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Palladium complex catalyzed reactions of conjugated dienes I. Reaction of butadiene with aldehydes
Tetrakledron Letters k.4:,
pp. j81j-5816, 1970.
Pergmon
Press.
Printed in Great Britain.
PALLADIUM COMPLM CATALYZED REACTIONS OF CONJUGATED I. REACTION OF BUTADIENE WITH ALDEHYDES R. M. Manyik,
DIENES
1. E. Walker, K. E. Atkins and E. S. Haaaack
Research and Development Department, Union Carbide Corporation Chemicals and Plastics, South Charleston, W. Va. (Received in USA 11 August 1970; received in UK for publicatioh 17 August 197'2)
Recently several reports butndiene with nucleophiles These reactions dominantly
have appeared concerning
catalyzed
have resulted
terminal addition
by soluble palladium complexes
in dimerization
to yield octadienyl
,,Z?-diketonesor
We wish to report a novel palladium catalyzed with aldehydes
to give the previously
(l-4).
of the butadiene along with pre-
of the nucleophile
amincs, esters, or C-alkadienylated
the reactions of
ethers,
Lj-keto esters. telomerization
unknown products,
of butadiene
I and II.
0 R&H
+
Pd catalyst
CH2=CH-CH=CH2
a. R = CH3 b.R=H ?" R-CH +
CH2=CH-;H-CH2CH=CH-CH-CH2 II
a. R = CH3 b.R=W Reaction of acetaldehyde presence of palladium
acetylacetonate
6-methyl-tetrahydropyran, These compounds palladium
with butadiene at 25' for 60 hours in the gave 2,5-divinyl-
Ia, and 1,5,7-octatrien-3-ylmethylcarbinol,
can be selectively
acetylacetonate
and triphenylphosphine
IIa.
produced by varying the triphenylphosphine:
(P:Pd) ratio.
Generally 3613
the reaction
is conducted
using 0.5-2.0 mmoles of palladium
per mole of butadiene
When the reaction of butadiene and acetaldehyde ratio, Ia (bp 95'/50 mm) was the predominant spectrum
(5).
was run using a 4:l P:Pd
product in 70% yield.
[c51.1 ppm, d, J = 6.3 cps -C!H3(3H); 1.5, m, -CH2-(4H);
(1H); 3.2, m, O-C-H was consistent equivalent
(1H);. 3.7, m, =C-CH-0
(1H); 5.0, m, =CH2
with the proposed structure,
indicating
vinyl groups by the unusual complexity
area distribution.
The nmr
2.0, m, -C-C-H
(4H); 5.6 =CH (2H)]
the presence of two non-
in that region as well as the
The methyl group absorbs as a pair of doublets
and 1.2 ppm probably signifying The infrared spectrum
the existence
of conformational
between 1.0
isomers
[cyclic C-O-C 8.95p and 9.2p; =CH and =CH2
(61.
6.lP, lO.ly,
and ll.Op] is also consistent with this structure. Anal. Calcd. for C10H160:
C, 78.89; H,10.59.
Found:
C, 79.04; H, 10.39.
When the reaction was run using a 1:l P:Pd ratio, IIa (bp 100'/20 mm) was produced
in high yield
positions was clearly
(70%).
indicated from the nmr spectrum
-CH3 (3H); 2.2, m, =CCH
infrared:
(1H); 5.1, m,
The wide range of low field absorption
of the peaks indicated a conjugated
of two vinyl groups.
C51.1 ppm, d, J = 6.5 cps
(3H); 3.0, s, O-H (1H); 3.7, m, O-C-H
=CH2 (4H); 6.0, m, =CH (4Hj.l. area distribution
The location of double bonds at the 1, 5, and 7
The other spectral data
[u.v.:
and the
system and the presence Amax
227 mP
E = 22,800;
3.0~ -OH, 10.1 and 11.0~ CH2= and =CHJ was consistent with the pro-
posed structure. Anal. Calcd. for C10H160: Intermediate IIa.
C, 78.89; H, 10.59.
Found:
C, 79.05; H, 10.45.
levels of P:Pd ratios were used and gave mixtures
In all cases some linear butadiene dimerization
of Ia and
to 1,3,7-octatriene
was
observed. as formalin, also reacted with butadiene under these condi-
Formaldehyde,
tions to give 2,5_divinyltetrahydropyran, The nmr spectrum
1s 1.6 ppm, m, -CH2-
J = 11.0 cps, O-C-H
IIb (bp 173') in good yield
(4H);' 2.2, m, =C-C-H
(axial) (1H); 3.7, m, O-C-H
(70-80%).
(1H); 3.1, t,
(equatorial) and 0-CH-C=
(2H);
5.0, m, =CH2 (4H); 5.6, m, =CH (2H)]was consistent with the proposed structure. Confirmation
of the assignment
hydrogens on position
of the
6 was confirmed
'53.1 signal to one of the methylene by a double resonance
experiment.
The
go.43
3815
original
triplet collapsed
This was also accompanied
was irradiated. the
63.7
to a doublet when the methine proton at position
signal, corroborating
tion 6 absorbed
there.
by the expected simplification
the fact that the equatorial
of
proton of posi-
The infrared spectrum [C-O-C 9.2-9.3p; =CH and =CH2
10.1~ and ll.oP] was also consistent with the proposed structure Anal. Calcd. for CgH14Q: Compound
5
C, 78.21; I-I,10.21.
Ib was hydrogenated,
(7).
C, 77.98; H, 9.92.
Found:
taking up two moles of hydrogen,
to yield
c61.0 ppm -CH3, 1.5 -CH2-, 1.9 The nmr spectrum 2,5-diethyltetrahydropyran. r C-CH (15H); 3.0, m, 0-C-C2H5 and O-C-H (axial) (2H); 3.7, m, O-C-H (equatorial) (1~)) indicated an upfield shift of the axial hydrogen on the Z-position the methine.hydrogen
on the 5-position,
Anal. Calcd. for CgH180: Thus far no compound boiling components
C, 76.00; H, 12.75.
these compounds will be discussed
can be dramatically acetaldehyde
Found:
the double bonds. C, 75.91; H, 12.67.
IIb has been isolated although a number of higher
have been observed
The rate of reaction
both due to removing
in varying yields.
The structures
of
later in a full paper.
of both formaldehyde
and acetaldehyde
increased by the use of appropriate
with butadiene
solvents.
For example,
and butadiene were reacted at 80' for 2 hours in ethanol using a
4~1 P:Pd ratio to give a 6% yield of IIa and a 74% yield of Ia. reaction
and
in isopropanol
and 8% of Ia.
A similar
for 3 hours using a 1:l P:Pd ra.tio gave 75% of IIa
There was no reaction of the alcohol solvent to yield octadienyl
ethers even though alcohols are known to react with butadiene using this and other palladium catalyst
systems
(1).
To see if IIa was an intermediate with palladium
acetylacetonate
and triphenylphosphine
4 hours at loo', only 17% conversion
aldehyde
a crude
reaction of butadiene and acet-
(containing IIa and Ia in a 70~30 mole ratio) was treated
with enough triphenylphosphine
to give a 4:l P:Pd ratio.
at 100' for 4 hours, no change
occurred in the relative quantities
and Ia.
After
In the presence of
In another experiment,
from a 1:l P:Pd catalyzed
in ethanol
(4:l P:Pd ratio).
to Ia had occurred.
ethanol, a similar result was obtained. reaction product
in the formation of Ia, IIa was heated
On further heating of IIa
These results indicate that IIa is probably not formed from Ia,
5316
No.43
although
both may be formed from a common intermediate.
The reaction of formaldehyde with butadiene was accelerated of tertiary amines but was not affected present in the commercial
by the use of alcohol beyond that already
formalin solution.
Sutadiene and formaldehyde were
reacted at 80' in the presence of triethylamine ladium catalyst
or N-methylmorpholine
to yield 75-80s of Ib within l-4 hours.
reaction of butadiene with acetaldehyde amines.
by the addition
and pal-
Interestingly,
the
is not aided by the presence of tertiary
Roth the amine and alcohol solvents are normally used in about 0.5:1
mole ratio to the butadiene. The increased rate achieved when using solvents is in part due to the higher temperature which can be used. temperatures
In the absence of solvent, reaction
of 60-80' lead to increased formation of by-products
1,3,7_octatriene.
such as
The nature of these solvent effects is not clearly under-
stood and the phenomenon
is under study.
Further extensions
aldehydes as well as the possible mechanism
of our work with
of this reaction will be published
as soon as it is completed. Acknowledgment:
The authors wish to thank W. T. Pace and M. L. Farmer
for the nmr spectra and aid in interpretation.
References 1.
S. Takahashi, T. Shibano, and N. Hagihara, Bull. of the Chem. Sot. of Japan 41 454-60 (1968); Tetrahedron Letters 1967 2451. -
2.
E. J. Smutny, J. Amer. Chem. Sot. 89 6793-4
3.
E. J. Smutny, U. S. Patent 3,267,169 (1967).
4.
G. Hata, K. Takahashi, and A. Miyake, Chem. Ind. (London) 1826 (1969).
5.
All reactions were run in a nitrogen atmosphere. nitrogen purged before use.
6.
VPC analyses indicate the presence of four stereoisomers, but they could not be separated by distillation or preparative-scale WC.
7.
Two steroisomers
(1967).
(1966) and U. S. Patent 3,350,451
All solvents were
are indicated by VPC but cannot be separated.
pp. j81j-5816, 1970.
Pergmon
Press.
Printed in Great Britain.
PALLADIUM COMPLM CATALYZED REACTIONS OF CONJUGATED I. REACTION OF BUTADIENE WITH ALDEHYDES R. M. Manyik,
DIENES
1. E. Walker, K. E. Atkins and E. S. Haaaack
Research and Development Department, Union Carbide Corporation Chemicals and Plastics, South Charleston, W. Va. (Received in USA 11 August 1970; received in UK for publicatioh 17 August 197'2)
Recently several reports butndiene with nucleophiles These reactions dominantly
have appeared concerning
catalyzed
have resulted
terminal addition
by soluble palladium complexes
in dimerization
to yield octadienyl
,,Z?-diketonesor
We wish to report a novel palladium catalyzed with aldehydes
to give the previously
(l-4).
of the butadiene along with pre-
of the nucleophile
amincs, esters, or C-alkadienylated
the reactions of
ethers,
Lj-keto esters. telomerization
unknown products,
of butadiene
I and II.
0 R&H
+
Pd catalyst
CH2=CH-CH=CH2
a. R = CH3 b.R=H ?" R-CH +
CH2=CH-;H-CH2CH=CH-CH-CH2 II
a. R = CH3 b.R=W Reaction of acetaldehyde presence of palladium
acetylacetonate
6-methyl-tetrahydropyran, These compounds palladium
with butadiene at 25' for 60 hours in the gave 2,5-divinyl-
Ia, and 1,5,7-octatrien-3-ylmethylcarbinol,
can be selectively
acetylacetonate
and triphenylphosphine
IIa.
produced by varying the triphenylphosphine:
(P:Pd) ratio.
Generally 3613
the reaction
is conducted
using 0.5-2.0 mmoles of palladium
per mole of butadiene
When the reaction of butadiene and acetaldehyde ratio, Ia (bp 95'/50 mm) was the predominant spectrum
(5).
was run using a 4:l P:Pd
product in 70% yield.
[c51.1 ppm, d, J = 6.3 cps -C!H3(3H); 1.5, m, -CH2-(4H);
(1H); 3.2, m, O-C-H was consistent equivalent
(1H);. 3.7, m, =C-CH-0
(1H); 5.0, m, =CH2
with the proposed structure,
indicating
vinyl groups by the unusual complexity
area distribution.
The nmr
2.0, m, -C-C-H
(4H); 5.6 =CH (2H)]
the presence of two non-
in that region as well as the
The methyl group absorbs as a pair of doublets
and 1.2 ppm probably signifying The infrared spectrum
the existence
of conformational
between 1.0
isomers
[cyclic C-O-C 8.95p and 9.2p; =CH and =CH2
(61.
6.lP, lO.ly,
and ll.Op] is also consistent with this structure. Anal. Calcd. for C10H160:
C, 78.89; H,10.59.
Found:
C, 79.04; H, 10.39.
When the reaction was run using a 1:l P:Pd ratio, IIa (bp 100'/20 mm) was produced
in high yield
positions was clearly
(70%).
indicated from the nmr spectrum
-CH3 (3H); 2.2, m, =CCH
infrared:
(1H); 5.1, m,
The wide range of low field absorption
of the peaks indicated a conjugated
of two vinyl groups.
C51.1 ppm, d, J = 6.5 cps
(3H); 3.0, s, O-H (1H); 3.7, m, O-C-H
=CH2 (4H); 6.0, m, =CH (4Hj.l. area distribution
The location of double bonds at the 1, 5, and 7
The other spectral data
[u.v.:
and the
system and the presence Amax
227 mP
E = 22,800;
3.0~ -OH, 10.1 and 11.0~ CH2= and =CHJ was consistent with the pro-
posed structure. Anal. Calcd. for C10H160: Intermediate IIa.
C, 78.89; H, 10.59.
Found:
C, 79.05; H, 10.45.
levels of P:Pd ratios were used and gave mixtures
In all cases some linear butadiene dimerization
of Ia and
to 1,3,7-octatriene
was
observed. as formalin, also reacted with butadiene under these condi-
Formaldehyde,
tions to give 2,5_divinyltetrahydropyran, The nmr spectrum
1s 1.6 ppm, m, -CH2-
J = 11.0 cps, O-C-H
IIb (bp 173') in good yield
(4H);' 2.2, m, =C-C-H
(axial) (1H); 3.7, m, O-C-H
(70-80%).
(1H); 3.1, t,
(equatorial) and 0-CH-C=
(2H);
5.0, m, =CH2 (4H); 5.6, m, =CH (2H)]was consistent with the proposed structure. Confirmation
of the assignment
hydrogens on position
of the
6 was confirmed
'53.1 signal to one of the methylene by a double resonance
experiment.
The
go.43
3815
original
triplet collapsed
This was also accompanied
was irradiated. the
63.7
to a doublet when the methine proton at position
signal, corroborating
tion 6 absorbed
there.
by the expected simplification
the fact that the equatorial
of
proton of posi-
The infrared spectrum [C-O-C 9.2-9.3p; =CH and =CH2
10.1~ and ll.oP] was also consistent with the proposed structure Anal. Calcd. for CgH14Q: Compound
5
C, 78.21; I-I,10.21.
Ib was hydrogenated,
(7).
C, 77.98; H, 9.92.
Found:
taking up two moles of hydrogen,
to yield
c61.0 ppm -CH3, 1.5 -CH2-, 1.9 The nmr spectrum 2,5-diethyltetrahydropyran. r C-CH (15H); 3.0, m, 0-C-C2H5 and O-C-H (axial) (2H); 3.7, m, O-C-H (equatorial) (1~)) indicated an upfield shift of the axial hydrogen on the Z-position the methine.hydrogen
on the 5-position,
Anal. Calcd. for CgH180: Thus far no compound boiling components
C, 76.00; H, 12.75.
these compounds will be discussed
can be dramatically acetaldehyde
Found:
the double bonds. C, 75.91; H, 12.67.
IIb has been isolated although a number of higher
have been observed
The rate of reaction
both due to removing
in varying yields.
The structures
of
later in a full paper.
of both formaldehyde
and acetaldehyde
increased by the use of appropriate
with butadiene
solvents.
For example,
and butadiene were reacted at 80' for 2 hours in ethanol using a
4~1 P:Pd ratio to give a 6% yield of IIa and a 74% yield of Ia. reaction
and
in isopropanol
and 8% of Ia.
A similar
for 3 hours using a 1:l P:Pd ra.tio gave 75% of IIa
There was no reaction of the alcohol solvent to yield octadienyl
ethers even though alcohols are known to react with butadiene using this and other palladium catalyst
systems
(1).
To see if IIa was an intermediate with palladium
acetylacetonate
and triphenylphosphine
4 hours at loo', only 17% conversion
aldehyde
a crude
reaction of butadiene and acet-
(containing IIa and Ia in a 70~30 mole ratio) was treated
with enough triphenylphosphine
to give a 4:l P:Pd ratio.
at 100' for 4 hours, no change
occurred in the relative quantities
and Ia.
After
In the presence of
In another experiment,
from a 1:l P:Pd catalyzed
in ethanol
(4:l P:Pd ratio).
to Ia had occurred.
ethanol, a similar result was obtained. reaction product
in the formation of Ia, IIa was heated
On further heating of IIa
These results indicate that IIa is probably not formed from Ia,
5316
No.43
although
both may be formed from a common intermediate.
The reaction of formaldehyde with butadiene was accelerated of tertiary amines but was not affected present in the commercial
by the use of alcohol beyond that already
formalin solution.
Sutadiene and formaldehyde were
reacted at 80' in the presence of triethylamine ladium catalyst
or N-methylmorpholine
to yield 75-80s of Ib within l-4 hours.
reaction of butadiene with acetaldehyde amines.
by the addition
and pal-
Interestingly,
the
is not aided by the presence of tertiary
Roth the amine and alcohol solvents are normally used in about 0.5:1
mole ratio to the butadiene. The increased rate achieved when using solvents is in part due to the higher temperature which can be used. temperatures
In the absence of solvent, reaction
of 60-80' lead to increased formation of by-products
1,3,7_octatriene.
such as
The nature of these solvent effects is not clearly under-
stood and the phenomenon
is under study.
Further extensions
aldehydes as well as the possible mechanism
of our work with
of this reaction will be published
as soon as it is completed. Acknowledgment:
The authors wish to thank W. T. Pace and M. L. Farmer
for the nmr spectra and aid in interpretation.
References 1.
S. Takahashi, T. Shibano, and N. Hagihara, Bull. of the Chem. Sot. of Japan 41 454-60 (1968); Tetrahedron Letters 1967 2451. -
2.
E. J. Smutny, J. Amer. Chem. Sot. 89 6793-4
3.
E. J. Smutny, U. S. Patent 3,267,169 (1967).
4.
G. Hata, K. Takahashi, and A. Miyake, Chem. Ind. (London) 1826 (1969).
5.
All reactions were run in a nitrogen atmosphere. nitrogen purged before use.
6.
VPC analyses indicate the presence of four stereoisomers, but they could not be separated by distillation or preparative-scale WC.
7.
Two steroisomers
(1967).
(1966) and U. S. Patent 3,350,451
All solvents were
are indicated by VPC but cannot be separated.