Synthesis of derivatives of the hydrazones of 5-phenylfuro[3,2-g]chromen-7- ones

Article abstract of DOI:10.1007/s10593-011-0667-6

Sulfur- and nitrogen-containing derivatives of 5-phenylfurocoumarins at the exocyclic oxygen atom were synthesized. The reaction of the obtained hydrazones with certain carbonyl compounds was investigated.

Full text of DOI:10.1007/s10593-011-0667-6

Chemistry of Heterocyclic Compounds, Vol. 46, No. 11, February, 2011 (Russian Original Vol. 46, No. 11, November, 2010)
SYNTHESIS OF DERIVATIVES OF THE HYDRAZONES
OF 5-PHENYLFURO[3,2-g]CHROMEN-7-ONES
D. P. Ostrovskiy1, Ya. L. Garazd1, M. M. Garazd2, and V. P. Khilya1*
Sulfur- and nitrogen-containing derivatives of 5-phenylfurocoumarins at the exocyclic oxygen atom
were synthesized. The reaction of the obtained hydrazones with certain carbonyl compounds was
investigated.
Keywords: benzopyran-2-thiones, hydrazones, coumarins, semicarbazones, thiosemicarbazones,
furocoumarins.
Furocoumarins represent a structurally varied group of natural compounds that are in most cases
derivatives of the linear furocoumarin psoralene [1]. The increased interest in the study of furocoumarins is
explained by the important role that these compounds play in the vital activity of plant and animal organisms
and also by their high and diverse biological activity [2]. Modification of furocoumarin systems is mainly
achieved by the introduction of substituents into the furan or benzopyran-2-one fragments of the molecule, while
derivatives of furocoumarins at the exocyclic oxygen atom have to this day hardly been studied at all [3].
The aim of the present work was to modify 5-phenylfurocoumarins at the exocyclic oxygen atom with
the formation of the corresponding thiones and hydrazones and also to study the reaction of the obtained
hydrazones with certain carbonyl compounds.
The 5-phenylfuro[3,2-g]chromen-7-ones 1-4 required for the subsequent transformations were obtained
by McLeod's reaction from the corresponding 7-hydroxy-4-phenylcoumarins [4]. It is known that direct
modification of coumarins at the exocyclic oxygen atom from derivatives of benzopyran-2-one is difficult to
achieve. Convenient synthons for the realization of such chemical transformations are derivatives of
benzopyran-2-thiones [5, 6].
We used Lawesson's reagent to replace the oxygen atom of the furocoumarin system by a sulfur atom [7,
8]. When 5-phenylfurocoumarins 1-4 were heated with a 10% excess of Lawesson's reagent (LR) in toluene the
benzopyran-2-thiones 5-8 were obtained smoothly and with high yields. In contrast to the colorless initial
coumarins 1-4 compounds 5-8 were bright-yellow substances, the color of which is due to the presence of C=S
group in their molecules.
_______
*To whom correspondence should be addressed, e-mail: vkhilya@mail.univ.kiev.ua.
1Taras Shevchenko Kiev National University, Kiev 01033, Ukraine.
2Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev 02094,
Ukraine; e-mail: gmm@i.com.ua.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1630-1637, November, 2010.
Original article submitted May 7, 2008.
1318
0009-3122/11/4611-1318©2011 Springer Science+Business Media, Inc.

Scheme 1
3"
4"
2"
O
9
O
O
O
S
O
O
NNH2
O
N
S
5"
6"
NH2NH2
LR
N
H
N
2
H
6
6
6
6
8"
4
7"
Me
Ph
Ph
Ph
Ph
N
20
9
1
5
2"
O
3"
N
H
N
H
1"
6
Ph
22
The furocoumarin hydrazones 9-12 were obtained by treating alcohol solutions of the respective thiones
5-8 with hydrazine hydrate [8,9] (Schemes 1-4).
The structure of the obtained compounds 5-12 is supported by the data from elemental analysis and
NMR spectroscopy. In the 1H NMR spectra of the furocoumarins 1-4 the one-proton singlet of the H-6 proton is
observed at 6.31-6.44 ppm. The transformation of furocoumarins into furocoumarinthiones 5-8 leads to a
1
downfield shift of the signal for the H-6 proton in the H NMR spectra (7.08-7.12 ppm). In the spectra of the
hydrazones 9-12 the signal of the H-6 proton is in the region of 6.03-6.16 ppm. Also in the spectra of the
hydrazones 9-12 a two-proton broad singlet for the amino group is observed at 5.65-6.05 ppm.
Scheme 2
O
N
N
4''
OMe
5''
2''
3''
5''
6
2''
O
N
6''
4''
N
N
Ph
7''
6''
6
Et
13
Ph
17
Me
O
O
O
S
O
O
NNH2
LR
NH2NH2
2
6
6
6
4
Ph
Ph
Ph
6'
2'
6
10
2
4'
S
3''
1''
CH2
O
N
N
H
N
H
2''
Me
3''
O
6
Ph
23
O
N
OEt
N
2''
H
6
Ph
26
1319

The heating of alcohol solutions of the hydrazones 10-12 with aldehydes (1-ethyl-5-methoxyindole-
3-carbaldehyde, 4-(dimethylamino)benzaldehyde, 3-phenylprop-2-enal, and 1-methylindole-3-carbaldehyde)
and ketones (cyclohexanone, isatin, acetone) leads to the rapid formation of the corresponding substituted
5-phenylfuro[3,2-g]chromen-7-ylidenehydrazones 13-19 (Schemes 2-4). The structure of the obtained
1
derivatives is supported by the data from elemental analysis and NMR spectroscopy. In the H NMR of these
compounds doubling of the signals for the protons both of the furocoumarin system and of the carbonyl
fragment is observed as a result of the existence of the compounds in the form of a mixture of the (Z)- and (E)-
isomers in almost equal amounts.
As a result of the reaction of the hydrazones 9-12 with isocyanates (phenyl isocyanate and 1-naphthyl
isocyanate) and isothiocyanates (isopropyl, allyl, cyclopropyl, and cyclopentyl isothiocyanates) with heat in dry
toluene [10, 11] the corresponding semicarbazones 20 and 21 and thiosemicarbazones 22-25 are formed
1
(Schemes 1-4). In the H NMR spectra of compounds 20-25 in the region of 7.20-10.20 ppm there signals for
the protons of the NH groups characteristic of semicarbazones and thiosemicarbazones groups.
The reaction of the hydrazones 10-12 with the esters of β-keto acids (acetoacetic ester, ethyl 2-benzyl-
acetoacetate and 2-oxocyclohexanecarboxylate) leads to the formation of the enamines 26-28 (schemes 2-4). In
the 1H NMR spectra of compounds 26-28 in the region of 11.90-12.74 ppm there is a signal for the proton of the
NH group, and for compound 26 there is a singlet for the H-2" proton at 4.67 ppm.
Scheme 3
5''
Ph
6''
7''
2''
1''
4''
O
N
3''
O
N
N
N
O
N
2''
3''
N
NH
6
6''
6
Ph
6
O
Ph
5''
15
Ph
NMe2
14
18
9
O
O
O
O
S
2
O
NNH2
NH2NH2
6
LR
4
2'
6
6
Ph
6'
5'
Ph
Ph
7
3'
3
11
Cl
O
O
N
Ph
1''
Me
S
N
N
O
Me
H
H
O
N
2''
3''
N
O
N
N
Me
N
OEt
H
H
H
Ph
6
Ph
6
6
Ph
24
Ph
21
27
1320

Scheme 4
1"
Me
O
N
O
N
4"
5"
N
N
Me
6
6
2"
2"
6"
7"
N
Ph
Ph
19
Me
16
Me
9
O
O
O
S
O
NNH2
O
LR
2
NH2NH2
Me
6'
6
6
6
4
Ph
Ph
Ph
2'
8
12
4
4'
4"
3"
2"
3"
S
5"
6"
4"
O
N
O
N
N
H
N
1"
N
H
5"
H
OEt
O
6
6
Ph
Ph
28
25
EXPERIMENTAL
1
The H NMR spectra were recorded on Varian VXR-300 (300 MHz) and Varian Mercury-400 (400
MHz) instruments in DMSO-d6 for compounds 5-13, 15-21, 23, and 26 and in CDCl3 for compounds 14, 22, 24,
25, 27, and 28 with TMS as internal standard. The melting points were determined on a Kofler bench. The
course of the reactions and the individuality of the compounds were monitored by TLC on Merck 60 F254 plates
with 9:1 and 95:5 chloroform–methanol as eluents.
The synthesis of the initial furocoumarins 1-4 was described in [4].
5-Phenylfuro[3,2-g]chromene-7-thiones 5-8 (General Method). A mixture of the furocoumarin 1-4
(10 mmol) and (1.23 g, 5.5 mmol) of Lawesson's reagent in absolute toluene (20 ml) was boiled for 2 h. (The
course of the reaction was monitored by TLC.) At the end of the reaction the solvent was evaporated, and the
oily residue was crystallized from aqueous 2-propanol.
1
3-Methyl-5-phenylfuro[3,2-g]chromene-7-thione (5). The yield 87%; mp 199-201°C. H NMR
spectrum, δ, ppm (J, Hz): 2.16 (3H, s, 3-CH3); 7.08 (1H, s, H-6); 7.59 (5H, s, C6H5); 7.64 (1H, s, H-9); 7.81 (2H,
s, H-2,4). Found, %: С 74.08; Н 4.19; S 10.84. C18H12O2S. Calculated, %: С 73.95; Н 4.14; S 10.97.
1
9-Methyl-3,5-diphenylfuro[3,2-g]chromene-7-thione (6). The yield 95%; mp 267-269°C. H NMR
spectrum, δ, ppm (J, Hz): 2.76 (3H, s, 9-CH3); 7.12 (1H, s, H-6); 7.34 (1Н, m, Н-4'); 7.42 (2Н, t, J = 7.6,
Н-3',5'); 7.52–7.64 (7Н, m, 5-C6H5, Н-2',6'); 7.81 (1H, s, H-4); 8.36 (1H, s, H-2). Found, %: С 78.19; Н 4.45;
S 8.79. C24H16O2S. Calculated, %: С 78.24; Н 4.38; S 8.70.
1
3-(4-Chlorophenyl)-5-phenylfuro[3,2-g]chromene-7-thione (7). The yield 91%; mp 232-234°C. H
NMR spectrum, δ, ppm (J, Hz): 7.12 (1H, s, H-6); 7.44 (2Н, d, J = 8.4, Н-3',5'); 7.56-7.66 (7Н, m, 5-C6H5,
Н-2',6'); 7.94 (1H, s, H-9); 7.97 (1H, s, H-4); 8.42 (1H, s, H-2). Found, %: С 71.01; Н 3.49; Cl 9.28; S 8.32.
C23H13ClO2S. Calculated, %: С 71.04; Н 3.37; Cl 9.12; S 8.25.
1321

1
2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromene-7-thione (8). The yield 95%; mp 289-291°C. H
NMR spectrum, δ, ppm (J, Hz): 2.59 (3H, s, 2-CH3); 2.73 (3H, s, 9-CH3); 7.08 (1H, s, H-6); 7.34 (1Н, m, Н-4');
7.39-7.57 (10Н, m, H-4, 5-C6H5, Н-2',3',5',6'). Found, %: С 78.63; Н 4.81; S 8.32. C25H18O2S. Calculated, %:
С 78.51; Н 4.74; S 8.38.
5-Phenylfuro[3,2-g]chromen-7-ones Hydrazones 9-12 (General Method). To a solution of the
furocoumarinthione 5-8 (10 mmol) in ethanol (30 ml) we added hydrazine hydrate (1 ml, 20 mmol). The mixture
was boiled for 2 h. (The course of the reaction was monitored by TLC). When the reaction had finished the
mixture was cooled to room temperature, and the precipitate was filtered off and recrystallized from 2-propanol.
1
3-Methyl-5-phenylfuro[3,2-g]chromen-7-one Hydrazone (9). The yield 73%; mp 148-149°C. H
NMR spectrum, δ, ppm (J, Hz): 2.09 (3H, s, 3-CH3); 5.70 (2Н, br. s, NH2); 6.03 (1H, s, H-6); 7.16 (1H, s, H-9);
7.30 (1H, s, H-4); 7.41-7.52 (5H, m, C6H5); 7.55 (1H, d, J = 1.2, H-2). Found, %: С 74.58; Н 4.94; N 9.66.
C18H14N2O2. Calculated, %: С 74.47; Н 4.86; N 9.65.
9-Methyl-3,5-diphenylfuro[3,2-g]chromen-7-one Hydrazone (10). The yield 87%; mp 203-204°C. 1H
NMR spectrum, δ, ppm (J, Hz): 2.76 (3H, s, 9-CH3); 5.70 (2Н, br. s, NH2); 6.08 (1H, s, H-6); 7.28 (1Н, m,
Н-4'); 7.34-7.50 (10Н, m, H-4, 5-C6H5, H-2',3',5',6'); 8.10 (1H, s, H-2). Found, %: С 78.81; Н 4.98; N 7.58.
C24H18N2O2. Calculated, %: С 78.67; Н 4.95; N 7.65.
3-(4-Chlorophenyl)furo-5-phenyl[3,2-g]chromen-7-one Hydrazone (11). The yield 76%; mp 193-194°C.
1H NMR spectrum, δ, ppm (J, Hz): 6.05 (2Н, br. s, NH2); 6.16 (1H, s, H-6); 7.45-7.55 (11Н, m, H-4, 5-C6H5,
H-9, Н-2',3',5',6'); 8.35 (1H, s, H-2). Found, %: С 71.59; Н 4.06; Cl 9.11; N 7.35. C23H15ClN2O2. Calculated, %:
С 71.41; Н 3.91; Cl 9.16; N 7.24.
2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromen-7-one Hydrazone (12). The yield 72%; mp 234-235°C. 1H
NMR spectrum, δ, ppm (J, Hz): 2.49 (3H, s, 2-CH3); 2.53 (3H, s, 9-CH3); 5.65 (2Н, br. s, NH2); 6.03 (1H, s,
H-6); 7.08 (1H, s, H-4); 7.25-7.45 (10Н, m, 3-C6H5, 5-C6H5). Found, %: С 79.05; Н 5.38; N 7.29. C25H20N2O2.
Calculated, %: С 78.93; Н 5.30; N 7.36.
(5-Phenylfuro[3,2-g]chromen-7-ylidene)hydrazones of Aldehydes 13-16 and Ketones 17-19
(General Method). A mixture of the hydrazone 10-12 (2 mmol) and respective aldehyde or ketone (2.2 mmol)
in ethanol (10 ml) was boiled for 2-4 h. (The course of the reaction was monitored by TLC.) When the reaction
had finished the mixture was cooled to room temperature, and the precipitate was filtered off and recrystallized
from 2-propanol.
1-Ethyl-5-methoxyindole-3-carbaldehyde (9-Methyl-3,5-diphenylfuro[3,2-g]chromen-7-ylidene)-
hydrazone (13). The yield 78%; mp 268-269°C. 1H NMR spectrum, δ, ppm (J, Hz): 1.38-1.49 (3Н, m, CH2СH3);
2.60 and 2.76 (3H, two s, 9-CH3); 3.70 and 3.72 (3H, two s, 5"-CH3O); 4.16-4.29 (2Н, m, CH2СH3); 6.41 and 7.35
(1H, s, H-6); 6.43 and 6.86 (1Н, two d, J = 2.4, H-4"); 7.36-7.62 (12Н, m, 3-C6H5, 5-C6H5, H-6",7"); 7.74 and 7.88
(1H, two s, H-4); 7.82 and 8.08 (1H, two s, H-2"); 8.27 and 8.29 (1H, two s, H-2); 8.60 and 8.64 (1H, two s,
N=CH). Found, %: С 78.69; Н 5.29; N 7.69. C36H29N3O3. Calculated, %: С 78.38; Н 5.30; N 7.62.
4-(Dimethylamino)benzaldehyde [3-(4-Chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-ylidene]-
hydrazone (14). The yield 72%; mp 272-273°C. 1H NMR spectrum, δ, ppm (J, Hz): 3.06 (6Н, s, N(CH3)2); 6.46
(1H, s, H-6); 6.75 (2Н, d, J = 8.8, H-3",5"); 7.38 (2Н, d, J = 8.8, H-3',5'); 7.42 (2Н, d, J = 8.8, H-2',6'); 7.50 (5Н,
m, 5-C6H5); 7.60 (1H, s, H-9); 7.67 (1H, s, N=CH); 7.76 (1H, s, H-4); 7.78 (2Н, d, J = 8.8, H-2",6"); 8.39 (1H,
s, H-2). Found, %: С 74.16; Н 4.69; Cl 6.89; N 8.19. C32H24ClN3O2. Calculated, %: С 74.20; Н 4.67; Cl 6.84;
N 8.11.
3-Phenylprop-2-enal [3-(4-chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-ylidene]hydrazone (15).
1
The yield 83%; mp 265-266°C. H NMR spectrum, δ, ppm (J, Hz): 6.46 and 7.21 (1H, two s, H-6); 7.15-7.67
(17Н, m, H-9, 5-C6H5, Н-2',3',5',6', Н-1",2", C6H5); 7.73 and 7.78 (1H, two s, H-4); 8.22 and 8.25 (1Н, two d,
J = 8.8, Н-3"); 8.40 and 8.42 (1H, two s, H-2). Found, %: С 76.64; Н 4.18; Cl 7.01; N 5.61. C32H21ClN2O2.
Calculated, %: С 76.72; Н 4.23; Cl 7.08; N 5.59.
1322

1-Methylindole-3-carbaldehyde [2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromen-7-ylidene]hydra-
1
zone (16). The yield 85%; mp 278-279°C. H NMR spectrum, δ, ppm (J, Hz): 2.60 and 2.71 (6H, two s,
2,9-CH3); 3.83 and 3.87 (3H, two s, NCH3); 6.35 and 7.22 (1H, s, H-6); 7.12-7.56 (14H, m, 3-C6H5, H-4,
5-C6H5, H-5",6",7"); 7.83 and 7.84 (1H, two s, H-2"); 8.14 and 8.62 (1Н, two d, J = 7.2, H-4"); 8.61 and 8.65
(1H, two s, N=CH). Found, %: С 80.67; Н 5.29; N 7.97. C35H27N3O2. Calculated, %: С 80.59; Н 5.22; N 8.06.
9-Methyl-3,5-diphenylfuro[3,2-g]chromen-7-one Cyclohexylidenehydrazone (17). The yield 59%;
1
mp 196-197°C. H NMR spectrum, δ, ppm (J, Hz): 1.48-1.75 (6Н, m, 3",4",5"-СН2); 2.37-2.76 (4Н, m,
2",6"-СН2); 2.61 and 2.66 (3H, two s, 9-CH3); 6.35 and 7.03 (1H, two s, H-6); 7.33-7.56 (11Н, m, 3-C6H5, H-4,
5-C6H5); 8.35 and 8.36 (1H, s, H-2). Found, %: С 80.75; Н 5.96; N 6.32. C30H26N2O2. Calculated, %: С 80.69; Н
5.87; N 6.27.
3-[3-(4-Chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-ylidene]hydrazono-1,3-dihydroindol-2-one
1
(18). The yield 89%; mp 269-270°C. H NMR spectrum, δ, ppm (J, Hz): 6.84 and 7.29 (1H, two s, H-6); 6.85
and 6.87 (1Н, two d, J = 7.2, H-7"); 6.91 and 7.00 (1Н, two t, J = 7.2, H-5"); 7.30-7.77 (11Н, m, 5-C6H5, H-9,
Н-2',3',5',6', H-6"); 7.86 and 7.94 (1H, two s, H-4); 8.24 and 8.28 (1Н, two d, J = 7.6, H-4"); 8.40 and 8.42 (1H,
two s, H-2); 10.55 and 10.63 (1H, two s, NH). Found, %: С 72.21; Н 3.57; Cl 6.90; N 8.18. C31H18ClN3O3.
Calculated, %: С 72.17; Н 3.52; Cl 6.87; N 8.14.
2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromen-7-one (1-Methylethylidene)hydrazone (19). The
1
yield 56%; mp 219-220°C. H NMR spectrum, δ, ppm (J, Hz): 1.92 (3Н, s, 1''-CH3); 2.02 and 2.03 (3Н, two s,
2-CH3); 2.09 (3Н, s, 2"-CH3); 2.61 and 2.65 (3H, two s, 9-CH3); 6.30 and 6.96 (1H, two s, H-6); 7.17 and 7.19
(1H, two s, H-4); 7.34-7.54 (10Н, m, 3-C6H5, 5-C6H5). Found, %: С 80.09; Н 5.71; N 6.49. C28H24N2O2.
Calculated, %: С 79.98; Н 5.75; N 6.66.
(5-Phenylfuro[3,2-g]chromen-7-ylidene)hydrazones Semicarbazones and Thiosemicarbazones
20-25 (General Method). A mixture of hydrazone 9-12 (2 mmol) and the respective isocyanate or
isothiocyanate (2.2 mmol) in dry toluene (10 ml) was boiled for 2 h. (The course of the reaction was monitored
by TLC). When the reaction had finished the mixture was cooled to room temperature, and the precipitate was
filtered off and recrystallized from 2-propanol.
3-Methyl-5-phenylfuro[3,2-g]chromen-7-one N-(1-Naphthyl)semicarbazone (20). The yield 56%;
1
mp 236-237°C. H NMR spectrum, δ, ppm (J, Hz): 2.11 (3H, s, 3-CH3); 6.46 (1H, s, H-6); 7.35 (1H, s, H-9);
7.48-7.69 (11Н, m, H-4, 5-C6H5, H-3",4",5",6",7"); 7.82 (1H, s, H-2); 7.96 (1H, d, J = 8.4, H-2"); 8.06 (1H, d,
J = 8.4, H-8"); 9.09 and 10.23 (2Н, two s, HNCONH). Found, %: С 75.91; Н 4.65; N 9.02. C29H21N3O3.
Calculated, %: С 75.80; Н 4.61; N 9.14.
3-(4-Chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-one N-Phenylsemicarbazone (21). The yield
1
92%; mp 269-270. H NMR spectrum, δ, ppm (J, Hz): 6.32 (1H, s, H-6); 7.06-7.55 (15Н, m, H-9, 5-C6H5,
Н-2',3',5',6', C6H5); 7.64 (1H, s, H-4); 7.78 (1H, s, H-2); 8.09 and 8.37 (2Н, two s, HNCONH). Found, %:
С 71.28; Н 3.91; Cl 7.12; N 8.30. C30H20ClN3O3. Calculated, %: С 71.22; Н 3.98; Cl 7.01; N 8.31.
3-Methyl-5-phenylfuro[3,2-g]chromen-7-one N-Cyclopropylthiosemicarbazone (22). The yield
1
58%; mp 222-223°C. H NMR spectrum, δ, ppm (J, Hz): 0.70-0.92 (4Н, m, 2",3"-CH2); 2.13 (3H, s, 3-CH3);
3.18 (1Н, m, Н-1"); 6.19 (1H, s, H-6); 7.32-7.55 (9Н, m, H-2,4, 5-C6H5, H-9, СSNH); 9.14 (1H, s, NNHCS).
Found, %: С 67.56; Н 5.48; N 10.70; S 8.26. C22H19N3O2S. Calculated, %: С 67.85; Н 4.92; N 10.79; S 8.23.
9-Methyl-3,5-diphenylfuro[3,2-g]chromen-7-one N-Allylthiosemicarbazone (23). The yield 86%;
mp 232-233°C. 1H NMR spectrum, δ, ppm (J, Hz): 2.64 (3Н, s, 9-CH3); 4.22 (2Н, t, J = 5.6, 1"-СН2); 5.11 (1Н,
dd, J = 1.6, J = 10.4, H-3"cis); 5.17 (1Н, dd, J = 1.6, J = 17.6, H-3"trans); 5.89-5.97 (1Н, m, H-2"); 6.28 (1Н, s,
Н-6); 7.34-7.55 (11Н, m, 3-C6H5, H-4, 5-C6H5); 8.38 (1H, s, Н-2); 8.42 (1Н, t, J = 5.6, СSNH); 10.03 (1H, s,
NNHCS). Found, %: С 72.11; Н 5.03; N 8.87; S 6.93. C28H23N3O2S. Calculated, %: С 72.23; Н 4.98; N 9.03;
S 6.89.
3-(4-Chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-one N-Isopropylthiosemicarbazone (24). The
1
yield 73%; mp 218-219°C. H NMR spectrum, δ, ppm (J, Hz): 1.33 (6H, d, J = 7.6, CH(СН3)2); 4.56-4.62
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(1Н, m, CН(CH3)2); 6.27 (1H, s, H-6); 7.18 (1Н, d, J = 5.6, СSNH); 7.35-7.54 (10H, m, 5-C6H5, H-9,
Н-2',3',5',6'); 7.64 (1H, s, H-4); 7.79 (1H, s, H-2); 9.05 (1H, s, NNHCS). Found, %: С 66.53; Н 4.51; Cl 7.32;
N 8.55; S 6.63. C27H22ClN3O2S. Calculated, %: С 66.45; Н 4.54; Cl 7.26; N 8.61; S 6.57.
2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromen-7-one N-Cyclopentylthiosemicarbazone (25). The
yield 72%; mp 268-269°C. 1H NMR spectrum, δ, ppm (J, Hz): 1.45-1.80 (8Н, m, H-2",3",4",5"-CH2); 2.54 (3H,
s, 2-CH3); 2.64 (3H, s, 9-CH3); 4.71-4.80 (1H, m, H-1"); 6.21 (1H, s, H-6); 7.26-7.48 (12Н, m, 3-C6H5, H-4,
5-C6H5, СSNH); 8.93 (1H, s, NNHCS). Found, %: С 73.46; Н 5.71; N 8.29; S 6.30. C31H29N3O2S. Calculated,
%: С 73.34; Н 5.76; N 8.28; S 6.32.
Ethyl 3-[2-(5-Phenylfuro[3,2-g]chromen-7-ylidene)hydrazinyl]but-2-enoates 26-28 (General
Method). A mixture of hydrazone 10-12 (2 mmol) and respective β-keto ester (2.2 mmol) in ethanol (10 ml)
was boiled for 4-6 h. (The course of the reaction was monitored by TLC). When the reaction had finished the
mixture was cooled to room temperature and recrystallized from 2-propanol.
Ethyl 3-[2-(9-Methyl-3,5-diphenylfuro[3,2-g]chromen-7-ylidene)hydrazinyl]but-2-enoate (26). The
1
yield 72%; mp 181-182°C. H NMR spectrum, δ, ppm (J, Hz): 1.23 (3H, t, J = 7.2, 2'" -CH3); 2.13 (3H, s, 3"-
CH3); 2.68 (3H, s, 9-CH3); 4.12 (2Н, q, J = 7.2, 1"'-CH3); 4.67 (1Н, s, Н-2"); 6.30 (1Н, s, H-6); 7.34-7.55 (11H,
m, 3-C6H5, H-4, 5-C6H5); 8.35 (1H, s, H-2); 11.90 (1Н, s, NH). Found, %: С 75.38; Н 5.56; N 5.79. C30H26N2O4.
Calculated, %: С 75.30; Н 5.48; N 5.85.
Ethyl
2-Benzyl-3-{2-[3-(4-chlorophenyl)-5-phenylfuro[3,2-g]chromen-7-ylidene]hydrazinyl}but-
2-enoate (27). The yield 69%; mp 178-179°C. 1H NMR spectrum, δ, ppm (J, Hz): 1.26 (3H, m, CH2CH3); 2.26
(3H, s, 3"-CH3); 3.75 (2H, s, 2"-CH2); 4.22 (2Н, m, CH2CH3); 6.29 and 6.40 (1H, two s, H-6); 7.18-7.54 (15Н,
m, Н-9, 5-C6H5, Н-2',3',5',6', C6H5); 7.57 and 7.60 (1H, two s, H-4); 7.74 and 7.77 (1H, two s, H-2); 12.74 (1Н,
s, NH). Found, %: С 73.46; Н 5.03; Cl 6.09; N 4.68. C36H29ClN2O4. Calculated, %: С 73.40; Н 4.96; Cl 6.02; N
4.76.
Ethyl
2-[2-(2,9-Dimethyl-3,5-diphenylfuro[3,2-g]chromen-7-ylidene)hydrazinyl]cyclohex-1-ene-
1
1-carboxylate (28). The yield 84%; mp 234-235°C. H NMR spectrum, δ, ppm (J, Hz): 1.32 (3H, t, J = 7.2,
CH2CH3); 1.62-1.74 (4H, m, 4",5"-CH2); 2.37 (2Н, m, 3"-CH2); 2.54 (3H, s, 2-CH3); 2.69 (2Н, m, 6"-CH2); 2.76
(3H, s, 9-CH3); 4.23 (2Н, q, J = 7.2, CH2CH3); 6.22 (1H, s, H-6); 7.22-7.46 (11H, m, 3-C6H5, H-4, 5-C6H5);
12.34 (1Н, s, NH). Found, %: С 76.58; Н 6.13; N 5.21. C34H32N2O4. Calculated, %: С 76.67; Н 6.06; N 5.26.
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