Synthesis and structure of 4-arylspirodihydro-pyranochromen-2-one derivatives

Article abstract of DOI:10.1007/s10593-007-0060-7

Syntheses are reported for sulfur-and nitrogen-containing derivatives of 4-arylspiro-2-benzopyranones modified at the exocyclic oxygen atom. The structure of these products was demonstrated by correlational NMR spectroscopy.

Full text of DOI:10.1007/s10593-007-0060-7

Chemistry of Heterocyclic Compounds, Vol. 43, No. 4, 2007
SYNTHESIS AND STRUCTURE OF 4-ARYLSPIRODIHYDRO-
PYRANOCHROMEN-2-ONE DERIVATIVES
V. S. Moskvina1, Ya. L. Garazd1, M. M. Garazd2, A. V. Turov1, and V. P. Khilya1
Syntheses are reported for sulfur- and nitrogen-containing derivatives of 4-arylspiro-2-benzopyranones
modified at the exocyclic oxygen atom. The structure of these products was demonstrated by
correlational NMR spectroscopy.
Keywords: 4-arylcoumarins, 2-benzopyranthiones, hydrazones, coumarins, oximes, spirodihydro-
pyranochromen-2-ones, heteronuclear correlation.
Derivatives of 4-phenylcoumarin (neoflavones) hold interest since they are widespread throughout the
plant kingdom. Thus, more than 130 compounds containing the 4-arylcoumarin system have so far been found in
natural sources. Neoflavones isolated from natural sources display antibacterial [2, 3], insecticidal [2, 3],
antimalarial [4], sugar-reducing [5], antitumor [6], and cytotoxic activity [7] as well as properties inhibiting
HIV-1 reverse transcriptase [8]. On the other hand, neoflavones hold considerable potential for chemical
transformation and extensive structural modification [9] and, thus, may display pharmacological properties.
Synthetic 4-arylcoumarin derivatives have displayed cytotoxic [10], antioxidant [11], antiatherosclerotic [12],
and antibacterial action [13, 14].
In the present work, we introduced the spirodihydropyran fragment into the 4-arylcoumarin molecule
and also modified synthetic spiropyranocoumarins at the exocyclic oxygen atom to form sulfur and nitrogen
derivatives at C-2. The structures of these products were established by correlational NMR spectroscopy.
Spiro[(7-hydroxychroman-4-one)-2,1'-cyclohexane] (1) required for subsequent transformations was
obtained by the Kabbe condensation of 2,4-dihydroxyacetophenone with cyclohexanone in the presence of
pyrrolidine [15, 16]. Spirochromanone 1 was reduced to spiro[(7-hydroxychroman-2,1'-cyclohexane] 2 under
Clemmensen reaction conditions. The Pechman condensation of chromanol 2 with ethyl benzoylacetate or ethyl
(4-methoxybenzoyl)acetate in the presence of concentrated sulfuric acid led to the fusion of the 2-pyranone ring
to the spirochromanone system and formation of spirodihydropyranocoumarins 3 and 4.
It is difficult to modify coumarins at the exocyclic oxygen atom starting directly from 2-benzopyranone
derivatives. 2-Benzopyranthiones are convenient synthones for carrying out such chemical transformations. The
much greater reactivity of 2-benzopyranthiones in comparison with 2-benzopyranones is related to the lower
electronegativity of sulfur and, thus, polarizability of the C=S bond.
__________________________________________________________________________________________
1Taras Shevchenko Kiev National University, 02033 Kiev, Ukraine; e-mail: vkhilya@mail.univ.kiev.ua.
2Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 02094
Ukraine; e-mail: gmm@i.com.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518-527,
April, 2007. Original article submitted June 16, 2006.
0009-3122/07/4304-0421©2007 Springer Science+Business Media, Inc.
421

2-Benzopyranones are converted smoothly and, in most cases, with high yield to the corresponding
2-benzopyranthiones. Phosphorus pentasulfide [17-19], 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane
2,4-disulfide (Lawesson’s reagent) [20, 21], boron sulfide [22, 23], and bis(9-borabicyclo[3.3.1]non-9-yl) sulfide
[24] have served as thionylation agents in this reaction.
ArCOCH2COOEt,
H2SO4
O
O
OH
O
OH
Zn, HCl
1
2
5"
2"
6"
8
4"
3"
10
5
9a
5a
10a
2
O
O
O
O
O
S
LR
3
7
4a
4
6
6'
2'
3'
3, 4
5, 6
5'
4'
R
R
NH2NH2
NNH2
NH2OH
O
O
O
O
NOH
7, 8
9, 10
R
R
3,5,7,9 R = H; 4,6,8,10 R = OMe
We employed Lawesson's reagent [25] for thionylation of the exocyclic oxygen atom.
2-Benzopyranthiones 5 and 6 were synthesized smoothly and in high yield by heating spiropyrancoumarins 3
and 4 with a 10% excess of Lawesson’s reagent in toluene. In contrast to colorless starting 2-benzopyranones 3
and 4, products 5 and 6 are bright yellow compounds, whose color is due to the C=S group.
The reaction of 2-benzopyranthiones 5 and 6 with hydroxylamine hydrochloride in pyridine gave
spirodihydropyranochromene oximes 7 and 8. Treatment of solutions of thiones 5 and 6 in ethanol with
hydrazine hydrate gave the corresponding spirodihydropyranochromene hydrazones 9 and 10.
The structures of these products were supported by elemental analysis data and NMR spectroscopy. The
1H NMR spectra of 3-10 given in Table 1 are in accord with the proposed structures but, since the molecular
skeleton is rather complicated and lactone derivatives are unstable to the action of nucleophilic reagents, the
13C NMR spectra were taken (Table 2) and experiments were carried out to determine 1H-13C HMQC correlation
(through one chemical bond) and HMBC correlation (through two or three chemical bonds).
422

TABLE 1. 1H NMR Spectra of Compounds 3-10 (J, Hz)
Chemical shifts, δ, ppm
Atom No.
3
5
7
9
4
6
8
10
H-3 (1Н, s)
H-5(1Н, s)
6.06
7.10
2.71
6.92
7.25
2.75
5.95
6.82
2.60
5.89
6.77
2.59
6.12
7.18
2.72
6.90
7.32
2.76
5.95
6.86
2.54
5.85
6.80
2.59
6-СН2
(2Н, t, J = 6.8)
7-СН2
1.80
1.82
1.71
1.74
1.81
1.82
1.68
1.74
(2Н, t, J = 6.8)
H-10 (1Н, s)
6.73
7.45
6.91
7.50
6.56
7.45
6.55
7.36
6.82
—
6.89
—
6.52
—
6.53
—
Н-2', Н-6'
(2Н, m)
Н-2', Н-6'
(2Н, d, J = 8.8)
—
—
—
—
7.38
—
7.46
—
7.42
—
7.28
—
Н-3', Н-4', Н-5'
(3Н, m)
7.53
7.55
7.53
7.43
Н-3', Н-5'
(2Н, d, J = 8.8)
—
—
—
—
—
—
—
—
7.03
3.87
7.07
3.87
7.01
3.79
6.96
3.82
4'-OСH3 (3Н, s)
2''-CH2, 6''-CH2
(4Н, m)
1.4-1.6 1.6-1.7 1.6-1.7 1.6-1.7 1.4-1.6 1.6-1.7 1.6-1.7 1.6-1.7
1.4-1.6 1.4-1.5 1.4-1.5 1.4-1.5 1.4-1.6 1.4-1.5 1.4-1.5 1.4-1.5
1.5-1.6 1.3-1.5 1.3-1.6 1.3-1.6 1.5-1.6 1.3-1.5 1.3-1.6 1.3-1.6
3''-CH2, 5''-CH2
(4Н, m)
4''-CH2 (2Н, m)
2-N=NH2
—
—
—
5.54
—
—
—
5.51
(2Н, br. s)
2-NОH (1Н, s)
—
—
10.02
—
—
—
10.16
—
TABLE 2. 13C NMR Spectra of Compounds 4, 6, 8, and 10
Chemical shift, δ, ppm.
Atom No.
4
6
8
10
С-2
161.9
111.3
155.7
112.5
127.7
119.0
21.4
196.3
125.1
147.2
113.7
128.0
121.0
21.5
149.9
113.2
140.3
113.5
126.9
117.6
21.0
143.0
115.7
137.9
114.1
126.5
116.5
21.2
С-3
С-4
С-4а
С-5
С-5а
С-6
С-7
31.4
31.2
31.2
31.8
С-8
76.6
77.1
76.2
75.1
С-9а
157.8
105.1
154.4
128.4
130.0
114.5
160.8
55.7
157.2
104.5
158.3
127.2
130.6
115.0
161.3
55.9
155.7
104.3
152.5
129.0
130.2
114.8
160.1
55.8
155.1
104.3
153.0
129.6
129.9
114.5
159.8
55.6
С-10
С-10а
С-1'
С-2', С-6'
С-3', С-5'
С-4'
4'-OCH3
С-2", С-6''
С-3'', С-5''
С-4''
35.5
35.4
35.1
35.2
21.9
21.9
22.0
21.9
26.0
25.9
25.9
26.1
423

1
All the signals in the H NMR spectra of spirocoumarin 4 may be assigned with confidence with the
exception of the signals of the exocyclic substituent, which are poorly resolved multiplets at 1.35-1.75 ppm. The
correlations of the proton signals with the signals of the carbon atom signals in the HMQC spectrum permitted a
reliable assignment of the signals of the carbon atoms directly bonded to protons. The existence of a correlation
in the HMBC spectrum permitted assignment of the quaternary carbon atoms if these atoms were removed from
the protons present by two or three chemical bonds.
H
1.4-1H.6
H1.4–1.6
H
6.82
21.9
1.5–1.6H
H26.0
H
35.5
105.1
161.9
O
O
O
157.8
154.4
76.6
H
112.5
H
119.0
111.3
31.4
H
6.12
7.38
H
21.4
H
H
155.7
127.7
H
1.81 H
128.4
H
2.72H
130.0
H
7.18
114.5
H 7.03
160.8
O
55.7
CH3
3.87
4
1.5
H H
6.89
H
1.6–1.7
21.9
1.3–1.5H
H
H
104.5
H
35.4
25.9
196.3
O
S
O
157.2
158.3
77.1
H
113.7
121.0
21.5
125.1
31.2
H
H
6.90
7.46
H
H
H
147.2
128.0
H
H
1.82
127.2
H
2.76H
130.6
H
7.32
115.0
H7.07
161.3
O
55.9
CH3
6
3.87
Fig. 1. Heteronuclear correlations of spiro compounds 4 and 6.
The assignment of the signal at 160.8 ppm to C-4' follows from the correlations for this atom with the
methyl group proton signal and protons H-2' and H-3' of the phenyl substituent. The signal at 128.4 ppm
corresponds to C'-1 since there are correlations for this signal with protons H-2' and H-3' of the aryl substituent
and also with H-3, which is removed from C'-1 by three chemical bonds. The assignment of the signal at
155.7 ppm to C-4 follows from the correlations found for this signal with H-5, H-3, and H-2. Angular
424

atom C-4a may be assigned on the basis of correlations with H-3, H-5, and H-10 and the ω-interaction with the
protons of the methylene group H-6. The chemical shift of this atom is 112.5 ppm. The assignment of the signal
at 154.4 ppm to C-10a follows from the correlations found with H-5 and H-10. A correlation is noted for angular
atom C-5a with H-5, H-10, and the protons of the methylene groups 6-CH2 and 7-CH2. The chemical shift of this
atom is 119.0 ppm. Correlations were found for C-9a, which gives rise to the signal at 157.8 ppm, with H-5 and
H-10 as well as with the signal for 6-CH2. Correlations are found for spiro atom C-8, which gives rise to the
signal at 76.6 ppm, with methylene groups 6-CH2 and 7-CH2. Methylene group 7-CH2 also has a correlation with
the signal of atoms C-2" and C-6", which supports a spiro structure for 4 (the heteronuclear correlations found
are given in Table 3). The assignments of the signals in the proton and carbon spectra and the correlations
serving as a basis for the assignments are given in the figures. The short distance between H-5 and methylene
group 6-CH2 is also proven from the NOESY spectrum data. A clear cross peak is noted in the NOESY spectrum
between the corresponding signals.
1.4–1.6
H
H
H1.4-1.6
H
6.52
1.4–1.5H
H
22.0
H
35.1
104.3
25.9
149.9
10.16
O
N
O
OH
155.7
76.2
152.5
113.5
H
H
117.6
113.2
31.2
H
5.95
H
H
H
21.2
140.2
126.9
H
H
129.0
H
1.68
2.54H
130.2
H
7.28
6.86
114.8
H7.01
160.1
O
55.6
CH3
8
3.79
1.4–1.5
H H
H1.6–1.7
H
6.53
21.9
1.3–1.6
H
H
H
35.2
104.3
143.0
26.1
5.51
O
153.0
N
O
NH2
155.1
75.1
H
H
114.1
116.5
31.8
115.7
H
5.85
H
H
H
21.2
137.9
126.5
H
H
1.74
129.6
H
2.59H
129.9
H
7.28
6.80
114.5
H6.96
159.8
O
55.6
CH3
3.82
10
Fig. 2. Heteronuclear correlations of spiro compounds 8 and 10.
425

The structures of compounds 6, 8, and 10 were similarly demonstrated. The observed heteronuclear
correlations and assignments made for the signals in the 1H and 13C spectra are given in Table 3 and the figures.
These findings indicate that virtually the same heteronuclear correlations in the HMBC spectra are seen for 4, 6,
8, and 10, which indicates lack of change in the molecular skeleton during the chemical transformations. Thus,
the assignments of the signals in the 13C NMR spectra of compounds 6, 8, and 10 are virtually the same as those
described for spirodihydropyranochromen-2-one 4.
TABLE 3. Heteronuclear Correlations for Compounds 4, 6, 8, and 10
Chemical shifts of 13C NMR signals,
Com-
pound
1H NMR signals,
with correlation, δ, ppm
HMBC
δ, ppm
HMQC
4
7.38
7.18
130.0
127.7
114.5
105.1
111.3
55.7
160.8, 155.7, 128.4
157.8, 155.7, 154.4, 21.4
160.8, 128.4, 114.5
157.8, 154.4, 119.0, 112.5
161.9, 128.4, 112.5
160.8
7.03
6.82
6.12
3.87
2.72
21.4
76.6, 31.4, 157.8, 112.5, 119.0
76.6, 35.5, 21.9, 119.0
–
1.81
31.4
1.4–1.6
7.46
35.5, 26.0, 21.9
130.6
128.0
115.0
125.1
104.5
55.9
6
161.3, 147.2, 127.2
157.2, 147.2, 158.3, 21.5
161.3, 127.2, 115.0
196.3, 127.2, 113.7
157.2, 158.3, 121.0, 113.7
161.3
7.32
7.07
6.90
6.89
3.87
2.76
21.5
77.1, 31.3, 157.2, 121.0, 128.0
77.1, 35.4, 21.5, 121.0
–
1.82
31.2
1.6–1.70
1.35, 1.5
10.16
7.73
35.4
25.9, 21.9
–
–
8
149.9
130.2
114.8
126.9
104.3
113.2
55.8
160.1, 140.3, 129.0, 114.8
160.1, 129.0, 114.8
155.7, 152.5, 140.3, 104.3
155.7, 152.5, 140.3, 117.6, 113.5
149.9, 140.3, 129.0, 117.6, 113.5
160.1, 117.6
7.01
6.86
6.52
5.95
3.79
76.2, 31.2, 155.7, 152.5, 126.9, 113.6,
117.6
2.54
21.0
1.68
1.25–1.6
7.28
31.2
35.1, 25.9, 22.0
129.9
114.5
126.5
104.3
115.7
–
76.2, 35.1, 21.0
–
10
159.8, 137.9, 129.6
159.8, 129.6, 114.5
155.1, 137.9, 153.0, 21.2
155.1, 153.0, 116.5, 114.1
143.0, 137.9, 129.6, 114.1
–
6.96
6.80
6.53
5.85
5.51
3.82
55.6
159.8
2.59
21.2
155.1, 126.5, 116.5, 114.1, 75.1, 31.8
75.1, 35.2, 21.2, 116.5
–
1.74
31.8
1.4–1.6
1.4–1.5
1.4–1.5
35.3
21.9
–
26.1
–
426

Comparison of the chemical shifts found in the 13C NMR spectra shows that the greatest changes, as
expected, are observed in the 2-pyranone fragment. The chemical shifts are altered not only for C-2, at which the
substituent changes, but also for more distant atoms. While the signal for C-4 in spirodihydropyranocoumarin 4
is observed at 155.7 ppm, the signal for C-4 is shifted upfield upon replacement of the exocyclic oxygen atom at
C-2 by a nitrogen atom in oxime 10 (140.2 ppm) and hydrazone 8 (137.9 ppm). This behavior is most likely
related to the bipolar structure in the conjugation system of double bonds C-3=C-4 and C-2=R. Support for this
hypothesis is found in the weak effect of the substituent at C-2 on the chemical shift of C-3. The signals in the
1H and 13C NMR spectra of the other molecular fragments are only slightly sensitive to change in the substituent
at C-2. A cross peak is noted in the NOESY spectra of 6, 8, and 10, as in the case of coumarin 4, between the
signals of H-5 and the protons of 6-CH2.
Therefore, the spirodihydropyran fragment was fused to neoflavone molecules to give sulfur and
nitrogen functional derivatives, which hold interest in the study of the biological activity of neoflavones.
EXPERIMENTAL
The course of the reactions and purity of the products obtained were monitored by thin-layer
chromatography on Merck 60 F254 plates using 9:1 chloroform–methanol as the eluent. The melting points were
determined on a Koefler block. The NMR spectra were taken on a Mercury-400 spectrometer for solutions in
DMSO-d6. The 1H NMR spectra were taken at 400 MHz and the 13C NMR spectra were taken at 100 MHz. The
NOE experiments were carried out by the 2D NOESY technique with 200 msec mixing time. The
HMQC spectra were obtained from 128 increments with 32 scans per increment. The spectral range was 4 kHz
1
for protons and 21 kHz for carbon. The mixing time corresponded to ICH = 140 Hz. The HMBC spectra were
taken for 400 increments with 32 scans per increment. The spectral range was 4 kHz for protons and 21 kHz for
2-3
carbon. The mixing time corresponded to
gradient selection of the signals.
I
= 8 kHz. The spectra were taken with proton detection and
CH
Spiro[(7-hydroxy-4-chromanone)-2,1'-cyclohexane] (1). A samples of pyrrolidine (0.25 mol, 20.9 ml)
and cyclohexanone (0.25 mmol, 25.9 ml) were added to a solution of 2,4-dihydroxyacetophenone (0.1 mol,
15.22 g) in acetonitrile (100 ml). The reaction mixture was maintained at 45°C for 8 h (the end-point was
determined using thin-layer chromatography). At the end of the reaction, the mixture was treated with 700 ml ice
water and acidified to pH 5. The precipitate formed was filtered off. The yield of 1 was 84%; mp 175-176°C
1
(168°C [26], 170-171°C [15, 16]). H NMR spectrum, δ, ppm (J, Hz): 1.15-1.95 (10H, m, 2'-CH2, 3'-CH2,
4'-CH2, 5'-CH2, 6'-CH2); 2.57 (2H, s, 3-CH2), 6.24 (1H, d, J = 2.0, H-8); 6.39 (1H, d.d, J = 2.0, J = 8.8, H-6),
7.54 (1H, d, J = 8.8, H-5); 10.32 (1H, s, 7-OH).
Spiro[(7-hydroxychroman)-2,1'-cyclohexane] (2). A sample of zinc dust (32 g, 0.5 mol) was added
with rapid stirring to a solution of spirochromanone 1 (50 mmol, 11.61 g) in methanol (50 ml) and, then,
(100 ml) concentrated hydrochloric acid was added dropwise. The reaction mixture was maintained at room
temperature with rapid stirring for 2 h (the end-point was determined using thin-layer chromatography). At the
end of the reaction, the residue of unreacted zinc was filtered off and (250 ml) saturated aq. sodium chloride was
added to the filtrate. The product was extracted with ethyl acetate. The organic phase was dried over anhydrous
magnesium sulfate. The solvent was removed in vacuum on a rotary evaporator. The yield of chromanol 2 as a
light yellow oil was 95%. This product was used in subsequent transformations.
Spirodihydropyranochromen-2-ones 3 and 4. A sample of 10 ml concentrated sulfuric acid was added
with rapid stirring to a solution of 10 mmols (2.18 g) 2 and 10 mmols of the corresponding ethyl benzoylacetate
in (10 ml) ethanol. The reaction mixture was left overnight at room temperature and then poured into 200 ml ice
water. The precipitate formed was filtered off and recrystallized from 2-propanol.
427

Spiro[(4-phenyl-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclohexane] (3) was obtained in
1
68% yield; mp 154-156°C. The H NMR spectral data are given in Table 1. Found, %: C 79.58; H 6.31.
C23H22O3. Calculated, %: C 79.74; H 6.40.
Spiro[(4-(4-methoxyphenyl)-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclohexane] (4) was
1
obtained in 76% yield; mp 199-201°C. The H and 13C NMR spectral data are given in Tables 1 and 2.
Found, %: C 76.61; H 6.39. C24H24O4. Calculated, %: C 76.57; H 6.43.
Spirodihydropyranochromene-2-thiones
5
and 6.
A
mixture of 10 mmol spirodihydro-
pyranochromen-2-one 3 or 4 and Lawesson's reagent (1.23 g, 5.5 mmol) in 20 ml toluene was heated at reflux
for 2 h (the end-point was determined using thin-layer chromatography). At the end of the reaction, the solvent
was evaporated and the oily residue was crystallized from aqueous 2-propanol.
Spiro[(4-phenyl-7,8-dihydropyrano[3,2-g]chromene-2-thione)-8,1'-cyclohexane] (5) was obtained in
1
90% yield, mp 187-189°C. The H NMR spectral data are given in Table 1. Found, %: C 76.33; H 5.98; S 8.81.
C23H22O2S. Calculated, %: C 76.21; H 6.12; S 8.85.
Spiro[(4-(4-methoxyphenyl)-7,8-dihydropyrano[3,2-g]chroman-2-thione)-8,1'-cyclohexane] (6) was
1
obtained in 94% yield, mp 204-206°C. The H and 13C NMR spectral data are given in Tables 1 and 2.
Found, %: С 73.32; Н 6.19; S 8.11. C24H24O3S. Calculated, %: С 73.44; Н 6.16; S 8.17.
Oximes of Spirohydropyranochromen-2-ones 7 and 8. A sample of hydroxylamine hydrochloride
(0.42 g, 6 mmol) was added to a solution of thione 5 or 6 (3 mmol) in 5 ml absolute pyridine. The mixture was
maintained at 100°C (the reaction course was monitored by thin-layer chromatography). At the end of the
reaction, the mixture was cooled to room temperature and poured into 100 ml 5% aq. acetic acid. The precipitate
formed was filtered off and recrystallized from 2-propanol.
Oxime of Spiro[(4-phenyl-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclohexane] (7) was
1
obtained in 84% yield; mp 153-155°C. The H NMR spectral data are given in Table 1. Found, %: C 76.31;
H 6.52; N 3.82. C23H23NO3. Calculated, %: C 76.43; H 6.41; N 3.88.
Oxime of Spiro[(4-(4-methoxyphenyl)-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclohexane]
1
(8) was obtained in 88% yield; mp 176-178°C. The H and 13C NMR spectral data are given in Tables 1 and 2.
Found, %: C 73.68; H 6.39; N 3.49. C24H25NO4. Calculated, %.: C 73.64; H 6.44; N 3.58
Hydrazones of Spirodihydropyranochromen-2-ones 9 and 10. A hydrazine hydrate (0.3 ml, 6 mmol)
was added to a solution of thione 5 or 6 (3 mmol) in 10 ml ethanol. The reaction mixture was heated at reflux
for 1 h with monitoring by thin-layer chromatography. At the end of the reaction, the mixture was cooled to
room temperature. The precipitate formed was filtered off and recrystallized from 2-propanol.
Hydrazone of Spiro[(4-phenyl-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclohexane] (9) was
1
obtained in 85% yield; mp 98-100°C. The H NMR spectral data are given in Table 1. Found, %: C 76.49;
H 6.78; N 7.59. C23H24O2N2. Calculated, %: C 76.64; H 6.71; N 7.77.
Hydrazone of Spiro[(4-(4-methoxyphenyl)-7,8-dihydropyrano[3,2-g]chroman-2-one)-8,1'-cyclo-
1
hexane] (10) was obtained in 91% yield, mp 184-186°C. The H and 13C NMR spectral data are given in
Tables 1 and 2. Found, %: C 73.89; H 6.69; N 7.29. C24H26N2O3. Calculated, %: C 73.82; H 6.72; N 7.17.
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