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Relationships Between Some Organosilicon Compounds and Their Carbon Analogs Gerald Emery Dunn Iowa State College

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Relationships Between Some Organosilicon Compounds and Their Carbon Analogs Gerald Emery Dunn Iowa State College Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1951 Relationships between some organosilicon compounds and their carbon analogs Gerald Emery Dunn Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Dunn, Gerald Emery, "Relationships between some organosilicon compounds and their carbon analogs " (1951). Retrospective Theses and Dissertations. 13425. https://lib.dr.iastate.edu/rtd/13425 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 BEL&.TI0I3SHIPS BETV®EI-I SOI® OEGMOSILICOK COltPOUM A® TiiEIR CAEBON AMLOGS by Gerald Emery Dunn A Dlssertatictti Submittsd to the Graduate Faculty in Partial Rilfillment of Th® R®qixir©ment8 for the Degree of DOCTOR OF PHIIXSOPHy likjor SubjeotJ Organic Chemistry Approvedi Signature was redacted for privacy. Signature was redacted for privacy. Head of l&jor Department Signature was redacted for privacy. Dean of Graduate College Iowa State College 1951 UMI Number: DP12676 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 DP12676 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 qD^/:I^.5C D 5 J. =5^ r ACKUamEDGlfEHTS IPha author wishes to oxpreas his appreciation to Dr, Henry Gilmn for the adTioe and enoouragement proffered during the course of this in- wstigation. Thanks are also due to B.I, Du Pont de Kemours and Co. for a Fellow­ ship •#iioh made part of the work possible, and to Dr. George S, Haismond for raeiE^ helpful and stixnulating discussions. T1f3 9 iii. TABLE OP COmHTS IHTRCffluCTION 1 HISTORICAL 3 F^sioal Propertiss 4 Chsmioal Properties * 14 Silioon-*os.rbon single bonds 14 Silioon**o&2%on double bonds .............................. 18 Silioon-*i:^dr(^en bonds 21 Silicoti*8iliaon bonds 26 Silicon'-silioon double bonds 29 SiliQon«h&l(^en bonds 30 Silioon*o3Qrg@n bonds 44 Silioon<^itrogen bonds .....«•• 50 Bonds betwwen silicon and various other elenwnts 53 Iffeot of silioon on adjacent bonds 53 H^siologioal Properties 58 EKFERimmAL 60 Cleairage of Organosilicon Compounds by Organome-tellio Beagents 60 l^iphe^lsiXa&ol 60 /Sodium tripher^Isilanolate 6S Attempted prepamtion of triphei^lsilylperoxide 62 Triph©3::^l8ilanol, absolute ethsmol, and sine chloride ..*• 64 Atte!?^ted preparation of tetraphenylsilane from tri- pheiiylsilanol 65 Cleavage of triphenylsilanol by n-butyllithium wi-tti Qopper-bronse 66 Gleavs^e of triphei^lsilanol by n-butyllithium w^-thout oopper^bronxe 68 Attempted oleamge of triphenylsilanol by n-butylmgnesium brc«dde 70 Attempted cleamg© of triphenylsilanol by p-tolyllithium.. 70 Uexaphenyldisiloxane 71 ^i*p«tolylsilanol 71 Cleavage of tri*p»to3ylsilanol by a»bu'tyllithium ......... 71 Atteii?>tod cleaYage of tri-jg-tolylsTlanol by pher^lliiiiittm# 71 Bi^exiyl-f-tolylsilanol ii.....• 72 Attes^ted preparation of tri-p^&nisylsilanol 72 iv. Trl«l«*naphthy Ichloros ilane 74 i/fri-l«mph.thylsilanol 74 ^ri'-l^mphthylsiXiiinolt sodliim salt ••••••••*•«••••*•.«*• 75 ^^.!&i«»p»xe}:^XallanoX 75 Atteaqpted prepamtioa of tri*^>«3tenjrlohloro8ilaii® 78 Cleamge of tri-p-xenylsilanol by pheE^llithiiaa 79 Atteiapted preparation of h«a»-p»x©nyldi3ilo3Ean0 79 Attempted ol«amg® of tetrapheaylsilen© by n»buiyl- lithlusi 80 /Attempted olsamge of tBtra«jg_-tolyl8ilaD,0 by j^butyl- ^ lithium «•««•»........t****************'************ @0 /friinsiS^ylplisr^lsilans 81 Att0J!^tod oleavags of triuietiqrlphenylsilarie by n-bulyl- litliium ..*•••• 82 Attenijted cleavago of tri]^oiiyl«n«bu1syl8ilane by , 82 /frijM^yl«l»naphthyIsilajia 83 Attenffted cleamgo 9f trime-ttorl-l-aaphthylsilans by a^butyllithixsa •••.•*•«**.86 PreparatTon and Reaotions of Hexaaryldisilanes .***«•***«.•• 87 .H«3»ph«iyldisilftne 87 Attiassptod reaebion between triphenylsilan® and sodium metal 88 Hempheti^ldisiXane from triphenylsiXane 8@ Hea^ioa between triphesgrlsilane and seleniwm dioxide », 90 Attested reaction between tripheHgrlsilane and ohloranll 90 Atteuipted cleave of hexaphenyldisilane by pheisyl-' lit^itan 91 Attempted cleavage of hexpheayldisilane by n*butyl- lit^iiim 91 6lBe9ca«^«a»i:iyldi8ilane 92 Attempted reaction of hexa-p-xenyldisilane with osgrgen and iodine 9S Preparatioa add Xlltwiriolet Absorption Spectra of I^DimettQrlasiinophenylsilioon Compounds 94 /Bis»Tp*diffiethylajBinophenyl)-6ilanediol .••**«..••t*.**.* 94 ^ris*(p-diraet!^lamnophenyl)-8ilanol .«•••*.t«*.•«••«••• 95 .?ftris«.(p->dimetligrlaminophenyl)*<jhlorosilan® 95 Attei5^t«d preps.ration of hexaki8*(p^imeti^lainijaephenyl)» dieiloxane 96 fri8'*>(p<i*dimetbylaminophei3yl)*8ilane 97 / fetmkia-*(p*diro8ti:^ylaminophejayl)*-8ilane 98 i^traki8<>»(£;<"diai®'t45ylaiainophenyl)-8ilan© Tetraiaethiodide. 99 , Pi|henyl-£;»dime'ti5ylaiaiaophenylsilanol 100 Bi^enyl'>p'>diBiethylaminophenyloarbinol 100 Preparation and Relative Eatos of i^drolysis of DiphanylCsub- ^ltuted«phex^l)sil&ne8 101 mphe)n^l(subeti'iRited-phenyl)ohlorosilaixe9 101 Diph«i^l--g^imetl3ylaminophenylohlorosilane 101 Dij^tnyl(suitstitut9d>phe]:^l)silanes 103 ^lph«myl<^-diin9thylaminophenylsilane lOS Relatl'TO artites of hydrolysis of diphei^l(substituted- phas^l)silanes 103 Msohaaism of %drolysis of Triarylsilansa 106 Effect of water ooncentration on •Ubie rate of hydrolysia of triarylsilanes in piperidine 106 Bffeot of piperidine ooncentration on the rate of %droly«i8 of trl-arylsilanes in methyloellosolire 110 Effeet of -snater concentration on the rate of I^drolys is of . triarylsilanes in methyloellosolve 111 ^iphez^ldeuterosilane 112 Belative rates of hydarotysis of triphenylsilane and triphenyldeuterosilane in wet piperidine US Preparaviion of TriphenylalkoxyBilanes from Tripher^ylsilane 113 Prepamtion of triphengrlaJJcossysilanes from triphenyl- silane* alcohol and piperidine 113 ^riphenyl*{2--meth03!y)*e#x03tysilane IIS Tri«l»naphthyl8ilanol-piperidine complex 116 DISCUSSIOH 118 Clea-roge of Organ<Miilicon Confounds by Organometallio Reagents 118 Preparation and Headtions of Hexaazyldisilanes 129 Preparation and UltraTiolet Absorption Spectra of £-I>imethyl- aiaino^ei^lsilioon Cotnpounds 131 Preparatiifei and Helativo Hates of %drolysis of Dipher5rl(sub- stituted'-phenyl)ailane8 13S Meehanism of %drolysis of Triaxylsilanes 140 Preparation of friphenylalkoxysilanes from Triphergrlsilane .«• 149 SUMMAM 151 BIBLIOGEiPffif OF GEIEEAI. BEIEHEMCES TO ORGAHOSILICOIf CHEMISTK? .... 153 vi. LIS I OP TABLES Sssi TABIE I* Liquid Bange of Organoailieon Cojspoands *»..***••...• 11 TABLE II. Physioal Properties of Silioon-^iAlogen and Carborf hftlc^en Bonds 21 lABIS III« Preparation of Monosubstituted Trlarylohlorosilanes from Di^^er^ldiehlorosilano 102 TABLE !?• Preparation of Monoaubetituted friary Is i lanes •,.•••• 104 TABUE V. %drolysi8 of Diphenyl-ja-tolylsilane in Piperidine Containing 0»96 mole of Tfater per Liter at 38.8® 107 TABLE VI, Hydrolysis of Triarylsilanes in Piperidine Contain­ ing 0»96 Mole of Water per Liter at S8»8° •.«.**••••• 109 TABLE VII, Hydrolysis of Monosubstituted Trlarylsilanes in Piperidine Containing 0.96 liole of Water per Liter at 88,8° 109 TABIE VIII, %drolysi8 of Diphenyl-jg«^olyl8ilane in Tiet Piper­ idine at 58,8° 110 tabu; IX, Bate of %drolysis of 0,020 M Diphei^l-jh-ohloro- phej^lsilane in Methyloellos^lve Containing 0,219 lole per Liter of Water at 58,8° Ill TABLE X, Bate of %drolyBis of 0,020 M Diphenyl-^gi-'ohlort)- I^e^lsilaae in Met^jyloellos^l'ro Containing 0.020 Ifole per Liter of Piperidine at 58.8° 112 TABIE XI, Preparation of TriphTOylalkoaysilanes from Tri- phenylsilane 116 TABIS: XII. Seaotion of n-^Bu-tyllithium with OrganoBietallio Compounds 120 TABIE XIII, cT-Constant for the _^Dijnethylamino Group 159 vii LIST OF FIGURES Figur® 1. Relationship betwaen the boiliug points (760 Em) of allioon and oarbon amloge 6 Figure Z» Relationship between the doneities of siliocaa and oarbon analogs 7 Figure 5. Relationship between -tfce refraotive indioes of silicon and oarbon analogs 10 Figure 4* Helationship between the melting points of silicon and <^rbon analogs IS Figure 5» Ifydrolysis of diphenyl-m-tolylsilane in piperidine containing 0.96 mole of mter per liter at 38.8° ... 108 Figure 6. Bolative rates of hydrolysis of triphenylsilane and triphexiyldeuterosilane Ili Figure 7. Belationahip between log (k x 10^) and •ioaa for the hydro3ysiB of dipheigrlCsubstituted-pheisylTailaneB in piperidine containing 0.96 mole of water per liter at 38.3° 137 IHTROmJCTION In 1865 FVi«d«l and Crafts synthesinod -an® first
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