VANILLIN ESTERS OFALIPHATICACIDS
709
70 eV. IR spectra were recorded on Fourier spectrom-
eter Nicolet Protege-460. NMR spectra were registered
on spectrometers Bruker AC-500 (500 MHz) and Tesla
BS-567 (100MHz) in DMCO-d6, internal reference TMS.
Melting points were measured on a Koeffler heating
block..
1.121.90 m (3 CN2), 2.58 m (CH2), 3.88 s (OMe),
7.13 d, 7.44 m (3H, H arom), 9.95 s (CH). Found, %:
C 66.39; H 7.73. C14H20O4.Calculated, %: C 66.67;
H 7.94.
Compound (Ig). Yield 82%, bp 163164°C (0.5 mm
Hg), nD20 1.5092. 1H NMR spectrum, d, ppm: 0.96 (Me),
1.151.88 m (4 CH2), 2.51 m (CH2), 3.86 s (OMe),
7.12 d, 7.45 m (3H, H arom), 9.91 s (CH). Found, %:
C 67.48; H 8.19. C15H22O4.Calculated, %: C 67.67;
H 8.27.
3-Methoxy-4-formylphenyl Iak. To a solution of
0.2 mol of vanillin in 500 ml of anhydrous CH2Cl2 was
charged 0.25 mol of anhydrous pyridine and by small por-
tions with intermittent shaking of the reactor flask was
added 0.2 mol of acyl chloride preliminary prepared in
the following fasion: 1 mol of an appropriate carboxylic
acid was boiled for 6 h with 1.3 mol of SOCl2 in 500 ml of
benzene with subsequent distilling off of benzene and dis-
tillation of the product (for tridecanoyl chloride in a
vacuum) The reaction mixture was heated at reflux for
1 h, CH2Cl2 was distilled off at heating on a water bath,
the residue was dissolved in 500 ml of benzene, thrice
washed with water, thrice with 5% water solution of
NaHCO3, and dried with CaCl2. The solvent was dis-
tilled off, the residue was distilled in a vacuum or recrystal-
lized from a mixture benzenehexane, 1:1. The residue of
compounds Iik was uncrystallizable viscous substance.
Compound (Ih). Yield 77%, bp 170171°C (0.5 mm
Hg) , nD20 1.5079. 1H NMR spectrum, d, ppm: 0.92 (Me),
1.32 m (4 CN2), 1.79 m (CN2), 2.60 m (CN2), 3.88 s
(OMe), 7.14 d, 7.47 m (3H, H arom), 9.90 s (CH). Found,
%: C 68.83; H 7.69. C16H22O4. Calculated, %: C 69.06;
H 7.91.
1
Compound (Ii). Yield 75%, viscous substance. H
NMR spectrum, d, ppm: 0.89 (Me), 1.30 m (9 CH2),
1.75 m (CH2), 2.59 m (CH2), 3.87 s (OMe), 7.16 d, 7.41 m
(3H, H arom), 9.91 s (CH). Found, %: C 72.10; N 8.84.
C21H32O4. Calculated, %: C 72.41; H 9.19.
1
Compound (Ij). Yield 78%, viscous substance. H
NMR spectrum, d, ppm: 3.88 s (OMe), 4.39 s (CH2),
7.24 d, 7.50 m (3H, H arom) 9.89 s (CH). Found, %:
C 52.36; H 3.98; Cl 15.40. C10H9ClO4. Calculated, %:
C 52.54: H 3.94: Cl 15.50.
Compound (Ia). Yield 92%, mp 7879°C (publ.: mp
7779°C [12]). 1N NMR spectrum, d, ppm: 2.32 s (Me),
3.92 m (OMe), 7.18 d, 7.48 m (3H, H arom), 9.92 s (CH).
Compound (Ib). Yield 79%, mp 3334°C. 1H NMR
spectrum, d, ppm: 1.25 t (Me), 2.52 q (CH2), 3.84 s
(OMe), 7.13 d, 7.42 m (3H, H arom), 9.88 s (CH). Found,
%: C 63.29; H 5.73. C11H12O4. Calculated, %: C 63.46;
H 5.77.
Compound (Ic). Yield 81%, bp 137138°C (0.5 mm
Hg), nD20 1.5281. 1N NMR spectrum, d, ppm: 1.02 t (Me),
1.63 m (CH2), 2.51 t (CH2), 3.84 s (OMe), 7.15 d, 7.40 m
(3H, H arom), 9.90 s (CH). Found, %: C 64.11; H 7.02.
C12H16O4. Calculated, %: C 64.28; H 7.14.
Compound (Id). Yield 89%, mp 2930°C. 1H NMR
spectrum, d, ppm: 1.35 d, 2.88 m (7H, i-Pr), 3.90
C (OMe), 7.21 d, 7.50 m (3H, H arom), 9.96 s (CH).
Found, %: C 64.72; H 6.19. C12H14O4. Calculated, %:
C 64.86; H 6.31.
1
Compound (Ik). Yield 76%, viscous substance. H
NMR spectrum, d, ppm: 2.28 s (Me), 3.06 t (CH2),
3.86 s (OCH3), 4.35 t (CN2), 6.637.52 m (8H, H arom),
9.90 C (CH). Found, %: C 71.22; H 5.94. C17H18O4. Cal-
culated, %: C 71.33; H 6.29 .
2-Methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydro-
benzo[b][4,7]phenanthrolin-12-yl)phenyl alkanoates
(Vak, VIak). A mixture of 0.005 mol of an appropri-
ate ester Iak, 0.005 mol of 6-aminoquinoline (II),
0.005 mol of 1,3-cyclohexanedione (III) or dimedone (IV),
and 20 ml of 1-butanol was boiled for 34 h. The precipi-
tate of reaction product Vad and VIad separated on
cooling (for compounds Veg, i, k, VIeg, j, k after
evaporating solvent to 1/31/2 of reaction mixture vol-
ume) was filtered off, twice treated with ethyl ether to
remove unreacted initial compounds, and dried. In case
of phenanthrolines Vh, VIh, i the solvent was evapo-
rated to formation of a resinuous residue that was ground
with a glass rod under ether till crystallization, the sepa-
rated crystals were filtered off and washed with ether.
Compound (Ie). Yield 76%, bp 149150°C (0.5 mm
Hg), nD20 1.5273. 1H NMR spectrum, d, ppm: 0.96 t (Me),
1.201.90 m (2 CN2), 2.62 t (CH2), 3.96 s (OMe),
7.15 d, 7.38 m (3H, H arom), 9.90 s (CH). Found, %:
C 65.31; N 7.42. C13H18O4.Calculated, %: C 65.55;
H 7.56.
The study was carried out under financial support of
Belarus Republic Foundation for Basic Research (grant
no. X03-079)
Compound (If). Yield 85%, bp 155156°C (0.5 mm
Hg), nD20 1.5068. 1H NMR spectrum, d, ppm: 0.90 (Me),
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004