Acetals and vinyl ethers of unsaturated aldehydes and ketones in the new syntheses of heterocyclic compounds: XII. New alternatives of acid condensation of cyclohexane-1,4-diones with hydroxyarylaldehydes under dehydration conditions. Fluorecence spectra of the products

Article abstract of DOI:10.1023/A:1012433903229

1,3-Diethoxy-2-R-5,5-R',R'-1-cyclohexenylium perchlorates in condensation with 2-hydroxyaryl-aldehydes under dehydration conditions give rise to 3-ethoxy-1,2-dihydroxanthylium perchlorates that with the second molecule of 2-hydroxyarylaldehyde afford 13H-chromeno[3,2-b]xanth-5-ylium perchlorates, and with primary and secondary amines yield 3-(R²,R³-amino)-1,2-dihydroxanthylium perchlorates. The condensation of 2-bromodimedone with salicylaldehydes in triethyl orthoformate and perchloric acid medium furnished 6-bromo-13,13-dimethyl-13H-chromeno[3,2-b]xanth-5-ylium perchlorates. The latter compounds show strong fluorescence in 530-630 nm region with 0.48-0.98 quantum efficiency. Under similar conditions the dimedone and 2-acetyldimedone afford with 2-hydroxyarylaldehydes tris-condensation products: 2,10-dimethoxy-6-(3-methoxy-6-oxo-2,4-cyclohexadienylidenemethyl)-7,7-dimethyl-7H-chromeno[2,3-a]-xanth-13-ylium perchlorate and 2,10-dimethoxy-6-(6-methoxychromylium-2-yl)-13,13-dimethyl-13H-chromeno[3,2-b]xanth-5-ylium diperchlorate respectively.

Full text of DOI:10.1023/A:1012433903229

Russian Journal of Organic Chemistry, Vol. 37, No. 4, 2001, pp. 527 538. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 4, 2001,
pp. 562 573.
Original Russian Text Copyright
2001 by E. Olekhnovich, Boroshko, Korobka, Metelitsa, L. Olekhnovich.
Acetals and Vinyl Ethers of Unsaturated Aldehydes and Ketones
in the New Syntheses of Heterocyclic Compounds: XII.* New
Alternatives of Acid Condensation of Cyclohexane-1,4-diones
with Hydroxyarylaldehydes under Dehydration Conditions.
Fluorecence Spectra of the Products**
E. P. Olekhnovich, S. L. Boroshko, I. V. Korobka, A. V. Metelitsa, and L. P. Olekhnovich
Research Institute of Physical and Organic Chemistry, Rostov State University, Rostov-on-Don, 344090 Russia
Received August 4, 1999
Abstract 1,3-Diethoxy-2-R-5,5-R ,R -1-cyclohexenylium perchlorates in condensation with 2-hydroxyaryl-
aldehydes under dehydration conditions give rise to 3-ethoxy-1,2-dihydroxanthylium perchlorates that with
the second molecule of 2-hydroxyarylaldehyde afford 13H-chromeno[3,2-b]xanth-5-ylium perchlorates, and
with primary and secondary amines yield 3-(R2,R3-amino)-1,2-dihydroxanthylium perchlorates. The
condensation of 2-bromodimedone with salicylaldehydes in triethyl orthoformate and perchloric acid
medium furnished 6-bromo-13,13-dimethyl-13H-chromeno[3,2-b]xanth-5-ylium perchlorates. The latter
compounds show strong fluorescence in 530 630 nm region with 0.48 0.98 quantum efficiency. Under
similar conditions the dimedone and 2-acetyldimedone afford with 2-hydroxyarylaldehydes tris-condensation
products: 2,10-dimethoxy-6-(3-methoxy-6-oxo-2,4-cyclohexadienylidenemethyl)-7,7-dimethyl-7H-
chromeno[2,3-a]-xanth-13-ylium perchlorate and 2,10-dimethoxy-6-(6-methoxychromylium-2-yl)-13,13-
dimethyl-13H-chromeno[3,2-b]xanth-5-ylium diperchlorate respectively.
The condensation of 1,3-diketones and 2-hydroxy-
arylaldehydes under treatment with perchloric acid is
known to occur at the central carbon atom of the
carbon triad of the diketone yielding 2-hydroxystyryl
derivatives that cyclize further into benzpyrylium
salts I [2]. With 1,3-diketones possessing terminal
methyl groups (acetylacetone, benzoylacetone) the
condensation affords 3-acetyl(benzoyl)-2-(2-hydroxy-
styryl)-1-benzopyrylium perchlorate (II) [3, 4].
Oxoenols containing a methyl group in 1 position
(benzoylacetone, pivaloylacetone) with triethyl ortho-
formate and perchloric acid give rise to 2-R-4-ethoxy-
pyrylium perchlorates III [5]. Under such conditions
from dimedone and dibenzoylmethane were obtained
stable perchlorates of 5,5-dimethyl-1,3-diethoxy-1-
cyclohexenylium (IVa) and 1,3-diphenyl-1,3-di-
ethoxypropenylium (V) respectively [6] that could
operate as synthons in preparation of cyclic and
acyclic oxoenols derivatives by replacement of the
ethoxy groups [7].
Thus in reaction of oxoenols with more basic
2-hydroxyarylaldehydes [8] the reactive form is the
protonated aldehyde function, and the condensation
occurs at the central atom of the oxoenol carbon triad.
On the contrary, in reaction with triethyl ortho-
formate the 1,3-diketone is more basic, and it is
*
For communication XI, see [1].
The study was carried out under financial support of the
**
Russian
Foundation
for
Basic
Research
(grant
nos. 96-03-33360a and 97-03-32895a).
1070-4280/01/3704-0527$25.00 2001 MAIK Nauka/Interperiodica

528
OLEKHNOVICH et al.
stabilized on protonation as 1,3-dihydroxypropenyl-
ium cation. Therefrom it may be concluded that the
choice of reagents and condensation conditions for
the reaction with 2-hydroxyarylaldehydes may result
in compounds with important physico-chemical
characteristics unlike the products of Knoevenagel
condensation [9].
In the IR spectra of perchlorates VIIa i are present
absorption bands in the region 1570 1590, 1200
1
1250, 1050 1150 cm characteristic of the bonds
C=C, C O C, and ClO respectively [11]. The data
on yields, melting points, and composition of com-
pounds VIIa i are given in Table 3, parameters of IR
1
and H NMR spectra in Table 5. Electron absorption
spectra of compounds VIIb h in acetonitrile solution
contain two bands in the longwave region with
pronounced vibronic structure: two strong [ (2.5
In the study were used 1,3-diethoxy-2-R-5,5-
R ,R -1-cyclohexenylium perchlorates, unsubstituted
and 2-substituted 5,5-dimethylcyclohexane-1,3-dione,
dehydrating reagents (triethyl orthoformate, acetic
anhydride), 70% perchloric acid, 16% solution of
perchloric acid in acetic acid, and various 2-hydroxy-
arylaldehydes. Since a propenyl cation of IV type
derived from dimedone has two activated methylene
groups in 4 and 6 positions it seemed promising to
use it in condensation with hydroxyarylaldehydes.
To this end were studied the previously described
perchlorate IVa [6], and also first obtained per-
chlorates of 2-bromo-5,5-dimethyl-1,3-diethoxy-
cyclohexenylium (IVb) and 1,3-diethoxy-1-cyclo-
hexenylium (IVc).
1
1
abs
6.0) 104 lmol cm ] bands with maxima
and
in the region 494 532 and 527 5581nmmax
abs
respec2tmivaexly (Table 1). Electron-donor substituents
(R3 = Br, CH3O) provide a shift of the maxima
abs
1max
abs
and
to the longwave region with
2max
respect to those in the unsubstituted compound VIIb
(R1 = H), and electron-acceptor group (R3 = NO2)
effects a shift to the shortwave region. The aceto-
nitrile solutions of perchlorates VIIa h show strong
fluorescence with the quantum efficiency 0.73 0.98
(Table 1). The fluorescence spectra of compounds
VIIb h solutions are wide bands with two maxima
fl
fl
and 2max, whereas the short-wave maximum
1max
fl
At equimolar ratio of 2-hydroxyarylaldehydes VI
with 1,3-diethoxy-2-R-5,5-R ,R -1-cyclohexenylium
perchlorates IVa c under dehydrating conditions
(triethyl orthoformate, acetic anhydride) the condens-
ation furnished perchlorates of substituted 3-ethoxy-
1,2-dihydroxanthylium VIIa i. Salts VII can form
along two alternative routes: the first path starts with
replacement of the ethoxy group by phenoxy one (P1)
with subsequent condensation; along the second path
occurs the condensation of a formyl group (P2)
followed by transetherification. The first path is
presumably more probable since as has been stated in
[1] perchlorate IVa does not react with anisaldehyde
apparently because of steric hindrance from the
methyl groups in position 5. The condensation of
perchlorates IVa, b with two moles of 2-hydroxy-
arylaldehyde VI, or of salts VIIa i with one mole of
aldehyde VI results in 13H-chromeno[3,2-b]xanth-5-
ylium perchlorates VIIIa n (Scheme 1). Certain
perchlorates of VIII type were prepared before [10]
and were used as luminescent dyes photoactive in the
region 600 650 nm. For instance, salts VIII were
prepared from dimedone sodium salts, its 2-alkyl
derivatives, butyllithium, and sodium salts of
2-hydroxyarylaldehydes with subsequent hydrolysis
and treatment with perchloric acid, and the yields did
not exceed 16%. Unlike that our procedure permits
application of 2-halosubstituted dimedones and
provides also nonsymmetrical salts VIIId f in 50
75% yield.
(
(
1max) is stronger than that in the longwave region
fl
2max). The latter maximum in the spectrum of
compound VIIc appears as a shoulder. The maxima
of the fluorescent bands are located in the regions
532 570 and 570 620 nm respectively. The position
of the bands in the fluorescence excitation spectra is
the same as the maxima in the corresponding electron
absorption spectra. The electron-acceptor character-
istics of the R3 substituent affect the fluorescent
spectra similarly to the effect on the electron absorp-
tion spectra discussed above.
Physical constants, yields, and elemental analyses
of perchlorates VIII are given in Table 4, the spectral
characteristics are presented in Table 6. In the elec-
tron absorption spectra of compounds VIIIa j, of
their bromoderivatives VIIIk v appear as in the
respective spectra of compounds VIIa h absorption
abs
1max
bands in the longwave region with two maxima
abs
and
.
2max
The electron-donor properties of the R1 = Br
substituent appear as red shift of the absorption
maxima in the brominated compounds with respect
to nonbrominated VIIIa j compounds (R1 = H) (e.g.
comparing compounds VIIIb with VIIIk, VIIIc with
VIIIn) (Table 2). In each series VIIIa j and VIIIk v
the effect of electronic properties of substituents
R3 R8 on the absorption spectra is similar to that
observed in the spectra of compounds VII: the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

ACETALS AND VINYL ETHERS OF UNSATURATED ALDEHYDES: XII.
529
Scheme 1.
VII, R1 = R2 = R4 = R5 = H, R3 = CH3O (a); R2 = CH3, R1 = R5 = H (b); R2 = CH3, R3 = CH3O, R1 = R4 =
R5 = H (c); R2 = CH3, R1 = R3 = R4 = H, R5 = CH2CH= CH2 (d); R2 = CH3, R3 = Br, R1 = R4 = R5 = H (e);
R2 = CH3, R3 = NO2, R1 = R4 = R5 = H (f); R2 = R4 = R5 = R6 = R7, R3 = CH3, R1 = R4 = R5 = H (g);
R1 = Br, R2 = CH3, R3 = R4 = R5 = H (h); R1 = Br, R2 = CH3, R3 = CH3O, R4 = R5 = H (i); VIII, R1 =
R2 = H, R4 = R5 = R6 = R7 = H, R3 = R8 = CH3O (a); R1 = H, R2 = CH3, R3 = R4 = R5 = R6 = R7 = R8 = H
(b); R2 = CH3, R1 = H, R3 = R8 = CH3O, R4 = R5 = R6 = R7 = H (c); R2 = CH3, R1 = H, R3 = CH3O, R8 =
NO2, R4 = R5 = R6 = R7 = H (d); R2 = CH3, R1 = H, R3 = CH3O, R8 = Br, R4 = R5 = R6 = R7 = H (e); R2 =
CH3, R1 = H, R3 = CH3O, R4 = R5 = R6 = R7 = R8 = H (f); R2 = CH3, R1 = H, R3 = CH3O, R6 =
CH2CH= CH2 (g); R2 = CH3, R1 = H, R3 = CH3O, R7 = OH, R4 = R5 = R6 = H, R8 = H (h); R2 = CH3, R1 =
H, R3 = R8 = CH3O, R6 = NO2, R4 = R5 = H, R7 = H (i); R2 = CH3, R1 = H, R3 = CH3O, R4 = R5 = H, R6 =
R8 = Cl, R7 = H (j); R2 = CH3, R1 = Br, R3 = R4 = R5 = R6 = R7 = R8 = H (k); R2 = CH3, R1 = Br, R3 =
R8 = CH3, R4 = R5 = R6 = R7 = H (l); R2 = CH3, R1 = Br, R4 = R7 = CH3, R3 = R5 = R6 = R8 = H (m);
R2 = CH3, R1 = Br, R3 = R8 = CH3O, R4 = R5 = R6 = R7 = H (n).
fl
electron-acceptor groups produce blue shift of the
maxima of the longwave band, the electron-donor
groups produce red shift. Note that perchlorate VIIIu,
VIIIa j are located in the region
537 590 and
1max
fl
570 630 nm.
2max
[R3
=
R8
=
N(CH3)2], has a single longwave
The maxima of the fluorescence bands of the salts
VIIIk v are somewhat shifted to more longwave
maximum in acetonitrile solution at 698 nm. The
acetonitrile solutions of compounds VIIIa j and
VIIIk v show fluorescence with quantum efficiency
0.54 0.96 and 0.48 0.87 respectively (Table 2). The
maxima of the fluorescence bands of perchlorates
fl
1max
fl
region:
558 590 and
595 634 nm.
2max
Therewith the fluorescence band of compound VIIIu
[R3 = R8 = N(CH3)2] has a single maximum at
715 nm. The quantum efficiencies of fluorescence for
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

530
OLEKHNOVICH et al.
Table 1. Electron absorption spectra and fluorescence
spectra of derivatives of 1,2-dihydroxanthylium VIIb e;
IXa k; Xa e, and XIIb in acetonitrile solution
Table 2. Electron absorption spectra and fluorescence
spectra of perchlorates of 13H-chromeno[3,2-b]xanth-5-
ylium (VIIIa v) in acetonitrile solution
No.
Absorption
Fluorescence
No.
Absorption
Fluorescence
a
a
,
103,
l mol cm
,
,
103,
l mol cm
,
max
max
max
max
1
1
1
1
nm
nm
nm
nm
VIIb
VIIc
VIIe
VIIf
VIIg
IXa
IXb
IXc
IXd
IXe
IXf
498
532
44.86
60.87
536
580
0.96
0.73
0.98
0.87
0.80
0.82
0.86
0.84
0.82
0.81
0.88
0.92
0.83
0.88
0.77
VIIIa
VIIIb
VIIIc
VIIId
VIIIe
VIIIf
VIIIg
VIIIh
VIIIi
VIIIj
VIIIk
VIIIl
VIIIm
VIIIn
VlIIo
VIIIp
VIIIq
VIIIr
VIIIs
VIIIt
528
562
498
532
521
558
521
559
502
539
534
573
521
558
534
573
521
558
521
561
512
548
519
556
525
563
532
573
510
548
519
558
517
556
514
553
514
551
514
553
698
532
573
31.33
36.56
69.70
85.56
51.75
74.34
57.57
81.81
49.36
64.70
54.68
84.34
58.50
83.88
37.22
62.91
46.03
63.25
69.28
96.87
22.59
33.54
53.12
82.80
25.00
40.16
56.03
85.65
36.26
57.69
27.76
45.02
71.00
102.25
59.15
87.73
66.77
105.16
60.73
90.38
81.79
66.23
113.76
580
0.51
0.96
0.70
0.74
0.72
0.78
0.74
0.54
0.67
0.76
0.48
0.82
0.69
0.53
0.61
0.65
0.75
0.78
0.85
0.87
537
570
570
620
570
620
543
588
588
630
570
620
590
625 fl
570
620
570
620
560
595 fl
570
620
573
620
590
634
558
628
570
618
565
620
564
605 fl
560
600 fl
565
620
715
570
620
521
558
38.75
59.20
570
620 fl
502
537
37.50
52.61
552
590
494
527
39.02
53.28
543
590
514
544
26.5
49.6
532
570
521
558
65.74
100.27
570
620
521
557
61.69
94.47
570
620
521
558
77.68
118.14
570
620 fl
527
558
62.28
95.07
570
620 fl
521
558
81.42
123.04
570
620
521
558
55.06
78.97
570
620
IXg
IXh
IXi
521
558
56.17
83.24
570
620
521
558
46.10
66.63
570
620
498
532
60.33
73.33
537
580
IXj
521
558
22.08
33.87
570
620
Xa
521
558
521
558
521
558
521
558
521
558
3.80
5.45
3.60
4.90
3.42
3.50
6.35
9.16
9.62
17.25
570
620
570
620
570
620
570
620
570
620
0.89
0.89
0.62
0.84
0.86
Xb
Xc
Xd
XIIb
VIIIu
VIIIv
0.66
a
a
Quantum efficiency of fluorescence.
Quantum efficiency of fluorescence.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

ACETALS AND VINYL ETHERS OF UNSATURATED ALDEHYDES: XII.
531
Table 3. Yields, melting points, and elemental analyses of derivatives of 1,2-dihyroxanthylium VIIb i, IXa j, Xa d,
XIa d, XIIa,b
Compd. Yield,
mp,
C
Found, %
Calculated, %
no.
%
Formula
C
H
Hlg
N
C
H
Hlg
N
VIIb
62
70
57
64
74
65
69
73
78
74
76
71
52
46
54
68
68
59
91
94
81
89
90
92
85
92
91
207 210
194 195
108 110
238 240
247 249
201 203
184 186
192 193
208 209
221 222
210 213
197 199
246 248
230 232
276 277
244 245
271 273
206 207
179 180
153 154
129 130
152 153
201 203
208 210
195 196
214 215
181 183
136 137
57.59 5.36
56.11 5.43
60.75 5.81
47.01 3.96
50.57 4.36
10.68
9.30
9.06
26.95
8.98
9.75
26.68
24.92
8.35
22.67
8.21
7.86
7.68
7.25
7.15
8.03
8.75
8.49
C17H19ClO6
C18H21ClO7
C20H23ClO6
C17H18BrClO6
57.55 5.40
56.18 5.50
60.84 5.87
47.08 4.18
51.07 4.45
58.62 5.74
47.08 4.18
46.62 4.35
61.18 5.14
9.99
9.21
8.98
26.60
8.87 3.50
9.61
VIIc
VIId
VIIe
VIIf
VIIg
VIIh
VIIi
IXa
IXb
IXc
IXd
IXe
IXf
IXg
IXh
IXi
IXj
Xa
Xb
Xc
Xd
3.64 C17H18ClNO8
C18H21ClO6
C17H18BrClO6
C18H20BrClO7
3.36 C22H22ClNO6
2.60 C22H21BrClNO6 51.73 4.15
58.5
5.70
47.02 4.25
46.51 4.39
61.01 5.04
51.70 4.22
61.63 5.32
59.70 5.14
57.65 4.40
59.43 5.07
59.44 5.14
61.82 5.32
58.21 6.31
56.18 5.51
79.60 6.32
79.82 6.60
76.29 6.35
64.28 4.79
64.01 5.29
64.68 5.60
62.36 5.39
53.68 4.23
79.50 6.21
74.85 6.22
26.60
24.88
8.21 3.24
22.59 2.74
7.95 3.14
7.68 3.03
7.45 2.94
7.04 2.78
7.04 2.78
7.95 3.14
8.61 3.40
8.33 3.29
4.23
3.25 C23H24ClNO6
3.22 C23H24ClNO7
2.99 C23H22ClNO8
2.93 C25H26ClNO8
2.91 C25H26ClNO8
3.22 C23H24ClNO6
3.47 C20H26ClNO6
3.52 C20H24ClNO7
4.30 C22H21NO2
4.15 C23H23NO2
3.99 C23H23NO3
3.50 C22H20BrNO2
3.48 C22H22BrNO2
3.35 C23H24BrNO2
3.26 C23H24crNO3
2.93 C22H21Br2NO2
C15H14O2
61.95 5.43
59.81 5.24
58.05 4.66
59.58 5.20
59.58 5.20
61.95 5.43
58.32 6.36
56.40 5.68
79.73 6.39
79.97 6.71
76.43 6.41
64.40 4.91
64.08 5.38
64.79 5.67
62.45 5.47
4.06
3.88
19.59
19.49
18.85
18.19
32.64
19.48 3.41
19.38 3.40
18.74 3.29
18.07 3.17
32.54 2.85
XIa
XIb
XIc
XId
XIIa
XIIb
53.79
79.62 6.24
74.98 6.29
4.31
95
C16H16O3
perchlorates VIIIk v solutions have lower values than
for salts VIIIa j apparently due to the presence in
the former of bromine atoms: The heavy atoms are
known to increase the velocity of intercombination
ylidene)-(R2-phenyl)amines XIa d. Perchlorates VII
in aqueous basic medium readily undergo hydrolysis
yielding 1H-2,3-dihydroxanthen-3-ones (XIIa, b)
(Scheme 2).
conversion S1
fluorescence [12].
T1 that reduces the efficiency of the
In the IR spectra of perchlorates and bromides of
3-(R2,R3-amino)-1,2-dihydroxanthylium IXa g and
XIa d should be noted the absorption bands at
It is presumable that salts VIIa i in the resonance
form VIIA the charge is localized mostly on the un-
saturated ring of the molecule for they readily
exchange the activated ethoxy group with amino-
containing nucleophiles to afford 3-(R2,R3-amino)-
1,2-dihydroxanthylium perchlorates IXa k. On
treating perchlorates IXa g with bases (sodium
acetate) were obtained (1H-2,3-dihydroxanthen-3-
1
3260 3280 cm characteristic of NH group, and by
xanthenones XIIa, b is noteworthy the absorption
1
band in the 1685 1700 cm region belonging to
1
carbonyl group C=O [11]. In the H NMR spectra
of perchlorates IXa g the proton signal from
= N + HAr group at 7.60 7.80 ppm evidences the
prevailing contribution from the immonium resonance
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

532
OLEKHNOVICH et al.
Scheme 2.
IX, R1 = CH3O, R2 = C6H5, R3 = H (a); R1 = CH3O, R2 = 4-BrC6H4, R3 = H (b); R1 = CH3O, R2 = 4-CH3C6H4,
R3 = H (c); R1 = = CH3O, R2 = 4-CH3OC6H4, R3 = H (d); R1 = CH3O, R2 = 4-HOOCC6H4, R3 = H (e); R1 =
CH3O, R2 = 4-C2H5COOC6H4, R3 = H (f); R1 = CH3O, R2 = 2-C2H5COOC6H4, R3 = H (g); R1 = CH3O, R2 =
C6H5, R3 = CH3 (h); R1 = CH3O, R2 = R3 = C2H5 (i); R1 = CH3O, R2 = R3 = (CH2)2O(CH2)2 (j); X, R1 = CH3O,
R2 = C6H5 (a); R1 = CH3O, R2 = 4-CH3C6H4 (b); R1 = CH3O, R2 = 4-CH3OC6H4 (c); R1 = CH3O, R2 = 4-BrC6H4
(d); XI, R1 = CH3O, R2 = C6H5 (a); R1 = CH3O, R2 = 4-CH3C6H4 (b); R1 = CH3O, R2 = 4-CH3OC6H4 (c); R1 =
CH3O, R2 = 4-BrC6H4 (d); XII, R1 = H (a); CH3O (b).
Table 4. Yields, melting points, and elemental analyses of 13H-chromeno[3,2-b]xanth-5-ylium perchlorates VIIIa v
Compd.
no.
Yield,
%
mp,
C
Found, %
H
Calculated, %
Formula
C
Hlg (N)
C
H
Hlg (N)
VIIIb
VIIIc
VIIId
VIIIe
VIIIf
VIIIg
VIIIh
VIIIi
VIIIj
VIIIk
VIIIl
VIIIm
VIIIn
VIIIo
VIIIp
VIIIq
VIIIr
VIIIs
VIIIt
VIIIu
VIIIv
55
59
54
63
55
48
58
52
57
55
44
41
54
55
69
63
51
67
46
41
43
294 297
303 305
314 315
355 358
291 292
247 249
312 314
301 303
296 297
308 310
305 307
303 305
307 309
342 344
341 343
301 303
322 324
219 220
348 350
318 320
345 347
63.86
60.91
56.51
52.90
62.31
64.60
60.16
55.69
53.95
33.12
55.41
55.42
52.30
45.58
32.55
40.91
47.31
59.05
47.43
54.21
33.50
4.03
4.40
3.65
3.55
4.36
4.72
4.11
3.74
3.31
3.23
3.84
3.94
3.85
8.71
7.64
C22H17ClO6
C24H21ClO8
64.01
60.96
56.62
52.95
62.38
64.66
60.20
55.66
53.98
33.47
55.46
55.46
52.24
4.15
4.48
8.59
7.50
7.39 (2.5) C23H18ClNO9
3.72 7.27 (2.87)
22.17
8.05
7.44
7.86
C23H18ClBrO7
C23H19ClO7
C26H23ClO7
C23H19ClO8
3.48
4.32
4.80
4.17
22.11
8.01
7.34
7.73
6.78 (2.67) C24H20ClNO10
3.89 6.85 (2.71)
20.85
23.51
22.07
22.12
19.92
C23H17Cl3O7
C22H16crClO6
C24H20crClO6
C24H20crClO6
C24H20crClO8
3.35
3.28
3.88
3.88
3.65
20.79
23.46
22.19
22.19
20.91
2.36 19.74 (4.72) C24H14BrClN2O10 45.42
2.42 19.83 (4.80)
1.72
2.03
2.63
4.22
53.80
42.48
33.07
20.07
C22H12cr5ClO6
C22H14cr3ClO6
C22H14crCl3O6
C28H24crClO6
32.73
40.68
47.13
58.81
47.27
54.04
33.23
1.50
2.17
2.52
4.23
53.88
42.56
33.23
20.17
2.80 18.75 (4.57) C24H18BrClN2O6
4.45 19.90 (4.87) C26H26crClN2O6
1.74
2.97 18.92 (4.60)
4.54 19.96 (4.85)
1.86
49.95
C24H16Br5ClO8
50.15
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ACETALS AND VINYL ETHERS OF UNSATURATED ALDEHYDES: XII.
533
Scheme 3.
VIII, R1 = NO2, R2 = R3 = H (n); R1 = R3 = Br, R2 = H (o); R1 = Br, R2 = R3 = H (p); R1 = Cl, R2 = R3 =
H (q); R1 = R2 = H, R3 = CH2CH=CH2 (r); R1 = CH3, R2 = NO2, R3 = H (s); R1 = R3 = H, R2 = N(CH3)2 (t);
R1
= = = CH3O (u).
R3 Br, R2
Scheme 4.
1
form. The H NMR spectra of bromides XIa d are
In compounds IX, X, XII with a common xanthyl-
ium core in the electron absorption spectra appear
characteristic bands in the longwave region with two
maxima at 521 and 558 nm; perchlorate IXi
identical to those from the corresponding perchlorates
IX. The data on IR and H NMR compounds IX XII
are presented in Table 5.
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

534
OLEKHNOVICH et al.
Scheme 5.
[=H(C2H5)2] forms an exception (Table 1). Accord-
ingly in the fluorescence spectra from acetonitrile
solutions of compounds IX, X, XII are observed two
significant difference in the spectral characteristics
when the aminoaryl fragment of perchlorates IXa g
or bases Xa d in position 3 is replaced by an oxygen
fl
fl
bands of
570 and
620 nm, and for
atom
[1,1-dimethyl-1H-2,3-dihydroxanthen-3-one
1max
2max
fl
1max
perchlorate IXi these bands are present at
537
(XII)].
fl
2max
and
580 nm. The quantum efficiency of
Since in the Knoevenagel type condensations [9]
1,3-diketones take part when in the carbon triad to the
middle carbon (position 2) are attached two hydro-
gens, it is natural to presume that 2-substituted
oxoenols, in particular, 2-bromodimedone, under the
applied dehydrating conditions can afford salts VIII.
Actually, the condensation of 2-bromodimedone
(XIII) with 2-hydroxyarylaldehydes in triethyl ortho-
fluorescence for these solutions amounts to 0.46 0.95.
As seen from Table 1, the substituent R1 in the
dihydroxanthylium ring significantly affects the
absorption and fluorescence spectra of perchlorates
VII, unlike the substituents in the aminoaryl moiety
of salts IX and X whose variation does not result in
any changes in the position of the maxima in the
absorption and fluorescence spectra. Also there is no
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ACETALS AND VINYL ETHERS OF UNSATURATED ALDEHYDES: XII.
535
Table 5. IR and 1H NMR spectra of derivatives of 1,2-dihydroxanthylium VIIc, e, g, i; IXb d, j; Xb; XIIb
1
Compd. no.
VIIc
IR spectrum, , cm
1H NMR spectrum, , ppm
1100, 1246, 1286, 1566, 1633 1.48 s (6H), 1.52 t (3H), 2.78 s (2H), 3.92 s (3H), 4.40 q (2H),
6.41 s (1H), 7.38 d (1H), 7.58 s (1H), 7.70 d (1H), 8.72 s (1H)
VIIe
1090, 1233, 1533, 1606
1100, 1220, 1513, 1633
1106, 1266, 1553, 1613
1.42 t (9H), 2.80 s (2H), 4.38 q (2H), 6.48 s (1H), 7.40 d (1H),
7.45 q (1H), 7.79 d (1H), 8.42 s (1H)
1.50 s (6H), 1.52 t (3H), 2.46 s (3H), 2.85 s (2H), 4.45 t (2H),
6.40 s (1H), 7.43 d (1H), 7.55 q (1H), 7.92 d (1H), 8.58 s (1H)
1.50 m (9H), 2.90 s (2H), 3.93 s (3H), 4.42 t (2H), 7.42 t (1H),
7.58 s (1H), 7.70 d (1H), 8.58 s (1H)
VIIg
VIIi
IXb
1090, 1266, 1540, 1606, 3220 1.52 s (6H), 3.10 s (2H), 3.82 s (3H), 6.10 s (1H), 7.01 d (1H),
7.12 d (1H), 7.15 d (1H), 7.28 m (5H), 7.60 s (1H)
IXc
1100, 1253, 1540, 1606, 3225 1.50 s (6H), 2.40 s (3H), 3.12 s (2H), 3.91 s (3H), 6.15 s (1H),
7.01 d (1H), 7.12 d (1H), 7.19 d (1H), 7.30 q (4H), 7.32 s (1H),
7.59 s (1H)
IXd
IXj
1090, 1260, 1540, 1606, 3206 1.50 s (6H), 3.14 s (2H), 3.82 s (3H), 3.96 s (3H), 6.07 s (1H),
6.98 d (1H), 7.12 d (1H), 7.16 d (1H), 7.35 m (5H), 7.64 s (1H)
1100, 1260, 1553, 1606
1206, 1533, 1573, 1600
1.47 s (6H), 3.08 s (2H), 3.68 m (2H), 3.90 s (3H), 4.25 m (6H),
6.10 s (1H), 6.97 d (1H), 7.09 d (1H), 7.13 d (1H), 7.30 m (4H),
7.60 d (1H)
1.38 s (6H), 2.33 s (3H), 3.01 s (2H), 4.87 s (3H), 6.02 s (1H),
6.84 d (1H), 6.98 d (1H), 7.07 d (1H), 7.15 m (4H), 7.17 d (1H)
Xb
XIIb
1213, 1506, 1580, 1633, 1700 1.39 s (6H), 2.56 s (2H), 3.90 s (3H), 6.32 s (1H), 7.05 d (1H),
7.16 s (1H), 7.30 d (1H), 7.98 s (1H)
Table 6. IR and 1H NMR spectra of 13H-chromeno[3,2-b]xanth-5-ylium perchlorates VIII
1
Compd. no.
VIIIc
IR spectrum, , cm
1H NMR spectrum, , ppm
1100, 1240, 1500, 1620
1.90 s (6H), 3.98 s (6H), 6.79 s (1H), 7.45 q (4H), 7.33 d (2H),
8.52 s (2H)
VIIIe
1100, 1246, 1273, 1500, 1606 1.77 s (6H), 3.89 s (3H), 6.71 s (1H), 7.79 d (2H), 7.84 m (4H),
8.61 s (2H)
VIIIk
VIIIl
VIIIm
1100, 1286, 1560, 1618
1.76 s (6H), 7.67 m (2H), 7.88 m (6H), 8.35 s (2H)
1090, 1273, 1566, 1593, 1620 1.73 s (6H), 2.51 s (6H), 7.70 m (6H), 8.22 s (2H)
1095, 1270, 1500, 1610, 1633 1.73 s (6H), 2.58 s (6H), 7.50 d (2H), 7.62 s (2H), 7.80 d (2H),
8.28 s (2H)
VIIIn
1090, 1273, 1566, 1585, 1620 1.75 s (6H), 3.96 s (6H), 7.32 d (2H), 7.45 d (2H), 7.75 d (2H),
8.25 s (2H)
VIIIo
VIIIp
VIIIq
VIllr
VIIIs
1100, 1246, 1540, 1605, 1633 1.73 s (6H), 7.72 m (4H), 7.85 d (2H), 8.24 s (2H)
1090, 1260, 1560, 1585, 1606 1.72 s (6H), 8.05 s (2H), 8.22 s (2H), 8.31 s (2H)
1100, 1260, 1500, 1540, 1606 1.73 s (6H), 7.80 m (4H), 7.91 d (2H), 8.20 s (2H)
1095, 1246, 1500, 1553, 1615 1.75 s (6H), 7.90 m (6H), 8.27 s (2H)
1070, 1246, 1546, 1587, 1620 1.75 s (6H), 3.86 d (4H), 5.30 q (4H), 6.18 m (2H), 7.60 t (3H),
7.80 t (3H), 8.31 s (2H)
VIIIt
VIIIu
1100, 1260, 1553, 1566, 1622 1.74 s (6H), 2.53 s (6H), 7.68 s (2H), 7.80 d (2H), 8.30 s (2H)
1090, 1193, 1260, 1500, 1633 1.75 s (6H), 3.28 s (6H), 7.58 d (2H), 7.69 s (1H), 7.82 d (2H),
8.25 s (2H)
VIIIv
1092, 1266, 1540, 1620
1.72 s (6H), 3.90 s (6H), 7.58 d (2H), 8.29 s (2H)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

536
OLEKHNOVICH et al.
1
formate in the presence of perchloric acid at the ratio
1: 2: 1 afforded perchlorates VIIIj u in 50 70%
yield. In acetic anhydride medium containing 16%
solution of perchloric acid in acetic acid salts VIIIj u
form in lower yield (20 40%). Obviously the yields
are reduced by participation of the intermediate
acyloxycation P4 in side processes, e.g. transacetyla-
tion, under the reaction conditions [13]. With
aldehyde of low basicity (e.g., nitrosalicylaldehyde)
perchlorate VIIIo may form via intermediate di-
ethoxypropenyl cation (IVb) (Scheme 3).
in mineral oil.The H NMR spectra were registered
on spectrometer Varian VXR-300: perchlorates
VIIIc, e in deuteroacetone, salts VIIg, VIIIk v in
deuteroacetonitrile, compounds VIIc, e, i, IXb d, j,
Xb, XIIb in deuterochloroform. Electron absorption
spectra were registered on spectrophotometer Specord
M-40. The fluorescence spectra and spectra of
fluorescence excitation were measured on spectro-
fluorimeter Elumin 2M. In determination of quantum
efficiency of fluorescence rhodamine C was used as
standard ( = 0.73 [15]). Elemental analyses were
carried out in the Microanalysis Laboratory of the
Research Institute of Physical and Organic Chemistry
of Rostov State University.
When dimedone has an acetyl as a substituent in
position 2, then in the condensation take part three
molecules of 2-hydroxyarylaldehyde yielding diper-
chlorate XV (Scheme 4).
2-Bromo-5,5-dimethyl-1,3-diethoxycyclohexenyl-
ium perchlorate (IVb) was prepared along procedure
[6] from 2.2 g (0.01 mol) of 2-bromodimedone
(XIII), 20 ml of triethyl orthoformate, and 1 ml of
70% perchloric acid. The product was purified by
recrystallization from a mixture AcOH Ac2O, 10: 1.
Colorless hygroscopic crystals. Yield 3.38 g (91%),
mp 81 83 C. IR spectrum, , cm : 1086, 1286,
1540. H NMR spectrum (CDCl3, , ppm): 1.03 s
(6H), 1.35 t (6H), 2.58 s (4H), 4.42 q (4H). Found,
%: C 38.35; H 5.41; Cl 30.68. C12H20BrClO6.
Calculated, %: C 38.37; H 5.37; Cl 30.71.
1
In its H NMR spectrum appear all the signals
corresponding by integral intensity and multiplicity
to the structure of diperchlorate XV.
Under similar conditions unsubstituted dimedone (XVI)
also affords a product of tris-condensation, 7H-
chromeno[2,3-a]-xanth-13-ylium (XVII) (Scheme 5).
1
1
Perchlorate XVII may have any of three alternative
structures XVIIA C. The 1H NMR data evidence that
it exists predominantly as structural isomer XVIIB.
Derivatives of xanthylium VII, IX XII and
1-benzopyrylium VIII are efficient phosphores in the
region 530 630 nm. First obtained in this study
dihydroxanthylium perchlorates VII should be
specially mentioned since their quantum efficiency of
fluorescence amounting to 0.98 is the highest among
the known xanthylium systems [12]. Apparently the
main contribution into the absorption and lumine-
scence spectral properties of the molecules originates
from the -system of the dihydroxanthylium ring.
These compounds can be also applied as reagents for
amino groups detection, also in the fluorescence
microscopy [14], and the derivatives of dihydro-
xanthylium with the substituted ethoxy groups can
serve as fluorescent dyes for various applications.
The developed synthetic procedures for the known
and new perchlorates VIII are the easiest and pre-
parative. The conversions revealed extend the
theoretical concepts on the reactivity of 1,3-oxoenoles
in the acid media and on practical opportunities for
preparation of dyes with excellent absorption and
luminescent characteristics.
7-Methoxy-3-ethoxy-1,2-dihydroxanthylium per-
chlorate (VIIa). To a solution of 1.1 g (0.01 mol) of
cyclohexane-1,3-dione in 20 ml of triethyl ortho-
formate was added at stirring 1 ml of 70% perchloric
acid. The mixture was left standing at 25 C for
0.5 h, then diluted with anhydrous ether, the upper
layer was decanted from the separated oily 1,3-di-
ethoxy1-cyclohexenylium perchlorate (IVc), the
bottom layer was washed with anhydrous ether (2
20 ml), and 20 ml of triethyl orthoformate and 1.5 g
(0.01 mol) of 5-methoxysalicylaldehyde (VIb) were
added thereto. The mixture was boiled for 30 min
with simultaneous distilling off the volatile fractions,
then on cooling the separated precipitate was filtered
off, washed with ethyl acetate and ether, and purified
by recrystallization from acetic acid. Yield 2.94 g
1
(82%), mp 131 132 C. IR spectrum, , cm : 1086,
1
1286, 1540, 1606. H NMR spectrum [(CD3)2CO, ,
ppm]: 1.52 t (3H), 3.05 t (2H), 3.39 t (2H), 3.98 s
(3H), 4.61 q (2H), 6.65 s (1H), 7.58 t (2H), 7.90 d
(1H), 8.67 s (1H). Found, %: C 53.91; H 4.82; Cl
9.87. C16H17ClO7. Calculated, %: C 53.86; H 4.80;
Cl 9.94.
EXPERIMENTAL
1,1-Dimethyl-3-ethoxy-1,2-dihydroxanthylium
perchlorates (VIIb i) (general procedure, Tables 1,
3, 5). (a) To a suspension of 0.01 mol of 2-R-5,5-
IR spectra of the compounds obtained were
recorded on spectrometer Specord 71IR from mulls
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ACETALS AND VINYL ETHERS OF UNSATURATED ALDEHYDES: XII.
537
dimethyl-1,3-diethoxy-1-cyclohexenylium perchlorate
(IVa, b) in 20 ml of triethyl orthoformate was added
at stirring 0.01 mol of 2-hydroxyarylaldehyde VI.
The mixture was boiled for 30 min while removing
the volatile compounds by distillation. On cooling the
separated precipitate was filtered off and recrystal-
lized from acetic acid.
(b) To a suspension of 0.01 mol of perchlorate
VIIa f in 20 ml triethyl orthoformate was added at
stirring 0.01 mol of 2-hydroxyarylaldehyde VI. The
mixture was boiled for 30 min, cooled, the separated
crystals were filtered off and treated as in the proce-
dure (a). Perchlorates VIIIa i prepared along both
procedures (a) and (b) were identical, no depression of
the melting point was observed with the mixed
samples.
(b) To a solution of 0.01 mol of 2-R-5,5-dimethyl-
1,3-diethoxy-1-cyclohexenylium perchlorate (IVa, b)
in 10 ml of acetic anhydride was added 0.01 mol of
2-hydroxyarylaldehyde VI. The mixture was stirred
for 15 20 min at 60 70 C and then cooled, diluted
with an equal volume of ether, the precipitate was
filtered off and recrystallized from acetic acid.
6-Bromo-13,13-dimethyl-13H-chromeno[3,2-b]-
xanthylium perchlorates VIIIk v (general proce-
dure, Tables 2, 4, 6). (a) To a suspension of 0.01 mol
of perchlorate IVb in 40 ml of triethyl orthoformate
was added at stirring 0.02 mol of 2-hydroxyaryl-
aldehyde VI. The mixture was boiled for 1 h, cooled,
the precipitated crystals were filtered off, washed
with ethyl acetate and ether, and purified by recrystal-
lization from nitromethane.
Perchlorates VIIb i prepared along both
procedures a and b were identical, no depression of
the melting point was observed with the mixed
samples.
(b) To a suspension of 0.01 mol of perchlorate
VIIh in 20 ml of triethyl orthoformate was added
at stirring 0.01 mol of 2-hydroxyarylaldehyde VI.
The mixture was boiled for 30 min, cooled, the
separated crystals were filtered off and worked up as
in the procedure (a).
2,10-Dimethoxy-13H-chromeno[3,2-b]xanth-5-
ylium perchlorate (VIIIa). 1,3-Diethoxy-1-cyclo-
hexenylium perchlorate (IVc) was obtained from
1.1 g (0.01 mol) of cyclohexane-1,3-dione, 20 ml
triethyl orthoformate, and 1 ml of 70% perchloric
acid. To perchlorate IVc was added 40 ml of triethyl
orthoformate, 3.0 g (0.02 mol) of 5-methoxysalicyl-
aldehyde, and the mixture was boiled for 30 min
while removing volatile compounds by distillation.
On cooling 40 ml of acetic acid was added (to
dissolve the intermediately arising perchlorate VIIa),
and the mixture was boiled for 30 40 min. On cool-
ing the separated precipitate was filtered off, washed
with ethyl acetate and ether, and purified by recrystal-
lization from nitromethane. Yield 3.0 g (67%), mp
(c) To a solution of 2.2 g (0.01 mol) of 2-bromo-
dimedone (XIII) in 20 ml of triethyl orthoformate
was added 0.01 mol of 2-hydroxyarylaldehyde VI,
and at stirring 1 ml of 70% perchloric acid. The
mixture was boiled for 1 h while distilling off the
volatile compounds. On cooling in 5 6 h precipitated
crystals which were filtered off and worked up as in
the procedure (a).
On replacing the triethyl orthoformate with acetic
anhydride (10 ml, 60 70 C, 20 30 min) perchlorates
VIIIk v were obtained in 20 40% yield.
1
247 249 C. IR spectrum, , cm : 1100, 1273, 1540,
1
1606. H NMR spectrum (CDCl3, , ppm): 3.91 s
Perchlorates VIIb i prepared along procedures (a),
(b), and (c) were identical, no depression of the melting
point was observed with the mixed samples.
(6H), 4.80 s (2H), 6.22 s (1H), 7.10 s (2H), 7.25 d
(2H), 7.44 d (2H), 8.08 s (2H). Found, %: C 59.32;
H 3.88; C 17.91. C22H17ClO8. Calculated, %: C
59.40; H 3.85; Cl 7.97.
3-(R2,R3-Amino)-1,2-dihydroxanthylium per-
chlorates IXa g (general procedure, Tables 1, 3, 5).
To a solution of 0.01 mol of perchlorate VIIa h in
20 ml of acetic acid was added at stirring 0.01 mol of
amine. The mixture was boiled for 5 min and cooled,
diluted with an equal volume of ether, the precipitate
was filtered off, washed with ethyl acetate and ether,
and purified by recrystallization from a mixture of
nitromethane and 70% perchloric acid, 100: 1.
3-(R2,R3-Amino)-7-methoxy-1,2-dihydroxanthyl-
ium perchlorates IXh j (general procedure,
Tables 1, 3, 5). To a solution of 0.01 mol of per-
chlorate VIIa h in 20 ml of chloroform was added at
stirring 0.01 mol of amine. The mixture was boiled
13H-Chromeno[3, 2-b]xanth-5-ylium per-
chlorates VIIIb j (general procedure, Table 2, 4, 6).
(a) To a suspension of 0.01 mol of perchlorate IVa in
40 ml of triethyl orthoformate was added at stirring
0.02 mol of 2-hydroxyarylaldehyde VI. The mixture
was boiled for 1 h while distilling off the volatile
compounds. On cooling the precipitate was filtered
off, washed with ethyl acetate and ether, and purified
by recrystallization from nitromethane.
On replacing the triethyl orthoformate with acetic
anhydride (20 ml, 60 70 C, 20 30 min) perchlorates
VIIIb j were obtained in 20 40% yield.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001

538
OLEKHNOVICH et al.
1
1
for 5 min, cooled, the precipitate was separated and
recrystallized from acetic acid.
, cm : 1100, 1233, 1260, 1540, 1620. H NMR
spectrum (CD3CN, , ppm): 1.12 s (3H), 1.85 s
(3H), 3.82 s (3H), 3.90 s (3H), 4.02 s (3H), 4.80 s
(1H), 6.50 d (1H), 6.70 d (1H), 6.80 d (1H), 7.12 d
(1H), 7.15 s (1H), 7.30 s (1N), 7.60 s (1N), 7.93 d
(1N), 8.20 d (1N), 8.85 s (1N), 9.31 s (1N). Found,
%: S 65.17; N 4.58; Sl 6.05. S32N27SlO9. Calculated,
%: S 65.03; N 4.61; Sl 6.00.
(2,3-Dihydro-1H-xanthen-3-ylidene)-(R2-phen-
yl)amines Xa d (general procedure, Tables 1, 3, 5).
To a solution of 0.01 mol of perchlorate IX in 20 ml
of anhydrous acetone was added at stirring 0.015 mol
of anhydrous potassium carbonate. The mixture was
stirred for 5 10 min till the solution became light
yellow. The precipitate was filtered off, the solution
was evaporated, and the residue was purified by re-
crystallization from methanol.
3-(R2, R3-Amino)-1, 2-dihydroxanthylium
bromides XIa d (general procedure, Table 3). To a
solution of 0.01 mol of imine X in 20 ml of ethyl
acetate was added dropwise at stirring 0.01 mol of
conc. HBr. The precipitate was filtered off, wash
ed with ethyl acetate and ether, and purified by
reprecipitation with ether from nitromethane solution.
REFERENCES
1. Olekhnovich, E.P., Boroshko, S.L., Borodkin, G.N.,
Kucher, V.I., and Olekhnovich, L.P., Zh. Org. Khim.,
1999, vol. 35, no. 10, pp. 1547 1554.
2. Lowenbein, A. and Katz, W., Ber., 1926, vol. 59,
pp. 1377 1383.
3. Czerney, P. and Hartmann, H., J. Pr. Chem., 1983,
vol. 325, pp. 505 508.
4. Czerney, P. and Hartmann, H., Houben-Weyl. Meth.
Org. Chem., E 1990, vol. 7a, pp. 64 66.
1,1-Dimethyl-1H-2,3-dihydroxanthen-3-ones
XIIa, b (general procedure, Tables 1, 3, 5). To a
solution of 0.01 of perchlorate VII in 20 ml of acetone
was added 0.012 mol of sodium acetate in 20 ml of
water. The mixture was stirred at heating on a water
bath till evaporation of acetone. On cooling to room
temperature precipitated yellow crystals that were
filtered off, washed with water, and purified by re-
crystallization from aqueous methanol (1: 5).
5. Olekhnovich, E.P., Korobka, I.V., and Mezheri-
tskii, V.V., Zh. Org. Khim., 1990, vol. 26, no. 1,
pp. 173 174.
6. Olekhnovich, P. and Korobka, V., Zh. Org. Khim.,
1990, vol. 26, no. 1, pp. 213 214.
7. Olekhnovich, E.P., Olekhnovich, L.P., and Korob-
ka, I.V., Abstracts of Papers, VII Vsesoyuznaya
konferentsiya Khimiya dikarbonil,nykh soedinenii
(6th All-Union Conf. on Chemistry of Dicarbonium
Compounds), Riga, 1991, p. 145.
8. March, D., Advanced Organic Chemistry, New York:
Wiley and Sons, 1985. Translated under the title
Organicheskaya khimiya, Moscow: Mir, 1987, vol. 1,
p. 328.
9. March, D., Advanced Organic Chemistry, New York:
Wiley and Sons, 1985. Translated under the title
Organicheskaya khimiya, Moscow: Mir, 1987, vol. 1,
pp. 387 393.
10. DOS N 2942931. 1980. BASF, Erf.: Schmidt, R. and
Koch, V.; Chem. Abstr., 1980, 95, 117065.
11. Silverstein, R., Bassler, G., and Morril, T., Spectro-
metric Identification of Organic Compounds, New
York: Wiley, 1963. Translated under the title Spek-
trometricheskaya identifikatsiya organicheskikh so-
edinenii, Moscow: Mir, 1977.
12. Parker, C.A., Photolumenescence of Solutions,
Elsevier, 1966.
13. Vatsuro, K.V. and Mishchenko, G.L., Imennye reak-
tsii v organicheskoi khimii (Name Reactions in
Organic Chemistry), Moscow: Khimiya, 1976,
pp. 431 432.
13,13-Dimethyl-2,10-dimethoxy-6-(6-methoxy-
chromylium-2-yl)-13H-chromeno[3,2-b]xanth-5-
ylium diperchlorate (XV). To a solution of 1.8 g
(0.01 mol) of 2-acetyldimedone (XIV) in 30 ml tri-
ethyl orthoformate was added 4.5 ml (0.03 mol) of
5-methoxysalicylaldehyde (VIa), and then at stirring
was added 1.5 ml of 70% perchloric acid. After 1.5
2 h the separated crystals were filtered off, washed
with ethyl acetate and ether, and recrystallized from
nitromethane. Yield 4.9 g (67%), mp 335 337 C. IR
1
spectrum, , cm : 1090, 1226, 1280, 1560, 1606.
1H NMR spectrum (CDCl3, , ppm): 1.50 s (6H),
3.97 s (3H), 4.03 s (6H), 7.41 d (1H), 7.55 m (3H),
7.80 m (5H), 8.45 s (1H), 8.80 m (3H). Found, %:
C 55.71; H 3.80; Cl 9.74. C34H28Cl2O14. Calculated,
%: C 55.83; H 3.86; Cl 9.69.
7,7-Dimethyl-2,10-dimethoxy-6-(3-methoxy-6-
oxo-2,4-cyclohexadienylidenemethyl)-7H-chromeno-
[2,3-a]xanth-13-ylium perchlorate (XVII). To a
solution of 1.4 g (0.01 mol) of dimedone (XVI) in
30 ml of triethyl orthoformate was added 4.5 ml
(0.03 mol) of 5-methoxysalicylaldehyde (VIa) and
1.5 ml of 70% perchloric acid. After 12 h the
separated crystals were filtered off, washed with
ethyl acetate and ether, and recrystallized from acetic
acid. Yield 3.7 g (63%), mp 281 284 C. IR spectrum,
14. Fraishtat, D.M., Reaktivy i preparaty dlya mikrosko-
pii (Reactives for Microscopy), Moscow: Khimiya,
1980, p. 480.
15. Parker, C.A. and Rees, W.T., Analyst., 1960, vol. 85,
pp. 857 862.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001