Diaminomethylidene derivatives of β-oxo sulfones as potential reagents in heterocyclic synthesis and chelating ligands

Article abstract of DOI:10.1007/s11172-010-0337-3

Active methylene β-oxo sulfones add to the C≡N bond of benzoylcyanamide in the presence of catalytic amounts of Ni(acac)₂. Debenzoylation of the reaction products under the action of MeONa in MeOH gives N,N′-unsubstituted diaminomethylidene derivatives of β-oxo sulfones (acyl(R-sulfonyl)ketene aminals), which can be used as reagents for heterocyclic synthesis and as chelating ligands. The syntheses of 2-amino-3- arylsulfonylpyridin-4(1H)-ones and 5-sulfonylcytosine derivatives are presented as examples.

Full text of DOI:10.1007/s11172-010-0337-3

Russian Chemical Bulletin, International Edition, Vol. 59, No. 10, pp. 1937—1945, October, 2010
1937
Diaminomethylidene derivatives of βꢀoxo sulfones as potential reagents
in heterocyclic synthesis and chelating ligands
V. A. Voronkova, S. V. Baranin, M. A. Prezent, L. S. Vasil´ev, and V. A. Dorokhov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: vador@ioc.ac.ru
Active methylene βꢀoxo sulfones add to the C≡N bond of benzoylcyanamide in the presꢀ
ence of catalytic amounts of Ni(acac)2. Debenzoylation of the reaction products under the
action of MeONa in MeOH gives N,N´ꢀunsubstituted diaminomethylidene derivatives of βꢀoxo
sulfones (acyl(Rꢀsulfonyl)ketene aminals), which can be used as reagents for heterocyclic
synthesis and as chelating ligands. The syntheses of 2ꢀaminoꢀ3ꢀarylsulfonylpyridinꢀ4(1H)ꢀones
and 5ꢀsulfonylcytosine derivatives are presented as examples.
Key words: βꢀoxo sulfones, benzoylcyanamide, nickel acetylacetonate, catalysis, diaminoꢀ
methylidene derivatives of βꢀoxo sulfones, 5ꢀsulfonylcytosines, diphenylboron chelates,
2ꢀaminoꢀ3ꢀarylsulfonylpyridinꢀ4(1H)ꢀones, intramolecular cyclization.
Scheme 1
We found two decades ago that active methylene
βꢀdiketones and βꢀoxo esters add to the C≡N bond of
cyanamides in the presence of catalytic or stoichiometric
amounts of Ni(acac)2 or Ni(OAc)2 to give α,αꢀdioxo
ketene aminals,1—5 which were used in various schemes of
designing nitrogenꢀcontaining heterocyclic systems and
in the synthesis of B and Ni chelate complexes.6—11
As reported in our latest communications,12,13 ketene
aminals with two unsubstituted NH2 groups are most effiꢀ
cient in heterocyclization reactions, probably because of
both electronic and steric effects. Such reagents can conꢀ
veniently be prepared by debenzoylation of adducts of apꢀ
propriate βꢀdicarbonyl compounds (including barbituric
acid14) and benzoylcyanamide.
To obtain new diaminomethylidene reagents combinꢀ
ing acyl and sulfonyl functions, we studied reactions of
βꢀoxo sulfones 1a—g with benzoylcyanamide. It turned
out that these reactions in boiling dioxane in the presence
of Ni(acac)2 give Nꢀbenzoyl ketene aminals 2a—g in modꢀ
erate yields, which are easily converted into N,N´ꢀunsubꢀ
stituted diaminomethylidene derivatives of oxo sulfones
3a—g upon treatment with MeONa in MeOH (Scheme 1).
It has been proved that the catalytic cycle in addition
reactions of cyanamides with acyclic βꢀdiketones and
βꢀoxo esters involves the formation of nickel chelates with
βꢀdicarbonyl compounds;7 however, we detected no cheꢀ
late intermediates in reaction mixtures of oxo sulfones and
benzoylcyanamide.
R1
Ph
Ph
Ph
Ph
R2
Ph
R1
e
f
R2
Me
Me
Me
a
b
c
d
Ph
4ꢀMeC6H4
4ꢀMeOC6H4
Me
4ꢀMeC6H4
4ꢀMeOC6H4
g
Reagents and conditions: i. 10 mol.% Ni(acac)2, dioxane, Δ;
ii. MeONa, MeOH, 20 °C.
amounts of Ni(OAc)2 (apparently, the reaction involves
nickel derivatives of the enolized diketone). One could
assume that oxo sulfones would behave alike. However,
our attempts to promote the reactions of compounds 1a—g
with benzoylcyanamide using Ni(OAc)2 failed. That is why
the catalytic effect of Ni(acac)2 in the synthesis of aminals
2 is rather difficult to explain. One can only assume that
compounds 1 can produce enol intermediates that add to
Nevertheless, cyclic βꢀdiketones, which cannot act as
chelating ligands, have been found2,14 to efficiently add to
the C≡N bond of cyanamides in the presence of equimolar
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1887—1895, October, 2010.
1066ꢀ5285/10/5910ꢀ1937 © 2010 Springer Science+Business Media, Inc.

1938
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
Voronkova et al.
Scheme 2
Scheme 3
benzoylcyanamide as illustrated in Scheme 2. Such metal
enolates are believed to form, e.g., in the alcoholysis of
metal βꢀdiketonates.15
Apparently, the formation of Ni enolates from Ni(OAc)2
is prevented by the liberation of AcOH.
Ketene aminals 2 and 3 are colorless crystalline solids
that are well soluble in acetone, DMSO, and DMF but are
insoluble in hexane. Compounds 2 are well soluble in
chloroform and moderately soluble in alcohols, while amꢀ
inals 3 are poorly soluble in chloroform and well soluble in
alcohols. Their mass spectra (EI) contain very weak moꢀ
lecular ion peaks and the intense peaks [M – SO2]+. The
IR (KBr) and 1H NMR spectra (CDCl3, DMSOꢀd6) fully
agree with structures 2 and 3.
Like previously described Nꢀbenzoyl and Nꢀarylureido
derivatives of acyl(alkoxycarbonyl)ketene aminals 4 and
5, compounds 2 relate to pushꢀpull systems with very low
barriers to rotation about the C=C bond (see the reꢀ
1
views16,17). Their H NMR spectra in DMSOꢀd6 show
one set of signals. In neutral solvents, however, the rotaꢀ
tion is hindered by intramolecular hydrogen bonding
R1 = Alk, Ar; R2 = Alk; R3 = Ph (4), ArNH (5)
...
(N—H O bonds) and the spectra of compounds 4 and 5
in CDCl3 indicate the presence of the Eꢀ and Zꢀisomers in
dynamic equilibrium13 (Scheme 3).
tuted ketene aminals 3 make compounds of the types 2
and 3 sufficiently promising reagents for heterocyclic synꢀ
thesis and sulfonylꢀcontaining chelating ligands.
This can be illustrated with the synthesis of 5ꢀsulfonylꢀ
cytosines from ketene aminals 3. Like 2ꢀ(diaminomethylꢀ
idene)ꢀ3ꢀoxoalkanoic acid esters,13 βꢀoxo sulfones 3e,f reꢀ
act with phenyl isocyanate to give the corresponding ureas
6a,b, which undergo cyclization in the presence of sodium
methoxide into 4ꢀaminoꢀ5ꢀarylsulfonylꢀ6ꢀmethylꢀ1ꢀphenylꢀ
pyrimidinꢀ2(1H)ꢀones 7a,b (Scheme 4).
A similar pattern is observed in the spectra of sulfonyl
ketene aminals (the ratio of the isomers is ~3.5 : 1). As
with compounds 4 and 5 (for our arguments, see Ref. 13),
the lowestꢀfield signal for the NH proton at δ ~15.3—15.7
should be assigned to the dominant Eꢀisomer (for the miꢀ
nor Zꢀisomer, the lowestꢀfield signal for the NH proton
appears at δ 12.4—12.7).
Compounds 2a—g and 3a—g are stable in air and reꢀ
main unchanged when stored. Despite the low yields of
Nꢀbenzoylaminals 2 (Table 1), their straightforward synꢀ
thesis and smooth debenzoylation leading to Nꢀunsubstiꢀ
When slightly heated, crystalline ureas 6a,b are soluble
in DMSO and DMF but remain insoluble in chloroform.

Diaminomethylidene derivatives of βꢀoxo sulfones
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
1939
Table 1. Yields, melting points, elemental analysis data, and IR spectra of compounds 2a—g and 3a—g
Comꢀ
pound
Yield
(%)
M.p./°C
Found
Calculated
Molecular
formula
IR (KBr),a
ν/cm–1
(%)
C
H
N
S
2ab
2bc
2cc
2dc
2eb
2fb
2gb
3ad
3b
36
42
39
38
20
20
24
84
72
77
91
77
96
44
187—188
240—241
212—213
232—233
147—148
134—135
153—154
127—128
208—209
217—218
183—184
155—156
163—164
157—158
64.59
65.01
65.73
65.70
62.99
63.29
59.02
59.29
59.54
59.29
60.31
60.32
57.75
57.74
59.23
59.59
60.40
60.74
57.65
57.82
50.20
49.99
50.22
49.99
52.34
51.95
49.03
48.88
4.53
4.46
4.77
4.79
4.64
4.62
4.71
4.68
4.69
4.68
5.00
5.06
4.93
4.85
4.74
4.67
5.11
5.10
4.72
4.85
4.96
5.03
4.96
5.03
5.42
5.55
5.13
5.22
6.94
6.89
6.52
6.66
6.63
6.42
8.30
8.13
8.13
8.13
7.71
7.82
7.51
7.48
8.96
9.27
8.77
8.85
8.50
8.43
11.80
11.66
11.85
11.66
11.20
11.02
10.40
10.36
7.82
7.89
7.60
7.63
7.34
7.35
9.25
9.31
9.34
9.31
9.00
8.95
8.82
C22H18N2O4S
C23H20N2O4S
C23H20N2O5S
C17H16N2O4S
C17H16N2O4S
C18H18N2O4S
C18H18N2O5S
C15H14N2O3S
C16H16N2O3S
C16H16N2O4S
C10H12N2O3S
C10H12N2O3S
C11H14N2O3S
C11H14N2O4S
3352, 3236, 1676, 1632, 1600, 1580,
1556, 1328, 1284, 1136
3368, 3248, 1680, 1620, 1600, 1580,
1552, 1320, 1284, 1132
3368, 3252, 1676, 1624, 1600, 1576,
1552, 1496, 1332, 1284, 1136
3384, 3264, 1680, 1624, 1600, 1580,
1544, 1348, 1280, 1128
3408, 3284, 1676, 1612, 1600, 1576,
1556, 1364, 1300, 1128
3384, 3260, 1676, 1616, 1600, 1580,
1560, 1496, 1364, 1300, 1132
3384, 3260, 1668, 1628, 1596, 1580,
1556, 1500, 1364, 1300, 1128
3392, 3312, 3232, 1692, 1572,
1536, 1504, 1312, 1148
3424, 3332, 3252, 1636, 1572,
1520, 1452, 1320, 1260, 1132
3436, 3336, 3232, 1652, 1596,
1556, 1496, 1312, 1260, 1132
3388, 3312, 3224, 1656, 1576,
1520, 1412, 1304, 1256, 1120
3404, 3340, 3064, 1628, 1596,
1520, 1492, 1360, 1248, 1124
3416, 3312, 3192, 1640, 1592,
1520, 1496, 1320, 1272, 1144
3408, 3312, 3200, 1640, 1592,
1556, 1496,1320, 1260, 1140
8.56
10.72
10.60
10.09
10.13
9.49
3c
9.65
3dd
3ed
3fd
3gd
12.98
13.34
12.94
13.34
12.45
12.61
11.73
11.86
a The IR spectra of compounds 2a—g and 3a—g in the ranges 3450—3000 and 1700—1100 cm–1
b The melting points of the samples recrystallized from PriOH—benzene.
c The melting points of the samples recrystallized from dioxane.
.
d The melting points of the samples recrystallized from benzene—methanol.
Scheme 4
Their structures were confirmed by mass spectrometry. In
their H NMR spectra (DMSOꢀd6), as in the spectra of
1
similar pushꢀpull compounds 5, each of the four NH proꢀ
tons appears as a broadened singlet (δ ~9.5, 9.8, 10.4, and
13.2). The Eꢀ and Zꢀisomers keep indistinguishable beꢀ
cause compounds 6a,b are insoluble in CDCl3.
Cytosines 7a,b are white crystalline solids that are well
soluble in DMF and DMSO and moderately soluble
in chloroform. In their mass spectra (EI), the peaks
[M – SO2 – H]+ have a maximum intensity. The 1H NMR
spectra in DMSOꢀd6 show, apart from signals for the proꢀ
tons of two aryl groups and a signal at δ ~2.15 (Me), two
broadened singlets for the NH protons at ~7.60 and ~8.00.
In the 2D spectrum (1H/15N HMBC NMR, DMSOꢀd6),
the signals for two NH protons at δ 7.58 and 8.02 correꢀ
spond to the same chemical shift of the signal for the
N atom (δ –278). Therefore, cytosine 7a contains the
NH2 group, existing in the form of an amino rather than
imino tautomer.
R = Ph (a), 4ꢀMeC6H4 (b)
Reagents and conditions: i. PhNCO, PhH, Δ; ii. MeONa, MeOH,
20 °C.

1940
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
Voronkova et al.
Scheme 6
Current interest in 5ꢀsubstituted cytosine derivatives is
worth noting (see Ref. 13 and references cited therein). An
earlier18 proposed route to 4ꢀaminoꢀ5ꢀsulfonylcytosines,
which are structural analogs of compounds 7a,b, starts
from (phenylsulfonyl)acetonitrile and Nꢀcyano imidates.
However, this approach seems to be unsuitable for the
synthesis of 1ꢀsubstituted cytosines.
Compounds 2 and 3 are functionalized aminovinyl keꢀ
tones, so they could be expected to form chelate complexꢀ
es with boron (see, e.g., Refs 6, 10, and 11 about boron
chelates with monoꢀ and diacylketene aminals).
Indeed, borylation of aminals 2e,f with methoxyꢀ
(diphenyl)borane gave crystalline diphenylboron chelates
8a,b (Scheme 5).
Scheme 5
R = Ph (a), 4ꢀMeC6H4 (b)
Reagents and conditions: i. DMF DMA, THF, Δ; ii. BuOH, Δ.
heterocyclization is accompanied by debenzoylation in the
presence of a liberated base (dimethylamine), while in
similar syntheses of pyridone derivatives from boron cheꢀ
lates prepared from diacetylketene aminals, the benzoyl
group is retained.6
Pyridones 10a,b are white crystalline solids well soluble
in DMSO and DMF. Their mass spectra contain intense
molecular ion peaks. The H NMR spectra in DMSOꢀd6
R = Ph (a), 4ꢀMeC6H4 (b)
1
Reagents and conditions: i. Ph2BOMe, oꢀxylene, Δ.
show, apart from signals for the aromatic protons (H(5),
H(6) of pyridine, and RSO2), two broadened singlets for
the NH and NH2 protons (δ ~10.50 and ~7.20, respecꢀ
tively). In the 13C NMR spectrum (DMSOꢀd6), the sigꢀ
nals for the C(4), C(5), and C(6) atoms of the pyridine
ring are strongly broadened, thus suggesting the dynamic
equilibrium pyridone—hydroxypyridine. However, this
equilibrium is appreciably shifted toward pyridone, which
is evident from the chemical shifts of the signals for the
C(4), C(5), and C(6) atoms (δ 173.77, 112.14, and 135.58,
respectively; cf. data for 3ꢀacetylꢀ2ꢀaminoꢀ4ꢀpyridone19).
The presented examples of the synthesis of pyridines
and pyrimidines from ketene aminals 2 and 3 undoubtedly
demonstrate that these reagents can be employed more
widely for the design of sulfonylꢀcontaining heterocyclic
systems.
Diphenylboron chelates 8a,b are airꢀstable white solꢀ
ids that are well soluble in most organic solvents, except
for hexane. The 11B NMR spectrum of chelate 8a in
oꢀxylene shows a signal characteristic of tetracoordinated
boron (δ 2.0). The 1H NMR spectra in CDCl3 exhibit two
broadened singlets for the NH protons and a downfield
shift (δ 2.49) of the singlet for the methyl protons comꢀ
pared to the starting ketene aminals (δ 2.20), which sugꢀ
gests the coordination of the acetyl group of compounds
2e,f to the B atom. The mass spectra of chelates 8a,b
contain characteristic intense peaks of the ions [M – Ph]+.
Using our strategy developed earlier,6 we obtained sulꢀ
fonylpyridones (Scheme 6). Condensation of diphenylꢀ
boron chelates 8a,b with dimethylformamide dimethyl
acetal (DMF DMA) in boiling THF yielded chelate comꢀ
plexes 9a,b with an enamine fragment in the side chain.
Compounds 9a,b are yellow crystalline solids that are
insoluble only in hexane. Their mass spectra also contain
intense peaks of the ions [M – Ph]+. The 1H NMR spectra
in CDCl3 show two singlets for the NMe2 protons (δ 2.86
and 3.16) and two doublets for the protons at the double
bond of the dimethylaminovinyl substituent (δ ~6.0 and
~7.9). The coupling constant (~12 Hz) suggests the
Eꢀconfiguration of the enamine fragment.
Experimental
1
H NMR spectra were recorded on a Bruker AMꢀ300 instruꢀ
ment (300 MHz). 13C NMR and 2D spectra (1H/13C and 1H/15N
HMBC) were recorded on a Bruker Avance 600 instrument
(600 (1H), 150 (13C), and 60.8 MHz (15N)) with residual signals
of the nondeuterated solvent as the internal standards: δ 7.27 for
CDCl3 and δ 2.50 for DMSOꢀd6 (1H) and δ 39.50 for DMSOꢀd6
(13C). The 15N chemical shifts are referenced to MeNO2 as the
external standard (highꢀfield signals are cited with a minus sign).
IR spectra were recorded on a SpecordꢀM82 instrument; mass
spectra were measured on a Kratos MSꢀ30 instrument (EI, 70 eV,
In boiling butanol, chelates 9a,b decompose and the
free ligands undergo cyclization into 2ꢀaminoꢀ3ꢀarylꢀ
sulfonylpyridinꢀ4(1H)ꢀones 10a,b. It is interesting that the

Diaminomethylidene derivatives of βꢀoxo sulfones
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
1941
ion source temperature 250 °C, direct inlet probe). Highꢀresoluꢀ
tion mass spectra were recorded on a Bruker micrOTOF II inꢀ
strument (ESI,20 positive ions (capillary voltage 4500 V), scan
range m/z 50—3000 D, external calibration). Samples were syꢀ
ringed as solutions in acetonitrile, flow rate 3 mL min–1, nitroꢀ
gen as a spraying gas (4 L min–1), interface temperature 180 °C.
Phenyl isocyanate, dimethylformamide dimethyl acetal (Lanꢀ
caster), and dry dioxane were used. Benzene and THF were
dehydrated by distillation over Na; methanol and butanol were
distilled before use. The starting βꢀoxo sulfones21 and methyl
diphenylboronate22 were prepared according to known proꢀ
cedures.
Acyl(Rꢀsulfonyl)ketene Nꢀbenzoylaminals 2a—g (general proꢀ
cedure). Nickel acetylacetonate (10 mol.%) was added to a soluꢀ
tion of an appropriate oxo sulfone 1a—g (1.9 mmol) and benꢀ
zoylcyanamide (1.9 mmol) in dioxane (5 mL). The reaction mixꢀ
ture was refluxed for 10 h. Workup was carried out in two ways
(methods A and B).
Method A. The solvent was evaporated in vacuo to dryness.
The residue was diluted with PriOH and heated. The undisꢀ
solved precipitate was filtered off and washed with hot PriOH.
The filtrate was concentrated and the residue was recrystallized
from PriOH—benzene. This procedure was used to obtain
3ꢀaminoꢀ3ꢀbenzoylaminoꢀ1ꢀphenylꢀ2ꢀphenylsulfonylpropꢀ2ꢀ
enꢀ1ꢀone (2a), 4ꢀaminoꢀ4ꢀbenzoylaminoꢀ3ꢀphenylsulfonylbutꢀ
3ꢀenꢀ2ꢀone (2e), 4ꢀaminoꢀ4ꢀbenzoylaminoꢀ3ꢀ(4ꢀtolylsulfonyl)ꢀ
butꢀ3ꢀenꢀ2ꢀone (2f), and 4ꢀaminoꢀ4ꢀbenzoylaminoꢀ3ꢀ(4ꢀmethꢀ
oxyphenylsulfonyl)butꢀ3ꢀenꢀ2ꢀone (2g).
of the compounds obtained are given in Table 1; their 1H NMR
(CDCl3 and DMSOꢀd6) and mass spectra are presented in Table 2.
4ꢀAminoꢀ3ꢀphenylsulfonylꢀ4ꢀ(N´ꢀphenylureido)butꢀ3ꢀenꢀ2ꢀ
one (6a). Phenyl isocyanate (0.09 mL, 0.83 mmol) was added to
ketene aminal 3e (0.2 g, 0.83 mmol) in dry benzene (3 mL). The
reaction mixture was refluxed for 16 h. The precipitate that
formed was filtered off and washed with benzene. The resulting
white crystalline solid is soluble only in DMF and DMSO on
slight heating. Yield 0.25 g (84%), m.p. 164—165 °C. Found (%):
C, 56.92; H, 4.76; N, 11.74; S, 8.61. C17H17N3O4S. Calculatꢀ
ed (%): C, 56.81; H, 4.77; N, 11.69; S, 8.92. MS, m/z (Irel (%)):
359 [M]+ (3), 294 [M – SO2 – H]+ (29), 176 [M – PhNCO –
– SO2]+ (79), 175 [M – PhNCO – SO2 – H]+ (87), 161
[M – PhNCO – SO2 – Me]+ (42), 141 [PhSO2]+ (45), 119
[PhNCO]+ (88), 101 (95), 93 [PhNH2]+ (100). IR (KBr,
3400—2900, 1710—1500 cm–1), ν/cm–1: 3364 (NH), 3260—2950
1
(NH, CH), 1708 (CO), 1640, 1532. H NMR (DMSOꢀd6), δ:
2.17 (s, 3 H, Me); 7.09 (t, 1 H, pꢀPhNH, J = 7.8 Hz); 7.33 (t, 2 H,
mꢀPhNH, J = 7.8 Hz); 7.50 (d, 2 H, oꢀPhNH, J = 7.8 Hz); 7.64
(m, 3 H, mꢀPhSO2, pꢀPhSO2); 7.91 (d, 2 H, oꢀPhSO2, J = 7.8 Hz);
9.50 (br.s, 1 H, NH); 9.84 (br.s, 1 H, NH); 10.43 (br.s, 1 H,
NH); 13.20 (br.s, 1 H, NH).
4ꢀAminoꢀ4ꢀ(N´ꢀphenylureido)ꢀ3ꢀ(4ꢀtolylsulfonyl)butꢀ3ꢀenꢀ2ꢀ
one (6b) was obtained as described for urea 6a from ketene amiꢀ
nal 3f and PhNCO. Yield 79%, m.p. 174—175 °C. Found (%): C,
58.01; H, 5.08; N, 11.32; S, 8.45. C18H19N3O4S. Calculated (%):
C, 57.90; H, 5.13; N, 11.25; S, 8.59. MS, m/z (Irel (%)): 373
[M]+ (1), 291 [M – SO2 – H2O]+ (24), 290 [M – SO2 – H2O – H]+
(74), 221 [M – SO2 – CO – NH2CN – H2O]+ (27), 189 (44),
155 [SO2C6H4Me]+ (45), 119 [PhNCO]+ (100). IR (KBr,
3400—2900, 1710—1500 cm–1), ν/cm–1: 3368 (NH), 3280—3000
Method B. The precipitate produced by the reaction was
filtered off and washed with dioxane. The solvent was evaporatꢀ
ed in vacuo to dryness and the residue was recrystallized from
dioxane. This procedure was used to obtain 3ꢀaminoꢀ3ꢀbenzoylꢀ
aminoꢀ1ꢀphenylꢀ2ꢀ(4ꢀtolylsulfonyl)propꢀ2ꢀenꢀ1ꢀone (2b), 3ꢀ
aminoꢀ3ꢀbenzoylaminoꢀ2ꢀ(4ꢀmethoxyphenylsulfonyl)ꢀ1ꢀphenylꢀ
propꢀ2ꢀenꢀ1ꢀone (2c), and 3ꢀaminoꢀ3ꢀbenzoylaminoꢀ2ꢀmethylꢀ
sulfonylꢀ1ꢀphenylpropꢀ2ꢀenꢀ1ꢀone (2d). The yields, melting
points, elemental analysis data, and IR spectra of the compounds
1
(NH, CH), 1708 (CO), 1640, 1532. H NMR (DMSOꢀd6), δ:
2.18 (s, 3 H, COMe); 2.39 (s, 3 H, Me); 7.08 (t, 1 H, pꢀPh,
J = 7.8 Hz); 7.33 (t, 2 H, mꢀPh, J = 7.8 Hz); 7.42 (d, 2 H,
mꢀC6H4Me, J = 7.8 Hz); 7.50 (d, 2 H, oꢀPh, J = 7.8 Hz); 7.78
(d, 2 H, oꢀC6H4Me, J = 7.8 Hz); 9.51 (br.s, 1 H, NH); 9.79
(br.s, 1 H, NH); 10.36 (br.s, 1 H, NH); 13.17 (br.s, 1 H, NH).
4ꢀAminoꢀ6ꢀmethylꢀ1ꢀphenylꢀ5ꢀphenylsulfonylpyrimidinꢀ
2(1H)ꢀone (7a). Sodium methoxide (0.7 mmol) in MeOH
(1 mL) was added to urea 6a (0.25 g, 0.7 mmol) in MeOH (5 mL).
The reaction mixture was stirred for 1 h. The precipitate that
formed was filtered off, washed with methanol, and dried. The
resulting white crystalline solid is well soluble in DMF and moderꢀ
ately soluble in chloroform. Yield 0.18 g (75%), m.p. 293—294 °C.
Found (%): C, 59.66; H, 4.48; N, 12.23; S, 8.93. C17H15N3O3S.
Calculated (%): C, 59.81; H, 4.43; N, 12.31; S, 9.39. MS, m/z
(Irel (%)): 341 [M]+ (11), 276 [M – SO2 – H]+ (100), 83 (25). Highꢀ
resolution MS: found: m/z 342.0922 [M + H]+. C17H15N3O3S.
Calculated: [M + H]+ = 342.0907. IR (KBr), ν/cm–1: 3428
(NH), 3360—2920 (NH, CH), 1648, 1564, 1484, 1452, 1376,
1300, 1280, 1152, 1080, 1044, 784, 720, 704, 688, 628. 1H NMR
(CDCl3), δ: 2.21 (s, 3 H, Me); 6.43 (br.s, 1 H, NH); 7.11 (d, 2 H,
oꢀPhN, J = 7.8 Hz); 7.49 (m, 3 H, mꢀPhN, pꢀPhN); 7.58 (t, 2 H,
mꢀPhSO2, J = 7.8 Hz); 7.67 (t, 1 H, pꢀPhSO2, J = 7.8 Hz); 7.93
(d, 2 H, oꢀPhSO2, J = 7.8 Hz); 8.15 (br.s, 1 H, NH). 1H NMR
(DMSOꢀd6), δ: 2.16 (s, 3 H, Me); 7.30 (d, 2 H, oꢀPhN, J = 7.8 Hz);
7.43 (t, 1 H, pꢀPhN, J = 7.8 Hz); 7.48 (t, 2 H, mꢀPhN, J = 7.8 Hz);
7.58 (br.s, 1 H, NH); 7.67 (t, 2 H, mꢀPhSO2, J = 7.8 Hz); 7.75
(t, 1 H, pꢀPhSO2, J = 7.8 Hz); 7.99 (d, 2 H, oꢀPhSO2, J = 7.8 Hz);
8.02 (br.s, 1 H, NH). 13C NMR (DMSOꢀd6), δ: 19.97 (Me);
103.62 (C(5)); 125.95 (oꢀPhS); 128.22 (oꢀPhN); 128.60 (pꢀPhN);
1
obtained are given in Table 1; their H NMR and mass spectra
are presented in Table 2.
Acyl(Rꢀsulfonyl)ketene aminals 3a—g (general procedure).
Sodium methoxide (0.55 mmol) in MeOH (1 mL) was added to
an appropriate ketene aminal 2a—g (0.55 mmol) in MeOH
(5 mL). The reaction mixture was stirred for 1 h and acidified
with acetic acid. Workup was carried out in two ways (methods A
and B).
Method A. The solvent was evaporated in vacuo to dryness
and chloroform was added. The undissolved sodium acetate was
filtered off, the filtrate was concentrated, and the residue was
diluted with light petroleum. The resulting precipitate was filꢀ
tered off and, if required, recrystallized from benzene—methaꢀ
nol. This procedure was used to obtain 3,3ꢀdiaminoꢀ1ꢀphenylꢀ
2ꢀphenylsulfonylpropꢀ2ꢀenꢀ1ꢀone (3a), 3,3ꢀdiaminoꢀ2ꢀmethylꢀ
sulfonylꢀ1ꢀphenylpropꢀ2ꢀenꢀ1ꢀone (3d), 4,4ꢀdiaminoꢀ3ꢀphenylꢀ
sulfonylbutꢀ3ꢀenꢀ2ꢀone (3e), 4,4ꢀdiaminoꢀ3ꢀ(4ꢀtolylsulfonyl)ꢀ
butꢀ3ꢀenꢀ2ꢀone (3f), and 4,4ꢀdiaminoꢀ3ꢀ(4ꢀmethoxyphenylꢀ
sulfonyl)butꢀ3ꢀenꢀ2ꢀone (3g).
Method B. The precipitate was filtered off and washed with
diethyl ether. This procedure was used to obtain 3,3ꢀdiaminoꢀ1ꢀ
phenylꢀ2ꢀ(4ꢀtolylsulfonyl)propꢀ2ꢀenꢀ1ꢀone (3b) and 3,3ꢀdiamiꢀ
noꢀ2ꢀ(4ꢀmethoxyphenylsulfonyl)ꢀ1ꢀphenylpropꢀ2ꢀenꢀ1ꢀone (3c).
The yields, melting points, elemental analysis data, and IR spectra

1942
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
Voronkova et al.
Table 2. 1H NMR (CDCl3 and DMSOꢀd6) and mass spectra of compounds 2a—g and 3a—g
Comꢀ
pound
1H NMR (δ, J/Hz)
MS, m/z
(Irel (%))
CDCl3
DMSOꢀd6
2aa
Еꢀisomer: 7.00—7.69 (m, 13 H, 3 Ph);
8.11 (d, 2 H, Ph, J = 7.8); 9.35, 10.38
(both br.s, 2 H, NH2); 15.35 (br.s, 1 H, NH)
Zꢀisomer (22%): 8.05 (d, 2 H, Ph, J = 7.8);
10.30, 11.84 (both br.s, 2 H, NH2);
12.66 (br.s, 1 H, NH)
Еꢀisomer: 2.39 (s, 3 H, Me); 7.01—7.37
(m, 9 H, 2 Ph, C6Н4); 7.50—7.66 (m, 3 H,
2 Ph); 8.11 (d, 2 H, Ph, J = 7.8); 9.33
и 10.35 (both br.s, 2 H, NH2);
7.23—7.37 (m, 5 H, 2 Ph);
7.48—7.54 (m, 4 H, 2 Ph);
7.57—7.65 (m, 2 H, 2 Ph);
7.70 (d, 4 H, 2 Ph, J = 7.8);
9.18, 9.54 (both br.s, 2 H, NH2);
12.93 (br.s, 1 H, NH)
2.36 (s, 3 H, Me);
7.22—7.34 (m,
7 H, 2 Ph, C6H4);
7.51—7.56 (m, 4 H, Ph, C6H4);
7.66 (t, 1 H, Ph, J = 7.8);
7.74 (d, 2 H, Ph, J = 7.8);
9.36 (br.s, 2 H, NH2);
13.10 (br.s, 1 H, NH)
342 [M – SO2]+ (17),
341 [M – SO2 – H]+ (29),
265 [M – PhSO2]+ (10),
105 [COPh]+ (100)
2ba
420 [M]+ (1), 355 [M – SO2 —
– H]+ (35), 265 [M –
— MeC6H4SO2]+ (12),
161 [M – MeC6H4SO2 —
– COPh + H]+ (22),
15.35 (br.s, 1 H, NH)
Zꢀisomer (21%): 8.05 (d, 2 H, Ph, J = 7.8);
10.25, 11.80 (both br.s, 2 H, NH2);
12.67 (br.s, 1 H, NH)
122 [PhCONH2 + H]+ (35),
105 [COPh]+ (71),
91 [C6H4Me]+ (84),
77 [Ph]+ (100)
2ca
Еꢀisomer: 3.83 (s, 3 H, ОMe); 6.76
(d, 2 H, С6Н4, J = 7.8); 7.03—7.34
(m, 7 H, 2 Ph, C6H4); 7.50—7.65 (m, 3 H,
2 Ph); 8.10 (d, 2 H, Ph, J = 7.8);
9.35, 10.34 (both br.s, 2 H, NH2);
15.35 (br.s, 1 H, NH)
Zꢀisomer (22%): 3.71 (s, 3 H, ОMe);
8.05 (d, 2 H, Ph, J = 7.8); 10.24
и 11.79 (both br.s, 2 H, NH2);
3.82 (s, 3 H, OMe);
254 [M – COPh – Ph]+
(85), 206 [M – COPh —
– Ph – SO]+ (34),
7.00 (d, 2 H, C6H4, J = 7.8);
7.24—7.74 (m, 12 H, 2 Ph, C6H4);
9.24, 9.54 (both br.s, 2 H, NH2);
13.10 (br.s, 1 H, NH)
175 [M – COPh – Ph —
– SO – OMe]+ (100),
147 [M – COPh – Ph —
– SO – OMe – CO]+ (42),
120 [PhCONH2 – H]+ (70),
105 [COPh]+ (96)
12.70 (br.s, 1 H, NH)
2da
Еꢀisomer: 2.93 (s, 3 H, Me); 7.37—7.68
(m, 8 H, 2 Ph); 8.11 (d, 2 H, Ph, J = 7.8);
8.98, 10.30 (both br.s, 2 H, NH2);
15.26 (br.s, 1 H, NH)
Zꢀisomer (20%): 8.00 (d, 2 H, Ph, J = 7.8);
10.25, 11.50 (both br.s, 2 H, NH2);
12.37 (br.s, 1 H, NH)
Еꢀisomer: 2.34 (s, 3 H, Me); 7.50—7.67
(m, 6 H, 2 Ph); 7.91 (t, 2 H, Ph, J = 7.8);
8.07 (d, 2 H, Ph, J = 7.8); 9.36, 10.25
(both br.s, 2 H, NH2); 15.73 (br.s,
1 H, NH)
Zꢀisomer (25%): 2.25 (s, 3 H, Me);
8.00 (d, 2 H, Ph, J = 7.8); 12.21
(br.s, 1 H, NH); 12.65 (br.s, 1 H, NH)
Еꢀisomer: 2.34 (s, 3 H, MeCO); 2.44
(s, 3 H, Me); 7.33 (d, 2 H, C6H4, J = 7.8);
7.55 (t, 2 H, Ph, J = 7.8); 7.64 (t, 1 H, Ph,
J = 7.8); 7.80 (d, 2 H, C6H4, J = 7.8); 8.06
(d, 2 H, Ph, J = 7.8); 9.37, 10.22 (both br.s,
2 H, NH2); 15.73 (br.s, 1 H, NH)
Zꢀisomer (24%): 2.26 (s, 3 H, MeCO);
7.99 (d, 2 H, Ph, J = 7.8); 12.18 (br.s, 1 H,
NH); 12.68 (br.s, 1 H, NH)
Еꢀisomer: 2.35 (s, 3 H, MeCO); 3.38
(s, 3 H, OMe); 7.00 (d, 2 H, C6H4, J = 7.8);
7.55 (t, 2 H, Ph, J = 7.8); 7.64 (t, 1 H, Ph,
J = 7.8); 7.85 (d, 2 H, C6H4, J = 7.8);
8.06 (d, 2 H, Ph, J = 7.8); 9.38,
10.21 (both br.s, 2 H, NH2); 15.74
(br.s, 1 H, NH)
Zꢀisomer (25%): 2.27 (s, 3 H, MeCO);
8.00 (d, 2 H, Ph, J = 7.8); 12.17 (br.s,
1 H, NH); 12.70 (br.s, 1 H, NH)
3.16 (s, 3 H, Me);
7.37 (m, 3 H, Ph);
344 [M]+ (13),
265 [M – SO2Me]+ (38),
105 [COPh]+ (92),
77 [Ph]+ (100)
7.46 (m, 2 H, Ph); 7.54 (t,
2 H, Ph, J = 7.8); 7.67 (t,
1 H, Ph, J = 7.8); 7.74 (d, 2 H,
Ph, J = 7.8); 9.10, 9.50 (both br.s,
2 H, NH2); 12.96 (br.s, 1 H, NH)
2.20 (s, 3 H, Me);
7.61—7.75 (m, 6 H, 2 Ph);
7.95 (d, 4 H, 2 Ph, J = 7.8);
9.64, 14.82 (both br.s, 2 H, NH2);
10.00 (br.s, 1 H, NH)
2еa,b
344 [M]+ (7),
280 [M – SO2]+ (67),
279 [M – SO2 – H]+ (100),
265 [M – SO2 – Me]+ (26),
203 [M – SO2 – Ph]+ (36),
105 [COPh]+ (92)
2fa,b
2.20 (s, 3 H, MeCO);
2.40 (s, 3 H, Me);
7.43 (d, 2 H, C6H4,
J = 7.8); 7.63 (t, 2 H, Ph,
J = 7.8); 7.73 (t, 1 H, Ph,
J = 7.8); 7.83 (d, 2 H, C6H4,
J = 7.8); 7.95 (d, 2 H, Ph,
J = 7.8); 9.63, 14.84 (both br.s,
2 H, NH2); 9.98 (br.s, 1H, NH)
2.21 (s, 3 H, MeCO);
358 [M]+ (15),
295 [M – SO2 + H]+ (100),
294 [M – SO2]+ (66),
280 [M – Me – SO2 + H]+
(33), 203 [M – Ph – Me —
– SO2 + H]+ (56),
187 [M – Ph – 2 Me –
– SO2]+ (50),
105 [COPh]+ (66)
2ga,b
374 [M]+ (5),
3.85 (s, 3 H, OMe);
310 [M – SO2]+ (19),
309 [M – SO2 – H]+ (26),
235 [M – SOC6H4 – Me]+
(25), 155 [SOC6H4OMe]+
(91), 127 [SOC6H4OMe —
– CO]+ (99), 105 [COPh]+
(72), 77 [Ph]+ (100)
7.14 (d, 2 H, C6H4, J = 7.8);
7.63 (t, 2 H, Ph, J = 7.8);
7.73 (t, 1 H, Ph, J = 7.8);
7.87 (d, 2 H, C6H4, J = 7.8);
7.95 (d, 2 H, Ph, J = 7.8);
9.65, 14.86 (both br.s, 2 H, NH2);
9.96 (br.s, 1 H, NH)
(to be continued)

Diaminomethylidene derivatives of βꢀoxo sulfones
Table 2 (continued)
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
1943
Comꢀ
pound
1H NMR (δ, J/Hz)
MS, m/z
(Irel (%))
CDCl3
DMSOꢀd6
3ac
3bc
0000—
0000—
6.83—7.89 (m, 10 H, 2 Ph);
8.95 (br.s, 2 H, NH2);
9.34 (br.s, 2 H, NH2)
2.37 (s, 3 H, Me);
6.80—8.01 (m, 9 H, Ph, C6H4);
8.89 (br.s, 2 H, NH2);
9.29 (br.s, 2H, NH2)
238 [M – SO2]+ (24),
133 [M – SO2 – COPh]+
(75), 77 [Ph]+ (100)
251 [M – SO2 – H]+ (42),
145 [M – SO2 – COPh —
– 2H]+ (17), 106 [COPh +
+ H]+ (56), 91 [C6H4Me]+
(99); 77 [Ph]+ (100)
3cc
3dc
3е
0000—
0000—
0000—
0000—
0000—
3.82 (s, 3 H, OMe);
332 [M]+ (1), 267 [M – SO2 —
– H]+ (15), 171
6.82—7.87 (m, 9 H, Ph, C6H4);
8.93 (br.s, 2 H, NH2);
9.48 (br.s, 2 H, NH2)
[MeOC6H4SO2]+ (17),
145 (38), 105 [COPh]+ (66),
76 [C6H4]+ (100)
2.92 (s, 3 H, Me);
240 [M]+ (24), 238 [M –
2 H]+ (69), 177 [M – SO2 +
+ H]+ (24), 121 [M – Me –
— COPh + H]+ (30),
105 [COPh]+ (100)
7.27—7.36 (m, 5 H, Ph);
9.18 (br.s, 2 H, NH2);
9.28 (br.s, 2 H, NH2)
2.10 (s, 3 H, Me);
7.11 (br.s, 2 H, NH2);
7.60 (m, 3 H, Ph);
7.80 (d, 2 H, Ph, J = 7.8);
9.06 (br.s, 2 H, NH2)
2.09 (s, 3 H, MeCO); 2.37 (s, 3 H,
Me); 7.37 (d, 2 H, C6H4, J = 7.8);
7.57 (br.s, 2 H, NH2); 7.68 (d,
2 H, C6H4, J = 7.8);
9.00 (br.s, 2 H, NH2)
2.09 (s, 3 H, MeCO);
3.82 (s, 3 H, OMe);
7.05 (br.s, 2 H, NH2);
7.10 (d, 2 H, C6H4, J = 7.8);
7.72 (d, 2 H, C6H4, J = 7.8);
9.10 (br.s, 2H, NH2)
240 [M]+ (2), 225 [M –
— Me]+ (13), 176 [M – SO2]+
(21), 175 [M – SO2 – H]+
(100), 141 [PhSO2]+ (25),
101 (34)
3f
254 [M]+ (9), 239 [M –
— Me]+ (5), 190 [M – SO2]+
(31), 189 [M – SO2 – H]+
(100), 91 [C6H4Me]+ (56),
83 (96)
3g
270 [M]+ (4), 206 [M –
— SO2]+ (19), 205 [M – SO2
– H]+ (44), 191 [M – SO2 —
– Me]+ (17), 189 [M – SO2 —
– Me – 2H]+ (33),
—
171 [SO2C6H4OMe]+ (25),
107 [C6H4OMe]+ (32),
92 [C6H4O]+ (71), 83 (100)
a In the 1H NMR spectra in CDCl3, the other signals of the minor isomer overlap the signals of the major isomer.
b In the 1H NMR spectra in CDCl3, one signal for the NH proton of the primary amino group in the minor isomer overlaps the signal
of the major isomer at δ 10.20—10.25.
c To identify the NH2 protons, the 1H NMR spectra in DMSOꢀd6 were recorded in the presence of CF3COOH.
129.30 (mꢀPhN); 129.62 (mꢀPhS); 133.72 (pꢀPhS); 138.07 (ipsoꢀ
PhN); 142.12 (ipsoꢀPhS); 152.91 (C(2)); 160.73 (C(4)); 162.61
[M – SO2 – CO – NH2CN]+ (58). Highꢀresolution MS: found:
m/z 356.1079 [M + H]+. C18H17N3O3S. Calculated: [M + H]+ =
= 356.1063. IR (KBr), ν/cm–1: 3420 (NH), 3380—2920 (NH,
CH), 1652, 1560, 1480, 1452, 1372, 1300, 1276, 1152, 1080,
1
(C(6)). The signals in the H and 13C NMR spectra were asꢀ
1
signed from the 2D experiment (1H/13C HMBC). 2D H/15N
1
HMBC (DMSOꢀd6), δ /δ : 7.58/–278 (NH/NH2); 8.02/–278
1048, 812, 784, 772, 700, 684, 668, 624. H NMR (CDCl3), δ:
H
N
(NH/NH2) (correlation peaks of the protons and the
N atoms across one bond); 7.30/–200 (oꢀNPh/N(1)); 2.16/–200
(Me/N(1)); 7.58/–172 (NH/N(3)) (correlation peaks of the proꢀ
tons and the N atoms across three bonds).
4ꢀAminoꢀ6ꢀmethylꢀ1ꢀphenylꢀ5ꢀ(4ꢀtolylsulfonyl)pyrimidinꢀ
2(1H)ꢀone (7b) was obtained as described for pyrimidine 7a from
urea 6b. Yield 59%, m.p. 285—286 °C. Found (%): C, 60.95;
H, 4.95; N, 11.88; S, 8.80. C18H17N3O3S. Calculated (%):
C, 60.83; H, 4.82; N, 11.82; S, 9.02. MS, m/z (Irel (%)): 355
[M]+ (2), 291 [M – SO2]+ (63), 290 [M – SO2 – H]+ (100), 276
[M – SO2 – Me]+ (33), 263 [M – SO2 – CO]+ (26), 221
2.20 (s, 3 H, Me); 2.47 (s, 3 H, MeC6H4); 6.40 (br.s, 1 H, NH);
7.11 (d, 2 H, oꢀPhN, J = 7.8 Hz); 7.37 (d, 2 H, mꢀC6H4Me,
J = 7.8 Hz); 7.46 (m, 3 H, mꢀPhN, pꢀPhN); 7.80 (d, 2 H,
oꢀC6H4Me, J = 7.8 Hz); 8.17 (br.s, 1 H, NH). 1H NMR
(DMSOꢀd6), δ: 2.15 (s, 3 H, Me); 2.42 (s, 3 H, MeC6H4); 7.29
(d, 2 H, mꢀC6H4Me, J = 7.8 Hz); 7.44 (m, 5 H, oꢀPhN, mꢀPhN,
pꢀPhN); 7.60 (br.s, 1 H, NH); 7.87 (d, 2 H, oꢀC6H4Me,
J = 7.8 Hz); 8.00 (br.s, 1 H, NH).
Diphenylboron chelate of compound 2e (8a). Methyl diphenylꢀ
boronate (0.2 mL, 1 mmol) was added to a solution of ketene
aminal 2e (0.14 g, 0.41 mmol) in oꢀxylene (3 mL). The reaction

1944
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
Voronkova et al.
mixture was refluxed for 3 h and concentrated. The residue was
triturated with light petroleum to produce a crystalline precipiꢀ
tate, which was filtered off and washed with light petroleum.
The resulting white crystalline solid is well soluble in benzene,
chloroform, and acetone. Yield 0.16 g (78%), m.p. 118—119 °C.
Found (%): C, 68.32; H, 4.90; N, 5.67; S, 6.41. C29H25BN2O4S.
Calculated (%): C, 68.51; H, 4.96; N, 5.51; S, 6.31. MS, m/z
(Irel (%)): 508 [M]+ (1), 431 [M – Ph]+ (74), 105 [PhCO]+
(100). Highꢀresolution MS: found: m/z 531.1509 [M + Na]+.
C29H25BN2O4S. Calculated: [M + Na]+ = 531.1525. IR (CHCl3,
3400—2900, 1700—1500 cm–1), ν/cm–1: 3260 (NH), 3160—3000
(s, 3 H, NMe); 3.16 (s, 3 H, NMe); 6.01 (d, 1 H, CH, J = 12.0 Hz);
6.99 (d, 2 H, Ph, J = 7.5 Hz); 7.22—7.27 (m, 8 H, 2 Ph); 7.39
(m, 4 H, Ph); 7.52 (t, 2 H, Ph, J = 7.5 Hz); 7.62 (t, 1 H, Ph,
J = 7.5 Hz); 7.89 (d, 1 H, CH, J = 12.0 Hz); 8.00 (d, 2 H, Ph,
J = 7.5 Hz); 10.50 (br.s, 1 H, NH); 11.98 (br.s, 1 H, NH).
2ꢀAminoꢀ3ꢀphenylsulfonylpyridinꢀ4(1H)ꢀone (10a). Comꢀ
pound 9a (0.1 g, 0.18 mmol) was refluxed in butanol (5 mL) for
12 h. On cooling, the precipitate that formed was filtered off and
washed with light petroleum. The resulting white crystalline solꢀ
id is well soluble in DMF and DMSO. Yield 0.03 g (61%), m.p.
289—290 °C. Found (%): C, 52.53; H, 4.12; N, 11.48; S, 12.73.
C11H10N2O3S. Calculated (%): C, 52.79; H, 4.03; N, 11.19; S,
12.81. MS, m/z (Irel (%)): 250 [M]+ (63), 184 [M – SO2 – 2H]+
(100). IR (KBr), ν/cm–1: 3448 (NH), 3330—2900 (NH, CH),
1624, 1508, 1480, 1380, 1280, 1232, 1136, 1080, 820, 720, 680.
1H NMR (DMSOꢀd6), δ: 5.55 (m, 1 H, CH); 7.23 (m, 3 H, CH,
NH2); 7.52 (m, 3 H, Ph); 7.89 (m, 2 H, Ph); 10.54 (br.s,
1 H, NH).
2ꢀAminoꢀ3ꢀ(4ꢀtolylsulfonyl)pyridinꢀ4(1H)ꢀone (10b) was obꢀ
tained as described for compound 10a from chelate 9b. Yield
59%, m.p. 295—296 °C. Found (%): C, 54.05; H, 4.52; N, 10.67;
S, 12.25. C12H12N2O3S. Calculated (%): C, 54.53; H, 4.58;
N, 10.60; S, 12.13. MS, m/z (Irel (%)): 264 [M]+ (47), 199
[M – SO2 – H]+ (100); 185 [M – SO2 – Me]+ (35). IR (KBr),
ν/cm–1: 3440 (NH), 3330—2850 (NH, CH), 1636, 1520, 1480,
1380, 1280, 1232, 1140, 1080, 824, 704, 676. 1H NMR (DMSOꢀd6),
δ: 2.35 (s, 3 H, Me); 5.53 (d, 1 H, CH, J = 7.5 Hz); 7.20 (br.s,
2 H, NH2); 7.25 (d, 1 H, CH, J = 7.5 Hz); 7.30 (d, 2 H, C6H4,
J = 7.5 Hz); 7.77 (d, 2 H, C6H4, J = 7.5 Hz); 10.50 (br.s, 1 H,
NH). 13C NMR (DMSOꢀd6), δ: 20.92 (Me); 103.62 (C(3));
112.14 (C(5)); 127.08 (oꢀC6H4); 128.58 (mꢀC6H4); 135.58 (C(6));
140.52 (ipsoꢀC6H4); 142.58 (pꢀC6H4); 153.15 (C(2)); 173.77
(C(4)).
1
(NH, CH), 1692 (CO), 1632, 1544. H NMR (CDCl3), δ: 2.49
(s, 3 H, COMe); 7.26—7.40 (m, 12 H, 3 Ph); 7.47 (m, 5 H,
2 Ph); 7.68 (t, 1 H, Ph, J = 7.5 Hz); 8.00 (d, 2 H, Ph, J = 7.5 Hz);
10.96 (br.s, 1 H, NH); 12.01 (br.s, 1 H, NH). 11B NMR
(oꢀxylene), δ: 2.0.
Diphenylboron chelate of compound 2f (8b) was obtained as
described for compound 8a from ketene aminal 2f and methyl
diphenylboronate. Yield 90%, m.p. 199—200 °C. Found (%):
C, 68.78; H, 5.17; N, 5.43; S, 6.25. C30H27BN2O4S. Calculatꢀ
ed (%): C, 68.97; H, 5.21; N, 5.36; S, 6.14. MS, m/z (Irel (%)):
445 [M – Ph]+ (4), 312 [M – Ph – PhCO – CO]+ (53), 311
[M – Ph – PhCO – CO – H]+ (71), 105 [PhCO]+ (100). IR
(CHCl3, 3400—2900, 1700—1500 cm–1), ν/cm–1: 3260 (NH),
3170—2980 (NH, CH), 1692 (CO), 1632, 1540. 1H NMR
(CDCl3), δ: 2.40 (s, 3 H, Me); 2.49 (s, 3 H, COMe); 7.12 (d, 2 H,
Ph, J = 7.5 Hz); 7.26 (m, 6 H, 2 Ph); 7.38 (m, 6 H, 2 Ph); 7.56
(t, 2 H, Ph, J = 7.5 Hz); 7.68 (t, 1 H, Ph, J = 7.5 Hz); 8.00 (d, 2 H,
Ph, J = 7.5 Hz); 10.93 (br.s, 1 H, NH); 12.04 (br.s, 1 H, NH).
Diphenylboron chelate of 1ꢀaminoꢀ1ꢀbenzoylaminoꢀ5ꢀdiꢀ
methylaminoꢀ2ꢀphenylsulfonylpentaꢀ1,4ꢀdienꢀ3ꢀone (9a). Diꢀ
methylformamide dimethyl acetal (0.03 mL, 0.24 mmol) was
added to a solution of compound 8a (0.12 g, 0.24 mmol) in THF
(4 mL). The reaction mixture was refluxed for 5 h and concenꢀ
trated. The residue was diluted with light petroleum and the
precipitate that formed was filtered off. The resulting yellow
crystalline solid is well soluble in chloroform and acetonitrile.
Yield 0.12 g (93%), m.p. 248—249 °C. Found (%): C, 67.93;
H, 5.35; N, 7.52; S, 5.76. C32H30BN3O4S. Calculated (%): C,
68.21; H, 5.37; N, 7.46; S, 5.69. MS, m/z (Irel (%)): 563 [M]+
(2), 486 [M – Ph]+ (55), 56(100). Highꢀresolution MS: found:
m/z 564.2152 [M + H]+. C32H30BN3O4S. Calculated: [M + H]+ =
We are grateful to A. V. Komkov (N. D. Zelinsky Inꢀ
stitute of Organic Chemistry, Russian Academy of Sciꢀ
ences) for his assistance during the experimental work and
discussion of the results obtained and to A. S. Shashkov
(N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences) for recording 2D NMR spectra.
This work was financially supported by the Presidium
of the Russian Academy of Sciences (Basic Research Proꢀ
gram "Development of the Methods for the Synthesis of
Chemical Compounds and Creation of Novel Materials").
= 564.2128. IR (CHCl3, 3400—2800, 1700—1500 cm–1), ν/cm–1
:
3280 (NH), 3160—2850 (NH, CH), 1684 (CO), 1632, 1596,
1
1532. H NMR (CDCl3), δ: 2.86 (s, 3 H, NMe); 3.16 (s, 3 H,
NMe); 5.99 (d, 1 H, CH, J = 12.0 Hz); 7.17—7.27 (m, 8 H,
2 Ph); 7.38 (m, 7 H, 2 Ph); 7.52 (t, 2 H, Ph, J = 7.5 Hz); 7.62
(t, 1 H, Ph, J = 7.5 Hz); 7.89 (d, 1 H, CH, J = 12.0 Hz); 8.00
(d, 2 H, Ph, J = 7.5 Hz); 10.52 (br.s, 1 H, NH); 11.94 (br.s,
1 H, NH).
Diphenylboron chelate of 1ꢀaminoꢀ1ꢀbenzoylaminoꢀ5ꢀdiꢀ
methylaminoꢀ2ꢀ(4ꢀtolylsulfonyl)pentaꢀ1,4ꢀdienꢀ3ꢀone (9b) was
obtained as described for compound 9a from chelate 8b and
dimethylformamide dimethyl acetal. Yield 95%, m.p. 176—177 °C.
Found (%): C, 68.35; H, 5.51; N, 7.38; S, 5.67. C33H32BN3O4S.
Calculated (%): C, 68.63; H, 5.59; N, 7.28; S, 5.55. MS, m/z
(Irel (%)): 577 [M]+ (1), 500 [M – Ph]+ (100). Highꢀresolution
MS: found: m/z 578.2273 [M + H]+. C33H32BN3O4S. Calculatꢀ
ed: [M + H]+ = 578.2285. IR (CHCl3, 3400—2800, 1700—1500
cm–1), ν/cm–1: 3284 (NH), 3160—2860 (NH, CH), 1684 (CO),
1632, 1596, 1532. 1H NMR (CDCl3), δ: 2.34 (s, 3 H, Me); 2.86
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Received July 9, 2010;
in revised form September 3, 2010