1
22
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
Nikishin et al.
and 2). After the reaction was over (a change of orange color of the
reaction mixture to light yellow), water (10—15 mL) was added to
the mixture and it was extracted with ether (3×20 mL). The
3 Н, OMe); 6.50 (d, 1 Н, CН, J = 13.9 Hz); 6.77 (d, 1 Н, CН, J =
13.9 Hz); 6.86 (m, Н(2), Н(6)); 7.24 (m, 2 Н, Н(3), Н(5)). MS,
+
m/z: 179 [М] .
combined extract was washed with saturated aq. NaHCO (10—
1ꢀBromoꢀ2ꢀ(3,4ꢀdimethoxyphenyl)ethylene (3c), m.p. 66 °C
3
1
1
5 mL), water (10—15 mL), and dried with MgSO . After
(see Ref. 17). H NMR (CDCl ), δ (Е)ꢀisomer: 3.82 (s, 3 Н, OMe);
4
3
concentrating, the yields of the reaction products were determined
by GLC with the use of an internal standard. The products were
isolated by preparative GLC (2000×10 mm copper column with 5%
SEꢀ30 on Chromaton NꢀAWꢀHMDS 0.25ꢀ0.36 mm).
Mechanically activated oxidative decarboxylation of acids 1
and 2 with CAN—MX system. Mechanical activation of a mixture
of acid 1 or 2, CAN and MX (total amount, ~1—2 g, ratio of the
reagents are given in Tables 1 and 2) was carried out at 20 °C on a
3.88 (s, 3 Н, OMe); 6.62 (d, 1 Н, CН, J = 14.0 Hz); 7.01 (d, 1 Н,
CН, J = 14.0 Hz); 6.98 (m, 1 Н, Н(3)); 7.12 (m, 1 Н, Н(4)); 7.22
(
6
(
m, 1 Н, Н(6)); (Z)ꢀisomer: 3.82 (s, 3 Н, OMe); 3.88 (s, 3 Н, OMe);
.30 (d, 1 Н, CН, J = 8.1 Hz); 6.90 (d, 1 Н, CН, J = 8.1 Hz); 6.98
m, 1 Н, Н(3)); 7.12 (m, 1 Н, Н(4)); 7.22 (m, 1 Н, Н(6)). MS,
+
m/z: 244 [M + H] .
Е)ꢀβꢀNitrostyrene (5a), m.p. 58 °C (see Ref. 18). H NMR
CDCl ), δ: 7.42 (d, 1 Н, CH, J = 14.0 Hz); 7.40 (m, 2 Н, Н(3),
1
(
(
3
vibrational mill with the frequency of 12 Hz and the amplitude of
Н(5)); 7.48 (m, 2 Н, Н(2), Н(6)); 7.56 (m, 1 Н, Н(4)); 7.79 (d, 1 Н,
3
1
1 mm in a sealed steel ~80ꢀcm reactor. Steel spheres 12.3 mm in
+
CН, J = 14.0 Hz). MS, m/z: 149 [M] .
diameter and total weight ~150 g were used as the activating packing.
Duration of the mechanical activation was 4 h, then the mixture
was treated as described above.
(
Е)ꢀ1ꢀ(4ꢀMethoxyphenyl)ꢀ2ꢀnitroethylene (5b), m.p. 82 °C (see
1
Ref. 19). H NMR (CDCl ), δ: 3.82 (s, 3 Н, OMe); 6.32 (m, 2 Н,
3
Н(2), Н(6)); 7.19 (m, 2 Н, Н(3), Н(5)); 7.72 (d, 1 Н, CН, J =
Oxidative decarboxylation acid 1 and 2 with CAN—LiBr
+
1
0.8 Hz); 7.96 (d, 1 Н, CН, J = 10.8 Hz). MS, m/z: 179 [M] .
system in МеCN—H O. A solution of acid 1 or 2, CAN and LiBr
1
2
2ꢀChlorofuran (6), b.p. 77 °C (see Ref. 20а). H NMR (CDCl ),
3
in aq. МеCN (20 mL) (ratio MeCN : H O = 10 : 1) was vigorously
2
δ: 6.28 (d, 1 Н, Н(3), J = 1.1 Hz); 6.54 (m, 1 Н, Н(4)); 7.48 (d, 1 Н,
stirred with a magnetic stirrer at ~20 °C until the complete
conversion of the oxidant (a change of orange color to light yellow).
Then it was extracted with ether (3×25 mL), the extract was washed
with saturated aq. NaHCO , water, dried with MgSO , and the
+
Н(5), J = 1.1 Hz). MS, m/z: 102 and 104 [M] .
Benzaldehyde (7a), b.p. 179 °C. IR, ν/cm–1: 1696 (C=O).
1
H NMR (CDCl ), δ: 7.53 (m, 2 Н, Н(3), Н(5)); 7.64 (m, 1 Н,
3
3
4
Н(4)); 7.89 (m, 2 Н, Н(2), Н(6)); 10.03 (s, 1 Н, CНO). MS,
solvent was evaporated. The yield of the reaction products was
determined by GLC (see Table 2).
+
m/z: 105 [M] . Benzaldehyde 7a 2,4ꢀdinitrophenylhydrazone,
m.p. 237 °C (see Ref. 20b).
Microwaveꢀactivated (MW) oxidative decarboxylation of
4
ꢀMethoxybenzaldehyde (7b), b.p. 118 °C (10 Torr). IR,
acids 1a,b with CAN—NaNO system. A mixture of 1a or 1b,
2
–1
1
ν/cm : 1700 (C=O). H NMR (CDCl ), δ: 3.88 (s, 3 Н, OMe);
CAN and NaNO (ratios of the reagents are given in Tables 1 and 2)
3
2
7
.01 (m, 2 Н, Н(2), Н(6)); 7.85 (m, 2 Н, Н(3), Н(5)); 9.89 (s, 1 Н,
was thoroughly triturated in air in a porcelain mortar for 5—10
min, placed in a capped glass, and subjected to the irradiation (a
Samsung consumer microwave oven). The power and the times of
the irradiation are given in Tables 1 and 2. After the reaction was
over (a change of orange color to light yellow), the reaction mixture
was extracted with ether and treated as in the preceding procedures.
Oxidation of acids 1 and 2 with CAN. The reaction of cinnamic
acids with CAN in the absence of a MX salt was carried out
according to the procedures with participation of MX (see Table 3).
βꢀBromostyrene (3a), b.p. 108 °C (20 Torr) (see Ref. 14а).
+
CНO). MS, m/z: 136 [M] . Benzaldehyde 7b 2,4ꢀdinitrophenylꢀ
hydrazone, m.p. 254 °C (see Ref. 20c).
3
,4ꢀDimethoxybenzaldehyde (7c), m.p. 44—45 °C. IR, ν/cm–1
:
1
1700 (C=O). H NMR (CDCl ), δ: 3.88 (s, 3 Н, OMe); 3.93 (s, 3 Н,
3
OMe); 6.97 (m, 1 Н, Н(3)); 7.43 (m, 1 Н, Н(6)); 7.47 (m, 1 Н,
+
Н(4)); 9.86 (s, 1 Н, CНO). MS, m/z: 166 [M] . Benzaldehyde 7c
2,4ꢀdinitrophenylhydrazone, m.p. 265 °C (see Ref. 20d).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 06ꢀ03ꢀ
2579а) and by the Russian Federation President Council
1
H NMR (CDCl ), δ (Е)ꢀisomer: 6.77 (d, 1 Н, CН, J = 14.0 Hz);
3
3
7.12 (d, 1 Н, CН, J = 14.0 Hz); 7.29 (m, 2 Н, Н(3), Н(5)); 7.38 (m,
for Grants (Program for the State Support of Leading
Scientific Schools, Grant 5022.2006.3).
1
Н, Н(4)); 7.59 (m, 2 Н, Н(2), Н(6)); (Z)ꢀisomer: 6.02 (d, 1 Н,
CН, J = 8.2 Hz); 6.94 (d, 1 Н, CН, J = 8.2 Hz); 7.29 (m, 2 Н, Н(3),
Н(5)); 7.38 (m, 1 Н, Н(4)); 7.59 (m, 2 Н, Н(2), Н(6)). MS,
+
m/z: 184 [M + H] .
References
βꢀChlorostyrene (4a), b.p. 90 °C (18 Torr) (see Ref. 14b).
1
H NMR (CDCl ), δ (Е)ꢀisomer: 6.64 (d, 1 Н, CН, J = 13.8 Hz);
1. V. Nair, S. B. Panicker, L. G. Nair, T. G. George, A. Augustꢀ
ine, Synlett, 2003, 156.
3
6
.84 (d, 1 Н, CН, J = 13.8 Hz); 7.33 (m, 2 Н, Н(3), Н(5)); 7.39 (m,
1
Н, Н(4)); 7.46 (m, 2 Н, Н(2), Н(6)). (Z)ꢀisomer: 5.83 (d, 1 Н,
2. V. Nair, L. Balagopal, R. Rajan, J. Methew, Acc. Chem. Res.,
CН, J = 8.1 Hz); 6.28 (d, 1 Н, CН, J = 8.1 Hz); 7.33 (m, 2 Н, Н(3),
2004, 37, 21.
Н(5)); 7.39 (m, 1 Н, Н(4)); 7.46 (m, 2 Н, Н(2), Н(6)). MS,
m/z: 138 and 140 [М] .
3. V. Nair, S. B. Panicker, A. Augustine, T. G. George, S. Tomas,
M. Vairamani, Tetrahedron, 2001, 34, 7417.
4. S. C. Roy, C. Guin, K. K. Rano, G. Maiti, Tetrahedron Lett.,
2001, 42, 6941.
+
1
ꢀBromoꢀ2ꢀ(4ꢀmethoxyphenyl)ethylene (3b), b.p. 160 °C (18
1
Torr) (see Ref. 15). H NMR (CDCl ), δ (Е)ꢀisomer: 3.82 (s, 3 Н,
3
OMe); 6.61 (d, 1 Н, CН, J = 13.9 Hz); 6.87 (m, 2 Н, Н(2), Н(6));
5. E. Baciocchi, M. Cresenzi, Tetrahedron, 1988, 44, 6525.
7
3
.05 (d, 1 Н, CН, J = 13.9 Hz); 7.24 (m, Н(3), Н(5)); (Z)ꢀisomer:
.82 (s, 3 Н, OMe); 6.32 (d, 1 Н, CН, J = 8.1 Hz); 6.87 (m, 2 Н,
6
. G. I. Nikishin, L. L. Sokova, A. O. Chizhov, V. D. Makhaev,
N. I. Kapustina, Izv. Akad. Nauk, Ser. Khim., 2004, 2105 [Russ.
Chem. Bull., Int. Ed., 2004, 53, 2200].
Н(2), Н(6)); 6.90 (d, 1 Н, CН, J = 8.1 Hz); 7.24 (m, Н(3), Н(5)).
+
MS, m/z: 214 [M + H] .
7
. N. I. Kapustina, L. L. Sokova, V. D. Makhaev, A. P. Borisov,
G. I. Nikishin, Izv. Akad. Nauk, Ser. Khim., 2000, 1870 [Russ.
Chem. Bull., Int. Ed., 2000, 49, 1842].
2
ꢀChloroꢀ1ꢀ(4ꢀmethoxyphenyl)ethylene (4b), b.p. 145 °C
1
(
20 Torr) (see Ref. 16). H NMR (CDCl ), δ (Е)ꢀisomer: 3.79 (s,
3