sponding butanediols. We found the method to be too severe for the dehydration of II. The product under these condi tions consisted chiefly of diene III. From this reaction we also managed to separate several mixtures, melting over short temperature ranges above 160°, which were the only other products. The mixtures were found to consist of 2,2,5,5- tetraphenyltetrahydrofuran (i) and l,l,4*4-"fcetraphenyl-l,3- butadiene (ill). Since the assignment of the tetrahydrofuran structure to the compound of Valeur (2) and Salkind and Teterin (3) had been found to be justified, there now remained the problem of identifying Acree’s compound, melting at 163-165°* which he had found to accompany the diol (II) in its formation from diethyl succinate (4). Towards that end, the investigation of the reaction of phenylmagnesium bromide with diethyl succinate was carried out. The aforementioned reaction had been attempted by Dilthey and Last (10), Valeur (ll), and Acree (4). Dilthey 7 and Last reported obtaining l,l,4>4~^e^raPfrenyl'“3.>4'“ butanediol (II) in quantitative yield when the reaction was run at room temperature with an extremely slow addition of a dilute ethereal solution of the ester to the Grignard reagent. Under similar conditions, Valeur obtained II in an 80$ yield. Acree, as stated earlier, obtained varying pro portions of II and a ”monodehydration product” of the diol (as indicated by a carbon and hydrogen analysis) from the reaction mixture. The proportions of the two constituents were dependent upon the temperature employed. When the re action was carried out at the temperature of refluxing ether, the only product obtained was the ”monodehydration product,” which was reported to melt at 163-165°• Houben and Hahn (12) carried out a similar reaction bet?/een succinic anhydride and phenylmagnesium bromide in boiling toluene. They ob tained a 26$ yield of II, and a large amount of a viscous yellow oil from which they were unable to crystallize a well defined compound. We attempted to carry out the reaction of phenyl magnesium bromide and diethyl succinate under two sets of reaction conditions. The first series of reactions were carried out under conditions of gentle ether reflux with a very slow rate of addition of ester to Grignard reagent. In the last run under violent ether reflux, the diethyl succinate was added at a very rapid rate. 8 From the reaction mixture obtained by carrying out the reaction under the milder conditions and hydrolyzing with ice-water acidified with hydrochloric acid, we were able to obtain a 21.5$ yield of l,l,4,4-tetraphenyl-l,4-butanediol (II). A second product, obtained in 6.3$ yield, as pale yel low needles, melted at 122.5-123.5°. This product was shown, by means of a Zerewitinoff analysis, to have one active hydrogen, and was also shoxra to be unsaturated by decolori- zation of a cold aqueous potassium permanganate solution. These results, and the carbon and hydrogen analysis led to the conclusion that the compound was the unsaturated alcohol, l,l,4,4-tetraphenyl-3-butene-l-ol (IV). To confirm the structure of the supposed unsaturated alcohol, the compound was submitted to ozonoylysis. One of the ozonolysis fragments was shown to be benzophenone (X), the 2,4-dinitrophenylhydrazone of which was found to cause no melting point depression when mixed with authentic benzophenone 2,4-dinitrophenylhydrazone. It was clearly demonstrated that the second fragment was -diphenyl-P - - hydroxypropionic acid (XI) by mixed melting point with the authentic material prepared as described by Rupe and Busolt (13). These two fragments would be the anticipated pro ducts from the ozonolysis of IV. In order to check the validity of ozonolysis as an analytical tool for the un saturated alcohol (IV), l,l,4,4-tetraphenyl-l,4-butanediol 9 (II) was also submitted to ozonolysis. After one hour II was recovered unchanged, indicating that no dehydration was effected under the ozonolysis conditions which were employed. chch2c-oh £12 00 + HOOC-CH IV X XI Since both of the reaction mixtures from the methyl [l-benzoylpropionate reactions with phenylmagnesium bromide had been hydrolyzed with ice and ammonium chloride while the diethyl succinate reaction mixture had been hydrolyzed with ice-water acidified with hydrochloric acid, and since only a relatively small amount of the reaction products from the latter reaction had been identified, the reaction of the diethyl succinate with Grignard reagent was repeated under mild ether reflux, using ice and ammonium chloride for the hydrolysis of the reaction mixture. Under these mildex con ditions ljlj^^-tetraphenyl-l^-butanediol (II) was obtained in 6b% yield, and l,1 +-diphenyl-lj^-butanedione (VI) in 11.6$ yield. No trace of 1,1 ,l f,l +«tetraphenyl-3-butene-l-ol (IV) was found during this run. 10 In order to determine whether Grignard reaction temperature or the hydrolytic conditions were responsible for this variation in results, the reaction of diethyl suc cinate with phenylmagnesium bromide was repeated, and 40$ of the reaction mixture was hydrolyzed with iee-water acidified with 5 ml. of hydrochloric acid, while the remaining 60$'was hydrolyzed with ice and ammonium chloride. The hydrochloric acid hydrolysis produced a 53$ yield of diol (II), a 10.5$ yield of diketone (VI), and a 6$ yield of 1,1,4,4-tetra- phenyl-3-butene-l-ol (IV), while the ammonium chloride hydroly sis resulted in a 56$ yield of II, an 11.5$ yield of VI and no trace of IV. In running the reaction of diethyl succinate and phenylmagnesium bromide under conditions of violent ether reflux, we approximated the more vigorous provisions of AcreeT s method (4). The only products obtained from the re action mixture were a series of>mixtures, many of them melt ing in the vicinity of 160°, and some of'them melting over short temperature ranges. One of the mixtures was finally separated into two definite compounds: one of these melted at 180.5-181.5°> and was found to be identical, by mixed melting point, with the material, melting at 181-182°, called 2,2,5j5-tetraphenyltetrahydrofuran (I) by both Valeur (2) and Salkind and Teterin (3)j and the other was identified as 1,1, 4,4-tetraphenyl-l,3-butadiene (ill) by mixed melting point 11 with authentic diene. Our results would seem to contradict those of Acree (4.). From the reactions of diethyl succinate and phenyl magnesium bromide, and also from the reaction of 1,1,4,4- tetraphenyl-l,4-butanediol (II) with glacial acetic acid, he obtained materials melting in the vicinity of 160°, which he believed to be a pure compound. Valeur, Salkind and Teterin, and ourselves have ail obtained 2,2,5,5-tetraphenyltetra- hydrofuran, melting at 180.5-181.5°, from the latter re action. Moreover, from the reaction of diethyl succinate and phenylmagnesium bromide, we have isolated mixtures melting over short temperature ranges near 160°, which were separable into components I and III. It appears likely that Acree’s material was actually a mixture of I and III. In surveying the results of the various aforedescribed reactions, it is evident that the reactions lead to a variety of products, the nature of which depend upon the reaction conditions employed. Under the most mild conditions, 1,4-diphenyl-1,4- butanedione (VI) was found to accompany the diol (il) in its formation, from both diethyl succinate and methyl P-benzoyl- propionate (V). Apparently the formation of VI was due to incomplete reaction of both V and the diethyl succinate with phenylmagnesium bromide, although it is generally believed that ketones are more reactive toward Grignard reagents than 12 are esters (14)- Possibly the steric hindrance of the phenyl group attached to the ketone, and the size of the incoming phenyl group of the Grignard reagent, are sufficient to allow significant formation of the diketone (VI). When refluxing ether is employed the keto-ester (V) reacts completely, to form only diol. The reaction of diethyl succinate with phenylmagnesium bromide in mildly refluxing ether apparently produces only diol (II) and diketone (VI), but, when hydrolysis of the reaction mixture is performed with cold dilute hydrochloric acid, some diol (or its mag nesium salt) is dehydrated to l,l,4,4-tetraphenyl-3-butene- l-ol (IV). If the hydrolysis is carried out with ammonium chloride and ice, no dehydration is observed. Finally, under the most drastic conditions employed, 2,2,5,5-tetraphenyltetrahydrofuran (i) and 1,1,4,4-tetra- phenyl-1,3-butadiene (III) were obtained. EXPERIMENTAL1 Preparation of 1.1«L.A-Tetraphenvl-1.A-butanediol and 1.A-Diphenyl-1.A-butanedione from Methyl $-Benzovlpropionate. /J-Benzoylpropionic acid was synthesized in 85%> yield from a Friedel-Crafts reaction between benzene and succinic anhy dride as described by Somerville and Allen (15). Conversion of the acid to methyl £-benzoylpropionate was accomplished in 80% yield by the experimental procedure outlined by KLoetzel (16). Methyl -benzoylpropionate semicarbazone, melting at 137-138°, was prepared by the method suggested by Shriner and Fuson (17), who reported a melting point at 138°. In a 500-ml. three-necked flask, equipped with a mer cury-sealed stirrer, a water-cooled reflux condenser, and a dropping funnel were placed a crystal of iodine, 2.9 g. (0.12 moles) of magnesium turnings, and 5 ml. of anhydrous ether. The stirrer was started, and 18.8 g. (0.12 moles) of anhydrous bromobenzene in 55 ml. of ether was added very slow ly by means of dropping funnel. A solution of 5.75 g. (0.03 mole) of methyl ^-benzoylpropionate in 25 ml. of ether was added over a period of one hour to the ethereal solution kept I at constant reflux. The mixture was stirred and allowed to 1 All melting points are uncorrected; analyses are by The Microanalytical Laboratory of the California Institute of Technology and by Dr. Adalbert Elek, Elek Microanalytical Laboratory, Los Angeles, California. 14- reflux for one-half hour. After standing for another hour at room temperature, while continuing the stirring operation, the mixture was hydrolyzed with ice and ammonium chloride, and was allowed to stand overnight. Ether and biphenyl were removed by steam distillation, and the residue was filtered by suction. The precipitate was extracted several times with hot acetone, the solutions were combined and cooled to room temperature, and the resulting solution was then placed in the refrigerator at 0°, overnight. The precipitate was filtered by suction and air dried. The l,l,4.>4--tetraphenyl- l,4.-butanediol, in the form of white needles,“melted at 202.5- 203.5°; yield 5.8 g. (4. 9^). Melting points at 204. 0, 208°, 205-206°, and 202° were reported, respectively, by Kloetzel (5), Valeur (ll), Houben and Hahn (12), and Dilthey and Last (10). The reaction between methyl ^-benzoylpropionate and phenylmagnesium bromide was carried out a second time with only one modification: the ester was added to the Grignard reagent, kept in an ice-bath, over a period of thirty-five minutes, instead of' the hour-long addition of the ester to the refluxing ethereal solution previously employed. Using the same procedure of working up the reaction mixture, the yield of l,l,4.,4.-tetraphenyl-l,4~butanediol from the low temperature reaction was 4-9 g. (4J-*5$).; melting point 15 203.5-204.5°. The remaining acetone solution yielded a by-product. This compound, shown to be identical with l,4-diphenyl-l,4- butanedione, melted at 145-146°; yield, 0.73 g. ( - 10.2$). It was found to be insoluble in either cold or hot sodium carbonate solution, showing that it could not be $,& -diphenyl- %-hydroxybutyrie acid. An alcoholic solution of the com pound reacted with 2,4-dinitrophenylhydrazine. The method of Fritz (6) was used to prepare 2-bromo- 1.4-diphenyl-l,4-hutanedione from phenacyl bromide in 45$ yield. Reduction of the bromodiketone to 1,4-diphenyl-1,4- butanedione was accomplished in 69$ yield by magnesium powder-alcohol reduction (7). The diketone melted at 144" 145°; Fritz reported a melting point of 145°. A mixed melt ing point of 1,4-diphenyl-l,4-butanedione with the compound obtained from the reaction of methyl -benzoylpropionate and phenylmagnesium bromide, melting at 145-146°, was I44-I460. Conversion of 1.1.4.4-Tetrauhenvl-1.4-butanediol to 2.2. 5.5-Tetraphenyltetrahvdrofuran. (a) With Acetic Acid. The method of Valeur (2) was employed, but the experimental proce dure had to be extended to enable attainment of the proper de hydration conditions, thus preventing either incomplete mono dehydration, or removal of the second molecule of water. Fifty ml. of glacial acetic acid was heated to boiling 16 2.03 g. of l,l)i +,! +-tetraphenyl-l,l 4 — butanediol was added, and the solution wa\s kept at the boiling point for five minutes-. The boiling solution was filtered by gravity and allowed to cool. A white crystalline product separated, which was filtered by suction and air-dried; yield, 1.32 g. (68.*+$). After two recrystallizations the product melted ait 180.5- 181.5°. Valeur (2) reported a melting point of 182°. The product did not react with a cold 2% potassium permanganate solution. A Zerewitinoff determination showed 0.0^2 atoms of active hydrogen, or, in effect, no active hydrogen in the molecule. Anal. Calculated for C2gH2lf0: C, 89.32; H, 6.>+2. 'Foundl: 0, 89.2*4-, 89.30; H, 6.76, 6.19. With Bromine. Salkind and Teterin’s directions for the bromine dehydration of the diol (3) were followed. Although the authors did not report the quantities of reagents employed, we found the following procedure to be satisfactory. To 1.00 g. of 1,1 jU-^-tetraphenyl-l,*+-butanediol dissolved in 100 ml. of chloroform was added dropwise ^.7 g. of a 12.7$ solution of bromine in chloroform. The solution stood at room temperature for six and one-half hours before the chloroform sand bromine were removed under reduced pres sure, and the residue was dissolved in 50 ml. of methanol. 17 2.2.5.5-Tetraphenyltetrahydrofuran was obtained in a yield of 0.5S g. (61$); after another recrystallization from methanol and three from acetone, the tetrahydrofuran melted at 180- 181°• Salkind and Teterin (3) reported a melting point of 182°. (c) With Anhydrous Hydrogen Chloride. A method used by Kloetzel (5) for the preparation of various tetrahydro- furans from the corresponding butanediols (such as 2-phenyl- 2.5.5-trimethyltetrahydrofuran from 2-methyl-5-phenyl-2,5- hexanediol) by means of anhydrous hydrogen chloride was adopted in an attempt to prepare 2,2,5,5-tetraphenyltetra- hydrofuran from 1,1,4-, 4--tetraphenyl-1, 4-butanediol. Anhydrous hydrogen chloride was passed through a suspension of 2.10 g. of l,l,4-,4-y'tetraphenyl-l,4--butanediol in 75 ml. of anhydrous benzene for one and one-half hours, keeping the solution bubbling gently. The diol was observed to go into solution during this period of time. The solution was cooled to 0° and a crystalline 1,1, 4. , 4,-tetr aphenyl-1, 3- butadiene, in the form of colorless prisms, was filtered off. The solution was washed thoroughly with 1% sodium hydroxide to remove the last traces of hydrogen chloride, and was then filtered. The only definite product isolated from the pre cipitates after many attempts at recrystallization ivas 1,1,4-, 4--tetraphenyl-l,3-butadiene, in the form of prisms with a greenish fluorescence. The yield was 0.4 g. (21$), melting 18 point, 201-202° after one recrystallization from benzene. The diene was reported to melt at 201° and 205-206° by Wittig and Von Lupin (18) and Lipp (19). Both authors re ported the butadiene to crystallize from benzene with a greenish blue fluorescence. The only other materials obtain ed were mixtures melting rather sharply (159-162°; 162-164°), which upon recrystallization from acetone gave further quantities of impure diene melting at 194.5-197.5°. A second run in which 1.15 g. of the diol in 75 ml. of benzene was treated with a slow stream of hydrogen chlo ride for"twenty minutes in mixtures melting at 160—174° and 153-167°. These mixtures were dissolved in the minimum amount of carbon disulfide necessary, 5 ml. of nitromethane was added, and the mixture was allov/ed to stand overnight. Small amounts of impure 2,2,5,5-tetraphenyltetrahydrofuran, melting at 172-178°, crystallized out. By evaporating off the remainder of the solvent under reduced pressure, small quantities of impure diene melting at-189-195° were also obtained. Preparation of 1.1.A.A-Tetraphenvl-1.3-butadiene from 2.2.5-. 5-Tetraphenvltetrahvdrofuran. A method used by Kloetzel (l) for the dehydration of l(oc-naphthyl)-cyclopent- anol to 1 (er-naphthyl)— cyclopentene was s,dopted for the de hydration of the tetrahydrofuran. 19 Five ml* of anhydrous (98-100$) formic acid was added to 0.18 g. of 2,2,5,5-tetraphenyltetrahydrofuran in a 10 ml. flask, equipped with a water-cooled reflux condenser. The material was not soluble in the acid at room temperature so it was heated on the steam-bath for thirty minutes. No change was observed. The acid was refluxed for three hours on a hot plate. A change in crystal structure was observed. Five ml. of water was added and the mixture was extracted with 30 ml. of benzene. The benzene solution was washed with 6 ml. of 5$ potassium hydroxide and then with 5 ml. of water. After filtration, the benzene solution was dried over anhydrous calcium chloride. The solution_.was filtered again, and the benzene was evaporated. The yield of crude 1,1,4,4-tetraphenyl-l,3-butadiene was 0.13 g. (76$). Two recrystallizations from acetone and one from benzene raised the melting point to 202.5-203.5°. The mixed melting point with the diene (melting point, 201-202°) obtained from the hydrogen chloride dehydration of 1,1,4,4-tetraphenyl-l,4- butanediol was 201.5-203°. Reaction of Diethyl Succinate with Phenvlmagneslum Bromide. (a) Preparation of 1.1.A.4-Tetraphenvl-1.4- butanediol and 1.1.4.4-Tetraphenvl-3-butene-l-ol. Dilthey and Last (10) reported that the reaction between diethyl succinate and phenylmagnesium bromide yielded 1,1,4,4-tetra- phenyl-l,4-butanediol as the only product. Their experimental 20 details, however, 'were incomplete. Since we isolated 1,1,4, 4-tetraphenyl-3-butene-l-ol in addition to the diol in re peating the work of Dilthey and Last, our experimental con ditions are here completely described. A crystal of iodine was added to 13.7 g. (0.56 moles) of magnesium turnings and 25 ml. of anhydrous ether in a 500-ml. three-necked flask, equipped with a mercury-sealed stirrer, water-cooled reflux condenser, and a dropping funnel. The dropping funnel was filled with a solution of 82.2 g. (0.52 moles) of anhydrous bromobenzene in 85 ml. of ether. Five milliliters of the solution was added to the re action vessel which was heated on the water—bath until the reaction started. The remainder of the solution was added at the rate of ten drops per minute, and the mixture was then refluxed for one-half hour. A solution of 17.6 g. (0.1 moles) of diethyl succinate (Eastman ¥\?hite Label product) in 70 ml. of ether was added to the reaction mix ture over a period of two and one-half hours, while keeping the mixture at constant reflux on-the water-bath. The mix ture was refluxed for another half hour, allowed to stand for three hours, and then transferred to a large beaker t where it was hydrolyzed with ice water acidified with hydrochloric acid. The hydrolysis mixture was filtered by suction, the ether layer was evaporated to dryness, and the residue was added to the hydrolysate which was washed with 21 water to remove traces of acid, and then extracted with hot ethanol. TWo products were obtained from the ethanol solution. 1,1 j^^-.fetraphenyl-l,*+-butanediol separated in the form of colorless needles. After four recrystallizations from acetone, the material was dried in a vacuum desiccator for three days. The diol melted at 203-20^°. Dilthey and Last reported a melting point of 202°. The yield was; 8.8lg. ( 21.5$). The second product, 1,1 ^^-tetraphenyl-S-butene-l-ol, originally crystallized in the form of pale yellow needles, but after repeated recrystallizations it became almost color less. After one recrystallization from ethanol and three from acetone, it was dried in a vacuum desiccator for four days; yield, 2>1 g. (6.3£); m. p. 122.5-123.5°. Anal. Calculated for CggHl^O: c> 89.32; H, 6.*+2. Found: C,'89.87; H, 6.56. l,l,l +,} +-.Tetraphenyl-3-butene-l-ol decolorized cold 2% potassium permanganate solution practically instant aneously. A Zerewitinoff determination showed 0.89*+ atoms of active hydrogen. A solution of 0.20 g. of l,l,l +,} +-tetraphenyl-3- butene-l-ol in 70 ml. of ethyl acetate was submitted to ozonolysis at room temperature, for one-half hour, employing 22 a stream of oxygen containing 2% ozone. The ozonide was de composed with 70 ml. of water and^mr.of 3% hydrogen peroxide over a period-of three days. The layers were then separated and the ethyl acetate layer was washed with 50 ml. of 10$ sodium bicarbonate solution. The two, layers were separated and worked up independently* The ethyl acetate layer was evaporated to dryness, and the residue was dissolved in 10 ml. of ethanol. To the filtered solution was added 0.15 g. of 2,4-dinitrophenyl- hydrazine. After heating the mixture to boiling, 0.2 ml. of C. P. hydrochloric acid was added, resulting in a clear .solution. This solution was refluxed for five minutes', until an orange crystalline substances was precipitated. The t precipitate was washed with cold alcohol, and recrystallized from 25 ml. of glacial acetic acid; yield of purified 2,4- dinitrophenylhydrazone, 0.05 g. (32$); m. p. 234-235°. An authentic sample of benzophenone 2,4-hinitrophenyl- hydrazone was prepared by the method described by Shriner and Fuson (20). It melted at 237-238°, and a mixed melting point with the derivative melting at 234-235° was 236.5-237.5°, in dicating that the two dinitrophenylhydrazones were identical and that benzophenone was one of the ozonolysis products. The sodium bicarbonate layer from the extraction of the hydrolyzed ozonide was acidified to litmus with C. P. hydro chloric acid (l ml.). Five 20 ml. portions of ether were used 23 to extract the acidified layer. The ether solution was evaporated to dryness and the residue was; reerystallized from "Skellysolve F. ' * f,^-Diphenyl-^-hydroxypropionic acid, m. p. 211-212°, was obtained as colorless; needles.;; yield, 0.05 g* (39$). A mixed melting point with authentic £,$-diphenyl-0-hydroxypropionic acid, m. p. 210.5-212°, prepared by the method of Rupe and Busolt (13), was 210.5- 211.5°. To test the validity of the ozonolysis as an ana lytical tool in this instance, 0.2 g. of 1,1 ^^-tetraphenyl- 1,^-butanediol was dissolved in 70 ml. of ethyl acetate and submitted to ozonolysis for one-half hour. The solution was placed in contact with 70 ml. of water for two days, and the ethyl acetate layer was evaiporated to dryness. The white product melted at 200-202°. A mixed melting point with the diol indicated the recovery of starting material. The yield of recovered diol was 0.19 g. (95$). Since the reaction mixtures from the reactions of phenylmaignesium bromide and methyl -benzoylpropionate had been hydrolyzed with ice and ammonium chloride instead1 of the acidified ice-water used in the diethyl succinate reaction mixture hydrolysis, and since only a relatively smasll amount of the products of the latter reaction were accounted for, it was decided to repeat the reaction and hydrolyze under the milder conditions. 24 (b) Preparation of 1.1.A.4-Tetraphenvl-1.4-butanediol and 1.A-Diphenvl-1.A-butanedione. The reaction of diethyl succinate with phenylmagnesium bromide was carried out as de scribed above until the hydrolysis stage was reached. After standing for three hours at room temperature, the reaction mixture Was transferred to a large beaker where it was hydrolyzed with ice and ammonium chloride. The sus pension was filtered by suction, the ethereal layer was evaporated to dryness, and the residue was added to the pre cipitate. Hot acetone was used to extract the residue. The acetone was evaporated slowly and small crystalline fractions were obtained. All fractions melting below 150° were re crystallized from methanol. The total yield of 1,1,4,4- tetraphenyl~l,4-butanediol, melting above 195°, was 25.2 g. (64%). The total yield of 1,4-diphenyl-1,4-butanedione, melting above 139°> was 2.75 g. (11*6$). (c) Preparation of 1.1.A.A-Tetraphenvl-1«A-butanediol. 1.4-Diphenvl-l,4-butanedione and 1.1.4.4-Tetraphenvl-3 butene ' -l-ol. The reaction between diethyl succinate and phenyl magnesium bromide was repeated under the aforedescribed con ditions. Hydrolysis of the reaction .mixture was accomplished by pouring a portion over ice and ammonium chloride as de scribed above, and the remainder into 300 ml. of ice-water 25 acidified with 5 ml. of C. P. hydrochloric acid. Measurement of the ether layer resulting from the two hydrolyses showed that 60$ of the mixture had been hydrolyzed by the ammonium chloride treatment and 4,0$ by the' hydrochloric acid. The two hydrolysates were irorked up as described previously. Fractionation of the ammonium chloride hydrolysate yielded 13.3 g. (56$) 1,1,4,,4-tetraphenyl-l,4,-butanediol melting above 198°, and 1.6 g. (11.5$) of l,4-diphenyl-l,4- butanedione melting above 14-1°. Ho l,l,4,4-tetraphenyl-3- butene-l-ol was found. The hydrochloric acid treatment of the reaction mix ture resulted in a yield of 8.5 g* (53$) of diol melting above 198.5°, 1.0 g. (10.5$) of diketone melting above I4J-0, and 0.9 g. (6$) of l,l,4,4-tetraphenyl-3-butene-l-ol melting at 117-118°. Two recrystallizations from acetone raised the melting point of the unsaturated alcohol to 122-123°. (h) Preparation of 2.2.5.5-Tetraphenvltetrahydrofuran and 1.1.A.Z.-Tetranhenvl-1.3-butadiene. The reaction of die- I thyl succinate with phenylmagnesium bromide.was repeated, but the rate of addition of the ester to the Grignard reagent was greatly increased, causing violent reflux, simulating the re action conditions of Acree (4. ) very closely. The amounts of reagents used were twice the quantities employed in the aforedescribed rim, while the ester was added to the Grignard 26 solution over a period of seventy minutes in place of the two and one-half hours used previously. Acree’s method was used in the working up of the re action mixture. After being allowed to stand for three and one-half hours following the addition, the mixture was poured into a large beaker containing cracked ice. A copious pale yellow precipitate appeared. Ten milliliters of 5$ sulfuric acid was added, the ether layer was evaporated to dryness, and the mixture was filtered by suction. Recrystallization from alcohol produced mixtures melting from 80-160°. Two recrystallizations from acetone produced 5.3 g. of a mixture melting from 156-163° (as well as other mixtures melting at 157-161°, 147-158°, 156-160°, 159.5-163.5°, 149-161°, 109-116°, etc.). This mixture iras dissolved in 15 ml. of carbon disul fide and 5 ml. of nitromethane was added. All but 1.92 g, of material went into solution. The insoluble material was re- crystallized twice from acetone, washing the crystalline prod uct with carbon disulfide each time. The final product melted at 180.5-181.5°, and weighed 0.7 g. A mixed.melting point with 2,2,5,5-tetraphenyltetrahydrofuran, melting at 180.5- 181.5°, was 180.5-181.5°> indicating the identity of the two substances. The only other definite compound obtained from the long series of mixtures was 1,1,4*4-tetraphenyl-l, 3-butadiene. The yield was 0.12 g., melting at 195-197°. A mixed melting point with an authentic sample of diene, melting at 202-203°, 27 was 199.5-201°. The Zerewitinoff Apparatus — Description and*“0peration. A Zerewitinoff apparatus, shown in the accompanying- "diagram, was constructed to make possible the active hydrogen de terminations previously described. It closely resembles the Lauer modification (21,22) of the Kohler Grignard Machine (23,24). Flask nd» is a 50 ml. Erlenmeyer with a 24/40 ground glass joint. It contains a glass-coated stirring magnet which is set into motion by means of a revolving horseshoe magnet securely fastened to the shaft of an electric motor. The flask is immersed in a beaker of mineral oil, which is heated by means of an electric heater, consisting of a twist of nichrome wire inside pyrex tubing, to a determined tem perature kept constant by use of a ’ ’ Variac” rheostat. A further description of the parts of the apparatus and their function is contained in the following outline of the procedure involved in making a Zerewitinoff determina tion. Stopcock Han is opened to allow a current of nitrogen, dried by passage through calcium chloride and ”Dehydriten tubes, to circulate through the apparatus and exit through open stopcock Hb.n Flask udf l is at first replaced, for ten to fifteen minutes, by a flask containing l f Dehydrite.” Then, 28 flask M,M dried thoroughly in a vacuum desiccator over ealcium chloride, containing a stirring magnet and a weighed amount of the compound to be analyzed (or water in case of a standardization) is attached to the ground glass joint with a small amount of stopcock grease. Rubber bands are placed over the Mears.n Nitrogen is passed through the system for ten to fifteen minutes longer. The current of nitrogen is shut off. Stopcock , ! b” is closed and MaM is left open (through the calcium chloride and nDehydrite, t tubes) until the system reaches equilibrium (about one minute), as determined by observation of mano meter ’ ’e" when stopcock ncn is turned so as to bring wen into the system. Levelling bulb i'fn is adjusted so as to bring the mercury in gas burette , T gI T as close to the zero mark as possible. Stopcock Man is closed after equilibrium is again attained. Projection nhH is closed with a self-sealing rubber stopple. The methylmagnesium iodide solution, prepared as described by Eohler and Richtmeyer (24-), is kept in a storage vessel \vhich has a projection closed by a rubber stopple. By means of a scrupulously cleaned, calibrated hypodermic needle, dried in a vacuum desiccator over calcium chloride, the Grignard Reagent is transferred from the storage vessel to the apparatus. The needle is filled by puncturing the rubber stopple, tipping the solution towards 29 the projection and withdrawing the plunger to the desired mark, after eliminating all bubbles by working the plunger up and down in the barrel several times. Immediately after removing the needle from the storage vessel stopple, it is alloired to pierce stopple "h.1 1 The plunger is forced down, the needle is allowed to drain one minute, and then removed. Levelling bulb nf, f is lowered to keep pace with the evolution of methane. ’ Flask 5 I dM is immersed in the bath, and the stirring motor is started. After one-half hour at room temperature, the heat is applied. The temperature is kept at 60° for a standardization, and at 90° for a regular run. Heating is continued for one to three hours, and then the oil bath and stirring motor are removed. > Equilibrium is attained.in thirty to sixty minutes. The levelling bulb nfn is kept approximately at the same height as the level of the mercury in gas burette ng.r i Manometer f , eM is brought into the system by means of stopcock «c," and the level of mercury in its arms is adjusted by means of levelling bulb ^f.1 1 At equilibrium the mercury in the manometer arms will be at equal height, and no further change in volume will occur when stopcock "c, J is1 turned back to bring t f gT t back into the system. The temperature of the water in the jacket ^surrounding the gas burette is read before and after the measurement, as are the barometric pressure, and the burette readings. 30 The apparatus is cleaned by removing flask nd,n clean ing the glass joint, and placing another flask in position. Stopple "h1 1 is removed, and by means of a dropper, dilute hydrochloric acid, alcohol, and finally ether are run through the arm. The , J Dehydriten flask is replaced and nitrogen is run through the system until it is dry (ten to fifteen minutes). a. ’ 31 SUMMARY Methyl #-benzoylpropionate and phenylmagnesium bromide reacted at 0° to give l,l,4*4-tetraphenyl-l,4-butane- diol and 1,4-diphenyl-l,4-kutanedione. On refluxing in ether these reactants yielded only 1,1,4,4-tetraphenyl-l,4-hutane- diol. The compound, melting at 132°, prepared from 1,1,4,4- tetraphenyl-l,4-*butanediol with glacial acetic acid and bromine by Valeur (2) and Salkind and Teterin (3), respec tively, was shown to be 2,2,5j5-tetraphenyltetrahydrofuran by carbon and hydrogen analysis, Zerewitinoff determination, and dehydration to 1,1,4,4-tetraphenyl-l,3-butadiene. The reaction of -diethyl succinate with phenylmag- nesiutn bromide at ether reflux temperatures with slow addi tion of ester to Grignard reagent yielded l,l,4*4-tetra- phenyl-l,4-butanediol and 1,4-diphenyl-l,4-butanedione when the reaction mixture was hydrolyzed with ice and ammonium chloride. Hydrolysis of the same reaction mixture with ice- water acidified with hydrochloric acid yielded 1,1,4,4-tetra phenyl-l, 4-butanediol, 1,4-hiphenyl-l,4-butanedione and 1,1, 4>4-tetraphenyl-3-butene-l-ol. The identity of the latter compound was established by Zerewitinoff analysis and ozonolysis.' Rapid addition of diethyl succinate to phenylmagnesium 33 bromide, and resultant violent ether reflux yielded 2,2,5,5- tetraphenyltetrahydrofuran and 1,1,4,4-'tetraphenyl-l,3- butadiene. Evidence was obtained which indicated that AcreeTs »compound” (4,), melting at 163-165°, prepared from the re action of diethyl succinate with phenylmagnesium bromide in rapidly refluxing ether, was probably" a mixture of 2,2,5,5- tetraphenyltetrahydrofuran and 1>1,4,4-tetraphenyl-1,3- butadiene . BIBLIOGRAPHY- 1) KLoetzel, M. C., private communication. 2) Yaleur, Compt. rend. 136. 695 (1903). 3) Salkind and Teterin, Ber. 62, 1747 (1929). 4) Acree, Am. Chem. J. 33. 192 (1905). 5) KLoetzel, J. Am. Chem. Soc. 62, 3405 (1940). 6) Fritz, Ber. 28, 3032 (1895). 7) Fritz, Ber. 29, 1751 (1896). 8) Borsche, Keltner, Gilles, Kuhn and Monteuffel, Ann. 526. 1 (1936). 9) Auger, Ann. Chim. Phys. (6) 22. 312 (1891). 10) Dilthey and Last, Ber. 37. 2639 (1904). 11) Yaleur, Bull, Soc. Chim. 2% 683 (1903). 12) Houben and Hahn, Ber. 41, 1580 (1908). 13) Rupe and Busolt, Ber. 40. 4538 (1907). 14) Gilman, "Organic Chemistry," John Wiley and Sons, New York, 1947, p. 501. 15) Somerville and Allen, "Organic Synthesis," Collective Yolume II, John Wiley and Sons, New York, 1947, p. 81. 16) KLoetzel, J. Am. Chem. Soc. 62, 1708 (1940). 17) Shriner and Fuson, "Identification of Organic Compounds," John Wiley and Sons, New York, 194&, p. 142. 18) Wittig and Yon Lupin, Ber. 61, 1630 (1928). 19) Lipp, Ber. 16, 571 (1923). 35 (20) Shriner and Fuson, “Identification of Organic Compounds,1 1 John Wiley and Sons, New York, 194-6, p. 14-3. (21) Fieser and Fieser, “Organic Chemistry,5 1 D. C. Heath and Company, Boston, 1944* P- 211. (22) Zaugg and Lauer, Anal. Chem. 20. 1022 (1948). (23) Kohler, Stone and Fuson, J. Am. Chem, Soc. 4.9. 3181 (1927). (24) Kohler and Hichtmeyer, J. Am. Chem. Soc. 52. 3736 (1930). UffidtvMMity of Soufcbbera

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Creator Wasserman, William J (author)

Core Title The reaction of phenylmagnesium bromide with methyl B-benzoylpropionate and with diethyl succinate

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

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Language English

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Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-794736

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