Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1942 Organothallium compounds Royal Kilburn Abbott rJ . Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Abbott, Royal Kilburn Jr., "Organothallium compounds " (1942). Retrospective Theses and Dissertations. 13556. https://lib.dr.iastate.edu/rtd/13556 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. UMI ORG^aTHALLIUM C(MPOOKDS J? by Royal Kilburn Abbott, St, A thesis Submitted to tJie Graduate Faculty for the ]>egree of DOCT€E OF PHILOSOPHT Major Subject Organic Clieaistry Approved; Signature was redacted for privacy. In CJaiari^ of Major Work Signature was redacted for privacy. ladT ^f'llkjor'^^^^^at Signature was redacted for privacy. Iowa state College 1942 UMI Number: DP12545 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform DP12545 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 - ii - ACKNOWLEDGMEHT flid author wishes to express his appreciation to Dr. Henry Gilman for his encouragement, criticism, and adTioe giTen throughout this research. T7 € 11 - ill - TABLE OF Q(mEmS ACIKOWIJDGMEHT ii IHTRG©T3DTI(li....- 1 HiSf 5 Otmpounds of tlie R,TI. 5 Ctmpoim&s of the Type E,T1.. 31 Gcmpoimds of the Type RT1«........ 39 Compoimds of the Type 4# Coapoimds of the Type BT1X«........................ Ocmpouads of the Type R,Tli;..@S ^thods of Synthesis and' Oheaioal Properties BZ Physical Properties.102 Physiological Properties of Organothallitua Gcsapounds. 119 Analyticsd ProQedurea. 1^ 'QualitatiTe Analysis........................ 128 Qtiantitatire Analysis....................... 1S9 S\uaffiax7 131 leferenoes 132 miaiMESTAL. 141 The Preparation of an Anhydrous Ither Solution of Thallium Tri<9hloride.... 142 The Preparaticm of Di^o-tolylthalliuoi Bromide 143 - IT - 1?iie Attempted Preparation of Dl-o-tolylthallim Sulfamate 143 fhe Preparation of Di-S-(4-sulfotolttene5thalliuffi Su3i'ate. 144 The Preparation of Thallous 2-Bromotoluene-4- sulf onate 144 fhe Preparation of Thalloua 2-Broaotoluene-4- sulfonate by an Authentic Beaetion 145 The il^eparation of Di-a-nitrophenylthalliiM Kitrate by Direct Nitration................ 146 The Preparation of Di-m-nitrophenylthaHium Nitrate frcxa m-Kitrophenylborie Acid and Thallium Trichloride 148 The Preparation of Thallous Hydroxide 149 Preparation of Thallous Sthoxide 151 The Preparaticm of Diethylthallium Ithoxide {1} WTCm Thallous Ithoxide. 152 (XI) From Sodium Ithoxide. 153 The Preparation of Di-o-hydroxyphenylthallium Bromide. 153 The Preparation of DimethyIthallium Saccharide.... 154 The Preparation of Diethylthallium Saccharide 155 The Preparation of Diphenylthallitim Saccharide.... 156 The Preparation of Diphenylthallium Sulfanilate... 157 Note on the Solubilities of Some Com­ pounds in Pyridine 158 - T - The Preparation of Di-2-pyridylthallium Ghlorid©. * 158 The Preparation of Di-2-pyridylthalliTim lactate 159 Th© Attempted Roarrangement of th© Pyridine Ccffliploc of Thalliim Triehlorid© to an Organothallium Compound. 160 Th© Rceparation of the Thallium Tribroaide Oompleis of Pyridin©........................ 161 Th© Preparation of th© Thallium Trichlorid© Compl@3C of 2-Bramopyridin9« 162 Th© Preparation of th© Thalliiim Trichlorid© Ccmplex of 2-Aminopyridine 162 Th© Preparation of th© Thalliim Trichlorid© Complex of Cysteine Hydroehlorid© 163 The Preparation at o-Braaaodimethylaniline 163 The Preparation of Di-o-dimethylamiaophenyl- thallium Bromide. 165 Th© Beaotion hdtwe©n |i-Dim©thylaminophenyllithliiM and Thalllim Triohloride 166 13i© Preparation of £-Din»thylamiaopheaylborie Aeid 167 The Preparaticm of £-Dimethylaminophenylaeretiry Chloride.. 1£^ The Beaetion b«tw©©n £-Dim©thylaainoph©nylborie Acid and Thallium Triohloride 168 - vl - fhe Pr®parati<m of Dl-^-dimetfaylamlaopliesyl- thallltm Bromide*....... 169 The Preparation of Di-£-anisylthalliim Bromide.... IfO fhe Preparation of Di-o-anisyltliallium Bromide.... 171 The AtteasJted Coupling of £-Nitrobenzenediazoniim Chloride with Di-£-difflethylamiaoph®nyl- thallium Bromide. 172 The Attanpted Coupling of £-Hitrobenz6nediazonium Chloride with Di-£-anlaylthalllum Bromide.. 173 The Attempted Coupling of £-Nitr©benzenedia3S€aiiua Chloride with Di-o-anisylthallium Bromide.* 174 The Atteiypted Coupling of £"-Nitroben2enediazonium Chloride with Dt-£-ani8ylthalH^ Breoide in the Presence of Ithyl Aoetate....•••.••• 174 The Attex^ted Coupling of £-Hitrobenzenediazonium Chloride with Di-o-aaiaylthallium Bromide in the Presence of Ithyl Aeetate175 The Attempted Coupling of £-iritrobensienediazonium Chloride with Di-£-anisylthallium Bromide in the Presence of Pyridine 175 The Beaetion between Methylmgnesium Chloride and Thallous Sulfate.... 176 f^e Reaction between CX-Kaphthyllithium aM Thallous Sulfate 177 The Action of Dia2somethane on Thallium Trichloride 177 - vii - fjie Preparation of Tliallous 2,4,6-Trinitro- benzoate. 178 Tlie Eeactioa betweea 2,4,6-frinitrobeiizoi0 Aoifl and Two SqmiTaleats of Thallous Hydroxide.. 179 fjie Aotioa of Tfaallous Hydroxide on 1,3,5- f riaitrobenzene 180 Deoarboxylatioa of Thallous 8,4,6- friaitrobeazoate la Pyridiae 181 fli© I^eparatioa of Thallous Oxalate 1^ file Preparatioa of ^-lodopheaylmagaesiusi IMlde... 184 Tim Halogea-Metal latereoaTersioa of jgi-Iodoplieaol 1^ Preparatioa of Thallous HapMtMleae-^ -sul- foaate,.... 186 Tim Preparatioa of Thallous Beazeaeaulfoaate•.•... 186 ti^e Preparatioa of Thalloue Lamrylsalfoaate....... 187 fhM Preparatioa of Tiiallous ^-Toltieaesmlfiaate.... 187 Ths Preparatioa of Lead o-Tolueaesmlfoaate........ 188 TMe Preparatioa of Moaotballous Pheaylpliospiioaate. 188 The Preparatioa of Dithallous Pbeaylpbospboaate... 189 The i^eparatioa of Thallous Mpheaylphospboaate•.. 190 fa© Preparatioa of the Tballous Salt of Nitroiaetiiaae. 191 fhe Preparatioa of Tballous HetiiyajBereaptide...... 192 file Preparatioa of Thallous a-Batylsaeroaptide..... 193 ®ie Preparatioa of fballous UtiiopiieaQlate.......... 193 - Tili - flis Preparatioa of Thallous jt-JThiosresolate........ 193 Th© Preparation of Thallous Thio- -naphtholate.. 19S The Attempted Preparation of Thallous AHylarsonate. 194 The Preparation of Thallium Diohloride £-Tolueaesulfinate (I) ?rom Sodium £*Toluenesttlfinate......... 19S (H) ?rom £-Toluenesulfinio Aoid.19§ The Preparation of Thallous Terephthalate. 190 The Aotioa of Thallous Formate oa Acetone Sodium Bisulfite, 196 The ReooTery of Thallium. 197 BISC^SICH or BSStJIlTS 199 smmr sis INTRODUOTION Althougli the first or^tnothalliua eompound,, diethyl- gA thallium chloride, was prepared by Hansen in 18?0, only nine years after the discovery of the elesient thallium by Crookes,®^ there is to this date no complete surrey of the organic chemistry of thallium or of organothallium chemistry, in a a^re restricted sense. Metallic hydrides and carbides may in a sense be regarded as or^uiometallic compounds: that is, they may be considered as first members of a series in which the hydrogen or carbon atoms may be replaced by methyl, ethyl, phenyl or other groups to produce what is more generally considered to be an organo- metallic compound. Ifhallium hydride has never been isolated, but its existence can be demonstrated speotrographically when an arc is caused to pass between thallium electrodes in an atmosphere of hydrogen.®® From the spectroscopic data the entropy of the gaseous diatomic hydride has been craoputed, and the thallium-hydrogen bond distance calculated to be 1.870 A. Thallium in the molten state does not dissolve any appreciable 114 amount of carbon, nor does it form a carbide. There is no record in the literature of a thallim carbonyl, or of a thallium acetylide. An amoniacal thallous salt solution does not yield a precipitate with acetylene, as do copper and silver. Thallium in this and in many other respects resembles the alkali metals. As a soft, low-melting, malleable metal, thalliiim ia its elementary form probably most resembles lead. In spite of its plae© in the third group of the periodic table, its ocaamon valence is one, and in many of its properties it resembles the alkali aetals, especially potassium. A long series of thalloua and potassiiia salts crystallizes in isomorphous systems. fhallous hydroxide and carbonate are strong bases and readily soluble ia water, in both of which respects they resemble the alkali metals. In the solubility of its fluoride, and insolu­