The Preparation of Aromatic Amines with Sodium Amide in Liquid Ammonia

132 Pages·6.625 MB·English

by  Buting, Walter Eugene

PURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
Walter Eugene Buting
by_______________
The Preparation of Aromatic Amines with
en titled
Sodium Amide in Liquid Ammonia♦
COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES
AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS
FOR THE DEGREE OF
Doctor of Philosophy
A
. Professor m Charge of Thesis
- C* 0 0 ^ F? l'Hr VVU. 0JLI ■ Heap of School or Department
(j> £ I
19
TO THE LIBRARIAN:----
m
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
PBoraesoB rar chakob
GRAD. SCHOOL FORM 8

THE PREPARATION OP AROMATIC AMINES WITH
SODIUM AMIDE IN LIQUID AMMONIA
A T h esis
Subm itted to the F a c u lty
of
Purdue U n iv e rsity
by
W alter Eugene B uting
In P a r t i a l F u lfillm e n t of th e
R equirem ents f o r the Degree
of
D octor of P h ilo so p h y
June, 1951
ProQuest Number: 27714205
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ACKNOWLEDGEMENT
The a u th o r w ish es to ex p ress h ere his in d e b te d n e ss
to Dr. R o b ert A. B enkeser fo r su g g e stin g th is problem,
and fo r h is in v a lu a b le guidance and encouragem ent so
g e n ero u sly o ffe re d d u rin g th e co u rse of th is in v e s tig a tio n .
A p p re c ia tio n is a ls o ex p ressed to the A llie d Chem ical
and Dye C o rp o ra tio n fo r f in a n c ia l a s s is ta n c e in the form
of a F ree-G ran t F e llo w sh ip .
TABUS OF CONTENTS
Page
ABSTRACT...................................................................................................... i
LITERATURE SURVEY OF THE ORGANIC COMPOUNDS OF LEAD. 1
I n tr o d u c tio n ..................................................................... 1
A lk y l Lead Compounds...................................................................... 1
A ry l Lead Compounds........................................................................ 3
P o ly n u c le a r Lead Com pounds. .................................. 6
H e te ro c y c lic Lead Compounds.................................................. 6
A lk y l-A ry l Lead Compounds........................................................ 7
A lkyl Lead H a lid e s ........................................................................... 8
A ryl Lead H a lid e s .............................................................................. 10
A ik y l-A ry l Lead H a l i d e s . . . ..................................... 12
Plum bonic A c i d s . . . ............................................................ 12
O rganic A cids C o ntaining L ead. ................... 13
O rganic E s te rs C o n tain in g L ead.......................................... 14
A lkylam ino and A rylam ino Lead Compounds................. 14
Compounds C o n tain in g a Le ad-M etal Bond................... l 6
O rganolead S a lts of O rganic A c id s.................................. 17
O rganolead S a lts o f In o rg a n ic A c i d s . . . . ................ 21
Azo Compounds C o n tain in g L ead............................................. 22
O rg an o lead -Iro n T e tr a c a rb o n y ls .............................. 25
O rganolead Compounds of M iscellan eo u s T y p e s ... 26
B ib lio g ra p h y .............................................................................. 30
PREPARATION OF AROMATIC AMINES WITH SODIUM AMIDE
IN LIQUID AMMONIA.................................................................. 32
TABLE OF CONTENTS (C ontinued)
Page
INTRODUCTION. ............. 32
DISCUSSION................................................................................................................ 33
EXPERIMENTAL.......................................................................................................... 31
6-B rom o-o-ere s o l ...................................................................................... 31
2-Brom.o-6 -m e th y la n is o le ................................................................... 32
2-M ethoxy-m -toluic a c id from. 2-Bromo- 6 -m ethy 1 -
a n is o le .T .................................................................................................... 32
R eactio n o f 2-Bromo-6 -m e th y la n iso le w ith Sodium
Amide in L iquid A m m o n ia ....................................................... 33
3-Ni t r o - o - c r e s o l ...................... 34
2 -M e th y l-3 -n itro a n i s o l e ................................................................... 33
4 -M ethyl -m -a n isid i n e ................... 36
2-B rom o-m -cresol. P rocedure 1 ................................................. 36
2 -B rom o-m -cresol. P ro ced ’ure I I .................. 38
2-B rom o-m -cresol. P rocedure I I I . . . .................................... 38
2-Bromo-3 -m e th y la n iso le ....................................................... 39
6 -M eth o x y -o -to lu ic a c id from 2-B rom o-3-m ethyl­
a n is o le .7. ............................................................................................... 60
R eactio n of 2-B rom o-3-m ethylanisole w ith Sodium
Amide in L iq u id Ammonia.............................................................. 6o
2-Ni tr o - m - c r e s o l ................................................................................ 63
2-N itro -3 -m e th y la n is o le ................................................................... 64
6 -Me th y l -o -a n i s id i n e ........................ 65
6 -M e th y l-o -a c e ta n is id e ...................................................................... 65
R eactio n o f 2-B rom o-3-m ethylanisole w ith L ithium
D iethylam ide in E th e r .......................................................... 65
-TABLE OF CONTENTS (Continued)
Page
2 -Br omo -£ - to 1 uid i n e ........................................................................ 66
2-Brom o-jgi-cresol................................*.............................................. 67
2-Bromo- 4 -m e th y la n iso le ............................................................. 68
R e ac tio n of 2-B rom o-4-m ethylanisole w ith Sodium
Amide in L iq u id Ammonia................ 68
3-N it r o - £ - to lu id in e ......................................................................... 10
3 - N itr o - p - c r e s o l 70
3 -N itro - 4 -me th y la n iso l e ............................................ 71
6 -Me th y l -m -ani s i d in e ...................................................................... 71
m-( T riflu o ro m e th y l)p h e n o l........................................................ 71
2-Bromo-5 -( t r i f lu o r ome th y l) p h e n o l................ 71
2-Bromo-5 -( t r i f luorom ethyl ) a n is o le ............................... 72
R e a c tio n of 2-Bromo- 5 - ( tr if lu o r o m e th y l) a n is o le
w ith Sodium Amide in L iquid Ammonia....................... 72
3 ,5 -D in itr o b a n z o trifl u o rid e ................................................... 74
3 -N itr 0-5- ( t r i f luorom ethyl) a n i l i n e ............................... 74
3 -N it r 0-5 -( t r i f luorom ethyl) p h e n o l.................................. 75
3-Ni tro -5 -( t r i f luorom ethyl) a n is o le ............................... 7 6
5- ( T rif luorom ethyl) -m -an isid i n e ..................................... 7 6
Attem pted P re p a ra tio n of p -m eth o x y b en z o tri-
f lu o r id e ................................................................................................ 7 6
p -M eth o x y b en zo trif lu o ri d e ....................................................... 77
B rom ination of p -m e th o x y b e n z o triflu o rid e ............... 78
3-Ni tr o -4 -c h lo r o b en zo tri flu o r i d e .................................... 79
2 - N itr 0 - 4 - ( tr if lu o r o m e th y l) a n is o le . P ro ced u re I 79
TABLE OF CONTENTS (C ontinued)
Page
2 -N itro - 4 - ( tr if lu o r o m e th y l) a n is o l e . P rocedure I I 80
3 -N itro -4 -m eth o x y b en zo ic acid from 2 -N itro -4 -
(triflu o ro m e th y l)a n is o le ................ 8 l
5 - ( T rif luo rome th y l ) -o -a n i s i d in e ................................................ 8 l
2-Bromo-4 - ( t r i f lu orom ethyl ) a n is o le ........................... 8l
3-Srom o-4-m ethoxybenzoic a c id from 2 -Bromo-4 -
(triflu o ro m e th y l) a n is o le ............................................ 82
R eactio n o f 2-Bromo- 4 - ( tr if lu o r o m e th y l)a n is o le w ith
Sodium Amide in L iq u id Ammonia............................................. 83
R eactio n of o-B rom otoluene w ith Sodium Amide in
L iquid Ammonia................................. 84
R eactio n o f o -N itro a n is o le w ith Sodium Amide in
L iq u id Ammonia .............................................. 85
m -A c e ta n isid e .. .......................................................................................... 86
4 -N itro -m -a c e ta n is id e .. . ................................................. 86
B e n z y ltr ie th y ls ila n e .............................. 86
T rim ethyl ( o -ch io ro b e n zy l ) si la n e ................................................ 87
R e a c tio n of T rim ethyK o -ch lo ro b e n zy l ) si lane w ith
Sodium Amide in L iq u id Ammonia...................... 88
A ttem pted R ed u ctio n of o-B rom oanisole w ith Sodium
H ydride in L iq u id Ammonia ............................................. 89
SUMMARY.............................................................................................................. 90
BIBLIOGRAPHY................... 92
STUDIES IN PROGRESS WITH QRGAN03ILIC0N AND OIxGANOGERMANIUM
COMPOUNDS................... 95
INTRODUCTION AND DISCUSSION................................................................... 95
A. S tu d ie s w ith ©rganogermanium Compounds.................... 95
B. S tu d ie s w ith O rg a n o silic o n Compounds.......................... 97
TABLE OF CONTENTS (C ontinued)
Page
EXPERIMENTAL............................................................................................................. 98
T etraphenylgerm ane •. .. ................................................................ 98
Bromo trip h e n y l germ ane........................................................................... 99
B en zy ltrip h e n y lg e rm a n e......................................................................... 99
M e ta la tio n and H y d ro ly sis o f B e n z y ltrip h e n y l-
germ ane..............................................................................................................100
M e ta la tio n and C arb o n atio n of B e n z y ltri phen y l-
germ ane........................... 101
R eactio n of T e trap h e n y le th y le n ed iso d iu m w ith T r i ­
me th y lc h lo rb s i la n e ................ 101
BIBLIOGRAPHY..............................................................................................................104