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Some Organometallic Compounds Containing Reactive Functional Groups Burt Frederick Hofferth Iowa State College

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Some Organometallic Compounds Containing Reactive Functional Groups Burt Frederick Hofferth Iowa State College Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1950 Some organometallic compounds containing reactive functional groups Burt Frederick Hofferth Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Hofferth, Burt Frederick, "Some organometallic compounds containing reactive functional groups " (1950). Retrospective Theses and Dissertations. 13966. https://lib.dr.iastate.edu/rtd/13966 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]. INFORMATION TO USERS This manuscript has been reproduced from the microfiim master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. 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 bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI 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. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. ProQuest Information and Learning 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 800-521-0000 NOTE TO USERS This reproduction is tiie best copy available. UMI* SOME ORGANOMETALLIC COMPOUNDS CONTAINING REACTIVE FUNCTIONAL GROUPS Burt Frederick Hofferth A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major SubjectJ Organic Chemistry Approvedt Signature was redacted for privacy. In Charge/of Major Work Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Dean of/ Graduat^College Iowa State College 1950 UMI Number: DP12759 UMI® UMI Microform DP12759 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'Vll H C:' 75"S ACKNOWLEDGMENT The author wishes to express his gratitude to Dr. Henry Oilman for his interest, enootiragenient and many helpful suggestions given throughout the course of this study. TABIS OF COSTENTS Fags ACKNOfflEDGMENT ii INDEX OP TABIES v I. INTRODUOTIOW 1 n. HISTORICAL S III. EXPBRBIEKTAL 50 A. General Procedure ...... ....... 50 B. Protection of Reactive Functional Groups 55 £->Nitrobroniobenzane and Fhenyllithium . 55 n-PropgrllithiuzB and Bromomesitylene .......... 56 Preparation of Nitrobromomesitylene 59 n-Propyllithium and Nitrobromcmesitylene 60 Reparation of 4<^Bronio-ffl-S7lene 60 n-FTopyllithium and 4-Br(»io««~xylene 61 Preparation of 2-Nitro-4-bromo-l,S-dlmethylbenzene . 62 n-Piropylllthiiaa and 2-lIitro-4-t)rcaiio-l,5- " dimethylbenzens * • * n-Propyllithium and N-(/3-Brranoethyl)-phthalinide ... 64 Ethylene Acetal of 2~BronoBoetophenone 64 Ethylene Acetal of £-Bromoaeetophenone and Lithium . 65 n-I^opyllithium and the Ethylene Acetal of ^Brraioacetophenone 65 n-ProHTllithium and Methyl jg-Bromobenaoate at -78° . 66 n-Rropyllithium and Methyl p-Iodobenzoate at -78° ... 67 t-Butyl £-Br(aiobenzoate 68 n-RroFyllithium and t-Butyl g-Bromobenzoato 69 Preparation of 4-Brcmopher(3rl S-Tetrat^ropsnrancirl Ether 70 2,4,6-Tribraiiophenyl 2-JretrahydroF5?ranyl Ether (Attempted) 70 2,4-Dibromo-l-naphthyl 2-TatrahydroRyTanyl Ether (Attempted) ................... 71 S-Tetrahydropyrasyl jg-Bromobenzoate (Attempted) .... 72 2-Bromophenyl 2-Tetrabydropyranyl Ether 72 2,4-Dibranophez]yl 2<^etrahydroFyracyl Ether ...... 7S n-Propyllithium and 2,4-Dibromopheiiyl 2-Tetrahydro- "" pyranyl Ether 75 n-Rpopyllithium and 4,6-Dibromo-^o-cresol ....... 74 IT C. Reduction* A Side Reaction in the Phenol Series . • n-Propsrllithiun and 2,&-Dibromophenol Purifioation of 2,4,6^ribromophenol Preparation of 5-Bramosalioylic Acid ^Bropsrllithiun and 2,4«6-^ribromophanol Reparation of 4<»Broao-2'methylphenol • Uethsrlation of Intereonverted 2,4,&-Tribrcxaoptonol • . j^Bropgrllithium and 2,4~Dibr^ophenol . ^nropyllithium and 2,4f6~Trlbromoanisole • l^paration of 2,&-Dibromoanisole . • . ^Propgrllithiuffl and 1,5,5-^ribromobenzane ....... n-Fropyllithium and Pentabromophenol D* Preparation of Some Alkamine Ethers I^eparation of a-Diatbylamino-l-phe&orlethanol . .. {Reparation of l-Ghloroisoquinoline • 2«(2>Dietfagrl8aino-l-ph6nylethoaQr)>benzothiasole . Preparation of 5-Diethylafflino-l,2-opox3rpropane .... l-Diethsrlamino-S-^henarl-2->F(ropanol l-Dletbylaiaino-8-{Axenarl-2-propanol Piorate Preparation of Diethgrlaminoaoetonitrile Benzgrlmagnesitoa Chloride and Diett^laminoaeetonitrile . Reduction of l-Diethgrlamino-5-phenyl-2-propanone . Oxidation of l-Diethylamlno-5-pheEQrl-2-propanol .... Oppenauer Oxidation of l-Diethylamlno-5-pher(jrl- 2>propanol (Attempted) Preparation of l-Chloro-5-f^ien3rl-2-propanol ...... EReparation of 5-Phenyl-l,2-epoxypropane 1-DietfaQrlamino-3>phetQrl-2~propanol . l^eparation of Dibenzylnethanol (Attempted) Preparation of Bibenzylmethanol 2-(l-Diethylamlno-S-phenDrl-2-propoxy)-benaothiazole .. Preparation of BeMshydryl Chloride 17. DISCUSSION A. Brotection of Reactive Functional Groups B* Reduction. A Side Reaction In the Phenol Series . 0. Preparation of Sane Alkamine Ethers D« Suggestions for fltrther Research 7. V INDEX OF TABI£S Page Table I Qrganometalllo Gcmpounds Classified Funoliional Giroups •••••*•*••••••• 34 Table II Stability of n.-Erop!jrllithiuni Solutions at 10°. ... 51 Table III Stability of n-Butyllithium Solutions at 10° .... 52 Table 17 Organolithlum Reagents and Some Nltrolodobenzenes at -78° 57 Table V n-ProRyUithium and Bromomesitylene at 26° 59 Table VI n-Propyllithlum and 4-Bromo-m-xylene at 27° 62 Table VII ^ProFyllithiua and 2,6-Dihromophenol ....... 77 Table VIII Interconversiai and Reductive ortho-DebronlnatIm of 2«4^6-Tribramophenol 80 Table H Ethers of 2-Diethylaiaino-l-pheni3rlethanol 95 Table X Organomstallle Compounds and Epioblorchordrin «... 104 Table XI Ethers of l-Diethylamlno-S-phenQrl-2-propanol .... 110 Table XII Physical Properties of l-Dlethylamlno-S-phecyl- 2-propanol 127 1 I. INTRODUCTION Prior to the independent discovery of the halogen-metal inter- oonversion reaction by Oilman, Langham and Jacoby^ and by Wittig and co-vTorkers^, relatively few types of reactive organometallic compounds -which contained a functional group were known. These compounds may be grouped into the following classes: enolates of esters and ketonesj enamates, acelgrlenic types, metallic derivatives of pyrrole and indole, and aromatic and aliphatic types containing halogen or another carbonr- metal linkage. The mode of preparation was either by the direct action of an organic halide upon metal or by the metalation reaction with other organcmetalllc compounds or alkali amides. The procedure, employing the direct reaction of an organic halide containing a reactive group upon the metal in a solvent, is subject to a number of well-known disadvantages. Ths reaction may be exceedingly slow because of the low reactivity of the halogen or because the metal becomes coated with the reaction product. In some cases, if the organo­ metallic compoxmd is formed, it may be as rapidly consumed in intra- and/cr inter-molecular reactions. On the other hand, this method has been particularly successful with preparations of Grignard reagents Oilman, Langham and Jacoby, J» Chan. Soc., 106 (1939). ^Wittig, Pockels and Drpge, Ber.« 71. 1903 (1938). z from ohloroaromatic brcaaides to give high yields of the chloroaryl- magnesium bromides* Mixtures of isomeric organomagnesium halides usually result when the halogens have the same order of reactivity. A striking example of the difficulties encountered with such mixtures Is the conclusion drawn hy Paty and Quelets that a irearrangement had taken place subsequent to carbonation of the monomagnesium derivative of 2,4-dibronioani8ole. However it was shown recently ty Hussey and Wilk^ that the results of these inTostigatora were easily interpreted when the presence of Isomeric bromomagnesium derivatives was established. The metalation reaction, generally employing n-butyllithium in ether, can be used with varying degrees of success with compounds containing groups which do not react beyond giving up an active hydro­ gen* Ths reaction time at ether refl\ix temperature is usually long, and this precludes the metalation of compounds which add the organo- metallic reagent or which are reduced tgr it. In general the yields are lower than would be obtained in a corresponding halogen-«ietal Interconverslon reaction. The halogen-metal interconverslon reac^on with organolithium reagents, because of the rapidity of the reaction and the good yields obtained, was emplcyed in the
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