Reaction of alicyclic reformatsky reagents with 2-arylmethylene-1,3- diphenylpropane-1,3-diones

Full text of DOI:10.1134/S1070363211060302

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 6, pp. 1243–1244. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.F. Kirillov, E.A. Nikiforova, M.I. Vakhrin , 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 6, pp. 1050–1052.
LETTERS
TO THE EDITOR
Reaction of Alicyclic Reformatsky Reagents
with 2-Arylmethylene-1,3-diphenylpropane-1,3-diones
N. F. Kirillov, E. A. Nikiforova, and M. I. Vakhrin
Perm State University, ul. Bukireva 15, Perm, 614990 Russia
e-mail: kirillov@psu.ru
Received December 2, 2010
DOI: 10.1134/S1070363211060302
Previously we found that the reaction of alicyclic
Reformatsky reagents with 1,3-diarylprop-2-ene-1-
ones resulted in the substituted spirodihydropyranones
[1, 2]. In continuation of these studies we examined
the reaction of the Reformatsky reagents IIa and IIb
derived from methyl 1-bromocycloalkylcarboxylates
Ia and Ib and zinc with 2-arylmethylene-1,3-diphenyl-
propane-1,3-dione IIIa–IIIf. Our study showed that
addition of the organozinc reagents IIa–IIb to the
unsaturated diketones IIIa–IIIf occurs in 1,4-position
to form the intermediates IVa–IVe, Va–Vf followed
by the cyclization with the release of bromozinc
methylate to form 10-aryl-9-benzoyl-8-phenyl-7-oxa-
spiro[4.5]dec-8-ene-6-ones VIa–VIf and 5-aryl-4-
benzoyl-3-phenyl-2-oxaspiro[5.5]undec-3-ene-1-ones
VIIa–VIIf, respectively.
COOMe
COOMe
(CH2)n
(CH2)n
Zn
ZnBr
Br
Iа, Ib
IIа, IIb
O
Ar
O
Ph
COPh
(CH2)n
O
PhCOC(=CHAr)COPh
Ph
IIIа_IIIf
(CH2)n
BrZnO
_MeOZnBr
Ph
MeO
IVа_IVe, Vа_Vf
O
VIа_VIe, VIIа_VIIf
n = 1 (Iа, IIа, IV, VI), 2 (Ib, IIb, V, VII). III–VII, Ar = 4-BrC6H4 (а), 4-ClC6H4 (b), 3-BrС6Н4 (c), 2,4-Cl2C6H3 (d), 2-Cl-
4-FC6H3 (e); III, V, VII, Ar = 4-FC6H4 (f).
The composition and structure of the compounds
obtained were confirmed by the elemental analysis, IR
solutions of these compounds are recorded on a
Fourier spectrometer TESLA BS-567A (100 MHz)
with internal reference TMS.
1
and H NMR spectroscopy data. The IR spectra of
compounds VIa–VIe, VIIa–VIIf contain the charac-
teristic bands of C=C bonds at 1610–1625 cm–1 and of
the ketone and lactone carbonyl groups at 1630–1640
10-Aryl-9-benzoyl-8-phenyl-7-oxaspiro[4.5]dec-
8-ene-6-ones (VIa–VIe). A mixture of 1.5 g of fine
zinc turnings, a catalytic amount of mercuric chloride,
5 mmol of 1,5-diaryl-1,4-pentadiene-3-one, 5.3 mmol
of methyl 1-bromocyclopentylcarboxylate, 20 ml of
benzene, 5 ml of ethyl acetate, 1 ml of HMPT was
refluxed for 4 h, cooled, decanted from excess zinc,
and quenched with 5% hydrochloric acid. The organic
layer was separated, and the reaction products were
extracted twice with ethyl acetate. After drying the
1
and 1765–1790 cm–1. In the H NMR spectra there is
one set of signals, among which the most characteristic
is a singlet of methine proton in the range of 4.00–
4.87 ppm.
The IR spectra of compounds VIa–VIe, VIIa–VIIf
were obtained on a Specord-75IR spectrophotometer
as mulls in mineral oil. The ¹H NMR spectra of CDCl3
1243

1244
KIRILLOV et al.
extract with anhydrous sodium sulfate the solvent was
evaporated, and the compounds VIa-VIe were
recrystallized from ethyl acetate.
NMR spectrum, δ, ppm: 1.10–2.25 m [10Н, (СН2)5],
4.18 s (1Н, C5H), 6.80–7.40 m (14Н, Ar). Found, %: С
69.71; Н 4.86; Br 16.13. С29Н25BrО3. Calculated, %: С
69.47; Н 5.03; Br 15.94.
9-Benzoyl-10-(4-bromophenyl)-8-phenyl-7-oxa-
spiro[4.5]dec-8-ene-6-one (VIа). Yield 0.88 g (36%),
mp 164–165°С. IR spectrum, ν, cm–1: 1620 (С=С),
4-Benzoyl-3-phenyl-5-(4-chlorophenyl)-2-oxa-
spiro[5.5]undec-3-ene-1-one (VIIb). Yield 1.17 g
(51%), mp 152–153ºС. IR spectrum, ν, cm–1: 1620
1
1635 (С=О, ketone), 1775 (С=О, lactone). Н NMR
1
spectrum, δ, ppm: 1.40–2.20 m [8Н, (СН2)4], 4.13 s
(1Н, C10H), 7.10–7.42 m (14Н, Ar). Found, %: С
68.80; Н 4.89; Br 16.61. С28Н23BrО3. Calculated, %: С
69.00; Н 4.76; Br 16.39.
(С=С), 1640 (С=О, ketone), 1780 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.08–2.26 m [10Н, (СН2)5],
4.22 s (1Н, C5H), 6.85–7.40 m (14Н, Ar). Found, %: С
76.37; Н 5.35; Cl 7.59. С29Н25ClО3. Calculated, %: С
76.22; Н 5.51; Cl 7.76.
9-Benzoyl-8-phenyl-10-(4-chlorophenyl)-7-oxa-
spiro[4.5]dec-8-ene-6-one (VIb). Yield 0.91 g (41%),
mp 160–161ºС. IR spectrum, ν, cm–1 : 1620 (С=С),
1635 (С=О, ketone), 1775 (С=О, lactone). 1Н NMR, δ,
ppm: 1.20–2.25 m [8Н, (СН2)4], 4.02 s (1Н, C10H),
6.75–7.40 m (14Н, Ar). Found, %: С 76.15; Н 5.11; Cl
8.19. С28Н23ClО3. Calculated, %: С 75.93; Н 5.23; Cl 8.00.
4-Benzoyl-5-(3-bromophenyl)-3-phenyl-2-oxa-
spiro[5.5]undec-3-ene-1-one (VIIc). Yield 1.10 g
(44%), mp 174–175ºС. IR spectrum, ν, cm–1: 1625
1
(С=С), 1635 (С=О, ketone), 1790 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.10–2.20 m [10Н, (СН2)5],
4.24 s (1Н, C5H), 6.94–7.44 m (14Н, Ar). Found, %: С
69.38; Н 4.97; Br 15.78. С29Н25BrО3. Calculated, %: С
69.47; Н 5.03; Br 15.94.
9-Benzoyl-10-(3-bromophenyl)-8-phenyl-7-oxa-
spiro[4.5]dec-8-ene-6-one (VIc). Yield 1.05 g (43%),
mp 171–172ºС. IR spectrum, ν, cm–1: 1625 (С=С),
4-Benzoyl-5-(2,4-dichlorophenyl)-3-phenyl-2-oxa-
spiro[5.5]undec-3-ene-1-one (VIId). Yield 0.69 g
(28%), mp 173–174ºС. IR spectrum, ν, cm–1: 1615
1
1635 (С=О, ketone), 1775 (С=О, lactone). Н NMR
spectrum, δ, ppm: 1.20–2.25 m [8Н, (СН2)4], 4.00 s
(1Н, C10H), 6.90–7.45 m (14Н, Ar). Found, %: С
69.26; Н 4.58; Br 16.47. С28Н23BrО3. Calculated, %: С
69.00; Н 4.76; Br 16.39.
1
(С=С), 1635 (С=О, ketone), 1775 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.10–2.20 m [10Н, (СН2)5],
4.19 s (1Н, C5H), 6.85–7.40 m (13Н, Ar). Found, %: С
70.98; Н 4.81; Cl 14.30. С29Н24Cl2О3. Calculated, %:
С 70.88; Н 4.92; Cl 14.43.
9-Benzoyl-10-(2,4-dichlorophenyl)-8-phenyl-7-
oxaspiro[4.5]dec-8-ene-6-one (VId). Yield 0.76 g
(32%), mp 181–182ºС. IR spectrum, ν, cm–1: 1625
4-Benzoyl-3-phenyl-5-(4-fluoro-2-chlorophenyl)-
2-oxaspiro[5.5]undec-3-ene-1-one (VIIe). Yield 0.85 g
(37%), mp 157–158ºС. IR spectrum, ν, cm–1: 1620
1
(С=С), 1640 (С=О, ketone), 1765 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.15–2.35 m [8Н, (СН2)4],
4.78 s (1Н, C10H), 6.82–7.48 m (13Н, Ar). Found, %:
С 70.69; Н 4.77; Cl 14.68. С28Н22Cl2О3. Calculated,
%: С 70.45; Н 4.65; Cl 14.85.
1
(С=С), 1640 (С=О, ketone), 1770 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.20–2.40 m [10Н, (СН2)5],
4.87 s (1Н, C5H), 6.80–7.45 m (13Н, Ar). Found, %: С
73.56; Н 5.18; Cl 7.36. С29Н24ClFО3. Calculated, %: С
73.34; Н 5.09; Cl 7.46.
9-Benzoyl-8-phenyl-10-(4-fluoro-2-chlorophenyl)-
7-oxaspiro[4.5]dec-8-ene-6-one (VIe). Yield 0.85 g
(37%), mp 157–158ºС. IR spectrum, ν, cm–1: 1610
4-Benzoyl-3-phenyl-5-(4-fluorophenyl)-2-oxa-
spiro[5.5]undec-3-ene-1-one (VIIf). Yield 0.95 g
(43%), mp 207–208ºС. IR spectrum, ν, cm–1: 1625
1
(С=С), 1635 (С=О, ketone), 1765 (С=О, lactone). Н
NMR, δ, ppm: 1.35–2.32 m [8Н, (СН2)4], 4.78 s (1Н,
C10H), 6.80–7.45 m (13Н, Ar). Found, %: С 73.18; Н
5.00; Cl 7.52. С28Н22ClFО3. Calculated, %: С 72.96; Н
4.81; Cl 7.69.
1
(С=С), 1635 (С=О, ketone), 1775 (С=О, lactone). Н
NMR spectrum, δ, ppm: 1.20–2.10 m [10Н, (СН2)5],
4.16 s (1Н, C5H), 7.02–7.60 m (14Н, Ar). Found, %: С
79.28; Н 5.90. С29Н25FО3. Calculated, %: С 79.07; Н 5.72.
5-Aryl-4-benzoyl-3-phenyl-2-oxaspiro[5.5]undec-
3-ene-1-ones (VIIа-VIIf) were obtained similarly
starting from methyl 1-bromocyclohexanecarboxylate.
REFERENCE
1. Kirillov, N.F. and Gavrilov, A.G., Zh. Obshch. Khim.,
4-Benzoyl-5-(4-bromophenyl)-3-phenyl-2-oxa-
spiro[5.5]undec-3-ene-1-one (VIIа). Yield 1.38 g
(55%), mp 179–180ºС. IR spectrum, ν, cm–1: 1625
2008, vol. 78, no. 7, p. 1189.
2. Kirillov, N.F. and Gavrilov, A.G., Zh. Org. Khim., 2008,
1
vol. 44, no. 7, p. 975.
(С=С), 1635 (С=О, ketone), 1785 (С=О, lactone). Н
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011