Synthesis and bactericidal activity of 6-H(nitro)-9- arylidenedeoxyvasicinones and their perchlorates

Article abstract of DOI:10.1007/s10600-008-9105-0

9-Arylidene-6H(nitro)deoxyvasicinones were synthesized by reaction of 6H(nitro)deoxyvasicinones and aromatic aldehydes and furfurol in glacial acetic acid.

Full text of DOI:10.1007/s10600-008-9105-0

Chemistry of Natural Compounds, Vol. 44, No. 4, 2008
SYNTHESIS AND BACTERICIDAL ACTIVITY OF 6- (NITRO)-9-
H
ARYLIDENEDEOXYVASICINONES AND THEIR PERCHLORATES
B. Zh. Elmuradov,* A. Sh. Abdurazakov, and Kh. M. Shakhidoyatov
UDC 547.944/945+547.856
H
H
9-Arylidene-6 (nitro)deoxyvasicinones were synthesized by reaction of 6 (nitro)deoxyvasicinones and
aromatic aldehydes and furfurol in glacial acetic acid.
Key words: deoxyvasicinone, aldehydes, condensation, bactericidal properties.
We have previouslystudied the condensation ofdeoxyvasicinone (1a) with several aromatic, aliphatic, and unsaturated
aldehydes by fusion of a mixture of the reagents [1]. It was found that the reaction occurs only with aromatic and heterocyclic
aldehydes. Aliphatic and unsaturated aldehydes do not react with 1a. The direction of the reaction depends on the nature of
the substituent in the aromatic ring of the aldehyde and the conditions. Thus, whereas - and -nitrobenzaldehydes form under
m
p
realtively mild conditions 9-α-hydroxybenzyl-1a, higher temperatures and other aromatic aldehydes give 9-arylidene-
deoxyvascinones. In contrast with this, condensation of 1a and 6-bromo-1a (R = Br) in glacial acetic acid with aromatic
aldehydes proceeds more smoothly and gives exclusively 9-arylidenedeoxyvasicinones (R = H, Br) [2-4]. It is known that
9-α-hydroxy(m- and p-nitro)benzyldeoxyvasicinones lose water under more forcing conditions and transform into 9-(m- and
p-nitro)benzylidene-1a [1].
We studied the reaction of 1a with 3,4-dimethoxybenzaldehyde, isovanillin, 2-bromoisovanillin, 5-bromovanillin, and
furfurol in glacial acetic acid in order to expand this condensation to other aldehydes and to seek potential biologically active
compounds.
We reacted 6-nitrodeoxyvasicinone (1b, R = NO ) with aromatic aldehydes in order to explain the effect of the
2
substituent on the aromatic ring on the reactivity and compared the results with those for 6-H(bromo)deoxyvasicinones (1,
R = H, Br) [5]. As it turned out, the electron-accepting nitro group, like bromine, had a positive effect, i.e., enhances formation
of the condensation products. Reactions of 1b, like for 6-H(bromo)deoxyvasicinones (1, R = H, Br) [2-4], were carried out by
refluxing equimolar amounts of a mixture of the reagents in glacial acetic acid for 3-5 h. Target compounds 3a-i were obtained
O
O
in good yields.
R
R
N
N
AcOH
Ar CHO
+
N
N
CH Ar
1a, b
2a - e
3a - i
2a: R = H, Ar = C6H3(OCH3)2-3,4
3e: R = NO2, Ar = C6H3(OCH3)2-3,4
3f: R = NO2, Ar = C6H2(Br)(OH)(OCH3)-2,3,4
3g: R = NO2, Ar = C6H2(OCH3)(OH)(Br)-3,4,5
3h: R = NO2, Ar = C6H2(OCH3)(OH)(Br)-3,4,6
2e: R = H; 3i: R = NO2
2b: R = H, Ar = C6H3(OH)(OCH3)-3,4
2c: R = H, Ar = C6H2(Br)(OH)(OCH3)-2,3,4
2d: R = H, Ar = C6H2(OCH3)(OH)(Br)-3,4,5
3a: R = NO2, Ar = C6H5
3b: R = NO2, Ar = C6H4OH-4
3c: R = NO2, Ar = C6H4N(CH3)2-4
3d: R = NO2, Ar = C6H4NO2-4
O
4'
2e, 3i: Ar =
1'
2'
3'
S. Yu. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan,
Tashkent, fax (99871) 120 64 75, e-mail: burkhon@rambler.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 4,
pp. 383-386, July-August, 2008. Original article submitted April 17, 2008.
0009-3130/08/4404-0475 ©2008 Springer Science+Business Media, Inc.
475

The reaction of 1b with aldehydes, like for 6-H(bromo)deoxyvasicinones (1, R = H, Br), occurred through formation
of intermediate 9-hydroxyarylmethylquinazolin-4-ones. However, these compounds were not observed in our experiments.
It is known that perchlorates of arylidene derivatives of bicyclic quinazolines possess bacteriocidal activity [6]. We
prepared perchlorates (4a-i) in high yields (68-99%) in order to seek potential bacteriocides. The reactions were carried out
with heating of a mixture of reagents in acetic acid in the presence of conc. HClO .
4
2a e
3a i
The structures of - and - were confirmed by IR, PMR, and mass spectra. Their IR spectra contained ν
C=O
stretching vibrations at 1650-1710 cm−1; ν
, at 1580-1610 cm−1; ν
, at 1540-1557 cm−1; ν
, at 1510 cm−1.
C–NO
C=N
C–N
2
3b
The synthesized compounds fragmented mainly by the following scheme ( as an example):
O
5
3
R
189
4
N
11
289
O
7
10
3'
N
O N
2
8
1
N
12
CH
229
1'
R
1
R
R
N
5
Ar
C
H
121
5'
R
2
4
R
3
242
2a - e
3a - i
3b
2a - e:
3a - i:
R = NO2
R = H;
Methylene protons in the β-position had chemical shfits (CS) in the PMR spectrum of 3.13-3.26 ppm (2H, triplet); in
the γ-position, of 4.15-4.29 ppm (2H, triplet). N(CH ) – methyl protons of 3c had CS at 3.07 ppm (6H, singlet); OCH of 3f
3 2
3
and 3g, 3.64 and 3.61 ppm (3H, singlet). Aromatic protons appeared at 6.72-8.86 ppm. Protons of β- and γ-methylenes were
observed as triplets, which confirmed that the condensation occurred at the α-carbon atom.
We studied the bacteriocidal properties of the synthesized compounds in various concentrations (0.01, 0.1, 1%) for
various gram-positive and gram-negative strains: Staphylococcus T50a, Klebsiella pneumoniae T3a, S. aureus T48a,
Acinetobacter sp. T16, Enterococcus hormaechei T2, Escherichia coli T60a, En. hormaechei T10, Proteus rettgerri T33a, B.
Cereus T80, Citrobacter freundii T1a, En. faecalis T23a, Pseudomonas aureginosa T31a, Pr. agglomerans T26, A. faecalis
T3, Micrococcus luteus T52a, P. aureginosa T145, S. saprophyticus T415, K. oxitoca T4a, and A. haumanii T15a. The results
showed that they possessed moderate (3a, 3f, 3i) and low (2a-e, 3b-e, 3g, 3h, 4a-i) bacteriocidal properties.
EXPERIMENTAL
Mass spectra were recorded on a MS-30 instrument (Kratos); IR spectra, in mineral oil on a System 2000 IR-Fourier
spectrometer; PMRspectra, in TFAon aUnity400+instrument (operatingfrequency400 MHz, TMS internal standard, δ scale).
The purity of products and course of reactions were monitored by TLC on Silufol UV-254 plates using benzene:methanol (3:1,
system A; 5:1, system B) and CHCl :CH OH (20:1, system C).
3
3
1a
Deoxyvasicinone ( ) was prepared by the literature method [7].
6-Nitrodeoxyvasicinone (1b) was synthesized by a modified method [8].
6-Nitrodeoxyvasicinone (1b). Deoxyvasicinone (1a, 12 g, 0.06 mol) was treated with cooling (0-2°C) with conc.
3
H SO (24 mL, 95.72%, ρ = 1.835 g/cm ), stirred at 0-2°C, treated dropwise with a nitrating mixture consisting of nitric
2
4
3
3
(9 mL, 59.69%, ρ = 1.365 g/cm ) and sulfuric (ρ = 1.835 g/cm ) acids. The reaction mixture was stirred at room temperature
for 2 h and poured into ice. The resulting precipitate was filtered off, washed with water until the rinsings were neutral, and
dried. Recrystallization from methanol afforded 1b (12.2 g, 82%), mp 188-189°C, which agreed with the literature [8].
9-(3′,4′-Dimethoxybenzylidene)deoxyvasicinone (2a). A mixture of 1a (0.3 g, 1.6 mmol) and 3,4-dimethoxy-
benzaldehyde (0.24 g, 1.7 mmol) in glacial acetic acid (5 mL) was refluxed for 3-5 h. The solvent was distilled off. The solid
was recrystallized from aqueous DMF to afford 2a (0.39 g, 72%), C H O N , mp 212-214°C (aq. DMF), R 0.65 (system B).
f
20 18
3 2
476

PMR spectrum (δ, ppm, J/Hz): 8.08 (1H, d, J = 8.04, H-5), 7.72 (1H, td, J = 8.3, H-7), 7.65 (1H, s, H-2′), 7.62 (1H,
d, J = 8.3, H-6′), 7.39 (1H, t, J = 7.3, H-6), 7.19 (1H, br.s, H-12), 7.18 (1H, d, J = 7.3, H-5′), 7.02 (1H, d, J = 7.8, H-8), 4.15
(2H, t, J = 6.8, H-11), 3.56 [6H, d, (OCH ) ], 3.25 (2H, br.t, J = 7.8, H-10).
3 2
9-(3′-Hydroxy-4′-methoxybenzylidene)deoxyvasicinone (2b) was synthesized analogously as above from 1a (0.3 g,
1.6 mmol) and isovanillin (0.25 g, 1.7 mmol) to afford 2b (0.45 g, 93%), C H O N , mp 212-214°C (aq. DMF), R 0.51
f
19 16
3 2
(system A).
PMR spectrum (δ, ppm, J/Hz): 8.85 (1H, s, OH), 8.07 (1H, d, J = 7.8, H-5), 7.71 (1H, td, J = 8.03, H-7), 7.63 (1H, s,
H-2′), 7.62 (1H, d, J = 8.03, H-6′), 7.38 (1H, t, J = 7.56, H-6), 7.1 (1H, br.s, H-12), 7.06 (1H, d, J = 8.7, H-8), 6.6 (1H, d,
J = 8.26, H-5′), 4.18 (2H, t, J = 7.56, H-11), 3.78 (3H, s, OCH ), 3.18 (2H, t, J = 6.61, H-10).
3
9-(2′-Bromo-3′-hydroxy-4′-methoxybenzylidene)deoxyvasicinone (2c) was synthesized analogously as above from
1a (0.3 g, 1.6 mmol) and 2-bromoisovanillin (0.39 g, 1.7 mmol) toafford 2c (0.62 g, 96%), C H O N Br, mp 232-234°C (aq.
19 15
3 2
DMF), R 0.38 (system B).
f
PMR spectrum (δ, ppm, J/Hz): 7.98 (1H, d, J = 7.84, H-5), 7.92 (1H, br.s, H-12), 7.61 (1H, t, J = 7.47, H-7), 7.39 (1H,
d, J = 7.85, H-8), 7.36 (1H, br.t, J = 8.22, H-6), 6.92 (1H, d, J = 8.9, H-6′), 6.63 (1H, br.d, J = 8.6, H-5′), 4.15 (2H, t, H-11),
3.57 (3H, s, OCH ), 3.1 (2H, br.t, H-10).
3
+
+
Mass spectrum (m/z, %): 398/400 (8) [M] , 319 (100) [M - Br] , 304 (47), 303 (68), 247 (22), 204 (6), 196 (3.5),
+
184 (5) [M - CHAr] , 160 (17.5).
9-(3′-Methoxy-4′-hydroxy-5′-bromobenzylidene)deoxyvasicinone (2d) was synthesized analogously as above from
1a (0.3 g, 1.6 mmol) and 5-bromovanillin (0.39 g, 1.7 mmol) to afford 2d (0.57 g, 88%), C H O N Br, mp 222-224°C (aq.
19 15
3 2
DMF), R 0.52 (system A).
f
PMR spectrum (δ, ppm, J/Hz): 8.08 (1H, d, J = 8.2, H-5), 7.65 (1H, t, J = 7.5, H-7), 7.58 (1H, br.s, H-12), 7.43 (1H,
t, J = 8.2, H-6), 7.38 (1H, d, J = 7.8, H-8), 7.11 (1H, s, H-6′), 6.74 (1H, s, H-2′), 4.25 (2H, t, H-11), 3.6 (3H, s, OCH ), 3.17 (2H,
3
br.t, H-10).
9-(Furfurylidene-2)deoxyvasicinone(2e)was synthesized analogouslyas above from 1a(0.3g, 1.6mmol)andfurfurol
3
(0.14 mL, 0.16 g, 1.7 mmol, ρ = 1.1598 g/cm ) to afford 2e (0.29 g, 70%), C H O N , mp 234°C (lit. [1] mp 228°C) (aq.
16 12
2 2
DMF), R 0.74 (system B).
f
PMR spectrum (δ, ppm, J/Hz): 8.07 (1H, dd, J = 1.4, 7.8, H-5), 7.72 (1H, td, J = 1.4, 7.08, H-7), 7.61 (1H, d, J = 8.2,
H-8), 7.48 (1H, t, J = 5.7, H-6), 7.39 (1H, br.s, H-12), 7.37 (1H, d, J = 1.18, H-4′), 6.81 (1H, d, J = 3.55, H-2′), 6.61 (1H, dd,
J = 1.65, 3.31, H-3′), 4.3 (2H, t, J = 7.09, H-11), 3.18 (2H, td, J = 2.8, 10.15, H-10).
6-Nitro-9-benzylidenedeoxyvasicinone (3a). A mixture of 1b (0.5 g, 2.16 mmol) was dissolved in glacial acetic acid
3
(5 mL), treated with benzaldehyde (0.23 mL, 0.24 g, 2.3 mmol, ρ = 1.0498 g/cm ), refluxed for 3-5 h, and left overnight.
Solvent was distilled off. The solid was recrystallized from benzene to afford 3a (0.48 g, 70%), C H O N , mp 258-259°C,
18 13
3 3
R 0.72 (system A).
f
PMR spectrum (δ, ppm, J/Hz): 8.85 (1H, d, J = 2.2, H-5), 8.41 (1H, dd, J = 9.0, 2.5, H-7), 7.82 (1H, br.s, H-12), 7.65
(1H, d, J = 9.0, H-8), 7.10-7.27 (5H, m, H-2′,3′,4′,5′,6′), 4.25 (2H, t, J = 7.6, H-11), 3.20 (2H, t, J = 6.4, H-10).
+
+
+
+
Mass spectrum (m/z, %): 319 (50.0) [M] , 273 (10.5) [M - NO ] , 242 (4.2) [M - Ar] , [M - 1] (100), 288 (44),
2
272 (35), 243 (38), 215 (7), 170 (7).
6-Nitro-9-benzylidenedeoxyvasicinone Perchlorate (4a). 6-Nitro-9-benzylidenedeoxyvasicinone (3a, 12 mg,
0.037 mmol) was dissolved with heating in glacial acetic acid (3 mL), treated with perchloric acid (2 drops, 58%,
3
ρ = 1.512 g/cm ), heated for 10 min, and left overnight. The resulting crystals were filtered off, washed with water and alcohol,
and dried to afford 4a perchlorate (15 mg, 95%), C H O N Cl, mp 233-235°C (dec.).
18 14
7 3
Perchlorates 4b-i were synthesized analogously.
6-Nitro-9-(4′-hydroxybenzylidene)deoxyvasicinone (3b) was synthesized analogously as above from 1b (0.5 g,
2.16 mmol) and 4-hydroxybenzaldehyde (0.26 g, 2.16 mmol) to afford 3b (0.47 g, 65%), C H O N , mp 306°C (dec.), R 0.68
f
18 13
4 3
(system A).
PMR spectrum (δ, ppm, J/Hz): 8.82 (1H, d, J = 2.3, H-5), 8.38 (1H, dd, J = 2.6, 9.0, H-7), 7.76 (1H, br.s, H-12), 7.62
(1H, d, J = 9.0, H-8), 7.26 (1H, d, J = 8.6, H-5′), 7.26 (1H, d, J = 8.6, H-3′), 6.72 (1H, d, J = 8.6, H-6′), 6.72 (1H, d, J = 8.6,
H-2′), 4.24 (2H, t, H-11), 3.15 (2H, br.t, H-10).
+
+
+
+
Mass spectrum (m/z, %): 335 (65) [M] , 289 (2.8) [M - NO ] , 242 (10.5) [M - Ar] , 229 (3.5) [M - (CH - Ar)] ,
2
+
[M - 1] (100), 288 (52), 202 (4.2), 170 (2.8), 144 (12.6).
477

Perchlorate of 3b (4b): C H O N Cl, yield 99%, mp 235°C (dec.).
18 14
8 3
6-Nitro-9-(4′-dimethylaminobenzylidene)deoxyvasicinone (3c) was synthesized analogously as above from 1b
(0.5 g, 1.95 mmol) and 4-dimethylaminobenzaldehyde (0.32 g, 2.2 mmol) to afford 3c (0.36 g, 46%), C H O N , mp 280°C
20 18
3 4
(dec. aq. DMF), R 0.69 (system B).
f
PMR spectrum (δ, ppm, J/Hz): 8.85 (1H, d, J = 2.3, H-5), 8.43 (1H, dd, J = 2.4, 9.0, H-7), 7.87 (1H, br.s, H-12), 7.72
(1H, d, J = 9.0, H-8), 7.52 (1H, d, J = 9.0, H-5′), 7.52 (1H, d, J = 9.0, H-3′), 7.42 (1H, d, J = 9.0, H-2′), 7.42 (1H, d, J = 9.0,
H-6′), 4.27 (2H, t, J = 7.2, H-11), 3.20 (2H, br.t, H-10), 3.07 [6H, s, N(CH ) ].
3 2
+
+
+
Mass spectrum (m/z, %): 362 (100) [M] , 316 (26) [M - NO ] , 242 (9) [M - Ar] , 332 (41), 315 (90), 300 (28.7),
2
272 (16.8), 243 (12), 215 (2), 158 (12.6).
Perchlorate of 3c (4c): C H O N Cl, yield 99%, mp 242-244°C (dec.).
20 19
7 4
6-Nitro-9-(4′-nitrobenzylidene)deoxyvasicinone (3d) was synthesized analogously as above from 1b (0.5 g,
2.16 mmol) and 4-nitrobenzaldehyde (0.33 g, 2.16 mmol) to afford 3d (0.54 g, 69%), C H O N , mp 308-310°C (aq. DMF),
18 12
5 4
R 0.91 (system C).
f
PMR spectrum (δ, ppm, J/Hz): 8.86 (1H, d, J = 2.0, H-5), 8.43 (1H, dd, J = 2.4, H-7), 8.03 (1H, d, J = 9.0, H-5′), 8.03
(1H, d, J = 9.0, H-3′), 7.92 (1H, br.s, H-12), 7.7 (1H, d, J = 9.4, H-8), 7.47 (1H, d, J = 8.6, H-6′), 7.47 (1H, d, J = 8.6, H-2′),
4.29 (2H, t, J = 6.8, H-11), 3.23 (2H, br.t, H-10).
+
+
+
+
Mass spectrum (m/z, %): 364 (53) [M] , 318 (15.4) [M - NO ] , 242 (16.8) [M - Ar] , 229 (5.6) [M - (CH - Ar)] ,
2
363 (100), 334 (20), 317 (50), 271 (33), 231 (14.7), 216 (18), 202 (6), 182 (6.3).
Perchlorate of 3d (4d): C H O N Cl, yield 86%, mp 270°C (dec.).
18 13
9 4
6-Nitro-9-(3′,4′-dimethoxybenzylidene)deoxyvasicinone (3e) was synthesized analogously as above from 1b (0.5 g,
2.16 mmol) and 3,4-dimethoxybenzaldehyde (0.35 g, 2.16 mmol) to afford 3e (0.64 g, 78%), C H O N , mp 229-230°C (aq.
20 17
5 3
DMF), R 0.78 (system A).
f
PMR spectrum (δ, ppm, J/Hz): 8.83 (1H, d, J = 2.5, H-5), 8.39 (1H, dd, J = 2.2, 8.9, H-7), 7.77 (1H, br.s, H-12), 7.64
(1H, d, J = 9.0, H-8), 7.05 (1H, d, J = 8.7, H-5′), 6.87 (1H, s, H-2′), 6.76 (1H, d, J = 8.4, H-6′), 4.26 (2H, t, J = 7.2, H-11), 3.60,
3.61 [6H, d, (OCH ) ], 3.19 (2H, t, H-10).
3 2
+
+
+
Mass spectrum (m/z, %): 379 (100) [M] , 333 (11.2) [M - NO ] , 229 (1.4) [M - (CH - Ar)] , 378 (23), 356 (22.3),
2
332 (14.7), 291 (7), 245 (2), 200 (11.2), 173 (4.2), 151 (12), 146 (4.8).
Perchlorate of 3e (4e): C H O N Cl, yield 68%, mp 262-264°C (dec.).
20 18
9 3
6-Nitro-9-(2′-bromo-3′-hydroxy-4′-methoxybenzylidene)deoxyvasicinone (3f) was synthesized from 1b(0.4g, 1.7
mmol) and 2-bromoisovanillin (0.4 g, 1.7 mmol) to afford 3f (0.6 g, 86%), C H O N Br, mp 298-299°C (aq. DMF), R 0.76
f
19 14
5 3
(system B).
PMR spectrum (δ, ppm, J/Hz): 8.85 (1H, d, J = 2.3, H-5), 8.4 (1H, dd, J = 2.2, 9.0, H-7), 8.09 (1H, br.s, H-12), 7.65
(1H, d, J = 9.0, H-8), 7.05 (1H, d, J = 8.8, H-5′), 6.7 (1H, d, J = 8.8, H-6′), 4.2 (2H, t, H-11), 3.64 (3H, s, OCH ), 3.13 (2H, t,
3
H-10).
+
+
+
Mass spectrum (m/z, %): 443/446 (4.2) [M] , 241/244 (3.5) [M - Ar] , 229 (1.4) [M - (CH - Ar)] , 362/365 (100),
332/335 (12.6), 318 (80), 302/305 (32), 273/276 (7.7), 244/247 (5.6), 216/219 (4.8), 182 (3.5), 142 (3.5).
Perchlorate of 3f (4f): C H O N BrCl, yield 79%, mp 224°C (dec.).
19 15
9 3
6-Nitro-9-(3′-methoxy-4′-hydroxy-5′-bromobenzylidene)deoxyvasicinone(3g)was synthesized analogouslyas above
from 1b (0.4 g, 1.7 mmol) and 5-bromovanillin (0.4 g, 1.7 mmol) to afford 3g (0.39 g, 52%), C H O N Br, mp 293-294°C
19 14
5 3
(aq. DMF), R 0.78 (system B).
f
PMR spectrum (δ, ppm, J/Hz): 8.83 (1H, d, J = 2.6, H-5), 8.39 (1H, dd, J = 2.3, 8.8, H-7), 7.70 (1H, br.s, H-12), 7.66
(1H, d, J = 9.1, H-8), 7.15 (1H, s, J = 2.0, H-2′), 6.76 (1H, d, J = 2.0, H-6′), 4.26 (2H, t, J = 6.8, H-11), 3.61 (3H, s, OCH ), 3.18
3
(2H, t, H-10).
+
+
+
Mass spectrum (m/z, %): 443/446 (100) [M] , 398 (2.1) [M - NO ] , 241/244 (3.5) [M - Ar] , 229 (2.8)
[M - (CH - Ar)] , 413/416 (10), 335 (8.4), 319/322 (11.2), 302/305 (6.3), 273/276 (3.5), 244/247 (10.5), 215 (9), 144 (3).
2
+
Perchlorate of 3g (4g): C H O N BrCl, yield 69%, mp 300°C (dec.).
19 15
9 3
6-Nitro-9-(3′-hydroxy-4′-methoxy-6′-bromobenzylidene)deoxyvasicinone(3h)wassynthesizedanalogouslyas above
from 1b (0.3 g, 1.3 mmol) and 6-bromoisovanillin (0.3 g, 1.3 mmol) toafford 3h (0.33 g, 58%), C H O N Br, mp 288-289°C
19 14
5 3
(aq. DMF), R 0.76 (system B).
f
478

PMR spectrum (δ, ppm, J/Hz): 8.84 (1H, d, J = 2.7, H-5), 8.4 (1H, dd, J = 2.4, 9.0, H-7), 8.07 (1H, br.s, H-12), 7.65
(1H, d, J = 9.0, H-8), 6.97 (1H, s, H-5′), 6.88 (1H, s, H-2′), 4.26 (2H, t, H-11), 3.6 (3H, s, OCH ), 3.19 (2H, t, H-10).
3
+
+
+
Mass spectrum (m/z, %): 444 (2.4) [M] , 241/244 (5.6) [M - Ar] , 229 (1.5) [M - (CH - Ar)] , 378 (92), 332/335 (100),
315/318 (23), 303/306 (16.8), 287/290 (19.6), 273/276 (10.5), 259/262 (10), 216 (5), 174 (5), 145 (8).
Perchlorate of 3h (4h): C H O N BrCl, yield 72%, mp 238-240°C (dec.).
19 15
9 3
6-Nitro-9-(furfurylidene-1′)deoxyvasicinone (3i) was synthesized analogously as above from 1b (0.5 g, 2.16 mmol)
3
and furfurol (0.18 mL, 0.2 g, 2.17 mmol, ρ = 1.1598 g/cm ) to afford 3i (0.52 g, 78%), C H O N , mp 240°C (dec., benzene),
16 11
4 3
R 0.72 (system B).
f
PMR spectrum (δ, ppm, J/Hz): 8.82 (1H, d, J = 2.2, H-5), 8.37 (1H, dd, J = 2.5, 9.0, H-7), 7.59 (1H, d, J = 9.0, H-8),
7.59 (1H, br.s, H-12), 7.48 (1H, s, H-4′), 6.82 (1H, d, J = 3.7, H-2′), 6.36 (1H, dd, J = 1.8, 3.7, H-3′), 4.21 (2H, t, J = 7.2, H-11),
3.23 (2H, t, J = 6.8, H-10).
+
+
Mass spectrum (m/z, %): 309 (86) [M] , 229 (1.4) [M - (CH - Ar)] , 308 (100), 280 (58.7), 268 (61.5), 262 (33.6),
250 (29), 234 (54.5), 222 (37.8), 208 (39), 205 (57), 192 (8), 179 (15.4), 152 (9.4), 143 (7).
Perchlorate of 3i (4i): C H O N Cl, yield 70%, mp 202°C (dec.).
16 12
8 3
ACKNOWLEDGMENT
The work was supported financiallybyRepublic of Uzbekistan TsNT (Project No. FA-F3-T047). We thank Candidate
of Chemical Sciences V. I. Vinogradova for supplying the substituted vanillins.
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