Esters of isoxazole- and isothiazolecarboxylic acids and oximes of β-isatin, isoxazole- and ferrocene-containing ketones and carborane alcohols

Article abstract of DOI:10.1134/S1070363213030225

Oximes of β-isatin, isoxazole- and ferrocene-containing ketones, o- and m-carborane alcohols react with isoxazol- and isothiazolecarboxylic acid chlorides in the presence of triethylamine to afford the corresponding esters.

Full text of DOI:10.1134/S1070363213030225

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 3, pp. 542–544. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © N.A. Zhukovskaya, E.A. Dikusar, V.I. Potkin, S.K. Petkevich, T.D. Zvereva, Yu.S. Zubenko, D.A. Rudakov, V.L. Shirokii, 2013,
published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 3, pp. 489–491.
Esters of Isoxazole- and Isothiazolecarboxylic Acids and Oximes
of β-Isatin, Isoxazole- and Ferrocene-Containing Ketones
and Carborane Alcohols
N. A. Zhukovskaya, E. A. Dikusar, V. I. Potkin, S. K. Petkevich, T. D. Zvereva,
Yu. S. Zubenko, D. A. Rudakov, and V. L. Shirokii
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: dikusar@ifoch.bas-net.by
Received January 19, 2012
Abstract―Oximes of β-isatin, isoxazole- and ferrocene-containing ketones, o- and m-carborane alcohols react
with isoxazol- and isothiazolecarboxylic acid chlorides in the presence of triethylamine to afford the
corresponding esters.
DOI: 10.1134/S1070363213030225
The synthesis of esters of 1,1'-diacetylferrocene di-
oxime has been previously reported [1]. 4,5-Dichloro-
isothiazol-, o- and m-carboranecarboxylic acids esters
possess a high antimicrobial and fungicidal activity
[2, 3].
potentially pharmacophore esters of isoxazole- and
4,5-dichloroisothiazolecarboxylic acids and oximes of
β-isatin, isoxazole- and ferrocene-containing ketones,
o- and m-carborane alcohols I–XXIX. The esterifica-
tion was carried out in anhydrous diethyl ether in the
presence of triethylamine to obtain the functionally
substituted esters I–XXIX in a 85–90% yield.
In this work we describe the synthesis of new
O
C
O
C
R
N
O
N
N
O
R
R
O
C
O
C
N
O
R
N
O
R
Me
Me
O
C
Fe
Fe
R1
O
O
N
O
N
H
Me
Me
V, XV
I, XI, XXI
II, III, XII, XIII, XXII, XXIII
IV, XIV, XXIV
R1
R1
C
O
C
O
O
C
C
(CH2)n
R
C
(CH2)n
O
C
R
IX, X, XIX, XX, XXVIII, XXIX
VI−VIII, XVI−XVIII, XXV−XXVII
Cl
R1 = H (II, IX, XII, XXII,
R =
(I−X);
(XI−XX);
N
Me
(XXI−XXIX);
N
N
Cl
S
O
O
XXVIII), Me (III, VI, XIII, XVI, XXII, XXV), Me2CH (VII, X, XVII, XX, XXVI, XXIX), CH2=C(Me) (VIII, XVIII,
XXVII); n = 1 (VI, XVI, XXV), 2 (VII–X, XVII–XX, XVI–XXIX).
542

ESTERS OF ISOXAZOLE- AND ISOTHIAZOLECARBOXYLIC ACIDS AND OXIMES
543
The initial oximes of isoxazole- (XXX, XXXI) and
ferrocene-containing ketones (XXXII, XXXIII) were
prepared by the reaction of the corresponding ketones
with hydroxylamine hydrochloride in the presence of
sodium hydrogen carbonate in ethanol according to the
standard procedure [4]. Yield of oximes XXX–
XXXIII was 77–82%.
The resulting esters I–XXIX and oximes XXX–
XXXIII are colorless or colored crystalline substances,
Yields, melting points, and the elemental analysis data of compounds I–XXXIII
Found, %
Calculated, %
Comp. Yield,
no.
mp,
Formula
%
°С
C
H
N
B (Fe)
Cl
S
C
H
N
B (Fe)
Cl
S
85 198–199 65.12 3.49 12.21
86 157–158 72.58 4.18 8.95
86 167–168 73.10 4.50 8.81
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
C18H11N3O4
64.86 3.33 12.61
72.31 4.05 9.37
72.72 4.36 9.09
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
I
C27H18N3O4
II
C28H20N3O4
III
90 124–125 64.07 4.30 6.25 13.04
88 165–166 63.94 4.17 8.32 6.16
C22H18FeN2O3
C34H26FeN4O6
C14H21B10NO3
C17H27B10NO3
C17H25B10NO3
C14H21B10NO3
C17H27B10NO3
C19H13N3O4
63.79 4.38 6.76 13.48
63.56 4.08 8.72 8.69
46.78 5.89 3.90 30.08
50.85 6.78 3.49 26.93
51.11 6.31 3.51 27.06
46.78 5.89 3.90 30.08
50.58 6.78 3.49 26.93
IV
V
87
92–93 47.02 6.08 3.59 29.88
VI
87 138–139 51.08 6.93 3.20 26.57
89 133–134 51.40 6.21 3.17 26.75
VII
VIII
IX
88
85
95–96 47.03 6.04 3.55 29.84
75–76 51.12 6.97 3.16 26.63
X
86 186–187 66.06 3.92 11.88
89 164–165 73.10 4.55 8.67
88 182–183 73.45 4.21 8.54
–
–
–
65.70 3.77 12.10
72.72 4.36 9.09
73.10 4.65 8.82
–
–
–
XI
C28H20N3O4
XII
C29H22N3O4
XIII
XIV
XV
88 150–151 64.91 4.57 6.25 12.58
87 168–169 64.84 4.36 7.93 7.90
86 128–129 48.80 6.43 3.27 28.49
86 133–134 52.42 7.19 3.01 25.62
87 137–138 52.55 6.50 2.98 25.77
88 155–156 48.69 6.42 3.44 28.50
C23H20FeN2O3
C36H30FeN4O6
C15H23B10NO3
C18H29B10NO3
C18H27B10NO3
C15H23B10NO3
C18H29B10NO3
64.50 4.71 6.54 13.04
64.49 4.51 8.36 8.33
48.24 6.21 3.75 28.95
52.03 7.03 3.37 26.02
52.28 6.58 3.39 26.14
48.24 6.21 3.75 28.95
52.03 7.03 3.37 26.02
XVI
XVII
XVIII
XIX
XX
85
22–23 52.46 7.24 3.03 25.88
90 167–168 42.65 1.28 11.89
86 137–138 55.41 2.66 8.85
85 144–145 56.20 3.37 8.72
–
–
–
20.46 9.04 C12H5Cl2N3O3S
15.05 6.62 C21H13Cl2N3O3S
14.64 6.42 C22H15Cl2N3O3S
42.12 1.47 12.28
55.03 2.86 9.17
55.94 3.20 8.90
–
–
–
20.72 9.37
15.47 7.00
15.01 6.79
XXI
XXII
XXIII
XXIV
XXV
XXVI
XXVII
XXVIII
XXIX
XXX
XXXI
XXXII
XXXIII
88 124–125 45.87 3.00 6.28 12.86 16.22 7.60 C16H12FeCl2N2O2S 45.42 2.86 6.62 13.20 16.76 7.58
88 118–119 26.42 4.24 3.55 18.97 18.99 8.22 C8H15B10Cl2NO2S 26.09 4.11 3.80 29.35 19.25 8.71
90 134–135 32.05 5.29 3.04 26.04 16.80 7.17 C11H21B10Cl2NO2S 32.19 5.16 3.41 26.34 17.28 7.81
87 123–124 32.64 4.40 3.17 26.10 16.95 7.32 C11H19B10Cl2NO2S 32.35 4.69 3.43 26.47 17.36 7.85
88
86
oil
26.43 4.25 3.46 28.88 18.86 8.62 C8H15B10Cl2NO2S 26.09 4.11 3.80 29.35 19.25 8.71
47–48 32.38 5.24 3.20 25.90 16.99 7.58 C11H21B10Cl2NO2S 32.19 5.16 3.41 26.34 17.28 7.81
82 119–120 73.81 5.22 9.70
80 135–136 74.19 5.38 9.14
–
–
–
–
–
–
–
–
–
–
C17H14N2O2
C18H16N2O2
C12H13FeNO
C14H16FeN2O2
73.37 5.07 10.07
73.95 5.52 9.58
–
–
–
–
–
–
–
–
–
–
77 172–173 59.63 5.15 5.43 22.51
78 141–142 56.34 5.44 9.02 18.12
59.29 5.39 5.76 22.97
56.02 5.37 9.33 18.61
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 3 2013

544
ZHUKOVSKAYA et al.
which may be used without additional purification.
Their structure was proved by the elemental analysis
(see the table), IR and 1H NMR spectroscopy.
ACKNOWLEDGMENTS
This work was supported by the Belarusian Republic
Foundation for Basic Research (grants nos. Х10Аz-001
and Х10М-102).
In the IR spectra of esters I–XXIX the following
characteristic absorption bands were observed (ν, cm–1):
1766–1729 (C=O, ester, I–XXIX), 1784–1778 (C=O,
I, XI, XXI); 1230–1210 and 1135–1095 (C–O, I–
XXIX), 2650–2530 (B–H, VI–X, XVI–XX, XXV–
REFERENCES
1. Zhukovskaya, N.A., Dikusar, E.A., Potkin, V.I.,
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1
XXIX). The H NMR spectra of esters I–XXIX and
oximes XXX–XXXIII contain the signals correspond-
ing to the structural fragments of these compounds.
The synthesized compounds I–XXXIII are interesting
as potential ligands for metal complexes and objects of
biological testing [2, 3, 5].
2. Dikusar, E.A., Zhukovskaya, N.A., Potkin, V.I.,
Shirokii, V.L., Petkevich, V.L., Yuvchenko, A.P., and
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“Biologically Active Compounds: Fundamental and
Applied Problems of Their Synthesis and Practical
Use”), Novyi Svet, Ukraine, Kiev: Izd. V.S. Martynyuk,
2009, p. 33.
EXPERIMENTAL
The IR spectra were recorded on a Nicolet Protégé-
460 FTIR spectrophotometer from thin layers or KBr
1
pellets. The H NMR spectra were registered on a
Tesla BS-587A spectrometer (100 MHz) using CDCl3
as a solvent and TMS as an internal reference.
3. Rudakov, D.A., Dikusar, E.A., Potkin, V.I., Yuvchen-
ko, A.P., Bey, M.P., Kozlov, N.G., Zvereva, T.D., and
Zheldakova, R.A., Book of Abstracts, Nauchno-
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veshchestva: fundamental’nye i prikladnye voprosy
polucheniya i primeneniya” (Scientific-Practical Conf.
“Biologically Active Compounds: Fundamental and
Applied Problems of Their Synthesis and Practical
Use”), Novyi Svet, Ukraine, Kiev: Izd. V.S. Martynyuk,
2009, p. 157
Esters I–XXIX. To a mixture of 10 mmol of oxime
or alcohol and 10 mmol of anhydrous triethylamine in
50 ml of anhydrous diethyl ether was added in portions
10 mmol of the appropriate isoxazole- or 4,5-dichloro-
isothiazolecarboxylic acid chloride. In all cases the
reagents ratio was 1:1:1 except for the synthesis of com-
pounds V, XV (1:2:2). The reaction mixture was kept
at 20–23°C for 24 h. The formed precipitate was filtered
off, washed successively with ether, water (3×200 ml),
and saturated NaHCO3 solution (3×200 ml). The
resulting compounds I–XXIX were dried in air at 25–
30°C for 2–3 days.
4. Zhukovskaya, N.A., Dikusar, E.A., Zvereva, T.D.,
Potkin, V.I., Lashitskaya, E.V., and Kurman, P.V.,
Vestn. NANBel, Ser. Khim. Nauk, 2011, no. 2, p. 86.
5. Dikusar, E.A., Potkin, V.I., and Styopin, S.G., Vestn.
Vitebsk. Gos. Tekhnol. Univ., 2011, no. 20, p. 132.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 3 2013