A NEW LIGAND SYSTEM BASED ON 7'-HYDROXY-3-METHYL-...
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100 ml of pyridine were mixed for 90 min at room
temperature. The mixture was then heated to 90°C and
maintained at this temperature for another 90 min. The
mixture was left for 12 h and then a solution of 25 g of
NaOH (0.625 mol) in 1 l of water was added and the
stirring was continued for 24 h. The mixture was
filtered, the filtrate was acidified with concentrated
HCl. The precipitate was filtered off, washed with
water, and dried. Yield 48%, mp 200°C (toluene) (mp
210°C [21]).
hydrazone in 30 ml of ethanol was added a hot solution
of 0.005 mol of zinc acetate in 10 ml of methanol. The
mixture was refluxed for 30 min. The precipitate was
filtered off, washed with 30 ml of boiling ethanol, and
dried in a vacuum at 100°C. Yield 32%, mp > 300°C.
IR spectrum (mineral oil), ν, cm–1: 3219 (N–H), 1672
1
(С=O), 1642 (С=O), 1596 (C=N). Н NMR spectrum,
δ, ppm (J, Hz): 3.14 s (3Н, NCH3), 4.12 s (5Н, С5Н5),
4.46 s (2Н, С5Н4), 4.84 s (2Н, С5Н4), 5.90 d (1Н, 3-Н,
J 9.34), 6.07 d (1Н, 6-Н, J 8.53), 6.95 d (1Н, 8-Н, J
10.91), 6.99 d (1H, 4'-Н, J 9.39), 7.23 m (2Н, 6-Н, 8-
Н), 7.57 t (1Н, 7-Н, J 7.07), 7.99 d (1H, 5'-Н, J 7.76),
8.43 s (1Н, СНО), 12.11 s (lH, NH). Found, %: C
58.8, H 3.5; N 7.2; Fe 9.6; Zn 5.6. С56H44Fe2N6O10Zn.
Calculated, %: C 59.1, H 3.9; N 7.4; Fe 9.8; Zn 5.7.
Methyl ferrocenecarboxylate. To 5.02 g of ferro-
cenecarboxylic acid (0.09 mol) was added 14 ml of
methanol and 0.05 ml of conc. H2SO4. The mixture
was heated for 25 h and then filtered. The mother
liquor was cooled and filtered. The precipitate was
washed with water. Yield 87%, mp 60°C (methanol–
water, 2:1) [22].
ortho-Methoxybenzaldehyde
ferrocenoylhyd-
razone. To a solution of 10 mmol of o-methoxy-benz-
aldehyde in 30 ml of ethanol was added a solution of
10 mmol of ferrocenecarboxylic acid hydrazide in 60 ml
of ethanol. The mixture was refluxed for 1 h until the
precipitate formation. The precipitate was filtered off
and washed twice with boiling ethanol. Yield 72%, mp
> 300°C (DMF). IR spectrum (mineral oil), ν, cm–1:
Ferrocenecarboxylic acid hydrazide. A mixture
of 2 g (0.082 mol) of methyl ferrocenecarboxylate and
2.1 g (0.042 mol) of hydrazine hydrate (90%) was
heated until complete dissolution and then for another
15 min. After cooling, the precipitate was filtered off,
washed with water, and dried. Yield 50%, mp 170°C
(toluene) [18].
1
3210 (N–H), 1637 (C=O), 1601 (C=N). H NMR
spectrum, δ, ppm (J, Hz): 3.90 s (3Н, ОCH3), 4.17 s
(5Н, С5Н5), 4.93 s (2Н, С5Н4), 5.07 s (2Н, С5Н4), 7.01
7-Hydroxy-3-methyl-8'-formyl-3,4-dihydro-2H-
1,3-benzoxazine-2-spiro-2(H)-chromene ferrocenoyl-
hydrazone. To a solution of 10 mmol of spiropyran I
[23] in 50 ml of ethanol was added a solution of
10 mmol of ferrocenecarboxylic acid hydrazide in 60 ml
of ethanol. The mixture was refluxed for 15 min until
the precipitate formation. The precipitate was filtered
off while hot and washed twice with the boiling
ethanol. Yield 52%, mp > 300°C (dioxane). IR
spectrum (mineral oil), ν, cm–1: 3234 (N–H), 1673
3
2
m (2Н, С6Н4), 7.33 d.d (1H, С6Н4, J 1.46, J 7.11),
2
7.94 d (1Н, J 7.09), 8.72 s (1Н, С=CН), 10.98 s (lH,
NH). Found, %: C 62.8, H 4.9; N 7.8; Fe 15.8. С19H18·
FeN2O2. Calculated, %: C 63.0, H 5.0; N 7.7; Fe 15.5.
The IR spectra were recorded on a Varian Scimitar
1000 spectrometer in the region of 4000–400 cm–1
from mulls in mineral oil or fluorinated hydrocarbons.
1H NMR spectra were obtained at 25°C on a Varian
Unity 300 instrument (300 MHz) from DMSO-d6
solutions relative to internal tetramethylsilane.
1
(С=O), 1664 (С=O), 1616 (C=N). Н NMR spectrum,
δ, ppm (J, Hz): 3.18 s (3Н, NCH3), 4.13 s (5Н, С5Н5),
4.35 s (2Н, С5Н4), 4.83 s (2Н, s, С5Н4), 6.05 d (1Н, 3-
Н, J 9.67), 6.62 d (1Н, 6'-Н, J 8.42), 6.95 d (1Н, 8-Н, J
8.13), 7.05 d (1Н, 4'-Н, J 9.63), 7.22 m (2Н, 6-Н, 8-
Н), 7.51 t (1Н, 7-Н, J 7.22), 7.95 d (1Н, 5'-Н, J 7.10),
8.28 s (1Н, СНО), 11.38 s (1Н, NH), 12.43 s (1Н,
ОН). Found, %: C 52.1, H 4.1; N 7.8; Fe 10.4.
С28H23FeN3O5. Calculated, %: C 51.8, H 4.4; N 7.6; Fe
10.5.
ACKNOWLEDGMENTS
The authors are thankful to G.S. Borodkin
(Southern Federal University) for the registration of 1H
NMR spectra.
REFERENCES
1. Minkin, V.I., Chem. Rev., 2004, vol. 104, p. 2751.
2. Kobatake, S. and Irie, M., Ann. Rep. Prog. Chem. (C),
7-Hydroxy-3-methyl-8'-formyl-3,4-dihydro-2H-
1,3-benzoxazine-2-spiro-2(H)-chromene ferrocenoyl-
hydrazone zinc(II) complex. To a solution of 0.01 mol
7-hydroxy-3-methyl-8'-formyl-3,4-dihydro-2H-1,3-
benzoxazine-2-spiro-2(H)-chromene ferrocenoyl-
2003, vol. 99, p. 277.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012