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Reactions of cis, trans, trans-1,5,9-cyclododecatriene III. The steric course of nitrosyl chloride addition
Tetrahedron Letters No.24, Printed in Great Britain.
PP.
1971-1975,
1965.
Pergamon
Press
Ltd.
\
REACTIONS III.
THE
OF
cis,
STERIC
Masaji Basic
trans,
trans-1,
COURSE
Ohno,
OF NITROSYL
Masaru
Resrar<,h
5, B-CYCLODODECATRIENE
Okamoto
Laboratories,
publications
on the nitrosyi us to report
chloride the
Addition
of one
of hydrochloric in either found
Cl,
methylene
7.92;
15. 79 ;
ligroin catalytic
15.6;
N,
5.95
N,
6.16.
easily
i,cdlic,tion.
Ltd.,
(3) and Metzger
trans-1,
along
prompt
similar
chloride
in the
lines. presence
5,9_cyclododecatriene
or trichloroethylene
(I),
at 10°C,
2-chlorocyclododecadienone
(Calcd. Found
for :
63. 15
;
was oxime
C12H18C1N0
C,
(4)
: H,
C,
7.85
63. 3
;
;
).
at 126 - 129°C.
and was
intensity
yields
Co.
of cyclododecatriene
investigations
at -loo
Naruse
Wilke
of nitrosyl
and provided
quantitative
Cl,
own
trans,
chloride
(2),
products
equivalent
to cis,
to be exothermic,
It melted
tion
of our
mole
acid
(III) in nearly H,
results
(1)
1965)
by Zakharkin
addition
Rayon
ADDITION
Japan
15 April
(Received
recent
and Norio
Toyo
Kamakura,
The
CHLORIDE
even
hydrogenated Its
at 98Ll c m
-I
infrared
after into spt’ctra
c haractcristi<.
1971
several
recrystallizations
cyclododecanone showed
that
<)f the trans
osime only double
from by
the absorpbond
No.24
1972 of 2-chlorocis-5, chloro-tram-5,
trans-9-cyclododecadienone cis-9-cyclododecadienone
The result
clearly
oxime oxime
showed that the first
(III.)
and 2-
(III b).
attack by nitrosyl
chloride
took place al; one of the trans double bonds and that there was a considerable
difference
in reactivity
between
the cis and trans double
bonds of the cyclododecatriene. Furthermore, of trans-
Wilke (3) observed
and cis-cyclododecene
the chloronitroso
dimer
thermodynamically
more
No satisfactory vities
that the treatment
with nitrosyl
of the former,
chloride
afforded
although the former
stable than the latter
explanation,
of a mixture
however,
only
is
(5).
for such competitive
reacti-
has been given.
I
II
Various reported
reactions
utilizing
and are summarized
mechanism
is closely
Generally, and acetic
the double bonds of the triene in Table
connected
the double bonds of cis,
trans,
trans-addition
III a
is concerned
These
have been
facts show that addition
with the selectivity
in the first
attack to
trans-1,5,9-cyclododecatriene.
reagents
such as halogen,
acid react with no selectivity
configuration
I.
III b
hydrogen
chloride
in so far as the cis or trans
and cis-addition
reagents
such as diethylborane,
1 1
Cl2
PhC03H
*
It was observed
cis-cyclododecene
11
glycol
monoacetate
mono- and dichloride
(C12H21)(BEt2)3
monoepoxide
diepoxide
monoepoxide
dichlorocyclododecadiene
tetrabromocycladodecene
tetrabromocyclododecene
1 -bromocyclododecatriene
Product
that the trans double bond keacted
excess
1
KMn04
H-N=N-H
1
OS o4
excess
HC1/FeC13 II
3
Et2BH
AcOH/BF3
1
H202-HC02H
2
2
11
11
1
mole
Br2
Reagent
faster
TABLE
addition
II
than the cis one.
11
II
trans
11
-
no selectivity
*
trans
cis and trans
tram3
no selectivity
cis and trans
no selectivity
double bond preferentially attacked
II
cis
1,
trans
11
II
II
cis
I,
I,
trans
mechanism
1
-
(46)
60-82‘:
59
89
50
20-40
80
76
80
80 - 90
70
20 - 40
20 - 30
61
Yield
: I /
1
11
11
10
10
9
8
7
6
6. 7
6
refwuwe
No.24
I974 peracid, with
osmium
the trans Meinw;
nitrosyl
tetroxide,
double
Id (12)
chloride
potassium
permanganate
and diimide
react
bond preferentially.
recently to double
showed bonds
that the addition
is dependent
mechanism
of
upon the structure
of
olefins. In case
of cis,
of nitrosyl
chloride
bonds
ether
like
competitive
for
(I,
II).
being
more
effect.
stable
Thus
selectivity
reasonably
transition
bond and V for than the latter double
may
the cis
because
(II)
may
tl-e addition
of nitrohyl
isomcrized
acid,
is more
slowly
isomerized
also
be mentioned
nitrosyl
chl
than the cis
one.
L
of hydrochlcrlc
It should
rapidly
of eclipsing
>I
112
be rapidly
in IV
the former
of the difference
iV After
as shown
bond,
more
of
or in cis-manner
be pictured
bond reacts
double
Such
in terms
state
double
the trans
above.
be explained transition
state
the addition for
as mentioned
at four-center
the trans
-c
reagents
might
The
double
5, d-cyclododecatriene,
a remarkable
cis-addition
stability
the tran;
trans-I,
showed
reactivities
conformatianal addition
trans,
sin(,e
chloride, into
the chloronitroso
o( -chlorooximes
the chloronitroso
(III)
dimer
in similar
that the treatment
of norbornenf
in the prrscnc’e
of hydrochloric,
by the action
or Wilke’s
d-chloroosimc
into
monomer
acid
easily
compound
conditions. with afforded
1975
No.24
3-chloronorcamphor from
oxime
(13).
which is known very difficult
2-chloro-3-nitrosonorbornane
dimer
by hydrochloric
to obtain
acid (14).
References
(1)
Part II, M. Ohno and M. Okamoto,
(2)
L.
(3)
G. Wilke,
(4)
H. Metzger,
(5)
A. 82,
(6)
I. Zakharkin, Angew.
Chem.,
Angew.
C. Cope,
56 =,
C. A.,
P.
T.
Letters,
2423 (1964)
5853 b (1962).
2,
Chem., Moore
Tetrahedron
10 (1963). 2,
980 (1963).
and W. R.
Moore,
J. Am.
Chem.
Sot.,
1744 (1960).
H. Takahashi
and M. Yamaguchi,
J. Chem.
Sot.
Japan,
z,
1042
(1962). (7)
L. I. Zakharkin E,
(8)
and V. V. Korneva,
Doklady
Akad.
Nauk SSSR,
1078 (1960).
H. Takahashi
and M. Yamaguchi,
Bull.
Chem.
Sot.
Japan,
g
1390 (1963). (9) (10)
R. K&ter
and G. Griaznov,
L. I. Zakharkin, Akad.
NaukSSSR,
V. V. Korneva 138,
M. Ohno and S. Torimitsu,
(12)
J. Meinwald, e.
, E,
Chem.,
and A.
E,
V. Iogansen,
Tetrahedron
C. Meinwald
Letters,
and T. N. Baker
4074 (1964).
(13)
M. Ohno,
N. Naruse,
(14)
J. B. Miller,
J. Org.
171 (1961). Doklady
373 (1961).
(11)
Y.
Angew.
unpublished Chem.,
2,
result. 4905 (1961).
2259 (1964). III, J. Am.
Chem.
PP.
1971-1975,
1965.
Pergamon
Press
Ltd.
\
REACTIONS III.
THE
OF
cis,
STERIC
Masaji Basic
trans,
trans-1,
COURSE
Ohno,
OF NITROSYL
Masaru
Resrar<,h
5, B-CYCLODODECATRIENE
Okamoto
Laboratories,
publications
on the nitrosyi us to report
chloride the
Addition
of one
of hydrochloric in either found
Cl,
methylene
7.92;
15. 79 ;
ligroin catalytic
15.6;
N,
5.95
N,
6.16.
easily
i,cdlic,tion.
Ltd.,
(3) and Metzger
trans-1,
along
prompt
similar
chloride
in the
lines. presence
5,9_cyclododecatriene
or trichloroethylene
(I),
at 10°C,
2-chlorocyclododecadienone
(Calcd. Found
for :
63. 15
;
was oxime
C12H18C1N0
C,
(4)
: H,
C,
7.85
63. 3
;
;
).
at 126 - 129°C.
and was
intensity
yields
Co.
of cyclododecatriene
investigations
at -loo
Naruse
Wilke
of nitrosyl
and provided
quantitative
Cl,
own
trans,
chloride
(2),
products
equivalent
to cis,
to be exothermic,
It melted
tion
of our
mole
acid
(III) in nearly H,
results
(1)
1965)
by Zakharkin
addition
Rayon
ADDITION
Japan
15 April
(Received
recent
and Norio
Toyo
Kamakura,
The
CHLORIDE
even
hydrogenated Its
at 98Ll c m
-I
infrared
after into spt’ctra
c haractcristi<.
1971
several
recrystallizations
cyclododecanone showed
that
<)f the trans
osime only double
from by
the absorpbond
No.24
1972 of 2-chlorocis-5, chloro-tram-5,
trans-9-cyclododecadienone cis-9-cyclododecadienone
The result
clearly
oxime oxime
showed that the first
(III.)
and 2-
(III b).
attack by nitrosyl
chloride
took place al; one of the trans double bonds and that there was a considerable
difference
in reactivity
between
the cis and trans double
bonds of the cyclododecatriene. Furthermore, of trans-
Wilke (3) observed
and cis-cyclododecene
the chloronitroso
dimer
thermodynamically
more
No satisfactory vities
that the treatment
with nitrosyl
of the former,
chloride
afforded
although the former
stable than the latter
explanation,
of a mixture
however,
only
is
(5).
for such competitive
reacti-
has been given.
I
II
Various reported
reactions
utilizing
and are summarized
mechanism
is closely
Generally, and acetic
the double bonds of the triene in Table
connected
the double bonds of cis,
trans,
trans-addition
III a
is concerned
These
have been
facts show that addition
with the selectivity
in the first
attack to
trans-1,5,9-cyclododecatriene.
reagents
such as halogen,
acid react with no selectivity
configuration
I.
III b
hydrogen
chloride
in so far as the cis or trans
and cis-addition
reagents
such as diethylborane,
1 1
Cl2
PhC03H
*
It was observed
cis-cyclododecene
11
glycol
monoacetate
mono- and dichloride
(C12H21)(BEt2)3
monoepoxide
diepoxide
monoepoxide
dichlorocyclododecadiene
tetrabromocycladodecene
tetrabromocyclododecene
1 -bromocyclododecatriene
Product
that the trans double bond keacted
excess
1
KMn04
H-N=N-H
1
OS o4
excess
HC1/FeC13 II
3
Et2BH
AcOH/BF3
1
H202-HC02H
2
2
11
11
1
mole
Br2
Reagent
faster
TABLE
addition
II
than the cis one.
11
II
trans
11
-
no selectivity
*
trans
cis and trans
tram3
no selectivity
cis and trans
no selectivity
double bond preferentially attacked
II
cis
1,
trans
11
II
II
cis
I,
I,
trans
mechanism
1
-
(46)
60-82‘:
59
89
50
20-40
80
76
80
80 - 90
70
20 - 40
20 - 30
61
Yield
: I /
1
11
11
10
10
9
8
7
6
6. 7
6
refwuwe
No.24
I974 peracid, with
osmium
the trans Meinw;
nitrosyl
tetroxide,
double
Id (12)
chloride
potassium
permanganate
and diimide
react
bond preferentially.
recently to double
showed bonds
that the addition
is dependent
mechanism
of
upon the structure
of
olefins. In case
of cis,
of nitrosyl
chloride
bonds
ether
like
competitive
for
(I,
II).
being
more
effect.
stable
Thus
selectivity
reasonably
transition
bond and V for than the latter double
may
the cis
because
(II)
may
tl-e addition
of nitrohyl
isomcrized
acid,
is more
slowly
isomerized
also
be mentioned
nitrosyl
chl
than the cis
one.
L
of hydrochlcrlc
It should
rapidly
of eclipsing
>I
112
be rapidly
in IV
the former
of the difference
iV After
as shown
bond,
more
of
or in cis-manner
be pictured
bond reacts
double
Such
in terms
state
double
the trans
above.
be explained transition
state
the addition for
as mentioned
at four-center
the trans
-c
reagents
might
The
double
5, d-cyclododecatriene,
a remarkable
cis-addition
stability
the tran;
trans-I,
showed
reactivities
conformatianal addition
trans,
sin(,e
chloride, into
the chloronitroso
o( -chlorooximes
the chloronitroso
(III)
dimer
in similar
that the treatment
of norbornenf
in the prrscnc’e
of hydrochloric,
by the action
or Wilke’s
d-chloroosimc
into
monomer
acid
easily
compound
conditions. with afforded
1975
No.24
3-chloronorcamphor from
oxime
(13).
which is known very difficult
2-chloro-3-nitrosonorbornane
dimer
by hydrochloric
to obtain
acid (14).
References
(1)
Part II, M. Ohno and M. Okamoto,
(2)
L.
(3)
G. Wilke,
(4)
H. Metzger,
(5)
A. 82,
(6)
I. Zakharkin, Angew.
Chem.,
Angew.
C. Cope,
56 =,
C. A.,
P.
T.
Letters,
2423 (1964)
5853 b (1962).
2,
Chem., Moore
Tetrahedron
10 (1963). 2,
980 (1963).
and W. R.
Moore,
J. Am.
Chem.
Sot.,
1744 (1960).
H. Takahashi
and M. Yamaguchi,
J. Chem.
Sot.
Japan,
z,
1042
(1962). (7)
L. I. Zakharkin E,
(8)
and V. V. Korneva,
Doklady
Akad.
Nauk SSSR,
1078 (1960).
H. Takahashi
and M. Yamaguchi,
Bull.
Chem.
Sot.
Japan,
g
1390 (1963). (9) (10)
R. K&ter
and G. Griaznov,
L. I. Zakharkin, Akad.
NaukSSSR,
V. V. Korneva 138,
M. Ohno and S. Torimitsu,
(12)
J. Meinwald, e.
, E,
Chem.,
and A.
E,
V. Iogansen,
Tetrahedron
C. Meinwald
Letters,
and T. N. Baker
4074 (1964).
(13)
M. Ohno,
N. Naruse,
(14)
J. B. Miller,
J. Org.
171 (1961). Doklady
373 (1961).
(11)
Y.
Angew.
unpublished Chem.,
2,
result. 4905 (1961).
2259 (1964). III, J. Am.
Chem.