Reaction of methyl 1-bromocyclopentane-and 1-bromocyclohexanecarboxylates with zinc and 2-arylmethylidene-2,3-dihydro-1H-inden-1-ones or 2-arylmethylidene-3,4-dihydronaphthalen-1(2H)-ones

Article abstract of DOI:10.1134/S1070428012030050

Methyl 1-bromocyclopentanecarboxylate and methyl 1- bromocyclohexanecarboxylate reacted with zinc and 2-arylmethylidene-2,3-dihydro- 1H-inden-1-ones or 2-arylmethylidene-3,4-dihydronaphthalen-1(2H)- ones to give 4'-aryl-4',5'-dihydro-2'H-spiro[cyclopentane(cyclohexane)-1,3'-indeno[1,2-b] pyran]-2'-ones or 4-aryl-5,6-dihydrospiro[benzo[h]chromene-3,1'- cyclopentane(cyclohexane)]-2(4H)-ones, respectively. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012030050

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 3, pp. 368–372. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © N.F. Kirillov, A.G. Gavrilov, M.I. Vakhrin, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 3, pp. 374–377.
Reaction of Methyl 1-Bromocyclopentane- and 1-Bromocyclo-
hexanecarboxylates with Zinc and 2-Arylmethylidene-
2,3-dihydro-1H-inden-1-ones or 2-Arylmethylidene-
3,4-dihydronaphthalen-1(2H)-ones
N. F. Kirillov, A. G. Gavrilov, and M. I. Vakhrin
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: kirillov@psu.ru
Received July 5, 2010
Abstract—Methyl 1-bromocyclopentanecarboxylate and methyl 1-bromocyclohexanecarboxylate reacted with
zinc and 2-arylmethylidene-2,3-dihydro-1H-inden-1-ones or 2-arylmethylidene-3,4-dihydronaphthalen-1(2H)-
ones to give 4′-aryl-4′,5′-dihydro-2′H-spiro[cyclopentane(cyclohexane)-1,3′-indeno[1,2-b]pyran]-2′-ones or
4-aryl-5,6-dihydrospiro[benzo[h]chromene-3,1′-cyclopentane(cyclohexane)]-2(4H)-ones, respectively.
DOI: 10.1134/S1070428012030050
Reformatsky reactions with α,β-unsaturated ketones
involve addition of organozinc compound at both 1,2-
and 1,4-positions of the conjugated system, and 1,4-ad-
dition products undergo cyclization to unsaturated lac-
tones that are derivatives of dihydropyran-2-one [1, 2].
Substituted spirodihydropyranones were isolated in
reactions of alicyclic Reformatsky reagents with unsat-
urated ketones [3–6]. In continuation of these studies,
we examined Reformatsky reactions of organozinc
compounds I and II derived from methyl 1-bromo-
cyclopentanecarboxylate and methyl 1-bromocyclo-
hexanecarboxylate with 2-arylmethylidene-2,3-dihy-
dro-1H-inden-1-ones IIIa–IIIf. The results showed
that compounds I and II add to compounds IIIa–IIIf
at positions 1,4 of the C=C–C=O fragment with forma-
tion of intermediates IVa–IVf or Va–Vf. Intramolec-
ular attack by the oxygen atom in the bromozinc
enolate fragment on the ester carbonyl carbon atom in
intermediate IV or V resulted in cyclization with
elimination of bromozinc methoxide and formation of
4′-aryl-4′,5′-dihydro-2′H-spiro[cyclopentane-1,3′-in-
deno[1,2-b]pyran]-2′-ones VIa–VIf or 4′-aryl-4′,5′-di-
hydro-2′H-spiro[cyclohexane-1,3′-indeno[1,2-b]pyr-
an]-2′-ones VIIa–VIIf (Scheme 1).
Likewise, organozinc compounds I and II reacted
with 2-arylmethylidene-3,4-dihydronaphthalen-1(2H)-
ones VIIIa–VIIIf through intermediates IXa–IXf or
Xa–Xf to produce 4-aryl-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclopentane]-2(4H)-ones XIa–XIf or
4-aryl-5,6-dihydrospiro[benzo[h]chromene-3,1′-cyclo-
hexane]-2(4H)-ones XIIa–XIIf (Scheme 2).
Scheme 1.
Br
ZnBr
Zn
( )n
( )n
COOMe
COOMe
I, II
Ar
Ar
Ar
I, II
( )n
O
O
–MeOZnBr
( )n
O
O
O
OMe
BrZn
IIIa–IIIf
IVa–IVf, Va–Vf
VIa–VIf, VIIa–VIIf
Ar = Ph (a), 4-BrC6H4 (b), 4-ClC6H4 (c), 4-MeOC6H4 (d), 2-FC6H4 (e), 3,4-(MeO)2C6H3 (f); I, IV, VI, n = 1; II, V, VII, n = 2.
368

REACTION OF METHYL 1-BROMOCYCLOPENTANE-
369
Scheme 2.
Ar
O
( )n
Ar
I, II
O
Ar
–MeOZnBr
BrZnO
MeO
O
O
( )n
VIIIa–VIIIf
IXa–IXf, Xa–Xf
XIa–XIf, XIIa–XIIf
Ar = Ph (a), 4-BrC6H4 (b), 4-ClC6H4 (c), 4-MeOC6H4 (d), 3-BrC6H4 (e), 3,4-(MeO)2C6H3 (f); IX, XI, n = 1; X, XII, n = 2.
The structure of compounds VIa–VIf, VIIa–VIIf,
XIa–XIf, and XIIa–XIIf was confirmed by their IR
and H NMR spectra and elemental analyses. The IR
sodium sulfate, the solvent was distilled off, and the
residue was recrystallized from ethyl acetate.
1
4′-Phenyl-4′,5′-dihydro-2′H-spiro[cyclopentane-
1,3′-indeno[1,2-b]pyran]-2′-one (VIa). Yield 1.03 g
(65%), mp 132–133°C. IR spectrum, ν, cm–1: 1770
(C=O), 1670 (C=C). 1H NMR spectrum, δ, ppm: 1.34–
2.15 m (8H, CH2), 3.17 d and 3.30 d (1H each, 5′-H,
J = 22.2 Hz), 3.56 s (1H, 4′-H); 7.09 d (J = 7.2 Hz),
7.19–7.27 m, 7.34 t (J = 7.8 Hz), 7.49 d (J = 7.8 Hz)
(9H, Harom). Found, %: C 83.66; H 6.49. C22H20O2.
Calculated, %: C 83.51; H 6.37.
spectra contained absorption bands due to stretching
vibrations of C=C bonds in the region 1655–1695 cm–1
and lactone carbonyl groups at 1745–1775 cm–1. Com-
pounds VIa–VIf and VIIa–VIIf characteristically dis-
1
played in the H NMR spectra doublets from non-
equivalent methylene protons in the indene fragment at
δ 3.13–3.20 and 3.27–3.32 ppm, as well as singlets at
δ 3.49–3.72 ppm from protons in the dihydropyran
ring. Nonequivalent protons in the two methylene
groups in the chromene fragment of XIa–XIf and
4′-(4-Bromophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclopentane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIb). Yield 1.09 g (55%), mp 109–110°C. IR spec-
1
XIIa–XIIf resonated in the H NMR spectra as multi-
plets at δ 2.10–2.45 and 2.66–2.91 ppm, and singlets
from 4-H were observed at δ 3.02–3.21 ppm.
1
trum, ν, cm–1: 1750 (C=O), 1660 (C=C). H NMR
spectrum, δ, ppm: 1.30–2.16 m (8H, CH2), 3.15 d and
3.30 d (1H each, 5′-H, J = 21.9 Hz), 3.53 s (1H, 4′-H),
6.97 d and 7.38 d (2H each, J = 8.1 Hz, BrC6H4);
7.24 t (J = 7.2 Hz), 7.31–7.41 m, 7.48 d (J = 7.2 Hz)
(4H, C6H4). Found, %: C 67.09; H 4.98; Br 20.02.
C22H19BrO2. Calculated, %: C 66.85; H 4.84; Br 20.21.
EXPERIMENTAL
The IR spectra were recorded on a Specord 75IR
spectrometer from samples dispersed in mineral oil.
The H NMR spectra were obtained on a Varian
Mercury Plus-300 spectrometer at 300 MHz using
CDCl3 as solvent and tetramethylsilane as internal
reference.
1
4′-(4-Chlorophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclopentane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIc). Yield 1.25 g (71%), mp 114–115°C. IR spec-
General procedure for the synthesis of com-
pounds VIa–VIf, VIIa–VIIf, XIa–XIf, and XIIa–
XIIf. A mixture of 1.5 g of fine zinc turnings, a cat-
alytic amount of mercury(II) chloride, 5 mmol of
2-arylmethylidene-2,3-dihydro-1H-inden-1-one IIIa–
IIIf or 2-arylmethylidene-3,4-dihydronaphthalen-
1(2H)-one, 5.1 mmol of methyl 1-bromocyclopentane-
carboxylate or methyl 1-bromocyclohexanecarbox-
ylate, 20 ml of benzene, 5 ml of ethyl acetate, and 1 ml
of hexamethylphosphoramide was heated for 2 h under
reflux. The mixture was cooled, the solution was
separated from excess zinc by decanting and treated
with 5% hydrochloric acid, the organic layer was sepa-
rated, and the aqueous layer was extracted with two
portions of ethyl acetate. The extracts were combined
with the organic phase and dried over anhydrous
1
trum, ν, cm–1: 1750 (C=O), 1660 (C=C). H NMR
spectrum, δ, ppm: 1.30–2.15 m (8H, CH2), 3.16 d and
3.30 d (1H each, 5′-H, J = 22.2 Hz), 3.55 s (1H, 4′-H),
7.02 d and 7.23 d (2H each, J = 8.4 Hz, ClC6H4); 7.25 t
(J = 7.8 Hz), 7.35 t (J = 7.8 Hz), 7.37 d (J = 7.8 Hz),
7.48 d (J = 7.8 Hz) (4H, C6H4). Found, %: C 75.53;
H 5.29; Cl 9.95. C22H19ClO2. Calculated, %: C 75.32;
H 5.46; Cl 10.11.
4′-(4-Methoxyphenyl)-4′,5′-dihydro-2′H-spiro-
[cyclopentane-1,3′-indeno[1,2-b]pyran]-2′-one
(VId). Yield 1.09 g (63%), mp 94–95°C. IR spectrum,
ν, cm–1: 1760 (C=O), 1660 (C=C). 1H NMR spectrum,
δ, ppm: 1.34–2.13 m (8H, CH2), 3.18 d and 3.29 d
(1H each, 5′-H, J = 21.9 Hz), 3.51 s (1H, 4′-H), 3.74 s
(3H, MeO), 6.78 d and 7.00 d (2H each, J = 8.4 Hz,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

KIRILLOV et al.
370
3.27 d (1H each, 5′-H, J = 22.2 Hz), 3.71 s (1H, 4′-H),
7.02 d and 7.28 d (2H each, J = 8.4 Hz, ClC6H4); 7.24 t
(J = 7.2 Hz), 7.34 t (J = 7.2 Hz), 7.35 d (J = 7.2 Hz),
7.46 d (J = 7.2 Hz) (4H, C6H4). Found, %: C 75.89;
H 5.63; Cl 9.88. C23H21ClO2. Calculated, %: C 75.71;
H 5.80; Cl 9.72.
MeOC6H4); 7.22 t (J = 7.2 Hz), 7.34 t (J = 7.2 Hz),
7.36 d (J = 7.2 Hz), 7.48 d (J = 7.2 Hz) (4H, C6H4).
Found, %: C 79.55; H 6.51. C23H22O3. Calculated, %:
C 79.74; H 6.40.
4′-(2-Fluorophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclopentane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIe). Yield 1.22 g (73%), mp 146–147°C. IR spec-
4′-(4-Methoxyphenyl)-4′,5′-dihydro-2′H-spiro-
[cyclohexane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIId). Yield 0.99 g (55%), mp 132–133°C. IR spec-
1
trum, ν, cm–1: 1770 (C=O), 1670 (C=C). H NMR
spectrum, δ, ppm: 1.34–2.21 m (8H, CH2), 3.17 d and
3.32 d (1H each, 5′-H, J = 21.9 Hz), 3.56 s (1H, 4′-H);
6.98–7.40 m, 7.48 d (J = 7.5 Hz) (8H, Harom). Found,
%: C 78.88; H 5.87. C22H19FO2. Calculated, %:
C 79.02; H 5.73.
1
trum, ν, cm–1: 1765 (C=O), 1660 (C=C). H NMR
spectrum, δ, ppm: 1.14–2.12 m (10H, CH2), 3.15 d and
3.27 d (1H each, 5′-H, J = 21.9 Hz), 3.68 s (1H, 4′-H),
3.74 s (3H, MeO), 6.77 d and 7.00 d (2H each, J =
8.4 Hz, MeOC6H4); 7.21 t (J = 7.2 Hz), 7.33 t (J =
7.2 Hz), 7.34 d (J = 7.2 Hz), 7.46 d (J = 7.2 Hz) (4H,
C6H4). Found, %: C 80.18; H 6.60. C24H24O3. Calculat-
ed, %: C 79.97; H 6.71.
4′-(3,4-Dimethoxyphenyl)-4′,5′-dihydro-2′H-
spiro[cyclopentane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIf). Yield 1.24 g (66%), mp 156–157°C. IR spec-
1
trum, ν, cm–1: 1775 (C=O), 1670 (C=C). H NMR
spectrum, δ, ppm: 1.38–2.14 m (8H, CH2), 3.20 d and
3.29 d (1H each, 5′-H, J = 22.2 Hz), 3.49 s (1H, 4′-H),
3.79 s and 3.82 s (3H each, MeO); 6.58 s, 6.64 d (J =
8.4 Hz), 6.75 d (J = 8.4 Hz) (3H, C6H3); 7.22 t (J =
7.2 Hz), 7.33 t (J = 7.5 Hz), 7.36 d (J = 7.2 Hz), 7.47 d
(J = 7.5 Hz) (4H, C6H4). Found, %: C 76.74; H 6.30.
C24H24O4. Calculated, %: C 76.57; H 6.43.
4′-(2-Fluorophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclohexane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIIe). Yield 1.18 g (68%), mp 128–129°C. IR spec-
1
trum, ν, cm–1: 1775 (C=O), 1670 (C=C). H NMR
spectrum, δ, ppm: 1.12–2.20 m (10H, CH2), 3.13 d and
3.27 d (1H each, 5′-H, J = 21.9 Hz), 3.72 s (1H, 4′-H);
6.92–7.38 m, 7.46 d (J = 7.5 Hz) (8H, Harom). Found,
%: C 79.48; H 6.23. C23H21FO2. Calculated, %:
C 79.29; H 6.08.
4′-Phenyl-4′,5′-dihydro-2′H-spiro[cyclohexane-
1,3′-indeno[1,2-b]pyran]-2′-one (VIIa). Yield 0.93 g
(56%), mp 192–193°C. IR spectrum, ν, cm–1: 1765
(C=O), 1660 (C=C). 1H NMR spectrum, δ, ppm: 1.14–
2.14 m (10H, CH2), 3.14 d and 3.27 d (1H each, 5′-H,
J = 22.2 Hz), 3.72 s (1H, 4′-H); 7.08 d (J = 7.2 Hz),
7.18–7.28 m, 7.33 t (J = 7.8 Hz), 7.47 d (J = 7.8 Hz)
(9H, Harom). Found, %: C 83.81; H 6.79. C23H22O2.
Calculated, %: C 83.60; H 6.71.
4′-(3,4-Dimethoxyphenyl)-4′,5′-dihydro-2′H-
spiro[cyclohexane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIIf). Yield 1.24 g (66%), mp 115–116°C. IR spec-
1
trum, ν, cm–1: 1765 (C=O), 1655 (C=C). H NMR
spectrum, δ, ppm: 1.16–2.12 m (10H, CH2), 3.17 d and
3.27 d (1H each, 5′-H, J = 22.2 Hz), 3.66 s (1H, 4′-H),
3.78 s and 3.81 s (3H each, MeO); 6.76 s, 6.64 d (J =
8.1 Hz), 6.74 d (J = 8.1 Hz) (3H, C6H3); 7.21 t (J =
7.5 Hz), 7.32 t (J = 7.5 Hz), 7.40 d (J = 7.5 Hz), 7.46 d
(J = 7.5 Hz) (4H, C6H4). Found, %: C 77.12; H 6.63.
C25H26O4. Calculated, %: C 76.90; H 6.71.
4′-(4-Bromophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclohexane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIIb). Yield 0.95 g (50%), mp 146–147°C. IR spec-
1
trum, ν, cm–1: 1765 (C=O), 1665 (C=C). H NMR
spectrum, δ, ppm: 1.12–2.14 m (10H, CH2), 3.13 d and
3.27 d (1H each, 5′-H, J = 22.2 Hz), 3.70 s (1H, 4′-H),
6.97 d and 7.37 d (2H each, J = 8.4 Hz, BrC6H4);
7.23 t (J = 7.5 Hz), 7.34 t (J = 7.5 Hz), 7.35 d (J =
7.5 Hz), 7.46 d (J = 7.5 Hz) (4H, C6H4). Found, %:
C 67.68; H 5.29; Br 19.31. C23H21BrO2. Calculated, %:
C 67.49; H 5.17; Br 19.52.
4-Phenyl-5,6-dihydrospiro[benzo[h]chromene-
3,1′-cyclopentan]-2(4H)-one (XIa). Yield 1.19 g
(72%), mp 161–162°C. IR spectrum, ν, cm–1: 1755
(C=O), 1660 (C=C). 1H NMR spectrum, δ, ppm: 1.28–
2.10 m (8H, CH2), 2.19–2.45 m and 2.69–2.87 m (2H
each, 5-H, 6-H), 3.08 s (1H, 4-H); 7.08–7.34 m, 7.62 d
(J = 7.5 Hz) (9H, Harom). Found, %: C 83.87; H 6.56.
C23H22O2. Calculated, %: C 83.60; H 6.71.
4′-(4-Chlorophenyl)-4′,5′-dihydro-2′H-spiro-
[cyclohexane-1,3′-indeno[1,2-b]pyran]-2′-one
(VIIc). Yield 1.20 g (66%), mp 150–151°C. IR spec-
4-(4-Bromophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclopentan]-2(4H)-one (XIb). Yield
1.06 g (52%), mp 117–118°C. IR spectrum, ν, cm–1:
1
trum, ν, cm–1: 1765 (C=O), 1665 (C=C). H NMR
1
spectrum, δ, ppm: 1.12–2.14 m (10H, CH2), 3.13 d and
1750 (C=O), 1680 (C=C). H NMR spectrum, δ, ppm:
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REACTION OF METHYL 1-BROMOCYCLOPENTANE-
371
1.23–2.10 m (8H, CH2), 2.15–2.44 m and 2.68–2.90 m
(2H each, 5-H, 6-H), 3.05 s (1H, 4-H), 7.03 d and
7.40 d (2H each, J = 8.4 Hz, BrC6H4); 7.13 d (J =
7.2 Hz), 7.22 t (J = 7.2 Hz), 7.25 t (J = 7.2 Hz), 7.60 d
(J = 7.2 Hz) (4H, C6H4). Found, %: C 67.70; H 5.33;
Br 19.27. C23H21BrO2. Calculated, %: C 67.49; H 5.17;
Br 19.52.
C 77.03; H 6.64. C25H26O4. Calculated, %: C 76.90;
H 6.71.
4-Phenyl-5,6-dihydrospiro[benzo[h]chromene-
3,1′-cyclohexan]-2(4H)-one (XIIa). Yield 1.29 g
(75%), mp 169–170°C. IR spectrum, ν, cm–1: 1760
(C=O), 1695 (C=C). 1H NMR spectrum, δ, ppm: 1.05–
2.10 m (10H, CH2), 2.14–2.43 m and 2.63–2.87 m (2H
each, 5-H, 6-H), 3.19 s (1H, 4-H); 6.92–7.31 m, 7.53 d
(J = 7.5 Hz) (9H, Harom). Found, %: C 83.78; H 6.93.
C24H24O2. Calculated, %: C 83.69; H 7.02.
4-(4-Chlorophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclopentan]-2(4H)-one (XIc). Yield
1.06 g (58%), mp 107–108°C. IR spectrum, ν, cm–1:
1
1755 (C=O), 1670 (C=C). H NMR spectrum, δ, ppm:
4-(4-Bromophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclohexan]-2(4H)-one (XIIb). Yield
1.44 g (68%), mp 133–135°C. IR spectrum, ν, cm–1:
1.24–2.10 m (8H, CH2), 2.16–2.44 m and 2.68–2.90 m
(2H each, 5-H, 6-H), 3.06 s (1H, 4-H), 7.09 d and
7.25 d (2H each, J = 8.7 Hz, ClC6H4); 7.12 d (J =
7.2 Hz), 7.22 t (J = 7.2 Hz), 7.25 t (J = 7.2 Hz), 7.61 d
(J = 7.2 Hz) (4H, C6H4). Found, %: C 75.94; H 5.66;
Cl 9.56. C23H21ClO2. Calculated, %: C 75.71; H 5.80;
Cl 9.72.
1
1760 (C=O), 1695 (C=C). H NMR spectrum, δ, ppm:
1.07–2.11 m (10H, CH2), 2.16–2.42 m and 2.67–
2.88 m (2H each, 5-H, 6-H), 3.18 s (1H, 4-H), 6.80 d
and 7.07 d (2H each, J = 8.7 Hz, BrC6H4); 7.11 d (J =
7.5 Hz), 7.19 t (J = 7.5 Hz), 7.24 t (J = 7.5 Hz), 7.58 d
(J = 7.5 Hz) (4H, C6H4). Found, %: C 68.27; H 5.34;
Br 19.09. C24H23BrO2. Calculated, %: C 68.09; H 5.48;
Br 18.87.
4-(4-Methoxyphenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclopentan]-2(4H)-one (XId). Yield
0.72 g (40%), mp 153–154°C. IR spectrum, ν, cm–1:
1
1755 (C=O), 1660 (C=C). H NMR spectrum, δ, ppm:
4-(4-Chlorophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclohexan]-2(4H)-one (XIIc). Yield
1.42 g (75%), mp 126–127°C. IR spectrum, ν, cm–1:
1.29–2.08 m (8H, CH2), 2.18–2.44 m and 2.69–2.89 m
(2H each, 5-H, 6-H), 3.02 s (1H, 4-H), 3.76 s (3H,
MeO), 6.80 d and 7.07 d (2H each, J = 8.7 Hz,
MeOC6H4); 7.12 d (J = 7.5 Hz), 7.20 t (J = 7.2 Hz),
7.25 t (J = 7.5 Hz), 7.61 d (J = 7.2 Hz) (4H, C6H4),
Found, %: C 80.21; H 6.54. C24H24O3. Calculated, %:
C 79.97; H 6.71.
1
1755 (C=O), 1680 (C=C). H NMR spectrum, δ, ppm:
1.05–2.12 m (10H, CH2), 2.13–2.43 m and 2.66–
2.89 m (2H each, 5-H, 6-H), 3.21 s (1H, 4-H), 7.09 d
and 7.24 d (2H each, J = 8.4 Hz, ClC6H4); 7.11 d (J =
7.5 Hz), 7.20 t (J = 7.5 Hz), 7.25 t (J = 7.5 Hz), 7.58 d
(J = 7.5 Hz) (4H, C6H4). Found, %: C 75.86; H 6.25;
Cl 9.19. C24H23ClO2. Calculated, %: C 76.08; H 6.12;
Cl 9.36.
4-(3-Bromophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclopentan]-2(4H)-one (XIe). Yield
0.90 g (44%), mp 122–123°C. IR spectrum, ν, cm–1:
1
1750 (C=O), 1680 (C=C). H NMR spectrum, δ, ppm:
4-(4-Methoxyphenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclohexan]-2(4H)-one (XIId). Yield
1.10 g (59%), mp 138–139°C. IR spectrum, ν, cm–1:
1.26–2.10 m (8H, CH2), 2.18–2.44 m and 2.70–2.91 m
(2H each, 5-H, 6-H), 3.04 s (1H, 4-H); 7.09 d (J =
8.4 Hz), 7.18 t (J = 8.4 Hz), 7.29 s, 7.40 d (J = 8.4 Hz)
(4H, BrC6H4); 7.11 d (J = 7.8 Hz), 7.22 t (J = 7.8 Hz),
7.25 t (J = 7.8 Hz), 7.60 d (J = 7.8 Hz) (4H, C6H4).
Found, %: C 67.28; H 5.01; Br 19.73. C23H21BrO2.
Calculated, %: C 67.49; H 5.17; Br 19.52.
1
1760 (C=O), 1695 (C=C). H NMR spectrum, δ, ppm:
1.07–2.10 m (10H, CH2), 2.16–2.42 m and 2.67–
2.88 m (2H each, 5-H, 6-H), 3.18 s (1H, 4-H), 3.76 s
(3H, MeO), 6.80 d and 7.07 d (2H each, J = 8.7 Hz,
MeOC6H4); 7.11 d (J = 7.2 Hz), 7.19 t (J = 7.5 Hz),
7.23 t (J = 7.2 Hz), 7.61 d (J = 7.5 Hz) (4H, C6H4).
Found, %: C 80.42; H 7.13. C25H26O3. Calculated, %:
C 80.18; H 7.00.
4-(3,4-Dimethoxyphenyl)-5,6-dihydrospiro-
[benzo[h]chromene-3,1′-cyclopentan]-2(4H)-one
(XIf). Yield 1.03 g (55%), mp 129–130°C. IR spec-
1
trum, ν, cm–1: 1760 (C=O), 1675 (C=C). H NMR
4-(3-Bromophenyl)-5,6-dihydrospiro[benzo[h]-
chromene-3,1′-cyclohexan]-2(4H)-one (XIIe). Yield
1.55 g (73%), mp 150–151°C. IR spectrum, ν, cm–1:
1745 (C=O), 1685 (C=C). H NMR spectrum, δ, ppm:
1.06–2.13 m (10H, CH2), 2.15–2.42 m and 2.68–
2.90 m (2H each, 5-H, 6-H), 3.18 s (1H, 4-H); 7.08 d
spectrum, δ, ppm: 1.08–2.09 m (8H, CH2), 2.17–
2.44 m and 2.68–2.89 m (2H each, 5-H, 6-H), 3.16 s
(1H, 4-H), 3.80 s and 3.84 s (3H each, MeO); 6.64 s,
6.71 d (J = 8.4 Hz), 6.77 d (J = 8.4 Hz) (3H, C6H3);
7.11 d (J = 7.2 Hz), 7.20 t (J = 7.2 Hz), 7.26 t (J =
7.2 Hz), 7.56 d (J = 7.2 Hz) (4H, C6H4). Found, %:
1
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KIRILLOV et al.
372
(J = 8.4 Hz), 7.15 t (J = 8.4 Hz), 7.30 s, 7.37 d (J =
8.4 Hz) (4H, BrC6H4); 7.12 d (J = 7.5 Hz), 7.23 t (J =
7.2 Hz), 7.24 t (J = 7.5 Hz), 7.59 d (J = 7.2 Hz) (4H,
C6H4). Found, %: C 68.35; H 5.56; Br 19.11.
C24H23BrO2. Calculated, %: C 68.09; H 5.48; Br 18.87.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 3.3925.2011).
REFERENCES
4-(3,4-Dimethoxyphenyl)-5,6-dihydrospiro-
[benzo[h]chromene-3,1′-cyclohexan]-2(4H)-one
(XIIf). Yield 1.17 g (58%), mp 118–119°C. IR spec-
1. Dubois, J.C., Guette, J.P., and Kagan, H.B., Bull. Soc.
Chim. Fr., 1966, p. 3008.
2. Ocampo, R. and Dolbier, W.R., Tetrahedron, 2004,
1
trum, ν, cm–1: 1760 (C=O), 1695 (C=C). H NMR
vol. 60, p. 9325.
spectrum, δ, ppm: 1.08–2.09 m (10H, CH2), 2.18–
2.44 m and 2.68–2.89 m (2H each, 5-H, 6-H), 3.17 s
(1H, 4-H), 3.81 s and 3.84 s (3H each, MeO); 6.65 s,
6.71 d (J = 8.4 Hz), 6.76 d (J = 8.4 Hz) (3H, C6H3);
7.12 d (J = 7.2 Hz), 7.20 t (J = 7.2 Hz), 7.25 t (J =
7.5 Hz), 7.58 d (J = 7.5 Hz) (4H, C6H4). Found, %:
C 77.44; H 7.09. C26H28O4. Calculated, %: C 77.20;
H 6.98.
3. Kirillov, N.F. and Gavrilov, A.G., Russ. J. Gen. Chem.,
2008, vol. 78, p. 1422.
4. Kirillov, N.F. and Gavrilov, A.G., Russ. J. Org. Chem.,
2008, vol. 44, p. 963.
5. Kirillov, N.F., Gavrilov, A.G., Vakhrin, M.I., and Fe-
shin, V.P., Russ. J. Gen. Chem., 2011, vol. 81, p. 1195.
6. Kirillov, N.F., Nikiforova, E.A., and Vakhrin, M.I., Russ.
J. Gen. Chem., 2011, vol. 81, p. 1243.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012