SYNTHESIS AND SOME TRANSFORMATIONS OF CYCLIC ACETALS
333
4
,5
2
4
(
1
С ), 96.5 (С ), 100.5 (С ), 128.2, 129.3, 129.6,
operating frequencies of 300 and 75 MHz, respec-
tively, using TMS as an internal reference. IR spectra
were recorded on a FSM-1201 instrument with Fourier
transform; spectra of the liquid samples were obtained
from a thin layer between the KBr pellets; spectra of
the solids were recorded from KBr pellets. Mass
spectra of electron ionization (70 eV) were recorded on
a Shimadzu GCMS-QP2010 Ultra chromatography-
mass spectrometer. The sample was introduced
through a Rtx-5MS capillary column containing 5%
diphenyl- and 95% dimethylpolysiloxane as a sta-
tionary phase (l 30 m). Purity of the resulting com-
pounds was monitored by TLC on Sorbfil plates
36.2, 161.2, 170.0. Found, %: С 57.10; Н 4.12.
C H ClNO . Calculated, %: С 57.27; Н 4.01.
1
2
10
3
3
-(4-Methoxyphenyl)-5(4)-(1,3-dioxan-2-yl)iso-
xazole (15) was prepared similarly from 112 mg of
alkyne 10 and 186 mg of benzhydroxymoyl chloride
3. Yield 183 mg (70%, regioisomers mixture),
colorless crystals, mp 54–56°С (aq. EtOH). Н NMR
spectrum (CDCl ), δ, ppm: 1.51 d (1H, H , J
3.8 Hz), 2.17–2.35 m (1H, H ), 3.85 s (3H, MeO),
.01 t (2H, H , J = 11.6 Hz), 4.29 d.d (2H, H , J
1.4, 4.0 Hz), 5.74 с (H , 5-isomer), 6.64 s (H ,
-isomer), 6.97 d (2H, H , J = 8.3 Hz), 7.28 s (1Н,
isoxazole), 7.48 s (1Н, isoxazole), 7.75 d (2H, H , J
1
1
5
=
3
НН
5
1
4
1
4
4,6
4,6
=
НН
НН
2
2
Ar
НН
(eluent ethyl acetate–petroleum ether mixture in various
=
Ar НН
1
3
ratios), as well as by GC method on a Crystallux
4000M chromatograph with a flame ionization detector
and a ZB-1 column (stationary phase 100% polydi-
methylsiloxane, column length 50 m, internal diameter
8
(
.4 Hz). С NMR spectrum (CDCl ), δ , ppm: 25.6
3 С
5
4,6
2
С ), 55.4 (MeO), 67.3 (С ), 95.0 (С , dioxane, 5-
4
2
isomer), 95.7 (С , isoxazole, 5-isomer), 99.9 (С , dioxane,
-isomer), 114.4 (С ), 114.5 (С , isoxazole, 4-isomer),
21.39 (С ), 128.29 (С ). Found, %: С 64.18; Н 5.84.
4
4
1
Ar
0
.25 mm, fixed phase film thickness 0.5 μm).
Ar
Ar
C H NO . Calculated, %: С 64.36; Н 5.79.
ACKNOWLEDGMENTS
1
4
15
4
4
-(1,3-Dioxan-2-yl)-1Н-pyrazole (16). To 112 mg
This work was financially supported by the Russian
(1 mmol) of compound 10 was added 3 mL of a 0.45 M
Science Foundation (project no. 15-13-10034).
solution of diazomethane in diethyl ether with ice
cooling. The mixture was kept at 5–7°C for 48 h, then
the crystals were filtered off and dried. Yield 133 mg
REFERENCES
1
. Kaplan, G.I. and Kukalenko, S.S., Sovremennye
problemy khimii i khimicheskoi promyshlennosti (Modern
Problems of Chemistry and Chemical Industry),
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2. Burkhart, D.J., Zhou, P., Blumenfeld, A., Twamley, B.,
and Natale, N.R., Tetrahedron, 2001, vol. 57, no. 38,
p. 8039. doi 10.1016/S0040-4020(01)00781-5
. Natale, N.R. and Zhou, P., Synth. Commun., 1998, vol. 28,
no. 18, p. 3317. doi 10.1080/00397919808004440
. Zlotskii, S.S., Raskildina, G.Z., Golovanov, A.A.,
Bormotin, A.A., and Bekin, V.V., Doklady AN, Ser.
Khim., 2017, vol. 472, no. 1, p. 43. doi 10.7868/
S0869565217010121
. Klochkov, V.V., Latypov, Sh.L., Rakhmatullin, A.I.,
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9. Schlotterbeck, F., Chem. Ber., 1909, vol. 42, no. 2,
1
(
87%), colorless crystals, mp 98–100°С. Н NMR
5
spectrum (CDCl ), δ, ppm: 1.36–1.50 m (1Н, Н ), 2.05–
3
5
4,6
2
.35 m (1Н, Н ), 3.87–4.05 m (2Н, Н ), 4.12–4.31 m
4
,6
2
3,5
(
(
(
2Н, Н ), 5.60 s (1Н, Н ), 7.64 s (2Н, Н ), 9.91 s
1
3
1Н, NH). С NMR spectrum (CDCl ), δ , ppm: 25.7
С ), 67.1 (2С ), 96.9 (С ), 120.8 (С ), 131.7 (2С ).
Mass spectrum, m/z (I , %): 153 (82) [M – Н] , 124
3
4
С
5
4,6
2
3,5
3
+
rel
(
10), 95 (100). Found, %: С 54.33; Н 6.58. C H N O .
7 10 2 2
4
Calculated, %: С 54.54; Н 6.54.
4-(5,5-Dimethyl-1,3-dioxan-2-yl)-1Н-pyrazole (17)
was prepared similarly from 140 mg of compound 11.
Yield 120 mg (66%), colorless crystals, mp 160–161°С.
5
1
eq
Н NMR spectrum (CDCl ), δ, ppm: 0.79 s (3Н, Ме ),
3
ax
4,6 2
1
3
.27 s (3Н, Ме ), 3.60 d (2Н, Н , J = 10.8 Hz),
.73 d (2Н, Н , J = 10.8 Hz), 5.51 s (1Н, Н ), 7.69
НН
4
,6
2
2
НН
3
,5
13
s (2Н, H ), 10.92 s (1Н, NH). С NMR spectrum
(
7
eq
ax
5
CDCl ), δ , ppm: 21.9 (Ме ), 23.0 (Ме ), 30.2 (С ),
3 С
4
,6
2
4
3,5
7.4 (2С ), 96.7 (С ), 120.5 (С ), 131.8 (2С ). Mass
+
spectrum, m/z (I , %): 181 (39) [M – Н] , 152 (5), 113
rel
(
5), 97 (100). Found, %: С 59.60; Н 7.55. C H N O .
9 14 2 2
8
Calculated, %: С 59.32; Н 7.74.
1
1
13
H and C NMR spectra of the solutions in CDCl
3
p. 2559. doi 10.1002/cber.190904202163
were recorded on a Bruker AM300 spectrometer at
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 2 2018