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Synthetic reaction by complex catalyst IV. Copper catalyzed reaction of alcohol with isocyanide
TetrahedronLetters No.6, pp. 521-524, 1967. Pergamon Press Ltd. Printed .inGreat Britain.
SYNTHETIC
HEACTION BY COMPLEX CATALYST
COPPEH CATALYZED
IV.
REACTION OF ALCOHOL WITH ISOCYANIDE
Trkeo Saegusa, Yoshihiko
Ito, Shiro Kobayashi
and Kiwami Hirota
Department
of Synthetic
Chemistry,
Kyoto University,
Faculty of Engineering,
Kyoto, Japan
(Beceived28 November 1966) Recently we have explored a series of copper catalyzed with isocyanide 1)_ (es.
reactions
of amine
carbon monoxide 2) (eq. (ii)), diazomethane 3) (en.
(ill,
(iii)), and ethyl diazoacetate 3) (eq. (iv)).
R”-N
‘C
/
co
7
(i )
I&N-C-"
---------
:>N-$-H
..__.__.__ (ii)
0
$N-H CH2N2
---____--.
(iii)
----
(iv)
-N2
N2CHCOOC2H5
p
$NCH2COOC2H5
-N2 These reactions cyanide,
are characterized
carbon monoxide,
lone pair electrons, As
an extension
trons, we examined
by a common feature that carbon atoms of iso-
and carbenes
from diazocompounds,
are inserted between nitrogen
each of which bears
and hydrogen
of amine.
of the insertion reaction of carbon having lone pair elec-
the reaction
of alcohol with isocyanide.
Based upon the fact
4,5) , the reaction of althat ally1 alcohol forms a complex with cuprous chloride lyl alcohol with isocyanide
by cuprous chloride catalyst was first investigated.
521
No.6
522
It has nor been found that in the presence reacts with isocyanide
to produce
CH2=CHCH20H
of cuprous chloride ally1 alcohol
ally1 formimidate
-
+ R-NSC
(II).
CH2=CHCHzO$H
CuCl
----(~1
(II)
(1) This constitutss
a new insertion
reaction
(I)
of isocyanide
NR
between oxygen and hydro-
gen of alcohol. In 4.1 g (0.070 mol) of ally1 alcohol, 0.79 g (0.008 mol) of cuprous chloride was dissolved.
To this solution, 4.4 g (0.040 mol) of cyclohexyl
The reaction mixture vas
added, and the mixture was heated at 120°C for 5 hours. subjected
to distillation
cyclohexylformimidafe
under reduced pressure,
was obtained,
(25 $6) of N-cyclohexylformamide In the absence
observation
both ally1 alcohol and cyclohexyl
almost quantitatively
The results
mental analysis
1.3 g
isocyanide
to give the corresponding
are given in Table 1.
mixture.
isoThis
activity of cuprous chloride.
alcohols such as methally
cinnamyl alcohol were reacted with cyclohexyl
acid.
from the heat-treated
the catalysis
other p,r-unsaturated
prous chloride catalyst
As a by product,
was isolated, b.p. 100-103'C/3 mm Hg.
is talcen to demonstrate
Similarly,
and 4.5 g (67 %) of ally1 N-
b.p. 105"C/32 mm Hg.
of cuprous chloride,
cyanide were recovered
isocyanide was
alcohol and
in the presence of cu-
esters of N-cyclohexylformimidic
The formimidates
were identified by ele-
and IR and NMR spectra analyses. TABLE I
Reaction
of fi,Y-Unsaturated Alcohol with Cyclohexyl
P,g-Unsaturated
Products
Isocyanide*
( Yield $ )
alcohol CH2=CHCH20H
CH2=CHCH20CH=N-@
CH2=C(CH3)CH20H
CH2=C(CH3)CH20CH=N-@
@CH&BCH~OH
Q-CH=CHCH~OCH=N-Q
a)
b.p.
*
Cyclohexyl
105'C/32 mm Hg,
pyridine
a) (67),
isocyanide
b)
b.p.
b, (50), ') (45),
116'C/27 mm Hg,
contains a small quantity
as impurities.
Q-NHCBO
(25)
@-NHCHO Q-NHCHO c)
b.p.
(32) (20) 13O'C/3 mm Hg
(about 0.5 '$ to 1 $J) of
No.6
523
The formation
of N-cyclohexylformamide
which a few possible
reaction
of the N-cyclohexylforramide The specific nature isocyanide
as a by-product
routes may be assumed. formation
tert-butanol catalyst.
of alcohol by cuprous chloride
did not react with isocyanide
The specificity
of the mechanism
alcohol in the insertion
on finding that saturated alcohols such
illustrated
Elucidation
for
is being made now.
of p,y-unsaturated
between oxygen and hydrogen
is usually observed,
8s ethanol,
in the presence
of &r-unsaturated
alcohol
reaction of catalyst was
isopropanolgand
of cuprous chloride
in the reaction with iso-
cyanide may be due to its nature of complex formation with cuprous chloride. fact, we6) have observed in a separate experiment
In
that the IB olefinic band at
1640 cm-' of ally1 alcohol ahifts to 1550 cm -1 when ally1 alcohol is mixed with cuprous chloride.
It seema likely that the cuprous chloride-ally1
by means of hydroxyl the present
group as well as olefinic group plays an important role in
reaction.
Catalysis When a mixture
behavior of cupric chloride differs from that of cuprous chloride. of ally1 alcohol , cyclohexyl
isocyanide
and a small amount of cu-
pric chloride was heated at 12O'C for 10 hours, no formimidate light brown powder of isocyanide polymer was produced. of cyclohexyl Hagihara catalyst,
alcohol complex
was formed, but
The IR spectrum
of polymer
isocyanide by cupric chloride waa quite similar to that prepared
and coworkers 7) using nikel and cobalt carbonyls for which the following
by
aa the polymerization
structure was presented.
c tp
i-
di
a H
In the reaction
of saturated alcohol with cyclohexyl
chloride catalyst, N-cyclohexylcarbamate hexylformamide Chlorides
metal halides.
of the corresponding
by cupric
alcohol and N-cyclo-
were formed in low yields. of nikel
ally1 alcohol-isocyanide when a mixture
isocyanide
(II), cabalt reaction.
of cyclohexyl
(II) and palladium
(II) do not catalyze the
The polymer of cyclohexyl
iaocyanide
iaocyanide was formed
and ally1 alcohol was treated with these
~0.6
521
The reaction
of mercaptan
tion of isocyanide
between
with isocyanide has also been examined.
sulfur and hydrogen
of mercaptan
The inser-
occurs without
copper
catalyst. _
Detailed
studies upon the reactions
will be reported
of alcohol and mercaptan
with isocyanide
in the near future.
REFERENCES 1)
T. Saegusa, Letters,
2)
Y. Ito, S. Kobayashi,
K. Hirota and H. Yoshioka,
Tetrahedron
1966 No.49.
T. Saegusa,
S.
Kobayashi,
K. Hirota,
and Y. Ito, Tetrahedron
Letters,
1966,
No.49.
3)
Y. Ito, S. Kobayashi,
T. Saegusa, Letters,
E,
K. Hirota,
and T. Shimizu, Tetrahedron
No.49.
4)
B. E. Kepner
and L. J. Andrews,
5)
R. M. Keefer and L. J. Andrews, J. Am. Chem. Sot., 2,
6)
T. Saegusa
7)
Presented
and N. Takeda,
J. Org. Chem., 13, 208 (1948). =
unpublished
at 14th Annual Meeting
1723 (1949).
work.
of Society of Polymer Science, Japan, 1965.
SYNTHETIC
HEACTION BY COMPLEX CATALYST
COPPEH CATALYZED
IV.
REACTION OF ALCOHOL WITH ISOCYANIDE
Trkeo Saegusa, Yoshihiko
Ito, Shiro Kobayashi
and Kiwami Hirota
Department
of Synthetic
Chemistry,
Kyoto University,
Faculty of Engineering,
Kyoto, Japan
(Beceived28 November 1966) Recently we have explored a series of copper catalyzed with isocyanide 1)_ (es.
reactions
of amine
carbon monoxide 2) (eq. (ii)), diazomethane 3) (en.
(ill,
(iii)), and ethyl diazoacetate 3) (eq. (iv)).
R”-N
‘C
/
co
7
(i )
I&N-C-"
---------
:>N-$-H
..__.__.__ (ii)
0
$N-H CH2N2
---____--.
(iii)
----
(iv)
-N2
N2CHCOOC2H5
p
$NCH2COOC2H5
-N2 These reactions cyanide,
are characterized
carbon monoxide,
lone pair electrons, As
an extension
trons, we examined
by a common feature that carbon atoms of iso-
and carbenes
from diazocompounds,
are inserted between nitrogen
each of which bears
and hydrogen
of amine.
of the insertion reaction of carbon having lone pair elec-
the reaction
of alcohol with isocyanide.
Based upon the fact
4,5) , the reaction of althat ally1 alcohol forms a complex with cuprous chloride lyl alcohol with isocyanide
by cuprous chloride catalyst was first investigated.
521
No.6
522
It has nor been found that in the presence reacts with isocyanide
to produce
CH2=CHCH20H
of cuprous chloride ally1 alcohol
ally1 formimidate
-
+ R-NSC
(II).
CH2=CHCHzO$H
CuCl
----(~1
(II)
(1) This constitutss
a new insertion
reaction
(I)
of isocyanide
NR
between oxygen and hydro-
gen of alcohol. In 4.1 g (0.070 mol) of ally1 alcohol, 0.79 g (0.008 mol) of cuprous chloride was dissolved.
To this solution, 4.4 g (0.040 mol) of cyclohexyl
The reaction mixture vas
added, and the mixture was heated at 120°C for 5 hours. subjected
to distillation
cyclohexylformimidafe
under reduced pressure,
was obtained,
(25 $6) of N-cyclohexylformamide In the absence
observation
both ally1 alcohol and cyclohexyl
almost quantitatively
The results
mental analysis
1.3 g
isocyanide
to give the corresponding
are given in Table 1.
mixture.
isoThis
activity of cuprous chloride.
alcohols such as methally
cinnamyl alcohol were reacted with cyclohexyl
acid.
from the heat-treated
the catalysis
other p,r-unsaturated
prous chloride catalyst
As a by product,
was isolated, b.p. 100-103'C/3 mm Hg.
is talcen to demonstrate
Similarly,
and 4.5 g (67 %) of ally1 N-
b.p. 105"C/32 mm Hg.
of cuprous chloride,
cyanide were recovered
isocyanide was
alcohol and
in the presence of cu-
esters of N-cyclohexylformimidic
The formimidates
were identified by ele-
and IR and NMR spectra analyses. TABLE I
Reaction
of fi,Y-Unsaturated Alcohol with Cyclohexyl
P,g-Unsaturated
Products
Isocyanide*
( Yield $ )
alcohol CH2=CHCH20H
CH2=CHCH20CH=N-@
CH2=C(CH3)CH20H
CH2=C(CH3)CH20CH=N-@
@CH&BCH~OH
Q-CH=CHCH~OCH=N-Q
a)
b.p.
*
Cyclohexyl
105'C/32 mm Hg,
pyridine
a) (67),
isocyanide
b)
b.p.
b, (50), ') (45),
116'C/27 mm Hg,
contains a small quantity
as impurities.
Q-NHCBO
(25)
@-NHCHO Q-NHCHO c)
b.p.
(32) (20) 13O'C/3 mm Hg
(about 0.5 '$ to 1 $J) of
No.6
523
The formation
of N-cyclohexylformamide
which a few possible
reaction
of the N-cyclohexylforramide The specific nature isocyanide
as a by-product
routes may be assumed. formation
tert-butanol catalyst.
of alcohol by cuprous chloride
did not react with isocyanide
The specificity
of the mechanism
alcohol in the insertion
on finding that saturated alcohols such
illustrated
Elucidation
for
is being made now.
of p,y-unsaturated
between oxygen and hydrogen
is usually observed,
8s ethanol,
in the presence
of &r-unsaturated
alcohol
reaction of catalyst was
isopropanolgand
of cuprous chloride
in the reaction with iso-
cyanide may be due to its nature of complex formation with cuprous chloride. fact, we6) have observed in a separate experiment
In
that the IB olefinic band at
1640 cm-' of ally1 alcohol ahifts to 1550 cm -1 when ally1 alcohol is mixed with cuprous chloride.
It seema likely that the cuprous chloride-ally1
by means of hydroxyl the present
group as well as olefinic group plays an important role in
reaction.
Catalysis When a mixture
behavior of cupric chloride differs from that of cuprous chloride. of ally1 alcohol , cyclohexyl
isocyanide
and a small amount of cu-
pric chloride was heated at 12O'C for 10 hours, no formimidate light brown powder of isocyanide polymer was produced. of cyclohexyl Hagihara catalyst,
alcohol complex
was formed, but
The IR spectrum
of polymer
isocyanide by cupric chloride waa quite similar to that prepared
and coworkers 7) using nikel and cobalt carbonyls for which the following
by
aa the polymerization
structure was presented.
c tp
i-
di
a H
In the reaction
of saturated alcohol with cyclohexyl
chloride catalyst, N-cyclohexylcarbamate hexylformamide Chlorides
metal halides.
of the corresponding
by cupric
alcohol and N-cyclo-
were formed in low yields. of nikel
ally1 alcohol-isocyanide when a mixture
isocyanide
(II), cabalt reaction.
of cyclohexyl
(II) and palladium
(II) do not catalyze the
The polymer of cyclohexyl
iaocyanide
iaocyanide was formed
and ally1 alcohol was treated with these
~0.6
521
The reaction
of mercaptan
tion of isocyanide
between
with isocyanide has also been examined.
sulfur and hydrogen
of mercaptan
The inser-
occurs without
copper
catalyst. _
Detailed
studies upon the reactions
will be reported
of alcohol and mercaptan
with isocyanide
in the near future.
REFERENCES 1)
T. Saegusa, Letters,
2)
Y. Ito, S. Kobayashi,
K. Hirota and H. Yoshioka,
Tetrahedron
1966 No.49.
T. Saegusa,
S.
Kobayashi,
K. Hirota,
and Y. Ito, Tetrahedron
Letters,
1966,
No.49.
3)
Y. Ito, S. Kobayashi,
T. Saegusa, Letters,
E,
K. Hirota,
and T. Shimizu, Tetrahedron
No.49.
4)
B. E. Kepner
and L. J. Andrews,
5)
R. M. Keefer and L. J. Andrews, J. Am. Chem. Sot., 2,
6)
T. Saegusa
7)
Presented
and N. Takeda,
J. Org. Chem., 13, 208 (1948). =
unpublished
at 14th Annual Meeting
1723 (1949).
work.
of Society of Polymer Science, Japan, 1965.