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B* Hydrochloric Acid And. Perchloric Acid 77 University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Fall 1964 KINETICS AND MECHANISM OF THE PROTONOLYSIS OF CERTAIN ALLYLTINS JOSEPH ANTHONY VERDONE Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation VERDONE, JOSEPH ANTHONY, "KINETICS AND MECHANISM OF THE PROTONOLYSIS OF CERTAIN ALLYLTINS" (1964). Doctoral Dissertations. 795. https://scholars.unh.edu/dissertation/795 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. KINETICS AND MECHANISM OF THE PROTONOLYSIS OP CERTAIN ALLYLTINS BY JOSEPH ANTHONY VERDONE B.S., Lebanon Valley College, 1958 A THESIS Submitted to tbe University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry November 1965 This thesis has been examined and approved. / 'u f * t 7 1 - ' y ■'‘'I'-- .r / v. ' A 'r J x r H ' ^ - 1 Xs\ + \uAj*- ( 3 z c c £ £ ? . ^ I T L A A (Date) ACKNOWLEDGEMENTS The author wishes to thank Dr. Henry G. Kuivila for his guidance and patience throughout the course of this work. Financial support from the Air Force Office of Scientific Research for part of this work is gratefully acknowledged. iii TABLE OP CONTENTS Page LIST OP TABLES............................. vi LIST OP F I GURES .................... .... viii I. INTRODUCTION ............................ 1 II. RESULTS AND DISCUSSION. • 6 1. Preliminary Investigations. 6 a. Conductimetrie Method for Following Rate of Cleavage. • • 6 b. Selection of Substrate and Acid • 7 c* Spectrophotometrie Method and Selection of Solvent . • • • 7 d. Products of Cleavage .... 8 2* Reaction of Allyltributyltin and Hydrochloric Acid . • • • . 9 a. Kinetic Treatment - Spectrophotometric Method ........ 9 b. Rates of Cleavage in Anhydrous Methanol ....... 12 3. Allyltrimethyltin Cleavage. 17 a. Rates of Hydrochloric Acid Cleavage in Anhydrous Methanol «... 17 b. Effect of Added Salts - Anhydrous Methanol Solvent ..... 20 c. Effect of Trace Amounts of Metal Ions 22 d. Effect of Vater ••«... 22 e. Rate of Cleavage by Hydrochloric Acid in 4.05# VatexS-Methanol • . • • 25 4. Cleavage of cis and trana- y -methyl- allyltrimethyliin 58 a. Objective of the Experiment . * • 58 b. Synthesis of-Methylallyltrimethyltin Isomers ........ 59 c. Structure Assignment of -Methyl­ allyl trimethyltin Isomers • • • • 41 d. Interconversion ofY-methylallyl- trimethyltin Isomers • • • • • 52 e. Olefin Products of Cleavage • • • 55 f. Kinetics of HC1 Cleavage in 4% Vater-Methanol. ...... 56 iv TABLE OF CONTENTS (CONTINUED) Page 5* Kinetics of Cleavage of Other Substrates* 58 a* Rate, of Cleavage of Allyltriphenyltin • • • • • 58 b* Rate of Cleavage of Y-Methylallyltriphenyltin • • • 59 c* Rate of Cleavage of $ -Methylallyltrimethyltin • • • 61 6* Mechanism of the Cleavage Reaction • • 62 a* Nature of the Transition State * • 62 b* Effect of Vater • ••••• 64 c* Effect of Inert Salt* * • • • 66 d. Effect of Added Chloride Ion* * * 66 e« Reactivities of the Various Substrates *•••••• 69 III* EXPERIMENTAL.................................. 74 1* Materials «••«•••• 74 a* Organotin Substrates* • • • * 74 b* Hydrochloric Acid and. Perchloric Acid 77 c* Salts* •••*••»• 77 d* Solvents •••••••78 2* Kinetic Procedure •••••• 78 a* Aliquot Method •••••• 78 b* Direct Method *••••• 80 3* Glassware Cleaning Procedure* • • • 80 4* Hydroboration ,«..**. 82 5. Products of Cleavage*. * • • • • 83 a* Allyltributyltin and Hydrochloric Acid* *••••••• 83 b* Y -Methylallyltrimethyltin and Hydrochloric Acid • • • • • 84 IV* T A B L E S ......................................86 1* Key to Tables of Kinetics •- • • • 86 2* Tables of Data • •••*•• 89 V* APPENDIX: CONDUCTIMETRIC TECHNIQUE FOR MEASURING RATES OF CLEAVAGE.................. 163 B I B L I O G R A P H Y * * * 171 v LIST OF TABLES Table Page I Rate of Cleavage of Allyltributyltin by HC1 in Anhydrous Methanol* • • • • • 16 II Rate of Cleavage of Allyltrimethyltin by HC1 in Anhydrous Methanol* • • • • • 18 III Rate of Cleavage of Allyltrimethyltin by HC1 in Anhydrous Methanol* • • « • • 19 IV Effect of Added Salt on the Rate of Allyltrimethyltin Cleavage in Anhydrous Methanol •*•••*•••• 21 V Effect of Added Water on Rate of Cleavage of Allyltrimethyltin. • • • 24 VI Rate of Allyltrimethyltin Cleavage in 4*05# Water-Methanol «•••••• 26 VII Rate of Allyltrimethyltin Cleavage in 4-.05# Water-Methanol Alternate Procedure* * 27 VIII The Effect of Addition of NaClO^ on the Rate of Cleavage *•*•••• 29 IX Rates of Allyltrimethyltin Cleavage in the Presence of 0*0250 M NaCl* • • • • 52 X Rates of Allyltrimethyltin Cleavage in the Presence of 0*0500 M NaCl. • • • • 55 XI Change in Rate of Allyltrimethyltin Cleavage with Change in Chloride Concentration 54 XII Rate of Cleavage of Allyltrimethyltin by Perchloric Acid in 4*05# Water-Methanol • • 56 X U I T '-Methylallyltrimethyltin Isomer Distribution ••••••••• 40 XIV N.M.R* Spectra •••••••• 4-5 XV Infra-Red Spectra* ••••••• 46 XVI Reactivity of nr"-Methylallyltrimethyltin Isomers Toward Disiamylborane* * * * * 50 vi i LIST OP TABLES (CONTINUED) Table Page XVII Products of Cleavage of els and trans V-me thylallyltrime thylt in. • • • • » 56 x v m Rate of Cleavage of trans Isoner • « « • 57 XIX Rate of Cleavage of cis Isomer « • « • 58 XX Rate of Cleavage of Allyltriphenyltin, • • 59 XXI Rate of Cleavage of T -methylallyltriphenyltin 61 XXII Rate of Cleavage of -6 -methylallyltrinethyItin 62 XXIII Reactivities of the Various Substrates * • 70 XXIV Effect of Washing Procedure on the Observed Rate Constant ••»••• 81 XXV Comparison of Spectrophotometric with Conductimetric Rate Data • • « • • « 166 vii LIST OF FIGURES Second Order Rate Plot Obtained by the Aliquot Method Tor the Protonolysis of Allyltrimethyltin in 4j& Water-Methanol* Run 110* *.♦...... Pseudo-First Order Rate Plot Obtained by the Direct Method for the Protonolysis of Allyltrimethyltin in 4$ Water-Methanol. Run 198..................................... Second Order Rate Plot Obtained by the Direct Method for the Protonolysis of S-Methylallyltrimethyltin in 4# Water- Methanol ^ Run 225 • ••*••• Dependence of Second Order Rate Constant on the Water Content of the Methanolic Solvent* « • « • • . * * Dependence of the Observed Rate Constant on Initial Hydrochloric Acid Concentration in the Presence of 0*0250 M NaCl * • • Pseudo-First Order Rate Plot Obtained by the Direct Method for the Protonolysis of Allyltriphenyltin in 4# Water-Methanol, Linear to 400 Reaction* Run 213 • « • Comparison of Spectrophotometric and Conductimetrie Techniques. Second Order Rate Plot for the Protonolysis of Allyltrimethyltin in 4# Water-Methanol* Run 141* «••••*••• viii SECTION I INTRODUCTION Electrophilic substitution which involves cleavage of a carbon-metal bond has commanded increasing attention in recent years. The Group IV metals have been examined in particular detail; the general reactions of the tetra- substituted Group IV metals with two commonly employed elec- trophiles, halogen and halogen acid, may be expressed as: (1) R4 M + HX --- » R^MX + RH (2) R^M + X2 - * R^MX + RX where R ■ alkyl or aryl 1 2 M « silicon , germanium, tin, or lead Extensive investigation of the mechanism of this re­ action where an aryl-metal bond is cleaved has been reported by Eaborn and coworkers • The rates of cleavage of substi­ tuted arylgermanium, -silicon, and -tin derivatives by both acids and halogens have been measured, and substituent ef­ fects discussed in detail. Aryl-tin cleavage proceeds most readily, and is found to be much less sensitive to the re­ sonance effects of substituents than either aryl-silicon or aryl-germanium cleavage. The second order rate constant for the cleavage of phenyltrimethyltin by perchloric acid in 4# water-ethanol at 5 0 ° is found to be 5*2 x IQ”*1, M*"^sec7^ 1 2 Organomercurials, although not members of the Group IV series, display similar behavior when subjected to elec- lL trophilic attack, Dessy and coworkers have measured the rates of cleavage of certain dialkyl mercury compounds by acids in water—dioxane solvent, A four-center mechanism, which features attack by molecular acid or acid existing as ion pairs on the mercury—carbon S bond, was proposed. Water added to the solvent system was found to decrease the rate, and chloride ion found to increase the rate markedly al­ though ionic strength effects were found to be small, 5 In a more recent paper, Dessy and Paulik-' have fo­ cused attention on the "assistor" role of chloride ion. The acid decomposition of certain carbomethoxymercurials in di­ methyl sulfoxide in the presence of chloride ion gave an empirical rate expression first order in organomercurial, in acid, and in chloride ion. The stoichemetric expression may be written as: CF*COOH P (5) ClHgCOOCH, + 3C1" 2--» HgCly, + CO + CH*OH p DMSO p Two chloride ions are involved in a post-rate determining step. The role of chloride is envisioned as a coordination of chloride ion with the mercury atom in a step which pre­ cedes the attack of acid, which is regarded as the rate de­ termining step, Nucleophilic assistance of this kind, Dessy states, will be observable whenever the solvent is relatively ineffective both as a nucleophile and
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