Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1953 Acetic-Oxalic Anhydride. Part I. A Study of Some N-Alkyl-Cyclohexylcarbinols. Part II. Walter Maurey Henley Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Part of the Chemistry Commons Recommended Citation Henley, Walter Maurey, "Acetic-Oxalic Anhydride. Part I. A Study of Some N-Alkyl-Cyclohexylcarbinols. Part II." (1953). LSU Historical Dissertations and Theses. 8034. https://digitalcommons.lsu.edu/gradschool_disstheses/8034 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. PART I ACETIC-OXALIC ANHYDRIDE PART II A STUDY OF SOME n-ALKYL~G YC WHBXYICARBINODS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College In partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Walter Maurey Henley B*S#, Southeastern Louisiana College# 1947 K.S«j Louisiana state university, 1949 August, 1952 UMI Number: DP69412 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 Dissertation Publishing UMI DP69412 Published by ProQuest LLC (2015). 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States Code uest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 MANUSCRIPT THESES Unpublished theses submitted for the master’s and doctor’s degrees and deposited in the Louisiana State University Library are available for inspection* Use of any thesis is limited by the rights of the author. Bibliographical references may be noted, but passages may not be copied unless the author has given permission. Credit must be given in subsequent written or published work. A library which borrows this.thesis for use by its clientele is expected to make sure that the borrower is aware of the above restrictions• LOUISIANA STATE UNIVERSITY LIBRARY ACKRCfitfX^DOMESJT The author wishes to express his appreciation for the advice and assistance of Pr« W. H* Edwards undex’ whose direction this work was performed. He is indebted to Dr* j* h* 1 * Erickson for helpful advice and for the loan of special equipment. HO wishes to express his appreciation to Dr* B« B. Williams and to Dr* 0 * !* MeLeXXan for their helpful suggestions and encouragement in carrying out this research* He is grateful to the Department of Chemistry for the Coates Besearch Fellowship which he held for one year during the development of this problem* } t a b u : o f c o n t e n t s Chapter Page X Introduction and Selected Literature Survey- • 1 2 Experimental Methods « * * ........ 10 3 Discussion 24 4 Summary »»••*•#•***•«•«»»*• 33 11 LIST OF TABLES Tables Page 1 Esterifleatien Studies of Some Mixed Anhydrides* 5 XI The Reactions of Some Mixed Anhydrides with AaBBonie and Aniline *•*•••*»«•*• 6 XXX Melting Feint Data for Several Amides* • 12 XV Determination of Acetyl-Oxalyl Ratios* . .... 17 V Reaction of Acetic-Oxalic Anhydride with Aniline * ....... ............... • 20 111 ABSTRACT The synthesis of acetie*©xallc anhydride was at* tempted la four ways; (X) by the reaction of acetic anhy­ dride with anhydrous oxalic acid; (a) by the reaction of acetyl chloride with ©odium oxalate| (3} by the reaction of acetyl chloride with silver oxalate1 and (4 ) by the reaction of ketone with anhydrous oxalic acid. Synthesis by method (1) was not successful and only slight success was obtained with method {£}• The moat favorable results were given by method (3). A thorough examination of the potentialities of process (4 ) was not made# though a certain amount of compound was obtained by this method* An approximate determination of the temperature at which the compound decomposes was made* The anhydride is quite thermo-labile# decomposes at -3*5° to give acetic anhydride# carbon dioxide# and carbon monoxide, it reacts vigorously with aniline to form oxamllldei hydrolyses readily forming oxalic and acetic acids; and to a slight degree is susceptible to aleoholysls* An explanation of the results obtained upon the interaction of one equivalent weight of the anhydride with 2 equivalent weights of aniline is offered* iv An explanation of the mode of decomposition of anhydrous ©acalie aeld by acetle anhydride has been offered# v o £ £ S € * ♦f ©*p #« i # « * « * * $ I I o ! a m ^eO f i** * »i s . 4•* M & aOm # e I1 3 Sg a n ? i I d i % * r ■ • i I rs 5 i i “ 3m eht alaes]*e yedne ydute fe nixed •Jill e l aefileld cfdien otfnBt decu«ndonrtnitiO»eJ s i 3 c» fi * T ; H 5 I iw I * 0 5 2 This property Is further enhanced by great differences between the length of H and R *, though this latter magnifi­ cation Is of a secondary nature. Thus, through the avoidance of prolonged elevated reaction temperatures, Hurd's method simplifies the purification process* The method is somewhat limited, however, since acetic acid is necessarily one of the acid constituents of the anhydride. The thermo-labile nature of double anhydrides be­ comes an advantage In the preparation of simple anhydrides of certain fatty acids which would otherwise be difficult to obtain (1 0 ,11,1 2 }. The preparation of simple anhydrides of aromatic acids by means of this disproportionation has been reported (2,13,1%) and la illustrated by the equation below. 0 8 9 Similar compounds of heterecylio acids such as the one shown in the equation below have been reported (2). 2 H To a large extent the development of double anhydrides in which one of the acid moieties Is dlcarboxyllc (12,13,1%) has lagged far behind that type of anhydride which consists exclusively of monocarboxylio components. The most complete study of this type anhydride has been that of Adams (12 ,1 3) who prepared nitro-substltuted benzoic -oxalic anhydrides In excellent yields by ref luxing the aromatic acid with exalyl chloride * It was f urther demonstrated that the presence of a nltro group In the aromatic nucleus was not a prerequisite to the formation of a reasonably stable anhydride* contrary to what might hare been expected, the interaction of the sodium salt of the acid and oxalyl chloride yielded the simple aromatic anhydride and not the mixed anhydride. The decomposition of oxalic acid anhydrides occurs in a manner somewhat analogous to the scission of mono* carboxyllc double anhydrides; the disproportionation being as follows: / 002 / GO As early as 188? It was noted by Behai (15) that formic- acetic anhydride when treated with pyridine evolved carbon monoxide and formed acetic acid* Whitford (1 6) showed that pyridine possessed a marked positive catalytic effect on the decomposition of oxalic acid by acetic anhydride* This may be Interpreted as a catalytic action of pyridine on the decomposition of the mixed oxalic anhydrides, as well as those of other types* 4 In to beli« useful for tbo preparation of simple anhydrides, « study of the utility of tbo double anhydrides for the purposes of ketone synthesis by means of tbo Priede1-crafts reaction bas boon carried out. An examl- nation of tbo reactions of sons unayamtrlosl aromatic anhydride* with benseno In the presence of aluminum chloride has been mute by seavln and Fisher (14). they found that the leetone of loner molecular weight was generally obtained Us the greater quantity or as the sole product. When unaymmetrleal aliphatic anhydrides were employed, Williams and eowerkere (17) showed that the yield of the higher ketone was larger. Studies of the above nature, as well as Investlga- tlons of the course of esterlflcation with mixed anhydrides, have attracted further attention because of the theoretical aspects* It was proposed by Barenl and cewerkers (13) that decomposition of mixed anhydrides by alcohols depends upon the strength of the acids composing the anhydride, i.e., the ester of the stronger acid is obtained In greater quantity or exclusively. Their experimental results were In partial agreement with those of Kahn (19) and Bebal (15). The latter, however, had proposed that the acid with the lower number of carbon atoms was the only one ess te rifled, gerevln (30) later pointed out that a generalisation such as Behai's does not apply to all mixed anhydrides. Data 5 from the esterlfication study of Baronl et. al. and Behai are given In Table X. ? Table I Bsterification Studies of Some Mixed Anhydrides Products Anhydride Ester Acid Benzole-acetic Acetate Benzoic Propionic-acetic _ Acetate Propionic Chloro-acetic--acetic Oh loro-ace tate Acetic Acetate (trace) Aceto-trichlorobutyric Trichlorobutyrate Acetic Acetate(trace} Acetic-formic Formate Acetic As an esterifying agent the mixed anhydrides have found limited use In eases where stronger agents would result in modification or decomposition of the alcohols. An example of this is the preparation of 2-furf uryl~f ormate by Edwards and Beeves (2 1 )* Strong acids produced resins on reacting with furfuryl alcoholj and lack of a suitable an­ hydride or acyl halide of formic acid made the usual methods of ester formation inapplicable, the reaction attempted be­ tween the alkyl halide and the sodium salt of the acid was unsuccessful.