Nitropyridines: IV. Synthesis of 3-(2-furyl)biphenyls by recyclization of nitropyridinium salts

Article abstract of DOI:10.1134/S1070428007040197

The two-component Hantzsch synthesis using 3-(2-furyl)-2-nitro-1- phenylprop-2-en-1-one and various enamines gave the corresponding nitro-substituted dihydropyridines which were converted into nitropyridines and N-methylpyridinium salts. Recyclization of

Full text of DOI:10.1134/S1070428007040197

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 4, pp. 602–606. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © G.P. Sagitullina, L.V. Glizdinskaya, R.S. Sagitullin, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 4,
pp. 604–608.
Nitropyridines: IV.* Synthesis of 3-(2-Furyl)biphenyls
by Recyclization of Nitropyridinium Salts
G. P. Sagitullina, L. V. Glizdinskaya, and R. S. Sagitullin
Dostoevskii Omsk State University, pr. Mira 55a, Omsk, 644077 Russia
e-mail: Sagitullina@orgchem.univer.omsk.su
Received Match 17, 2006
Abstract—The two-component Hantzsch synthesis using 3-(2-furyl)-2-nitro-1-phenylprop-2-en-1-one and
various enamines gave the corresponding nitro-substituted dihydropyridines which were converted into nitro-
pyridines and N-methylpyridinium salts. Recyclization of the latter by the action of aqueous–alcoholic alkali
led to the formation of 3-(2-furyl)-2-nitrobiphenyl derivatives.
DOI: 10.1134/S1070428007040197
3-(2-Furyl)biphenyls are generally synthesized by
cross-coupling reactions [2], cyclization of α-isoni-
troso-α-furoylacetone with enamines [3], and intramo-
lecular Thorpe and Claisen cyclizations of the Michael
adducts derived from alkylidenemalononitriles, furfur-
ylidenemalononitrile, or furfurylideneacetophenone
and ethyl but-2-enoate [4–6].
the Hantzsch reaction of nitrochalcone I with enamines
IIa–IIe and subsequent aromatization of 1,4-dihydro-
pyridines IIIa–IIIe thus formed by treatment with so-
dium nitrite in acetic acid (Scheme 1). The alkylation
of compounds IVa–IVe to pyridinium salts Va–Ve was
performed by heating with 3 equiv of dimethyl sulfate.
Recyclization of pyridinium salts Va–Ve to
3-(2-furyl)biphenyl derivatives is likely to involve
initial addition of hydroxide ion to the most electron-
deficient carbon atom in the α-position with respect to
the nitrogen atom and the nitro group. Pseudobase A
thus formed undergoes isomerization with cleavage of
the endocyclic C–N bond to give open-chain form B.
In the present communication we describe a new
synthetic approach to 3-(2-furyl)biphenyls, which is
based on recyclization of pyridinium salts Va–Ve by
the action of aqueous–alcoholic alkali. The key inter-
mediate products in the proposed reaction sequence
were nitropyridines IVa–IVe which were prepared by
Scheme 1.
NO2
NO2
Ph
Ph
O2N
O
O
H2N
NaNO2, AcOH
Ph
X
+
HN
N
Me
X
X
O
O
Me
Me
I
IIa–IIe
IIIa–IIIe
IVa–IVe
NO2
Ph
O
Me2SO4
A–
N
Me
X
Me
Va–Ve
X = Ac (a), Bz (b), CN (c), O2N (d), EtOCO (e); A = ClO4 (a, e), MeSO4 (b–d).
* For communication III, see [1].
602

NITROPYRIDINES: IV. SYNTHESIS OF 3-(2-FURYL)BIPHENYLS
603
Scheme 2.
NO2
NO2
NO2
HO
Ph
O
HO
Ph
OH–
O
O
O
Va–Ve
Ph
N
N
X
Me
X
Me
X
Me
Me
Me
NHMe
A
B
C
OH
NO2
NHMe
NO2
Ph
O
X
X
O
C
O
O
X
Me
NO2
OH
D
VIIa, VIIb
VIa–VIf
X = Ac (a), Bz (b), CN (c), O2N (d), EtOCO (e), HOCO (f).
Closure of benzene ring in the latter occurs via intra-
molecular aldol condensation with participation of the
benzoyl and methyl groups in structure C which is
tautomeric to B (Scheme 2). The recyclization of
quaternary salts Vc and Vd derived from 4-(2-furyl)-2-
methyl-5-nitro-6-phenylpyridine-3-carbonitrile (IVc)
and 4-(2-furyl)-2-methyl-3,5-dinitro-6-phenylpyridine
(IVd), respectively, was completely regioselective, and
the yields of 3-(2-furyl)biphenyls VIc and VId were
66 and 68%, respectively. In the reactions with
3-acetyl- and 3-benzoyl-5-nitropyridinium salts Va and
Vb we obtained mixtures of two products, VIa/VIIa
and VIb/VIIb. 5-Hydroxy-3-(2-furyl)biphenyls VIIa
and VIIb were the minor products. Presumably, they
were formed from open-chain structure D resulting
from hydrolysis of the enamine fragment in C.
intensity (1–2% of the base peak), while no molecular
ion peaks were found in the spectra of IIIc and IIIe.
A probable reason is facile elimination of the C4H3O2
radical under electron impact. The most abundant ions
(Irel = 100%) in the spectra of IIIa, IIId, and IIIe were
[M – C4H3O2]+; the relative intensity of the corre-
sponding fragment ion peak in the mass spectra of
IIIb and IIIc was 89 and 46%, respectively. The mass
spectra of IIIa–IIIe also contained strong peaks
from the [M – NO2]+, [M – HNO2]+, and [M – NO2 –
C4H3O]+ ions.
To conclude, it should be emphasized that recy-
clization of accessible nitropyridinium salts under mild
conditions ensures preparation of 3-(2-furyl)biphenyls
with various sets of substituents in the benzene ring
linked to the furan ring.
The structure of the newly synthesized compounds
1
was confirmed by the IR, H NMR, and mass spectra
EXPERIMENTAL
and elemental analyses. The IR spectra of VIa–VIf
contained absorption bands belonging to stretching
vibrations of the secondary amino group (3430–
3420 cm–1), cyano group (2210 cm–1), carbonyl group
(1680–1640 cm–1), and nitro group (1530–1520 and
1360–1350 cm–1). In the spectra of 3-(2-furyl)-5-hy-
droxy-2-nitrobiphenyls VIIa and VIIb, stretching
vibrations of the hydroxy group give rise to a weak
broad absorption band at a reduced frequency due to
strong intramolecular hydrogen bonding with the ace-
tyl or benzoyl carbonyl group, which is overlapped by
C–H stretching vibration band near 3000 cm–1 [7].
1
The H NMR spectra were recorded on a Bruker
AC-200 spectrometer (200 MHz) using tetramethyl-
silane as internal reference. The IR spectra were meas-
ured on a Specord 75IR instrument from solutions in
chloroform. The mass spectra (electron impact, 70 eV)
were obtained on a Finnigan MAT-8200 mass spec-
trometer with direct sample admission into the ion
source. The elemental compositions were determined
on a Perkin–Elmer analyzer. The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV-254 plates using chloroform and chloro-
form–ethyl acetate (9:1) as eluents. The melting points
were determined on a Boetius melting point apparatus.
The molecular ion peaks in the mass spectra of
dihydronitropyridines IIIa, IIIb, and IIId had a low
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SAGITULLINA et al.
604
3-(2-Furyl)-2-nitro-1-phenylprop-2-en-1-one (I)
C6H5, 5'-H), 9.99 s (1H, NH). Mass spectrum, m/z
(Irel, %): 260 (100) [M – HNO2]+, 224 (46.4) [M –
C4H3O2]+, 194 (71.4) [M – NO2 – C4H3O]+, 193 (15.4)
[M – HNO2 – C4H3O]+, 77 (11.0). Found, %: C 66.29;
H 4.35; N 13.82. C17H13N3O3. Calculated, %: C 66.44;
H 4.26; N 13.67.
was synthesized by the procedure described in [8].
Compounds IIIe and IVe [9] and 3-(2-furyl)biphenyls
VIa, VIb, VIe, and VIf [10] were reported by us
previously.
Dihydropyridines IIIa–IIIe (general procedure).
A solution of 2.43 g (10 mmol) of compound I and
10 mmol of enamine IIa–IIe in 15 ml of glacial acetic
acid was stirred for 20 h at room temperature. The
solvent was distilled off under reduced pressure, and
the residue was recrystallized from ethanol.
4-(2-Furyl)-2-methyl-3,5-dinitro-6-phenyl-1,4-
dihydropyridine (IIId). Yield 32%, yellow crystals,
mp 194–196°C. IR spectrum, ν, cm–1: 1320, 1490
1
(NO2); 3420 (NH). H NMR spectrum (DMSO-d6), δ,
ppm: 2.53 s (3H, CH3), 5.91 s (1H, 4-H), 6.31 d (1H,
3'-H, J3',4' = 3.1 Hz), 6.42 d.d (1H, 4'-H, J4',3' = 3.1,
J4',5' = 1.8 Hz), 7.39–7.59 m (6H, C6H5, 5'-H), 10.49 s
(1H, NH). Mass spectrum, m/z (Irel, %): 327 (0.5) [M]+,
280 (3.3) [M – HNO2]+, 263 (2.3) [M – HNO2 – OH]+,
244 (100) [M – C4H3O2]+, 214 (61.4) [M – NO2 –
C4H3O]+, 197 (14.6) [M – C4H3O2 – HNO2]+, 168
(36.2) [M – C4H3O2 – NO – NO2]+, 77 (14.3). Found,
%: C 59.01; H 4.19; N 12.60. C16H13N3O5. Calculated,
%: C 58.72; H 4.00; N 12.84. M 327.29.
1-[4-(2-Furyl)-2-methyl-5-nitro-6-phenyl-1,4-
dihydropyridin-3-yl]ethan-1-one (IIIa). Yield 45%,
yellow crystals, mp 189–190°C. IR spectrum (KBr), ν,
cm–1: 1320, 1490 (NO2); 1640 (CO); 3300, 3430 (NH).
1H NMR spectrum (CDCl3), δ, ppm: 2.37 s (6H, CH3,
COCH3), 5.64 s (1H, 4-H), 6.15 d (1H, 3'-H, J3',4'
=
3.1 Hz), 6.31 d.d (1H, 4'-H, J4',3' = 3.1,J4',5' = 1.8 Hz),
7.30–7.52 m (6H, C6H5, 5'-H), 9.44 s (1H, NH). Mass
spectrum, m/z (Irel, %): 324 (1.0) [M]+, 307 (39.7) [M –
OH]+, 279 (29.9), 278 (74.7) [M – NO2]+, 277 (25.4)
[M – HNO2]+, 262 (36.0), 241 (100) [M – C4H3O2]+,
235 (76.5) [M – NO2 – COCH3]+, 211 (43.1) [M –
NO2 – C4H3O]+, 196 (89.4) [M – NO2 – C4H3O – CH3]+,
168 (39.4) [M – NO2 – C4H3O – COCH3]+, 77 (49.6),
43 (92.8). Found, %: C 66.49; H 4.79; N 8.92.
C18H16N2O4. Calculated, %: C 66.66; H 4.97; N 8.64.
M 324.34.
Oxidation of dihydropyridines IIIa–IIIe (general
procedure). Sodium nitrite, 3 mmol, was added in
portions under stirring to a suspension of 2 mmol of
dihydropyridine IIIa–IIIe in 6 ml of glacial acetic
acid, heated to 60–70°C. The mixture was then stirred
for 1 h at that temperature, cooled, diluted with
3 volumes of water, and neutralized with aqueous am-
monia. The precipitate was filtered off, washed with
water, dried, and recrystallized from ethanol.
[4-(2-Furyl)-2-methyl-5-nitro-6-phenyl-1,4-dihy-
dropyridin-3-yl]phenylmethanone (IIIb). Yield 62%,
yellow crystals, mp 219–221°C. IR spectrum (KBr), ν,
cm–1: 1300, 1490 (NO2); 1630 (CO); 3310, 3420 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.80 s (3H,
1-[4-(2-Furyl)-2-methyl-5-nitro-6-phenylpyridin-
3-yl]ethan-1-one (IVa). Yield 60%, colorless crystals,
mp 124–126°C. IR spectrum, ν, cm–1: 1340, 1530
1
(NO2); 1700 (CO). H NMR spectrum (CDCl3), δ,
CH3), 5.55 s (1H, 4-H), 6.11 d (1H, 3'-H, J3',4'
=
ppm: 2.25 s (3H, COCH3), 2.63 s (3H, CH3), 6.56 d.d
(1H, 4'-H, J4',3' = 3.4, J4',5' = 1.7 Hz), 6.77 d (1H, 3'-H,
J3',4' = 3.4 Hz), 7.43–7.65 m (6H, C6H5, 5'-H). Mass
spectrum, m/z (Irel, %): 322 (2.5) [M]+, 306 (7.6)
[M – O]+, 305 (39.0) [M – OH]+, 277 (33.3) [M – OH –
CO]+, 263 (11.6), 249 (12.2), 235 (13.8), 207 (11.4),
206 (10.3), 105 (18.5), 77 (17.1), 43 (100), 28 (10.0).
Found, %: C 67.39; H 4.23; N 8.38. C18H14N2O4. Cal-
culated, %: C 67.07; H 4.38; N 8.69. M 322.32.
3.1 Hz), 6.36 d.d (1H, 4'-H, J4',3' = 3.1, J4',5' = 1.8 Hz),
7.42–7.64 m (11H, C6H5, COC6H5, 5'-H), 10.00 s (1H,
NH). Mass spectrum, m/z (Irel, %): 386 (2.2) [M]+, 369
(37.9) [M – OH]+, 340 (65.2) [M – NO2]+, 339 (60.5)
[M – HNO2]+, 303 (88.9) [M – C4H3O2]+, 273 (45.4)
[M – NO2 – C4H3O]+, 272 (81.0) [M – HNO2 – C4H3O]+,
105 (100), 77 (84.0). Found, %: C 71.72; H 4.79;
N 7.13. C23H18N2O4. Calculated, %: C 71.49; H 4.70;
N 7.25. M 386.41.
[4-(2-Furyl)-2-methyl-5-nitro-6-phenylpyridin-3-
yl]phenylmethanone (IVb). Yield 48%, colorless
crystals, mp 101–103°C. IR spectrum, ν, cm–1: 1340,
4-(2-Furyl)-2-methyl-5-nitro-6-phenyl-1,4-dihy-
dropyridine-3-carbonitrile (IIIc). Yield 60%, yellow
crystals, mp 193–195°C. IR spectrum, ν, cm–1: 1310,
1
1530 (NO2); 1670 (CO). H NMR spectrum (CDCl3),
1
1490 (NO2); 2210 (CN); 3430 (NH). H NMR spec-
δ, ppm: 2.52 s (3H, CH3), 6.30 d.d (1H, 4'-H, J4',3'
3.5, J4',5' = 1.8 Hz), 6.62 d.d (1H, 3'-H, J3',4' = 3.5,
J3',5' = 0.7 Hz), 7.29 d.d (1H, 5'-H, J5',4' = 1.8, J5',3'
0.7 Hz), 7.40–7.81 m (10H, C6H5, COC6H5). Mass
=
trum (DMSO-d6), δ, ppm: 2.11 s (3H, CH3), 5.20 s
(1H, 4-H), 6.27 d (1H, 3'-H, J3',4' = 3.2 Hz), 6.39 d.d
(1H, 4'-H, J4',3' = 3.2, J4',5' = 1.7 Hz), 7.35–7.51 m (6H,
=
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NITROPYRIDINES: IV. SYNTHESIS OF 3-(2-FURYL)BIPHENYLS
605
1
spectrum, m/z (Irel, %): 384 (12.2) [M]+, 368 (11.6)
[M – O]+, 367 (40.8) [M – OH]+, 339 (27.3) [M – OH –
CO]+, 311 (21.3), 105 (100), 77 (99.0), 28 (21.2).
Found, %: C 71.77; H 4.48; N 7.20. C23H16N2O4. Cal-
culated, %: C 71.87; H 4.20; N 7.29. M 384.39.
colorless crystals, mp 271–274°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.57 s (3H, COCH3), 2.79 s (3H,
CH3), 3.83 s (3H, CH3), 6.90–6.98 m (1H, 4'-H), 7.16 d
(1H, 3'-H, J3',4' = 3.7 Hz), 7.53–7.86 m (5H, C6H5),
8.31 s (1H, 5'-H). Found, %: C 51.93; H 3.81; N 6.36.
C19H17ClN2O8. Calculated, %: C 52.25; H 3.92; N 6.41.
4-(2-Furyl)-2-methyl-5-nitro-6-phenylpyridine-
3-carbonitrile (IVc). Yield 53%, colorless crystals,
mp 152–154°C. IR spectrum, ν, cm–1: 1340, 1540
3-Benzoyl-4-(2-furyl)-1,2-dimethyl-5-nitro-6-
phenylpyridin-1-ium methyl sulfate (Vb). Yield
85%, colorless crystals, mp 230–232°C. 1H NMR spec-
trum (DMSO-d6), δ, ppm: 2.71 s (3H, CH3), 3.38 s
(3H, CH3SO4–), 3.89 s (3H, CH3), 6.72 d.d (1H, 4'-H,
1
(NO2); 2220 (CN). H NMR spectrum (DMSO-d6), δ,
ppm: 2.93 s (3H, CH3), 6.66 d.d (1H, 4'-H, J4',3' = 3.7,
J4',5' = 1.7 Hz), 7.42 d (1H, 3'-H, J3',4' = 3.7 Hz), 7.45–
7.63 m (5H, C6H5), 7.68 d (1H, 5'-H, J5',4' = 1.7 Hz).
Mass spectrum, m/z (Irel, %): 305 (7.4) [M]+, 289 (19.6)
[M – O]+, 288 (100) [M – OH]+, 261 (15.4), 260 (85.7)
[M – OH – CO]+, 248 (13.3), 247 (18.4) [M – NO –
CO]+, 232 (34.4), 206 (30.5), 205 (15.0), 152 (17.1),
151 (18.5), 105 (19.9), 77 (36.1), 63 (12.8), 55 (19.9),
43 (29.1), 39 (17.0) 28 (21.5). Found, %: C 66.61;
H 3.56; N 13.66. C17H11N3O3. Calculated, %: C 66.88;
H 3.63; N 13.76. M 305.29.
J4',3' = 4.0, J4',5' = 1.8 Hz), 6.98 d (1H, 3'-H, J3',4'
=
4.0 Hz), 7.60–8.05 m (11H, C6H5, COC6H5, 5'-H).
Found, %: C 58.69; H 4.33; N 5.47. C25H22N2O8S. Cal-
culated, %: C 58.82; H 4.34; N 5.49.
3-Cyano-4-(2-furyl)-1,2-dimethyl-5-nitro-6-
phenylpyridin-1-ium methyl sulfate (Vc). Yield
80%, colorless crystals, mp 177–179°C. 1H NMR spec-
trum (DMSO-d6), δ, ppm: 3.17 s (3H, CH3), 3.35 s
(3H, CH3SO4–), 3.87 s (3H, CH3), 7.10–7.16 m (1H,
4-(2-Furyl)-2-methyl-3,5-dinitro-6-phenylpyri-
dine (IVd). Yield 43%, colorless crystals, mp 141–
142°C. IR spectrum, ν, cm–1: 1350, 1540 (NO2).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.66 s (3H,
4'-H), 7.53–7.80 m (5H, C6H5), 8.11 d (1H, 3'-H, J3',4'
=
3.7 Hz), 8.43 s (1H, 5'-H). Found, %: C 53.23; H 4.09;
N 9.78. C19H17N3O7S. Calculated, %: C 52.90; H 3.97;
N 9.74.
CH3), 6.78–6.81 m (1H, 4'-H), 6.95 d (1H, 3'-H, J3',4'
=
4-(2-Furyl)-1,2-dimethyl-3,5-dinitro-6-phenyl-
3.5 Hz), 7.51–7.69 m (5H, C6H5), 8.09 s (1H, 5'-H).
Mass spectrum, m/z (Irel, %): 325 (49.9) [M]+, 309 (2.4)
[M – O]+, 308 (16.0) [M – OH]+, 297 (9.6) [M – CO]+,
280 (17.6) [M – OH – CO]+, 234 (33.5), 221 (38.2),
220 (37.2), 206 (63.1), 193 (30.9), 192 (40.6), 180
(35.4), 167 (30.7), 166 (39.9), 163 (34.4), 152 (43.3),
140 (73.7), 139 (54.0), 127 (43.9), 126 (55.4), 105
(72.1), 104 (73.1), 83 (66.4), 81 (46.7), 77 (100), 63
(49.0), 55 (72.2), 51 (41.0), 39 (37.8), 29 (18.1) 28
(28.4), 27 (37.2). Found, %: C 58.98; H 3.60; N 12.69.
C16H11N3O5. Calculated, %: C 59.08; H 3.41; N 12.92.
M 325.28.
pyridin-1-ium methyl sulfate (Vd). Yield 94%,
1
colorless crystals, mp 201–203°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.90 s (3H, CH3), 3.37 s (3H,
CH3SO4–), 3.90 s (3H, CH3), 6.98–7.05 m (1H, 4'-H),
7.39 d (1H, 3'-H, J3',4' = 3.9 Hz), 7.54–7.87 m (5H,
C6H5), 8.41 s (1H, 5'-H). Found, %: C 47.50; H 3.67;
N 9.16. C18H17N3O9S. Calculated, %: C 47.89; H 3.80;
N 9.31.
3-Ethoxycarbonyl-4-(2-furyl)-1,2-dimethyl-5-
nitro-6-phenylpyridin-1-ium perchlorate (Ve). Yield
85%, colorless crystals, mp 241–243°C. 1H NMR spec-
trum (DMSO-d6), δ, ppm: 1.31 t (3H, CH3CH2O, J =
7.1 Hz), 2.88 s (3H, CH3), 3.83 s (3H, CH3), 4.55 q
(2H, OCH2, J = 7.1 Hz), 6.95 d.d (1H, 4'-H, J4',3' = 3.9,
J4',5' = 1.7 Hz), 7.24 d (1H, 3'-H, J3',4' = 3.9 Hz), 7.59–
7.75 m (5H, C6H5), 8.33 d (1H, 5'-H, J5',4' = 1.7 Hz).
Found, %: C 51.51; H 4.07; N 5.75. C20H19ClN2O9.
Calculated, %: C 51.46; H 4.10; N 6.00.
Alkylation of pyridines IVa–IVe (general proce-
dure). A mixture of 5 mmol of pyridine IVa–IVe and
1.9 ml (20 mmol) of dimethyl sulfate was heated for
20–24 h at 100°C. The mixture was cooled and washed
with anhydrous diethyl ether (3×10 ml). Methyl pyri-
dinium sulfates Vb–Vd crystallized from the mixture
and were filtered off. In the synthesis of salts Va and
Ve, the oily residue was dissolved in 5 ml of water,
a saturated aqueous solution of 0.64 g (5.3 mmol) of
sodium perchlorate was added, and the precipitate was
filtered off, dried, and recrystallized from ethanol.
3-(2-Furyl)biphenyls VIa–VIf, VIIa, and VIIb
(general procedure). Pyridinium salt Va–Ve, 1 mmol,
was dispersed in 4 ml of ethanol, 1.8 ml (5 mmol) of
10% aqueous sodium hydroxide was added, and the
mixture was stirred at room temperature for a time
indicated below and was then diluted with water. The
3-Acetyl-4-(2-furyl)-1,2-dimethyl-5-nitro-6-
phenylpyridin-1-ium perchlorate (Va). Yield 83%,
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SAGITULLINA et al.
606
precipitate of biphenyl VIa–VIe was filtered off and
washed with water. Biphenylcarboxylic acid VIf was
isolated by acidification with 50% aqueous acid of
the filtrate obtained after separation of biphenyl VIe.
5-Hydroxybiphenyls VIIa and VIIb were isolated in
a similar way from the filtrates obtained after separa-
tion of products VIa and VIb. Compounds VIa–VIf,
VIIa, and VIIb were purified by recrystallization from
ethanol.
7.64 s (1H, 5'-H), 11.92 s (1H, OH). Mass spectrum,
m/z (Irel, %): 323 (4.1) [M]+, 306 (12.5) [M – OH]+,
278 (29.5) [M – OH – CO]+, 277 (6.1) [M – NO2]+,
276 (17.6) [M – HNO2]+, 264 (20.8), 251 (41.6), 236
(51.9), 208 (21.6), 180 (36.9), 176 (18.7), 165 (24.3),
152 (21.3), 139 (18.0), 77 (17.6), 43 (100). Found, %:
C 66.56; H 4.22; N 4.22. C18H13NO5. Calculated, %:
C 66.87; H 4.05; N 4.33. M 323.30.
1-[3-(2-Furyl)-5-hydroxy-2-nitrobiphenyl-4-yl]-
phenylmethanone (VIIb). Yield 12% (reaction time
18 h), colorless crystals, mp 180–181°C. IR spectrum,
ν, cm–1: 1360, 1530 (NO2); 1630 (CO). 1H NMR spec-
trum (CDCl3), δ, ppm: 6.03 d.d (1H, 4'-H, J4',3' = 3.5,
J4',5' = 1.8 Hz), 6.35 d (1H, 3'-H, J3',4' = 3.5 Hz), 7.12–
7.55 m (12H, C6H5, COC6H5, 6-H, 5'-H), 9.66 s (1H,
OH). Mass spectrum, m/z (Irel, %): 385 (7.3) [M]+, 368
(5.0) [M – OH]+, 356 (7.4), 340 (23.0) [M – OH –
CO]+, 339 (10.5) [M – NO2]+, 338 (29.5) [M – HNO2]+,
328 (31.4) [M – CO – CHO]+, 312 (40.1), 105 (78.5),
77 (100), 28 (18.0). Found, %: C 71.39; H 3.79;
N 3.31. C23H15NO5. Calculated, %: C 71.68; H 3.92;
N 3.63. M 385.38.
3-(2-Furyl)-5-methylamino-2-nitrobiphenyl-4-
carbonitrile (VIc). Yield 66% (reaction time 4 h),
yellow crystals, mp 185–186°C. IR spectrum, ν, cm–1:
1
1350, 1520 (NO2); 2210 (CN); 3430 (NH). H NMR
spectrum (CDCl3), δ, ppm: 2.99 d (3H, NHCH3, J =
5.1 Hz), 5.23 br.s (1H, NHCH3), 6.54 s (1H, 6-H),
6.56 d (1H, 4'-H, J4',5' = 1.7 Hz), 6.97 d (1H, 3'-H,
J3',4' = 3.4 Hz), 7.32–7.45 m (5H, C6H5), 7.55 d.d (1H,
5'-H, J5',4' = 1.7, J5',3' = 0.7 Hz). Mass spectrum, m/z
(Irel, %): 319 (37.6) [M]+, 302 (33.7) [M – OH]+, 291
(45.1), 275 (28.1), 274 (100) [M – OH – CO]+, 262
(27.0), 259 (41.4), 247 (69.2), 246 (85.7), 232 (27.4),
231 (44.3), 230 (20.9), 220 (27.8), 219 (60.1), 218
(28.9), 206 (24.7), 205 (60.6), 193 (27.0), 192 (33.0),
190 (34.2), 77 (23.5), 28 (27.5). Found, %: C 67.61;
H 4.24; N 13.35. C18H13N3O3. Calculated, %: C 67.71;
H 4.10; N 13.16. M 319.32.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 04-03-32652).
REFERENCES
5-(2-Furyl)-N-methyl-4,6-dinitrobiphenyl-3-
amine (VId). Yield 68% (reaction time 2 h), yellow
crystals, mp 162–164°C. IR spectrum, ν, cm–1: 1360,
1. Sagitullina, G.P., Glizdinskaya, L.V., and Sagitul-
lin, R.S., Russ. J. Org. Chem., 2006, vol. 42, p. 1203.
2. Reuter, K.H. and Scott, W.J., J. Org. Chem., 1993,
1
1530 (NO2); 3430 (NH). H NMR spectrum (CDCl3),
δ, ppm: 2.99 d (3H, NHCH3, J = 5.1 Hz), 6.48 d.d (2H,
NH, 4'-H, J4',3' = 3.4, J4',5' = 1.7 Hz), 6.61 d.d (1H,
3'-H, J3',4' = 3.4, J3',5' = 0.7 Hz), 6.76 s (1H, 6-H), 7.35–
7.49 m (5H, C6H5), 7.51 d.d (1H, 5'-H, J5',4' = 1.7,
J5',3' = 0.7 Hz). Mass spectrum, m/z (Irel, %): 339 (75.9)
[M]+, 322 (27.4) [M – OH]+, 294 (13.8) [M – OH –
CO]+, 276 (9.2) [M – NO2 – OH]+, 248 (32.9), 247
(33.9) [M – 2NO2]+, 222 (30.9), 221 (48.3), 220 (100)
[M – 2NO2 – HCN]+, 219 (69.1), 208 (40.7), 207
(53.0), 206 (52.9), 205 (67.2), 193 (77.8), 192 (57.7),
191 (58.5), 180 (54.2), 77 (42.2), 55 (37.9), 28 (34.3).
Found, %: C 60.14; H 3.85; N 12.68. C17H13N3O5. Cal-
culated, %: C 60.18; H 3.86; N 12.38. M 339.31.
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1-[3-(2-Furyl)-5-hydroxy-2-nitrobiphenyl-4-yl]-
ethan-1-one (VIIa). Yield 14% (reaction time 4 h),
colorless crystals, mp 155–157°C. IR spectrum, cm–1:
1
1370, 1530 (NO2); 1650 (CO). H NMR spectrum
9. Sagitullina, G.P., Glizdinskaya, L.V., and Sagitul-
(CDCl3), δ, ppm: 1.90 s (3H, COCH3), 6.57 d.d (1H,
lin, R.S., Khim. Geterotsikl. Soedin., 2005, p. 858.
4'-H, J4',3' = 3.3, J4',5' = 1.8 Hz), 6.69 d (1H, 3'-H, J3',4'
=
10. Sagitullina, G.P., Glyzdinskaya, L.V., and Sagitul-
3.3 Hz), 7.10 s (1H, 6-H), 7.37–7.46 m (5H, C6H5),
lin, R.S., Mendeleev Commun., 2006, p. 56.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007