Some Correlations Between Organosilicon Compounds and Organogermanium Compounds Mark Bernard Hughes Iowa State College
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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1958 Some correlations between organosilicon compounds and organogermanium compounds Mark Bernard Hughes Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Hughes, Mark Bernard, "Some correlations between organosilicon compounds and organogermanium compounds " (1958). Retrospective Theses and Dissertations. 1631. https://lib.dr.iastate.edu/rtd/1631 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]. SOME CORRELATIONS BETWEEN ORC-ANOSILICON COMPOUNDS AND ORGANO GERMANIUM COMPOUNDS by Mark Bernard Hughes A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject : Organic Chemistry Approved: Signature was redacted for privacy. In Chargfe of Major Work Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Dean of 1 Graduate College Iowa State College 1958 ii TABLE OF CONTENTS Page INTRODUCTION I HISTORICAL 3 Trialkylgermylmetallic Compounds 3 Trialky1silylmetallic Compounds 7 Organosilicon Hydrides Im préparation 15 By direct synthesis 15 By reduction 20 By disproportionation or redistribution 24 Reactions 28 With metals and organometallie compounds 28 With carbon-carbon multiple bonds 31 With alcohols 33 With compounds that are easily reduced 35 With acids and bases 37 EXPERIMENTAL 4l Trialkylgermylmetallic Compounds 42 Tetraethylgermane 42 Triethylgermane 43 n-But yltrie thylgermane 43 Benzyltriefchylgermane 44 2-Biphenylyltriethylgermane 45 Metalation of triethylgermane 45 With n-butyllithium 45 With phenyllithium 46 Cleavage of tetraethylgermane with lithium wire 46 In ethylene glycol dimethyl ether 46 In te t rahydr-of ur an 47 Cleavage of tetraethylgermane with lithium dispersion 48 Cleavage of tetraethylgermane with sodium- potassium alloy 49 ill Page In the absence of any solvent 49 In ether 49 In ethylene glycol dimethyl ether 50 In triethylaaine 52 In tetrahydrofuran 52 In di-n-butyl ether 52 In jg-dioxane 53 In benzene 53 In xylene 54 Cleavage of hexaethyldigermane with sodium- potassium alloy 54 Reaction of triethylchlorogermane with lithium 55 In ether 55 In tetrahydrofuran 55 Trialkylsilylraetallic Compounds 56 Cleavage of hexaethyldisilane 56 With lithium in ether 56 With lithium in tetrahydrofuran 56 With sodium-potassium alloy in tetrahydrofuran 57 Cleavage of trimethylphenyleilane 57 With lithium 57 With sodium-potassium alloy 59 Cleavage of triethylphenylsilane 59 With lithium in tetrahydrofuran 59 With sodium-potassium alloy in ether 60 With sodium-potassium alloy in tetrahydrofuran 61 Cleavage of 2-biphenylyltrimethylsilane 62 With lithium in ether 62 With lithium in ethylene glycol dimethyl ether 62 With sodium-potassium alloy in ether 62 Cleavage of 2-biphenylyltriethylsilane with lithium in tetrahydrofuran 63 Cleavage of trimethyl-jo-tolylsilane with lithium 64 iv Page In ether 64 In tetrahydrofuran 64 Cleavage of trimethyl-o-tolylsilane with sodium-potassium alloy in ether 65 At room temperature 65 At 0° 65 Cleavage of trimethyl-l-naphthylsilans with lithium in ether 65 Cleavage of 9-fluorenyltrimethylsilane with lithium 66 In ether 66 In tetrahydrofuran 67 Cleavage of 9-methy1-9-trimethylsilylfluorene with lithium 67 In ether 67 In tetrahydrofuran 68 Cleavage of 9,9-bis(trimethylsilyl)fluorene with lithium 68 In ether 68 In tetrahydrofuran 69 Cleavage of allylt rime t hyls ilane with lithium in ether 70 Cleavage of t rimet hylet hoxy6 ilane with lithium 70 In ether 70 In tetrahydrofuran 70 Cleavage of trimethylethoxysilane with sodium- potassium alloy 71 In ether 71 In tetrahydrofuran 71 Cleavage of hexamet hyldi s iloxane 72 With lithium in tetrahydrofuran 72 With sodium-potassium alloy in ether 72 V Page Organosillcon Hydrides 73 n-Dode cyls ilane 74 n-Hexade cyls ilane 76 Al1yl-n-he xade cyls ilane 76 Diallyl-n-hexadecyleilane 77 n- Hexade eylphenyls ilane 78 n-Hexadecyldiphenylsilane 79 Benzyl-n-hexadecylsilane 79 n-Butyl-n-hexadecylsilane 80 Cyclohexylsilane 81 Dicyclohexylsilane 81 tert-But ylphe ny1s ilane 82 Di-n-butylsilane 83 Allyldi-n-butylsilane 83 Tri-n-butylsilane 84 Di-n-decylsilane 84 Allyldi-n-decylsilane 85 Benzyldi-n-decylsllane (attempted) 85 Di-n-decylphenylsilane (attempted) 86 Di-n-octadecylsilane 86 Allyldi-n-octadecylsilane (attempted) 87 Di-n-octadecylphenylsilane (attempted) 87 Tri-n-dodecylsilane 87 Mono-, di-, and tri-n-hexylsilane 88 Mono-, di-, and tri-n-octylsilane 89 Bensyldi-n-octylsilane 91 Di-n-o ctylphe ny1s ilane 91 Mono- and dl-£-anisylsilane 92 Tri-£-anisylsilane 93 Mono-, di-, and tri-o-anisylsilane (attempted) 93 Mono- and di-j>-tolyls ilane 94 DISCUSSION 95 Trialkylgermylmetallic Compounds 95 Trialkylsilylmetallic Compounds 98 Organosillcon Hydrides 101 Suggestions for Further Research 105 SUMMARY 106 ACKNOWLEDGMENT 109 1 INTRODUCTION The excellent thermal stabilities of some organogermanlum and organosillcon compounds have made these classes of com pounds important ones in the field of high temperature lubri cants. However, the methods available for the introduction of a germanium or silicon atom into custom-made molecules are very limited. Triarylgermyllithium compounds attack reactive sites of various organic compounds,but the resultant products usually exhibit melting points too high for the compounds to be utilized as lubricants over the temperature range desired. Polychlorogermanes react with organometallic reagents to give partially substituted ehlorogermanes, but the difficulties of separating the mixtures obtained militate against use of these compoîands as intermediates for the preparation of tetrasubsti- tuted organogermanes. The present situation is somewhat better for the prepara tion of organosillcon compounds. The recent preparation of *H. Oilman and C. ¥. Gerow, Am.., Chem. Soc., 77. 5740 (1955). 2H. Oilman and C. ¥. Gerow, ibid.. 22 > 4675 (1955). %. Gilman and C. W. Gerow, ibid.. 22» 5509 (1955). ^H. Gilman and C. W. Gerow, ibid.. £9, 3^2 (1957). 2 methyl&iphenyl- and dimethylphenyleilylllthiua^ should permit the'preparation of more unsymmetrically substituted silanes. At the time this work was initiated, however, essentially the same methods of preparation were available in this area as for the analogous germanium compounds. The original purpose of this investigation was to prepare trialkylgermyl- and trialkylsilylmetallie compounds and to study their reactions. Previous attempts to prepare inter mediates of this type have failed or have been only partially successful. There is little doubt that the derivatives of these organometallic compounds would have lower melting points than the corresponding triaryl compounds and evaluation of their thermal stabilities would be of great interest. A second phase of this research involved a study of the reaction of alkyl G-rignard reagents with organosillcon hy drides in tetrahydrofuran, which would enable one to prepare highly uneymmetrical silanes for evaluation as lubricants. Furthermore, an attempt was made to elucidate some of the chemical and physical properties of the s11icon-hydrogen bond. Gilman and G. D. Llchtenwalter. ibid.» 80. 608 (1958). 3 HISTORICAL For the purpose of this review, the following reference sources have been checked to the dates indicated: CA. through no. 5, vol. 52, 1958; Am. Chem. Soc. through no. 7> vol. 80, 1958; J. Org. Chem. through no. 3, vol. 23, 1958; J. Chem. Soc. through no. 3» 1958; and Current Chemical Papers through no. 3» 1958. Furthermore, all cross references con tained in individual papers were checked. All of the pertinent references are not given in some sections, and this fact is so indicated, due to the large number of references to reactions which involve only minor variations in experimental conditions. In such cases, the references cited contain good bibliographies to related studies. The major sections of this thesis have all been divided into three subdivisions: trialkylgermylmetallic compounds, trialkylsilylmetallic compounds, and organosillcon hydrides, for ease in locating data pertinent to each topic. Trialkylgermylmetallic Compounds The preparation and characterization of only one trialkylgermylmetallic compound has been reported in the 4 literature. Kraue and Flood® were successful in cleaving hexaethyldigermane with metallic potassium In ethylamine over a period of 6 weeks. Dérivâtizatlon with ethyl bromide gave tetraethylgermane In near quantitative yield. Hexaethyldiger mane and sodium in liquid ammonia did not react to any extent, most likely due to the low solubility of the digermane in the solvent. 6 Cleavage of hexaethyldigermane with lithium in ethylamine was successful, but the germyllithium compound im mediately underwent ammonolysis to give triethylgermane.6 These same authors investigated the reaction of triethyl- halogermanes with metals in ammonia and in ethylamine. When t rle t hylchloroge rmane was treated with lithium in ethylamine, the only product isolated was hexaethyldigermane in low yields. The reaction was accompanied by the evolution of large quan- titles of hydrogen