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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1946 The introduction of functional groups into some organosilanes Russell N. Clark Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Clark, Russell N., "The introduction of functional groups into some organosilanes " (1946). Retrospective Theses and Dissertations. 13393. https://lib.dr.iastate.edu/rtd/13393 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 •mi IMTRODUGTION OF PUNCTIOHAL GROUPS INfO SOME 0RGAN08II.ANgS Rttseell K. cn.ark A fhesla Sul^ltted to the Graduate Faculty for the Degree of DOCTOR OF PHILOSOPHT Major Subject: Organic Ohemlsti^ Approved; Signature was redacted for privacy. Signature was redacted for privacy. Head of Major Deparfeent Signature was redacted for privacy. Hean of Graduate College Iowa State College 1946 UMI Number: DP12644 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 DP12644 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 11 c^4-; ACKNOWLEDGMENT author Is eincerely grateful to Dr. Henry Q-llman, whose valuable suggestlone and encouragement have been of great assistance during the course of these studies. r^o ^ ill TABLE OP CONTENTS INTRODUCTION NOMKNGLATURE HISTORIGAL • • • A. A Brief Review of Organoslllcon Cheraistiy from 1863 to 1927 B. Organosilioon Chemistry from 1937 to 1945 Introduction Alkyl Derivatives of the Type H^Si , , Alltyl Derivatives of the Type E'R^Sl . Aryl Derivatives of the Type R^^^i • • Aryl Derivatives of the Type R*RgSi , , Alkyl Derivatives of the Tsrpe RSlXg . , Aryl Derivatives of the Type RQiX^ . Alkyl Derivatives of the Type RgSlXg . Ai^l Derivatives of the Type RgSiXg , . Allsiyl Derivatives of the Type RR'SiXg . Mixed Aryl-Alkyl Derivatives of the Type RH^SiXg Alkyl Derivatives of the Type R^SiX . , Aiyl Derivatives of the Type R^SiX . • Alkyl Derivatives of the Type RgR'SiX . Alkyl Derivative.^ of the Type {RO)^Si . Aryl Derivatives of the Type (RO)^Si . iv Pag© Alkyl Derivatives of the Type (RO)gSiOR', 3I Mixed Aryl-Alkyl Derivatives of the Type (RO)_SiOR' 45 O Alkyl Derivatives of the Type (ac igSiCOR*)^ Mixed Ai'vl-Mkyl Derivatives of the Type (RO^gSKOROg .. » Alkyl Derivatives of the Type R3i(OR')j5 Aryl Derivatives of the Type RSi(OR)„ • O Alkyl Derivatives of the Type RgSiCOR') Aryl Derivatives of the Type R^SiCOROo /Z Alkyl Derivatives of the Type RR*Si(OR")g Mixed Aiyl-Alkyl Derivatives of the Tjrp® RR'Si(ORO Alkyl Derivatives of the Type R^SiOR' Aryl Derivatives of the Type RgSiOR' Alkyl Derivatives of the Type R§iOR' Alkyl Derivatives of the Type ROSiXg Aryl Derivatives of the Type ROSiXg . Alkyl Derivatives of the Type (R0)2SiXg Aryl Derivatives of the Type (R0)pSiX2 Alkyl Derivatives of the Type {R0){R'0)CiX2 . Alkyl Derivatives of the T?/pe Aryl Derivatives of the Type (R0)331X . .Hkyl Derivatives of the T;^/pe (R0)(R'0), Six ' V Alkyl Derivatives of the Type Paf-e Q (R-a-0)j,SiY^^^j^ 70' Alltyl Derivatives of the Type R^SlNRg . 72 Alkyl Derivatives of the Type {RS)^_S1 . 73 ' Alkyl Derivatives of the Type (RS)pSl(SR*)^ •••• 75 t-./ Alkyl Derivatives of the Tyne (HS^^SlCOR') 75 Alkyl Derivatives of the Type (RS)23iX. 75 Alkyl Derivatives of the Type (H3)gSlXp . 76 Alkyl Derivatives of the Type RSGIX^ . 76 Alkyl Derivatives of the Tyoe Iw31-0-31R^ 76 o o Aryl" Derivatives of the Ty:oe R„3103111^. « 78 o o Alkyl Derivatives of the Type /rR0)gJ^7oC. 79 Alkyl Derivatives of the Ty_)e /R0(R'0)gSj720 80 Alkyl Derivatives of the Type /Rgll'01337^0 31 Alkyl Derivatives of t}iG Type Hi[^her Liner r 611ozane Derivatives ... 81 Alkyl Derivatives of the Type • 82 Alkyl Derivatives of the Type R^SI-SIR^ . 83 v Aryl Derivatives of ttie Type R^SI-SIR^ . 84 Silicon Polymers 35 EXPERI1.1ENTAL 93 A. Silicon Compounds . .••••• 93 vl Pa^je ^ ITetraethylsllane 93 Tetra-n-butylsllane 94 TetralBopropylsllBue (Attempted) .... 95 Tetra-t-butylsllane (Attempted). ...» 97 ^Tetraphenylsilcoie ........... 98 /^rlphsnyl-^-tolylsllaiie 99 /Trl-2-"fcolylphenylsllane 100 J^-PlQolyltrlphenylsllane (Attempted). , 100 Dlphenyldi-j^-tolylsilane lOE /ferlphenylmethylsilane 1S3 /yrlmethylphenylsllane 104 / •^•riphenylolleiiol .....•«•*••• 104 -^rlphenylethoxysilane 105 'irlmethyl-j^broBJophenylsllane ..... 106 Trlmethyl-j3-llthiophenylBilane ..... 108 /Benzyltriethoxyailane ......... 103 '^frJjBethylbenzylsllane 110 Attempted biHsmination of trlnetl-iyl- benzylailane . Ill Attempted nitration of triraethylbenzyl- silsjie 112 Phenyl trie thoxyallane 113 Attempted nitration of phenyltrlethoxy- sllane ,,... ........ 114 • p-AolnophenyltriethoxyQilane ...... 114 J^riethylohlorosilane ... ...... 116 vll Page Refonuatslcy reaction with trlphenyl- chlorosllane ...» 116 Refortnatsky reaction with trlethyl- cJilorosllane ..••••••«.•• 117 Etliyl trlethylsllylacetete (Atterrpted). 117 Ethyl trlphenylsilylacetate (Attempted) , 118 Reaction 'oet^een trleth^^-lchlorosllane and ethjl sodloacetoacetate ...» 118 Reaction of trlphenylcjilorosllaJie and ethyl sodloacetoacetate 122 Reaction hetr-'C-on triphenylcliloronllrne sud diethyl socllonalonr.te ..... 122 Reaction of trlethylclrilorosllajie viith diethyl sodiomelonate 123 B. ^-Lactame of yi-ARlllno- i^-phenyl- proplonlc Aclae ............. 123 i^-Lactara of /6-an 11 lno-/4-phenyl- propionic acid • . • 123 Basic hydrolysis of the /^lactain of ^aiillino- y5-phenylproplonic acid. 124 Acid hydrolysis of the ^lactan of ^enlllno- ^-p}ienylpropionic acid . 124 Ethyl ^anlllno- /J-phenylpropionate . 125 Ethyl ^-anillno-/^ ~phenylpropionate ... 125 Reactlon'-^of ethyl ^anllino-/5-phejiyl- propioiiate with methylmagneslum iodide 126 Reaction of ethyl ^anlllno-/^-phenyl- propionate with n-butylllthluin ... 127 Reaction of ethyl y^anillno-/^-phenyl- propionate vjith lithium diethyla^ilde 127 Reaction of ethyl i^anllino-/^-phenyl- propionate wixh dlethylzinc . ... 127 vlll i» y» Reaction of eti^ayl fl-anlllno- fVphenyl- proplonate with phenylllthlum . • * • 128 Reaction of ethyl (^anlllno-A-phenyl- propionate with Ejethyllithium .... 128 Reaction of ethyl [Vanlllno-^-phenyl- propionate with phenylethynylmagnesli® iodide 129 Reaction of ethyl /^anlllno- /i-phenyl- proplonate with phenylethynylllthiura. 129 Acetosesityl^e 130 Reaction of ethyl /3-anilino- /3-phenyl- proplonate with aoeto/m eeltyl- magnesliaa brcaaide , . 130 Variation of solvent in the preparation of the /J-lactaiB of >^anilino<-A-phenyl- propionic acid 130 Variation of the zinc employed in the pre­ paration of the y^lactao of ^anllino- ^-phenylpropionic acid ....... 131 o-Chlorobenzal-^-chloroaniline ...... 131 I^Lactara of As-chloroanilino- /5-o - chlorophenylpiHspionic acid ..... 132 ^-Anlflal-£-anisidine 132 ^Lactam of ^£-anieidino-/^-jg-anisyl- propionic acid . 132 _2-Anisal-^chloroaniline 133 A-Lactam of /5-^-chloroanillno->4-j2- anlsylpjfopionic acid 133 ji-Anisal-ra-chloroaniline 134 A-Lactam of A-m-chloroanillno-^ ' anlsylpifoplonic acid ........ 134 £-Ani8al-o-chloroaniline 134 Ix Page Attempted preparation of the ^lactam of A-o-chloroanlllno- ^ -£-anisyl- pi^pionio acid ........... 135 o-Chlorobenzal-o-ohloroanillne ..... 135 Attempted preparation of the ^^lactaa of /i-o- chloroan il Ino- /^o- cnloro- phenylpropionic acid T ...... 135 Benz.al-^-chLoroaniline ......... 136 ^-Lactam of chloroanilino- ^-phenyl- propionlo acid 135 Benfcal-p-ani0iaine ........... 136 ^-Laetaai of /i-£-anisidlno~ id-phenyl- propionic acid 137 D-ChloiKJbenzalaniline 137 A-Lactam of /5-anilino- A-£-chloro- phenylpropionic acid 137 H,N*-Benzal-bis-JL-pyridylaiaine ..... 138 Benzal- Ji -pyridylamine 138 Attempted preparation of the /^-laetam of -A.-pyridylRinino-/S-phenylpropionic acid ' 138 Attenrpted preparation of benzal-o-chloro- aniline .........T .... 139 Benzal-o-ohloroaniline 139 Attemoted prepsj^ation of. the/^lactam of A-o-cnloroanilino- A-phenylpropionio acid . ' ~. 140 C. Phenylpyridlne Derivatives 140 2-Phenylpyridlne ...... ...... 140 E-Nitrophenylpyridinee ......... 140 X Page 2-(4•-AsInophenyl)pyridine 141 2-(4•-Benzalarolni phenyl)pyridine . • • 142 2-(4*-SalloylalejBlnophenyl)pyridlne « • 142 '-Z4'~(2", 5"-Dimethylpyrryl-l" )phenyl7- pyridlne .......... ... 142 2-(4'-FormylanInophenyl)pyrldine • • • • 143 2-(4'-Acetartiinophenyl)pyrldlne . « • • 143 2-(3' -IIitro-4 *-acet02ninophenyl} pyridine. 144 2-(5'-nitro-4'-aifllnophenyl)pyridine « • 145 2-(u *-Hitro-4 Inophenyl )i)yridjln e 145 jj-Anlsylllthlum ..•••••••••*
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    DEAN #37261 (McGHP) RIGHT INTERACTIVE top of rh PHYSICAL PROPERTIES 5.157 base of rh cap height TABLE 5.29 Van der Waals’ Constants for Gases base of text The van der Waals’ equation of state for a real gas is: na2 ͩͪP ϩ (V Ϫ nb) ϭ nRT for n moles V2 where P is the pressure, V the volume (in liters per mole ϭ 0.001 m3 per mole in the SI system), T the temperature (in degrees Kelvin), n the amount of substance (in moles), and R the gas constant. To use the values of a and b in the table, P must be expressed in the same units as in the gas constant. Thus, the pressure of a standard atmosphere may be expressed in the SI system as follows: 1 atm ϭ 101,325 N · mϪ2 ϭ 101,325 Pa ϭ 1.01325 bar The appropriate value for the gas constant is: 0.083 144 1 L · bar · KϪ1 · molϪ1 or 0.082 056 L · atm · KϪ1 · molϪ1 The van der Waals’ constants are related to the critical temperature and pressure, tc and Pc, in Table 6.5 by: 27 RT22 RT a ϭ ccand b ϭ 64 Pcc8 P Substance a,L2 · bar · molϪ2 b,L·molϪ1 Acetaldehyde 11.37 0.08695 Acetic acid 17.71 0.1065 Acetic anhydride 26.8 0.157 Acetone 16.02 0.1124 Acetonitrile 17.89 0.1169 Acetyl chloride 12.80 0.08979 Acetylene 4.516 0.05218 Acrylic acid 19.45 0.1127 Acrylonitrile 18.37 0.1222 Allene 8.235 0.07467 Allyl alcohol 15.17 0.1036 Aluminum trichloride 42.63 0.2450 2-Aminoethanol 7.616 0.0431 Ammonia 4.225 0.03713 Ammonium chloride 2.380 0.00734 Aniline 29.14 0.1486 Antimony tribromide 42.08 0.1658 Argon 1.355 0.03201 Arsenic trichloride 17.23 0.1039 Arsine 6.327 0.06048 Benzaldehyde 30.30 0.1553 Benzene 18.82
  • Influence of Silicon on High-Temperature

    Influence of Silicon on High-Temperature

    Solar Energy Materials & Solar Cells 160 (2017) 410–417 Contents lists available at ScienceDirect Solar Energy Materials & Solar Cells journal homepage: www.elsevier.com/locate/solmat Influence of silicon on high-temperature (600 °C) chlorosilane interactions with iron crossmark ⁎ Josh Allera, , Nolan Swainb, Michael Babera, Greg Tatarb, Nathan Jacobsonc, Paul Gannonb a Mechanical and Industrial Engineering, Montana State University, Bozeman, MT 59717, USA b Chemical and Biological Engineering, Montana State University, Bozeman, MT 59717, USA c NASA Glenn Research Center, Cleveland, OH 44135, USA ARTICLE INFO ABSTRACT Keywords: High-temperature ( > 500 °C) chlorosilane gas streams are prevalent in the manufacture of polycrystalline Iron silicon, the feedstock for silicon-based solar panels and electronics. This study investigated the influence of Chlorosilane metallurgical grade silicon on the corrosion behavior of pure iron in these types of environments. The Silicon experiment included exposing pure iron samples at 600 °C to a silicon tetrachloride/hydrogen input gas mixture Silicon tetrachloride with and without embedding the samples in silicon. The samples in a packed bed of silicon had significantly Iron silicide higher mass gains compared to samples not in a packed bed. Comparison to diffusion studies suggest that the Corrosion increase in mass gain of embedded samples is due to a higher silicon activity from the gas phase reaction with silicon. The experimental results were supported by chemical equilibrium calculations which showed that more- active trichlorosilane and dichlorosilane species are formed from silicon tetrachloride in silicon packed bed conditions. 1. Introduction most common material added to a chlorosilane gas stream is silicon. Silicon may be present in a fluidized bed reactor used to convert silicon Chlorosilane species are used at high temperatures in the refine- tetrachloride to trichlorosilane or deposition equipment used to deposit ment, manufacture, and deposition of silicon and silicon-containing silicon on a wafer.
  • Silicon Tetrafluoride Interim AEGL Document

    Silicon Tetrafluoride Interim AEGL Document

    Silicon Tetrafluoride INTERIM: 06-2008 1 2 3 4 ACUTE EXPOSURE GUIDELINE LEVELS (AEGLs) 5 FOR 6 Silicon Tetrafluoride 7 (CAS Reg. No. 7783-61-1) 8 9 Si-F4 10 11 12 13 14 INTERIM 15 16 17 18 19 20 21 22 Silicon Tetrafluoride INTERIM: 06-2008/ Page 2 of 26 1 2 ACUTE EXPOSURE GUIDELINE LEVELS (AEGLs) 3 FOR 4 SILICON TETRAFLUORIDE 5 (CAS Reg. No. 7783-61-1) 6 7 8 INTERIM 9 10 Silicon Tetrafluoride INTERIM: 06-2008/ Page 3 of 26 1 2 PREFACE 3 4 Under the authority of the Federal Advisory Committee Act (FACA) P. L. 92-463 of 5 1972, the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous 6 Substances (NAC/AEGL Committee) has been established to identify, review and interpret 7 relevant toxicologic and other scientific data and develop AEGLs for high priority, acutely toxic 8 chemicals. 9 10 AEGLs represent threshold exposure limits for the general public and are applicable to 11 emergency exposure periods ranging from 10 minutes to 8 hours. Three levels C AEGL-1, 12 AEGL-2 and AEGL-3 C are developed for each of five exposure periods (10 and 30 minutes, 1 13 hour, 4 hours, and 8 hours) and are distinguished by varying degrees of severity of toxic effects. 14 The three AEGLs are defined as follows: 15 16 AEGL-1 is the airborne concentration (expressed as parts per million or milligrams per 17 cubic meter [ppm or mg/m3]) of a substance above which it is predicted that the general 18 population, including susceptible individuals, could experience notable discomfort, irritation, or 19 certain asymptomatic, non-sensory effects.