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The Relative Reactivities of Some Organometallic Compounds

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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1935 The elr ative reactivities of some organometallic compounds Kenneth E. Marple Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Marple, Kenneth E., "The er lative reactivities of some organometallic compounds " (1935). Retrospective Theses and Dissertations. 13644. https://lib.dr.iastate.edu/rtd/13644 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 TiiS RELATIim REACTIVITIES OF SOME ORGAtiOliBTALLIO COflPOUIDS Kenneth E. Marple A Thesis Submitted to the Graduate Faculty for th© Degree of DOCTOR OF PHlLOSOPiH Major Subject Organic Chemistry ApprovedI Signature was redacted for privacy. In eiia'r^e oif Major work Signature was redacted for privacy. mm of Ma Signature was redacted for privacy. Dean of Graduate Gollegi"^' Iowa State College 19S5 UMI Number: DP12833 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 DP12833 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 OiJA-n - g - n • AGKNOWLBDOSMENT fh© writer wishes to express iiis appreciation to Dr. Henrj Gilaea for the suggestion of tliis problem and for the generous advioa and enoooragement givexi during this work. "f 5 I 3 5 - 3 - , vf fABlJS OF GONTSIITS |, Page IHTRODUOTIOii 5 A. TliS COLOR TEST wiTIl ORGMOMSTALLIO COUPOmOS 9 lUTROBUOTION 9 EXPSRIMENTAL 12 DISCUSSION OF BSSULTS 18 mmmi 19 • B. QOm RBAGTIOHB OF OfiGMO-iL'tMIHUM GOMPOUNDS 20 IHTiiOi^ljaflOW 20 aXPEHIMEMT.iL 28 Beaotioa with Plieayl Isooyanate 26 Heaotioii with Garboii Dioxide 37 Heactioa with Benaophenon© 3B Reaotlon with Oxygen 38 Keaction with BenzaMehyde 38 Reac11 on witlx Benzoaitril© 39 Reaction with Esters 39 DISOUSSIOH Of HKSULTS 40 SmiAiii' 42 0. SmSi RSAOTIOKS OF ORGANQBOROn COMPOUHDS 43 INSRODUOl'ION 43 Ji;XI'i;;RIiIU,uTAL 51 Reaotion with Phenyl Isocyaaate 57 liQaotioa -with Benzaldeliyde 57 DISCUSSION Oj? RESULTS 59 SUKMaRY • 61 - 4 - Page 'D, tSOMii REACTIONS OF QBQANOZINO 00L5P0UNDS 62 IN'TROiWGTION 68 SXPSRIMSJSim 65 Beaotloii ifith Carbon Dioxide .......................... 67 Reaotion with [email protected] 67 Reaction with Phenyl Isooy-anate ....................... 68 Roaction with Benzonitrile 68 DISOTJSGICHJ OF RESITLTS 69 SIIMAI^Y 70 1. THE: RBLATIVB REAGTITITIES OF ORGAMOMSTALLIG 00:1?0U!IDS •OF ALUMIMUM, BOHyii AKD SING 71 Iim-iOOTOTION 71 SXPiSilMEMTAL 80 Keaatioa Bates with Miehler* s Ketone 84 Mlnimma Ooneentratioa Giving the Oolor Test ........... 87 Heaotion Rates with BeuzaMehyde, Benzophonone and Benzoaitrile 89 Bat© of Bisplaeerasnt of llerotiry froai Organomeroury Ooapounds by Aluminum aad Zino 93 DICGUSSION OF RiiSUL^IB . 95 SUMMIKY 99 5 - fHg RBLATra RSASTITITIES Of SOME QRGAMOMKTALLIO gOMPOUNDS Introduction Organic sjntiiesis is, in general, based upon the use of selectiw or preferential reactions. Organic chemistry is built upon the reaction of an organic compound with one or more other elements or coapounds, The success of any reaction depends to a large extent on the reactivities of the groups in­ volved, The ability to predict how a reaction will proceed or the best synthesis to us© in each case depends upon knowledge of the relative reaotivities of the compounds or groups involved. Organosetallic coapounds have often been used in reactions with polyfunctional compounds, fhus, Noller and Adams (1) by the proper use of a Grigaard reagent on aldehyde esters obtained compounds taat showed addition to the aldehyde group but not to the ester group. A large number (2) of such preferential reactions with polyfuactional compounds are found in the chemis­ try of organomagnesium coapounds. In some cases, however, preferential reaction does not take place as the Grignard reagent reacts equally well with all functional groups present. Thus, Boyd and Ladhams (3) hoped that by the use of preferential (liMoller and Adams, £. Am. Qhem. Soo.^ 48, 1074 (1926). (g| (a) Grignard, Oompt. rend.. 154. 849"Tl902)i (b) Fordyce and Johnson, £. Am.' d'hem. Soo., 55. 3368 (1933)'j (c) Mavrodin, Bui, soc. ohim. Reaaania. 15, 99 (19S3). (3) Boyd and Ladhams, j'l" '^hem. SOc. > 19S8« 2lfe9. — 6 ^ reaetion they could convert methyl o-oyaaobenzoate into o-cyano«« triphenylcarblnol. They found, however, that phenylmagneslum bromide in ether solution reacted with both the cyano and the ester groups. No trace of o-cyanotriphenylcarbinol could be detected. Finger and Gaul {4) report that in the reaction of Qrignard reagents on methyl ayanoformate both the ester and cyano groups were attacked by the Grignard reagent. It is hoped that by the use of organometallic compounds less reactive than the Grignard reagent preferential reactions of this type oan be carried out without difficulty. This may open new fields whereby other­ wise inaccessible compounds may be prepared through the medium of selective or preferential reactions involving organosetallie ooapounds less reactive than the Grignard reagents, Organonetallie compounds probably constitute the most impor­ tant group of compounds used in synthesis. They include all compounds which are characterized by the carbon-metal linkage and may be represented as falling into three ixaportant classes: first, those containing only like R groups attached to the metal; second, those having different H groups attached to the metalj and third, those having both R groups and halogen attached to the metal. The task of comparing the reactivities of all of these different compounds is great, and it is only through continued effort that it may be achieved, (4) Finger and Gaul, £. prakt. Chem., 111. 54 (1923). The proper method of approach in a study of this kind seems to be to attempt a correlation between the oheraical reactivities of the organometellic compound and the position of the metal in th© periodic table. Ifie raore reactive or- ganoaetallio compounds seem to be forraed from the metals in the lower left hand corner of the periodic table; that is, th© more positive the aietal the greefcer the reactivity, and the organorub idiura and organocesiuia compounds appear to be more reactiv® than. t>ios0 higher in the group (5). The orgaiioiQOtalliQ compounds of the second group ele- aents appesir to be less reectlve than the organoalkali com­ pounds (6), while the alltalln® earth metals end magnesium form the most active, organometallic compounds of the second group metals. In this studj an attempt has bean made to compare the relative rasotivity of the organometallic compounds of zinc of the second group olemonts witii tliose of aluminum and boron in the third group. Due to the wide range of reactivity of the many organometallic compounds, from the very reactive organoalkali compounds to the relatively stable orgsnocom- pounds of tin, bismuth and lead, it is difficult, if not impossible, to find any on© reaction which could be used in (5) For a genaral reviav and references saa: Julius Schraidt, •'Organoaetallverbindungen#" Stuttgart. 1934, (6) Oilman and ICirby, £. Am. Qhem. ^oc.. 55, 1265 (1933). a quantitative laanner to measure all tliair relatlTC reaction velocities or reaotivitiee. In the case of the three metals ohosen the reaetions entered into by all three are very fe^/. The raaetions of organoeluBiiama and -boron corapounds with Qoapomds coatainlng differeat functional groups have been little studi©d« Therefor©, it is first aQoessary to inves­ tigate the reaction of organoziac, -aluminum, and -boron ooiapounds with Qertain funetional groups and then to choose those best suited for a oomparison of the relative reactivities. A. 'ms OOLOH T3CT Wim OTtf>AHOiaTALLIO GOKPOUHDo Introduction The color test for reactlTe organometallic compounds has 1)6011 of xmrj great use in measuring the relati^a reaoti- Tities of sueli compomds# It has been used in GOiaparing organoiaetallio couipouMs of different metals with each other f6); for comparing the reactivity of organometallic compounds with diffarent H groups with selected reactants (7); and for distinguishing between RMgl, and Hsf% compounds (8). The color test as developed by Gilinan and Schulze (9) depended upon the formtion of tertiary alcohols by the in­ teraction of Michlsr's keton© (tetramethyl-p-diaminobenzo- pheaon©) and an organometallic coiapound, Th© test was desig­ nated as £i color test for reactive organomatallic cofflpounds, as it was thought that only th© mora reactive of these com­ pounds formed by raetals of th® first
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  • Signature of Author

    Signature of Author

    NEW METHODS FOR THE FORMATION OF CARBON-CARBON BONDS VIA ORGANOMETALLIC COMPOUNDS by BRIAN SCOTT BRONK B.A. (High Honors), Colgate University (1989) SUBMITTED TO THE DEPARTMENT OF CHEMISTRY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY February 1995 © Massachusetts Institute of Technology, 1995 Signature of Author.. ........................................................... Department of Chemistry September 19, 1994 /' I . N 'N Certified by....................... ......... .. ........................................ Certifiedby Rick L. Danheiser Thesis Supervisor Certified by ......... ... ...................................... Stephen J. Lippard A Thesis Supervisor // . Accepted by.................. .................... /../.!.............................................. Dietmar Seyferth Departmental Committee on Graduate Studies I:;. .i., . : .1'_I_ , This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: n An Professor Stephen L. Buchw ald ....... ............................. m L. BcChairman Professor Rick L. Danheiser . ................... Thesis Supervisor Professor Stephen J. Lippard ........... ........ .................... Thesis Supervisor Professor Dietmar Seyferth ............ .......... -.... 2 ACKNOWLEDGMENTS After writing a thesis totaling over 300 pages, the task of writing one final page would seem quite simple. Unfortunately, I am left with a single page to express my gratitude to :l who have made