Reaction of 1,5-diarylpenta-1,4-dien-3-ones with methyl 1-bromocycloalkanecarboxylates and zinc

Article abstract of DOI:10.1134/S1070363211060211

Methyl 1-bromocyclopentane-, 1-bromocyclohexane- and 1- bromocycloheptanecarboxylates react with zinc and 1,5-diarylpenta-1,4-dien-3- ones to form 10-aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-en-6- ones, 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.5]undec-3-e

Full text of DOI:10.1134/S1070363211060211

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 6, pp. 1195–1197. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.F. Kirillov, A.G. Gavrilov, M.I. Vakhrin, V.P. Feshin, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 6,
pp. 1002–1004.
Reaction of 1,5-Diarylpenta-1,4-dien-3-ones
with Methyl 1-Bromocycloalkanecarboxylates and Zinc
N. F. Kirillova, A. G. Gavrilova, M. I. Vakhrina, and V. P. Feshinb
a Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: kirillov@psu.ru
b Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Received June 10, 2010
Abstract—Methyl 1-bromocyclopentane-, 1-bromocyclohexane- and 1-bromocycloheptanecarboxylates react
with zinc and 1,5-diarylpenta-1,4-dien-3-ones to form 10-aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-en-6-
ones, 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.5]undec-3-en-1-ones, and 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.6]-
dodec-3-en-1-ones, respectively.
DOI: 10.1134/S1070363211060211
Previously we found that the reaction of alicyclic
Reformatsky reagents with 1,3-diarylprop-2-ene-1-
ones affords substituted spirodihydropyranones [1, 2].
Continuing these studies, we investigated the reaction
of Reformatsky reagents derived from methyl 1-
bromocycloalkanecarboxylates (Ia–Ic) with zinc and
1,5-diarylpenta-1,4-dien-3-ones (IIa–IId). According
to our research, the organozinc reagents formed added
to compounds (IIa–IId) in 1,4-position of C=C–C=O
fragment with the formation of intermediates (IIIa–
IIIc, IVa–IVd, Va, and Vb). In the course of the
reaction, these intermediates undergo cyclization due
to the attack of the oxygen atom on the carbonyl
carbon atom of the ester group with the cleavage of
bromozinc methoxide, affording substituted spirodi-
hydropyran-2-ones, namely, 10-aryl-8-(2-arylethenyl)-
7-oxaspiro[4.5]dec-8-en-6-ones (VIa–VIc), 5-aryl-3-
(2-arylethenyl)-2-oxaspiro[5.5]undeca-3-en-1-ones
(VIIa–VIId), and 5-aryl-3-(2-arylethenyl)-2-oxaspiro
[5.6]dodec-3-en-1-ones (VIIIa, VIIIb).
Br
(CH2)n
Zn,
Ar
Ar
COOMe
Iа_Ic
(CH2)n
Ar
Ar
OZnBr
COOMe
O
IIа_IId
IIIа_IIIc, IVа_IVd, Vа, Vb
Ar
O
(CH2)n
_MeOZnBr
Ar
O
VIа_VIc, VIIа_VIId, VIIIа, VIIIb
I: n = 1 (а), 2 (b), 3 (c); II: Ar = Ph (а), 4-ClC6H4 (b), 4-МеОС6Н4 (c), 4-BrC6H4 (d); III, VI: n = 1; Ar = Ph (а), 4-ClC6H4
(b), 4-МеОС6Н4 (c); IV, VII: n = 2; Ar = Ph (а), 4-ClC6H4 (b), 4-МеОС6Н4 (c), 4-BrC6H4 (d); V, VIII: n = 3; Ar = Ph (а),
4-BrС6Н4 (b).
1195

1196
KIRILLOV et al.
The composition and structure of the compounds
(P=C), 1760 (C=O). 1H NMR spectrum, δ, ppm: 1.28–
2.12 m [8H (CH2)4], 3.35 d (1H, C10H, J 6.6 Hz), 5.51
d (1H,=C9H, J 6.6 Hz), 6.45 d, 7.06 d (2H, CH=CH,
J 15.6 Hz), 7.04 d, 7.25 d, 7.30 d, 7.37 d [8H,
2(4-ClC6H4), J 8.4 Hz]. Found, %: C 68.97, H 5.16; Cl
17.92. C23H20Cl2O2. Calculated, %: C 69.18, H 5.05,
Cl 17.76.
obtained were confirmed by elemental analysis, IR and
1H NMR spectroscopy. The IR spectra of compounds
VIa–VIc, VIIa–VIId, VIIIa, and VIIIb include
characteristic bands of C=C bonds at 1655–1665 cm–1
and of lactone carbonyl groups at 1755–1770 cm–1. In
1
the H NMR spectra there is one set of signals, among
which are the characteristic doublets of the dihydro-
pyran ring protons at 3.30–3.79 and 5.37–5.70 ppm
and doublets of protons of vinyl fragment at 6.35–6.85
and 6.92–7.12 ppm with spin–spin coupling constants
15–16 Hz, which correspond to the E-isomers.
10-(4-methoxyphenyl)-8-[2-(4-methoxyphenyl)-
ethenyl]-7-oxaspiro[4.5]dec-8-en-6-one (VIc). Yield
1.03 g (52%), mp 130–131ºC. IR spectrum, ν, cm–1:
1
1660 (P=C), 1760 (C=O). H NMR spectrum, δ, ppm:
1.32–2.10 m [8H, (CH2)4], 3.30 d (1H, C10H, J 6.5 Hz),
3.76 s (3H, OMe), 3.81 s (3H, OMe), 5.46 d (1H,
=C9H, J 6.5 Hz), 6.36 d , 7.06 d (2H, CH=CH, J 16.2 Hz),
6.81 d, 6.87 d, 7.03 d, 7.38 d [8H, 2(4-MeOC6H4),
J 8.4 Hz]. Found, %: C 77.05, H 6.83. C25N26O4.
Calculated, %: C 76.90, H 6.71.
EXPERIMENTAL
The IR spectra of compounds VIa–VIc, VIIa–
VIId, VIIIa, and VIIIb were obtained on a spectro-
photometer Specord-75IR from mulls in mineral oil.
1
The H NMR spectra of solutions in CDCl3 of these
5-Aryl-3-(2-arylethenyl)-2-oxaspiro[5.5]undec-3-
en-1-ones (VIIa–VIId) were prepared similarly to
compounds VI. Methyl 1-bromocyclohyxylcarboxylate
was used as initial compound.
compounds were recorded on a Mercury Plus-300
(300 MHz) spectrometer, internal reference TMS.
10-Aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-
en-6-ones (VIa–VIc). In a round-bottom 250 ml flask
fitted with a reflux condenser were placed 1.5 g of fine
zinc turnings, a catalytic amount of mercuric chloride,
5 mmol of 1,5-diaryl-1,4-pentadien-3-one, 5.1 mmol of
methyl 1-bromocyclopentanecaroboxylate, 20 ml of
benzene, 5 ml of ethyl acetate, and 1 ml of hexame-
thyltriamidophosphate. The reaction mixture was re-
fluxed for 2 h, then cooled, the liquid was decanted
from excess zinc, and decomposed with 5% hydro-
chloric acid. The organic layer was separated from the
water layer, and the reaction products were extracted
twice with ethyl acetate. After drying the extract with
anhydrous sodium sulfate, the solvents were distilled
off, and compound VIa–VIc were recrystallized from
ethyl acetate.
5-Phenyl-3-(2-phenylethenyl)-2-oxaspiro[5.5]-
undeca-3-ene-1-one (VIIa). Yield 1.05 g (61%), mp
110–111ºC. IR spectrum, ν, cm–1: 1655 (C=C), 1765
(C=O). 1H NMR spectrum, δ, ppm: 1.07–2.10 m [10H,
(CH2)5], 3.49 d (1H, C5H, J 6.5 Hz), 5.46 d (1H, =C4H,
J 6.5 Hz), 6.48 d, 7.10 d (2H, CH=CH, J 15.6 Hz),
7.11 d, 7.22–7.30 m, 7.34 m, 7.44 d (10H, 2Ph, J 6.9 Hz).
Found, %: P 83.81, H 6.90. C24H24O2. Calculated, %: P
83.69, H 7.02.
5-(4-Chlorophenyl)-3-[2-(4-chlorophenyl)ethenyl]-
2-oxaspiro[5.5]undec-3-en-1-one (VIIb). Yield 1.10 g
(53%), mp 175–176ºC. IR spectrum, ν, cm–1: 1655
(C=C), 1770 (C=O). 1H NMR spectrum, δ, ppm: 1.05–
1.95 m [10H, (CH2)5], 3.79 d (1H, C5H, J 6.5 Hz), 5.70
d (1H, =C4H, J 6.5 Hz), 6.85 d, 6.92 d (2H, CH=CH,
J 15.6 Hz), 7.13 d, 7.39 d, 7.42 d, 7.60 d [8H,
2(4-ClC6H4), J 8.4 Hz]. Found, %: C 69.91, H 5.45; Cl
16.97. C24H22Cl2O2. Calculated, %: C 69.74, H 5.36;
Cl 17.15.
10-Phenyl-8-(2-phenylethenyl)-7-oxaspiro[4.5]-
dec-8-en-6-one (VIa). Yield 0.79 g (48%), mp 150–
151ºC. IR spectrum, ν, cm–1: 1665 (C=C), 1770 (C=O).
1H NMR spectrum, δ, ppm: 1.26–2.13 m [8H, (CH2)4],
3.36 d (1H, C10H, J 6.3 Hz), 5.52 d (1H,=C9H, J 6.3 Hz),
6.48 d, 7.12 d (2H, CH=CH, J 15.9 Hz), 7.11 d, 7.21–
7.36 m, 7.43 d (10H, 2Ph, J 7.2 Hz), Found, %: C
83.81, H 6.62. C23H22O2. Calculated, %: C 83.60, H
6.71.
5-(4-Methoxyphenyl)-3-[2-(4-methoxyphenyl)-
ethenyl]-2-oxaspiro[5.5]undec-3-en-1-one (VIIc).
Yield 0.96 g (47%), mp 148–149ºC. IR spectrum, ν,
cm–1: 1655 (C=C), 1755 (C=O). 1H NMR spectrum, δ,
ppm: 6.1–2.10 m [10H, (CH2)5], 3.43 d (1H, C5H, J
6.6 Hz), 3.76 s (3H, OMe), 3.81 s (3H, OMe), 5.38 d
(1H, =C4H, J 6.6 Hz), 6.35 d, 7.03 d (2H, CH=CH, J
16.2 Hz), 6.85 d, 6.87 d, 7.02 d, 7.37 d [8H,
10-(4-Chlorophenyl)-8-[2-(4-chlorophenyl)ethenyl]-
7-oxaspiro[4.5]dec-8-en-6-one (VIb). Yield 0.78 g
(39%), mp 204–205ºC. IR spectrum, ν, cm–1: 1655
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

REACTION OF 1,5-DIARYLPENTA-1,4-DIEN-3-ONES
1197
2(4-MeOC6H4), J 7.4 Hz]. Found, %: C 77.38, H 6.84.
(CH2)6], 3.44 d (1H, C5H, J 6.6 Hz), 5.45 d (1H, =C4H,
J 6.6 Hz), 6.47 d, 7.10 d (2H, CH=CH, J 16.2 Hz),
7.09 d, 7.22–7.37 m, 7.43 d (10H, 2Ph, J 7.2 Hz).
Found, %: C 83.92, H 7.46. C25H26O2. Calculated, %:
C 83.76, H 7.31.
C26H28O4. Calculated, %: C 77.20, H 6.98.
5-(4-Bromophenyl)-3-[2-(4-bromophenyl)ethenyl]-
2-oxaspiro[5.5]undec-3-en-1-one (VIId). Yield 1.24 g
(49%), mp 204–206ºC. IR spectrum, ν, cm–1: 1655
(C=C), 1770 (C=O). 1H NMR spectrum, δ, ppm: 1.04–
2.10 m [10H, (CH2)5], 3.46 d (1H, C5H, J 6.6 Hz), 5.43
d (1H, =C4H, J 6.6 Hz), 6.45 d, 7.02 d (2H, CH=CH,
J 16.2 Hz), 6.97 d, 7.29 d, 7.40 d, 7.46 d [8H, 2(4-
BrC6H4), J 8.4 Hz]. Found, %: C 57.64, H 4.55; Br
31.56. C24H22Br2O2. Calculated, %: C 57.39, H 4.42;
Br 31.82.
5-(4-Bromophenyl)-3-[2-(4-bromophenyl)ethenyl]-
2-oxaspiro[5.6]dodecyl-3-en-1-one (VIIIb). Yield
1.26 g (49%), mp 204–206ºC. IR spectrum, ν, cm–1:
1
1660 (C=C), 1770 (C=O). H NMR spectrum, δ, ppm:
1.00–2.10 m [12H, (CH2)6], 3.38 d (1H, C5H, J 6.6 Hz),
5.37 d (1H, =C4H, J 6.6 Hz), 6.36 d, 6.96 d (2H,
CH=CH, J 16.2 Hz), 6.88 d, 7.21 d, 7.34 d, 7.39 d [8H,
2(4-BrC6H4), J 8.4 Hz]. Found, %: C 58.39, H 4.78; Br
30.66. C25H24Br2O2. Calculated, %: C 58.16, H 4.69;
Br 30.95.
5-Aryl-3-(2-arylethenyl)-2-oxaspiro[5.6]dodecyl-
3-en-1-ones (VIIIa, VIIIb) were obtained similarly to
compounds VI. Methyl 1-bromocycloheptanecarboxy-
late was used as initial compound.
REFERENCES
1. Kirillov, N.F. and Gavrilov, A.G., Zh. Obshch. Khim.,
5-Phenyl-3-(2-phenylethenyl)-2-oxaspiro[5.6]-
dodecyl-3-en-1-one (VIIIa). Yield 0.97 g (54%), mp
99–100ºC. IR spectrum, ν, cm–1: 1655 (C=C), 1770
(C=O). 1H NMR spectrum, δ, ppm: 1.14–2.10 m [12H,
2008, vol. 78, no. 7, p. 1189.
2. Kirillov, N.F. and Gavrilov, A.G., Zh. Org. Khim.,
2008, vol. 44, no. 7, p. 975.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011