1-Arylideneamino-2,2,2-trichloroethanols as synthetic equivalents of arylideneimines in the reaction with cyclopropenone derivatives

Article abstract of DOI:10.1007/s11172-011-0301-x

1-Arylideneamino-2,2,2-trichloroethanols react regiospecifically with cyclopropenones to form 2,2′-diaryl-1,1′,2,2′-tetrahydro- 3′,3′H-2,2′-bipyrrole-3,3′-diones. A new preparative method was developed for the synthesis of 1-arylideneamino-2,2,2- trichlor

Full text of DOI:10.1007/s11172-011-0301-x

Russian Chemical Bulletin, International Edition, Vol. 60, No. 10, pp. 1989—1994, October, 2011
1989
1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols as synthetic equivalents
of arylideneimines in the reaction with cyclopropenone derivatives
N. A. Lozinskaya, S. E. Sosonyuk, Yu. N. Firsova, M. V. Proskurnina, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 935 0290. Eꢀmail: natalylozinskaya@mail.ru
1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols react regiospecifically with cyclopropenones to
form 2,2´ꢀdiarylꢀ1,1´,2,2´ꢀtetrahydroꢀ3Н,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdiones. A new preparative
method was developed for the synthesis of 1ꢀarylideneaminoꢀ2,2,2ꢀtrichloroethanols.
Key words: 1ꢀarylideneaminoꢀ2,2,2ꢀtrichloroethanols, dihydropyrrolones, cyclopropenones,
oxidative dimerization.
A general strategy of our studies is the search for physꢀ
iologically active compounds containing two covalently
bonded pharmacophoric groups in the molecule ("twinꢀ
drugs"), in particular, for their synthesis from easily availꢀ
able bis(imines), viz., 1ꢀarylꢀN,N´ꢀbis(arylidene)methaneꢀ
diamines 1 (see Ref. 1). We have earlier shown2 that
bis(imines) 1 can be used as synthetic equivalents of
Nꢀunsubstituted arylideneimines in the reaction with
cyclopropenones (Scheme 1). The process is regioselecꢀ
tive and allows one to synthesize both dihydropyrrolones 2
and bis(1,2ꢀdihydropyrrolonyl)methanes 3 that form subꢀ
stituted 2,2´ꢀbis(dihydropyrrolones) 4 upon hydrolysis and
subsequent oxidative dimerization of intermediate 2ꢀarylꢀ
4,5ꢀdiphenylhydropyrrolꢀ3ꢀones (see Scheme 1).
tion total yields of bis(pyrrolones) 4 in two steps do not
exceed 40%. In this work we continued to search for
potent synthetic equivalents of arylideneimines. We asꢀ
sumed that 1ꢀarylideneaminoꢀ2,2,2ꢀtrichloroethanols 5,
which have first been prepared by Schiff4 in 1877, can
be used for our purpose. The synthesis of the latter
were repeatedly described5 in 1948 as a oneꢀstep process
from cheap chloral hydrate, ammonia, and benzaldehyde
(Scheme 2).
However, we have confirmed many times that the only
product formed under the described conditions is the adꢀ
duct of ammonia and benzaldehyde, PhCH(N=CHPh)2
(1a). The further study of the process made it possible to
modify it, and we showed that 1ꢀarylideneaminoꢀ2,2,2ꢀ
trichloroethanols 5 can be obtained by the exothermic
reaction in yields from 50 to 85% by passing dry ammonia
through a solution of aromatic aldehyde and chloral excess
At the same time, this reaction is not universal: the
starting compounds containing aryl groups with electronꢀ
withdrawing substituents are poorly available.3 In addiꢀ
Scheme 1
Ar = Ph (a), 4ꢀMeOC6H4 (b), 4ꢀMeC6H4 (c)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1955—1959, October, 2011.
1066ꢀ5285/11/6010ꢀ1989 © 2011 Springer Science+Business Media, Inc.

1990
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
Lozinskaya et al.
Scheme 2
first, which was, most likely, a mixture of several comꢀ
pounds, with unknown exact composition,6,7 and then
a twofold excess of this adduct was introduced into the
reaction with aromatic aldehyde in dichloromethane in
the presence of catalytic amounts of pꢀtoluenesulfonic
acid. This modification of the process makes it possible to
obtain nitro derivative 5d, from which poorly available
N,Nꢀbis(4ꢀnitrobenzylidene)methanediamine 1d can be
synthesized in turn. The latter is formed in 84% yield on
heating of compound 5d in benzene for 8.5 h (Scheme 4).
Compound 1d undergoes ring closure and is oxidized to
imidazole 6 by longer heating (18 h) under normal condiꢀ
tions. Since the melting points measured for compounds
1d and 6 did not coincide with the published values and
the literature data for these compounds are contradictory,
the formation of the corresponding product was confirmed
by elemental analysis in the both cases.
Ar = Ph (a), 4ꢀMeOC6H4 (b), 4ꢀMeC6H4 (c), 4ꢀO2NC6H4 (d),
2ꢀthienyl (e), 3ꢀpyridyl (f), 2,6ꢀCl C6H3 (g),
3,5ꢀdimethylꢀ1ꢀphenylꢀ1Нꢀpyrazolꢀ4ꢀyl (h)
2
(1.5—2 equiv.) in diethyl ether on cooling to –10 °С
(see Scheme 2).
The process can be catalyzed by anhydrous zinc chlorꢀ
ide, pꢀtoluenesulfonic acid, or ammonium chloride. In
the presence of catalyst, the major part of product 5 is
formed within several minutes; however, the highest yields
are achieved when the reaction is carried out for several
hours. The yield does not decrease substantially without a
catalyst; however, the reaction is retarded and completed
within ~20 h. Aromatic aldehydes with both electronꢀdoꢀ
nating and electronꢀwithdrawing substituents in the aroꢀ
matic ring can be involved in the process, which makes
the transformation rather general. The exception is
the reaction with 4ꢀnitrobenzaldehyde forming 2,4,5ꢀtrisꢀ
(4ꢀnitrophenyl)ꢀ1Hꢀimidazole (6) (Scheme 3). It is likely
that the reaction proceeds via formation of imine transꢀ
formed into 1ꢀ(4ꢀnitrophenyl)ꢀN,Nꢀbis(4ꢀnitrobenzylꢀ
idene)methanediamine (1d), which undergoes electrocyclic
ring closure to form cisꢀimidazoline. The latter is readily
oxidized with air oxygen to the corresponding imidazole 6
(see Scheme 3).
Scheme 4
Ar = 4ꢀO2NC6H4
We also showed that 1ꢀarylideneaminoꢀ2,2,2ꢀtriꢀ
chloroethanols 5 reacted with diphenylcyclopropenone
at room temperature in methanol to form 2,2´ꢀdiarylꢀ
4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀtetrahydroꢀ3Н,3´Hꢀ2,2´ꢀ
bipyrroleꢀ3,3´ꢀdiones (4a—f) (Scheme 5). In the case of
compounds 5g,h, a complicated mixture of nonꢀidentified
products was formed.
Scheme 3
Scheme 5
Ar = 4ꢀO2NC6H4
1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols 5 with both
electronꢀwithdrawing and electronꢀdonating groups were
synthesized in 38—95% yields using the modified Schiff
procedure.6 The process was accomplished in two particular
steps: the adduct of chloral with ammonia was obtained
Ar = Ph (a), 4ꢀMeOC6H4 (b), 4ꢀMeC6H4 (c), 4ꢀO2NC6H4 (d),
2ꢀthienyl (e), 3ꢀpyridyl (f)

1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
1991
The removal of the protective group followed by oxidaꢀ
tive dimerization occurs during the reaction (see Scheme 5).
The intermediate can be assumed to undergo the nucleoꢀ
philic attack by methanol with the elimination of
Cl3CCH(OMe)OH. This compound was detected in
aldehyde, and makes it possible to extend the scope of
aromatic aldehydes, including heteroaromatic aldehydes
and aldehydes containing electronꢀwithdrawing groups.
Experimental
1
the reaction mixture by Н NMR spectroscopy (two sinꢀ
glets at δH 3.61 and 4.86, integral intensity ratio 3 : 1).
Compounds 4a—c were synthesized and characterized
earlier.2,3
Nonsymmetric 3ꢀmethylꢀ2ꢀphenylcyclopropenone reꢀ
giospecifically reacts with 1ꢀarylideneaminoꢀ2,2,2ꢀtriꢀ
chloroethanols 5 to form only one isomer 7 (Scheme 6).
This fact is due apparently to the greater stability of the
intermediate with the phenylketene structure compared to
that with the methylketene structure.
1
Н NMR spectra were recorded on a Bruker Avanceꢀ400
instrument with a working frequency of 400.13 MHz for 1Н and
100.61 NHz for 13С. IR spectra were measured on a Carl Zeiss
URꢀ20 spectrophotometer in Nujol. Elemental analysis was carꢀ
ried out on a Carlo Erba automated analyzer. Melting points
were measured using an Electrothermal 9100 melting point indiꢀ
cator in a sealed capillary and uncorrected. Mass spectrometric
analyses were carried out on a Finnigan MATINCOSSO mass
spectrometer (EI, 70 eV, direct inlet).
1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols 5a—h (general proꢀ
cedure). A. Dry ammonia was passed through a solution of chloꢀ
ral, aromatic aldehyde, and catalytic amounts of pꢀtoluenesulfonꢀ
Scheme 6
–
–
ic acid in dry diethyl ether cooled to 20— 15 °С with vigorous
stirring maintaining the reaction temperature below 0 °С, after
which stirring continued at room temperature. The precipitate
formed was collected by filtration, and an additional portion of
the product was isolated from the mother liquor after evaporaꢀ
tion of the solvent and washing of the residue with a small amount
of diethyl ether. An analytically pure sample was obtained by
recrystallization from benzene.
B. Dry ammonia was passed through a solution of chloral
(19.6 g, 0.133 mol) in anhydrous chloroform (30 mL) with vigorꢀ
ous stirring at temperatures from –5 to –10 °С until the reaction
mixture solidified. A colorless amorphous product (13.2 g) was
separated by filtration and washed with diethyl ether. The obꢀ
tained material was dissolved in anhydrous dichloromethane and
aromatic aldehyde and catalytic amount of pꢀtoluenesulfonic
acid were added. The reaction mixture was stirred at room temꢀ
perature. The precipitate formed was separated by filtration. An
analytically pure sample was obtained by recrystallization from
benzene.
Ar = 4ꢀMeOC6H4 (b), 4ꢀO2NC6H4 (d)
The formation of 5ꢀmethylꢀ4ꢀphenylpyrrolone 7 rathꢀ
er than its regioisomer was proved for product 7b (Ar =
1ꢀ[(Е)ꢀBenzylideneamino]ꢀ2,2,2ꢀtrichloroethanol (5а). Comꢀ
pound 5а was synthesized by method А from chloral (1.66 g,
11.3 mmol) and benzaldehyde (1.8 g, 9.9 mmol) in anhydrous
diethyl ether (5 mL) within 18 h in a yield of 1.21 g (48%),
colorless crystals, m.p. 131—132 °С (benzene) (cf. Refs 6 and 7:
1
= 4ꢀMeOC6H4) by Н NMR spectroscopy using the nuꢀ
clear Overhauser effect. Additional irradiation was carried
out at the proton frequency δН 9.37 (NH moiety), which
induced proton responses at δН 2.11 (CH3, 7.5%) and 7.82
(HAr in the metaꢀposition to the МеO group, 6.3%), and
no response on the orthoꢀprotons of the phenyl group
(δН 6.91) was observed.
1
m.p. 130 °С (benzene)). H NMR (CDCl3), δ: 3.75 (br.s, 1 H,
ОН); 5.21 (s, 1 Н, О—СН—N=); 7.46—7.55 (m, 3 Н, НAr);
7.86 (d, 2 Н, НAr, J = 7.4 Hz); 8.59 (s, 1 Н, CH=N). 13C NMR
(DMSOꢀd6), δ: 93.61 (O—CH—N); 102.64 (quatern., CCl3);
129.59; 132.20; 132.35; 134.25 (quatern.); 159.58 (C=N). IR,
ν/cm–1: 1580; 1605; 1640 (С=N); 2600—3400 (bonded, ОН).
Compound 5a was synthesized by method B from the adduct
of chloral with ammonia (5.08 g) and benzaldehyde (2.10 g,
19.8 mmol) in anhydrous dichloromethane (3 mL) within 15 h in
a yield of 2.78 g (56%).
The dimeric structure of compounds 7 is indicated
by the absence of a signal of the proton in position 2 of
1
the pyrrole ring in the Н NMR spectra (for 7b) and the
presence of peaks corresponding to decomposition with
1,5ꢀmigration of the hydrogen atom in the mass spectrum
(m/z 279, 277 for 7b and m/z 294, 292 for 7d), as well as
the elemental analysis data (in the corresponding monoꢀ
meric products the hydrogen content would be higher).
This method of synthesis of 2,2´ꢀdiarylꢀ4,4´,5,5´ꢀtetraꢀ
phenylꢀ1,1´,2,2´ꢀtetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀ
diones 4 have several advantages over both the earlier proꢀ
posed method2 and the synthesis of the latter from azines8:
the process is oneꢀstep, occurs without losses of aromatic
1ꢀ[(Е)ꢀ(4ꢀMethoxybenzylidene)amino]ꢀ2,2,2ꢀtrichloroethaꢀ
nol (5b). Compound 5b was synthesized by method А from chloꢀ
ral (8.46 g, 57.9 mmol) and 4ꢀmethoxybenzaldehyde (4.48 g,
33.2 mmol) in anhydrous diethyl ether (10 mL) within 23 h in
a yield of 6.64 g (72%); colorless crystals, m.p. 140—141 °С
1
(cf. Ref. 7: m.p. 141—142 °С (benzene)). H NMR (СDCl3), δ:
3.87 (s, 3 H, ОСН3); 4.17 (br.s, 1 H, ОН); 5.15 (s, 1 Н,
О—СН—N=); 6.96 (d, 2 Н, НAr, J = 8.6 Hz); 7.81 (d, 2 Н, НAr
,

1992
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
Lozinskaya et al.
J = 8.6 Hz); 8.49 (s, 1 Н, CH=N). 13C NMR (DMSOꢀd6),
δ: 55.86 (CH3O); 94.82 (N—CH—O); 103.72 (quatern.,
CCl3); 114.71; 128.45 (quatern.); 130.99; 162.55 (quatern.);
163.13 (C=N). IR, ν/cm–1: 1610; 1640 (С=N); 2800—3280
(bonded, ОН).
Compound 5b was synthesized by method B from the adduct
of chloral with ammonia (2.75 g) and 4ꢀmethoxybenzaldehyde
(1.12 g, 8.3 mmol) in anhydrous dichloromethane (3 mL) within
23 h in a yield of 2.04 g (88%).
1ꢀ[(Е)ꢀ(4ꢀMethylbenzylidene)amino]ꢀ2,2,2ꢀtrichloroethanol
(5c). Compound 5c was synthesized by method А from chloral
(2.43 g, 16.4 mmol) and 4ꢀmethylbenzaldehyde (1.8 g, 15.0 mmol)
in anhydrous diethyl ether (5 mL) within 2 h in a yield of 2.57 g
(64%); colorless crystals, m.p. 143—144 °С (cf. Ref. 5: m.p.
144—145 °С (benzene)). 1H NMR (СDCl3), δ: 2.40 (s, 3 H, СН3);
5.10 (br.s, 1 H, ОН); 5.25 (s, 1 Н, О—СН—N=); 7.24 (d, 2 Н,
НAr, J = 7.8 Hz); 7.73 (d, 2 Н, НAr, J = 7.8 Hz); 8.55 (s, 1 Н,
CH=N). 13С NMR (CDCl3—DMSOꢀd6), δ: 21.47 (CH3); 95.05
(N—CH—O); 102.74 (quatern., CCl3); 128.92; 129.26; 132.62
(quatern.); 142.01 (quatern.); 163.44 (C=N). IR, ν/cm–1: 1580;
1610; 1640 (С=N); 2800—3300 (bonded, ОН).
J = 7.6 Hz, J = 4.8 Hz); 8.14 (dt, 1 Н, НAr, J = 7.8 Hz,
J = 1.8 Hz); 8.60 (dd, 1 Н, НAr, J = 4.8 Hz, J = 1.8 Hz); 8.64
(d, 1 Н, НAr, J = 1.8 Hz); 8.89 (s, 1 Н, CH=N). 13С NMR
(DMSOꢀd6), δ: 93.86 (O—CH—N); 103.20 (quatern., CCl3);
124.58; 131.17 (quatern.); 135.62; 150.82; 152.78; 161.30 (C=N).
IR, ν/cm–1: 1600; 1645 (С=N); 2400—3250 (bonded, ОН).
Compound 5f was synthesized by method А from chloral
(3.93 g, 26.7 mmol) and 3ꢀpyridinecarboxaldehyde (2.85 g,
26.6 mmol) in anhydrous diethyl ether (10 mL) within 15 h in
a yield of 5.72 g (85%).
1ꢀ[(2,6ꢀDichlorobenzylidene)amino]ꢀ2,2,2ꢀtrichloroethanol
(5g) was synthesized by method А from chloral (4.38 g, 30.0 mmol)
and 2,6ꢀdichlorobenzaldehyde (2.69 g, 15.0 mmol) in anhydrous
diethyl ether (10 mL) within 16 h in a yield of 3.57 g (72%);
colorless crystals, m.p. 134—136 °С. Found (%): С, 33.84;
Н, 2.03; N, 4.28. C9H6Cl5NО. Calculated (%): С, 33.63; Н, 1.88;
N, 4.36. 1H NMR (СDCl3), δ: 3.94 (br.s, 1 H, ОН); 5.41 (s, 1 Н,
О—СН—N=); 7.20—7.24 (m, 1 Н, НAr); 7.28—7.31 (m, 2 Н,
НAr); 8.87 (s, 1 Н, CH=N). 13С NMR (DMSOꢀd6), δ:
95.63 (N—CH—O); 102.64 (quatern., CCl3); 129.57; 129.83;
128.45; 129.83 (quatern.); 132.32; 132.48 (quatern.); 134.26;
159.57 (C=N). IR, ν/cm–1: 1585, 1660 (С=N), 2600—3400
(bonded, ОН).
1ꢀ[(Е)ꢀ(4ꢀNitrobenzylidene)amino]ꢀ2,2,2ꢀtrichloroethanol
(5d). Compound 5d was synthesized by method B from the adꢀ
duct of chloral with ammonia (6.51 g) and 4ꢀnitrobenzaldehyde
(3.0 g, 19.9 mmol) in anhydrous dichloromethane (16 mL) withꢀ
in 2 h in a yield of 4.0 g (68%); light yellow crystals, m.p.
124—127 °С (cf. Ref. 5: m.p. 123.5—124 °С (benzene)). 1H NMR
(СDCl3), δ: 3.85 (br.s, 1 H, ОН); 5.41 (s, 1 Н, О—СН—N=);
8.04 (d, 2 Н, НAr, J = 8.6 Hz); 8.32 (d, 2 Н, НAr, J = 8.6 Hz);
8.72 (s, 1 Н, CH=N). 13С NMR (DMSOꢀd6—CDCl3), δ: 93.18
(O—CH—N); 102.06 (quatern., CCl3); 123.48; 129.44; 140.59
1ꢀ[(3,5ꢀDimethylꢀ1ꢀphenylꢀ1Нꢀpyrazolꢀ4ꢀyl)methylideneꢀ
amino]ꢀ2,2,2ꢀtrichloroethanol (5h) was synthesized by method А
from chloral (0.81 g, 10.3 mmol) and 3,5ꢀdimethylꢀ1ꢀphenylꢀ
1Нꢀpyrazoleꢀ4ꢀcarboxaldehyde (1.01 g, 5.04 mmol) in anhydrous
benzene (12 mL) in the presence of a catalytic amount of
pꢀtoluenesulfonic acid within 21 h in a yield of 1.35 g (78%);
colorless crystals, m.p. 159—162 °С. Found (%): С, 48.40;
Н, 4.14; N, 12.23. C14H14Cl3N3О. Calculated (%): С, 48.51;
Н, 4.07; N, 12.12. 1H NMR (СDCl3), δ: 2.49 (s, 3 H, СН3); 2.52
(s, 3 H, СН3); 3.69 (br.s, 1 H, ОН); 5.07 (s, 1 Н, О—СН—N=);
7.41—7.44 (m, 3 Н, НAr); 7.50 (m, 2 Н, НAr); 8.57 (s, 1 Н,
CH=N). 13С NMR (DMSOꢀd6), δ: 11.60 (CH3); 13.43 (CH3);
95.29 (N—CH—O); 104.12 (quatern., CCl3); 115.67 (quatern.);
125.36, 128.45; 129.86; 139.11 (quatern.); 142.23 (quatern.);
149.73 (quatern.); 159.80 (C=N). IR, ν/cm–1: 1500, 1600,
1640 (С=N), 2800—3300 (bonded, ОН). MS, m/z (Irel (%)):
(quatern.); 149.00 (quatern.); 160.36 (C=N). IR, ν/cm–1
:
1350 (symm., NO2); 1525 (asymm., NO2); 1600; 1645 (С=N);
2800—3300 (bonded, ОН).
An attempt to prepare compound 5d by method A gave
2,4,5ꢀtris(4ꢀnitrophenyl)ꢀ4Нꢀimidazole (6) (see below).
1ꢀ[(Thiophenꢀ2ꢀyl)methylideneamino]ꢀ2,2,2ꢀtrichloroethanol
(5e) was synthesized by method A from chloral (7.87 g, 53.9 mmol)
and 2ꢀthiophenecarboxaldehyde (3.03 g, 27.0 mmol) in anꢀ
hydrous diethyl ether (10 mL) within 21 h in a yield of 3.37 g
(48%); colorless crystals, m.p. 139—140.5 °С. Found (%):
С, 32.53; Н, 2.25; N, 5.35. C7H6Cl3NОS. Calculated (%):
С, 32.52; Н, 2.34; N, 5.42. 1H NMR (DMSOꢀd6), δ: 5.28 (s, 1 Н,
О—СН—N=); 7.06 (dd, 1 Н, НAr, J = 5.1 Hz, J = 3.5 Hz); 7.32
(br.s, 1 H, ОН); 7.44 (d, 1 Н, НAr, J = 3.5 Hz); 7.49 (d, 1 Н,
НAr, J = 4.8 Hz); 8.67 (s, 1 Н, CH=N). 13С NMR (DMSOꢀd6),
δ: 99.89 (N—CH—O); 103.39 (quatern., CCl3); 128.60; 131.84;
134.37; 141.78 (quatern.); 157.14 (C=N). IR, ν/cm–1: 1630
(С=N); 2600—3280 (bonded, ОН).
228 [M – CCl3]+ (30), 198 [M – СCl3СHOH]+ (100), 77
•
•
[C6H5]+ (33).
•
Reaction of 1ꢀarylideneaminoꢀ2,2,2ꢀtrichloroethanols with
cyclopropenone derivatives (general procedure). A solution of
2,3ꢀdiphenylcyclopropenone or 2ꢀmethylꢀ3ꢀphenylcyclopropenꢀ
one and 1ꢀarylideneaminoꢀ2,2,2ꢀtrichloroethanol 5a—f in anꢀ
hydrous methanol was stirred at room temperature. In some
cases, catalysis with anhydrous NH4OAc was added. The precipiꢀ
tate formed was separated by filtration and washed with diethyl
ether. An analytically pure sample was obtained by recrystallizaꢀ
tion from xylene.
2,2´,4,4´,5,5´ꢀHexaphenylꢀ1,1´,2,2´ꢀtetrahydroꢀ3H,3´Hꢀ
2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4а) was synthesized from 2,3ꢀdiꢀ
phenylcyclopropenone (208 mg, 1.0 mmol) and compound 5a
(224 mg, 0.89 mmol) in a yield of 118 mg (43%); light yellow
crystals, m.p. 274—276 °С (decomp.) (cf. Ref. 2: m.p. 275—277 °С
(decomp., xylene) and Ref. 8: 279—284 °С (sublim., DMF)).
2,2´ꢀBis(4ꢀmethoxyphenyl)ꢀ4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀ
tetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4b) was syntheꢀ
sized from 2,3ꢀdiphenylcyclopropenone (300 mg, 1.46 mmol)
and compound 5b (376 mg, 1.33 mmol) in anhydrous methaꢀ
nol (5 mL) in the presence of anhydrous NH4OAc (100 mg,
Compound 5e was synthesized by method B from the adduct
of chloral with ammonia (30 g) and 2ꢀthiophenecarboxaldehyde
(8.52 g, 76.1 mmol) in anhydrous dichloromethane (22 mL)
within 45 h in a yield of 17.8 g (90%).
1ꢀ[(Pyridinꢀ3ꢀyl)methylideneamino]ꢀ2,2,2ꢀtrichloroethanol
(5f) was synthesized by method B from the adduct of chloral with
ammonia (4.09 g) and 3ꢀpyridinecarboxaldehyde (1.71 g, 16.0
mmol) in anhydrous dichloromethane (3 mL) within 16 h in
a yield of 3.83 g (95%); colorless crystals, m.p. 120—122.5 °С.
Found (%): С, 38.07; Н, 2.89; N, 11.11. C8H7Cl3N2О. Calcuꢀ
1
lated (%): С, 37.90; Н, 2.78; N, 11.05. H NMR (DMSOꢀd6—
СDCl3), δ: 5.41 (s, 1 Н, О—СН—N=); 7.32 (dd, 1 Н, НAr
,

1ꢀArylideneaminoꢀ2,2,2ꢀtrichloroethanols
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
1993
1.3 mmol) in a yield of 340 mg (75%); light yellow crystals, m.p.
278—282 °С (decomp.) (cf. Ref. 2: m.p. 278—281 °С (decomp.,
xylene) and Ref. 8: m.p. 282—285 °С (benzene)). The spectral
data correspond to the published2 values.
2,2´ꢀBis(4ꢀmethylphenyl)ꢀ4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀ
tetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4c) was syntheꢀ
sized from 2,3ꢀdiphenylcyclopropenone (208 mg, 1.0 mmol) and
compound 5c (271 mg, 1.0 mmol) in anhydrous methanol
(5 mL) in the presence of anhydrous NH4OAc (203 mg, 2.6 mmol)
within 21 h in a yield of 212 mg (65%); light yellow crystals, m.p.
260—261 °С (decomp.) (cf. Ref. 2: m.p. 260—262 °С (decomp.,
xylene) and Ref. 8: m.p. 269—271 °С (benzene)). The spectral
data correspond to the published2 values.
2,2´ꢀBis(4ꢀnitrophenyl)ꢀ4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀ
tetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4d) was syntheꢀ
sized from 2,3ꢀdiphenylcyclopropenone (205 mg, 1.0 mmol) and
compound 5d (267 mg, 0.90 mmol) in anhydrous methanol
(4 mL) within 5 days in a yield of 75 mg (23%); light orange
crystals, m.p. 274—278 °С (decomp.). Found (%): С, 74.24;
Н, 4.28; N, 7.90. C44H30N4О6. Calculated (%): С, 74.36; Н, 4.25;
N, 7.88. IR, ν/cm–1: 1355 (symm., NO2); 1540 (asymm., NO2);
1585; 1610; 1645 (С=О); 3140—3400 (bonded, ОН). 1H and
13C NMR spectra were not recorded because of low solubility of
264 [C17H14NO2]+ (45), 116 [C6H5С≡СCH3]+ (100). 1H NMR
(DMSOꢀd6—СDCl3), δ: 2.01 (s, 6 H, CH3); 3.66 (s, 6 H, ОMe);
6.70 (d, 4 Н, НAr, J = 8.8 Hz); 6.91 (d, 4 Н, НPh, J = 7.3 Hz);
7.04 (t, 2 Н, НPh, J = 7.6 Hz); 7.16 (t, 4 Н, НPh, J = 7.4 Hz);
7.79 (d, 4 Н, НAr, J = 8.8 Hz); 8.43 (s, 2 Н, NH). 1H NMR NOE
(DMSOꢀd6—СDCl3), additional irradiation at the proton freꢀ
quency δ 9.37 (NH) δ: 2.11 (CH3, 7.5%); 7.82 (HArꢀmeta to
МеO group, 6.3%). IR, ν/cm–1: 1610; 1640 (С=О), 3150—3400
(bonded, ОН).
5,5´ꢀDimethylꢀ2,2´ꢀbis(4ꢀnitrophenyl)ꢀ4,4´ꢀdiphenylꢀ
1,1´,2,2´ꢀtetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (7d)
was synthesized from 2ꢀmethylꢀ3ꢀphenylcyclopropenone (287 mg,
2.0 mmol) and compound 5d (594 mg, 2.0 mmol) in anhydrous
methanol (3 mL) within 5 days in a yield of 247 mg (42%);
yellowishꢀorange crystals, m.p. 284—285 °C (decomp., from
xylene). Found (%): С, 69.50; Н, 4.53; N, 9.56. C34H26N4О6.
Calculated (%): С, 69.62; Н, 4.47; N, 9.55. MS, m/z (Irel (%)):
294 [C17H14N2O3]+ (60), 292 [C17H12N2O3]+ (17), 116
[C6H5С≡СCH3]+ (100). IR, ν/cm–1: 1360 (symm., NO2); 1470;
1550 (asymm., NO2); 1610; 1640 (C=O), 3000—3400 (bonded,
ОН). 1H and 13C NMR spectra were not recorded because of low
solubility of the substance in CDCl3, DMSOꢀd6, and HMPAꢀd18
.
N,N´ꢀBis(4ꢀnitrobenzylidene)ꢀ1ꢀ(4ꢀnitrophenyl)methaneꢀ
diamine (1d). A solution of compound 5d (228 mg, 0.77 mmol) in
anhydrous benzene (10 mL) was refluxed for 8.5 h with stirring,
the solvent was removed, and the residue was suspended in diꢀ
ethyl ether and filtered off. Compound 1d was obtained in a yield
of 92 mg (84%); bright yellow crystals, m.p. 148—151 °С (decomp.,
from benzene) (cf. Ref. 5: m.p. 154 °С (benzene), Ref. 9: m.p.
140 °С (acetonitrile), and Ref. 10: m.p. 75 °С (aqueous methanol)).
Found (%): С, 58.92; Н, 3.34; N, 16.49. C21H15N5О6. Calculatꢀ
ed (%): С, 58.20; Н, 3.49; N, 16.16. 1H NMR (СDCl3), δ: 6.19
(s, 1 H, N—CH—N); 7.72 (d, 2 Н, НAr, J = 8.6 Hz); 8.05 (d, 4 Н,
НAr, J = 8.6 Hz); 8.29 (d, 2 Н, НAr, J = 8.6 Hz); 8.33 (d, 4 Н,
НAr, J = 8.6 Hz); 8.69 (s, 2 Н, N=CH). IR, ν/cm–1: 1360 (symm.,
NO2); 1525 (asymm., NO2); 1605 (С—CАr); 1645 (С=N).
2,4,5ꢀTris(4ꢀnitrophenyl)ꢀ1Hꢀimidazole (6). Dry ammonia
was passed through a solution of chloral (3.78 g, 25.7 mmol),
4ꢀnitrobenzaldehyde (4.0 g, 26.5 mmol), and catalytic amount
of pꢀtoluenesulfonic acid in anhydrous diethyl ether (18 mL)
the substance in CDCl3, DMSOꢀd6, and HMPAꢀd18
.
2,2´ꢀBis(thiophenꢀ2ꢀyl)ꢀ4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀ
tetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4e) was syntheꢀ
sized from 2,3ꢀdiphenylcyclopropenone (204 mg, 0.99 mmol)
and compound 5e (230 mg, 0.89 mmol) in anhydrous methanol
(4 mL) within 5 days in a yield of 174 mg (61%); light yellow
crystals, m.p. 212—217 °С (decomp.). Found (%): С, 75.80;
Н, 4.58; N, 4.32. C40H28N2О2S2. Calculated (%): С, 75.92;
Н, 4.46; N, 4.43. IR, ν/cm–1: 1530; 1550; 1585; 1610; 1650
1
(С=О); 3130—3380 (bonded, ОН). H and 13C NMR were not
recorded because of low solubility of the substance in CDCl3,
DMSOꢀd6, and HMPAꢀd18. Compound 4e was also obtained in
a yield of 39% (124 mg) from 2,3ꢀdiphenylcyclopropenone
(208 mg, 1.0 mmol) and compound 5e (263 mg, 1.0 mmol) in
anhydrous MeOH (5 mL) in the presence of anhydrous NH4OAc
(174 mg, 2.3 mmol) within 2 h.
2,2´ꢀBis(pyridinꢀ3ꢀyl)ꢀ4,4´,5,5´ꢀtetraphenylꢀ1,1´,2,2´ꢀtetraꢀ
hydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (4f) was synthesized
from 2,3ꢀdiphenylcyclopropenone (207 mg, 1.0 mmol) and comꢀ
pound 5f (226 mg, 0.89 mmol) in anhydrous methanol (4 mL)
within 7 days in a yield of 75 mg (27%); light yellow crystals,
m.p. 255—258 °С (decomp.). Found (%): С, 80.98; Н, 4.90;
N, 8.90. C42H30N4О2. Calculated (%): С, 81.01; Н, 4.86;
N, 9.00. IR, ν/cm–1: 1520; 1545; 1585; 1610; 1645 (С=О);
–
–
cooled to 20— 15 °С with vigorous stirring maintaining the
reaction temperature below 0 °С, after which the mixture was
stirred for 90 h at room temperature. A precipitate that formed
was separated by filtration, and an additional portion of the prodꢀ
uct was isolated from the mother liquor after evaporation of the
solvent and washing the residue with a small amount of diethyl
ether. An analytically pure sample was obtained by recrystallization
from chloroform. Compound 6 was obtained in a yield of 2.44 g
(32%); yellow crystals, m.p. 204—205 °С (CHCl3) (cf. Ref. 11:
m.p. 321—323 °С (aqueous pyridine) and Ref. 12: m.p. 331—334 °С
(aqueous pyridine)). Found (%): С, 58.43; Н, 2.85; N, 16.20.
C34H26N4О6. Calculated (%): С, 58.47; Н, 3.04; N, 16.24.
1
3110—3400 (bonded, ОН). H and 13C NMR spectra were not
recorded because of low solubility of the substance in CDCl3,
DMSOꢀd6, and HMPAꢀd18
.
2,2´ꢀBis(4ꢀmethoxyphenyl)ꢀ5,5´ꢀdimethylꢀ4,4´ꢀdiphenylꢀ
1,1´,2,2´ꢀtetrahydroꢀ3H,3´Hꢀ2,2´ꢀbipyrroleꢀ3,3´ꢀdione (7b)
was synthesized from 2ꢀmethylꢀ3ꢀphenylcyclopropenone (144
mg, 1.0 mmol) and compound 5b (281 mg, 1.0 mmol) in anꢀ
hydrous methanol (4 mL) in the presence of anhydrous NH4OAc
(105 mg, 1.4 mmol) within 19 h in a yield of 84 mg (33%); light
yellow crystals, m.p. 264—266 °C (decomp.). An analytically
pure sample was washed with DMF and then with acetonitrile
and diethyl ether. Found (%): С, 77.33; Н, 5.62; N, 5.18.
C36H32N2О4. Calculated (%): С, 77.68; Н, 5.79; N, 5.03. MS,
m/z (Irel (%)): 279 [C18H17NO2]+ (81), 277 [C18H15NO2]+ (41),
1H NMR (СDCl3), δ: 5.78 (br.s, 1 Н, NH); 7.20 (d, 4 Н, НAr
J = 8.6 Hz); 7.97 (d, 4 Н, НAr, J = 8.7 Hz); 8.20 (d, 2 Н, НAr
,
,
J = 9.1 Hz); 8.41 (d, 2 Н, НAr, J = 9.1 Hz). IR, ν/cm–1: 1530
(С—CАr); 1605 (С—CАr); 3420 (NH). MS, m/z (Irel (%)): 431
[M]+ (5.5), 283 [M – O2NC6H4C≡N]+ (14), 102 [C6H4CN]+
(41), 76 [C6H4]+ (100), 63 (91), 51 (94), 39 (65).
Product 6 is also formed by refluxing of compound 5d
(1.00 g, 3.4 mmol) in benzene within 18 h in a yield of 61%
(330 mg).

1994
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 10, October, 2011
Lozinskaya et al.
6. R. Schiff, Chem. Ber., 1878, 11, 2166.
7. O. Aschan, Chem. Ber., 1915, 48, 874.
References
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mennyi organicheskii sintez [Modern Organic Synthesis],
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Received July 1, 2011