High-molecular-weight aliphatic amines and their derivatives

179 Pages·2017·10.68 MB·English

Iowa State University Capstones, Theses and
Retrospective Theses and Dissertations
Dissertations
1940
High-molecular-weight aliphatic amines and their
derivatives
William Irving Harber
Iowa State College
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Recommended Citation
Harber, William Irving, "High-molecular-weight aliphatic amines and their derivatives " (1940).Retrospective Theses and Dissertations.
13702.
https://lib.dr.iastate.edu/rtd/13702
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HlC^I~iJ0L:!3CUL\i:-;/HIGIIT -iLIHL.TIC ,.^[€ 11:^3
AI® TIHIR D3RIV.^TIY1S
by /5
Williaa Irvine Harber
A fhasis Submitted to the Graduate Faculty
for tile Degree of
DOGTOH OF PHILOSOPHY
Lfeijor Subject Orc:anic Chomistry
ipproTed:
Signature was redacted for privacy.
la oiiarge of Major work
Signature was redacted for privacy.
Hea^ of ilaj or Bepartment
Signature was redacted for privacy.
lovm State College
1940
UMI Number: DP12736
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- g -
ACKIIOWLIDGIOTT
Tha author wishes to express his appreciation to
Professor Henry Giliaan for the initiation of the problem
and to Professor W, F# Goober for guidance in the success­
ful termination of the work, 1?he author also wishes to
thank Dr» A, ih Ealston of Armour and Co., Ghioago, 111,,
for supplying liberal amounts of mterlals required in
this study.
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fABLl OF COHlSfTS
page
msmmoTioM, lo
HISTORICAL. ........... 14
Ptirifleation of Stearic Acid. 14
Hitriles........... • 17
Maiaing of ilmines 20
Preparation of High-Moleeular-'Weight iiMines.,.., 21
Synthesis of Higb-Molecular-Weight Primary
Iminas 23
Foiiifition of Higli-Moleoular-Weigiit Primary
Amines 28
Syntliesis of Higla-Molecular~»veight Secondary
34
Foraatioa of Hlgh-Molecular-Weight Secondary
Mines* .................................... 35
Synthesis of High-Mol©eular-WQight Tertiary
imines 36
Formtion of Hi^-Molecular-Weight Tertiary
iuiines 37
Preparation of Higb-Molecular-i'eight Alkylated
Amines by Diraet Alkylation................ 37
Physical Properties of High-Molecular-Weight
Aain@s 39
DeriTatiaation of High-Moleeular-Weight Aliphatic
Amines..................................... 40
Dariiratlzing Reactions of High-Molecular-wfeight
Primary iimines............................. 41
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page
Otiisr BeaetloEs of High-Moleoular-Wtiglit
47
Dir@et Goadensatioa of iaaines and Carboxyllc
A c i d s , 5 1
Direct CoMsjasation of Amines aad Dibasic
E s t e r s . • 5 6
Pkarmaco-logy of High-Molecular-Weight Aliphatic
Amln&s asd a®ir DeriTOtiT®s 61
Uses of Higb-Molaoular-'isiglit Aliphatic Aiaiaes
aad 1?h®ir DeriTatlTes 65
i^olysis of Aliphatic Amine HydrochloridsB..,,,... 68
6-iiaiiiopyrimidin@@« • 70
KPllIMf TAL.. ........................................... 74
Purification of Stearic Acid 74
Preparatioa of Stearonitrile.•75
Preparation of Lauronitril® 77
Prsparatiom of Setoaeonitril©.78
Att^pt to Prepare Oleonitril©..................... 78
Attempt to Prepare llaidonitrile................... 79
Preparatioa of ja-Octadecylaaine.................... 79
Hasipulatioii of High-Molscular-Weight Primary
Aidiids 81
Praparation of Di-a-octadecylaaine................. 8S
Preparation of Di-n-octadecylajaine Hydrochloride... 83
Preparation of fri-B-octadecylamine
Hytrochloride.T............................... 84
Attempt to Prepare Oleylamine.. 85
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page
Atteiapt to Prapar© Slaidyla.ffline. 86
Preparation of l,lO-D®ean0cli;aiaine, 87
Preparation of a-Octadecylurea,.................... 88
Preparatioli of NjH-Di-a-octadscylurea, 89
Preparation of N,H*-Di-n-ootadeeyltiiiourea,....... 90
Preparation of II,K*-Di-n-octad©Gyl'urea. . 91
Preparation of !I,N*-Di-a-doa©oylthiourea, 91
Reaotion of ^-Dodeeylamine and Carbon Disulfide... 92
Beaotioji of ii-Octadecylaiiin© and Carbon
Bisulif [email protected]
Atteaipt to Prepare N,N,K%If*-f0tra-.m-octadecyl-
thiotirea*. ................................... 94
Preparation of K-.n-Dod«eyl-l'*~pfeenyltiiiour©a...... 94 '
Attempt to Prepare H-ll-Di-a-oetadeoyl-H^-phenyl-
tiiiomrea, .T. 95
Frsparatioa of M^H-Di-a-oetadecyl-M'-phenyl-
urea..T,.......................... 95
Prepai'ation of IJ-n-'Do4eoyl-K*-o^aaplith.ylurea.,.... 96
Preparation of II-n-Octadeeyl-lJ^-otEaplithylurea,.97
Preptiration of M,!f-Di-ii-o0taaecyl-n*-^-naplitIiyl-
u r s a . 9 7
Attempt to Prepare K-n-I)oa©cyl-N'-o(-naph,thyl-
tbiourea. 98
' Preparation of M-n-Dodecyl'benzeiiesuJ.fon&iaide.• .... 99
Preparation of tl-a-Octadecylbenzeneaulfonaraide,,.. 99
Prepareitioa of II-n-Dodaoylacetaiaiae,.............. 100
Prapai'ation of a-I)ofi0cyl8i;Utto.niiirft K-n-Dodeoyl-
c a r t o a a a t ®, T . 1 0 1
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page
Preparatioa of IJ-n«Dod©ojl-£'-tolueiie<-
.T.
sulfonamid® 101
Preparatloa of H-a-Dodecylst©arainid©
Indireet Method. 102
Direct Method.,103
Preparation of l-a-Ootad©eylst©aramid©............ 104
Preparation of l-a-Ootadeeylljeiizaiiid©
ladirset MetKoi 105
Direet Method................................ 105
Preparation of N-JQ-Dod©oylpaliaitaiaide............. 106
Preparation of H-a-Octadecylpaladtamide 107
Preparation of N-n-Dodeeylayristamid©............. 108
Preparation of H~»-O0tad©cyliByristamide........... 108
Preparation Of H«n-.Dodecyllaureiaid@ 109
Preparation of S-iwOotadecyllauraniide HO
Preparation of l-n-Dodacyl-o-chlorobensaiaide...... HO
Preparation of H-^-Oetadecyl-o-chlorobenzamide.... HI
Praparation of H-n-Dod©oylciimaiaid©. 112
Preparation of M-n-Oetadeoyleiimamide............. 113
Prsparation of K-n-Dodeeyl-^-chlorobeazamide...... 113
Preparation of H-a-Oetadaeyl-jgt-oliloro^jeiizamide.,.. 114
Attempt to Prepare N-n-Bodecyl-j^-nitrobenzataide... 115
Attempt to Prepare H-n-0etad©cyl-£-3aitro-
BEAZAMIDE•••....T.............116
Preparatioa of H-a-Dodeeyl-o-toluaiiide............ 117
Preparation of M-n-Oetadecyl-o-toluaiaide.......... 117
Preparation of H-n-Dodeeyl-m-toluaald©..'. 118