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Synthesis of Mono- and Di- substituted Aryl- and HeterocyclicMalononitrile Derivatives and Secondary Alkylation Selectivity
An Honors Thesis (HONRS 499)
By
Ryan Miller
Thesis Advisor
Dr. Robert Sammelson
Ball State University
Muncie, Indiana
May 2007
Expected Date of Graduation
May 3rd , 2007
Synthesis of Mono- and Di- substituted Aryl- and HeterocyclicMalononitrile Derivatives and Secondary Alkylation Selectivity
RYAN MILLER AND ROBERT E. SAMMELSON
Department o/Chemistry, Ball State University, Muncie, Indiana 47306
Recently, our lab has developed an efficient method for the synthesis of
monosubstituted malononitriles via reductive alkylation. By using various
aryl- and heterocyclic substituents, monosubstituted derivatives are
created by reductive alkylation through a Knoevenagel condensation and
subsequent conjugated reduction. The monosubstituted derivatives can
then undergo simple alkylation techniques for addition of new functional
groups, such as methyl- or allyl-, creating asymmetrically disubstituted
malononitrile derivatives. These derivatives can then be reacted by further
alkylation of the pre-existing aryl- or heterocyclic functional groups, such
as phenol or pyridine centers.
Introduction
The reactivity of malononitrile allows it
to be used as either a reactant or reaction
intermediate because either cyano group can
take part in condensation, and the a-carbon
is easily reduced to create additional
products and heterocyclic compounds. l The
reactivity of the cyano groups allows these
products to undergo reductive alkylation to
mono and disubstituted (both symmetric
and asymmetric) derivatives, which have
been shown to have numerous applications
in
medicinal,
pharmaceutical
and
Many of these
agricultural fields. l -4
compounds can be used as pesticides or
herbicides, as well as important drug
intermediates. The cyano functional group
has been found to be effective on a number
of biological receptors, making it an
appropriate group for addition to medicinal
scaffolds, which are a part of modem drug
discovery.s Also, substituted malononitrile
derivatives have been found to be useful
pest combatants, but their maximum
efficiency has yet to be achieved. 6•7
Therefore, developing a simple, costeffective method for synthesizing these
compounds is of great use to the scientific
community.
Recently, methods have been discovered
for creating primary and secondary
monosubstituted malononitriles through
selective synthesis. 3,4 These methods offer
relatively quick and simple procedures for
generating high yields of product, but, in
most cases, require two steps: preparation
and isolation.2 In continuation of our
discovery of a method for one-pot
monosubstituted
malononitrile
2
derivatives ,4, we are reporting its
application to disubstituted derivatives.
These compounds contain a disubstituted
malononitrile center with addition of an
alkyl group as well as the previously added
aryl or heterocyclic functional group.
NC~CN
Malononitrila
NC'y'CN
R
Malononitrile, monosubstituted
malononitrile
derivative,
and
asymmetrically disubstituted malononitrile
derivative, respectively.
Figure 1.
2
There have been many different reactions
for production of malononitrile derivatives.!
The chemistry of malononitrile has been
studied for years, with its uses spanning:
hydrolysis, reduction, orthoester, complex,
salt and ylide formation, halogenation
reactions, and carbonyl condensation
reactions.!
Specifically,
carbonyl
condensation reactions have been used to
create derivatives from aldehydes and
ketones using the Knovenegal reaction with
sodium borohydride reduction?,4 This oneof
monosubstituted
pot
synthesis
malononitriles has been found to create
heterocyclic derivatives using the sodium
borohydride reduction technique; these
compounds are also available for further
alkylation?
E.OH
~y
~y
Ar
Ar
~)'
R:-X.
NCfC:
K,Co,
Ar
Autone
A-E
Ar
1-10
Method for synthesis of
asymmetrically disubstituted malononitrile
derivatives.
Scheme 1.
The second goal of our research was to
use our alkylation technique to react with
other aryl functional groups on the
disubstituted derivatives, to create a catalog
of compounds from similar chemistry to be
tested for biological activity. With respect
to disubstituted phenols, the same alkylation
technique was applied to the resulting
disubstituted derivatives to create methoxy
or allyloxy substituents via a-alkylation
(Scheme 2). Due to the lack of any other
reactive centers on the compounds, an
excess of alkyl agent was used to ensure
complete alkylation.
Figure 2. One-pot procedure for creation
of
monosubstituted
malononitrile
derivatives. 4
The first goal was the alkylation of these
malononitrile derivatives to asymmetrically
disubstituted derivatives (Scheme 1). Our
research is an attempt to create these
alkylated derivatives as well as explore the
selectivity of the malononitrile, phenol and
pyridl reactive centers. These reactions
were carried out under basic conditions
using a direct alkylation technique?
However, this method has its disadvantages,
mainly, direct alkylation can result in loss
of selectivity and over-alkylation of starting
material? Our method for alkyl addition to
our monosubstituted derivatives involved a
1: 1 reductive alkylation under basic
conditions to limit over-alkylation.
Scheme 2. Method for alkylation of phenol
as part of aromatic ring.
The final goal of our research was to
develop a method for alkylation of nitrogen
as part of a pyridyl substituent (Scheme 3).
We also attempted to determine the chemoselectivity of the malononitrile center
The
relative to the pyridine nitrogen.
pathway best suited for this reaction was
found to be an excess of iodomethane, with
respect to starting material, in acetone at
room temperature. 8,9 Again, a large excess
of reagent is made possible by the
3
availability of only one center for reductive
alkylation.
c
d
~
~
N
I
7-10
c:
d
C
X-R'
_one, bo':
48
c:
~
~@ I
I
N
19-22
R'
Scheme 3. Method for alkylation of pyridl
nitrogen as part of asymmetrically
disubstituted derivative. 8,9
Results and Discussion
All
monosubstituted
malononitrile
derivatives (A-E) were created from the
outlined procedure in our lab with 1H NMR
and l3e NMR data reported by Tayyari et.
a1. 4 These compounds were then used as
the starting material for the creation of
asymmetrically disubstituted malononitrile
derivatives by the following reactions with
reported results.
created malononitrile derivatives containing
phenol or pyridine substituents. These
starting compounds were reacted in a 1: 1
ratio with either iodomethane or allyl
bromide to form the asymmetrical
derivatives. These reactions were run on
scales varying from 1 to 10 mmols and
resulted in good to excellent yields (6698%). The compounds (1-10) were purified
through either recrystallization or column
chromatography in preparation for further
alkylation.
Synthesis of asymmetrically
Table 1.
disubstituted malononitrile derivatives. All
yields are crude, before purification, and an
* denotes newly developed compounds.
I
Starting
Compound
R
Group
Product
A
Allyl
Methyl
Allyl
Methyl
Allyl
Methyl
Allyl
Methyl
Allyl
Methyl
1*
2*
3*
4*
5*
6*
7*
8*
9*
10*
B
C
D
E
Figure
3.
Originally
created
monosubstituted malononitrile derivatives
for testing of further alkylation techniques. 4
Disubstituted malononitrile derivatives
were created from the five previously
%
Yield
98
70
98
82
79
87
90
81
79
66
These derivatives were created by
running the synthesis reaction in as close to
a 1: 1 ratio as possible to consume all of the
starting material, but our chemistry has
shown that alkyl groups, in the presence of
base, will reductively add to the
malononitrile center, and only add to the
phenol if excess alkyl group is present.
When 1: 1 ratio could not be exactly
achieved, a very slight excess of alkyl
halide was added to create the less polar,
over-alkylated
products
for
easier
separation before the next alkylation
reaction. Purification of these compounds
4
was usually achieved via column
chromatography, where the polarity of the
desired product made for much more facile
separation than would have been possible if
any starting material remained. With this
selectivity, and our knowledge of the
polarity of the starting material, desired
product, and over-alkylated product, we
conclude that it is worth the slight loss of
yield to add excess alkyl reagent to ease
later separation of products.
The synthesized disubstituted derivatives
were then reacted with a slight excess of
iodomethane or allyl bromide at their only
remaining reducible center. The synthesis
for reduction of phenols was executed on
the
resulting
compounds
from
monosubstituted derivatives A, B, and C on
scales of 1-10 mmols to produce allyloxy
and methoxy substituents in good to
excellent yields (75-98%).
These
compounds were then purified via
recrystallization
or
column
chromatography.
Table 2. Synthesis of new compounds by
reductive alkylation of phenol as part of
asymmetrically disubstituted malononitrile
derivative. All yields are crude; * denotes
newly developed compounds.
:
Starting
I Compound
i
i
A
1
2
A
!
3
4
5
6
R
Group
Allyl
Methyl
Allyl
Ethyl,
Allyl
Methyl
Allyl
Methyl
Allyl
Product
I
%
. Yield
11*
12
13*
14*
98
78
75
91
15
16*
17*
18*
95
77
92
92
!
With the elimination of the malononitrile
reactivity center due to complete alkylation,
the alkyl group has no choice but to react
with the phenol on the starting compound.
Because of the elimination of reaction
selectivity, we were able to create these
compounds by reacting reagents on a 1: 1.1
ratio to ensure complete alkylation of
starting material. However, even with the
excess alkyl group present, there were still
impurities of unreacted starting material,
which were separated from desired product
by
column
chromatography
or
recrystallization, respectively.
Production of 11 * was achieved by
reacting starting compound A with an
excess of allyl bromide to eliminate the
importance of alkylation selectivity. We
found that this dialkylation was effective,
yet required a longer reaction time and
addition of fresh base to ensure complete
reaction. Even with this excess alkyl group,
some side products were formed and final
product was purified via recrystallization.
The reaction to produce 14* was examined
by first adding the ethyl substituent
(iodomethane), followed, 7 hours later, by
complete, immediate reaction of all product
through addition of allyl bromide to create a
fully substituted compound. Because of the
immediate reaction of all material, no
disubstituted derivative containing phenol
was purified; only isolation of final product
was achieved. This reaction was explored
to attempt a synthesis method that could be
completed in a single step, but we found
that a heavy excess of the second alkyl
group had to be added as well as fresh base
to ensure complete reaction. There was also
the possibility of numerous side products
that are already fully substituted, making
purification difficult. From this result, we
conclude that it is important to separate the
dialkylated side product from the previous
step before starting the phenol reaction to
eliminate the possibility of two products
5
with similar polarity, making separation
more difficult. Overall, because of the
elimination of reaction selectivity, these
compounds were created with better
efficiency than when side products are
possible.
The disubstituted derivatives containing a
pyridyl functional group (D and E)
underwent N-alkylation with excess
iodomethane to produce pyridinium salts
via the alkylation method for pyridyl
compounds. Reactions were run on roughly
0.5 mmol scales to provide enough excess
of iodomethane.
These products were
created with excellent yields (-100%) due
to complete alkylation and precipitation.
Table 3. Synthesis of new compounds by
simple alkylation of pyridyl-nitrogen as part
of
asymmetrically
disubstituted
malononitrile derivative. All yields are
crude; * denotes newly developed
compounds.
Starting
Compound
7
8
9
10
R
Group
Methyl
Methyl
Methyl
Methyl
Product
%
Yield
19*
20*
21 *
22*
-100
-100
-100
-100
Alkylation of pyridl substituents was
achieved with great efficiency by dissolving
the starting material in acetone and adding
an excess of alkyl group in at least an 8: 1
mmol ratio.
In the creation of the
asymmetrically disubstituted derivatives,
we did not see alkylation of the pyridl
nitrogen because of the presence of base in
the form of K2C03. However, because this
reaction was not run under basic conditions,
we conclude that the reactivity of the
nitrogen in the pyridyl group is more
selective than the malononitrile center. This
was tested by reacting a monosubstituted
pyridl derivative under the non-basic
conditions for pyridinium formation and the
pyridinium salt was formed. This salt was
isolated, placed in acetone-D6, and K2C03
was added to test for removal of pyridinium
and alkylation of the malononitrile center
(Scheme 4). Our results showed that the
methyl group does change from the pyridine
nitrogen to the malononitrile in the presence
of base, making the nitrogen more selective
under neutral conditions.
Scheme 4. Method for testing alkylation
selectivity of pyridyl substitutents.
Yields of these pyridinium compounds
showed that complete alkylation was
achieved, but masses were slightly greater
than the limiting agent predicted. Because
of the quality of IH NMR and DC NMR
spectra of these compounds, we conclude
that the excess mass must be a result of the
remaining iodine anions produced during
the reaction. Methods are being explored
for purification of these compounds, as
separation of pyridinium salts from organic
salts has proven to be difficult.
Experimental
Thin layer chromatography (TLC) was
performed with Baker-Flex silica gel plates
and viewed with a UV lamp. Plates were
stained using basic KMN04. Alumina used
in traditional columns was obtained from
Fischer Scientific; column chromatography
was also run with silica gel using an
6
AnaLogix Flash Column with prepackaged
silica cartridges for purification.
All
reagents were used commercial grade,
without purification. A 400 MHz JEOL
Eclipse NMR spectrometer was used for
recording all IH NMR and 13 C NMR
spectra. 1H NMR chemical shifts were
reported in ppm, using CDCh (with TMS as
internal standard), Acetone-D6, or DMSOD6 when applicable. DC NMR chemical
shifts were reported in ppm using above
solvents.
following day, ethyl acetate was added to
wash round bottom and reaction mixture
was filtered through a vacuum filter
containing W' sea sand and an adequate
amount of Analytical Celite, to a clean
round bottom flask. The resulting solution
was then placed on the rotary evaporator to
remove solvent and then moved to a high
vacuum to ensure complete removal of
solvent. Purification was then carried out
through recrystallization or column
chromatography.
Standard Procedure for Reductive
Alkylation of Malononitrile Derivatives. 4
Malononitrile was combined with one of
five aryl- or heteroaryl compounds (4· or 3Hydroxybenzaldehyde, Vanillin, 3- or 4Pyridinecarboxaldehyde)
III
a
1: 1
equivalency of each compound, and
dissolved in an 80/20 ethanol/water solution
(ImL solution/mmol starting material).
Reaction was left at room temperature while
stirring overnight.
The following day,
excess 9S% ethanol was added and the
reaction was cooled to OoC before adding
O.S equivalents of NaBl:4 while spinning, in
ice bath, for 30 minutes. Any solid residue
was washed back into reaction using excess
ethanol. Cold HCI was then added until just
acidic and water was added to facilitate
crystallization.
Compound was then
separated by vacuum filtration.
Standard Procedure for Alkylation of
Phenol as Part of Disubstituted
Derivative. (11-18) Disubstituted derivative
(-1 mmol) was dissolved in SmL of reagent
grade acetone in round bottom flask. Base
was added in the form of K2C03 at 2:1
equivalency to starting material and alkyl
halide was added in a 1: 1.1 equivalency to
ensure complete alkylation. Reaction workup procedure same as above.
Standard Procedure for Alkylation to
Create
Asymmetric
Disubstituted
Derivatives.
(1-10)
Monosubstituted
derivative (1-10 mmol) was dissolved in
reagent grade acetone (-SmL: 1 mmol
starting material) in a round bottom flask.
Base was added in the form ofK2C03 at 2:1
equivalency to starting material and alkyl
halide was added in a 1: 1 equivalency to
avoid over-alkylation. The reaction was
allowed to proceed overnight at room
temperature with constant stirring. The
Standard Procedure for Alkylation of
Nitrogen as Part of Pyridyl-Disubstituted
Derivative.
(19-22)
Disubstituted
derivative « 1 mmol) was dissolved in
reagent grade acetone in small vial or cone
bottom flask. Iodomethane was then added
in excess of, at least, 8:1 equivalency.
Reaction was left covered at room
temperature for 48 hours for complete
reaction, after which, cover was removed
for solvent and excess reagent to evaporate
to isolate the pyridinium salt.
The chemical structures and NMR spectra
of the following compounds can be found in
AppendixA.
2-Allyl-2-(4-hydroxybenzyl)
malononitrile (1 *). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(4-
7
hydroxybenzyl)malononitrile (0.519 g, 3
mmol) and allyl bromide (0.364 g, 3 mmol),
were reacted to give 1* (0.6284 g, 97%).
IH NMR (400 MHz) b 7.23 (d, J = 7.7 Hz,
2H), 6.82 (d, J= 7.7 Hz, 2H), 5.98-5.88 (m,
lR), 5.66 (s, IH), 5.45 (d, J = 10.2 Hz, IH),
5.42 (d, J= 17.6 Hz, lR), 3.14 (s, 2H), 2.70
(d, J= 7.0 Hz, 2H); l3e NMR (100 MHz) b
156.3, 131.5, 128.5, 123.8, 123.4, 115.9,
114.9,41.9,41.1,39.6.
2-Methyl-2-(4-hydroxybenzyl)
malononitrile (2*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(4hydroxybenzyl)malononitrile (0.173 g, 1
mmol) and iodomethane (0.147 g, 1 mmol),
were reacted to give 2* (0.130 g, 70%). IH
NMR (400 MHz) b 7.16 (d, J = 8.4 Hz,
8.4 Hz, 2H), 5.32 (brs,
2H), 6.77 (d, J
IH), 3.07 (s, 2H), 1.73 (s, 3H); J3e NMR
(100 MHz) b 156.2, 131.5, 123.9, 115.9,
115.8,43.8,33.5,24.2.
2-Allyl-2-(3-hydroxybenzyl)
malononitrile (3*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(3hydroxybenzyl)malononitrile (0.346 g, 2
mmol) and allyl bromide (0.243 g, 2 mmol)
were reacted to give 3* (0.419 g, 98%). IH
NMR (400 MHz) b 7.25 (d, J
3.3 Hz,
IH), 7.25 (d, J = 2.2 Hz, 1H), 6.93 (d, J:;:
7.4 Hz, IH), 6.85 (d, J = 7.0 Hz, IH), 5.985.88 (m, 1H), 5.46 (d, J = 11.0 Hz, lR),
5.42 (d, J = 17.6 Hz 1H), 5.27 (s, IH), 3.15
(s, 2H), 2.70 (d, J = 7.3 Hz, 2H); l3e NMR
(100 MHz) b 155.9, 133.4, 130.3, 128.5,
123.5, 122.9, 117.0, 116.0, 114.9, 42.4,
41.3,39.0.
2-Methyl-2-(3-hydroxybenzyl)
malononitrile (4 *). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(3-
hydroxybenzyl)malononitrile (0.861 g, 5
mmol) and iodomethane (0.706 g, 5 mmo1),
were reacted to give 4* (0.609 g, 66%). IH
NMR (400 MHz) b 7.25 (d, J = 7.7 Hz,
IH), 6.90 (d, J = 7.7 Hz, IH), 6.85 (d, J =
8.8, 2H), 5.82 (brs, 1H), 3.14 (s, 2H), 1.79
(s, 3H); Be NMR (100 MHz) b 156.0,
133.4, 130.3, 122.5, 117.0, 116.0, 115.9,
44.1,33.1,24.3.
2-Allyl-2-(4-hydroxy-3-methoxybenzyl)
malononitrile (5*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following differences: 2-(4-hydroxy-3methoxybenzyl)malononitrile (0.208 g, 1
mmol) and allyl bromide (0.123 g, 1 mmol)
were reacted to give 5* (0.195 g, 79%). IH
NMR (400 MHz) b 6.91 (d, J = 8.1 Hz,
2H), 6.84 (d, J= 7.7 Hz, 1H), 5.98-5.87 (m,
IH), 5.77 (brs, 1H), 5.44 (d, J = 10.2 Hz,
1H), 5.41 (d, J:;: 17.2 Hz IH), 3.88 (s, 3H),
3.13 (s, 2H), 2.67 (d, J= 7.3 Hz, 2H); l3e
NMR (100 MHz) b 146.6, 146.1, 128.6,
123.6, 123.3, 123.2, 115.1, 114.7, 112.4,
55.9,42.4,41.1,39.4.
2-Methyl-2-(4-hydroxy-3methoxybenzyl)malononitrile (6*). The
general procedure for creation of
asymmetric disubstituted derivatives was
employed to scale with the following
differences:
2-(4-hydroxy-3methoxybenzyl)malononitrile (1.011 g, 5
mmol) and iodomethane (0.721 g, 5 mmol),
were reacted to give 6* (0.9365 g, 87%).
IH NMR (400 MHz) b 6.91 (d, J 8.1 Hz,
1H), 6.90 (d, J = 5.5 Hz, 1H), 6.83 (d, J =
8.1 Hz, 1H), 5.80 (s, 1H), 3.89 (s, 3R), 3.13
(s,2H), 1.77 (s, 3H); l3e NMR (100 MHz)
b 146.6, 146.1, 123.6, 123.3, 116.0, 114.6,
112.4,55.9,44.2,33.4,24.1.
2-AlIyl-2-(3-pyridylmethyl)
malononitrile (7*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(3-
8
pyridylmethyl)malononitrile (0.475 g, 3
mmol) and allyl bromide (0.363 g, 1 mmol)
were reacted to give 7* (0.530 g, 90%). lH
NMR (400 MHz) b 8.67 (dd, J = 4.8, 1.5
Hz, IH), 8.63 (d, J = 2.2 Hz, IH), 7.78
(ddd, J 7.7,2.2, 1.5 Hz, IH), 7.38 (dd, J =
7.7, 4.8 Hz, IH), 6.00-5.90 (m, IH), 5.525.42 (m, 2H), 3.22 (s, 2H), 2.76 (d, J = 7.3
2H); l3C NMR (100 MHz) b 151.0, 150.3,
137.5, 128.1, 127.8, 123.8, 123.7, 114.4,
41.3,39.8,38.9.
2-Methyl-2-(3-pyridylmethyl)
malononitrile (8*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(3pyridylmethyl)malononitrile (0.160 g, 1
mmol) and iodomethane (0.140 g, 1 mmol),
were reacted to give 8* (0.130 g, 81%). IH
NMR (400 MHz, Chloroform-D) b 8.66
(dd, J 4.8, 1.5 Hz, IH), 8.61 (d, J = 2.2
Hz, IH), 7.76 (d, J = 8.1 Hz, IH), 7.37 (dd,
J = 7.7, 4.8 Hz, IH), 3.23 (s, 2H), 1.85 (s,
3H); l3C NMR (100 MHz, Acetone-D6) b
152.0, 150.5, 138.5, 130.1, 124.3, 117.0,
41.0, 34.4, 24.3.
2-Allyl-2-(4-pyridylmethyl)
malononitrile (9*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(4pyradylmethyl)malononitrile (0.157 g, 1
mmol) and allyl bromide (0.118 g, 1 mmol),
were reacted to give 9* (0.150 g, 79%). IH
NMR (400 MHz) b 8.67 (d, J = 5.8 Hz,
2H), 7.32 (d, J= 5.8 Hz, 2H), 5.97-5.88 (m,
IH), 5.51-5.43 (m, 2H), 3.17 (s, 2H), 2.75
(d, J 7.3 Hz, 2H); 13C NMR (100 MHz) b
150.6, 140.6, 128.0, 125.0, 124.0, 114.3,
41.7,41.6,38.4.
2-Methyl-2-(4-pyridylmethyl)
malononitrile (10*). The general procedure
for creation of asymmetric disubstituted
derivatives was employed to scale with the
following
differences:
2-(4-
pyridylmethyl)malononitrile (0.158 g, 1
mmol) and iodomethane (0.142 g, 1 mmol),
were reacted to give 10* (0.114 g, 66%).
IH NMR (400 MHz) in b 8.68 (d, J = 4.8
Hz, 2H), 7.32 (d, J = 4.8 Hz, 2H), 3.19 (5,
2H), 1.86 (s, 3H); BC NMR (100 MHz) b
150.5, 140.4, 124.9, 115.2,43.5,32.5,24.6.
2-AlIyl-2-(4-aUyloxybenzyl)
malononitrile (11 *). The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-(4-hydroxybenzyl)
malononitrile (0.172 g, 1 mmol) and excess
allyl bromide (0.304 g, 2.5 mmol), were
reacted to give 11* (0.248 g, 98%).
IHNMR (400 MHz) b 7.29 (d, J = 6.6 Hz,
2H), 6.94 (d, J= 8.8 Hz, 2H), 6.09-6.01 (m,
IH), 5.99-5.89 (m, IH), 5.45 (d, J = 10.2
Hz, 2H), 5.42 (d, J = 18.0 Hz, IH), 5.30
(dd, J= 10.4,1.1 Hz, IH), 4.55 (d, J= 5.5,
2H), 3.15 (s, 2H), 2.69 (d, J 7.3 Hz,2H);
I3C NMR (100 MHz) b 159.0,133.0,131.3,
128.6, 124.0, 123.3, 117.9, 115.1, 115.0,
68.8,42.0,41.2, 39.4.
2-Allyl-2-(4-methoxybenzyl)
malononitrile (12). The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-allyl-2-(4-hydroxybenzyl)
malononitrile (0.216 g, 1 mmol) and
iodomethane (0.180 g, 1.1 mmol), were
reacted to give 12 (0.203 g, 78%). IH NMR
(400 MHz) b 7.29 (d, J = 6.6 Hz, 2H), 6.92
(d, J = 6.6 Hz, 2H), 5.98-5.88 (m, IH), 5.44
(d, J = 9.9 Hz, IH), 5.41 (d, J = 16.8 Hz,
IH), 3.81 (s, 3H), 3.14 (s, 2H), 2.68 (d, J =
5.9 Hz, 2H); 13C NMR (100 MHz) b 159.9,
131.3, 128.6, 123.8, 123.1, 115.0, 114.3,
55.2,41.9,41.1,39.4.
2-Methyl-2-(4-ally loxybenzyl)
malononitrile (13*). The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-methyl-2-(4hydroxybenzyl)malononitrile (0.186 g, 1
9
mmol) and allyl bromide (0.140 g, 1.1
mmol), were reacted to give 13* (0.168 g,
75%). IH NMR (400 MHz~ Acetone-D6) in
b 7.37 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4
Hz, 2H), 6.13-6.03 (m, 1H), 5.43 (dd, J
17.2, 1.2 Hz, 1H), 5.26 (dd, J = 10.2, 1.2
Hz, 1H), 4.60 (d, J = 5.2 Hz, 2H), 3.34 (s,
2H), 1.89 (s, 3H); l3e NMR (100 MHz,
Acetone-D6) b 160.0, 134.6, 132.4, 126.3,
117.5, 117.4~ 115.6, 114.8,69.3,43.4,34.7,
24.4.
2-Ethyl-2-(4-allyloxybenzyl)
malononitrile (14*). The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-(4-hydroxybenzyl)
malononitrile (0.860 g, 5 mmol) and
iodoethane (0.780 g, 5 mmol) were reacted
for 7 hours. Allyl bromide was added (1.00
g, 8 mmol) to reaction flask to produce 14*
(1.10 g, 91%). IH NMR (400 MHz) b 7.27
(d, J 8.4 Hz, 2H), 6.93 (d, J = 8.4 Hz,
2H), 6.10-6.00 (m, IH), 5.42 (d, J = 17.2,
IH), 5.30 (d, J = 10.6 Hz, IH), 4.50 (d, J
5.2 Hz, 2H)~ 3.14 (s, 2H), 1.99 (~, J = 7.3
Hz, 2H), 1.31 (t, J 7.3 Hz, 3H); 3e NMR
(100 MHz) b 159.0, 133.0, 131.3, 124.2,
117.9, 115.3, 115.1,68.8,42.4,40.6,31.1,
10.0.
2-Allyl-2-(3-methoxybenzyl)
malononitrile (15), The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-allyl-2-(3-hydroxybenzyl)
malononitrile ( 0.105g, 0.5 mmol) and
iodomethane (0.097 g, .6 mmol) were
reacted to give 15 (0.1067 g, 95%). IH
NMR (400 MHz) b 7.32 (d~ J = 9.2 Hz,
IH), 7.30 (d, J 7.0 Hz~ IH), 6.95 (d, J =
7.7 Hz, IH), 6.93 (d, J = 9.5 Hz, IH), 5.9910.6 Hz~ 1H),
5.89 (m, IH), 5.46 (d~ J
5.42 (d, J= 18.0 Hz IH), 3.82 (s, 3H), 3.17
(s, 2H), 2.69 (d, J = 7.3 Hz, 2H); l3e NMR
(100 MHz) b 160.0, 133.2, 130.0, 128.6,
123.4, 122.4, 115.7, 114.9, 114.4~ 55.3,
42.6, 41.3~ 39.0.
2-Methyl-2-(3-allyloxybenzyl)
malononitrile (16*). The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences: 2-methyl-2-(3-hydroxybenzyl)
malononitrile (0.200 g, 1.1 mmol) and allyl
bromide (0.152 g, 1.2 mmol), were reacted
to give 16* (0.187 g~ 77%). IH NMR (400
MHz) b 7.31 (d, J= 8.1 Hz, 1H), 7.29 (d, J
= 7.7 Hz~ IH)~ 6.93 (d~ J
8.1 Hz, 1H),
6.92 (d~ J = 5.5, IH)~ 6.08-6.00 (m, IH),
5.41 (ddd, J = 17.2, 3.3, 1.5 Hz, IH), 5.29
(ddd, J = 10.2, 2.6, 1.5 Hz, 1H), 4.55 (ddd,
J = 5.5, 4.0, 1.8 Hz, 2H), 3.17 (s, 2H), 1.79
(s, 3H); l3e NMR (100 MHz) b 1158.9,
133.2, 132.9, 130.0, 122.6, 117.9, 116.5,
115.9, 115.3,68.9,44.5,33.0,24.4.
2-Allyl-2-(3,4-methoxybenzyl)
malononitrile (17*), The general procedure
described for alkylation of a phenol was
employed to scale with the following
differences:
2-allyl-2-(4-hydroxy-3methoxybenzyl)malononitrile (0.193 g, 0.8
mmol) and iodomethane (0.129 g, 0.9
mmol) were reacted to give 17* (0.188 g,
92%). IH NMR (400 MHz) b 6.90 (d, J =
12.5 Hz, 2H), 6.86 (s, IH), 5.99-5.88 (m,
IH), 5.45 (d, J= 10.2 Hz, IH), 5.41 (d, J=
16.8 Hz IH), 3.88 (d, J = 5.1 Hz, 6H), 3.14
(s, 2H), 2.69 (d, J = 7.0 Hz, 2H); l3e NMR
(100 MHz) b 149.3, 148.9, 128.5, 124.1,
123.1, 122.5, 115.0, 113.0, 111.2, 55.75,
55.68,42.2,41.0,39.3.
2-Methyl-2-(4-allyloxy-3methoxybenzyl)malononitrile (18*). The
general procedure described for alkylation
of a phenol was employed to scale with the
following
differences:
2-methyl-2-(4hydroxy-3-methoxybenzyl)malononitrile
(0.219 g, 1 mmol) and allyl bromide (0.159
g, 1.1 mmol) were reacted to give 18*
(0.250 g, 96%). IH NMR (400 MHz) b
6.90-6.86 (m, 3H), 6.12-6.03 (m, IH), 5.41
(dq, J = 17.6, 1.8 Hz, IH), 5.34 (dq, J
10
10.6, 1.5 Hz, IH), 4.62 (d, J= 5.5 Hz, 2H),
3.89 (s, 3H), 3.14 (s, 2H), 1.78 (s, 3H); I3 C
NMR (100 MHz) b 149.5, 148.5, 133.0,
124.6, 122.6, 118.2, 116.1, 113.4, 133.3,
69.8,56.0,44.4,33.4,24.4.
2-AlIyl-2-(3-(N-methylpyridinium)
methyl)malononitrile (19*). The general
procedure described for alkylation of
nitrogen was employed to scale with the
following
differences:
2-allyl-2-(3pyridylmethyl)malononitrile (0.099 g, 0.5
mmol) and iodomethane (0.595 g, 4 mmol)
were reacted to give 19* (0.154 g, ~100%).
IH NMR (400 MHz, DMSO-D6) b 9.06 (d,
J 5.9 Hz, IH), 8.61 (d, J 8.1 Hz, IH),
8.26 (d, J = 6.6 Hz, IH), 8.25 (d, J 7.7
Hz, IH), 5.97-5.86 (m, IH), 5.45 (dd, J
11. 7, 1.5 Hz, 2H), 4.39 (s, 3Hl' 3.76 (s, 2H),
2.96 (d, J 7.3 Hz, 2H); I C NMR (100
MHz, DMSO-D6) b 146.6, 146.2, 145.7,
133.7, 129.5, 127.8, 123.1, 114.6, 48.3,
38.5,36.5.
2-Methyl-2-(3-(N-methylpyridinium)
methyl)malononitrile (20*). The general
procedure described for alkylation of
nitrogen was employed to scale with the
following
differences:
2-methyl-2-(3pyridylmethyl)malononitrile (0.172 g, 1
mmol) and iodomethane (1.472 g, 10
mmol), were reacted to give 20* (0.219 g,
~IOO%). IH NMR (400 MHz, DMSO-D6)
b 9.06 (d, J 9.9 Hz, 2H), 8.60 (d, J = 8.4
Hz, I H), 8.25 (dd, J 8.1, 1.8 Hz, 1H), 4.39
(s, 3H), 3.75 (s, 2H), 1.91 (s, 3H); BC NMR
(100 MHz, DMSO-D6) b 146.5, 146.2,
145.7, 133.7, 127.7, 115.7,48.3, 37.8, 32.4,
22.7.
2-AUyl-2-(4-(N-methylpyridinium)
methyl)malononitrile (21*). The general
procedure described for alkylation of
nitrogen was employed to scale with the
following
differences:
2-allyl-2-(4pyradylmethyl)malononitrile (0.057 g, 0.3
mmol) and iodomethane (l.455 g, 10
mmol), were reacted to give 21 * (0.072 g,
~100%). IH NMR (400 MHz, DMSO-D6)
b 9.05 (d, J 6.6 Hz, 2H), 8.25 (d, J = 6.6
Hz, 2H), 5.96-5.89 (m, IH), 5.47-5.43 (m,
2H), 4.36 (s, 3H), 3.84 (s, 2H), 2.97 (d, J =
7.3 Hz, 2H); l3C NMR (100 MHz, DMSOD6) b 151.8, 145.8, 129.4, 128.9, 123.2,
114.4,47.9,38.7,38.1,30.7.
2-Methyl-2-(4-(N -methylpyridinium)
methyl)malononitrile (22 *). The general
procedure described for alkylation of
nitrogen was employed to scale with the
following
differences:
2-methyl-2-(4pyridylmethyl)malononitrile (0.033 g, 0.2
mmol) and iodomethane (1.71 g, 12 mmol),
were reacted to give 22* (0.043 g, ~100%).
IH NMR (400 MHz, DMSO-D6) b 9.05 (d,
J = 6.6 Hz, 2H), 8.11 (d, J = 6.6 Hz, 2H),
4.36 (s, 3H), 3.83 (s, 2H), 1.93 (s, 3H); l3C
NMR (100 MHz, DMSO-D6) b 151.8,
145.8, 128.9, 115.6,47.9,32.1,23.2.
References
1. Fillmore, F. "The Chemistry of
Malononitrile." Chern. Review, 1965, 69,
591.
2. Sammelson, R.E., and Allen, M.J.
Synthesis. 2004, 4, 543.
3. Dunham, J.C., Richardson, A.D., and
Sammelson, R.E. Synthesis, 2006, 4, 680.
4. Tayyari, F., Wood, D.E., Fanwick, P.E.,
and Sammelson, RE. Synthesis, 2008, 2,
279.
5. Evdokimov, N.M., Kireev, A.S.,
Yakovenko, A.A., Antipin, M.Y., Magedov,
LV., and Komienko, A. J. Org. Chern.,
2007, 72, 3443.
5. Okada S, inventor. W0/2004/020399. 3
Nov 2004.
6. Hoffman M, inventor.
W0/20071017414. 15 Feb 2007.
8. Wakabayashi, S.; Kato, Y., Mochizuki,
K., Suzuki, R, Matsumoto, M., Sugihara,
and Y., Makoto, S. J. Org. Chern. 2007, 72,
744.
9. Katritzky, A.R; Takahashi, I.; Marson,
C.M. J. Org. Chern. 1986,51,4914.
11
Acknowledgements
Acknowledgement is made to the Donors
of the American Chemical Society
Petroleum Research Fund for partial
support of this research. This work was
also supported by the Lilly Endowment and
Ball State University. The author would
like to thank Robert E. Sammelson for the
helpful suggestions and supervision while
carrying out this research, as well as Fariba
Tayyari and Dwight E. Wood for helpful
counsel and observations.
12
Appendix A
Structures of created compounds 1-22, followed by attached 1H NMR and l3C NMR
spectra for each compound
~
NO~
,
I'
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c1e!
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7·
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.. lO-APR-2008 15.'7:56
.. 30-APR-20D8 15.48.01
Ccmtlmt
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Site
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.. 9.3897"[~] (400[KBB]
.. 2.7312128 r.]
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.. 5[ppm]
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.. 0
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.. 5.99880024(kKz]
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30-APR-2008 11.56 48
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.. Bc:lipse+ 400
~
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.. 2. 731.1128 [a]
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.. 39'.78219838[MBz]
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.. 16384
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• 25-~-2008 12,03,5'
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150.0
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11
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• 27-~-2008 15:t9:01
.. 27-KAR-200a 16:32:03
.. 27-~-2008 16:32:36
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.. 8!.ngle Pu.188 E::I:perime
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q
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1'11_
5.55[us)
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30-ARR-200B 12:18 39
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30-APR-2008 12.24.15
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21-APa-2008 10:49.59
21-APa-2008 10:29:10
2l-APa-2008 10.31:43
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