University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1975 THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES MARIS BUZA Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation BUZA, MARIS, "THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES" (1975). Doctoral Dissertations. 1089. https://scholars.unh.edu/dissertation/1089 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]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. 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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 I 75-23,390 BUZA, Maris, 1937- THE PREPARATION AND REACTIONS OF 3 ,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES. t University of New Hampshire, Ph.D., 1975 Chemistry, organic Xerox University Microfilms f Ann Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. THE PREPARATION AND REACTIONS OF 3,3-DISUBSTITUTED THIETANES AND THEIR DERIVATIVES by MARIS BUZA B.A. , Rutgers, The State University, 1963 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry June, 1975 This thesis has been examined and approved. Thesis director, Kenneth K. Andersen Professor of Chemistry / Albert F. Daggett, Professor of Chemistry C7&4a £ QrYUZ^ Paul R. Jones, Professor of Chemistry j/lr..,4-----:- ^ .(//<>----------------- Gloria G. Lyle, Professor of Chemistry Charles E. Wyman, Assistant Professor of Chemical Engineering ir,m5 Date This thesis is dedicated to my parents. ACKNOWLEDGEMENT The author wishes to express his most sincere appreciation to Dr. Kenneth K. Andersen whose guidance, help and encouragement led to the completion of this work. Thanks are also extended to all of the people of this Department and others who have been so helpful during these years, in particular to Dr. Paul R. Jones, Dr. Gloria G. Lyle, Dr. J. John Uebel, Indulis Gleske and Ms. Anne Kohl, among many others too numerous to mention. The author is very grateful for the financial support from the National Science Foundation and the Department, without which this work would have been impossible. TABLE OF CONTENTS LIST OF TABLES.................................................... xi LIST OF FIGURES.................................................xiii ABSTRACT.......................................................... xiv INTRODUCTION........................................................ 1 HISTORICAL...........................................................3 RESULTS AND DISCUSSION................... 15 EXPERIMENTAL.......................................................92 Instrumentation............................................. 92 Materials.....................................................92 I. Preparation of Propane-1, 3-diols.......................... 93 Preparation of 2-Carboalkoxy-3-methyl-3-phenyloxi- ranes (7_4) by the Darzene Condensation. Method 1................................................93 Method 2................................................93 Preparation of Hydratropaldehyde........................ 94 Preparation of 2-Methyl-2-phenylpropane-l,3-diol (75) by the Tollens Condensation...................95 Preparation of Diethyl Methylphenylmalonate...........96 Reduction of Diethyl Methylphenylmalonate..............96 Preparation of 2-Phenylpropane-l, 3-diol (7_6) by the Reduction of Diethyl Phenylmalonate............... 97 Preparation of 2-Carboalkoxy-3-p-bromophenyl-3- methyloxiranes (7_7) by the Darzens Condensation...........................................98 Preparation of p-Bromohydratropaldehyde (7_8)........... 99 Preparation of 2-p-Bromophenyl-2-methylpropane-l,3- diol (2J7) by the Tollens Condensation........... 100 Preparation of Dialkyl Esters of Isopropylphenyl- malonic Acid..........................................101 v Preparation of 2-Phenyl-2-(2-propyl)-propane-1,3- diol (2_6) by the Reduction of the Dialkyl Esters of Isopropylphenylmalonate Acid.......... 103 Preparation of 2-Methyl-2-nitropropane-l,3-diol (79 ) by the Tollens Condensation..................104 Preparation of 3-Cyclohexene-l,1-dimethanol (80) by the Tollens Condensation........................105 Preparation of Cyclohexane-1,1-dimethanol (8_1) by Reduction of 3-Cyclohexene-l,1-dimethanol (80)................................................... 105 Preparation of Isopropyl Chloroacetate................ 106 The Preparation of ,l-Oxa-2-carboisopropoxy-4- methylspiro [2 . 5] octanes (8_2) by the Darzens Condensation..........................................106 Preparation of 2-Methylcyclohexane-l-carboxalde- hydes.................................................. 107 Preparation of 2-Methylcyclohexane-l,1-dimethanol (83) by the Tollens Condensation..................108 Preparation of l-Oxa-2-carboalkoxy-5-methylspiro- [2. 5] octanes (8_4) by the Darzens Condensation.. 109 Preparation of 3-Methylcyclohexane-l-carboxaldehyde. Method 1 .............................................. 109 Method 2 .............................................. 110 Method 3.............................................. 110 Preparation of 3-Methylcyclohexane-l-dimethanol (85) by the Tollens Condensation.................Ill The Preparation of l-Oxa-2-carboisopropoxy-6- methylspiro [2 . 4] octanes (8_6) by the Darzens Condensation..........................................112 Preparation of 4-Methylcyclohexane-l-carboxalde- hyde................................................... 112 Preparation of 4-Methylcyclohexane-l,1-dimethanol (87 ) by the Tollens Condensation.................113 General Procedure for the Preparation of Dibenzene- sulfonate Esters of Propane-1, 3-diols.............117 Dibenzenesulfonate of 2-Methyl-2-phenylpropane- 1,3-diol 117 Dibenzenesulfonate of 2-Phenylpropane-l,3-diol.......118 Dibenzenesulfonate of 2-(p-Bromopheny1)-2-methyl- propane-1,3-diol.....................................119 vi Dibenzenesulfonate of 2-Phenyl-2-(2-propyl)- propane-1, 3-diol.....................................119 Dibenzenesulfonate of Butane-1, 3-diol................ 120 Dibenzenesulfonate of 2-Methyl-2-nitropropane- 1,3-diol 120 Dibenzenesulfonate of 3-Cyclohexene-l,1- dimethanol............................................121 Dibenzenesulfonate of Cyclohexane-1,1-dimethanol.... 122 Dibenzenesulfonate of 2-Methylcyclohexane-l,1- dimethanol................ ..........................122 Dibenzenesulfonate of 3-Methylcyclohexane-l,1- dimethanol............................................123 Dibenzenesulfonate of 4-Methylcyclohexane-l,1- dimethanol............................................123 Preparation of 3-Methyl-3-phenylthietane (7_) . Preparation..1 ....................................... 130 Preparation..2 ....................................... 132 Preparation of 3-Methy1-3-phenylthietane-l,1- dioxide (3_1) . General Method for Preparation of Sulfones...........................................134 Preparation of 3 - (p-Bromophenyl)-3-methylthietane (9)...........7 ........................................135 Preparation of 3 - (p-Bromophenyl)-3-methylthietane- 1,1-dioxide {32) .....................................136 Preparation of 2-Methylthietane (1JU...................137 Preparation of 3-Phenyl-3-(2-propyl)-thietane (10). Preparation 1