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A Study of The Decomposition of Some Aromatic Diazonium Hexafluor
A Study of The Decomposition of Some Aromatic Diazonium Hexafluor
Scholarship at UWindsor
1-1-1964
Recommended Citation
Redmond, William A., "A study of the decomposition of some aromatic diazonium hexafluorophosphate
salts." (1964). Electronic Theses and Dissertations. 6038.
https://scholar.uwindsor.ca/etd/6038
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A STUDY OF THE DECOMPOSITION OF SOME AROMATIC
BY
WILLIAM A. REDMOND
A Thesis
Submitted to the Faculty of Graduate Studies through' the
Department of Chemistry in Partial Fulfillment
of the Requirements for the Degree of
Doctor of Philosophy at the
University of Windsor
Windsor, Ontario
1964
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UMI Number: DC52601
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ABSTRACT
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iii
amine.
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ACKNOY/LEDGEMENTS
iv
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TABLE OF CONTENTS
Page
ABSTRACT .......... ii
ACKNOWLEDGEMENTS .............. . . . . . . . . iv
Chapter
1. INTRODUCTION . ............ 1
BIBLIOGRAPHY.............. 90
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LIST OP TABLES
Table Page
1. A Comparison of the Use of Pluosilicate versus
Pluoborate in the Schiemann Reaction . . . . . 12
vi
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LIST OP ILLUSTRATIONS
Pigure Page
1. The Schiemann R e a c t i o n ..................... 3
5. Preparation of 4-Trimethylammonium-2,6-di-
chlorobenzenediazonium Pluoborate Chloride . 40
7. Reaction of 2,4,6-Trichlorobenzenediazonium
Pluoborate with 2-Phenyl-l,3-di::~elare . . . 52
8.. Reduction of 4-Trimethylammonium-2,6-dichlor-
obenzenediazonium Pluoborate Chloride with
Substituted Dioxolanes ..................... 55
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A Study of the Decomposition of Some Aromatic
Diazonium Hexafluorophosphate Salts
CHAPTER I
IITRODUCTION
1* The Replacement of an Aromatic Amino Group by Fluorine.
diazonium salt.
b) The preparation of aryliodides, bromides, chlorides,
and -SCH2C00H,
1 2
d) The preparation of nitroaromatics. ’
Reaction.
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2
g) The preparation of arylphosphonic or diarylphos-
3
phinic acids.
Reaction.
k) Arylation reactions - Meerwein Arylation.
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o) The preparation of arylgermaniunr1-1 and arylselenium
compounds.12
ative.
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4
The Schiemann Reaction is of great interest in organic
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13
Finger found that 2 ,5-difluorochlorobenzene and 2,4-di-
derivatives.
The purification of diazonium fluoborates usually in
substantially.
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6
1. Carbonium ion..
A r+ + N2 -f B F
A r+ + A r :F: + BF■
2 4 Free radical.
A r* + N2 4- B F3 + ’F :
• •
3. Rearrangement.
Ar : n ==tn:
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results of decomposition of diazonium fluoborates and
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compounds it is not surprising that this procedure has
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9
22
prepared by the use of nitrosyl fluoborate or the complex
of boron trifluoride with dinitrogen trioxide.^ A variety
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10
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11
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Table 1
Diazonium Fluosilicate cl
Fluoroaromatic aromatic by Schiemann
Aniline 87 50.lt 27
p-Aminophenol 79.2 65 - 27
2-Aminopyr idine 0
O
34 \ 27,28
1
1
*\
3-Aminopyrid ine 33 28
a Yields reported are taken from A. Roe, Org. Reactions/ 5, I93 (1949)
(V)
13
29-31
It has been reported by Bergman in a series of
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Table 2
p-Aminoacetanilide — — 82a 30
m-Aminoacetanilide 75S 30
4-^100-^' -acetamido-3, y -
dimethoxybipheny1 -------
57a 30
if-Fluoro-l-acetamidonaphthalene — - 69a 30
5-Fluoro-l-acetamidonaphthalene _ _ _ _
55a 30
m-Phenylenediamine 96 28 31
o-Nitroaniline 95 52 31
m-Nitroaniline 97 itT 31
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Table 2 (contd.)
p-Nitroaniline 98 61 51
o-Aminobenzoic acid 51 51
p-Aminoacetophenone 8 8 -90 2k 51
Benzidine 90 72 31,29
p-Aminophenylacetic acid —
87 31
p-Aminocinnamic acid 76 k8 31
1-Naphtbylamine 92 h6 31,29
2-Naphthylamine 95 5k 31,29
1-Aminoanthraquinone 88 72 31,29
2-Aminofluorene 77 60 31
p-Aminophenol ------ 71 31
o-Aminophenol _ — 1+0 31
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Table 2 (contd.)
p-Aminoacetanilide 65 55 31
o-Chloroaniline — l6a 29
5-Chloroanthranilic acid —
56a 29
p-Bromoaniline 50 30 29
o-Toluidine 81 21 29
m-Toluidine 75 21 29
p-Toluidine 82 17 29
2,3-Dimethylaniline 85 30 29
2, 5-Dimethylaniline 82 19 29
2-Aminobiphenyl 75 2k 29
2,2’-Diamino-6,61-dimethyl-
biphenyl 75 20.5 29
CT\
17
preparation of 5-fluorobenzimidazole from the corresponding
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18
vided.
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Table 3
k-Bromoani1ine 5^ 38
2,4-Dichloroaniline 68.7 39
2}5-Dichloroaniline 69 68.5 39
Table 3 (contd.)
4-Fluoroaniline 44 45
2,3>5-Trifluoroaniline 89 h3& 47
3, 5-Difluoroaniline 98 62.8a 48
2-Chloro~4-fluoroaniline — — 46
2-Fluoro-5-bromoaniline 84 8a 49
p-Benzylaniline 50
Aminonitrodurene 59 51
Table 3 (contd.)
Nitromesidine 95 53-7 52
p-t-Butylaniline n.d. 5^
if-(2-chloroethyl)aniline 75 n.d. 55
o-Toluidine 87 56
p-Anisidine 62a 38
2}6-Dibromo-it-aminophenol quant. —
59
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Table 3 (contd.)
............ . •
Amine Yield of ArNgBF^ Yield of ArF Reference
p-Aminophenol 65 n.d. 60
fr-Chloro-2,5“diethoxyaniline 90 n.d. 61
m-Aminophenol 79 n.d. 60
o-Trifluoromethoxyaniline --- 2 8 .8 a 63
m-Tr ifluoromethoxyani1ine 35 a 63
0-(1,1.2-Trifluoro-2-chloro-
ethoxy)an i1 ine --- --- Gk
m-(1,1.2-Trifluoro-2-chloro-
ethoxy)aniline --- 6k
p-(1,1,2-Trifluoro-2-chloro-
ethoxy)an i1ine --- --- 6k
Table 3 (contd.)
Methyl-2-aminoveratrate --- — ■
p-Aminosalicylic acid
methyl ester ---- 3la 68
°2 failed 70
Cl
0)-
E-*, H. 0
quant. n.d. 71
/ N~C“CH3
OEt
1-Amino-h-diethylamino-
2-ethoxybenzene 90 n.d. 72
o-Amino-N-methylbenzanilide —
n.d. 73
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Table 3 (contd.)
^ ~ ^ h -c 6 h 4n h 2 failed 50
2-Amino-N-methylbenzo-l'-
naphthalide n.d. 7*t
2-Amino-N-methylbenzo-2’-
naphthalide --- n.d. 7^
Ketones
2-Aminobenzophenone 6o n.d. 75
o-Aminopropiophenone 79 n.d. 76
m-Aminopropiophenone 88 n.d. 76
2- (k'-Methylbenzoyl)aniline 56 n.d. 75
2- (i).' -Methylbenzoyl )aniline 70 n.d. 75
2- (31-Nitrobenzoyl)aniline 90 n.d. 75
25
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Table 3 (contd.)
2-NN-Dimethylamino-l-
fluorenamine 80 3la 79
Heterocyclic Compounds
Sulfathiazole 76 5 68
5-(p-Aminopheny1)thiazole 90 15 68
5(6) Aminobenzimidazole 86 38 83
If(7) Aminobenzimidazole 6l 17 83
3-Aminoquinoline 80 9 1 .5 8^
5-Aminoquinoline 9% 59 8k
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Table 3 (contd.)
6-Aminoquinoline 95.5 60 8k
8-Aminoquinoline jk 33 8k
3-Aminoisoquinol ine —
kf 85
if-Aminoisoquinoline — - - 36a 85
2-Amino-Jf-methylthiazole — 5a 86
—r0o
(lt-H2NC6H^)2CMeAc, 76 87
( p - h 2n c 6h 4 ) 2 c h 2 __ - 50
t
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Table 3 (contd.)
Miscellaneous Compounds
v 0EI
/~\ 1 ^
H2N \ Ch2 f S o E t 50b 88
v-- '/ HN
'c- c h 3
o" 3
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30
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31
68 P. Zuber, E. Sorkin, and H. Erlenmeyer, Helv. Chim.
Acta.. 32, 1269 (1950).
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32
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33
gen Atom.
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34
Reactions.
line and toluene from any one of the three isomeric methyl-
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35
cuprous oxide was used and if the reaction mixture was heat
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use of this method they were able to prepare 3,5-difluoro-
+
C H2 N H 2 C h2Nh 3
h! N o NOo
pH < 3
I
N H2
amino group.
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37
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38
c h 2n h 3 CH2 NH3 c h 2 nh
H+ H*
0 - I I
n h 3 NH N H,
b h 2 BH B
dH 1 2 3 4
B 1 100 6,700 167,00c
BH 2 , 380,000 2 2 ,7 9 0 ,0 0 0 1 5 9 .5 2 0 .0 0 0 3 9 8 , 7 0 0 , 00C
B H ?4 7 6 ,1 9 0 ,0 0 0 4 5 5 , 780,000 3 1 9 .0 4 0 .0 0 0 7 9 , 700,000
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39
105
recently reported by Hendrickson. ^ His method involves
very few examples were given and further work will be re
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40
107
more recent work on diazonium fluoborates Meerwein has
Cl C H 3- i y - C H 3 Cl
+ N=N
deamination procedure.
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CHAPTER II
41
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42
is shown in Figure 6.
J ^ ^ S - N S N ] PF6- a + N2 + p f5
I * I
has been shown that the larger the anion in the diazonium
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43
2
are approximately equal. In addition to the increased
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44
gloves were used to protect the hands but it was not found
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schock and B.C. McKusick, the checkers on a submission to
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46
benzene is low.
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47
ses in yields of the above compounds were 52, 49, 35, 27,
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Table 4
-ts-
00
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Table h (contd.)
methylurea.
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51
in marked contrast to the yields obtained by reductions
the reaction
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52
N= N
C I
h2 c
\
h2 c - / ‘G6 H 5
Cl
h2 c
■m |m \ +
;g - g 6h 5 BF,
c •Cl
h2 c /
o
55 % 80%
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Table 5
Aniline 5 60 60 25-30
o-Toluidine o-Methylphenetole,ca.50 70-75 80
p-Toluidine o-Methylphenetole,ca,50 77-83 80 25-30
o-Anisidine Amount unstated 75 33
Anthranilic acid Ethyl benzoate,53 25 80-85
p-Aminobenzoic acid p-Ethoxybenzoic acid, 50
+ ethyl benzoate .82
o-Nitroaniline 82 75-80 20 75
p-Nitroaniline 70 55-60 10 62
p-Chloroaniline 87 50 7°
o-Bromoaniline 72-80 80
p-Bromoaniline 68-80 72
p-Aminoacetophenone k3
a Unless otherwise specified, the amino group has been replaced by hydrogen,
b Data taken from Nathan Kornblum, Org. Reactions, 2, 262 (19^0
vn
u>
54
8
More recently Meerwein has reported the reaction of
methylammonium-2,6-dichlorobenzenediazonium fluoborate,
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55
N =N B F4“ ljl=N B F/
i C H 3
C l-r ^ ^ r C I 3 C l-rf'^ v -C I
+ N -C H 3
I °
C H 3
Cl C H 3*N” C H 3 Cl
CH*
N: N s f 4“
I 0
h 2 c
Cl -Cl
+
h 2 c
l
C H 3- N ; C H 3 Cl
c h 3
?
+? h 3
+ n 2 + CH3-IS1-H BF4
c r ' s ^ -ci CH3
H C
stituted dioxolanes.
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In the above reaction sequence an ionic mechanism is
occurs.
CH3
+' 0
C H3*N-C H3 c r
A *
BE
HoC'
HoC
v
/
H
x C H 3
N: IN
+c h 3
CH^N-C H3
ri2 c
Cl- -Cl
+ h 2c ./
c-ch3 + c r + n2
h2 c*
H»C \C-CH3 Cl
h 2c
I *?\
/
P-CH3
Ho C- /
e
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57
Cl HoC 0
I II
ride.
might be operative.
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Ar + n - c - nn -> ArH + N -C -N
H jt/ CH3 H 3 C/ H3
a) P F b) P F 6"
f h 2 cn ?i .c h 3
H2 C\V ft / CH3
PF5 + . N -C - PF6“ N -C -N
h3 c 7 g h 3 N Chl3
solvent
H3< \ ^ C H 3
h3 c ft CH3
Ar + N -C -N ■* A r - 0 - i^+
h3 c/ 'c h 3
H3C^NiCH3
h 3 c ^ c h 3
/
Ar- 0 — C P Fc
.N n
■h3 c ch 3
Pig, 11, The aryl cation forms a salt with the sol
vent ,
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59
phate anion.
H3
CH 3 -ISI-CH 3 Cl
CH3
1 I
+ CH3 - N - C H 3
ci- B Fy
N=N
CH3-N-CH3
?
+/
+ CH. :N
\
CH3
B F4 ” + N2
methylamine.
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60
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of diazonium hexafluorophosphates in tetramethylurea. Again
fluoride was-obtained.
Evidence for reaction as in Pigure 11, however, is con-
h 3 c c h 3
fluorophosphate.
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62
+
A r N 2 PF6 ---------------+ Ar- ■+ : n =N * -P P F6 ~
hexafluorophosphates.
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63
/ \
h 3c c h 3
X « N 0 2 ,Cl
predominant.
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CHAPTER .III
EXPERIMENTAL
1. The Preparation of Aryldiazonium Hexafluorophosphates.
64
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further dried overnight in a vacuum desiccator. The prod
recorded.
The general method is illustrated by the following ex
be given.
mixture did not rise above -3°. When all the sodium nitrite
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66
Toluene-4-diazonium Hexafluorophosphate.-
yield 119.7 g.
percent yield 97
melting point 112° dec.
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Nitrobenzene-4-diazonium Hexafluorophosphate.-
Nitrobenzene-3-diazonium Hexafluorophosphate.-
diazotization temperature
1
yield 106.9 g.
percent yield 100
Nitrobenzene-2-diazonium Hexafluorophosphate.-
o-nitroaniline 1Q0 g . , 0.72 mole
hydrochloric acid 700 ml.’
water 1000 m l .
sodium nitrite 54 g . , 0.78 mole
hexafluorophosphoric acid 150 ml., 1.22 mole
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o
ro
i
diazotization temperature
o
yield 200 g.
percent yield 97
melting point 133° dec.
Bromobenzene-2-diazonium Hexafluorophosphate.-
diazotization temperature — F°
yield 120 g.
percent yield 100
Bromobenzene-4-diazonium Hexafluorophosphate.-
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Toluene-3-diazonium Hexafluorophosphate.-
Chlorobenzene-4~diazonium Hexafluorophosphate,-
diazotization temperature
yield 97 g.
percent yield 97
melting point 137° dec.
Anisole-2-diazonium Hexafluorophosphate.-
o-anisxdine 62 g . , 0.50 mole
hydrochloric acid 120 ml.
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diazotization temperature -10°
yield 140 g.
Anisole-4-diazonium Hexafluorophosphate
Quinoline-8-diazonium Hexafluorophosphate.-
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Acetophenone-4-diazonium Hexafluorophosphate.-
0
i-*
1
diazotization temperature
0
yield 106.4 g.
percent yield 99
melting point 109° dec.
Phenol-4-diazonium Hexafluorophosphate•-
diazotization temperature 0°
yield 45.2 g.
percent yield 68
Biphenyl-2-diazonium Hexafluorophosphate.-
o-aminobiphenyl 50 g., 0,30 mole
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72
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73
Diazonium Hexafluorophosphates.
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74
aromatic.
ceased the oil bath was removed and the reaction vessel was
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75
the flask and the third neck stoppered with a glass stopper.
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bath was then removed and the reaction vessel cooled in a
cold water bath, When the flask had cooled to room temp
tained.
the two layers separated and the organic layer dried over
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77
fluorotoluene.
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78
nj*° 1.4972.
n22 1.5336*
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79
o - F l u o r o a n i s o l e o-Methoxybenzenediazonium hexafluoro-
the aqueous layer. The organic layer was dried over anhy
drous sodium sulfate and distilled from a Claisen-Vigreux
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diazonium hexafluorophosphate (106 g., 0.36 mole) was car
extracted with ether and the ether solution dried over anhy
tube. The system was evacuated through a side arm from the
U tube to a vacuum pump and the receiving flask was cooled
were heated rapidly with an open flame and the product sol
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81
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82
in Tetramethylurea.
The dry aryldiazonium hexafluorophosphates prepared as
previously described were decomposed bythe stepwise addition
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separated by filtration. After it was dried in a vacuum
60°) solvent pair gave pure benzoic acid, m.p. 122°, The
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84
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85
prepared according to standard procedures. Its melting
1.5529).
mixture was then poured into 1500 ml. of water and the
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sodium sulfate and distilled from a Claisen-Vigreux flask.
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87
salt prepared from aniline was carried out in the same man
o-Methylphenoxytetramethylamidinium Hexafluorophosphate.-
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88
was led from the top of the condenser into a gas washing
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89
41.
16%.
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BIBLIOGRAPHY
90
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91
DeTar, D. P., and T. E. Whitely. J, Am. Chem. Soc., 79,
2498 (1957). “
DeTar, D. P., and Yun-Wen Chu. J. Am. Chem. Soc., 76,1686
(1954). “
Doak, G. 0., and L. ,D. Preedman. J. Am. Chem. Soc., 73,
5658 (1951). ~ “
Doak, G, 0., and H. G. Steinman. J. Am. Chem. Soc., 68,
1987 (1946). “ ~
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92
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93
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94
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Roe. A., and C. E. Teague Jr. J. Am. Chem. Soc., 73, 687
(1951).
Rutherford, K, G., and W. Redmond. l-Bromo-2-fluorobenzene,
in Organic Synthesis. ed. B. CMcKusick'. Vol. 43.
New York:John Wiley and.Sons, Inc., 1963. p. 12.
Schenk, W, J . , a n d G. R. Pellon. U. S. Pat. 2,563,796.
C. A., 4b, P9125 (1952). “
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VITA AUCTORIS
Born:
May 21, 1938; Ottawa, Ontario, Canada.
Son of Mr. and Mrs. William G. Redmond.
Primary School:
S. S. # 5 Gloucester, Ontario, Canada.
Secondary School:
St. Patrick’s College,High School, Ottawa, Ontario,
Canada. Academic Course. 1951-1958.
University:
St. Patrick’s College, Ottawa, Ontario, Canada.
1956-1959. Degree: B. Sc., 1959.
Publications:
The Use of Hexafluorophos'phoric Acid in the Schiemann
Reaction, J. Org. Chem., 26., 5149 (1981).
Professional Societies:
Chemical Institute of Canada.
American Chemical Society.
96
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
95
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
VITA AUCTORIS
Born:
May 21, 1938; Ottawa, Ontario, Canada.
Son of Mr. and Mrs. William G. Redmond.
Primary School:
S. S. # 5 Gloucester, Ontario, Canada.
Secondary School:
St. Patrick’s College,High School, Ottawa, Ontario,
Canada. Academic Course. 1951-1958.
University:
St. Patrick’s College, Ottawa, Ontario, Canada.
1956-1959. Degree: B. Sc., 1959.
Publications:
The Use of Hexafluorophos'phoric Acid in the Schiemann
Reaction, J. Org. Chem., 26., 5149 (1981).
Professional Societies:
Chemical Institute of Canada.
American Chemical Society.
96
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.