HEACTTONS or UREAHosvaLHvaHTaEs WITH (Tammi-"3 ‘- ° .f ' commas caHTAzmHa AH Asian: WDROGEN :3. CATALYZED BY GROUP VIN METAL COMPLEXES ; . : YbE‘sis far the Begree 0le S MICHIGAN STATE UHWERSW ' NWIN DAVID CHOSSAN _ 1972 . ~ 0 d n-u- - vw WIT-'— L I I 9, R Y Michigan ‘3 rate University ABSTRACT REACTIONS OF ORGANOSILILHIDRIDES NITH ORGANIC COMPOUNDS CONTAINING AN ACIDIC HYDROGEN CATALYZED BY GROUP VIII METAL COMPLEXES By Irvin David Crossan A study was made to determine if the homogeneous catalysts tris-(triphenylphosphine)chlororhodium (I), bis-(triphenylphosphine)carbonylchloroiridium (I) and (triethylphosphite)bromoOOpper (I) would catalyze the addition of alcohols to organosilylhydrides. It was found that the catalysts tris-(triphenylphOSphine)chloro- rhodium (I) and bis-(triphenylphosphine)carbonylchloro- iridium (I) provide a convenient way to prepare the cor- reSponding organoalkoxysilanes. A number of organoalk- oxysilanes were synthesized. It was also discovered thattris-(triphenylphosphine)chlororhodium (I) cata- lyzed the addition of amines, water and ketones to the organosilylhydride. A relative rate study of different alcohols added to triethylsilane showed that the rate was l°>2°> 3%:phenol and that the longer the aliphatic portion of the alcohol. the faster the rate. It was also found that the relative rates of different silanes reacted with an alcohol were as follows: (CH3)2(C6HS)81H) (C2H5)381H1) HSi(OC2H5)3. REACTIONS OF ORGANOSILYLHYDRIDES WITH ORGANIC COMPOUNDS CONTAINING AN ACIDIC HYDROGEN CATALYZED BY GROUP VIII METAL COMPLEXES By Irvin David Crossan A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Chemistry 1972 ACKNOWLEDGEMENTS The author would like to thank Dr. Robert Grubbs for initially suggesting the problem and for his counsel during the stay at Michigan State University. He is also grateful to the Dow Corning Corporation for the financial and equipment assistance. The author would like to thank both the members of Dr. Grubb's research group and friends at Dow Corning for many interesting and helpful discussions. Finally the author would like to thank his wife, Patsy, for inspiration and understanding. 11 ‘1‘") Hf h I TABLE OF CONTENTS List of Tables I. II. III. Introduction Results and Discussion A. Synthetic Utility B. Effect of Organosilane and Alcohol on the Reaction Rate C. Discussion of PrOposed Mechanism Experimental A. Materials B. Reactions using Tris-(triphenylphosphine)- chlororhodium (I) as Catalyst. 1. 2. Preparation of Triethylsilane Preparation of Tris-(triphenyl- phosphine)chlororhodium (I) Preparation of Triethylethoxysilane Preparation of Dimethylphenylethoxy- silane Preparation of Triethyl(sec-butoxy)- silane Preparation of Triethy1(4-methyl- cyclohexanoxy)silane Preparation of Triethylcyclohexan- oxysilane Preparation of Tetraethoxysilane Preparation of Triethyl(n-butoxy)silane iii vi 10 15 19 19 19 19 20 20 23 2h 25 26 27 Reactions Using Bis-(triphenylphosphine)- carbonylchloroiridium (I) as Catalyst 1. Preparation of Triethylethoxysilane 2. Preparation of Dimethylphenylethoxy- silane Reactions Using Triethylphosphitebromo- cOpper (I) as Catalyst 1. Attempted Preparation of Triethyl- (g-butoxy)silane 2. Preparation of Dimethylphenyl(n- butoxy)silane Other Reactions Using Tris-(triphenyl- phosphine)chlororhodium (I) as Catalyst 1. Preparation of Dimethylphenyl(g- butylamino)silane 2. Preparation of Dimethylphenylsilanol 3. Preparation of Dimethylcyclohexanoxy- silane 4. Reaction of Cyclohexanone with Tri- ethylsilane Using Triethylamine as a Catalyst Reactions of an Organosilane with an Alcohol Catalyzed by an Acid 1. Reaction of Triethylsilane with Ethanol Catalyzed by Dimethylchloro- silane Competition Reactions of Triethylsilane for Various Alcohols 1. Competitive Reactions of Triethylsilane for Ethanol and 2-Butanol 2. Competitive Reaction of Triethylsilane for Ethanol and tert-Butanol 3. Competitive Reaction of Triethylsilane for Methanol and g-Butanol iv 28 28 28 29 29 29 30 3O 31 33 34 34 34 34 36 IV. ' 5. Competitive Reaction of Triethylsilane for Ethanol and Phenol Competitive Reaction of Triethylsilane for 1-Butanol and 2-Butanol H. Competition Reactions of Various Organo- silanes for a Single Alcohol 1. Competition Reaction of g-Butanol for Dimethylphenylsilane and Triethylsilane 2. Competition Reaction of Ethanol for Triethylsilane and Triethoxysilane 3. Competition Reaction of Butanol for Triethylchlorosilane and Dimethyl- phenylchlorosilane I. Alkoxy Exchange on Silicon 1. Reaction of Triethy1(sec-butoxy)silane with Ethanol 2. Reaction of Triethyl(sec-butoxy)silane with Triethylethoxysilane BibliOgraphy Appendixes A. Infrared Spectra B. Proton NMR Spectra 36 37 37 37 38 39 4O 40 no 42 46 46 59 II. III. IV. LIST OF TABLES Compounds Prepared Using Tris-(triphenyl- phosphine)chlororhodium (I) as Catalyst Compounds Prepared Using Bis-(triphenyl- phosphine)carbonylchloroiridium (I) as Catalyst Competitive Reactions of Triethylsilane for Various Alcohols Competitive Reactions of Organosilanes for a Single Alcohol vi 12 14 I. INTRODUCTION In organic chemistry the element most commonly as- sociated with carbon is hydrogen. This is not true in organosilicon chemistry. This is due to the higher reac- tivity of the silicon-hydrOgen bond in comparison to the carbon-hydrogen bond. Thus. for example. the ESi-H bond is readily cleaved by water1‘6, alcohols7'18, ammonia19'21, 19,20,22-24 in the presence of suitable bases and amines such as hydroxides, alcoholates and amides of alkali metals. By contrast, the ESi-H bond exhibits adequate stability towards dilute mineral acids and is completely inert to pure water and alcohols. All of these reactions of substitution of the hydrOgen atom linked to silicon have no analogy in organic chemistry. What physical prOperties of the bonds can eXplain the difference in reactivity? The silicon-hydrogen bond is weaker than the carbon-hydrogen bond25. This energy difference is much too small to account for the reactivity difference26. The bonds also have about the same amount of ionic characterzs, but the great difference lies in the direction of polarization. The relative electronegi- tivities of carbon. hydrogen and silicon are 2.5, 2.1 and 1.8 reapectively. This means that the hydrogen atom has the positive end of the dipole in the carbon-hydrogen bond and in the silicon-hydrogen bond the negative end. This suggests that the chemistry of the ESi-H bond should be compared not to the EC-H bond but with the similarly polarized carbon-halogen bond. It has also been demonstrated that the silicon-hydro- gen bond is extremely labile in the presence of catalytic amounts of transition metalsz7'28. As a result, a large number of reactions involving the cleavage of this bond have been studied29'30'32. The metals of Group VIII and some of their salts are known to catalyze the addition and substitution reactions of silanes with various organic functionalities. The re- action of hydrosilation, the addition of silicon hydrides for unsaturated organic compounds (I), has been the most widely studied reaction33. (I) R1R2R3SiH + RCH=CHR'-9&I) R1R2R3SiCHRCH2R' The catalysts used to promote the hydrosilation reaction above are: platinum on carbon or alumina supports and chlorOplatinic acid. The catalysts palladium. nickel, cobalt, ruthenium. rhodium or iridium on supports, as well as some of their salts, have shown some successz9. It has also been demonstrated34 that the class of Group VIII metals catalyzes the addition of various or- ganic compounds containing hydroxy35‘45 or aminob’u'“6 functions to an organosilicon hydride. Reactions of this type provide a convenient method for the preparation of silanols36'38. siloxanes35'36, alkoxy or aryloxysilanes37' 39-42 43-45 44.46. , silyl esters and aminosilanes In the majority of instances the reactions are be- lieved to be examples of heterogeneous catalysisz9. Despite the numerous studies dealing with synthetic utility. little has been related about their mechanism35'46. Very little work has been reported concerning the homogeneous catalysis of these reactions. Lukevits and Voronkov37 have studied the rates of chlorOplatinic acid catalyzed alcoholysis of triethylsilane. These authors found (a) second order kine- tics, (b) dependence of rate on catalyst concentrations, (c) large rate dependence on steric hindrance in the alco- hol. (d) faster rates in non-polar than in polar solvents and (e) reduction of chlorOplatinic acid to platinum metal during the course of the reaction. This thesis deals with the use of homogeneous transition metal complexes which might promote these types of reactions under more control- led conditions. The variables affecting the reactions will also be studied since results obtained from homoge- neous catalysts are more amenable to mechanistic interpre- tation than those obtained from heterogeneous catalysts. II. RESULTS AND DISCUSSION A. Synthetic Utility The transition metal complex tris-(triphenylphosphine) chlororhodium (I) has been found to catalyze the addition of various alcohols to various organosilicon compounds possessing a silicon-hydride bond. The transition metal complex bis-(triphenylphosphine)carbonylchloroiridium (I) was also found to catalyze the addition of ethanol to tri- ethylsilane and dimethylphenylsilane but was not studied as extensively as the rhodium complex. The reaction scheme is: ROH + R1R2R3SiH .9519 ROSiR1R2R3 + H2. The preposed mechanism will be discussed in a later sec- tion. Table 1 gives the compounds synthesized and the yields obtained by the use of a catalytic amount of the rhodium complex (2.2 x 10'6 moles to 0.01 moles of silane). The reactions proceed to completion in 8 to 36 hours when the reactions are run at a temperature between 40° and 70° C. The reactions were conveniently followed by gas chromato- graphy. No observable side products were produced in any of the reactions. All of the pure products were isolated by flash distillation of the product from the catalyst under reduced pressure after removal of the solvent. The structures of the compounds were confirmed by infrared and nmr Spectrosc0py. The reaction is a convenient way to pre- pare silylether compounds from the silyl hydride and alcohol. 5 Table I Compounds Prepared Using Tris-(triphenylphosphine)chlororhodium (I) Ag Catal st Compound Solvent Time Temp Yield (C2H5)3SiOC2H5 Benzene 24 hours 600 92% ¢(C33)ZSiOCH2CH3 Benzene 8 hours 800 100% (CZHS)BSiOCH(CH3)(C2H5) Benzene 24 hours 50° 80% H3C-<:::>»OSi(CéH5)3 Benzene 48 hours 700 75% <:::>-OSI(CZR5)3 Benzene 72 hours 70° 100%* Si(0CZHS)u Benzene 60 hours 70° 80% (C2H5)3310(CH2)3CH3 Benzene 24 hours 60° 85% * All starting alcohol consumed during this period; products identified by g.1.c. In the absence of a catalyst the trialkylsilanes do not re- act with alcoholsu7. Table 2 gives the compounds synthesized and the yields obtained when the complex bis-(triphenylphosphine)carbonyl- chloroiridium (I) was substituted for the rhodium complex. It should be noted that the reaction would not proceed at room temperature but proceeded at a moderate rate at slightly elevated temperatures. No further reactions were run using the iridium complex since the reactions proceeded at a rate comparable to the rhodium complex reactions. No side products were seen by gas chromatography in these reactions. Miller. Peake and Nabergallua have reported that c0pper powder catalyzes the addition of a ESi-H to an H-OR when the silicon atom possesses more than one hydrogen. Thus. the complex (triethylphosphite)bromocOpper (I) was prepared and used as a catalyst in the reaction of butanol with triethyl- silane. At reflux in a benzene solvent in 24 hours, no reac- tion was observed. When dimethylphenylsilane was substituted for the triethylsilane. the reaction went to completion in 48 hours. No further experiments were run using homOgene- ous cOpper catalysts since the reaction was relatively slow and proved to be limited in SCOpe in comparison with the rhodium complex. Sommer and Citron33 have reported that heterOgeneous catalysts, such as Pd/C and Pd/A1203. catalyze the reaction of primary and secondary amines with a silylhydride to give 7 Table 2 Compounds Prepared Using Bis-(triphenylphOSphine)carbonylchloroiridiumA(I) Ag Catalyst Compound Solvent Time Temp Yield (C235)3810C2H5 Benzene 20 hours 400 71% ¢(CH3)ZSi0C2H5 Benzene 12 hours 60° 91% the corresponding silylamine. It was found that the tran- sition metal complex tris-(triphenylphosphine)chlororhodium (I) also catalyzes this reaction. The compound dimethyl- phenyl(p-butylamino)silane was prepared by reacting di- methylphenylsilane with pebutylamine using the transition metal complex tris-(triphenylphosphine)chlororhodium (I). The reaction did not proceed at room temperature but did proceed at a moderate rate at 800 C. The reaction was followed by gas chromatOgraphy. In 36 hours the reaction was complete, and no side products were detected. An 3 nmr Spectrum of the product confirmed its structure. In the nmr absorptions due to [(CH3)2(C6H5)Si]20 which comes from hydrolysis of the silylamine were observed. No further work was done on changing the alkyl group on the amine or silane to see Just how much synthetic utility this reaction would have. It could be assumed that it would possess quite broad synthetic utility since the reaction is only slightly slower in rate than the reaction of dimethylphenylsilane with a primary alcohol. It was found also that the transition metal complex tris—(triphenylphosphine)chlororhodium (I) would also cat- alyze the reaction of dimethylphenylsilane with water to form the corresponding silanol. The reaction proceeded at room temperature and was complete in 8 hours. The reaction progress again was followed by gas chromatOgraphy. Two pro- ducts resulted from the reaction. These were dimethylphenyl- sdlanoland 1,1,3,3-tetramethyldiphenyldisiloxane. The second product resulted from the Side reaction (II) which is known to be catalyzed by transition meta1835’36. (II) (CH3)2(C6H5)SiOH + (CH3)2(C6H5)SiH 4—-—# [(033)2(c635)31] 20 + H2 This side reaction could be minimized by changing the re- action parameters. A reaction was run to see if the enol form of a ke- tone would react with silicon hydride in the presence of a transition metal catalyst to form the unsaturated silyl- ether. The ketone used was cyclohexanone. A catalytic amount of tris-(triphenylphosphine)chlororhodium (I) and triethylamine was used. The amine was expected to facili- tate the formation of the enol form of the ketone. A re- action did take placa,but no hydrogen was evolved. The isolated product was triethylcyclohexanoxysilane instead of the expected product triethyl(l-cyclohexenoxy)silane (a). It is widely known that transition metals catalyze the ad- dition of a silylhydride across a carbon-carbon double bond9. In this case the silylhydride has added across a carbon-oxygen double bond. It is possible that compound (a) was formed but then hydrogenated. The catalyst tris-(tri- phenylphOSphine)chlororhodium (I) has proved to be an ex- cellent hydrOgenation catalyst. It seems more likely. however, that there was addition across the carbon-oxygen double bond. It has been reported that under the influence of ultraviolet light addition of silylhydrides across carbon- oxygen double bond does occur. Also, Calas, Frainnet and 10 Bonastre49 have reported that aliphatic ketones and cyclo- hexanone react with triethylsilane in the presence of the catalyst zinc chloride to give the addition product. i.e. the alkoxysilane. It also has been reported that trialkyl- silanes have been added to furfural. 5-methylfurfural and thiOphenaldehyde on prolonged heating in the presence of chloroplatinic acid50. It might be postulated that the catalyst is triethyl- amine and not tris-(triphenylphosphine)chlororhodium (I). A mixture of cyclohexanone. triethylsilane and a catalytic amount of triethylamine gave no observable reaction (g.1.c.) after refluxing together for 24 hours. This indicates that the catalyst for the reaction is indeed tris-(triphenyl- phosphine)chlororhodium (I). This reaction could have synthetic utility as a means of conveniently reducing ketones to their correSponding al- cohols under mild conditions. Also, this is another way of preparing silylethers from ketones instead of alcohols. The reaction needs to be explored much more deeply than was pos- sible here to determine its synthetic utility. B. Effect of Organosilane and Alcohol on the Reaction Rate In the reaction of an organosilane with an alcohol using a transition metal catalyst, such as tris-(triphenyl- phOSphine)chlororhodium (I). different reaction rates should be observed depending on the silane and alcohol used. Dif- ferences in rate were determined. Another parameter to be considered is solvent. The solvent used should also have 11 some effect on the rates of reactionsl. The solvent used in the rate studies was benzene. This may not necessarily be the Optimum solvent. Although other solvents were not studied, it is likely that changing the solvent could give different results. A way to determine relative rates is to competitively react equal molar ratios of two different alcohols with a limited amount of triethylsilane and to determine the amounts of the two silylethers obtained. This was the route taken. The molar ratios used were 1:121 (silane: alcoholzalcohol). The reaction was followed by gas chroma- tography and hydrogen gas evolution. The final molar ratios of the two resulting alkoxysilanes were determined by gas chromatOgraphy using standard samples of the alkoxysilanes to determine relative reaponse factors. The data obtained is given in Table 3. As one can see, the tris-(triphenyl- phosphine)chlororhodium (1) catalyzed reactions of triethyl- silane are affected by the bulk and basicity of the hydro- carbon portion of the alcohol. The order of reactivity is in general 10) 2°) 30::phenol. It was found that chain lengthening of the hydrocarbon portion of the alcohol re- sulted in an increase in the rates. Similar effects have been reported for the reaction of silanes with alcohols 48 and chlorOplatinic acid37 as catalysts. using cOpper powder In the base or acid catalyzed reactions of alcohols with a silylhydride the Opposite effect is seen, i.e. the longer the organic radical, the slower the reaction rateu7. 12 Table 3 Competitive Reactions pf Triethylsilane For Various Alcohols 0 (C2H5)381H + ROH + H 0H 5 BL CZHS' CH3ECZH5 C2H5' (CH3)3C- C2H5' <:::>- CH3(CH2)3‘ CH3-ECZH5 CH3»OSI "'0.9 432315 «- 0.7 (quartet) CH3-CHZSiE A 0.9 (triplet) 7. Preparation of Triethyleyclohexanoxysilane To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 1.00 g (0.01 mols) of dried cyclohexanol and 5 ml of anhydrous benzene. The mixture was refluxed for one hour under nitrOgen to remove any dissolved oxygen present. Then a catalytic amount, 0.002 g (2.2 x 10'6 mols), of tris-(triphenylphosphine)chloro- rhodium (I) was added. The mixture was kept at a tempera- ture of 70-8000. The hydrOgen evolution proceeded at a slow rate. After 48 hours, the reaction had only gone 50% (by glc) to completion. The mixture was kept at 70- 80°C for an additional 24 hours. The reaction was still not completely finished. The solvent was removed by dis- tillation, and the product and residual cyclohexanol was flash-distilled from the catalyst. The cyclohexanol was then distilled from the pure product. An ir and nmr con- firmed the structure. The ir spectrum gave the following bands:at 1380 cm-1 (symmetric CH3 deformation, at 1420 cm"1 (CH2 deformation), at 1460 cm"1 (asymmetric CH3 deformation, at 1100 cm"1 (Si- O-CH), at 1020 and 980 cm'1 (Si-CH2), at 1240 cm"1 (CH2 wag), at 1070 cm.1 (Si-O-CH), and no band at 2100 cm'1 (due to (Si-H). The nmr Spectrum showed the following absorptions. Proton ratio g values H 3231-0—30 1 ~3.6 ~CH2-Si'5': “'0-7 17 ~ 0. 9 01130112812. 2331-00 10 A 101-200 8. Preparation of tetraethoxysilane To a single-necked 10 m1 flask was added 1.64 g (0.01 mols) of triethoxysilane, 0.46 g (0.01 mols) of ab- solute ethanol and 5 ml of anhydrous benzene. The mixture was refluxed under nitrogen for one-half hour to remove any dissolved oxygen present. Then the mixture was cooled and 0.002 g (2.2 x 10'6mols) of tris-(triphenylphosphine)chloro- rhodium (I) was added. The hydrOgen evolution at room tem- perature was very slow. At 700C the evolution of hydrOgen was somewhat faster. The reaction was kept at 70°C and followed by gas chromatography. The reaction was complete in 60 hours. The benzene solvent was removed by distillation, and the pure tetraethoxysilane was flash-distilled from the catalyst. An nmr confirmed the structure. The nmr Spectrum gave the following absorption data. 27 Proton ratio d values ESi-OCHZ’ 6 /~3.4 (triplet) 'ESi-OCHZCHB 9.2 ”’0.8 (quartet) 9. Preparation of Triethyl(n-butoxy)silane To a 10 ml single-necked flask was added 0.88 g (0.005 mols) of triethylsilane, 0.37 g (0.005 mols) of dried n-butanol and 3 g of anhydrous benzene. The mixture was refluxed for one-half hour under nitrogen. Then 0.002 g (2.2 x 10-6 mols) of tris-(triphenylphosphine)chlororho- dium (I) was added. The reaction was run at 60°C. In 24 hours all the triethylsilane had disappeared (by glc). The benzene was distilled away and the product flash-dis- tilled from the catalyst. A total of 0.80 g (85% yield) of pure product was obtained. The ir spectrum shows bands at 1240 cm"1 (CH2 wag), at 1380 cm"1 (symmetric CH3 deformation, at 1420 cm‘1 (CH2 deformation), 1460 cm‘1 (asymmetric CH3 deformation), at 980 and 1020 cm"1 (Si-CH2), 1100 cm"1 (Si-O-CHZ), 1120 cm’1 (Si-O-CHZ) and no band at 2100 cm'1 (Si-H). The nmr Spectrum showed the following absorptions. Proton ratio d values ESi-CHg’ 6.0 "0.65 (quartet) ESi-CHZCH3 9.0 “0.9 (triplet) -OCH2‘ 1.9 ’53.58 (triplet) 28 C. Reactions Using Bis-(triphepylphosphine)carbonyl- chloroiridium (I) as catalyst 1. Preparation of Triethylethoxysilane To a single-necked 10 ml flask was added 1.16 g (0.01 mols) of triethylsilane, 0.46 g (0.01 mols) of absolute ethanol and 4 ml of anhydrous benzene. Then 0.002 g (2.6 x -6 mols) of bis-(triphenylphOSphine)carbonylchloroiridium 10 (I) was added. There was no reaction. The catalyst did not seem to go into solution. The mixture was heated tOIVSOOC. HydrOgen gas started to evolve at a moderate rate at this temperature. ,The heating was stOpped. The hydrogen evolu- tion kept up at room temperature. In 18 hours the reaction had gone almost to completion. The volatiles were distilled off and the pure product flash-distilled away from the cata- lyst. A total of 1.15 g (71% yield) of triethylethoxysilane was obtained.- Ir and nmr spectra confirmed the structure of the compound. Spectra were in agreement with compound tri- ethylethoxysilane prepared previously. 2. Preparation of Dimethylphenylethoxysilane To a single-necked 10 ml flask was added 1.36 g (0.01 mols) of dimethylphenylsilane, 0.46 g (0.01 mols) of absolute ethanol and 5 ml of anhydrous benzene. Then 0.002 g (2.6 x 10‘6_mols) of bis-(triphenylphOSphine)carbonylchloro- iridium (I) was added. The mixture was heated to 60°C. Hy- drogen evolution was at a moderate rate. The reaction was complete in'~10 hours. The solvent was removed by distilla- tions from the mixture and the product flash-distilled from 29 the catalyst. The amount of dimethylphenylethoxysilane obtained was 1.6533 g (91% yield). An nmr confirmed the structure. The Spectrum was in agreement with compound dimethylphenylethoxysilane prepared previously. D. Reactions Using TriethylphOSphitebromocOpper (I) as Catalyst 1. Attempted Preparation of Triethyl(n-butoxy)silane To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.74 g (0.01 mols) of dried p—butanol and 3 ml of anhydrous benzene. Then 0.5 g of a benzene solution of the complex triethylphOSphitebromocOpper (I) (0.67 x 10"3 mols) was added. No gas evolution was seen. The mixture was heated to reflux for one hour. Again there was no gas evolution. At this time a gas chromatograph was run. No products were detected. The mixture was allowed to stand at room temperature under a nitrogen atmOSphere over night. A gas chromatograph run after this time showed no reaction had taken place. 2. Preparation of_Qimethylphenyl(n-butoxy)silane To a single-necked 10 ml flask was added 1.36 g (0.01 mols) of dimethylphenylsilane, 0.74 g (0.01 mols) of dried prbutanol and 5 m1 of anhydrous benzene. Then 0.5 g of a benzene solution of triethylphosphitebromocOpper (0.67 x 10"3 mols) was added. A very slow evolution of hydrogen was observed at room temperature. The mixture was heated to 70°C. At this temperature the evolution of hydrogen was slow. The reaction took 48 hours to go to completion. During this 30 time some of the catalyst had plated-out as metallic cOp- per along the sides of the flask. The solvent was removed by distillation and the product flash-distilled from the catalyst. An ir and nmr confirmed the structure. The ir Spectrum showed bands at 3080 cm’1 (phenyl), 1590 cm‘1 (phenyl), at 1430 cm"'1 (phenyl), at 1250 cm“1 (Si- CH3), at 1090 cm“1 ( Si-O-CHZ), at 1120 cm"1 (Si-O-CHZ), at 790 cm"1 (Si-CH3), and no band present at 2100 cm'1 ( Si-H). Ir spectrum also showed bands at 3480 cm”1 and 3640 cm‘1 (due to small amounts of free alcohol present). The nmr Spectrum showed the following absorptions. Proton ratio 5 values 06R5-Sis 5.2 /»2.4-2.8 (broad) -0-CHZ- 2.5* ”V3.6 -CH2CHZCH3 9.3* 531-CH3 5.9 ”50.32 *High proton ratio due to small amount of free alcohol present E. Other Reactions Using Tris-(triphenylphOSphlpe)chloro- rhodium (I) as Catalyst 1. gpeparation ofwgimethylphenyl(n-butylamino)silane To a 10 ml single-necked flask was added 1.36 g (0.01 mols) of dimethylphenylsilane, 1.46 g (0.02 mols) of dried p—butylamine and 3 m1 of anhydrous benzene. The mix- ture was refluxed under nitrogen for one hour to remove any 6 idissolved oxygen present. Then 0.002 g (2.2 x 10’ mols) of tris-(triphenylphosphine)chlororhodium (I) was added. The mixture was kept at 80°C. The evolution of hydrOgen was 31 slow at this temperature. The reaction was complete in 36 hours. There were two product peaks present on the gas chromatograph. The small peak is probably 1.1.3.3- tetramethyldiphenyldisiloxane which was formed by traces of water present. The benzene and excess butylamine were removed by distillation. The product and disiloxane com- ponent were flash-distilled from the catalyst. A gas chromatograph of the product showed that more of the amino- silane had hydrolyzed to the disiloxane during the distil- lation. An nmr Showed the product to be a mixture of the dimethylphenyl(n-butylamino)silane and l,l,3,3-tetramethyl- diphenyldisiloxane. The nmr gave the following absorption data. Proton ratio .5 values CH3SiE 6 4-0.4 (singlet) ‘3‘ ESi-N-CHg- 2.5 ‘4-2.8 (broad) ‘i‘ ESi-N-CHg-CHz-CHZ 5 ~ 1.4 (septet) 1? ESi-N-(CH2)3-CH3 3.3 ~1.0 (quartet) 2. Preparation of Dimethylphenylsilangl To a small vial (3 ml) was added 0.5 g of di- methylphenylsilane, 2 m1 of benzene, 2 drOps of water and 0.002 g of tris-(triphenylphosphine)chlororhodium (I). HydrOgen gas evolution started immediately. The color of the solution was yellow. In‘~8 hours two more drOps of 32 water were added. In 24 hours the reaction was complete. A gas chromatograph of the reaction mixture showed two pro- duct peaks. These peaks were believed to be dimethylphenyl- silanol and 1,1,3,3-tetramethy1diphenyldisiloxane. The benzene was distilled off and the products flash-distilled from the catalyst. An ir and nmr confirmed that the pro- ducts were dimethylphenylsilanol and 1.1.3.3-tetramethyldi- phenyldisiloxane. The ir spectrum Showed the bands at 3600 cm'"1 (OR), at 3280 cm‘1 (OH), at 1600 cm'1 (phenyl), at 1490 cm"1 (phenyl), at 1430 cm'1 (phenyl), at 1250 cm'1 (Si-CH3), at 1050cm"1 (Si-O-Si), at 1000 cm‘1 (Si-phenyl), at 860 cm‘1 (OR), at 790 cm'1 (Si-CH3) and no band at 2100 cm'1 (due to Si-H). The nmr Spectrum showed the following absorptions. 5 values CH3-SiE ,.0,5 (singlet C6H5" ’r7.4 (broad) ESi-OH 4-3.2 (broad) 3. Preparation of Triethylcyclohexanoxysilane To a 15 m1 single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 1.00 g (0.01 mols) of dried cyclohexanone and 5 ml of anhydrous benzene. The mixture was refluxed under nitrOgen for one-half hour to remove any 6 dissolved oxygen present. Then 0.002 g (2.2 x 10' mols) of tris-(triphenylphosphine)chlororhodium (I) and one drOp of triethylamine were added. The mixture was kept at 70°C for 24 hours. There was a product peak seen by gas chromatography during this time. There was, however, very little gas evolution. The solvent was removed by distillation and the product flash-distilled away from the catalyst. A gas chromatograph of the product showed it to be pure. An nmr and ir showed that the product was a mixture of hexaethyl- disiloxane and triethylcyclohexanoxysilane. A gas chroma- tograph of the mixture of pure hexaethyldisiloxane and the compounds prepared showed that they had exactly the same retention times. A mass Spectrum of the sample could only be explained if both compounds were present. Hydrolysis of the prepared compound produced one new peak in the gas chromatograph which had the same retention time as cyclo- hexanol. The nmr spectrum showed the following absorption data. Proton ratio g values ESi-Ob l ~3.5 (broad) 231-00 10 ~ 1. 0-2.0 (very broad) CH3CHZSEE 20.8 “~0.4-1.0 (due to hexa- ethyldisiloxane present) 4. Reaction of Cyclohexanone with Triethylsilane Using Triethylamine as a Catalyst To a 10 ml single-necked flask was added 1.00 g (0.01 mols) of dry cyclohexanone, 1.16 g (0.01 mols) of tri- ethylsilane, 3 drOps of triethylamine and 5 ml of anhydrous benzene. The mixture was heated for 24 hours between 80—9000. 34 A gas chromatograph after this time showed only starting materials present. There was no triethylcyclohexanoxy- silane detected. F. Reactions of an Organosilane with an Alcohol Catalyzed by an Acid 1. Reaction of Triethylsilane with Ethanol Catalyzed by Dimethylchlorosilane To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.46 g (0.01 mols) of ab- solute ethanol and 5 ml of anhydrous benzene. Then 0.1 g of dimethylchlorosilane was added. The mixture was kept at 60°C under a nitrOgen atmosphere for two days. After this time a gas chromatograph of the reaction mixture show- ed a very small amount of triethylethoxysilane present. The starting materials were distilled from the product. A total of 0.12 g of triethylethoxysilane was obtained. This amounts to a 7.5% yield. G. Competitive Reactions of Triethylsilane for Various Alcohols 1. Competitive Reactions of Triethylsilane for Ethanol and 2-Butanol To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.46 g (0.01 mols) of ab- solute ethanol, 0.74 g (0.01 mols) of dry 2-butanol and 5 g of anhydrous benzene. The mixture was refluxed for one hour under nitrOgen to remove any dissolved oxygen present. Then 0.002 g (2.2 x 10"6 mols) of tris-(triphenylphosphine)- chlororhodium (I) was added. The mixture was heated at 60°C 35 for 24 hours. At this time the reaction was complete (i.e. no starting materials were seen by glc and no hy- drogen evolution). A gas chromatograph of the mixture was run three times and the ratio of areas determined and av- eraged. The areas under the curves were determined by height times width at half height. The reSponse factors for the two products were determined from standard solu- tions of the two pure components. The response factors for the two components were equal to 1. The following was determined: Area [(02R5)3SIOCZH5]/Aree [(C2H5)3SiOCH(CH3) (C2H5)]= 4.50/2.84 = 1.595. 2. Competitive Reaction of Triethylsilane for Ethanol and tert-Butanol To a 10 ml Single-necked flask was added 1.16 g (0.01 molS) of triethylsilane, 0.46 g (0.01 mols) of ab- solute ethanol, 0.74 g (0.01 mols) bf dried tert-butanol and 5 ml of anhydrous benzene. The mixture was refluxed under nitrOgen to remove any dissolved oxygen. Then 0.002 6 mols) of tris-(triphenylphosphine)chloro- g (2.2 x 10' rhodium (I) was added. The mixture was kept at 60°C for 24 hours. A gas chromatograph at this time showed very little triethylsilane present. There was also much tert- butanol present and no ethanol. A product peak was seen for triethylethoxysilane, but no further product peaks were seen. The conclusion is that the ethanol reacts at a much greater rate than tart-butanol. 36 3. Competitive Reaction of Triethylsilane for Methanol and n-Butanol To a 10 ml Single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.32 g (0.01 mols) of an- hydrous methanol, 0.74 g (0.01 mols) of dried n-butanol and 5 g of anhydrous benzene. The mixture was refluxed for one hour under nitrOgen to remove any dissolved oxygen present. The mixture was then cooled and 0.002 g (2.2 x 10P6 mole) of tris-(triphenylphosphine)chlororhodium (I) was added. The mixture was kept at 50°C for 10 hours. At this time the reaction had gone to completion. A gas chroma- tograph of the mixture was run three times, and the areas of the two products averaged. The average areas obtained were: Area [(C2H5)3SiOCH3]/Area [(0235)3SIOCL,39]= 3.169/3.97u = 0.798. The reSponse factors are again found to be 1 for the two pure components. 4. Competitive Reaction of Triethyleglane for Ethanol and Phenol To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.46 g (0.01 mols) of abso- lute ethanol, 0.94 g (0.01 mols) of phenol and 5 g of an- hydrous benzene. The mixture was heated at reflux for one hour under nitrOgen to remove any dissolved oxygen. Then the mixture was cooled and 0.002 g (2.2 x 10"6 mols) of tris-(triphenylphosphine)chlororhodium (I) was added. The mixture was kept at 60°C for 24 hours. A gas chromatograph after this time showed complete reaction of the triethyl- silane. The only product peak seen was triethylethoxysilane. 37 The peak due to phenol was still present, and the peak due to ethanol had completely disappeared. The conclusion drawn was that ethanol reacts at a much faster rate than phenol. 5. Competition Reaction of Triethylsilane for l-Butanol and 2-Butanol To a 10 ml single-necked flask was added 1.16 g (0.01 mols) of triethylsilane, 0.74 g (0.01 mols) of dried 1-butanol, 0.74 g of dried 2-butanol and 5 m1 of anhydrous benzene. The mixture was refluxed for one hour under ni- trOgen to remove any dissolved oxygen present. Then the mixture was cooled, and 0.002 g (2.2 x 10"6 mols) of tris- (triphenylphosphine)chlororhodium (I) was added. The reac— tion was kept at 50°C for 24 hours and then at room temper- ature for another 24 hours. At this time the reaction was complete (by glc). Three gas chromatographs were run. The average areas obtained were: Area [(C2H5)3SiOCH(CH3) (02115)] /Area [(C2H5)3SiOCH2CH2CH2CH3]= 1.499/4.275 - 0.351. The reSponse factor for this system was determined to be 0.85. Therefore, the true ratio is 0.298. H. Competition Reactions of Various Organosilanes for a Single Alcohol 1. Competitipp Reaction of n-Butanol for Dimethylphepylsilane and Triethylsilane To a 10 m1 Single-necked flask was added 0.58 g (0.005 mols) of triethylsilane, 0.68 g (0.005 mols) of di- methylphenylsilane, 0.37 g (0.005 mols) of n-butanol and 5 ml anhydrous benzene. The mixture was refluxed under 38 nitrOgen for one hour to remove any dissolved oxygen pre- sent. Then 0.002 g (2.2 x 10'6 mols) of tris-(triphenyl- phosphine)chlororhodium (I) was added. The mixture was heated at 60°C for one hour, then cooled to room temperature and followed by gas chromatography. When the reaction was complete, the mixture was run three times on the gas chroma— tograph. The average areas determined are as follows: Area [(CZR5)BSIOCL,R9]/Area [(06H5)(CRB)ZSIOCL,R9]= .669/ 2.700 = 0.248. The response factor determined for the two pure components is 0.810. Therefore, the true ratio be- comes 0.201. 2. Competition Reaction Of Ethanol for Triethylsilane and Triethoxysilane To a single-necked 10 ml flask was added 1.64 g (0.01 mols) of triethoxysilane, 1.16 g (0.01 mols) of tri- ethylsilane, 0.46 g (0.01 mols) of absolute ethanol and 5 ml of anhydrous benzene. The mixture was refluxed under nitrogen for one hour to remove any dissolved oxygen pre- sent. Then the mixture was cooled and 0.002 g (2.2 x 10"6 mols) of tris-(triphenylphOSphine)chlororhodium (I) was added. The reaction was kept at 60°C and followed by gas chromatography. The reaction had not progressed to any extent in 36 hours. One drOp of triethylamine was added at this time to rid the system of any residual hydrOgen chloride present which could have come from the triethoxy- silane since it was prepared from trichlorosilane and ethanol without a hydrogen chloride acceptor present. A precipitate did form and hydrogen evolution started. It is known that hydrOgen chloride will inhibit the activity of the catalyst in hydrOgenation reactions. When the reaction had reached completion, three gas chromatOgraphs were run, and the average areas were determined as follows: Area [(C2H5)3SiOC2H5]/Area [(C2H50)3310C2H5]= 2.2942/2.5338 = 0.905. The reSponse factor determined for the two pure compounds was determined to be 1.82. The true ratio is 1.65. 3. Competition Reaction of Butanol for Triethylchloro- and Dimethylphepylchlorosilane To a 50 ml three-necked flask equipped with a con- densor, drying tube, magnetic stirrer, ice bath and gas tube was added 2.72 g (0.02 mols) of dimethylphenylsilane, 2.32 g (0.02 mols) of triethylsilane and 35 ml of dry car- bon tetrachloride. The mixture was cooled to 0°C and then chlorine gas was slowly bubbled through the stirring mix- ture. The chlorine gas was added until the stirring mix- ture stayed a green color. The reaction was then allowed to stir at room temperature for one-half hour. A gas chromatOgraph at this time confirmed that no starting mate- rials remained. The carbon tetrachloride was then distilled off at room temperature under reduced pressure. Then 10 ml of anhydrous benzene was added to the residue followed by 1.48 g (0.02 mols) of dried n-butanol. The mixture was allowed to stir for one hour. A gas chromatOgraph showed that the n-butanol had been consumed. Then’V5 ml of benzene was removed under reduced pressure. Three gas chromatographs 40 of the mixture were run and the areas averaged to give the following data: Area [:(C2H5)33iOChH§]/Area [(C6H5)(CH3)2 SiOCuH§]= .49/3.73 = .132. The response factor determined for the pure components is 0.810. Therefore, the true ratio is 0.107. I. Alkoxy Exchange on Silicon 1. Reaction of Triethyl(sec-butoxy)silane with Ethanol To a 10 m1, single-necked flask was added 2.0 g of anhydrous benzene, 0.2 g (1.1 x 10'3 mols) of triethyl(sec- butoxy)silane and 0.1 g (2.2 x 10"3 mols) of absolute ethanol. The mixture was then refluxed under nitrogen for one hour to remove any dissolved oxygen. Then 0.002 g (2.2 x 10"6 mols) of tris-(triphenylphOSphine)chlororhodium (I) was added. The mixture was kept at 70°C for 24 hours. A gas chromato- graph at this time showed no triethylethoxysilane had form- ed. An additional 0.1 g of absolute ethanol was added. The mixture was kept at 70°C for an additional 24 hours. After this time a gas chromatograph of the mixture Showed no tri- ethylethoxysilane had formed. 2. Reaction of Triethyl(sec-butoxy)silane with Tri- ethylethoxyeilane To a 10 ml, single-necked flask was added 2.0 g of anhydrous benzene, 0.1 g (5.3 x 10‘“ mols) of triethyl(sec- butoxy)silane and 0.1 g (6.25 x 10-4 mols) of triethylethoxy- silane. A gas chromatograph of the mixture was run. The mixture was then heated at reflux for one hour under nitrOgen to remove any dissolved oxygen. Then 0.002 g (2.2 x 10"6 mols) of tris-(triphenylphOSphine)chlororhodium (I) was added. 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Chatt, C. Eaborn. S. D. Ibekwe and P. N. Kapoor. J. Chem. Soc., A. 1343 (1970). A. L. Smith. Spectrochem. Acta.. lg. 87 (1960). APPENDIX A Infrared Spectra 1..‘4‘1li.14..._. II n‘ L: ‘C...1 ll IV. ~u.. it“ : o . . . . ..~ . . ~ \ ... my" M-fl. . a . . . . K .. 82.133182. ..e. Se. :82. Mom can . 83 one . . . II . . I .. ‘i . ‘I‘...’ -J‘..- a: [Hit- -.'I ill I .. ..." -I.. ”'0'. I'. h. ' M. | I.“ I .‘ A 3 .. .. .. . .. «”2411 EH ”4.”. . . T . .....Tlr (H. T (M ....ch a |_|mvlmt._ - 4| .Lfiu}? .) . . -__ Jul . . .b.‘ u. . .r . . . a —L. .“ .me_— .l...— O .. . .... .. ... w.vn h.~. .F. n . c. ”.11“ m. u. _ . .Aj — . o o. .- .. .. . -.l: _ ..L a... .1 . u. .... . . . ...d ,. .1 .. 1......1 ...H". _L . 1 .m . . ... r1. _ a . . L _ . . ..Lirtl...h- 11.2.1. . ....qi. .11.}... .- . a Taxis... e . .... 6.1 -1111. . , .-.: . Nuthl I .-.IMTTU .. .. ... .. . Li... . .. no. . .1 . 1 . 1'. x7... (I— llr. 111...?” ...!!31 ms... m. . .IP . (Ila .. A A , . .. u.- .u. .. I .‘hu «a 4‘ — u)".N . 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