New esters of vanillin and vanillal with some alkane- and arenecarboxylic acids

Article abstract of DOI:10.1134/S1070427206060322

Previously unknown esters were synthesized by the reaction of vanillin and vanillal with carboxylic acid chlorides. Pleiades Publishing, Inc., 2006.

Full text of DOI:10.1134/S1070427206060322

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 6, pp. 1035 1037.
Pleiades Publishing, Inc., 2006.
Original Russian Text
E.A. Dikusar, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 6, pp. 1043 1045.
BRIEF
COMMUNICATIONS
New Esters of Vanillin and Vanillal
with Some Alkane- and Arenecarboxylic Acids
E. A. Dikusar
Institute of Physicoorganic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus
Received February 13, 2006
Abstract Previously unknown esters were synthesized by the reaction of vanillin and vanillal with car-
boxylic acid chlorides.
DOI: 10.1134/S1070427206060322
Natural plant aldehydophenols, vanillin and vanil-
lal (Ia, Ib), are available precursors for preparing
fragrance compounds and food aromatizers [1 3],
medical products, and biologically active compounds
[4 8]:
Esters IIa IIh and IIIa IIIv were synthesized by
the reaction of vanillin and vanillal (Ia, Ib) with chlo-
rides of the corresponding alkane- and arenecarboxylic
acids in anhydrous benzene in the presence of pyri-
dine. We used the stoichiometric ratio of the reactants,
1 : 1 : 1. As a result of this reaction, the initial alde-
hydophenols Ia and Ib were converted to the corre-
sponding esters IIa IIh and IIIa IIIv with a yield of
90 96%.
CHO
RO
Vanillin and vanillal esters IIa IIh and IIIa IIIv
are colorless viscous liquids or crystalline substances
(crystallized from a mixture of benzene and hexane)
(see table). The esters do not require additional puri-
fication, distillation, or recrystallization.
OC(O)R
IIa IIh, IIIa IIIv
where II, R is Me, R is (a) (CH2)7Me, (b) (CH2)14Me,
(c) cyclo-C6H11, (d) (CH2)2C6H5, (e) CBrCCl=CCl2,
(f) (CH2)2C(O)OMe, (g) C(CN)=CHC6H5, and (h)
3,5-C6H3(NO2)2; III, R is Et, R is (a) (CH2)4Me,
(b) (CH2)5Me, (c) (CH2)6Me, (d) (CH2)7Me,
(e) (CH2)8Me, (f) (CH2)11Me, (g) (CH2)14Me,
(h) (CH2)16Me, (i) cyclo-C6H11, (j) CH2C6H5,
(k) (CH2)2C6H5, (l) CH2CHMeC6H5, (m) trans-
CH=CHC6H5, (n) CBrCCl=CCl2, (o) CHBrCHBrC6H5,
(p) (CH2)2C(O)OMe, (q) C(CN)=CHC6H5, (r) 2,4-
C6H3C12, (s) 2,4-CH2OC6H3C12, (t) 3-C6H5NO2,
(u) 4-C6H5NO2, and (v) 3,5-C6H3(NO2)2.
The structure and composition of vanillin and van-
illal esters IIa IIh and IIIa IIIv were confirmed
by elemental analysis, cryoscopic determination of
1
the molecular weight (see table), and H NMR, IR,
1
and UV spectra. According to the H NMR data, the
purity of the resulting compounds was 98 1%.
In the IR spectra of vanillin and vanillal esters IIa
IIh and IIIa IIIv, there are the following character-
1
istic absorptions bands, , cm : 3100 3000 (CHAr),
2990 2795 (CHAlk), 2740 5 (CH of CHO group),
1720 1770 (C=O of ester group), 1695 1705 (C=O
of CHO group), 1600 1350 (vibrations of aromatic
system), 1300 1000 (C O vibrations), and 800 600
(CHAr) [1, 3].
Here we describe a convenient procedure for pre-
paring new esters of vanillin and vanillal with a num-
ber of alkane- and arenecarboxylic acids (IIa IIh and
IIIa IIIv).
In the UV spectra of vanillin and vanillal esters
IIa IIh and IIIa IIIw, there are the following absorp-
tion peaks, max, nm ( ): 206 (9000), 224 (15000),
260 (8000), and 310 (3000), caused by the presence
of the 4-alkanoyloxy-3-alkoxybenzaldehyde fragment
Esters IIa IIh and IIIa IIIv were prepared by
simpler, more convenient, and more practically feasi-
ble procedure in comparison with that described pre-
viously for similar compounds [1 3].
1035

1036
DIKUSAR
Characteristics of vanillin and vanillal esters IIa IIh and IIIa IIIv
Found, %
Yield,
Calculated, %
M
Ester
IIa*
mp,
C
Formula
%
C
H
C
H
found
calculated
90
92
90
93
93
90
94
96
90
93
92
92
93
91
90
96
92
91
93
94
93
94
94
92
93
90
91
91
90
90
70.02
74.05
68.90
71.94
36.08
58.91
70.58
52.17
68.37
69.18
70.02
70.64
71.45
73.08
74.30
75.14
69.75
71.98
72.74
73.32
73.21
37.66
47.50
60.27
71.54
56.92
55.68
61.20
61.15
53.60
8.34
9.93
7.11
5.75
2.12
5.42
4.35
3.10
7.65
8.01
8.29
8.60
8.95
9.49
10.00
10.31
7.42
5.77
6.19
6.58
5.60
2.47
3.59
5.85
4.76
3.70
3.95
4.25
4.20
3.38
C17H24O4
69.84
73.81
68.69
71.82
35.81
58.65
70.35
52.03
68.16
69.04
69.84
70.56
71.22
72.89
74.22
74.96
69.55
71.82
72.47
73.06
72.96
37.49
47.40
60.00
71.33
56.66
55.31
60.95
60.95
53.34
8.27
9.81
6.92
5.67
2.00
5.30
4.26
2.91
7.63
7.91
8.27
8.55
8.81
9.45
9.96
10.25
7.29
5.67
6.08
6.45
5.44
2.42
3.54
5.75
4.70
3.57
3.82
4.16
4.16
3.36
281.9
372.3
252.7
275.5
393.4
254.4
300.2
328.3
258.6
270.1
286.6
299.2
313.0
354.7
395.6
426.8
270.0
277.1
290.3
300.5
288.7
402.9
442.3
271.7
314.6
329.8
354.2
303.4
308.0
348.9
292.4
390.6
262.3
284.3
402.5
266.3
307.3
346.3
264.3
278.3
292.4
306.4
320.4
362.5
404.6
432.6
276.3
284.3
298.3
312.4
296.3
416.5
456.1
280.3
321.3
339.2
369.2
315.3
315.3
360.3
IIb
IIc
37 38
73 74
46 47
103 104
72 73
165 166
163 164
C24H38O4
C15H18O4
C17H16O4
C12H8BrCl3O4
C13H14O6
C18H13NO4
C15H10N2O8
C15H20O4
C16H22O4
C17H24O4
C18H26O4
C19H28O4
C22H34O4
C25H40O4
C27H44O4
C16H20O4
C17H16O4
C18H18O4
IId
IIe**
IIf
IIg**
IIh**
IIIa*
IIIb*
IIIc*
IIId*
IIIe*
IIIf
42 43
35 36
47 48
61 62
IIIg
IIIh
IIIi
IIIj*
IIIk
73 74
IIIl*
IIIm
IIIn**
IIIo**
IIIp*
IIIq**
IIIr**
IIIs**
IIIt**
IIIu**
IIIv**
C19H20O4
C18H16O4
107 108
84 85
110 111
C13H10BrCl3O4
C18H16Br2O4
C14H16O6
C19H15NO4
C16H12Cl2O4
C17H14Cl2O5
C16H13NO6
C16H13NO6
C16H12N2O8
127 128
117 118
107 108
133 134
155 156
137 138
*
20 20
d
, n : 0.9908, 1.5090 (IIa); 0.9169, 1.5090 (IIIa); 0.9679, 1.5070 (IIIb); 0.9358, 1.5065 (IIIc); 0.9103, 1.5060 (IIId);
D
20
0.9213, 1.5030 (IIIe); 1.2079, 1.5700 (IIIj); 1.0866, 1.5580 (IIIl); 1.1222, 1.5234 (IIIp).
**
Br + Cl, %: found 46.10, calculated 46.28 (IIe); N, %: found 4.30, calculated 4.56 (IIg); N, %: found 7.90, calculated 8.09 (IIh);
Br + Cl, %: found 44.45, calculated 44.72 (IIIn); Br, %: found 34.88, calculated 35.04 (IIIo); N, %: found 4.03, calculated
4.36 (IIIq); Cl, %: found 20.70, calculated 20.91 (IIIr); Cl, %: found 18.93, calculated 19.21 (IIIs); N, %: found 4.37, calcu-
lated 4.44 (IIIt); N, %: found 4.30, calculated 4.44 (IIIu); N, %: found 7.51, calculated 7.78 (IIIv).
[1]. In addition, the UV spectra of esters of function-
ality substituted and aromatic carboxylic acids (IId,
IIe, IIg, IIh, IIIj IIIo, and IIIq IIIv) contain ab-
sorption bands typical of the corresponding fragments
of these acids [3].
(CH2). The aromatic protons of esters IIa IIh and
IIIa IIIv (C6H3) give a multiplet in the range 7.10
7.60 ppm, and the aldehyde proton of the CHO group
gives a singlet in the range 9.95 10.0 ppm. The H
NMR spectra of compounds IIa IIh and IIIa IIIv
1
contain characteristic signals of ester fragments [1, 3].
1
In the H NMR spectra of vanillin derivatives IIa
IIh, the MeO group gives a singlet in the range 3.90
3.96 ppm, and in the H NMR spectra of vanillal de-
EXPERIMENTAL
1
rivatives IIIa IIIv the EtO group gives a triplet at
1.40 1.45 ppm (Me) and a quartet at 4.08 4.18 ppm
The IR spectra were recorded on a Protege-460
Nicolet Fourier spectrophotometer in thin layer or
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 79 No. 6 2006

NEW ESTERS OF VANILLIN AND VANILLAL WITH SOME ALKANE- AND ARENECARBOXYLIC ACIDS 1037
4
in KBr. The UV spectra of 1 10 M solutions in
methanol were recorded on a Specord UV-Vis spec-
CONCLUSIONS
1
trophotometer. The H NMR spectra were recorded on
(1) An improved procedure was developed for
preparing vanillin and vanillal esters with a yield of
90 96%.
a Tesla BS-587A spectrometer operating at 100 MHz
(5% solutions in CDCl3, TMS internal reference).
The molecular weights were determined cryoscopical-
ly in benzene.
(2) Some of the resulting compounds may be of
interest as components for perfume and food industry
and can serve as accessible precursors in synthesis of
biologically active substances and medicinals.
Carboxylic acid chlorides were synthesized by re-
fluxing the corresponding carboxylic acids with a
1.5-fold excess of SOCl2 in benzene. Freshly distilled
carboxylic acid chlorides and anhydrous benzene and
pyridine were used.
REFERENCES
1. Dikusar, E.A., Vyglazov, O.G., Moiseichuk, K.L., et al.,
Vanillin and vanillal alkanoates IIa IIh and
IIIa IIIv. To a solution of 0.02 M of vanillin or van-
illal (Ia, Ib) and 0.02 mol of alkene- or arenecarbox-
ylic acid chlorides in 50 ml of benzene, a solution of
0.02 mol of pyridine in 10 ml of benzene was added
with shaking. The vessel with the reaction mixture
was hermetically sealed and the mixture allowed to
stay for 10 12 h at 20 23 C with intermitted careful
shaking. Then it was placed in a separating funnel,
thoroughly washed with water and 20% NaCl for sup-
pression of emulsion formation, and washed 2 3 times
with 5% NaHCO3. The organic layer was separated
and filtered through a paper filter. Benzene was re-
moved in a vacuum, with heating of the residue above
30 C avoided. Compounds IIb IIh, IIIf IIIi, IIIk,
IIIm IIIo, and IIIq IIIv were crystallized from
a mixture of benzene and hexane.
Zh. Prikl. Khim., 2005, vol. 78, no. 1, pp. 122 126.
2. Dikusar, E.A. and Kozlov, N.G., Khim. Prirodn. So-
edin., 2005, no. 1, pp. 74 75.
3. Dikusar, E.A. and Kozlov, N.G., Zh. Org. Khim., 2005,
vol. 41, no. 7, pp. 1015 1019.
4. Kozlov, N.G., Basalaeva, L.I., and Dikusar, E.A.,
Khim. Prirodn. Soedin., 2004, no. 1, pp. 70 73.
5. Dikusar, E.A., Kozlov, N.G., Zhukovskaya, N.A., and
Moiseichuk, K.L., Khim. Prirodn. Soedin., 2004, no. 2,
pp. 154 156.
6. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., et al., Khim.
Prirodn. Soedin., 2005, no. 2, pp. 164 169.
7. Dikusar, E.A., Kozlov, N.G., and Potkin, V.I., Vestsi
Nats. Akad. Navuk Bel., Ser. Khim., 2005, no. 4,
pp. 39 46.
8. Kozlov, N.G., Basalaeva, L.I., and Dikusar, E.A.,
Zh. Org. Khim., 2005, vol. 41, no. 11, pp. 1671 1680.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 79 No. 6 2006