practical heterocyclic chemistry - gbv
TRANSCRIPT
PRACTICAL HETEROCYCLIC CHEMISTRY
A. O. Fitton and R. K. Smalley University of Salford, Lancs, England
ACADEMIC PRESS
London and New York
1968
CONTENTS
Page
Introduction . . . . . . . . . . v
Preface . . . . . . . . . . . vii
C H A P T E R l : Five-membered Systems Containing One Hetero-atom . . . . . . . . . . . 1
M e . X 0 2 E t 2,4-Diethoxycarbonyl-3,5- p "~T| ^
dimethylpyrrole E t 0 2 C ^ N - ^ M e H
2,5-Dimethylpyrrole M e ^ K T ^ M e 2
H
Ph-. ^ C 0 2 H 4,5-Diphenyl-2-methylfuran-3-carboxylic acid I I 3
P h ^ N ) ^ M e
2,5-Dimethylthiophen I II 5
C H A P T E R 2: Benzoderivatives of Five-membered Systems Containing One Heteroatom . . . . . . . 7
Carbazole ^ ^ , „ H
1,2,3,4-Tetrahydrocarbazole ^ ^^
H
0 2,3-Dioxoindoline (isatin) I II I 11
H (ix)
X CONTENTS
^ ^° H Indigotin (indigo) -^ ^^A 1 ,
H 0S
12
2-Phenylindole ^ . J ^ T J V ™ 1 3
\ - N Ph H
2-Benzoylbenzofuran (2-benzoylcoumarone) I | | 15 > ^ - O ^ C O P h
HO 5-Hydroxycyclo-octano[&]coumaran [ j! | 15
2-Methylcoumaran [ X I 1 6
5-Chloro-3-methylbenzo[ö]thiophen [ ]| j| 17
C H A P T E R 3 : Five-membered Systems Containing More Than One Heteroatom . . . . . . . . . 19
° S NH 2,4-Dioxoimidazolidine (hydantoin) [ ^L 19
H
4,5 -Diphenylimidazole (4,5 -diphenylglyoxaline)
2-Methyl-A2-imidazoline
3,5 -D imethylpyrazole
P h - ^ N H
P h - ^ S T
| NH
1 * H
21
22
23
CONTENTS
3-Methyl-l-phenyl-5-pyrazolone
Me
N-
I Ph
24
1,3,5 -Triphenyl-A2-pyrazoline
-Ph
P h ^ ] s r N
I Ph
25
3,5 -Dimethylisoxazole M E
11 1 28
3 -Phenyl-5 -isoxazolone f Ph
i1 29
4-Benzylidene-2-phenyl-5-oxazolone
Cyclohexanespiro-2'-(l',3'-oxazoiidine)
°Y-o P h C H ^ N ^ - p h
-O/
30
31
2-Methyl-A2-oxazoline -O I
^ N ^ - M e 32
2,4,5-Triphenyloxazole Ph O
33 P h ^ N ^ P h
^-Chlorophenylsydnone N - O
-CVC6Hi-N~®J%0
H 34
3,4-Dimethyl-l,2,5-oxadiazole (3,4-dimethylfurazan)
M e N / M e 1 II 36 N. 0 .N
2,5 -Diphenyl-1,3,4-oxadiazole N N
1 X P h ^ C T ^ P h
37
Xl l
2,4-Dimethylthiazole
2-Methyl-A2-thiazoline
CONTENTS
( 1 — s
M e ^ N ^ M e
1 S
39
40
C H A P T E R 4: Benzoderivatives of Five-membered Systems Containing More Than One Heteroatom . . . . 42
r i—N
Benzimidazole H
f ^ \ NH
kAAo 43 H
1,2-Dihydro-2-oxobenzimidazole (benzimidazolone)
6-Nitroindazole „ I S T ^ - W / V N ^ N 44
H
N
1 -Aminobenzotriazole ^^v^-N' ' 45 I
NH,
f^\ N
Benzotriazole W / \ >-N ^7 H
-N
l-(/)-Nitrophenyl)-4,5,6,7-tetrahydrobenzotriazole ' \ / ^ N ' ' N 48 I
/>-N02C6H4
3-Methyl-S-nitrobenzisoxazole ( || II 51 v O"^
3-Phenylbenzo-2,l-isoxazole i ^ ^ l f (3-phenylanthranil) [. L ^ 5 3
CONTENTS
r ^ i — o 2-Methylbenzoxazole I I 55
0 2 N ^ \ 0
2-Methyl-6-nitrobenzoxazole I II I 56
Benzo-2.1,3-oxadiazole 1-oxide (benzofuroxan) I 57
5(6)-Chlorobenzo-2,l,3-oxadiazole r ^ ^ j = N ' ^ 1-oxide [S(6)-chlorobenzofuroxan] I - I ^ S S ^ W M ' - O °
a—NH
N X B \ D , 61 H
a—NH D«5* 62
H
I II 1 A ^
2-Phenylbenzo-l,3-oxaza-2-borole ks. J k - . ^ i u 0 J
r ^ — o
^Ph H
2-Phenylbenzothiazole I | I 64 N ^ P h
Benzo-2,l,3-thiadiazole [ I y 65 kANi
C H A P T E R 5: Six-membered Systems Containing One Hetero-atom . . . . . . . . . . . 67
3-Chloro-2,6-dimethylpyridine || 67 M e - ^ N ^ M e
XIV CONTENTS
3,5-Diethoxycarbonyl-2,6-dimethyl-4-(wj-nitrophenyl)pyridine
m-N02-C6H4
E t 0 2 C v ^ L ^ C 0 2 E t 68
M e A N A M e
4-Nitropyridine iV-oxide
N O ,
70
Me A^CN
3-Cyano-4,6-dimethyl-2-pyridone: Method 1 jj | 71
H
3-Cyano-4,6-dimethyl-2-pyridone: Method 2
3,5-Diacetyl-l,4-dihydro-2,4,6-trimethylpyridine
Me
^ v CN
Me' '
A c \
Me-"
H
Me
r\ V1 H
^ O
^Ac
x M e
72
72
4-Pyridone-2,6-dicarboxylic acid (chelidamic acid)
O
74 H02CT ^Nr ^ C 0 2 H
H
3-Acetyl-3,4-dihydro-6-methyl-4-oxo-a-pyrone (dehydroacetic acid)
O
75
Me-^Cr^o
2,6-Dimethyl-y-pyrone
O
76
M e ^ ^ O - ^ M e
CONTENTS XV
6-Isobutenyl-4-methyl-a-pyrone
Me
\ Me, C=CH ^ 0 ^ * 0
77
C H A P T E R 6: Benzoderivatives of Six-membered Systems Containing One Heteroatom . . . . . . . 79
3 -Methyl-1 -phenylisoquinoline
Ph
6-Chloroquinoline Ck
82 -N*
4-Methyl-2-phenylquinoline
Me
83
N T x P h
2,4,6 -Trimethylquinoline
2-Methyl-4-quinolone
Me Me
84 •N-^Me
O
•KT^Me H
86
4-Methyl-2-quinolone
Me
87
H O
4-Phenyl-2-quinolone
Ph
N ^ o
CONTENTS
9-Acridone 90
Phenanthridine 91
6-Phenanthridone 93
Chromone-2-carboxylic acid
O
* * % > 94
O ^ C 0 2 H
2-Methyl-5,6,7,8-tetrahydrochromone
O
O-^-Me 95
7-Hydroxy-4-methylcoumarin (4-methylumbelliferone)
Me
H C K ^ - ' ^ O ' ^ o 97
Benzo[/]chroman-4-one O 98
B enzo [/ ] chromone 99
CONTENTS
O
Xanthone [ |T \\ 1 101
C H A P T E R 7: Six-membered Systems Containing More Than One Heteroatom . . . . . . . . . 103
4-Cyano-2,3-dihydro-5,6-diphenyl- 1 1^ ..„,, P h ^ N . N H
ro-5,6-diphenyl-3-oxopyridazine
CN
H
2,4-Dioxo-6-methyl-l,2,3,4- i ; 1 0 4
tetrahydropyrimidine (6-methyluracil) " \ - N H
O
H O ^ N o
Hexahydro-2,4,6-trioxopyrimidine j ' (barbituric acid) \ / N H
O
105
H
2,5-Dioxopiperazine [ 107
H
^ N ^ C 0 2 H Pyrazine-2,3-dicarboxylic acid U J ^ 108
-N^^COzH
Hexahydro-l,3,5-tri-j>-tolyl- />-Me-C6H4-N N—C6H4.p-Me s-triazine ^1V^
I £-Me-C6H4
C H A P T E R 8: Benzoderivatives of Six-membered Systems Containing More Than One Heteroatom . . . 1 1 1
O
4-Cinnolone y |j |] 111
H N-N
xvm CONTENTS
Quinazoline
3-Amino-3,4-dihydro-2-methyl-4-oxoquinazoline
C O »2
O
N / N H 2
114 N ^ M e
Quinoxaline 115
3,4-Dihydro-l-hydroxy-4-oxophthalazine
O
NH
N
OH
116
3,4-Dihydro-l-methyl-4-oxophthalazine
O
NH I
^ N
Mc
117
Dibenzo[a,c]phenazine 118
3,4-Dihydro-4-oxo-l,2,3-benzotriazine: Method 1
O
N H
^ / ^ N ^ N 118
3,4-Dihydro-4-oxo-l,2,3-benzotriazine: Method 2
O
NH I
N*N 120
2-Ethyl-4-oxo-3,l-benzoxazine
O
O
N * ^ E t
121
CONTENTS XIX
2,3 -Dihydro-3 -oxo-1,4-benzoxazine (benzo-3-morpholone): Method 1
O
N H X. 123
O
2,3-Dihydro-3-oxo-1,4-benzoxazine (benzo-3-morpholone): Method 2
O 124
g~o
2,4-Dinitrophenoxazine 0 ^ / ^ / N 0 2
NO,
125
Phenothiazine 127
2-Oxo-l ,4-benzodioxan O ^
128
Phenoxathiin o-
128
C H A P T E R 9 : Miscellaneous Systems . 130
Cyclohexa-2,5-diene-4-one-spiro-2'-oxetano[3',4']cyclo-octane 130
4,6-Dinitrobenzimidazo[l,2-a]pyridine NO,
% ^ N -
131
NO,
2-Phenylimidazo[l,2-a]pyridine N
Ph 132
XX CONTENTS
2,3)4,5-Tetrahydropyrido[l,2-a]- f ^ \ ^ ' ^ 133 benzimidazole ^ / ^ N ^ \ /
l,4-Dihydro-erarfo-l,4-oxanaphthalene [I Q II I 135
Bibliography . . . 137
Subject Index 139