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Kurbangalieva et al.
46%, whiteꢀcolored precipitate, m.p. 95 °C (from a CCl4—benzene
mixture), Rf 0.48. Found (%): C, 34.92; H, 2.76; Cl, 14.72;
S, 13.28. C7H7ClO5S. Calculated (%): C, 35.23; H, 2.96;
Cl, 14.86; S, 13.44. IR, ν/cm–1: 3093, 2731, 2597 (ОН); 1772,
1700 (С=О); 1595 (C=C). 1Н NMR, δ: 3.57 (s, 3 Н, OMe);
4.07, 4.21 (AB quadruplet, 1 H each, SCH2, J = 16.3 Hz); 6.25
(s, 1 H, Н(5)).
Table 2. Crystal parameters of compounds 6 and 8 and Xꢀray
diffraction experiment details
Parameter
6
8
Molecular formula
М
Crystal system
Space group
C6H4Cl2O4S
243.05
C6H5ClO5S
224.61
Monoclinic
P21
Triclinic
(3ꢀChloroꢀ5ꢀethoxyꢀ2ꢀoxoꢀ2,5ꢀdihydrofuranꢀ4ꢀylthio)ethanoic
acid (10) was prepared similarly to compound 8 from ether 3
(0.92 g, 4.67 mmol), 2ꢀmercaptoacetic acid (0.33 mL, 4.68 mmol),
and triethylamine (0.65 mL, 4.68 mmol). Yield 52%, colorless
crystals, m.p. 93—94 °C (from a hexane—benzene mixture),
Rf 0.55. Found (%): C, 38.12; H, 3.46; Cl, 14.00; S, 12.58.
C8H9ClO5S. Calculated (%): C, 38.03; H, 3.59; Cl, 14.03;
S, 12.69. IR, ν/cm–1: 3095, 2706, 2599 (ОН); 1768, 1723 (С=О);
–
P1
a/Å
b/Å
c/Å
α/deg
6.9452(7)
7.4525(8)
9.942(1)
108.895(9)
99.925(3)
101.027(2)
462.41(8)
2
7.775(3)
6.542(1)
8.865(2)
90.00
102.67(2)
90.00
439.9(2)
2
1.696
β/deg
γ/deg
3
V/Å3
1590 (C=C). 1Н NMR, δ: 1.28 (t, 3 Н, Me, J = 7.2 Hz); 3.85,
Z
3.90 (both m, 1 Н each, ОСН2, 2J = 9.5 Hz, 3J = 7.2 Hz); 4.06,
4.22 (AB quadruplet, 1 H each, SCH2, J = 16.6 Hz); 6.29 (s,
1 H, Н(5)).
dcalc/g cm–3
1.746
83.08
μ/cm–1
60.34
Scanning range
Number of measured
4.86 ≤ θ ≥ 74.24 5.11 ≤ θ ≥ 74.20
(3ꢀChloroꢀ5ꢀisopropoxyꢀ2ꢀoxoꢀ2,5ꢀdihydrofuranꢀ4ꢀylthio)ꢀ
ethanoic acid (11) was synthesized similarly to compound 8
from ether 4 (1.00 g, 4.74 mmol), mercaptoacetic acid (0.33 mL,
4.74 mmol), and triethylamine (0.66 mL, 4.74 mmol), reaction
time 2 h. Yield 48%, colorless crystals, m.p. 89—90 °C (from a
petroleum ether—benzene mixture), Rf 0.49. Found (%): C, 40.23;
H, 3.98; Cl, 13.24; S, 11.89. C9H11ClO5S. Calculated (%):
C, 40.53; H, 4.16; Cl, 13.29; S, 12.02. IR, ν/cm–1: 3221, 2679,
2576 (ОН); 1770, 1721 (С=О); 1594 (C=C). 1Н NMR, δ: 1.29,
1.33 (both d, 3 Н each, Me, J = 6.1 Hz); 4.07, 4.24 (AB
quadruplet, 1 H each, SCH2, J = 16.5 Hz); 4.22 (sept, 1 Н, СН,
J = 6.1 Hz); 6.35 (s, 1 H, Н(5)).
(4ꢀChloroꢀ5ꢀhydroxyꢀ2ꢀoxoꢀ2,5ꢀdihydrofuranꢀ3ꢀylthio)ethanoic
acid (12). A solution of mercaptoacetic acid (0.41 mL, 5.9 mmol)
and potassium hydroxide (0.66 g, 11.84 mmol) in water (12 mL)
was added dropwise with vigorous stirring to a solution of
mucochloric acid 1 (1 g, 5.9 mmol) and potassium hydroxide
(0.33 g, 5.9 mmol) in water (12 mL). The reaction mixture was
stirred for 2 h, acidified with dilute hydrochloric acid to рН 2,
and evacuated to dryness. The oily residue was purified by column
chromatography (elution with a hexane—diethyl ether mixture,
1 : 3), and the product was recrystallized from chloroform. Yield
39%, m.p. 86 °C, Rf 0.44. Found (%): C, 31.96; H, 2.01; Cl,
15.72; S, 14.11. C6H5ClO5S. Calculated (%): C, 32.08; H, 2.24;
Cl, 15.78; S, 14.28. IR, ν/cm–1: 3311, 2682, 2569 (ОН); 1760,
1705 (С=О); 1598 (C=C). 1Н NMR, δ: 4.08, 4.12 (AB quadruplet,
1 H each, SCH2, J = 16.2 Hz); 6.13 (d, 1 H, Н(5), J = 8.4 Hz);
7.30 (d, 1 Н, ОН, J = 8.4 Hz).
1947
(0.077)
1729
1022
(0.1167)
669
reflections (Rint
)
Number of reflections
with I ≥ 2σ(I)
Number of refined
parameters
120
119
R1 (I ≥ 2σ(I))
wR2 (for all reflections)
0.0837
0.2059
0.0625
0.1789
λ(CuꢀKα) = 1.54184 Å, 293 К, ω/2θꢀscanning). The crystal
data and selected structure refinement parameters for 6 and 8
are summarized in Table 2. The absorption corrections were
applied using the experimental azimuthal scanning curves
(Tmin/Tmax = 0.7981/0.9968 for the crystal of 6 and Tmin/Tmax
=
= 0.9061/0.9982 for the crystal of 8). The structure was solved
by the direct method.21 The positions and thermal parameters of
nonꢀhydrogen atoms were refined in the isotropic and then in
the anisotropic approximation by the fullꢀmatrix leastꢀsquares
method. The hydrogen atoms were placed into geometrically
calculated positions and included in the refinement in the riding
model. All calculations were carried out using SHELXLꢀ97
software.22
The structures of compounds 6 and 8 were calculated by the
B3LYP/6ꢀ31G(d,p) method using the Gaussianꢀ98 program (see
Ref. 23) with full geometry optimization without symmetry
limitations; for all stationary points the matrix of second
derivatives was calculated. The structures had only positive
frequencies.
Methyl
(3ꢀchloroꢀ5ꢀhydroxyꢀ2ꢀoxoꢀ2,5ꢀdihydrofuranꢀ
4ꢀylthio)acetate (13) was synthesized similarly to compound 8
from compound 1 (1.0 g, 5.9 mmol), methyl mercaptoacetate
(0.44 mL, 5.9 mmol), and triethylamine (0.83 mL, 5.9 mmol) in
acetone, reaction time 4 h. Yield 31%, m.p. 68 °C (from CCl4),
Rf 0.38. Found (%): C, 35.35; H, 2.45; Cl, 14.47; S, 13.57.
C7H7ClO5S. Calculated (%): C, 35.23; H, 2.96; Cl, 14.86;
S, 13.44. IR, ν/cm–1: 3365 (ОН); 1772, 1734 (С=О); 1591
(C=C). 1Н NMR, δ: 3.75 (s, 3 Н, Ме); 4.09, 4.30 (AB
quadruplet, 1 H each, SCH2, J = 16.3 Hz); 6.42 (s, 1 H, Н(5));
7.38 (br, 1 Н, ОН).
This work was supported by the CRDF and the Rusꢀ
sian Federation Ministry of Education and Science (Baꢀ
sic Research and Higher Education Program, joint grant
REC KSU 007, No. Y2ꢀCꢀ07ꢀ17).
References
1. F. Bellina, R. Rossi, Curr. Org. Chem., 2004, 8, 1089.
2. A. A. Avetisyan, M. T. Dangyan, Usp. Khim., 1977, 46, 1250
[Russ. Chem. Rev. (Engl. Transl.), 1977, 46].
XꢀRay diffraction analysis. The single crystals of compounds
6 and 8 were prepared by crystallization from benzene. The
Xꢀray diffraction experiments were carried out on an Enrafꢀ
Nonius CAD 4 diffractometer (graphite monochromator,
3. Y. S. Rao, Chem. Rev., 1976, 76, 625.