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Organolead Compounds Edmund B Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1932 Organolead compounds Edmund B. Towne Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Towne, Edmund B., "Organolead compounds" (1932). Retrospective Theses and Dissertations. 14733. https://lib.dr.iastate.edu/rtd/14733 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]. BY Signature was redacted for privacy. Signature was redacted for privacy. Signature was redacted for privacy. UMI Number: DP14602 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 DP14602 Copyright 2006 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 Q^XJH i'A,, r ^ T" 6:= & o ACniO??13DC3£S!l1' Th® writer -wislieB to ©xpross hia appreeiatloa to Doe tor Henry G'ilmaii irliose InTalaable advice aad, encouragement haTe ' made tliis work possible. TliB OF H,/JjIG>a.3 FRQi: iJlJ lilCii ORGv;EOL:;. D COlir'OUITDS. A SWUI OF TiD-: R:3I,.iTIVi] L^uilLITIES OF OHG.^IIC fliJ^IG.vLS . o INTaODUCTlON ........ 5 DISCUSSION 01? THl GL3A¥AG:3 IvrB^KOD ..... 10 DiaCUSSlOM 0? RidULTS . • 17 J. i'^Xt « « • Apparatus and Procedure ......... 20 Prepara t ion of Triplienyl-bet a-s tyry 1-163Cid . 21 Cleavage of Triphenyl-beta-styryl-laad Preparation of Triphenyl-ellyl-lead . 27 ^'ittempted Preparation of Diphenyl-allyl-le a . 29 Cleavage of Tripheayl-allyl-lead .... 31 Preparation of But0n-l-ol-4 ....... 36 Preparation of Buten-3-yl Broraide .... ^0 Preparation of Buten-3-yl-magnesium Bromide . 41 CarbonatioEL of Buten-3-yl-maeniesium Broiiide . 42 Preparation of Triphenyl-lbuton-S-ylJ-lead . 45 Cleavage of Triphenyl-(buten-S-yl)-lead . « ft 44 Preparation of Diphenyl-di-biohenyl-lead . 49 Cleavage of Diphenyl-di-biphenyl-lead . 51 iHiRLwiir . , , 55 HE INTHODUCTIOM Uii" 3uLlJBL3 GROUPS IHTQ OHGi^JOL.K.J} C0iiP0u!?Da . , 56 lOTRODUCTIOK 56 .liiXPiliUMSK-Tii 64 Some Organic Complexes of Lead Salts with Diazonium Gouipounds and \iith iaaines .............64 Discussion . ............. 64 Benzcnediazoniura Chloride-Lead Chloride Complez . 66 lieaction with Copper in Acetone 68 Reaction with Copper in /jmoniurn Hydroxide ... 68 «Mr u-ag-.e Heaction with Zinc in iicetone 69 Reaction with liino in Sodium Hydroxide .... 69 p-iolyldiazonium Chloride~3jead Chloride CoiTiplex . 71 Beaction with Copper in iaiimoriium Hydroxide » 72 Heaction with Different IJetals . 73 Benzenediazoniura Chloride-Lead Tetrachloride ... 73 Beaction ivith Copper in Acetone 74 Benzenediazonium Chloride—-Tetraphenyl-lead , , . 75 /.niline-Laad iicetate 3alt 76 Sumary ..................... 77 Some Coupling Heactions of Organoload Ilalides .... 78 Discussion 78 Tri ethyl-lead Broiaide 81 Heaction with iithyl Broraoaoetate and Zinc ... 83 Beaction with lithyl Bromoacetate and SodiuBi . 84 Reaction with Benzene and Aluminum Chloride , . 84 Heaction with Magnesiura . 85 Triethyl-tin Chloride and Magnesium ....... 88 Triphenyl-lead Chloride . ....... 89 % Heaction with iithyl Bromoacetate 89 Beaction ?/ith Ethyl Chloroacetate ....... 90 Heaction with Chlorobenzene and Sodium .... 90 'rriphenyl-lead Broraide . 91 Reaction with ^thyl Bromoacetate 9S The irreparation of Some Syraaetrical and Unsyiariietrical Organoload Compounds ................ 93 Discussion .................... 93 Tetraphenyl-lead .......... .. 99 Triphenyl-^p-anisyl-lead 101 Diethyl-lead Dibroraide 102 S...103 - 5 - A. TkiE CL:;A¥AGA 03* RADIOALS mmmilSMClO. OHGAilOLEAD w A STUDi OF fll!3 iria.lTIYE LABILIIIISS OF OHGiiHIC ^ iCALS IMTliODUGTION Many reactions have been used to determine the relative negativity or Isibllity of organic radicals. Lability or negativity series of radicals based on these various reac­ tions are not always in agreeaent an€ quite often agree only in a general way. fhis is to be expected when w© ecmsider the many factors such as experimental conditions, reagents and the intra-moleeular forces that may inflnence the results obtained by the various methods, ii method based on the preferential cleavage of radicals from nnsyimetrical organometallic compounds is perhaps the most direct and at the sma© tiiae is, in gsffieral,. the raost applicable. The results obtained by this method are apparently the same \fhether unsymaetrical inBrcury, tin or lead coiapoundB are used. However, the nature of the splitting agent has an effect for anomalous results are obtained in the case of the benzyl group when halogens are used es the splitting aigent (1). This particular anoiaaiy does not occur "^hen hydrogen chloride is used and is probably due to substitution or oxidation which il) These results are described in more de.tail with original references under "Discussion of the Cleavage Method". precedes splittiae'. (Th© cleavage of a few iiaSnRa^ and PbR#* ecaapouads •with hydrogen chloride splits off one 3 and oa« B* group when 1 and H®" are of nearly the saiae negativity.) Because of this abnormal behavior of haloe;eiis, the present study of the cleavag© of unsyimetpioal orgaaolead coxapoonds containing unsaturated radicals has been carried out using hydrogen chloride as the splitting agent. Ixeaninatioa of the results of cleavage of orcanie radicals from misyiraaetrical organoiaetallic compounds has shown thet the group or groups reiaoved first are those T/hich are generally considered the most negative or labile. Thus eroiriatic I'adicals are split off before aliphatic radicals. The position that aliphatic unsaturated radicals will occupy in the general lability series (aromatic, aliphatic, unsaturated aliphatic) is not known (2), It m'as pointed out many years ago, however, that the negativity of radicals (hydrocarbon radicals containing other elements as substituents for the most part) was directly depmdent on their degree of unsaturation (3). In a study of the preferential cleavage of some phmyl- thienyl--, phenyl-furyl- and thienyl-furyl-lead compounds, the result of which is published, elsewhere (4), it has been shown (2) Austin, J» Am., Chm. Soc,, 3514 (1931), has Bho^ai that triphenyl-allyl«lead is split bjr hydrogen bromide to give triphenyl-lead bromide. (3) Heinrich, Ber., 668 (1899). (4) Oilman and Towne, Hec. trov. chiM., 51, iiov. (1932). that tbe relative labilit:/ or neeatlTity of tiiess I'adlctils increases in the orfler? phenyl, tlaieiiyl, furyl. It was also pointed out that these facts could be correlated wltii tha increasing degree of aromatlcity ez'ni'bited by the hydrocarbons from which these radicals are derived, that is, benzene, thio- phene and furan. Since any definition or caasideration of aromaticity involves a conception of unsaturated linkages, a nuiaber of unsaturated radicals other than aroaatio have been studied. The present investigation is ooacemcd with the cleavage of SOB® ansymfaetrical lead eoEipouads contcining unsaturated aliphatic radicals in order to determine to what extent an ethylanie double bond and its po-sition with respect to the carbon-lead linkage influences the lability or negativity of a radical* For this purpose lead compounds containing the allyl-, beta-styryl- and (buten-^S-yl)-lead linkage were investigated. Tho splitting of triphonyl-allyl-lead, triphenyl-bota- styryl-^le.ad and trlphenyl-(buten-5-yl}-lead (5) with hydrogen chloride showed that allyl and bata-styryl radicals were re­ moved before phenyl ¥&ile the j>benyl radical is split off before the buten-S-yl radical. (5} The nanes of these ;aixed organolead compounds may be written laore corroctly iflthout hyphens but for the sake of clarity they are used to denote a r.ietal-cerbon linka^'e when follow­ ing the aarae of a radical., fhtis triphenyl»aliyl-lead is usually m'ritteri triphenylallyllead. This anomalous clsairage of the allyl radical v/as not entirely unexpected^ Ilie extreiae lability- of this tjpe of radical is well known, von Bratm and Kohler (6) have pointed out th© labile nature of allyl and ciniiaRijrl radicals in tlieir week linkages to aitrogen, Qxy{xea and the halogens, Pliyslo- locieally, conpomias containing these croups boliave quite differently frcra conpounds containing the penton-4-3'1 (0H3»GHGH3CiisCH3-»} fcroup. 'Bie latter are less toxic end: beliaTe like compounds ?jith aliphatic substituents while allyl and clnnamyl groups increase the toxicity of the corupoBJids, The enhanced activity or lability of groups of the allyl type is deeiionstratefl by the ready coupling of allyl brcialde evideiiced by the difficulty of the Independent preparation of allyliaaenesiuia bromide under oitiUnary coriditions
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