Nitropyridines: III. Synthesis of meta-terphenyls by recyclization of nitropyridinium salts

Article abstract of DOI:10.1134/S1070428006080173

A two-component Hantzsch synthesis was applied to preparation of nitropyridines and their quaternary salts from various enamines and chalcones based on nitroacetophenone. The recyclization of nitropyridinium quaternary salts under the treatment with an aq

Full text of DOI:10.1134/S1070428006080173

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 8, pp. 1203-1207. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó G.P. Sagitullina, L.V.Glidzinskaya, R.S. Sagitullin, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42,
No. 8, pp. 1222-1226.
Dedicated to Academician of the Russian Academy of Sciences N.S.Zefirov
on occasion of his 70th anniversary
Nitropyridines: III.* Synthesis of meta-Terphenyls
by Recyclization of Nitropyridinium Salts
G.P. Sagitullina, L.V. Glidzinskaya, and R.S. Sagitullin
Omsk State University, Omsk, 644077 Russia
e-mail: Sagitullina@orgchem.univer.omsk.su
Received June 7, 2005
Abstract—A two-component Hantzsch synthesis was applied to preparation of nitropyridines and their quaternary
salts from various enamines and chalcones based on nitroacetophenone. The recyclization of nitropyridinium
quaternary salts under the treatment with an aqueous-alcoholic alkali led to preparation of 5'-methylamino-2'-
nitro-m-terphenyl derivatives.
DOI: 10.1134/S1070428006080173
The most of the known m-terphenyls were prepared
by building up the central benzene ring using the recycliz-
ation of pyrilium, thiopyrilium, and 5-nitropyrimidine
salts under the treatment of C-nucleophiles [2–4], by the
central ring closure from acyclic precursors followed
by aromatization [5–8], by cross-coupling [9, 10] and
1,2-addition of Grignard reagents to 1,5-diaryl-3-oxocyclo-
hexenes [11]. The m-terphenyls derivatives exhibit a wide
range of biological activity [12–15].
The new approach to the m-terphenyls effected in
this study was based on the recyclization of diphenyl-
pyridinium salts Va–Vf by treating with an aqueous-
alcoholic alkali. The key substances in this synthesis are
unsymmetrical nitropyridines IVa–IVf obtained by a two-
component Hantzsch synthesis from nitrochalcones Ia
and Ib and various enamines with subsequent aromatiza-
tion using sodium nitrite in the acetic acid. Pyridines IVc–
IVf we described before [16], and compounds IVa and
IVb were newly prepared in this study (Scheme 1). Both
stages of the Hantzsch synthesis provided preparative
yields. The alkylation of nitropyridinium salts was
performed by prolonged heating of pyridines IVa–IVf with
a triple excess of dimethyl sulfate.
Scheme 1.
5
2
5
2 1
3K
;
2 1
3K
;
The recyclization of diphenylpyridinium salts Va, Vd–
Vf at the treatment with the aqueous-alcoholic alkali
occurred by an attack of the hydroxy anion on the most
electron-deficient position 6 of the pyridinium salt (in the
ortho-position relative to the nitro group) followed by the
isomerization of the pseudobase A into an open form B.
The closure of the central benzene ring in terphenyls VIa,
VId–VIf involved an intramolecular aldol-crotonic
condensation of the arising benzoyl group with the methyl
group in the open form C (Scheme 2). Yields of m-ter-
phenyls amount to 46–70%. 5'-Methylaminoterphenyls
VIa and VId are the only products of salts Va and Vd
recyclization. The recyclization of salts Ve and Vf
occurred with a partial hydrolysis of the enamine fragment
of the open form C under the alkali action giving rise to
5'-hydroxyterphenyls IXe and IXf, but the contribution
of the process is insignificant.
ꢀ
+ 1
0H
1
+
0H
,, ꢁꢂ,,E
,,, ꢁꢂ,,,E
, ꢁꢂ,E
5
5
2 1
3K
;
2 1
3K
;
1D12
$F2+
0H 62
1
0H
1
0H
$
0H
9 ꢁꢂ9E
,9 ꢁꢂ,9E
X = CONHPh, R = Ph, A = MeSO4 (a); X = CO2Et, R =
4-MeOC6H4,A= ClO4 (b).
* For communication II, see [1].
1203

SAGITULLINA et al.
1204
Scheme 2.
3K
3K
3K
3K
2 1
3K
;
2 1
3K
;
2 1
+2
3K
;
2 1
3K
;
2+
1+0H
1
0H
1
0H
0H
2 0H
2+
1
$
0H
0H
0H
B
9 ꢀꢁ9Gꢁꢁꢁ9I
%
&
1+0H
2+
;
;
ꢀ
12
12
,;Hꢁꢂ,;I
X = CONHPh (a), CN (d),Ac (e), Bz (f); V,A= MeSO4 (a, d), ClO4 (e), FSO3 (f).
B
9, ꢁꢂ9,Gꢂꢂꢂ9,I
group of the enamine fragment of open form B arising
as a result of an attack of the hydroxy anion on the position
2 of the pyridinium salt (into the ortho-position with
respect to the ester group). It should be noted that for
the nicotinic acid esters salts containing in the position 5
electron-withdrawing substituents less strong than the nitro
group (CN, COCH3, COPh, CONHPh) this reaction path
The recylization of quaternary salts Vb and Vc led
mainly to the formation of 4'-ethoxycarbonyl-m-terphenyls
VIb and VIc and 4'-carboxy-m-terphenyls VIIb and VIIc
(Scheme 3). The heterocyclization process involving the
ester group and giving pyridone VIII competes with the
recyclization of salt Vc. The closure of pyridone VIII
ring occurs via intramolecular acylation with the ester
Scheme 3.
5
5
5
5
2 1
3K
&2 (W
0H
2 1
3K
&2 (W
2 1
3K
&2 (W
2 1
3K
&2 (W
0H
2+
ꢀ
0H
2+
2(W
2
1
1
1+
0H
$
2
1+
0H
0H
0H
%
$
5ꢀ ꢀ+
1+0H
1+0H
3K
(W2 &
+2 &
2 1
3K
&20H
ꢀ
1
2
12
12
0H
5
5
9,Eꢁꢂ9,F
9,,Eꢁꢂ9,,F
9,,,
V–VII, R = OMe,A= ClO4 (b); R = H,A= MeSO4 (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

NITROPYRIDINES:III.
1205
1
of recyclization involving the ester group to form
pyridones is the principal one [17].
1320, 1500 (NO2), 1690 (CO), 3440 (NH). H NMR
spectrum (CDCl3), d, ppm: 1.25 t (3H, CH2CH3,
J 7.0 Hz), 2.35 s (3H, CH3), 3.78 s (3H, OCH3), 4.12 q
(2H, CH2CH3, J 7.0 Hz), 5.40 s (1H, H4), 6.06 s (1H,
NH), 6.83 d (2H, H3", H5", J 8.6 Hz), 7.30–7.44 m (7H,
Ph, H2", H6"). Found, %: C 67.38; H 5.76. C22H22N2O5.
Calculated, %: C 66.99; H 5.62.
In the 1H NMR spectra of terphenyls VIa–VIf, VIIb,
and VIIc the singlet from the aromatic proton of the
central benzene ring appeared in the region d 6.59–
7.07 ppm, and the methyl attached to NH gave rise to
a doublet at 2.57–2.93 ppm.
2-Methyl-5-nitro-N,4,6-triphenylnicotinamide
(IVa). To a stirred suspension of 4.11 g (10 mmol) of
dihydropyridine IIIa in 25 ml of glacial acetic acid was
added at 60–70°C by portions 1.04 g (15 mmol) of sodium
nitrite. On completion of addition of the oxidant the reaction
mixture was stirred for 1 h more at the same temperature
and then it was diluted with a three-fold volume of ice
water and neutralized with ammonia solution. The
precipitated crystals were filtered off and washed with
water.Yield 2.43 g (80%), mp 201–203°C (from ethanol).
The composition and the structure of the newly syn-
thesized compounds were proved by elemental analysis,
by IR, 1H NMR, and mass spectra.
It should be stated in conclusion that the recyclization
of the available nitropyridines quaternary salts provided
a possibility to obtain under mild conditions m-terphenyls
with a versatile set of substituents in the central benzene
ring.
EXPERIMENTAL
–1
IR spectrum, cm : 1360, 1540 (NO2), 1680 (CO), 3420
1H NMR spectra were registered on a spectrometer
BrukerAC-200 (operating frequency 200 MHz), internal
referenceTMS. IR spectra were recorded on a spectro-
photometer Specord 75IR from chloroform solutions, mass
spectra were measured on Finnigan MAT-8200
instrument with direct admission of the sample into the
ion source, ionizing electrons emergy 70eV. The reaction
progress was monitored and the purity of compounds
obtained was checked by TLC on Silufol UV-254 plates,
eluents chloroform, chloroform-ethyl acetate, 9:1 or 1:1.
1
(NH). H NMR spectrum (DMSO-d6), d, ppm: 2.69 s
(3H, CH3), 7.03–7.57 m (15H, 3 Ph), 10.58 s (1H,
NHamide). Found, %: C 73.65; H 4.72. C25H19N3O3.
Calculated, %: C 73.34; H 4.68.
Ethyl 2-methyl-4-(4-methoxyphenyl)-5-nitro-6-
phenylnicotinate (IVb) was prepared in the same way
as dihydropyridine IVa. Yield 68%, mp 104–106°C (from
–1
ethanol). IR spectrum, cm : 1360, 1540 (NO2), 1730
1
(CO). H NMR spectrum (CDCl3), d, ppm: 0.97 t (3H,
CH2CH3, J 7.1 Hz), 2.70 s (3H, CH3), 3.79 C (3H,
OCH3), 4.06 q (2H, CH2CH3, J 7.1 Hz), 6.89 d (2H, H3",
H5", J 8.8 Hz), 7.24 d (2H, H2", H6", J 8.8 Hz), 7.39–
7.65 m (5H, Ph). Found, %: C 67.80; H 5.29.
C22H20N2O5. Calculated, %: C 67.34; H 5.14.
..
Melting points were determined on a Boetius heating
block.
Compounds Ia, IIIc–IIIf–Vc–Vf we described in
[16], m-terphenyl VId, in [18], Ib was synthesized by
procedure [19], IIa, by that of [20].
1,2-Dimethyl-5-nitro-N,4,6-triphenylnicotin-
amide methylsulfate (Va).Amixture of 2.05 g (5 mmol)
of pyridine IVa and 1.4 ml (15 mmol) of dimethyl sulfate
was heated for 10 h at 100°C, then cooled, washed with
anhydrous ether, the precipitated crystals were filtered
off. Yield 2.57 g (96%), mp 258–260°C (from ethanol,
2-Methyl-5-nitro-N,4,6-triphenyl-1,4-dihydro-
pyridine-3-carboxamide (IIIa). A solution of 2.51 g
(10 mmol) of reagent Ia and 1.76 g (10 mmol) of enamine
IIa in 10 ml of glacial acetic acid was stirred for 12 h
at room temperature. The precipitated crystals were
filtered off and washed with ether to obtain 3.21 g (78%),
mp 143–145°C (from aqueous ethenol). IR spectrum,
1
decomp.). H NMR spectrum (DMSO-d6), d, ppm:
–
2.99 s (3H, CH3), 3.42 s (3H, CH3SO4), 4.00 s (3H, CH3),
–1
cm : 1310, 1520 (NO2), 1670 (CO), 3380, 3420 (NH).
7.10–7.75 m (15H, 3 Ph), 10.80 s (1H, NH). Found, %:
C 60.29; H 4.67. C27H25N3O7S. Calculated, %: C 60.55;
H 4.71.
1H NMR spectrum (DMSO-d6), d, ppm: 2.06 s (3H,
CH3), 5.43 s (1H, H4), 7.04–7.61 m (15H, 3Ph), 9.63 s
(1H, NH Ht), 9.95 c (1H, NHamide). Found, %: C 72.72;
H 5.09. C25H21N3O3. Calculated, %: C 72.98; H 5.14.
1,2-Dimethyl-4-(4-methoxyphenyl)-5-nitro-6-
phenyl-3-ethoxycarbonylpyridinium perchlorate
(Vb). Amixture of 1.96 g (5 mmol) of pyridine IVb and
1.4 ml (15 mmol) of dimethyl sulfate was heated for 20 h
at 100°C, then cooled and washed with ether (3´10 ml).
The oily residue was dissolved in 5 ml of water, and
Ethyl 2-methyl-4-(4-methoxyphenyl)-5-nitro-6-
phenyl-1,4-dihydropyridine-3-carboxylate (IIIb)
was similarly prepared from dihydropyridine IIIa. Yield
–1
52%, mp 132–134°C (from ethanol). IR spectrum, cm :
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

SAGITULLINA et al.
1206
a saturated water solution containing 0.64 g (5.3 mmol)
of NaClO4 was added. The separated crystals were
filtered off and dried. Yield 1.59 g (63%), mp143–145°C
(from ethanol). 1H NMR spectrum (DMSO-d6), d, ppm:
1.02 t (3H, CH2CH3, J 7.1 Hz), 2.93 s (3H, CH3), 3.83 s
(3H, OCH3), 3.93 s (3H, CH3), 4.24 q (2H, CH2CH3,
J 7.1 Hz), 7.18 d (2H, H3", H5", J 8.8 Hz), 7.33 d (2H,
H2", H6", J 8.8 Hz), 7.61–7.73 m (5H, Ph). Found, %:
C 54.37; H 4.49. C23H23ClN2O9. Calculated, %: C 54.50;
H 4.57.
(5H, Ph). Found, %: C 67.69; H 5.32. C23H22N2O5.
Calculated, %: C 67.97; H 5.46.
5'-Methylamino-4''-methoxy-2'-nitro-1,1':3'1''-
terphenyl-4'-carboxylic acid (VIIb). Yield 60%
(reaction time 30 min), mp 201–202°C (from ethanol).
–1
IR spectrum, cm : 1360, 1530 (NO2), 1630 (CO), 3440
(NH). 1H NMR spectrum (CDCl3), d, ppm: 2.62 d (3H,
NHCH3, J 4.9 Hz), 3.86 s (3H, OCH3), 5.45 br.s (1H,
NHCH3), 7.01 d (2H, H3", H5", J 8.8 Hz), 7.04 s (1H,
H6'), 7.30 d (2H, H2", H6", J 8.8 Hz), 7.34–7.50 m (5H,
Ph), 13.14 s (1H, COOH). Found, %: C 66.78; H 4.81.
C21H18N2O5. Calculated, %: C 66.66; H 4.79.
Synthesis of m-terphenyls VIa–VIf, VIIb, VIIc,
IXe, and IXf. To a suspension of 1 mmol of an appropriate
pyridinium salt Va–Vf in 4 ml of ethanol was added
1.8 ml of 10% aqueous NaOH, and the mixture was stirred
at room temperature for a time interval indicated further.
Then the mixture was diluted with water, the precipitated
crystals of terphenyls VIa–VIf were filtered off and
washed with water. The filtrates after separating VIe
and VIf were acidified with 50% aqueous AcOH, and
the formed crystals of compounds IXe and IXf were
filtered off and washed with water. Terphenyl VIc
contained pyridone VIII, therefore the mixture was sub-
jected to column chromatography on Silicagel L 60/100,
eluent chloroform. Compounds VIIb and VIIc were
isolated by acidifying with 10% HCl filtrates obtained
after separation of compounds VIb and VIc.
Ethyl-5'-methylamino-2'-nitro-1,1':3'1''-ter-
phenyl-4'-carboxylate (VIc). Yield 42% (reaction time
–1
3 h), mp 183–185°C (from ethanol). IR spectrum, cm :
1
1360, 1520 (NO2), 1680 (CO), 3420 (NH). H NMR
spectrum (CDCl3), d, ppm: 0.66 t (3H, CH2CH3,
J 7.2 Hz), 2.93 s (3H, NHCH3, J 5.0 Hz), 3.81 q (2H,
CH2CH3, J 7.2 Hz), 6.59 s (1H, H6'), 6.69 br.s (1H,
NHCH3), 7.24–7.41 m (10Harom). Mass spectrum, m/z
·
(Irel, %): 377 (24.6), 376 (100) [M]+ , 330 (10.2) [M–
·
NO2]+, 301 (10.5) [M–NO2–C2H5]+ , 300 (16.9) [M–
·
NO2–NHCH3]+ , 285 (9.6), 273 (10.2), 256 (14.1), 228
(11.1), 226 (9.4), 215 (10.6). Found, %: C 69.86; H 5.42.
C22H20N2O4. Calculated, %: C 70.20; H 5.36. M 376.41.
5'-Methylamino-2'-nitro-1,1':3'1''-terphenyl-4'-
carboxylic acid (VIIc). Yield 6% (reaction time 3 h),
5'-Methylamino-2'-nitro-N-phenyl-1,1':3’1''-ter-
phenyl-4'-carboxamide (VIa). Yield 70% (reaction time
–1
mp 243–245°C (from ethanol). IR spectrum, cm : 1370,
1530 (NO2), 1640 (CO), 3440 (NH). 1H NMR spectrum
(CDCl3), d, ppm: 2.57 d (3H, NHCH3, J 4.8 Hz),
5.27 br.s (1H, NHCH3), 7.07 s (1H, H6'), 7.36–7.53 m
(10Harom), 13.02 s (1H, COOH). Mass spectrum, m/z
–1
3 h), mp 193–194°C (from ethanol). IR spectrum, cm :
1
1360, 1520 (NO2), 1670 (CO), 3420 (NH). H NMR
spectrum (DMSO-d6), d, ppm: 2.84 d (3H, NHCH3,
J 4.6 Hz), 6.12 br.s (1H, NHCH3), 6.60 s (1H, H6'), 7.16–
7.49 m (15Harom), 10.12 s (1H, NHamide). Mass spectrum,
m/z (Irel, %): 424 (29.9), 423 (100) [M]+·, 332 (19.2), 331
(88.8) [M–NHPh]+, 315 (21.0), 314 (90.7) [M–NHPh–
OH]+·, 298 (21.8), 297 (93.8), 285 (16.5)[M–NHPh–
NO2]+·, 269 (18.5), 256 (17.6) [M–NHPh–OH–NO–
CO]+, 93 (56.5). Found, %: C 73.91; H 5.12.
C26H21N3O3. Calculated, %: C 73.74; H 5.00. M 423.47.
·
(Irel, %): 349 (24.8), 348 (100) [M]+ , 347 (15.8) [M–
H]+, 318 (10.0) [M–NHCH3]+, 317 (31.6) [M–H–
·
·
NHCH3]+ , 300 (9.3), 272 (15.5) [M–NO2–NHCH3]+ ,
244 (10.7), 231 (9.3), 216 (13.0), 215 (44.5), 213 (18.5),
204 (9.4), 202 (14.3), 189 (9.6), 129 (19.8). Found, %:
C 69.30; H 4.77. C20H16N2O4. Calculated, %: C 68.96;
H 4.63. M 348.46.
3-Acetyl-1-methyl-5-nitro-4,6-diphenylpyridin-
Ethyl-5'-methylamino-4''-methoxy-2'-nitro-
1,1':3'1''-terphenyl-4'-carboxylate (VIb). Yield 17%
(reaction time 30 min), mp 142–143°C (from ethanol).
2(1H)-one (VIII). Yield 9% (reaction time 3 h), mp 166–
–1
168°C (from ethanol). IR spectrum, cm (CHCl3): 1700,
1
1640 (CO), 1530, 1360 (NO2). H NMR spectrum
–1
IR spectrum, cm : 1360, 1520 (NO2), 1690 (CO), 3420
(CDCl3), d, ppm: 2.27 s (3H, COCH3), 3.31 s (3H,
NCH3), 7.25–7.56 m (10Harom). Mass spectrum, m/z (Irel,
(NH). 1H NMR spectrum (CDCl3), d, ppm: 0.75 t (3H,
·
%): 349 (14.3), 348 (66.95) [M]+ , 347 (37.6)[M–H]+,
CH2CH3, J 7.1 Hz), 2.92 s (3H, NHCH3, J 5.1 Hz)
,
334 (9.0), 333 (40.6) [M–CH3]+, 331 (20.6)[M–OH]+,
3.81 s (3H, OCH3), 3.86 q (2H, CH2CH3, J 7.1 Hz),
6.65 br.s (2H, NHCH3, H6'), 6.88 d (2H, H3', H5",
J 8.8 Hz), 7.19 d (2H, H2", H6", J 8.8 Hz), 7.35–7.52 m
·
·
316 (12.4) [M–CH3–OH]+ , 301 (26.8) [M–OH–NO]+ ,
300 (100), 299 (13.0), 287 (11.1) [M–NO2–CH3]+., 286
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

NITROPYRIDINES:III.
1207
(43.8), 258 (12.4), 230 (9.5), 202 (11.9), 189 (11.2), 118
(76.6), 77 (43.7) [Ph]+, 43 (18.3) [COCH3]+. Found, %:
C 69.35; H 4.59. C20H16N2O4. Calculated, %: C 68.96;
H 4.63. M 348.46.
spectrum (CDCl3), d, ppm: 7.00–7.44 m (16H arom),
13.04 s (1H, OH). Mass spectrum, m/z (Irel, %): 396
·
(28.4), 395 (100) [M]+ , 394 (70.3) [M – H]+, 347 (11.7),
215 (17.1), 105 (83.3) [COPh]+, 77 (51.5) [Ph]+. Found,
%: C 76.09; H 4.47. C25H17NO4. Calculated, %: C 75.94;
H 4.33. M 395.41.
1-(5'-Methylamino-2'-nitro-1,1':3'1''-terphenyl-
4'-yl)ethanone (VIe). Yield 46% (reaction time 6 h),
–1
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant
no. 04-03-32652).
mp 158–160°C (from ethanol). IR spectrum, cm : 1340,
1510 (NO2), 1640 (CO), 3420 (NH). 1H NMR spectrum
(CDCl3), d, ppm: 1.65 s (3H, COCH3), 2.90 d (3H,
NHCH3, J 5.0 Hz), 6.59 s (1H, H6'), 6.87 br.s (1H,
NHCH3), 7.31–7.44 m (10Harom). Mass spectrum, m/z
REFERENCES
·
(Irel, %): 347 (25.1), 346 (100) [M]+ , 332 (14.1), 331
1. Shkil’, G.P., Berdovich, L.V., Lusis, V., Mutsenietse, D., and
Sagitullin, R.S., Khim. Geterotsikl. Soedin., 1995, p. 86.
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Geterotsikl. Soedin., 2005, p. 633.
3. Zimmermann, T., J. Prakt. Chem., 1993, vol. 335, p. 644.
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vol. 330, p. 35.
5. VanderPlas,H.C.andBarczynski,P., Rec. Trav. Chim, Pays-
Bas, 1978, vol. 97, p. 256.
6. Sadek, K.U., Selim, M.A., andAbdel-Motaleb, R.M., Bull.
Chem. Soc. Jpn., 1990, vol. 63, p. 652.
7. Ivanov, C. and Tcholakova, T., Synthesis, 1981, p. 392.
8. Eichinger, K., Nussbaumer, P., Balkan, S., and Schulz, G.,
Synthesis, 1987, p. 1061.
9. Lee, E., Hur, C.U., Rhee, Y.H., Park, Y.C., and Kim, S.Y.,
J. Chem. Soc., Chem. Commun., 1993, p. 1466.
10. Mitsudo, T., Naruse, H., Kondo, T., Ozaki, Y., and Watana-
be, Y., Angew. Chem., 1994, vol. 106, p. 595.
11. Haglund, O., Hai,A.A.K.M., and Nillson, M., Synthesis, 1990,
p. 942.
·
(65.0) [M – CH3]+, 314 (12.0) [M – CH3 – OH]+ , 297
·
(15.7), 286 (11.1), 285 (18.3) [M – NO2 – CH3]+ , 257
(10.7), 256 (11.9), 215 (10.5), 43 (15.2) [COCH3]+. Found,
%: C 72.65; H 5.34. C21H18N2O3. Calculated, %: C 72.82;
H 5.24. M 346.39.
(5'-Methylamino-2'-nitro-1,1':3'1''-terphenyl-4'-
yl)phenylmethanone (VIf) was obtained by heating for
15 min at 70°C followed by stirring at room temperature
for 2 h. Yield 52%, mp 180–181°C (from ethanol). IR
–1
spectrum, cm : 1360, 1520 (NO2), 1640 (CO), 3440
(NH). 1H NMR spectrum (CDCl3), d, ppm: 2.87 d (3H,
NHCH3, J 4.6 Hz), 5.39 br.s (1H, NHCH3), 6.65 s (1H,
H6'), 7.05–7.45 m (15Harom). Mass spectrum, m/z (Irel,
%): 409 (30.8), 408 (100) [M]+·, 407 (50.6) [M –H]+, 391
(12.7) [M–OH]+, 360 (10.9), 332 (10.0) [M–NO2 –
·
NHCH3]+ , 331 (24.8) [M–Ph]+, 105 (28.3) [COPh]+,
77 (30.3) [Ph]+. Found, %: C 76.23; H 4.87. C26H20N2O3.
Calculated, %: C 76.45; H 4.94. M 408.46.
12. Arumugam, N. and Kumaraswamy, A., Synthesis, 1981,
p. 367.
1-(5'-Hydroxy-2'-nitro-1,1':3'1''-terphenyl-4'-yl)-
13. Domer, F.R., Chihal, D.M., Charles, H.C., and Koch, R.C.,
J. Med. Chem., 1980, vol. 23, p. 541.
14. Markovas,A. and LaMontagne, M.P., J. Med. Chem., 1980,
vol. 23, p. 1198.
ethanone (IXe). Yield 8% (reaction time 6 h), mp 109–
111°C (from ethanol). IR spectrum, cm : 1370, 1530
–1
(NO2), 1640 (CO). 1H NMR spectrum (CDCl3), d, ppm:
1.76 s (3H, COCH3), 7.08 s (1H, H6'), 7.30–7.64 m
(10Harom), 12.24 s (1H, OH). Mass spectrum, m/z (Irel,
%): 334 (23.2), 333 (100) [M]+·, 316 (12.9) [M–OH]+,
15. Li,J.J.,Norton,M.B.,Reinhard,E.J.,Anderson,G.D.,Gre-
gory, S.A., Isakson, P.C., Koboldt, C.M., Masferrer, J.L.,
Perkins, W.E., Seibert, K., Zhang, Y., Zweifel, B.S., and
Reitz, D.B., J. Med. Chem., 1996, vol. 39, p. 1846.
16. Chavatte, P.,Yous, S. , Marot, C., Baurin, N., and Lesieur, D.,
J. Med. Chem., 2001, vol. 44, p. 3223.
17. Sagitullina, G.P., Glizdinskaya, L.V., Sitnikov, G.V., and
Sagitullin, R.S., Khim. Geterotsikl. Soedin., 2002, p. 1518.
18. Sagitullina, G.P., Glizdinskaya, L.V., Oleinikova, S.I., Ata-
vin, E.G., and Sagitullin, R.S., Zh. Org. Khim., 2005, vol. 41,
p. 1395.
·
301 (11.1) [M–OH–CH3]+ , 287 (16.0), 286 (63.6) [M–
·
OH–NO]+ , 284 (24.1), 274 (12.0), 271 (12.8), 268 (11.1),
244 (14.1), 239 (11.6), 216 (13.1), 215 (49.5), 213 (17.6),
202 (15.6), 189 (11.8), 77 (13.4) [Ph]+, 43 (69.7)
[COCH3]+. Found, %: C 71.98; H 4.68. C20H15NO4.
Calculated, %: C 72.06; H 4.54. M 333.34.
(5'-Hydroxy-2'-nitro-1,1':3'1''-terphenyl-4'-yl)-
phenylmethanone (IXf) was obtained by heating for
15 min at 70°C followed by stirring at room temperature
for 2 h. Yield 22%, mp 118–120°C (from ethanol). IR
19. Ciller, J.A., Seoane, C., Soto, J.L. and J. Heterocycl. Chem.,
1985, vol. 22, p. 1663.
–1
spectrum, cm : 1380, 1540 (NO2), 1650 (CO). 1H NMR
20. Knorr, L., Chem. Ber., 1892, vol. 25, p. 775.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006