Cyanophenylation of aromatic nitriles by terephthalonitrile dianion: Is the charge-transfer complex a key intermediate?

Article abstract of DOI:10.1002/ejoc.200400851

The interaction of terephthalonitrile (1) dianion (1^2-) with benzonitrile (2) or m-tolunitrile (3) provides 4,4′-dicyanobiphenyl (4) or 4,4′-dicyano-2-methylbiphenyl (5), respectively. This result shows that dianion 1^2- serves as a reagent for p-cyanophenylation of aromatic nitriles. Based on experimental data, such as the chemical trapping of the 4,4′-dicyanobiphenyl precursor 4-cyano-1-(p-cyanophenyl)cyclohexa-2,5-dienyl anion (7) and the failure to obtain biphenyl 4 through the interaction of independently generated radical anions (RAs) 1^- and 2^-, as well as on the results of quantum-chemical calculations, a mechanism is suggested that includes a charge-transfer complex (CTC) between 1^2- and the aromatic nitrile as the key intermediate. The formation of this CTC is followed either by an intracomplex electron transfer (ET) and recombination of terephthalonitrile and aromatic nitrile RAs within an unequilibrated RA pair, or by synchronous ET and bonding of the ipso-carbon atom of terephthalonitrile with the p-carbon atom of the aromatic nitrile. The synthetic significance of p-cyanophenylation of arenecarbonitriles by dianion 1^2- is illustrated by the high yield of biphenyl product 4 (approx. 90%) as well as by the possibility of a one-pot synthesis of 4-butyl-4′-cyanobiphenyl and 4-butyl-4′-cyano-2-methylbiphenyl by successive treatment of dianion 1^2- with nitrile 2 or 3 and butyl bromide. Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejoc.200400851

FULL PAPER
Cyanophenylation of Aromatic Nitriles by Terephthalonitrile Dianion: Is the
Charge-Transfer Complex a Key Intermediate?[‡]
Elena V. Panteleeva,[a,b] Lyudmila N. Shchegoleva,[a] Viktor P. Vysotsky,[a,b]
Leonid M. Pokrovsky,[a] and Vitalij D. Shteingarts*[a,b]
Keywords: Biaryls / Cyanides / Electron transfer / Reaction mechanisms / Reactive intermediates
The interaction of terephthalonitrile (1) dianion (12–) with
benzonitrile (2) or m-tolunitrile (3) provides 4,4Ј-dicyanobi-
phenyl (4) or 4,4Ј-dicyano-2-methylbiphenyl (5), respectively.
This result shows that dianion 12– serves as a reagent for p-
cyanophenylation of aromatic nitriles. Based on experimental
followed either by an intracomplex electron transfer (ET) and
recombination of terephthalonitrile and aromatic nitrile RAs
within an unequilibrated RA pair, or by synchronous ET and
bonding of the ipso-carbon atom of terephthalonitrile with
the p-carbon atom of the aromatic nitrile. The synthetic signi-
data, such as the chemical trapping of the 4,4Ј-dicyanobi- ficance of p-cyanophenylation of arenecarbonitriles by di-
phenyl precursor 4-cyano-1-(p-cyanophenyl)cyclohexa-2,5-
dienyl anion (7) and the failure to obtain biphenyl 4 through
the interaction of independently generated radical anions
(RAs) 1·– and 2·–, as well as on the results of quantum-chemi-
cal calculations, a mechanism is suggested that includes a
charge-transfer complex (CTC) between 12– and the aromatic
nitrile as the key intermediate. The formation of this CTC is
anion 12– is illustrated by the high yield of biphenyl product
4 (approx. 90%) as well as by the possibility of a one-pot
synthesis of 4-butyl-4Ј-cyanobiphenyl and 4-butyl-4Ј-cyano-
2-methylbiphenyl by successive treatment of dianion 12– with
nitrile 2 or 3 and butyl bromide.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
rivatives. Also, the 2,3Ј-biquinolyl dianion is arylated with
aryl and heteroaryl halides.[10]
Introduction
Previously we have shown that RAs, especially cyanocy-
clohexadienyl anions and dianions generated by reduction
of aromatic nitriles with an alkali metal in liquid ammonia,
are quite stable in the absence of oxygen and moisture.
These anionic reduced forms have been successfully used as
highly reactive reagents for arylation of alkyl halides, pro-
viding good yields of alkylarenes or alkylcyanoarenes.[11–21]
In particular, the synthesis of p-alkylbenzonitriles by the
interaction of two-electron-reduced terephthalonitrile, di-
anion 12–,[20] with various alkyl halides has been devel-
oped.[22] With the aim of developing a general synthetic
methodology based on reductive activation of aromatic ni-
triles and utilisation of their anionic reduced forms as ver-
satile cyanoarylating reagents, it is worthwhile to extend the
structural diversity of the electrophilic substrate, particu-
larly on aromatic compounds. The present article is devoted
to the investigation of the interaction of 12– with the aro-
matic nitriles benzonitrile (2) and m-tolunitrile (3).
Conversion of aromatic compounds into their anionic re-
duced forms by means of one- or two-electron reduction
has proved to be a fruitful approach to their activation to-
ward interaction with electrophiles, most commonly with
alkyl or acyl halides and anhydrides of carbon acids.[1–8]
The utilisation of functionalised arenes as electrophiles in
reactions with these anionic reduced forms is still extremely
scarce. As a rule, it concerns aryl halides, which undergo
reductive dehalogenation while reacting with the arene an-
ionic reduced form.[1] However, there are few examples of
bond formation between the neutral and reduced arenes
during their interaction, either when the arene radical anion
(RA) combines with its neutral precursor or when the re-
duced arene serves as an arylating reagent for neutral arenes
of different structural types.[9] The latter case is of special
synthetic value; for instance, quinoline,[9a] pyridine[9b] or 2-
methylpyridine[9c] N-oxides react with ketyl and the dianion
of benzophenone to form N-oxide diphenyloxymethyl de-
Results and Discussion
[‡] Reductive Activation of Arenes, XVIII. Part XVII: T. A. Va-
ganova, V. D. Shteingarts, Russ. J. Org. Chem. 2004, 5, 747–750.
[a] N. N. Vorozhtsov Institute of Organic Chemistry of the Siberian
Branch of the Russian Academy of Sciences
As reported earlier,[20] 12– was generated by the addition
of two equivalents of alkali metal (Na, K) to a suspension
of dinitrile 1 in liquid ammonia under inert atmosphere (ar-
gon or ammonia). The interaction of the thus-obtained salt
of 12– with nitrile 2 results in the formation of 4,4Ј-dicya-
Ac. Lavrentiev Avenue, 9, Novosibirsk, 630090, Russia
E-mail: shtein@nioch.nsc.ru
[b] Novosibirsk State University,
Pirogova Str., 2, Novosibirsk, 630090, Russia
2558
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400851
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Cyanophenylation of Aromatic Nitriles by Terephthalonitrile Dianion
FULL PAPER
Scheme 1.
Table 1. The reaction of dianion 12– with nitriles 2 and 3 in liquid ammonia.
Entry Amount of reagents [mmol]
12– conc.
Alkali metal Nitrile [molL–1]
Temp.
[°C]
Time Product weight
Product composition [mmol] (mol-%)[a,b]
1
[h]
[g]
1
2, 3
Biphenyls
1
2[c]
3
5.0
5.0
2.5
2.5
5.0
2.5
2.5
15.0
25.0
5.0
5.0
K 10.0
K 10.0
Na 5.0
Na 5.0
Na 10.0
Na 5.1
Na 5.0
Na 31.0
Na 51.0
K 10.0
Na 10.0
2 5.0
2 5.0
2 2.5
2 2.5
2 5.0
2 5.2
2 10.0
2 18
0.1
0.1
0.08
0.08
0.1
0.06
0.06
0.5
–33
–40 to –45
–33
–75
–70 to –78
–33
1
6
1
1
4
1
3
1
1
1.03
1.02
0.45
0.36
0.87
0.66
1.08
3.11
6.8
0.4 (7)
2 3.2
2 3.7
2 1.2
2 1.0
2 2.8
2 2.8
2 6.6
2 5.9
2 20
4 3.2 (64)
4 3.0 (60)
4 1.1 (45)
4 0.5 (20)
4 0.8 (16)
4 1.7 (68)
4 1.9 (76)
4 12 (80)
4 23 (92)
0.8 (32)
0.7 (28)
0.5 (10)
0.2 (8)
0.1 (4)
0.4 (3)
4[c]
5[c]
6
7
8
9
10
11
–50
–33
–33
–33
2 51
0.5
0.1
0.15
3 5.0
3 5.0
1.2
0.9
0.90
0.70
0.3 (6)
0.2 (4)
3 2.8 2 2.1 5 1.2 (24) 4 0.2 (4)
3 0.3 2 0.1 5 2.2 (44) 4 0.7 (14)
–33
[a] Calculated as mean values of no less than three runs. Deviation does not exceed 5%. [b] During the experimental procedure the
volatile nitriles 2 and 3 partially (up to 30%) evaporated off with the ammonia. An additional amount of nitrile 2 can be formed due to
protonation[20,23,24] of dianion 12– during the reaction course or its treatment. [c] Besides compounds included in the table, the reaction
mixtures also contained p-cyanobenzamide, which results from partial hydrolysis of dinitrile 1 [entry 2: 0.2 mmol (4%); entry 4: 0.4 mmol
(16%); entry 5: 2.4 mmol (48%)].
nobiphenyl 4 (see Scheme 1). The yield of 4 varies from 16 ments in the biphenyl product come from different reaction
to 90% depending on the reaction conditions (see entries 1– participants. The presence of a small amount of biphenyl 4
9, Table 1): an increase of the reaction temperature (en- among the products is most probably caused by the interac-
tries 3–5) and an increase of the amount of 2 (entries 3, 6 tion of 12– with 2, which could be formed by the proton-
and 7) and of the reagents’ concentration (entries 3, 8 and ation of 12– by entrapped moisture[20,23,24] or by nitrile 3
9) increase the yield of the biphenyl product.
itself.[25]
Thus, the results obtained show that the dianion 12– is
On the addition of nitrile 3 to a suspension of 12– salt in
liquid ammonia p-cyanophenylation also takes place to give the reagent of choice for p-cyanophenylation of aromatic
4,4Ј-dicyano-2-methylbiphenyl (5; see entries 10 and 11 in nitriles. The intermediate formation of biscyclohexadienyl
Table 1, and Scheme 1). No spectroscopic data for biphenyl dianion 6, followed by rapid cyanide-ion elimination re-
5 could be found in the literature. Its structure was con- sulting in the relatively stable phenylcyclohexadienyl anion
firmed by 1H NMR and IR spectroscopy and HR mass 7 (see Scheme 1), is highly probable. The contact of the lat-
spectrometry (see Experimental Section). The substituent ter with air leads to the biphenyls 4 and 5. The reality of
positions in the biphenyl framework are indicated by the the suggested reaction course is proved by the following ex-
presence of the following signals in the 1H NMR spectrum: perimental facts: cyclohexadienyl anions containing, like
an AB pattern at δ = 7.62 and 7.91 ppm (Jortho = 8 Hz) due the dianion 6, a cyano group and hydrogen atom[23,24] or
to the protons H2Ј, H6Ј and H3Ј, H5Ј of the p-disubstituted alkyl group[19,20] in geminal positions undergo rapid aroma-
ring, the doublet at δ = 7.46 ppm (Jortho = 7.5 Hz), attrib- tisation due to decyanation,whereas cyclohexadienyl anions
uted to H6, the low-field-shifted doublet of doublets at δ = like 7, without a good leaving group at the saturated carbon
7.71 ppm (Jortho = 7.5, Jmeta = 1.5 Hz), and the doublet atδ atom, are quite stable under the given experimental condi-
= 7.75 ppm (Jmeta = 1.5 Hz) belonging, respectively, to H5 tions.[19,26]
and H3 ortho to the cyano group.
That anion 7 is a relatively stable reaction intermediate
The formation of 5 as the main product of the reaction is confirmed by the formation of 4-butyl-4Ј-cyanobiphenyl
of dianion 12– and nitrile 3 testifies that the aromatic frag- (8) or two other “butoxided” products − 4-butyl-4-cyano-
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E. V. Panteleeva, L. N. Shchegoleva, V. P. Vysotsky, L. M. Pokrovsky, V. D. Shteingarts
FULL PAPER
1-(p-cyanophenyl)-2-methylcyclohexa-2,5-diene (9) and 4- lated (RHF/6-31+Gء, see Figure 1) HOMO energy level of
butyl-4Ј-cyano-2-methylbiphenyl (10) − when butyl bro- dianion 12– is significantly higher than the levels of both
mide was added to the reaction mixture of 12– and nitriles LUMO (b1) and even next vacant MO (a2) of nitrile 2.
2 or 3 before allowing it to come into contact with the air Thus, the possibility of ET from the dianion HOMO (b1u)
(see Scheme 1). Besides the main compounds 8–10, the pro- to both b1 and a2 MOs of the mononitrile should be taken
duct mixtures also contained components formed by the into account. The total energies (Etot) of 12– and 2 as well
butylation of dianion 12– and RA 1·– (p-butylbenzonitr- as 1·– and 2·– (Table 2), together with the energy changes
ile[18,20]) and the anionic reduced forms of nitriles 2 or 3 (Erel) due to the ET (Table 3), show the thermodynamic
(butylarenes and butyldihydroarenes[11,16a] respectively). possibilities of all the above-mentioned variants of ET. This
Butylbiphenyl 8 has been described previously,[27,28] while implies that the RA pair could appear not only in the
no information about products 9 and 10 was found. Diene ground but also in an exited electronic state.
9 was formed and isolated as a mixture of nearly equal
1
amounts of cis- and trans-isomers. The signals in the H
NMR spectrum of 9 (see Experimental Section) were attrib-
uted on the basis of a comparison with the spectrum of
cyclohexadienyl products formed by the alkylation of an-
ionic reduced forms of m- and p-tolunitriles.[16a,16b] Assign-
1
ment of the signals in the H NMR spectrum of 10 was
similar to that described above for the biphenyl 5.
It is obvious that the key to understanding the mecha-
nism of p-cyanophenylation of cyanoarenes by dianion 12–
is the answer to the question of how the dimeric dianion 6
is formed. In this connection it is important to determine
whether the p-orientation is typical for the reactions of cya-
noarenes with carbanionic reagents in liquid ammonia or
not. We have shown that the cyanomethyl anion, generated
from acetonitrile by treatment with sodium amide in liquid
ammonia and which, to some extent, models the fragment
of dianion 12– that bears the main part of the negative
Figure 1. The diagram of dianion 12– and nitrile 2 boundary MO
energies (RHF/6-31+G*).
charge (compare with the charge distribution in the dianion
of 9-cyanoanthracene[26]), reacts with 2 to give β-aminocin-
namonitrile (11).[29,30] This result shows that the carbanion
adds to the cyano group of 2 and suggests that the interac-
tion of dianion 12– with an aromatic nitrile proceeds
through a mechanism that is different from that typical for
Secondly, incorporation of the cyanophenyl fragment
α-cyano-substituted carbanions (see Scheme 2). On this ba- into the nitrile moiety at the para position is the regioselec-
sis, while considering the mechanism of the interaction of tivity typical for the recombination of aromatic nitrile
dianion 12– with aromatic nitriles within the dichotomy be- RAs[31–34] because of the maximum spin-density localis-
tween straight nucleophilic attack, on the one hand, and ation in the para position of the nitrile RA.[35,36] Small
electron transfer (ET), on the other, the latter seems prefer- amounts of compounds formed by butylation of RAs 1·–,
able. There are at least two reasons for that. Firstly, the 2·– and 3·– found among the products of those experiments
correlation of reduction potentials of 1 and 2 (E0
= 1.25, when dianion 12– was successively treated with aromatic ni-
1/1·–
E0
= 1.99, E0
= 2.20 V, AgCl/DMF/TMACl[24]
1·–/12–
)
trile and butyl bromide also testify, to a certain extent, in
2/2·–
makes ET from 12– to 2 exothermic. Additionally, the calcu- favour of an ET mechanism.
Scheme 2.
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Cyanophenylation of Aromatic Nitriles by Terephthalonitrile Dianion
FULL PAPER
Table 2. Results of the HF/6-31+G* and MP2/6-31+G*//HF/6- of RAs 1·– and 2·– cannot be excluded due to the rapid
31+G* calculations on dianion 12–, nitrile 2, and their vertical RA
irreversible decyanation of the initially formed dimeric di-
anion 6 to provide monoanion 7. We tried to realise cross-
states 1·– and 2·–.[a]
recombination of 1·– and 2·– in two ways: solutions of RAs
prepared by the reduction of each nitrile (1 or 2) by sodium
in liquid ammonia were mixed, or one equivalent of dini-
trile 1 was added to a solution of two equivalents of RA
2·–. The reduction potentials of nitriles 1 and 2 given above
indicate that 2·– should reduce dinitrile 1 to 1·–. In both
cases no traces of biphenyl 4 were observed among the
products formed after oxidation of the reaction mixtures by
atmospheric oxygen. Treatment of the mixture prepared in
the second case with butyl bromide resulted in the forma-
tion of the butylation products of both 1·– (p-butylbenzon-
itrile and 2-butyl-1,4-dicyanbenzene[18]) and 2·– (butylben-
zene and 1-cyano-1-butylcyclohexa-2,5-diene[11]). No bi-
phenyl products were formed. These results suggest that in
the course of the reaction between dianion 12– and nitrile 2
the dimeric dianion 6 cannot be a product of diffusional
cross-recombination of 1·– and 2·–, and must thus be formed
by some other pathway.
System
(state)
Electron
configuration
Etot [a.u.]
HF
MP2
12– (1A1g)
...(b2g)2 (b1u
...(b2g)2 (b1u
...(a2)2
)
)
–414.013856
–414.171698
–322.447642
–322.398775
–322.376229
–415.369547
–415.519347
–323.484440
–323.455423
–
2
1·– (2B1u
)
1
20 (1A1)
2·– (2B1)
2·– (2A2)
...(a2)2 (b1)1
...(a2)2 (b1)0 (a2)1
[a] The RA states were calculated by the ROHF/6-31+G* method
with the geometry of the respective closed-shell systems.
Table 3. Relative energies of initial and resulting states of vertical
ET between dianion 12– and nitrile 2 from the data in Table 2.
Pair of isolated particles
Erel [kcalmol–1]
HF[a]
MP2
12– (1A1g)
20 (1A1)
2·– (2B1)
2·– (2A2)
0
0
–75.8
–
1·– (2B1u
1·– (2B1u
)
)
–68.4
–64.4
[a] See footnote to Table 2.
All the above results induced us to consider a mechanism
involving the charge-transfer complex (CTC) as a key inter-
mediate formed in a reaction stage preceding ET.[37] This
mechanism is the equivalent of an inner-sphere ET.[38] Ap-
plying the main ideas of this approach to the reaction under
investigation, it is necessary to suppose the formation of a
CTC between dianion 12– as a donor and nitrile 2 as ac-
ceptor, followed by an adiabatic ET (see Scheme 3).
In light of these considerations it is necessary to examine
the possibility of biphenyl formation by the diffusional re-
combination of independently generated 1·– and 2·–. It is
well known that 1·– generated electrochemically[23,24] or by
the action of alkali metal in liquid ammonia[18] doesn’t un-
dergo self-recombination. Dimerisation of RA 2·– has
proved to be reversible[31,32] and, when generated in liquid
ammonia, this RA doesn’t yield dimeric products,[11] par-
In accordance with this concept we performed single-
ticularly biphenyl 4. These data, along with the origin of point MP2/6-31+G* calculations to test the expected char-
the phenyl moieties in the biphenyl product from different acter of the total energy changes of 12– and 2 under their
reaction participants, allow us to exclude self-recombina- plane-parallel and coaxial approach with mutual rotational
tion of RAs as the main route of biphenyl formation. Nev- orientation, which ensures maximal proximity of the bond-
ertheless, the possibility of diffusional cross-recombination forming positions when the CTC transforms into dianion
Scheme 3.
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E. V. Panteleeva, L. N. Shchegoleva, V. P. Vysotsky, L. M. Pokrovsky, V. D. Shteingarts
FULL PAPER
Figure 2. Energy changes at the plane-parallel and coaxial approaches of dianion 12– and mononitrile 2 (RHF/6-31+G* and MP2/6-
31+G*).
6 (“eclipsed” conformation[39,40]). The fragments’ geometry
was found to be invariable. These results demonstrate that
the system of 12– and 2 stabilizes under approach of its
components to each other and reaches an energy minimum
at a distance between the ring planes, Req, of about 3.15 Å
(Figure 2). This finding entirely complies with the CTC for-
mation so far, as typical stacking distances in CTCs formed
by radical cation[37b] or RA[41,42] and the neutral precursor
molecule lie in the range 2.9–3.6 Å. It is worthwhile to note
that the orientation indicated above is not necessarily opti-
mal. Thus, rotation of one of the CTC fragments by 90°
whilst retaining the coaxial arrangement of the rings (“stag-
gered” conformation) leads to an additional energy re-
duction of 3.4 kcalmol–1, obviously due to a moving apart
Figure 3. HOMO view of the CTC.
of the fragments bearing the principal parts of the negative
charge. However, even if the “staggered” conformation is
more stable than the “eclipsed” one, there are no reasons
to anticipate obstacles preventing interconversion of these The electron transfer in the CTC is most probably ac-
two conformations by means of free rotation. complished adiabatically. Two main factors may be signifi-
Comparison of the results of the RHF and MP2 calcula- cant for tuning the system coordinates that are necessary
tions (see Figure 2) shows that the existence of the CTC is for the reaction course. The first one implies a certain in-
almost completely due to electron correlation effects. The crease in distance between the ring planes, with a concomi-
population analysis within the Löwdin scheme characterises tant decrease in the energy gap between the ground and
the CTC by a substantial degree of charge transfer from 12– excited states of CTC to a value that allows a thermal ET
to 2 (0.582 according to MP2 calculations). This value is to occur. The pair of 1·– and 2·– thus formed differs from
caused by considerable mixing of the MOs of the CTC the “vertical” one by a larger separation of the RAs.[43] At
participants when the intermolecular distance reaches Req. the same time, in contrast to a diffusion encounter the dis-
Thus, the CTC HOMO is mainly the b1u HOMO of dianion tance between the RAs, and their reciprocal orientation,
12–, with a small “admixture” of the b1 LUMO of nitrile 2 could be favourable for recombination to give dimer 6 (see
(Figure 3), which, in turn, contributes predominantly to the Scheme 3). The second factor is the easy accessibility of the
CTC LUMO. The lowest excited state of the CTC corre- “eclipsed” conformation, which ensure closeness of the 12–
sponds to electron transfer between its components.
i- and 2 p-carbon atoms necessary for bond formation to
According to the CISD/6-31 calculations in restricted provide dianion 6. This process could proceed synchro-
active space, including the π-orbitals of CTC components, nously with ET and, in such a way, compensate the energy
the energy of the Frank–Condon ET in the CTC with the consumption somewhat. The recombination of RAs re-
formation of RAs 1·– to 2·–, separated by Req, is about 60 sulting from the intracomplex ET and therefore closely
kcalmol–1. Although the real endothermicity of this vertical brought together as well as synchronous ET-recombination
conversion could be markedly lowered by solvation and as- process seem to be electrostatically favourable. The reason
sociation with a counterion, it hardly occurs in the dark. for this lies in the fact that in going from the CTC to di-
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Cyanophenylation of Aromatic Nitriles by Terephthalonitrile Dianion
FULL PAPER
CTC formation was neglected. Electronic correlation was consid-
ered at the level of single point MP2/6-31+G*//RHF/6-31+G* cal-
culations. The excitation energies in the CTC were estimated by the
CISD/6-31+G* method in restricted active space constructed from
all π-orbitals of the fragments. The calculations of RAs 1·– and 2·–
were performed using the geometry of the corresponding particles
with closed electronic shell in frames of the spin-restricted ROHF/
6-31+G* method; the excited states were obtained by vectors per-
mutation in the initial guess. The calculations of the ground states
of the RAs were made by the spin-restricted MP2/6-31+G*
anion 6 the negative charges concentrate predominantly at
cyano groups (compare ref.[26]) moving away from each
other.
The scheme proposed for the reaction under investiga-
tion to some extent resembles the dynamics of ion pairs
formed upon electron-transfer quenching of perylene by tet-
racyanoethylene, which is defined by ultrafast recombina-
tion within the primary quenching product − a contact ion-
pair formed in an electronically exited state.[44] It was found
that a rise of quencher concentration results in an increase method.
of the recombination product yield. As applied to the inter-
Starting Materials: Liquid ammonia was purified just before use
action of 12– with nitriles 2 or 3, this finding means that the
yield of biphenyls 4 or 5 must increase with the mononitrile
concentration. The experimental data agree with this as-
sumption (see entries 3, 8 and 9–11 in Table 1).
by dissolving metallic sodium in it, followed by distillation into a
reaction vessel cooled to between –80 and –70 °C. Metallic potas-
sium and sodium were freed from their oxide film under dry hex-
ane. Commercial terephthalonitrile (1) was purified by sublimation
and dried over P2O5 in vacuo (m.p. 222 °C; 222–223 °C[50]). Com-
It’s worthwhile to point out the synthetic significance of
this p-cyanophenylation of arenecarbonitriles 2 and 3 by mercial benzonitrile was distilled from over P2O5 just before use.
Commercial m-tolunitrile was purified by distillation [b.p. 57–
58 °C/3 mm (84 °C/10 mm[51])]. Commercial butyl bromide and
acetonitrile were purified by passing through a layer of aluminium
oxide, followed by distillation.
terephthalonitrile dianion. The yield of biphenyl 4 in this
reaction reaches 92% (see Table 1, entry 10). The methods
for the synthesis of compound 4 previously described in the
literature involve either a bisaryl condensation catalysed by
complexes of Ni[45]and Pd[46] or oxidative condensation of
the corresponding organomagnesium derivative.[47] All
Generation of Terephthalonitrile Dianion 12–: The alkali metal (see
Table 1 for the reagent amounts) was added to a stirred suspension
those approaches utilize less accessible precursors and more of dinitrile 1 in liquid ammonia at –33 °C under argon or evaporat-
ing ammonia atmosphere. The mixture was kept for 5 min under
the same conditions. The resulting dark-brown suspension of the
dianion 12– salt was used in further experiments.
complicated experimental techniques and provide lower
yields (up to 80%) than the method described in the present
article. The scope of aromatic substrates suitable for p-cya-
nophenylation by dianion 12– is currently under investiga-
tion. Our preliminary results show that 1-naphthonitrile
and 9-cyanoanthracene also undergo this reaction. Also,
General Procedure for Treatment of Dianion 12– with Aromatic Ni-
trile: The desired amount of benzonitrile (2) or m-tolunitrile (3; see
Table 1) was added dropwise to a stirred suspension of 12– salt, and
the possibility of a one-pot synthesis of 4-alkyl-4Ј-cyanobi- the reaction mixture was stirred for the required time. Then, the
phenyl by successive treatment of dianion 12– with aromatic
ammonia was evaporated by half, diethyl ether (approx. 50 mL)
was added and the reaction mixture was put into contact with air.
nitrile and alkyl halide has potential synthetic merit. These
Stirring was continued until the ammonia had evaporated com-
compounds are well known and are widely used as liquid
pletely and room temperature reached. Water (approx. 50 mL) was
crystals components. All previously described methods of
poured onto the residue to dissolve the inorganic salts. The solid
their synthesis[27,28,48] are multi-stage and provide low total
organic products were filtered off, washed with diethyl ether and
yields.
water, dried in air and analysed. The products from the liquid frac-
tion were extracted with diethyl ether (3×50 mL). The combined
organic extracts were dried with MgSO4, filtered and the solvent
was removed. The crude residue was analysed by H NMR spec-
Experimental Section
1
troscopy and GCMS. The pure products were isolated by TLC on
plates with a fixed layer of silica gel (40/70 μm, containing 12 wt.-
% of mineral white) and a hexane/diethyl ether mixture (9–8:1 vol-
ume ratio) as eluent. The separation was monitored by irradiating
the plate with UV light. The fractions were washed with diethyl
ether. The structure of the individual products was confirmed by
1H NMR and IR spectroscopy and HR mass spectrometry.
The 1H NMR spectra were recorded with a Bruker WP-200 instru-
ment for solutions in [D6]acetone (concentration 10–15%). The IR
spectra were recorded on a UR-20 instrument for samples pelleted
with KBr (0.25%) or as thin films. The reaction mixtures were ana-
lysed by GCMS on a Hewlett–Packard G1081A instrument con-
sisting of an HP-5890 Series II gas chromatograph and an HP-5971
mass-selective detector (IE, 70 eV) with an HP5 capillary column
(30000×0.25) mm×0.25 μm. A He flow (1 mLmin–1) was used as
carrier gas. The following temperature regime program was applied:
2 min at 50 °C, 50 °C to 280 °C at a rate of 10 °Cmin–1, 5 min at
280 °C. The evaporator temperature was 280 °C and the ion source
temperature 173 °C. The scanning velocity was 1.2 scans per second
in the mass interval 30–650 amu. The precise molecular ion weights
were determined with a Finnigan MAT-8200 high-resolution mass
spectrometer.
4,4Ј-Dicyanobiphenyl (4): Metallic sodium (1.18 g, 51.0 mmol) was
added in five portions to a suspension of dinitrile 1 (3.20 g,
25.0 mmol) in liquid ammonia (50 mL) at –50 °C (see entry 9,
Table 1). The suspension of dianion 12– salt thus formed was stirred
for 10 min to reach a temperature of –33 °C and nitrile 2 (5.3 mL,
51 mmol) was added dropwise. The reaction mixture was stirred for
one hour at the same temperature and treated as described above
in the general procedure. The resultant light-ivory powder was
identified as biphenyl 4 (4.3 g, 21 mmol), m.p. 237–239 °C (235–
238 °C[52]). The extracted residue (2.5 g) consisted of nitrile 2
(20 mmol) and biphenyl 4 (2.0 mmol). Total yield of 4: 23 mmol
(92%).
Quantum-chemical calculations were performed using the
GAMESS package.[49] The geometry optimisation of dianion 12–
and nitrile 2 was made in frames with the RHF/6-31+G* method,
the geometry changes upon approach of these particles during the
Eur. J. Org. Chem. 2005, 2558–2565
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2563

E. V. Panteleeva, L. N. Shchegoleva, V. P. Vysotsky, L. M. Pokrovsky, V. D. Shteingarts
FULL PAPER
4,4Ј-Dicyano-2-methylbiphenyl (5): Part of the reaction mixture 9.0, J6,1 = 4.0 z, 1 H, 6-H), 7.45 (d, Jortho = 7.5 Hz, 2 H, 2Ј-H and
(0.39 g) resulting from the reaction of dianion 12– with nitrile 3
(see entry 11, Table 1) was separated by TLC. Biphenyl 5 (0.2 g,
6Ј-H), 7.78 (d, Jortho = 7.5 Hz, 2 H, 3Ј-H and 5Ј-H) ppm. IR: ν =
˜
2229 cm–1 (CϵN). HRMS: calculated for C19H20N2 [M+]
0.9 mmol) was obtained (Rf = 0.2) as a white solid, m.p. 168–
170 °C. H NMR: δ = 2.32 (s, 3 H, CH3), 7.46 (d, J5,6 = 7.5 Hz, 1 10: H NMR: δ = 0.95 (t, 3 H, -CH3), 1.34 (m, 4 H, 2 CH2), 1.61
276.16264, found 276.16255.
1
1
H, 6-H), 7.62 (d, Jortho = 8.0 Hz, 2 H, 2Ј-H and 6Ј-H), 7.71 (dd,
J5,6 = 7.5, J5,3 = 1.5 Hz, 1 H, 5-H), 7.75 (d, J3,5 = 1.5 Hz, 1 H, 3-
(m, 2 H, CH2), 2.22 (s, 3 H, CH3), 2.62 (t, 2 H, CH2), 7.08–7.15
(m, 4 H, 3-H, 5-H, 6-H), 7.50 (d, Jortho = 7.5 Hz, 2 H, 2Ј-H and
H), 7.91 (d, Jortho = 8.0 Hz, 2 H, 3Ј-H and 5Ј-H) ppm. IR: ν =
6Ј-H), 7.78 (d, Jortho = 7.5 Hz, 2 H, 3Ј-H and 5Ј-H). IR: ν =
˜
˜
2226 cm–1 (CϵN). HRMS: calculated for C15H10N2 [M+]
2228 cm–1 (CϵN). HRMS: calculated for C18H19N [M+]
218.08449; found 218.08434.
249.15074; found 249.15005.
The Interaction of Acetonitrile Anion with Benzonitrile: Acetonitrile
(0.42 mL, 8.1 mmol) was added to sodium amide prepared by the
standard procedure from metallic sodium (0.188 g, 8 mmol) in li-
quid ammonia (50 mL). The mixture was stirred for 5 min, and
then nitrile 2 (0.85 mL, 8.3 mmol) was added and the mixture was
stirred at –33 °C for 1 h 15 min. Further treatment was performed
as described above. The product mixture thus obtained (1.7 g) con-
sisted of nitrile 2 (2.1 mmol) and β-aminocinnamonitrile (11;
5.8 mmol, 94% of consumed monitrile 2). Nitrile 11 was separated
as light-yellow needles from nitrile 2 by washing with cold hexane
(3×1.5 mL). Further crystallisation from hexane/benzene (5:1 vol-
ume ratio) gave 11 as white needles (0.70 g, 4.9 mmol), m.p. 87 °C
(84–87 °C[30]).
4-Butyl-4Ј-cyanobiphenyl (8): a) Benzonitrile (0.52 mL, 5 mmol)
was added to a suspension of dianion 12– salt prepared by the ac-
tion of metallic potassium (0.39 g, 10 mmol) on dinitrile 1 (0.64g,
5 mmol) in liquid ammonia (50 mL). The reaction mixture was
stirred for 50 min, then butyl bromide (0.53 mL, 5 mmol) was
added and stirring was continued for a further 50 min. Subsequent
treatment was performed as described above. The product mixture
thus obtained (1.05 g) consisted of dinitrile 1 (1.6 mmol, 32%), ni-
trile 2 (2.5 mmol), 1-butyl-1-cyanocyclohexa-2,5-diene (0.14 mmol,
3% relative to dinitrile 1), p-butylbenzonitrile (0.5 mmol, 10%), bi-
phenyl
4 (0.4 mmol, 8%) and 4-butyl-4Ј-cyanobiphenyl (8;
1.5 mmol, 30%). The latter was obtained as a light-yellow oil
(0.04g, 0.16 mmol) by TLC of part (0.11 g) of the reaction mixture.
1H NMR: δ = 0.92 (t, 3 H, CH3), 1.36 (m, 2 H, -CH2-), 1.62 (m,
2 H, -CH2-), 2.66 (t, 2 H, -CH2-), 7.34 (d, Jortho = 9.0 Hz, 2 H, 3-
H and 5-H), 7.63 (d, Jortho = 9.0 Hz, 2 H, 2-H and 6-H), 7.82 (s, 4
11: 1H NMR: δ = 4.23 (s, 1 H, =CH), 6.19 (br. s, 2 H, NH2), 7.43–
7.49 (m, 3 H, 3-H, 4-H, 5-H), 7.64 (dd, Jortho = 7.5, Jmeta = 3.0 Hz,
2 H, 2-H, 6-H) ppm.
Modelling of the Diffusional Encounter Between RAs 1·– and 2·–: a)
Liquid ammonia (30 mL) was condensed into two three-necked
flasks each supplied with a stirring rod, a bubbler and a gas vent.
H, 2Ј-H, 3Ј-H, 5Ј-H and 6Ј-H) ppm. IR: ν = 2225 cm–1 (CϵN).
˜
HRMS: calculated for C17H17N [M+] 235.13609; found 235.13620.
b) Benzonitrile (2.32 mL, 22.5 mmol) was added to a suspension of
dianion 12– salt prepared by the action of metallic sodium (0.71 g,
31 mmol) on dinitrile 1 (1.92 g, 15 mmol) in liquid ammonia
(50 mL). The reaction mixture was stirred for 30 min, then butyl
bromide (1.90 mL, 18 mmol) was added and stirring was continued
for 1.5 h. Further treatment was performed as described above. The
product mixture thus obtained (4.35 g) consisted of dinitrile 1
(2.8 mmol, 19%), nitrile 2 (11 mmol), butylbenzene (1.3 mmol, 9%
relative to dinitrile 1), p-butylbenzonitrile (1.2 mmol, 8%), biphenyl
4 (2.3 mmol, 15%) and 4-butyl-4Ј-cyanobiphenyl (8; 8.4 mmol,
56%).
Dinitrile
1 (0.32 g, 2.5 mmol) and metallic sodium (0.05 g,
2.2 mmol) were put into one of the flasks under argon. The forma-
tion of a dark-green solution in 2 min showed the generation of
the RA 1·– salt. Another flask was charged under argon with nitrile
2 (0.26 mL, 2.5 mmol) and sodium (0.05 g, 2.2 mmol). The dark-
red solution of RA 2·– salt formed in 2 min was kept stirring for
1 min and then poured into the flask containing the solution of
RA 1·– salt. The mixture of RAs thus obtained was kept stirring
for 3 h at between –40 and –35 °C and processed as described
above. The resultant mixture (0.46 g) contained dinitrile
(1.5 mmol), p-cyanobenzamide (0.2 mmol) and nitrile 2 (2.3 mmol).
1
4-Butyl-4-cyano-1-(p-cyanophenyl)-2-methylcyclohexa-2,5-diene (9)
and 4-Butyl-4Ј-cyano-2-methylbiphenyl (10): Tolunitrile 3 (0.29 mL,
2.5 mmol) was added to a suspension of dianion 12– salt prepared
by the action of metallic sodium (0.115g, 5 mmol) on dinitrile 1
(0.32 g, 2.5 mmol) in liquid ammonia (30 mL). The reaction mix-
ture was stirred for 1 h, then butyl bromide (0.26 mL, 2.5 mmol)
was added and stirring was continued for 1 h 15 min. Further treat-
ment was performed as described above. The product mixture thus
obtained (0.59 g) consisted of dinitrile 1 (0.20 mmol, 8%), nitrile
3 (0.50 mmol, 20%), 1-butyl-1-cyano-3-methylcyclohexa-2,5-diene
(0.16 mmol, 6% relative to dinitrile 1), m-butyltoluene (0.1 mmol,
4% relative to dinitrile 1), p-butylbenzonitrile (0.19 mmol, 8%), bi-
phenyl 4 (0.04 mmol, 2%), 4-butyl-4Ј-cyanobiphenyl 8 (0.08 mmol,
b) Liquid ammonia (40 mL) was condensed into a three-necked
flask containing a stirring rod, a bubbler and a gas vent. Mononit-
ile 2 (0.53 mL, 5.1 mmol) and metallic sodium (0.115g, 5 mmol)
were added under argon, and stirring of the reaction mixture for
2 min resulted in formation of a dark-red solution of the RA 2·–
salt. A solution of dinitrile 1 (0.32 g, 2.5 mmol) in THF (17 mL)
was immediately added dropwise over 15 min and the mixture was
stirred for 2 h at –35 °C. Quenching of the reaction mixture was
performed in two ways − by contact with air or by addition of butyl
bromide (0.53 mL, 5.1 mmol). Further treatment was performed as
described above. The product mixture obtained in the first case
(0.52 g) was composed of dinitrile
1 (0.5 mmol), nitrile 2
(3.6 mmol) and 1-cyanocyclohexa-2,5-diene (0.8 mmol), whereas
the second product mixture (0.68 g) consisted of butyl bromide
(2.0 mmol), nitrile 2 (1.6 mmol), butylbenzene (1.1 mmol), 1-butyl-
1cyanocyclohexa-2,5-diene (0.15 mmol), dinitrile 1 (0.25 mmol), p-
butylbenzonitrile (0.1 mmol) and 2-butyl-1,4-dicyanobenzene
(0.1 mmol).
3%),
4-butyl-4-cyano-1-(p-cyanophenyl)-2-methylcyclohexa-2,5-
diene (9) as a mixture of nearly equal amounts of two isomers (total
content 0.43 mmol, 17%) and 4-butyl-4Ј-cyano-2-methylbiphenyl
(10; 0.87 mmol, 35%). Part of the reaction mixture (0.334 g) was
separated by TLC to give 9 (0.062 g, 0.22 mmol) as a white solid
(a mixture of two isomers; Rf = 0.1, m.p. 86–89 °C) and 10 (0.115 g,
0.22 mmol) as a sticky light-yellow oil (Rf = 0.6).
Acknowledgments
1
9: H NMR: δ = 0.91 (t, 3 H, CH3), 1.38 (m, 4 H, 2 CH2), 1.59 (s,
3 H, CH3), 1.82 (m, 2 H, CH2), 4.00 (m, 1 H, 1-H), 5.66 (m, 1 H, This work was supported by the Department of Chemistry and
3-H), 5.83 (dd, J5,6 = 9.0, J5,1 = 2.5 Hz, 1-H, 5-H), 5.98 (dd, J6,5 Materials Science of the Russian Academy of Sciences through pro-
=
2564
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 2558–2565

Cyanophenylation of Aromatic Nitriles by Terephthalonitrile Dianion
FULL PAPER
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Received: December 01, 2004
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