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Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones

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Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-1959 Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones. Stanley Selman University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Selman, Stanley, "Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones.. " PhD diss., University of Tennessee, 1959. https://trace.tennessee.edu/utk_graddiss/2958 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Stanley Selman entitled "Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones.." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: D. A. Shirley, Carl Buehler, John W. Prados Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) August 5, 1959 To the Graduate Council: I am submitting herewith a dissertation written by Stanley Selman entitled ''Rearrangements of the Benzilic Acid Type; Preparation and Use of Dialkali Metal Adducts of Aromatic Ketones.11 I reconnnend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a major in Chemistry. We have read this dissertation and recommend its acceptance: Accepted for the Council� REARRANGEMENTS OF THE BENZILIC ACill TYPE; PREPARATION USE AND OF DIALKALI METAL ADDUCTS OF AROMATIC KETONES A DISSERTATION Submitted to The Graduate Council or The University o£ Tennessee in Partial Fulfillment o£ the Requirements for the Degree o£ Doctor or Philosophy by Stanley Selman August, 1959 ACKNOWLEDGMENT The author wishes to express his sincere gratitude to Dr. Jerome F. Eastham for helpful and encouraging guidance during his entire graduate career and throughout the course of this research. He would like to extend a special thanks for Dr . Eastham's invaluable assistance in the preparation of this dissertation . Thanks are also due to the Union Carbide Nuclear Corporation for the fellowship which helped support this work. It is the author's pleasure to acknowledge his indebtedness to his wife whose patience, help, and understanding have been of inestimable value. To the Memory of My Beloved Mother TABLE OF CONTENTS CHAPI'ER PAGE I. INTRODUCTION • . • . • • • • • • • . • 1 A. The Benzilic Acid Rearrangement. 1 B. The Benzilic Ester Rearrangement . .. 6 C. Tertiary Ketol Rearrangement . 11 D. The Dialkali Salts of Benzophenones. 18 E. Statement of the Problem • • • • • 27 II. PRESENTATION DISCUSSION RESULTS • 29 AND OF A. Synthesis of Methyl Anisilate-l-cl4 . 32 B. Proof of Position of Labeling in Methyl Anisilate-l-c14 and Irreversibility of the Ben- zilic Ester Rearrangement. • • • • . • 35 C. Additional Evidence Indicating Irreversibility of the Benzilic Ester Rearrangement. 38 D. Related Rearrangements • • • • • •• 41 1. Reaction of Benzils With Amide Ion • 41 2. The Reaction of Benzil With Grignard Reagents and Organolithium Reagents • • • • • • • 46 Preparation of the Pialkali Salts of Benzo- E. phenones and Their Reaction Carbon Dioxide, With Ethyl Chloroformate and Alkyl Carbonates • • • • 49 F. Reaction of the Dialkali Salts of Benzophenones With Aromatic Aldehydes•• •• 60 iv PAGE OHAPrER II. (Continued) G. Reaction of the Dialkali Salts of Benzophenones With Aromatic Nitriles • • • 0 • . 65 III • EXPERIMENTAL • • • • • • • 68 A. Synthesis of Methyl Anisilate-l-cl4. 68 1. Anisoyl Chloride ••• 68 l 2. Anisoyl Cyanide-l-c 4 •• . 0 • • • • 69 l 3. Alcoholysis of Anisoyl Cyanide-l-c 4 • . 69 4. Attempted Hydrolysis of Anisoyl Cyanide. 72 . � 1 �· Methyl Anisilate-1-C 4 ..• •• ••••• • 73 B. P.roof of Position of Labeling in Methyl Anisilate-l-cl4, and Irreversibility of the Ben- zilic Ester Rearrangement. • . 74 1. Anisil . • . 74 2. Anisilic Acid. 74 3. Methyl Anisilate . • . • • . 75 4. Treatment of Methyl Anisilate With Sodium Methoxide. • • • • • • • • • • • • • • 75 5. Attempted Oxidation of Methyl Anisilate. 76 6. Oxidation of Anisilic Acid • • • • • • • 76 7. Saponification of Methyl Anisilate-l-cl4 . 77 l 8. Oxidation of Anisilic Acid-l-c 4 •••• •• 77 9. Reaction of Methyl Anisilate-l-cl4 and • • Sodium Methoxide at 100° • • • • • . 78 v CHAPTER PAGE III. (Continued) 10. Reaction of Methyl Anisilate-l-c14 and Sodium Methoxide at 200° • 0 Q 0 !) 19 C. Additional Evidence Indicating Irreversibility of the Benzilic Ester Rearrangement. 0 0 0 0 0 0 79 1. Methyl Benzilate • • • • • • 79 2. Reaction of Methyl Benzilate and Sodium Ethoxide o • o • • • • • • • COct4e•tt• 80 3. Reaction of Methyl Anisilate and Sodium Ethoxide . • • • • • • • . 81 D. Related Rearrangements 81 1. Amide Ion Catalysis. 81 2. Grignard Reagent Catalysis • 83 3. Tertiary Ketal Rearrangement . 85 E. Preparation of the Dialkali Salts Benzo- of phenones and Their Reaction With Carbon Dioxide. 87 1. Preparation of Benzilic Acid • • • • • • • • 87 2. Preparation of Methoxy Substituted Benzilic Acids . o • • () • (; o Q 4) o • • • " Q: • 91 3. Preparation of Methyl Substituted Benzilic Acids. • • • • 94 4. Preparation of 2-Phenylbenzilic Acid 0 • . 97 vi CHAPI'ER PAGE III. (Continued) F. Preparation of the Dialkali Salts of Benzo- phenones and Their Reaction With Esters. • 99 1. Reactions With Ethyl Chloroformate • • • • • 99 2. Reactions With Alkyl Carbonates •.• • 0 • • 100 G. Reaction of the Dialkali Salts of Benzophenone With Aromatic Aldehydes. • • • • • 109 1. Reactions With Benzaldehyde. 109 2. Reactions With Anisaldehyde. 112 H. Reaction of the Dialkali Salts of Benzophenones With Aromatic Nitriles • • • • • • • • 115 l. Preparation of a-Phenylbenzoin . • 0 • • 115 2. Preparation of a-Phenyl-4-methylbenzoin. 116 3. Attempted Preparation of a-Anisyl-4-methoxy- benzoin. o . " . .. 117 4. Attempted Preparation of a-Phenyl-4-methoxy- benzoin. • Q • 0 118 IV. SUMMARY••.. 120 BIBLIOGRAPHY•• ••• 122 CHAPI'ER I INTRODUCTION A. The Benzilic Acid Rearrangement The benzilic acid rearrangement is the base-catalyzed transforma- tion of an a.-diketone to the salt of an a.--hydroxy acid. This rearrange­ ment can be effected in aromatic, in semi=aromatic (�-quinones), in alicyclic, and in aliphatic, as well as in heterocyclic a.-diketones. Examples of the rearrangement in the above type compounds are illus­ trated in equations 1-6. Aromatic diketones:1 R * g Ph-C-C-� ---+ (1) Benzil Benzilic Acid Semi-aromatic diketones:2,3 Q9 (2) HO/ 'cooH Phenanthraquinone 9-Hydrox:yfluorene-9-carboxylic acid 5_ ,..,. HOOQ__ o hOH HO� o .yoo (3) Rhodizonic Acid Croconic Acid *nphn is used to represent the phenyl group, 11 An11, the E.-anisyl group, 11Ar", other aryl groups and 11Rrt, alkyl groups throughout this dissertation. Another convention emplqyed is that in Grignard reaction equations, the hydrolysis of the addition complex has been omitted for brevity. 2 Alicyclic diketones: 4 OH Cf'cooH (4) 1, 2-Cyclohexadione 1-Hydroxycyclopentane­ carboxylic Acid Aliphatic diketones:5 (5 ) Ketipic Acid Citric Acid Heterocyclic diketones:6 _))H �-c O=C l"cOOH (6) "'.NH--G=O Alloxan Alloxanic Acid Westheimer7 in his studies of the kinetics of this rearrangement, found the reaction to be strictly bimolecular between benzil and hydroxide ion, becoming pseudo-unimolecular in the presence of a large excess of alkali. The reaction is not one of general base catalysis (removal of a proton), as shown by the fact that phenoxide or£-chlorophenoxide ions do not catalyze the reaction, nor does it involve a free-radical mech- anism since the rate is not affected by the addition of peroxides. Roberts and UreyB studied the rate of exchange between benzil andol8_ labeled water in neutral and in alkaline solution. That the exchange occurred slowly in neutral solution but was complete within four minutes in basic solution and was imperceptible in acid solution, suggested that 3 the rearrangement occurs after th e preliminary reversible addition of hydroxide ion (equation 7). 1 Ph-�-�-Ph + o �- (7) Doering and Urb an9 found that the rearrangement is not catalyzed specifically by hydroxide ion but that benzil would rearrange in the presence of properly selected alkoxide ions to yield the corresponding benzilic acid esters. That the rearrangement does not involve a proton transfer in the rate-determining step was shown by Hine and Haworth10 who found that the rate of the rearrangement at 50° was about 85 per cent faster in 66.7 per cent dioxane-33.3 per cent deuterium oxide than in 66.7 per cent dioxane-33.3 per cent water. The reversal of the benzilic acid rearrangement has been observed a few isolated cases. For example, the lead salt of camphenylic in acid (I) yields carbocamphenilonone (II) wh en heated. Since the oxida­ tion of camphene (IV) with permanganate
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