G. I. Roshchupkina, Y. V. Gatilov, T. V. Rybalova, V. A. Reznikov
FULL PAPER
(
CϪO) cmϪ1. A cross reaction involving equimolar amounts of the
H), 7.86 (J ϭ 4 Hz, 1 H, β-furyl), 7.99Ϫ8.03 (m, 2 H) ppm. IR
(KBr): ν˜ ϭ 2213 (CN), 1601, 1585, 1523 (CϭO, CϭN) cm . 12B:
MS: calcd. for C14H NO m/z ϭ 239.0582, found 239.0581. Treat-
9 3
ment of diaroylacetonitrile (12AϪC) mixtures Ϫ obtained under
the conditions indicated for the synthesis of dibenzoylacetonitriles
Ϫ with NaCN was carried out under the same conditions but for
24 h. After having been poured into brine, the solution was acidi-
fied to pH ϭ 5 and the precipitate formed was filtered off or ex-
Ϫ1
β-diketones 9a and 9g and NaCN and subsequent isolation of a
mixture of respective nitriles was carried out in the same manner.
Treatment of the β-diketones 9dϪf with NaCN was carried out in
the same way, with the formation of mixtures of the nitriles
1
2AϪC. The reaction mixture obtained after treatment of the β-
diketone 9c with NaCN was treated somewhat differently: after
having been poured into brine, the mixture was acidified with di-
luted hydrochloric acid to pH ϭ 6. The resulting solution was ex-
3
tracted with CHCl , with subsequent treatment as indicated above.
tracted with CHCl
washed with brine and water and dried with MgSO
3
(2 ϫ 20 mL), and the combined extracts were
. The water
In the case of the 168 h reaction duration a threefold excess of
NaCN was used. Reaction products were isolated as described
above, from aqueous solution acidified to pH ϭ 3.
4
solution and organic extract were treated separately. The obtained
organic extracts contained mixtures of the corresponding aroylace-
tonitriles 13 with the diaroylacetonitriles 12. These mixtures were
separated on silica gel columns. Aroylacetonitriles 13 were eluted
with chloroform and then with chloroform/methanol mixtures
2-Oxo-2-phenylethyl N-[(2Z)-4-Benzoyl-5-phenyl-1,3-oxathiol-2-yli-
dene]-NЈ-benzoylimidothiocarbamate (19a): Dibenzoylchlorome-
thane (9a, 1 g, 3.9 mmol) was added to a solution of KSCN (0.75 g,
7.7 mmol) in anhydrous DMSO (30 mL) and the resulting mixture
(5:1), diaroylacetonitriles 12 were eluted in the form of their sodium
was stirred at room temp. for 5 h. The reaction mixture was then
cooled to 0 °C and poured into cold brine (40 mL). The solution
salts. To obtain free diaroylacetonitriles 12 they were suspended
in water/ether mixtures (1:1; 20 mL) and the aqueous phases were
acidified with diluted hydrochloric acid to pH ϭ 2 with shaking.
3
was extracted with CHCl (3 ϫ 15 mL) and the combined extracts
were washed with brine and water and then dried with MgSO
4
.
4
The diethyl ether phases were separated and dried with MgSO ,
Subsequent concentration of the obtained solution yielded a red,
crystalline mixture of two products 19a and 19b (the weight was
and the solvents were evaporated to give mixtures of free diaroyla-
cetonitriles 12. Aqueous solutions obtained on the first step of
treatment, containing the main proportions of diaroylacetonitriles
0.7 g), the separation of which was achieved by multiple fractional
recrystallization from ethyl acetate.
1
2, were acidified to pH ϭ 2 with diluted hydrochloric acid and
extracted with diethyl ether (2 ϫ 20 mL). The combined extracts
were washed with brine and water, and dried with MgSO . Concen-
tration of these extracts yielded mixtures of diaroylacetonitriles 12.
): 1H NMR
Compound 19a: Red, crystalline solid, more soluble in ethyl acetate,
4
1
m.p. 229Ϫ232 °C (ethyl acetate).
00.14 MHz): δ ϭ 4.77 (s, 2 H, CH
7.38Ϫ7.41 (m, 1 H), 7.48Ϫ7.58 (m, 5 H, Ph), 7.63Ϫ7.66 (m, 3 H),
6
H NMR ([D ]DMSO,
4
2
), 7.26Ϫ7.33 (m, 5 H, Ph),
Mixture of Aroylacetonitriles 13 (R ؍
4-ClC
CDCl , 200.13 MHz): δ ϭ 4.06 (s, 2 H, CH CN), 4.09 (s, 2 H,
CH CN), 7.83Ϫ7.93 (m, 3 H, C ), 7.47Ϫ7.55 (m, 2 H, C ),
.83Ϫ7.93 (m, 3 H, C
) ppm. IR (KBr): ν˜ max. ϭ 2952, 2922
CH), 2264, 2195 (CN), 1689 (CϭO) cm . MS: calcd. for
ClNO m/z ϭ 179.01379, found 179.0136.
6 4
H
7
.67Ϫ7.73 (m, 2 H), 8.01Ϫ8.12 (m, 2 H), 8.16Ϫ8.19 (m, 2 H) ppm.
(
3
2
1
3
C NMR ([D
6 2
]DMSO, 100.64 MHz): δ ϭ 59.6 (t, CH ), 118,8 (s),
2
6
H
5
6 5
H
126.2 (s), 128.2 (d), 128.6 (d), 128.9 (d), 129.2 (d), 129.5 (d), 131.0
7
(
6 5
H
Ϫ1
(d), 132.9 (d), 133.1 (d), 133.5 (d), 134.7 (s), 135.0 (s), 151.5 (s),
69.9 (s), 171.2 (s), 175.2 (s), 187.4 (s), 194.4 (s) ppm. IR (KBr):
1
9 6
C H
ν˜ ϭ (KBr) 1677, 1640, 1631 1609, 1597, 1540 (OϭCϪCϭC, CϭC,
13 (R ؍
Ph): MS: calcd. for C
9
H
7
NO m/z ϭ 145.0528, found
Ϫ1
CϭN) cm . UV (ethanol): λmax. (lg ε) ϭ 249 (4.24), 354 nm (3.93).
145.0525.
32 22 2 4 2
C H N O S (562.1): calcd. C 68.3, H 3.9, N 5.0, S 11.4; found
6 4
H
): 1H NMR
C 68.6, H 3.8, N 4.9, S 11.2.
Mixture of Diaroylacetonitriles 12 (R ؍
4-ClC
CDCl , 200.13 MHz): δ ϭ 7.33Ϫ7.77 (m, 6 H), 7.99Ϫ8.15 (m, 5
H), 18.25 (s, 1 H, OH) ppm. IR (KBr): ν˜ ϭ 2217 (CN), 1594,
(
3
Compound 19b: Red, crystalline solid, less soluble in ethyl acetate,
m.p. 227Ϫ229 °C (ethyl acetate).
1
6
H NMR ([D ]DMSO,
Ϫ1
1
537 (CϭO, CϭC) cm . 12B: MS: calcd. for C16
H
10ClNO
2
m/z ϭ
NO
4
7
00.14 MHz): δ ϭ 7.51Ϫ7.60 (m, 10 H), 7.63Ϫ7.67 (m, 4 H),
.77Ϫ8.05 (m, 5 H), 8.09Ϫ8.14 (m, 1 H, 4Ph), 13.08 (1 H, OH)
283.0400, found 283.0392. 12C: MS: calcd. for C16
H
9
Cl
2
2
m/z ϭ 317.0010, found 317.0006.
1
3
ppm. C NMR ([D
6
]DMSO, 100.64 MHz): 56.6 (d), 118.9 (s),
1
1
(
(
s, 3 H, OCH
m, 4 H), 18.50 (s, 1 H, OH) ppm. IR (KBr): ν˜ ϭ 2840 (OCH
3
OC
6
H
4
): H NMR (CDCl
3
, 200.13 MHz): δ ϭ 3.88 127.1 (d), 127.2 (d), 127.9 (d), 128.0 (d), 128.4 (d), 131.5 (s), 132.4
3
), 6.96Ϫ7.01 (m, 2 H), 7.47Ϫ7.64 (m, 2 H), 8.00Ϫ8.16
(d), 133.4 (d), 134.1 (s), 154.0 (s), 163.2 (s), 165.5 (s), 185.1 (s),
), 191.4 (s) ppm. IR (KBr): ν˜ ϭ 3379 (OH), 1674, 1597, 1578, 1526
214 (CN), 1603, 1585, 1513 (CϭO, CϭC), 1254 (CϪO) cm . UV (CϭO, CϭN, CϭC), 1257 (CϪO) cm . UV (ethanol): λmax. (lg
3
Ϫ1
Ϫ1
2
(
C
C
ethanol): λmax. (lg ε) ϭ 238 (3.76), 351 (4.17). 12B: MS: calcd. for
22 2 4 2
ε) ϭ 251 (4.22), 279 (4.15), 362 nm (3.91). C32H N O S (562.1):
calcd. C 68.3, H 3.9, N 5.0, S 11.4; found C 68.3, H 3.9, N 5.0,
S 11.1.
17
H13NO
15NO
3
m/z ϭ 279.0895, found 279.08997. 12C: MS: calcd. for
18
H
4
, 309.1001, found 309.0995.
1
.51 (s, 3 H, CH
ppm. IR (KBr): ν˜ ϭ 3060, 2918 (CH aromatic and aliphatic) 2261
CN), 1601, 1547 (CϭO, CϭC) cmϪ1
3
): H NMR (CDCl
3
, 200.13 MHz): δ ϭ X-ray Crystallography: Single crystals of 19a were obtained by
2
3
), 7.44Ϫ7.64 (m, 3 H), 7.98Ϫ8.06 (m, 2 H, C
6
H
5
)
recrystallization from ethyl acetate, mounted and transferred to a
Bruker P4 diffractometer. Crystal data: C H N O S , M ϭ
3
2
22
2
4 2
(
.
562.64, triclinic system, space group P 1¯ , a ϭ 8.2201(7), b ϭ
˚
˚
1
9
2.558(1), c ϭ 13.874(1) A, α ϭ 101.506(7), β ϭ 99.904(7), γ ϭ
6 4 3
Compound 12 (R ؍
p-FC H , 200.13 MHz):
): 1H NMR (CDCl
3
3
9.341(7)°, V ϭ 1353.5(2) A , Z ϭ 2, dcalcd. ϭ 1.381 Mg/m . Data
δ ϭ 7.08Ϫ7.23 (m, 3 H), 7.41Ϫ7.62 (m, 3 H), 8.03Ϫ8.15 (m, 4
H) ppm. 12B: MS: calcd. for C16 10FNO m/z ϭ 267.0696, found
67.0697. 12C: MS: calcd. for C16 NO m/z ϭ 285.0601,
found 285.06059.
collection: Bruker P4 diffractometer, graphite-monochromated
Mo-K radiation, crystal size 2.8 ϫ 0.2 ϫ 0.08 mm, ω-scans, Θ Ͻ
5°, Ϫ9 Ͻ h Ͻ 9, Ϫ14 Ͻ k Ͻ 14, Ϫ16 Ͻ l Ͻ 16, 5105 reflections
measured, 4756 reflections independent, Rint ϭ 0.0188, absorption
H
2
α
2
H
9
F
2
2
2
1
Ϫ1
Compound 12 (R ؍
2-furyl): H NMR (CDCl
3
, 200.13 MHz): δ ϭ correction by integration method (µ ϭ 0.239 mm , transmission
6.65 (d, J ϭ 4 Hz, 1 H, β-furyl), 7.50Ϫ7.56 (m, 3 H), 7.77 (m, 1 0.949Ϫ0.981). The structure was solved by direct methods
1772
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1765Ϫ1773