O-Vinyldiaryl- and O-vinylaryl(hetaryl)ketoximes: A breakthrough in O-vinyloxime chemistry

Article abstract of DOI:10.1016/S0040-4020(02)01304-2

O-Vinyldiarylketoximes and O-vinylaryl(hetaryl)ketoximes, a novel family of stable O-vinyloximes, are synthesized by a straightforward, unusually fast vinylation of diarylketoximes and aryl(hetaryl)ketoximes with acetylene in a superbase system of KOH-DMSO (60-80°C, 5-7min). Yields of up to 90% were obtained, thus introducing into organic synthesis a new group of highly promising building blocks and monomers.

Full text of DOI:10.1016/S0040-4020(02)01304-2

Tetrahedron 58 (2002) 10043–10046
O-Vinyldiaryl- and O-vinylaryl(hetaryl)ketoximes: a
breakthrough in O-vinyloxime chemistry
Alexey B. Zaitsev, Alexander M. Vasil’tsov, Elena Yu. Schmidt, Al’bina I. Mikhaleva,
*
Ludmila V. Morozova, Andrey V. Afonin, Igor’ A. Ushakov and Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Street,
Irkutsk 664033, Russian Federation
Received 19 July 2002; revised 18 September 2002; accepted 10 October 2002
Abstract—O-Vinyldiarylketoximes and O-vinylaryl(hetaryl)ketoximes, a novel family of stable O-vinyloximes, are synthesized by a
straightforward, unusually fast vinylation of diarylketoximes and aryl(hetaryl)ketoximes with acetylene in a superbase system of KOH–
DMSO (60–808C, 5–7 min). Yields of up to 90% were obtained, thus introducing into organic synthesis a new group of highly promising
building blocks and monomers. q 2002 Elsevier Science Ltd. All rights reserved.
Vinyl ethers of alcohols and phenols are well established
monomers, building blocks and auxiliaries in organic
synthesis, steadily expanding their scope of applications.1–4
Vinyl ethers of oximes (O-vinyloximes) had been remaining
almost unknown for a long time until their synthesis by the
straightforward vinylation of oximes with acetylene was
systematically developed,5 –9 although only ketoximes
happened to enter the reaction, whereas aldoximes were
found to dehydrate to nitriles.5
vinylation of diaryl- and aryl(hetaryl)ketoximes which
turned out to be a new family of entirely stable
O-vinyloximes. Here, we briefly report on the results
attained.
Diarylketoximes 2a–e and phenyl(2-pyridyl)ketoxime 2f
were vinylated with acetylene in the KOH–DMSO system
at 60–808C for 5–7 min under pressure (initial pressure of
14 atm, maximum pressure of 30 atm), thus representing an
unusually fast nucleophilic addition to the triple bond
(Scheme 1).
Recently,10,11 O-vinylamidoximes were also synthesized. In
spite of being unstable, both O-vinyldialkyl(alkylaryl)-
ketoximes5–9 and O-vinylamidoximes10,11 are actively
employed for the synthesis of a number of new unsaturated
heteroatomic compounds (pyrroles,5–8,12 hydroxypyrro-
lines,5 3H-pyrroles,13 trifluoroacetyl derivatives9–11), and
polymers,5,6,14 as well as for theoretical and spectroscopic
studies.15–17 However, a drawback of the O-vinyldi-
alkyl(alkylaryl)oximes so far synthesized is their chemical
and thermal instability seriously limiting their broader use
in organic synthesis. In fact, O-vinyldialkyl(alkylaryl)-
ketoximes having a CH2 group at the a-position to the
oxime function are non-isolable intermediates in the
Trofimov pyrrole synthesis,5,6 while O-vinylacetoxime,
O-vinylmethyl(iso- and tert-alkyl)ketoximes and O-vinyl-
methylarylketoximes explode above 1438C,7 and hence
should be handled with caution.5,7
The highest yields (80–90%) of O-vinylketoximes 3 were
obtained at 708C (Table 1). Both increasing and decreasing
the reaction temperature by 108C leads to a decrease in the
product yield (Table 1).
Prior to use, the initial ketoximes 2a–f were dried under
vacuum and kept in hermetically sealed containers (benzo-
phenone oxime, for example, is known to decompose in the
presence of moisture and oxygen to give benzophenone and
nitric acid18).
The distinction between the E- and Z-isomers of O-vinyl-
diarylketoximes was made based on the fact that the
ipso-carbon resonance in the aryl substituent having a syn-
orientation relative to the oxygen atom in the oxime
function is ,3 ppm shifted to higher field compared to
that with an anti-orientation.17
To circumvent this obstacle for furthering O-vinyloxime
chemistry, we have for the first time developed a facile
1
In order to attribute the H and 13C NMR spectroscopy,
peaks of symmetrical diaryl- 3a, 3c and unsymmetrical
phenyl(2-pyridyl)- 3f ketoximes, 2D homonuclear COSY
and NOESY routines, as well as 2D heteronuclear HSQC
Keywords: vinylation; ketones; oximes; acetylene; superbase system.
*
Corresponding author. Tel.: þ7-3952-42-44-11; fax: þ7-3952-39-60-46;
e-mail: bat@irioch.irk.ru
0040–4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)01304-2

10044
A. B. Zaitsev et al. / Tetrahedron 58 (2002) 10043–10046
Scheme 1.
A study of the thermal stability of O-vinylbenzophenone
oxime 3a was performed using the previously described
technique.11 Upon heating to 2208C in a sealed ampoule,
compound 3a transforms without an explosion to a tarry
viscous mass consisting of benzophenone and, probably,
benzophenone imine (13C NMR, d, ppm: 196.84 and
158.95, correspondingly) and products giving rise to a
Table 1. Vinylation of diarylketoximes and phenyl(2-pyridyl)ketoxime in
the KOH–DMSO system under acetylene pressure
O-Vinylketoxime
Reaction
temperaturea
(8C)
Yield
(%)
Isomer
(E/Z) ratio
3a
3b
3c
3c
3d
3e
3e
3f
70
70
60
70
70
70
80
70
90
83
68
82
87
80
75
47
1:1b
1:1
1
weak broad multiplet in the 7.1–7.5 ppm region of the H
1:1b
1:1b
3:5
NMR spectrum (presumably, oligomers of benzophenone
imine, acetaldehyde and acetylene). Higher-field peaks of
probable products of polymerization involving the vinyl
group are absent. Among gaseous and low-boiling
decomposition products is acetaldehyde (1H NMR, d,
CDCl3, ppm: 9.80 q, 2.20 d, 3J¼2.9 Hz).
1:1
1:1
2:1
a
Reaction time at the given temperature is 5–7 min.
Degeneration of the isomers due to the symmetric structure.
b
O-Vinyldiarylketoximes 3 do not explode even on contact
with open flames. Instead, they smoothly inflame and evenly
burn out. Storing compound 3a at a temperature of 108C in
air for 8 months has not led to formation of any noticeable
and HMBC techniques were used. For attribution of 1H and
13C NMR spectroscopy, peaks in the case of unsymmetrical
oximes 3b, 3d and 3e, the tabulated substituent chemical
shifts19 were analyzed in comparison with the correspond-
ing parameters for oximes 3a and 3c.
1
amounts of admixtures (by H NMR spectroscopy).
To conclude, the present paper for the first time describes a
simple and efficient method for the synthesis of a novel
family of stable and safe in handling O-vinyldiaryl- and
aryl(hetaryl)ketoximes, thus opening opportunities for their
broader use in organic synthesis, polymer chemistry and the
design of advanced materials.
A predominance of the Z-isomer for 3d and the E-isomer for
3f can most likely be accounted for by the repulsion of the
lone pair of the oxygen atom and the more electron-rich
4-methoxyphenyl group (3d) and the lone pair of nitrogen
atom (3f). In the initial oxime 2f, there is an exactly
opposite, but quite explainable, picture: the Z-isomer
dominates (E/Z¼,1:3) due to formation of a hydrogen
bond between the nitrogen atom of the pyridine ring and the
oxime function.
1. Experimental
1H and 13C NMR spectra were taken on a Bruker DPX 400
spectrometer (400.13 and 100.61 MHz, respectively) in
CDCl3 using HMDS as an internal standard. For assignment
of the signals the following designation was used.
The E/Z ratio for ketoxime 2d is ,1:1.

A. B. Zaitsev et al. / Tetrahedron 58 (2002) 10043–10046
10045
IR spectra were recorded on a Bruker IFS 25 instrument.
Oximes 2a–e were prepared from commercial benzo-
phenones 1a–e using literature procedure18 in nearly
quantitative yields, oxime 2f was synthesized by our own
improved technique20 allowing to increase the yield from 50
to 87%.
H 6.39; N 6.80. C16H15NO requires C 80.98; H 6.37; N
6.74%]; nmax (liquid film) 3058 (nCH), 1636 (ntransCvC),
1325, 1305, 1179 (nC–O), 1147, 988 (nN–O), 947
(dtransvCH), 865 (gC–C–C), 837, 824 (gCH2), 774,
696 cm21
;
dH (E-isomer) 7.49 (d, 2H, Ho-anti,
3JH H ¼7.9 Hz), 7.40–7.20 (m, 5H, Ho-syn, Hm-syn,
o
m
3
Hp-syn), 7.11 (d, 2H, Hm-anti, J
HoHm
1H, HX, JAX¼ 6.8 Hz, JBX¼14.2 Hz), 4.59 (dd, 1H, HB,
¼7.9 Hz), 6.95 (dd,
3
3
1.1. Oximation of phenyl(2-pyridyl)ketone (1f)
2JAB¼1.9 Hz, 3JBX¼14.2 Hz), 4.11 (dd, 1H, HA,
3
10.00 g (55 mmol) of phenyl(2-pyridyl)ketone and 5.98 g
(86 mmol) of NH2OH·HCl was mixed with 40 mL of 95%
ethanol and 4 mL of water. To the mixture, 11.00 g
(275 mmol) of fine-powdered NaOH was gradually added
upon shaking. After introduction of the whole NaOH
amount, the mixture was stirred for 1 h at room temperature,
and 50 mL of water was added. The obtained homogeneous
solution was neutralized with excess of dry ice, the
precipitate formed was filtered off and washed with water.
After drying in vacuum and recrystallization from chloro-
form, 9.51 g (48 mmol) of oxime 2f was obtained in 87%
yield. The product represents slightly pink crystals, mp
149–1518C (lit.:20 mp 150–1528C).
2JAB¼1.9 Hz, JAX¼6.8 Hz), 2.35 (s, 3H, Me). dC (E-iso-
mer) 158.93 (CvN), 152.62 (Ca), 139.91 (Cp-anti), 133.02
(Ci-anti), 132.92 (Ci-syn), 129.14 (Co-syn), 128.98 (Cp-syn),
128.96 (Cm-anti), 128.41 (Co-anti), 128.00 (Cm-syn), 88.29
(Cb), 21.35 (Me); dH (Z-isomer) 7.40–7.20 (m, 9H, Ho-syn,
Hm-syn, Ho-anti, Hm-anti, Hp-anti), 6.97 (dd, 1H, HX,
3JAX¼6.8 Hz, JBX¼14.2 Hz), 4.61 (dd, 1H, HB, JAB
¼
3
2
3
2
1.6 Hz, JBX¼14.2 Hz), 4.13 (dd, 1H, HA, JAB¼1.6 Hz,
3JAX¼6.8 Hz), 2.40 (s, 3H, CH3); dC (Z-isomer)¼159.25
(CvN), 152.65 (Ca), 139.06 (Cp-syn), 135.98 (Ci-anti),
129.86 (Ci-syn), 129.74 (Cp-anti), 129.29 (Co-syn), 128.73
(Cm-syn), 128.23 (Cm-anti), 128.18 (Co-anti), 88.37 (Cb),
21.47 (Me).
1.2. General procedure: vinylation of benzophenone
oxime (2a)
1.2.3. O-Vinyl(di-p,p0-methyl)benzophenone oxime (3c).
White crystals, mp 54–568C. [Found: C 81.19; H 6.80; N
5.53. C17H17NO requires C 81.24; H 6.82; N 5.57%]; nmax
(KBr) 1637 (ntransCvC), 1612, 1510 (ncisCvC in benzene
ring), 1323, 1176 (nC–O), 983 (nN–O), 947 (dtransvCH),
863 (gC–C–C), 826 (gCH2) cm21; dH 7.38 (d, 2H, Ho-anti,
3JH H ¼7.9 Hz), 7.22 (s, 4H, Ho-syn, Hm-syn), 7.12 (d, 2H,
Into a steel 0.5-liter rotating autoclave, 2.00 g (10 mmol) of
benzophenone oxime 2a, 1.14 g (17.5 mmol) of
KOH·0.5H2O (15% water content) and 50 mL of DMSO
were loaded. The mixture was saturated with acetylene to
14 atm and heated up to 708C during 30 min (the maximum
acetylene pressure in the autoclave thus reached ,30 atm),
with the following instant removal of heating and opening
the autoclave oven (time of the reaction at maximum
temperature made ,5–7 min). After cooling to room
temperature the reaction mixture was unloaded, diluted
with water up to 100 mL and extracted with diethyl ether
(30 mL£4). The ether extracts were washed with water
(20 mL£3), dried over anhydrous K2CO3 and filtered.
Distilling off ether and vacuuming produced raw product
o
m
3
3
Hm-anti, J
¼7.9 Hz), 6.96 (dd, 1H, HX, JAX¼6.7 Hz,
HoHm
2
3
3JBX¼14.1 Hz), 4.61 (dd, 1H, HB, JAB¼1.7 Hz, JBX
¼
2
3
14.1 Hz), 4.12 (dd, 1H, HA, JAB¼1.7 Hz, JAX¼6.7 Hz),
2.40 (s, 3H, Me-syn), 2.35 (s, 3H, Me-anti); dC 159.37
(CvN), 152.81 (Ca), 139.93 (Cp-anti), 139.06 (Cp-syn),
133.29 (Ci-anti), 130.15 (Ci-syn), 129.41 (Co-syn), 129.05
(Cm-anti), 128.83 (Cm-syn), 128.49 (Co-anti), 88.33 (Cb),
21.64 (Me-syn), 21.51 (Me-anti).
1.2.4. O-Vinyl-p-methoxybenzophenone oxime (3d). A
transparent viscous liquid, n2D0¼1.6074. [Found: C 75.86; H
5.94; N 5.57. C16H15NO2 requires C 75.87; H 5.97; N
5.53%]; nmax (liquid film) 1637 (ntransCvC), 1607, 1510,
(ncisCvC in benzene ring), 1326, 1305, 1251 (nC–O), 1174
(nC–O), 1147, 1033, 988 (nN–O), 947 (dtransvCH), 865
(gC–C–C), 835 (gCH2), 774 cm21; dH (E-isomer) 7.43–
7.27 (m, 7H, Ho-syn, Hm-syn, Hp-syn, Ho-anti), 6.92 (dd, 1H,
1
(.90% purity, H NMR), which was additionally purified
using column chromatography (Al2O3, petroleum ether). As
a result, 2.04 g (9 mmol) of O-vinylbenzophenone oxime 3a
in 90% yield was obtained.
1.2.1. O-Vinylbenzophenone oxime (3a). A transparent
viscous liquid, n2D0¼1.6050. [Found: C 80.72; H 5.88; N
6.24. C15H13NO requires C 80.69; H 5.87; N 6.27%]; nmax
(liquid film) 3060 (nCH), 1634 (ntransCvC), 1610, 1591,
1493 (ncisCvC in benzene ring), 1444, 1381 (dCH2), 1325,
1305, 1179 (nC–O), 1145, 988 (nN–O), 945 (dtransCH),
3
3
HX, JAX¼6.7 Hz, JBX¼14.2 Hz), 6.80 (d, 2H, Hm-anti,
3
2
3
JH H ¼6.8 Hz), 4.57 (dd, 1H, HB, JAB¼1.7 Hz, JBX
¼
o
m
2
3
14.2 Hz), 4.09 (dd, 1H, HA, JAB¼1.7 Hz, JAX¼6.7 Hz),
3.76 (s, 3H, OMe); dC (E-isomer) 161.04 (Cp-anti), 158.85
(CvN), 152.69 (Ca), 133.11 (Ci-syn), 129.65 (Co-syn,
Co-anti), 128.14 (Ci-anti), 127.98 (Cp-syn), 113.63 (Cm-
anti), 88.11 (Cb), 55.05 (OMe); dH (Z-isomer) 7.43–7.27
(m, 5H, Ho-syn, Hm-anti, Hp-anti), 7.48 (d, 2H, Ho-anti,
864 (gC–C–C), 838 (gCH2), 774, 694, 667, 650 cm21; dH
3
7.51 (d, 2H, Ho-anti, J
Ho-syn, Hm-syn, Hp-syn, Hm-anti, Hp-anti), 6.99 (dd 1H, HX,
¼7.0 Hz,), 7.30–7.45 (m, 8H,
HoHm
3JAX¼6.6 Hz, JBX¼14.2 Hz), 4.63 (dd, 1H, HB, JAB
¼
3
2
3
3
2
3
1.4 Hz, JBX¼14.2 Hz), 4.15 (dd, 1H, HA, JAB¼1.4 Hz,
3JAX¼6.6 Hz); dC¼159.47 (CvN), 152.72 (Ca), 135.75
(Ci-anti), 132.81 (Ci-syn), 130.03 (Cp-anti), 129.29 (Co-syn,
Cp-syn), 128.39 (Co-anti, Cm-anti), 128.20 Cm-syn), 88.56
(Cb).
JH H ¼6.8 Hz), 6.96 (dd, 1H, HX, JAX¼6.7 Hz,
o
m
3
3JBX¼14.2 Hz), 6.89 (d, 2H, Hm-syn, JH H ¼7.0 Hz),
o
m
2
3
4.61 (dd, 1H, HB, JAB¼1.7 Hz, JBX¼14.2 Hz), 4.11 (dd,
1H, HA, 2JAB¼1.7 Hz, 3JAX¼6.7 Hz), 3.80 (s, 3H, OMe); dC
(Z-isomer) 160.18 (Cp-syn), 158.79 (CvN), 152.69 (Ca),
136.22 (Ci-anti), 131.17 (Co-syn), 129.05 (Cp-anti), 128.57
(Co-anti, Cm-anti), 124.85 (Ci-syn), 113.36 (Cm-syn), 88.30
(Cb), 55.05 (OMe).
1.2.2. O-Vinyl-p-methylbenzophenone oxime (3b). A
transparent viscous liquid, n2D0¼1.6000. [Found: C 81.05;

10046
A. B. Zaitsev et al. / Tetrahedron 58 (2002) 10043–10046
1.2.5. O-Vinyl-p-bromobenzophenone oxime (3e).
Keeping the liquid mixture of E- and Z-isomers (E/Z,1:1)
of ketoxime 3e for 2 days resulted in crystallization of
Z-isomer. The liquid phase thus became enriched with the
E-isomer. Washing the crystals with a small amount of
hexane allowed to isolate the Z-isomer, which represents
white crystals, mp 83–848C. [Found: 59.68; H 4.02; Br
26.34; N 4.67. C15H12BrNO requires C 59.62; H 4.00; Br
26.44; N 4.64%]; nmax (KBr) 1636 (ntransCvC), 1486
(ncisCvC in benzene ring), 1179 (nC–O), 1145, 1071, 991
(nN–O), 947 (dtransvCH), 829 (gCH2), 775, 697 cm21; dH
(E-isomer) 7.55–7.15 (m, 9H, Ho-syn, Hm-syn, Hp-syn, Ho-
References
1. Reppe, W. Neue Entwicklungen auf dem Gebiete der Chemie
des Acetylens und Kohlenoxyds. Springer: Berlin, 1949.
2. Shostakovsky, M. F. Vinyl Ethers. Akademie Nauk SSSR:
Moscow, 1952; in Russian.
3. Trofimov, B. A. Heteroatomic Derivatives of Acetylene: New
Polyfunctional Monomers, Reagents, and Intermediates.
Nauka: Moscow, 1981; in Russian.
4. Tedeschi, R. J. Acetylene-Based Chemicals from Coal and
Other Natural Resources. Marcel Dekker: New York, 1982.
5. Trofimov, B. A. Advances in Heterocyclic Chemistry, Katritzky,
A. R., Ed.; Academic: San Diego, 1990; Vol. 51, pp 177–301.
6. Trofimov, B. A. In Pyrroles. The Chemistry of Heterocyclic
Compounds. Part 2, Jones, R. A., Ed.; Wiley: New York,
1992; Vol. 48, pp 131–298.
3
3
anti, Hm-anti), 6.94 (dd, 1H, HX, JAX¼6.7 Hz, JBX
¼
2
3
14.2 Hz), 4.59 (dd, 1H, HB, JAB¼1.9 Hz, JBX¼14.2 Hz),
2
3
4.13 (dd, 1H, HA, JAB¼1.9 Hz, JAX¼6.7 Hz); dC
(E-isomer) 161.04 (Cp-anti), 158.03 (CvN), 152.43 (Ca),
134.57 (Ci-anti), 132.24 (Ci-syn), 131.34 (Cm-anti), 129.68
(Co-anti), 129.24 (Cp-syn), 129.02 (Cm-syn), 128.49
(Co-syn), 124.38 (Cp-anti), 88.78 (Cb); dH (Z-isomer)
7.55–7.15 (m, 9H, Ho-syn, Hm-syn, Ho-anti, Hm-anti,
7. Trofimov, B. A.; Schmidt, E. Yu.; Mikhaleva, A. I.; Vasil’tsov,
A. M.; Afonin, A. V. Mendeleev Commun. 2000, 29–30.
8. Trofimov, B. A.; Mikhaleva, A. I.; Vasil’tsov, A. M.; Schmidt,
E. Yu.; Tarasova, O. A.; Morozova, L. V.; Sobenina, L. N.;
Preiss, Th.; Henkelmann, J. Synthesis 2000, 1125–1132.
9. Vasil’tsov, A. M.; Schmidt, E. Yu.; Mikhaleva, A. I.; Zaitsev,
A. B.; Tarasova, O. A.; Afonin, A. V.; Toryashinova, D.-S. D.;
Il’icheva, L. N.; Trofimov, B. A. Zh. Org. Khim. 2001, 37,
362–366.
3
3
Hp-anti), 6.93 (dd, 1H, HX, JAX¼6.7 Hz, JBX¼14.2 Hz),
2
3
4.58 (dd, 1H, HB, JAB¼1.9 Hz, JBX¼14.2 Hz), 4.12 (dd,
1H, HA, 2JAB¼1.9 Hz, 3JAX¼6.7 Hz); dC (Z-isomer) 157.94
(CvN), 152.43 (Ca), 135.17 (Ci-anti), 131.51 (Ci-syn),
131.42 (Cm-syn), 130.84 (Co-syn), 129.98 (Cp-anti),
128.17 (Cm-anti), 128.14 (Co-anti), 123.48 (Cp-syn), 88.78
(Cb).
10. Trofimov, B. A.; Schmidt, E. Yu.; Mikhaleva, A. I.; Vasil’tsov,
A. M.; Larina, L. I.; Klyba, L. V. Mendeleev Commun. 1999,
238–239.
1.2.6. O-Vinyl(2-pyridyl)phenylketoxime (3f). A trans-
parent viscous liquid, n2D0¼1.6070. [Found: C 74.94; H 5.46;
N 12.41. C14H12N2O requires C 74.98; H 5.39; N 12.49%];
nmax (liquid film) 1637 (ntransCvC), 1183, 1168 (nC–O),
11. Trofimov, B. A.; Schmidt, E. Yu.; Vasil’tsov, A. M.;
Mikhaleva, A. I.; Zaitsev, A. B.; Morozova, L. V.; Gorshkov,
A. G.; Arndt, J.-D.; Henkelmann, J. Synthesis 2001,
2427–2430.
1144, 982 (nN–O), 947 (dtransvCH), 696 cm21; dH
12. Varlamov, A. V.; Voskresensky, L. G.; Borisova, T. N.;
Chernyshev, A. V.; Levov, A. N. Khim. Geterotsikl. Soed.
1999, 683–687, Chem. Geterocycl. Compd. 1999, 613–616
(Engl. Transl.).
3
(E-isomer) 8.65 (d, 1H, H6, J
3
¼4.7 Hz), 7.85 (d, 1H,
H5H6
H3, JH H ¼7.5 Hz), 7.72 (t, 1H, H4, JH H ¼3JH H
¼
3
3
4
3
4
4
5
7.5 Hz), 7.47 (s, 5H, Ho, Hm, Hp), 7.29 (dd, 1H, H5,
3JH H ¼7.5 Hz, JH H ¼4.7 Hz), 7.14 (dd, 1H, HX,
13. Korostova, S. E.; Shevchenko, S. G.; Sigalov, M. V. Khim.
Geterotsikl. Soed. 1991, 1371–1374.
3
4
5
5
6
3JAX¼6.9 Hz, JBX¼14.2 Hz), 4.72 (dd, 1H, HB, JAB
¼
3
2
3
2
1.9 Hz, JBX¼14.2 Hz), 4.22 (dd, 1H, HA, JAB¼1.9 Hz,
3JAX¼6.9 Hz); dC (E-isomer) 158.56 (CvN), 153.85 (C2),
152.58 (Ca), 149.34 (C6), 136.25 (C4), 131.58 (Ci), 129.29
(Co), 129.21 (Cp), 127.84 (Cm), 123.90 (C5), 123.09 (C3),
14. Trofimov, B. A.; Mikhaleva, A. I.; Morozova, L. V. Usp.
Khim. 1985, 55, 1034–1050, Chem. Abstr. 1985, 103, 123936.
15. Sohlberg, K.; Leary, S. P.; Owen, N. L.; Trofimov, B. A. Vibr.
Spectrosc. 1997, 13, 227–234.
89.03 (Cb); dH (Z-isomer) 8.77 (d, 1H, H6, 3J
¼4.7 Hz),
16. Shagun, V. A.; Sinegovskaya, L. M.; Toryashinova, S.-D. D.;
Tarasova, O. A.; Trofimov, B. A. Izv. Akad. Nauk 2001,
732–738, Russ. Chem. Bull. 2001, 50, 764–770 (Engl. Transl.).
17. Afonin, A. V.;Ushakov, I. A.;Zinchenko, S. V.;Tarasova, O. A.;
Trofimov, B. A. Magn. Reson. Chem. 2000, 38, 994–1000.
18. Organic Syntheses. Collect. Vol. 2. 3rd ed. Blatt, A., Ed.; Wiley:
New York, 1946; A revised edition of annual volumes X–XIX.
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20. Trusell, F.; Diehl, H. Anal. Chem. 1959, 31, 1978–1980.
H5H6
3
7.80 (t, 1H, H4, J
¼3JH H ¼7.5 Hz), 7.57 (d, 2H, Ho,
H3H4
4
5
3JH H ¼7.4 Hz), 7.53 (d, 1H, H3, 3J
¼7.5 Hz), 7.40 (m,
H3H4
1H, Hp), 7.37 (m, 2H, Hm), 7.34 (dd, 1H, H5, JH H
o
m
3
¼
4
5
3
3
7.5 Hz, JH H ¼4.7 Hz), 7.05 (dd, 1H, HX, JAX¼6.7 Hz,
5
6
3JBX¼14.2 Hz), 4.68 (dd, 1H, HB, JAB¼1.7 Hz, JBX
¼
2
3
2
3
14.2 Hz), 4.23 (dd, 1H, HA, JAB¼1.7 Hz, JAX¼6.7 Hz);
dC (Z-isomer) 157.92 (CvN), 152.37 (Ca), 151.72 (C2),
149.59 (C6), 135.95 (C4), 134.13 (Ci), 129.93 (Cp), 128.23
(Cm), 127.79 (Co), 125.00 (C3), 123.51 (C5), 88.76 (Cb).