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Studies of heteroaromaticity-LXVII. Syntheses of N-vinyliminopyridinium ylides and their intermolecular reactions with acetylenic compounds
Pergamon Pree a.
TetrahedronLettera No. 51, PP 5245 - 5240s 1972.
STUDIES OF HETEROAROMATICITY-LXVII.l
Printed in Great Britain.
SYNTHESES OF N-VINYL-
IMINOPYRIDINIUM YLIDES AND THEIR INTERMOLECULAR REACTIONS WITH ACETYLENIC COMPOUNDS Tadashi Institute
of
Sasaki,
Applied
Nagoya University,
Ken Kanematsu
Organic
and Akikazu
Chemistry,
Chikusa,
Nagoya,
Faculty
Kakehi of
Engineering,
464 Japan
(Receivedin Japm 2 November1972; receivedin UK for publication21 Iiovember 1972) N-Vinyliminopyridinium and vinylhalide character the
in the
and the
preparation On the
scarcely
presence
resulting
of
readily
hand,
investigated
cyclization
Recently,
of
reaction
we have
highly
reported
but
adduct.
its
die-isomer
2
Related
to
N-vinyliminopyridinium their
to
acetylenic
dinium
with
1,5-dipolar
a useful
ylides
has been
in the
cyclization
derivative to give
effect,
the
for
in N-(ta%m-2', hinders
the
cycli-
dihydro-bicyclo-
we attempted
3’, 3’-disubstituents
method
dihydro-compounds.
3 ‘-substituent
facility
substituent
ylides
report compound
to prepare
the
and some reactions
of
here of
the preparation
and the
intermolecular
reaction
N-(3’-methyl-3’-methoxycarbonylethenyl)iminopyri-
ylides. Treatment
crylate
this
such
reactivity
ylide with
are
N-imines
ylides. We wish
with
cyclizes
pyridinium
and their of
that
3’-dimethoxycarbonylethenyl)iminopyridinium zation
2,3,4
heteroaromatics
their
from
show a remarkable
reactions
intermolecular
because
obtainable
alkali,
of
nitrogen-bridged
other
reactions.
ylides,
L in
of
the
pyridinium
presence
temperature
gave
the
accompanied
with
two kinds
derivatives
&
and 1.48(each
N-imine
of
excess
corresponding of
CH3),
potassium ylide
bicyclic
and -5a as unstable 3H, s,
hydriodide
3.56
pale
z
with
carbonate
3a(21%),
m-p.
compounds(57%), yellow oils,
and 3.68Ceach
5245
3H, s,
methyl
b-bromometha-
in chloroform at room 0 1540cm-l, 85-87 9 v,"-";; dihydropyrazolopyridine
6(CC14), 0CH3),
i%teP 4.33
dlca,
1.31
and 4.84(each
No. 51
5246
lH,
3a-H)
br s,
ppm, and
6 (CC14) t 2.26(3H,
s,
7.0,
8.OH2,
7.28(1H,
(lH,
dd,
7.0,
products,
not
obtained,
but
J=8.0,
in the
same reaction the
these
case
1,3-dipolar
ylides,
room temperature and $b,
2-6 1 I
to
in good
R,&
R2
a
H
H
b
H
Me
Me
H
C
1. -*
the
analogous
these
bromide
the
yields,
from and 5
corresponding
respectively.
of
-2b and -2c and 1,
and 3c(77%, &
uith
1,4c --
140-143’
and -5c were
among N-vinyliminopyridinium supported
compounds
did
bicyclic
not
primary were
under
were
N-imines
produced with
cycloadducts. aromatized
are
1,
by us. the a followed
By contrast, readily
3-metylpyrazolopyridine These
proposed
reported
cyclize
compounds
pyridinium
and 3,
those
as previously
even
ylides
2,
in Scheme 1.
e
1.
-3b and -3c with
dimethyl
at
derivatives,
summarized
K2
the
m.p.
-C02Me
Scheme
J=
and 8.26
-HBr
1
I
of
t,
treatments
of
-C02Me
Reactions
br
2-H),
reaction
the
6.86(111, s,
and 6b(59%),
of
6-H),
116-119’,
7.55(1H,
be expected,
reactions5
and &,
give
4-H),
nmr spectra
suggested
2
Br_Me
of
as might
of hydrogen
dihydro-compounds
5
m.p.(picrate)
7.OH2,
and pyrazolopyridine
cycloaddition
by elimination
J~7.0,
1.5H2,
s,
similar
with
conditions
g,
From similar
145-148’),
in comparison
br t,
ppm.
Grossly
That of
@
dd,
dihydropyrazolopyridine
structures
the
6.50(1H,
7-H)
m.p.
produced.
ylide,
CH3),
1.5Hz,
3b(25%,
were
),
5-H),
3-methylpyrazolopyridine
acetylenedicarboxylate
2
5a7
No. 51 in benzene
at room temperature
-7a(30%)
ylides, 124-126’). 8(28%, were
(lH,
powders,
Furthermore,
in
obtained:
2;
G(CDC13),
3.78(3H,
s,
0CH3),
J=a.OHz,
4.27(28,
d,
Table
1.
Compd. -3a
C-2 a.23 m
-3b
7.95
-3c
2.65
-7a
8.39 m
-7b
8.12
-7c
2.64
8
2.66
2.33
S
6.94
S
7.43 d
7.71 q
7.40 d
7.37
pyridinium
that
with
of
8.12
8.40
7.43
7.76
7.42
2.66
the
acetylenic
on the basis
strongly
to have
d
of
the ylides
methoxycarbonyl
1,3-dipolar
other
group6
hand,
These
4.12
S
molecule
results
reported
rearranged of are
6.OHz
J=8.0,
t
of
addition
on dimethyl
rearrangement
reaction
1.26
as a result
ylide
the
J=8.0,
9
Michael-type
has been
S
S
3.70
1.96 d
3.72
3.71(6H) S
S
S
S
3.58
2.03
3.76
3.69 S
after
similar
6.OHz
S
3.64
may be considered
cycloaddition
compound. 899
S
S
S
3.73
3.67
1.95
7.66
Js9.0,
S
S
S
same reagent
On the
3.60
S
7.69
N-vinyliminopyridinium
with
1.88
S
S
S
1.98
S
d
Q
3.65
S
S
Interestingly,
and Zugravescu. to
2.40
2.64
/
the
S
S
S
a.35
7.43 d
methylide
of
3.67
1.89
7.61
8.39 m
7.79 q
dicarboxylate.
J=12.0Hz,
elucidation
showed
S
S
S
7.45 d
ilO;in -
br d,
OCH, (OCH,CH,)
1.94
S
2.65
S
of
123-125’)
was accomplished
C-3’
8.10
S
rearrangement
m.p.
1.
S
S
The formation
7.47(1H,
Structural
8.19
7.75
7.65m
S
carbanion
2.33 S
2.40
propiolate,ylide
9(51%,
nmr spectra
m
S
S
4-H))
C-2’
8.23
S
-
their
C-6
c-5
7.37m
S
m.p.
N-Ylides
c-4
C-3
-3c and ethyl
-7c and&
as shown in Table
NMR Data of
and -7c(80%,
0CH2CH3), 1.62(3H, d, J=l.SHz, OCH2CH3), 6.05(1H, br, NH), 7.06
J=7.0Hz,
E,
105-lOa’),
J=7.0Hz,
=CHNH). -
analyses;
structure
m.p. of
J=a.OHz,
2,
N-dienyliminopyridinium
derivative
t,
d,
ylides
and spectral
common ylide
reaction
q,
J=13.0Hz,
N-dienyliminopyridinium physical
-7b(53%,
1.30(3H,
7.37(1H,
5-H),
NHCH=), and 7.73(1H, -
of
the
corresponding
and 3-vinylpyridine
147-1500),
d,
the
as amorphous
m.p.
CH3),
gave
in the
cationotropic of
the
acetylene-
reaction
recently
of
by Leonte
compound
2 was similar
N-acyliminopyridinium summarized
6.0 Hz
in Scheme 2.
ylide
5248
No. 51
,
C02Et J
F02Et
Mmv: M%eQ R
M
ADC;
Et)
-uAfJ
‘C02Et(or Me)
9 EP; *C02Et,
CO Me(or
-2
2e
M
Cf$tO:M:
Z
11
MeOOCGCOOMe
Scheme
2.
References 1. Part LXVI of this series, T. Sasaki, K. Kanematsu and M. Murata, Jetrahedron, in press. 2. T. Sasaki, K. Kanematsu and A. Kakehi, J. Org. Chem., 37, 3106(1972) 3. Y. Tamura, N. Tsujimoto, Y. Sumida and M. Ikeda, Tetrahedron, g,
21(1972)
4. Y. Tamura, N. Tsujimoto and M. Ikeda, Chem. Commun., 310(1971) 5. Y, Tamura, A. Yamagami and M. Ikeda, Yakugaku Zasshi, 9l, 1154(1971) 6. R. M. Acheson, Accounts Chem. Res., i,
177(1971)
7. C. Leonte and I. Zugravescu, Tetrahedron Lett., 2029(1972) 8. T. Sasaki, K. Kanematsu and A. Kakehi, J. Org. Chem., 36, 2978(1971) 9. T. Sasaki, K. Kanematsu, A. Kakehi and G. Ito, Bull. Chem. Sot. Japan, 45, 2050(1972)
TetrahedronLettera No. 51, PP 5245 - 5240s 1972.
STUDIES OF HETEROAROMATICITY-LXVII.l
Printed in Great Britain.
SYNTHESES OF N-VINYL-
IMINOPYRIDINIUM YLIDES AND THEIR INTERMOLECULAR REACTIONS WITH ACETYLENIC COMPOUNDS Tadashi Institute
of
Sasaki,
Applied
Nagoya University,
Ken Kanematsu
Organic
and Akikazu
Chemistry,
Chikusa,
Nagoya,
Faculty
Kakehi of
Engineering,
464 Japan
(Receivedin Japm 2 November1972; receivedin UK for publication21 Iiovember 1972) N-Vinyliminopyridinium and vinylhalide character the
in the
and the
preparation On the
scarcely
presence
resulting
of
readily
hand,
investigated
cyclization
Recently,
of
reaction
we have
highly
reported
but
adduct.
its
die-isomer
2
Related
to
N-vinyliminopyridinium their
to
acetylenic
dinium
with
1,5-dipolar
a useful
ylides
has been
in the
cyclization
derivative to give
effect,
the
for
in N-(ta%m-2', hinders
the
cycli-
dihydro-bicyclo-
we attempted
3’, 3’-disubstituents
method
dihydro-compounds.
3 ‘-substituent
facility
substituent
ylides
report compound
to prepare
the
and some reactions
of
here of
the preparation
and the
intermolecular
reaction
N-(3’-methyl-3’-methoxycarbonylethenyl)iminopyri-
ylides. Treatment
crylate
this
such
reactivity
ylide with
are
N-imines
ylides. We wish
with
cyclizes
pyridinium
and their of
that
3’-dimethoxycarbonylethenyl)iminopyridinium zation
2,3,4
heteroaromatics
their
from
show a remarkable
reactions
intermolecular
because
obtainable
alkali,
of
nitrogen-bridged
other
reactions.
ylides,
L in
of
the
pyridinium
presence
temperature
gave
the
accompanied
with
two kinds
derivatives
&
and 1.48(each
N-imine
of
excess
corresponding of
CH3),
potassium ylide
bicyclic
and -5a as unstable 3H, s,
hydriodide
3.56
pale
z
with
carbonate
3a(21%),
m-p.
compounds(57%), yellow oils,
and 3.68Ceach
5245
3H, s,
methyl
b-bromometha-
in chloroform at room 0 1540cm-l, 85-87 9 v,"-";; dihydropyrazolopyridine
6(CC14), 0CH3),
i%teP 4.33
dlca,
1.31
and 4.84(each
No. 51
5246
lH,
3a-H)
br s,
ppm, and
6 (CC14) t 2.26(3H,
s,
7.0,
8.OH2,
7.28(1H,
(lH,
dd,
7.0,
products,
not
obtained,
but
J=8.0,
in the
same reaction the
these
case
1,3-dipolar
ylides,
room temperature and $b,
2-6 1 I
to
in good
R,&
R2
a
H
H
b
H
Me
Me
H
C
1. -*
the
analogous
these
bromide
the
yields,
from and 5
corresponding
respectively.
of
-2b and -2c and 1,
and 3c(77%, &
uith
1,4c --
140-143’
and -5c were
among N-vinyliminopyridinium supported
compounds
did
bicyclic
not
primary were
under
were
N-imines
produced with
cycloadducts. aromatized
are
1,
by us. the a followed
By contrast, readily
3-metylpyrazolopyridine These
proposed
reported
cyclize
compounds
pyridinium
and 3,
those
as previously
even
ylides
2,
in Scheme 1.
e
1.
-3b and -3c with
dimethyl
at
derivatives,
summarized
K2
the
m.p.
-C02Me
Scheme
J=
and 8.26
-HBr
1
I
of
t,
treatments
of
-C02Me
Reactions
br
2-H),
reaction
the
6.86(111, s,
and 6b(59%),
of
6-H),
116-119’,
7.55(1H,
be expected,
reactions5
and &,
give
4-H),
nmr spectra
suggested
2
Br_Me
of
as might
of hydrogen
dihydro-compounds
5
m.p.(picrate)
7.OH2,
and pyrazolopyridine
cycloaddition
by elimination
J~7.0,
1.5H2,
s,
similar
with
conditions
g,
From similar
145-148’),
in comparison
br t,
ppm.
Grossly
That of
@
dd,
dihydropyrazolopyridine
structures
the
6.50(1H,
7-H)
m.p.
produced.
ylide,
CH3),
1.5Hz,
3b(25%,
were
),
5-H),
3-methylpyrazolopyridine
acetylenedicarboxylate
2
5a7
No. 51 in benzene
at room temperature
-7a(30%)
ylides, 124-126’). 8(28%, were
(lH,
powders,
Furthermore,
in
obtained:
2;
G(CDC13),
3.78(3H,
s,
0CH3),
J=a.OHz,
4.27(28,
d,
Table
1.
Compd. -3a
C-2 a.23 m
-3b
7.95
-3c
2.65
-7a
8.39 m
-7b
8.12
-7c
2.64
8
2.66
2.33
S
6.94
S
7.43 d
7.71 q
7.40 d
7.37
pyridinium
that
with
of
8.12
8.40
7.43
7.76
7.42
2.66
the
acetylenic
on the basis
strongly
to have
d
of
the ylides
methoxycarbonyl
1,3-dipolar
other
group6
hand,
These
4.12
S
molecule
results
reported
rearranged of are
6.OHz
J=8.0,
t
of
addition
on dimethyl
rearrangement
reaction
1.26
as a result
ylide
the
J=8.0,
9
Michael-type
has been
S
S
3.70
1.96 d
3.72
3.71(6H) S
S
S
S
3.58
2.03
3.76
3.69 S
after
similar
6.OHz
S
3.64
may be considered
cycloaddition
compound. 899
S
S
S
3.73
3.67
1.95
7.66
Js9.0,
S
S
S
same reagent
On the
3.60
S
7.69
N-vinyliminopyridinium
with
1.88
S
S
S
1.98
S
d
Q
3.65
S
S
Interestingly,
and Zugravescu. to
2.40
2.64
/
the
S
S
S
a.35
7.43 d
methylide
of
3.67
1.89
7.61
8.39 m
7.79 q
dicarboxylate.
J=12.0Hz,
elucidation
showed
S
S
S
7.45 d
ilO;in -
br d,
OCH, (OCH,CH,)
1.94
S
2.65
S
of
123-125’)
was accomplished
C-3’
8.10
S
rearrangement
m.p.
1.
S
S
The formation
7.47(1H,
Structural
8.19
7.75
7.65m
S
carbanion
2.33 S
2.40
propiolate,ylide
9(51%,
nmr spectra
m
S
S
4-H))
C-2’
8.23
S
-
their
C-6
c-5
7.37m
S
m.p.
N-Ylides
c-4
C-3
-3c and ethyl
-7c and&
as shown in Table
NMR Data of
and -7c(80%,
0CH2CH3), 1.62(3H, d, J=l.SHz, OCH2CH3), 6.05(1H, br, NH), 7.06
J=7.0Hz,
E,
105-lOa’),
J=7.0Hz,
=CHNH). -
analyses;
structure
m.p. of
J=a.OHz,
2,
N-dienyliminopyridinium
derivative
t,
d,
ylides
and spectral
common ylide
reaction
q,
J=13.0Hz,
N-dienyliminopyridinium physical
-7b(53%,
1.30(3H,
7.37(1H,
5-H),
NHCH=), and 7.73(1H, -
of
the
corresponding
and 3-vinylpyridine
147-1500),
d,
the
as amorphous
m.p.
CH3),
gave
in the
cationotropic of
the
acetylene-
reaction
recently
of
by Leonte
compound
2 was similar
N-acyliminopyridinium summarized
6.0 Hz
in Scheme 2.
ylide
5248
No. 51
,
C02Et J
F02Et
Mmv: M%eQ R
M
ADC;
Et)
-uAfJ
‘C02Et(or Me)
9 EP; *C02Et,
CO Me(or
-2
2e
M
Cf$tO:M:
Z
11
MeOOCGCOOMe
Scheme
2.
References 1. Part LXVI of this series, T. Sasaki, K. Kanematsu and M. Murata, Jetrahedron, in press. 2. T. Sasaki, K. Kanematsu and A. Kakehi, J. Org. Chem., 37, 3106(1972) 3. Y. Tamura, N. Tsujimoto, Y. Sumida and M. Ikeda, Tetrahedron, g,
21(1972)
4. Y. Tamura, N. Tsujimoto and M. Ikeda, Chem. Commun., 310(1971) 5. Y, Tamura, A. Yamagami and M. Ikeda, Yakugaku Zasshi, 9l, 1154(1971) 6. R. M. Acheson, Accounts Chem. Res., i,
177(1971)
7. C. Leonte and I. Zugravescu, Tetrahedron Lett., 2029(1972) 8. T. Sasaki, K. Kanematsu and A. Kakehi, J. Org. Chem., 36, 2978(1971) 9. T. Sasaki, K. Kanematsu, A. Kakehi and G. Ito, Bull. Chem. Sot. Japan, 45, 2050(1972)