Synthesis of higher spiroacetals by condensation of alkyl- and cycloalkylcyclopentanones and cyclohexanones with dihydric alcohols in the presence of heterogenic catalysts

Article abstract of DOI:10.1134/S1070428011080069

The condensation of C₃-C₇ alkyl- and cycloalkylcyclopentanones and cyclohexanones with 1,2-ethane-, 1,2-propane-, and 1,3-butanediols in the presence of heterogenic acid catalysts provided new representatives of spiroacetals. The highest yields of reaction products were obtained in the presence of phosphomolybdic heteropolyacid additionally modifi ed with cobalt and bromine, and also in the presence of the chlorinated cationite KU-23 at 110-130°C. The synthesized spiroacetals possess the jasmine and menthol-wooden fragrance of various tinges.

Full text of DOI:10.1134/S1070428011080069

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1153−1160. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Kh.M. Alimardanov, O.A. Sadygov, M.F. Abbasov, E.T. Suleimanova, N.A. Dzhafarova, M.Ya. Abdullaeva, S.M. Abbasova, 2011,
published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1136−1143.
Synthesis of Higher Spiroacetals by Condensation
of Alkyl- and Cycloalkylcyclopentanones
and Cyclohexanones with Dihydric Alcohols
in the Presence of Heterogenic Catalysts
Kh. M. Alimardanov, O. A. Sadygov, M. F. Abbasov, E. T. Suleimanova,
N. A. Dzhafarova, M. Ya. Abdullaeva, and S. M. Abbasova
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
Baku,1025Azerbaijan
e-mail: omar.sadiqov@gmail.com
Received April 29, 2009
Abstract—The condensation of С3–С7 alkyl- and cycloalkylcyclopentanones and cyclohexanones with 1,2-ethane-,
1,2-propane-, and 1,3-butanediols in the presence of heterogenic acid catalysts provided new representatives
of spiroacetals. The highest yields of reaction products were obtained in the presence of phosphomolybdic
heteropolyacid additionally modified with cobalt and bromine, and also in the presence of the chlorinated cationite
KU-23 at 110–130°C. The synthesized spiroacetals possess the jasmine and menthol-wooden fragrance of various
tinges.
DOI: 10.1134/S1070428011080069
Spiroacetal containing various functional groups along-
side the acetal moieties are included into many pharma-
ceuticals and, соdержащandе наряdу с ацеtальныmand
фрагmенtаmand разлandчные фunqцandональные
группы, [1], are applied as synthetic fragrant substances
[2], solvents for cellulose ethers [3], biologically active
preparations in the agrochemistry [4], promising mono-
mers [5], insecticides of high biological destruction [6].
Scarce published papers describe the preparation of
spiroacetals from cyclohexanone [7–9] and its derivatives
[10] in the presence of homogenic [7–10] and hetero-
genic catalysts [11]. Yet the information on the synthesis
of higher spiroacetals is virtually absent. We formerly
developed the ways and processes of the preparation of
С5–С7 alkyl- and cycloalkyl-substituted cyclopentanones,
cyclohexanones, and a norcamphor [12–14].
and cycloalkyl-substituted cyclanones with 1,2-ethane-,
1,2-propane-, and 1,3-butanediols in the presence of vari-
ous heterogenic acid catalysts.
The following catalysts were used: phosphomolyb-
dic heteropolyacid modified with cobalt and bromine
(PMHA) Р0.17Mо2.4СоBr0.27O6.8, chlorine-containing
cationites KU-2×8 and KU-23, zeocar-2, modified forms
of synthetic mordenite (НNaZn-mordenite), and of natu-
ral clintoptilolite (Ai-Dag deposit).
The yields of spiroethylene- and propyleneacetals of
alkyl-, dialkyl-, and cycloalkylcyclanones and the selec-
tivity of the reactions depended essentially on the catalyst
nature, structures, and the molar ratio of initial compounds
(Table 1). As seen from Table 1, the most efficient among
the applied catalysts were PMHA modified with cobalt
and bromine, chlorinated KU-23 (content of Cl 2.2–9.5%),
and НNaZn-mordenite that provided the yields of the cor-
responding spiroacetals on the level 59–80%.
The ketones obtained are analogs of the naturally occur-
ring jasmone and possess odors of jasmine and menthol-
wooden type with various tinges. Some of them found the
application in perfume and cosmetic production [2].
The dependence of the yield of the target product on
the ratio of reacting components , temperature, time of the
run, and the structure of the initial ketones was monitored
by GLC. The reaction proceeds selectively in the medium
This article describes the preparation of higher
spiroacetals by the condensation of С3–С7 alkyl-, dialkyl-,
1153

ALIMARDANOV, et al.
1154
of the azeotrope-forming solvent (toluene or xylene)
at the molar ratio ketone–diol 1 : 1–3. The increase in
this ratio from 1 : 1 to 1 : 3 favored the increase in the
yield of the corresponding acetals by 25–35% (Table 2).
The yield of acetals also grew at increasing the tem-
perature from 110 to 140°C. The maximum yield of the
target product was attained at 130°C and was 52–80%
for spiroacetals of alkyl- and dialkylcyclopentanones,
56–79% for cycloalkylcyclopentanones, and 48–83%
for cycloalkylcyclohexanones. The raising of the tem-
perature above 140°C decreased the yield of acetals by
~7–10%, apparently due to partial tarring or because of
the increased dehydration rate of the used diols.
The composition and structure of synthesized acetals
ХIa–XIg–ХХа–XXd was confirmed by elemental analy-
sis and the IR and 1Н NMR spectra.
In the IR spectra of these compounds the absorption
bands in the region 1660 and 1703 cm–1 characteristic of
the stretching vibrations of the С=О group and the wide
band at 3400–3500 cm–1 belonging to the associated OH
group disappeared. The appearance of absorption bands
at 950, 1060, 1150 cm–1 characteristic of the stretching
vibrations of ether bond may be regarded as the proof
of the presence of the spiroacetal structure [16, 17]. The
other absorption bands in the spectra correspond to the
stretching and bending vibrations of the С–H bonds in the
СH, СH2, and СH3 groups in the acetal rings containing
4–7 carbon atoms.
The presence of alkyl or cycloalkyl substituents in
the molecules of cyclopentanone and cyclohexanone es-
sentially affects their reactivity (Table 3). For instance, in
going from cyclopentane to the strained bicycloheptane
skeleton the yields of the acetals decrease by ~8–25% ap-
parently due to steric factors hampering the nucleophilic
attack on the carbonyl group of the ketones.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
Carl Zeiss UR-20 from thin films. 1Н NMR spectra were
registered on a spectrometer Bruker (300 MHz) in ССl4,
internal reference HMDS.
At all conditions being the same the yields of acetals
depend on the structure of initial diols and grow in the
sequence 1,2-ethanediol < 1,2-propanediol < 1,3-butane
diol. The effect of the methyl group on the condensation
process is due to decreasing the role of the steric factors
in the conjugation of the hydroxy groups of the diol
molecule with the carbonyl group of cyclic ketones [15].
The purity and the isomeric composition of com-
pounds were checked by TLC on Silufol UV-254 plates,
eluent hexane–ether, 2–4 : 1, development in iodine vapor.
GLC was carried out on a chromatograph LKhM -8M-5
equipped with a katharometer, a column 0.3 × 300 cm,
stationary phase 5% of ХЕ-60 on Chromaton N-AW
DMCS, ramp from 140 to 200°C, carrier gas helium, flow
rate 40 ml/min, detector current 75 mА.
The obtained spiroacetals like the initial ketones
possess odors of jasmine and menthol-wooden type but
with more delicate various tinge. Some of them found
the application as aromatizers of soaps and detergents.
Initial ethane-1,2-, propane-1,2-, and butane-1,3-diols
Table 1. Dependence of the yield of spiroacetals on the catalyst nature (ketone–diol 1 : 2, quantity of catalyst 15 wt %)
Yield, %
Compd. no.
Chlorinated
KU-2×8
Chlorinated
KU-23
НNaZn-
mordenite
PMHA
Zeocar-2
НNaK-clinoptilolite
ХIe
XVa
52
80
59
80
69
79
70
78
67
74
65
46
50
47
38
42
50
35
41
32
50
45
64
60
58
51
48
48
47
52
40
49
52
31
34
31
25
28
30
22
27
31
32
25
55
60
56
50
51
48
47
41
47
51
52
27
26
28
19
16
27
26
19
11
25
19
XVIa
XVIIb
XVIIc
XVIIIb
XVIIIc
ХIХb
ХIХc
ХХb
ХХc
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

SYNTHESIS OF HIGHER SPIROACETALS
1155
O
HO
( )k
CH
R1
CH2(CH2)mCH3
( )n
R1
R5
R4
R2
IVа_IVg, Vа_Vc
OH
O
O
( )k
CH
VIII_X
( )n
R2
O
R4
Hx
C
( )y
R1
XIа_XIg, XIIа_XIIc, XIIIа_XIId, XIVа_XIVf,
XV, XVI, XVIIа_XVIId, XVIIIа_XVIIIc,
XIXа_XIXc, XXа_XXd
( )n
R2
C
( )z
Hx
R3
VIа_VId, VIIа_VIIf
IV, n = 1: R1 = R2 = H, m = 1 (a), 2 (b), 3 (c), 4 (d), 5 (e); m = 5, R1 = H, R2 = Me (f), R1 = Me, R2 = H (g); V, n = 2, R1
= R2 = H, m = 3 (a), 4 (b), 5 (c); VI, R1 = R2 = R3 = H; n = z = 1, x = 2, y = 0, (a); n = 1, x = z = 2, y = 0 (b); n = x = y =
1, z = 2 (c); R1=R2=H, R3= Me (d); VII, R1 = R2 = R3 = H; n = x = 2, y = 0, z = 1 (a); n = x = z = 2, y = 0 (b); n = z = 2,
x = y = 1 (c); R1 = R2 = H, R3 = Me (d); R1 = Me, R2 = R3 = H (e); R2 = H, R1 = R3 = Me (f); k = 1, R4 = H VIII, Me IX;
R4 = Me, k = 2 X; XI, n = k = 1: R1 = R2 = R4 = H, R5 = Pr (a), Bu (b), C5H11 (c), C6H13 (d), C7H15 (e); R5 = C7H15, R1 =
R4 = H, R2 = Me (f); R1 = Me, R2 = R4 = H, R5 = C7H15 (g); XII, n = 2, k = 1, R1 = R2 = R4 = H, R5 = C5H11 (a), C6H13
(b), C7H15 (c); XIII, n = k = 1, R1 = R2 = R4 = H, R5 = C5H9 (a), C6H11 (b), C7H11 (c), C8H14 (d); XIV, n = 2, k = 1, R1 =
R2 = R4 = H, R5 = C5H9 (a), C6H11 (b), C7H11 (c), C8H14 (d); R1 = Me, R2 = R4 = H, R5 = C7H11 (e), C8H14 (f); n = 1, R1 =
R2 = H, R4 = CH3, R5 = C7H15, k = 1 (XV), 2 (XVI); XVII, n = k = 1, R1 = R2 = H, R4 = Me, R5 = C5H9 (a), C6H11 (b),
C7H11 (c), C8H13 (d); XVIII, k = 1, n = 2, R1 = R2 = H, R4 = Me, R5 = C5H9 (a), C6H11 (b), C7H11 (c); XIX, n = 1, k = 2,
R1 = R2 = H, R4 = Me: R5 = C5H9 (a), C6H11 (b), C7H11 (c); XX, n = 2, k = 2, R1 = R2 = H, R4 = Me: R5 = C5H9 (a), C6H11
(b), C7H11 (c), C8H13 (d).
Table 2. Dependence of the yield of spiroacetals (%) on the reagents ratio (Сketone 1 mol, 130°C, 6 h)
Diol VIII, mol
Diol ХIХ, mol
Diol Х, mol
Ketone Spiroacetal
Spiroacetal
no.
Spiroacetal
no.
no.
no.
1
2
3
1
2
3
1
2
3
IVe
Vc
VIc
VIIc
XIe
XVa
XVIа
41
37
53
47
52
66
72
69
56
71
78
78
65
–
54
53
60
–
69
70
89
–
75
74
44
–
36
38
59
–
67
65
61
–
71
71
XIIc
XIIIc
XIVc
XVIIc
XVIIIc
XIXc
XXc
Table 3. Dependence of the yield of spiroacetals on the structure of initial ketone (ketone–VIII 1 : 2, 130°C, 6 h)
Yield, %
Ketone no.
Spiroacetal no.
PMHA
Chlorinated KU-23
НNaZn-mordenite
IVа
IVb
IVc
IVd
IVe
IVf
IVg
Vc
VIc
VIIc
VIIe
VIIf
XIа
XIb
XIc
XId
XIe
XIf
XIg
XIIc
XIIIc
XIVc
XIVe
XIVf
64
62
66
57
52
76
53
66
72
69
59
55
63
61
65
57
64
76
50
62
65
68
61
52
58
55
56
52
55
69
39
44
52
43
40
35
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

ALIMARDANOV, et al.
1156
Bu), 2.13 m (1Н, Н5, СН), 3.84–3.96 d (4Н, Н2,3, 2СН2О).
Found, %: С 71.96; Н 11.06. С11Н20О2. Calculated, %:
С 71.74; Н 10.97.
were of “chemically pure” grade. Ketones were obtained
by the procedure we formerly developed [12]. Into a pres-
sure reactor of 2 liter capacity was charged a desired
amount of cyclopentanone [methylcyclopentanone (II),
cyclohexanone (III)], С3–С7 α-olefins (or cycloolefins),
and di-tert-butylperoxide in a molar ratio 4 : 1 : 0.25,
the reaction proceeded at 140−160°C for 4–6 h. On
cooling the reactor the reaction products were subjected
first to distillation at the atmospheric pressure, then in a
vacuum to isolate the corresponding alkyl-, dialkyl-, or
cycloalkylcyclopentanones or cyclohexanones.
5-Pentyl-1,4-dioxaspiro[4.4]nonane (ХIc) was
obtained from 15.4 g of compound IVc and 12.4 g of
compound VIII. Yield 13 g (66%), bp 115–117°C (18 mm
Hg), d420 0.9608, nD20 1.4556. IR spectrum, ν, cm–1:
1140–1060, 650. 1Н NMR spectrum, δ, ppm: 0.97 t (3Н,
СН3), 1.25–1.85 m (14Н, 3СН2 of cycle and 4СН2 Alk),
2.13 m (1Н, Н5, СН), 3.88–4.02 d (4Н, Н2,3, 2СН2О).
Found, %: С 72.86; Н 11.18. С12Н22О2. Calculated, %:
С 72.73; Н 11.11.
The modified PMHA was obtained by boiling a mix-
ture of orthophosphoric acid molybdenum(VI) oxide, and
hydrobromic acid followed by mixing the separated pre-
cipitate with cobalt(II) carbonate, evaporation, and drying
of the mass obtained at 100–120°C [18]. The chlorinated
KU-2×8 and KU-23 were prepared as described in [19].
HNaZn-form of mordenite was obtained by impregnation
of HNa-mordenite with a solution of Zn(NO3)2 followed
by drying at 100–120°C and calcining at 450–500°C.
5-Hexyl-1,4-dioxaspiro[4.4]nonane (ХId) was
obtained from 16.8 g of compound IVd and 12.4 g of
compound VIII. Yield 11.9 g (57%), bp 124–125°C
(17 mm Hg), d420 0.9613, nD20 1.4558. IR spectrum, ν,
cm–1: 1150–1050, 660. 1Н NMR spectrum, δ, ppm: 0.97 t
(3Н, СН3), 1.24–1.85 m (16Н, 3СН2 of cycle and 5СН2
Alk), 2.12 m (1Н, Н5), 3.88–4.02 d (4Н, Н2,3, 2СН2О).
Found, %: С 73.72; Н 11.51. С13Н24О2. Calculated, %:
С 73.58; Н 11.32.
Synthesis of spiroacetals. General procedure. The
condensation was carried out in a glass reactor of ca-
pacity 250 ml equipped with the temperature control
(110–140 ± 0.2°С), thermometer, reflux condenser,
and Dean-Stark trap. The necessary amount of reagents
(0.1 mol of ketone and 0.2 mol of diol) and the solvent
was charged into the reactor. The reaction was terminated
when the calculated amount of water was separated with
the azeotrope. The organic layer was separated from the
catalyst, washed till the neutral reaction (against litmus),
dried with Na2SO4 , and the target product was isolated
by distillation.
5-Heptyl-1,4-dioxaspiro[4.4]nonane (ХIe) was
obtained from 18.2 g of compound IVe and 12.4 g of
compound VIII. Yield 11.8 g (52%), bp 141–142°C
(10 mm Hg), d420 0.9524, nD20 1.4584. IR spectrum, ν,
cm–1: 1150–1055, 660. 1Н NMR spectrum, δ, ppm: 0.97 t
(3Н, СН3), 1.22–1.84 m (18Н, 3СН2 of cycle and 6СН2
Alk), 2.13 m (1Н, Н5), 3.85–3.98 d (4Н, Н2,3, 2СН2О).
Found, %: С 74.86; Н 11.62. С14Н26О2. Calculated, %:
С 74.74; Н 11.50.
5-Heptyl-6-methyl-1,4-dioxaspiro[4.4]nonane (ХIf)
was obtained from 19.6 g of compound IVf and 12.4 g
of compound VIII. Yield 18.1 g (76%), bp 126–128°C
(1.2 mm Hg), d420 0.9524, nD20 1.4598. IR spectrum, ν,
cm–1: 1150–1070, 650. 1Н NMR spectrum, δ, ppm: 0.85 t
(3Н, СН3 Alk), 1.22 d.d (3Н, 6-СН3), 1.28–1.55 d (16Н,
2СН2 of cycle and 6СН2 Alk), 2.81 d (1Н, Н6, СН),
3.02 m (1Н, Н5, СН), 3.48–3.60 d (4Н, Н2,3, 2СН2О).
Found, %: С 74.63; Н 12.42. С15Н28О2. Calculated, %:
С 75.0; Н 11.67.
5-Propyl-1,4-dioxaspiro[4.4]nonane (ХIа) was
obtained from 12.6 g of compound IVа and 12.4 g of
compound VIII. Yield 10.8 g (64%), bp 109–111°C
(18 mm Hg), d420 0.9826, nD20 1.4548. MRD 46.92,
calc. 46.89. IR spectrum, ν, cm–1: 1155–1040, 650.
1Н NMR spectrum, δ, ppm: 0.97 t (3Н, СН3), 1.26–
1.83 m (10Н, 3СН2 of cycle and 2СН2 Pr), 2.13 m (1Н,
Н5, СН), 3.84–3.96 d (4Н, Н2,3, 2СН2О) [20]. Found,
%: С 70.06; Н 10.72. С10Н18О2. Calculated, %: С 70.89;
Н 10.59.
5-Methyl-8-heptyl-1,4-dioxaspiro[4.4]nonane (ХIg)
was obtained from 19.6 g of compound IVg and 12.4 g
of compound VIII. Yield 12 g (53%), bp 125–127°C
(1.2 mm Hg), d420 0.9518, nD20 1.4591. IR spectrum, ν,
cm–1: 1150–1060, 650. 1Н NMR spectrum, δ, ppm: 0.95 t
(3Н, СН3Alk), 1.20 d (3Н, 5-СН3), 1.28–1.55 m (16Н,
2СН2 of cycle and 6 СН2 Alk), 2.84 d (Н8, СН), 3.00 m
5-Butyl-1,4-dioxaspiro[4.4]nonane (ХIb) was
obtained from 14 g of compound IVb and 12.4 g of
compound VIII. Yield 11.4 g (62%), bp 112–113°C
(18 mm Hg), d420 0.9615, nD20 1.4552. IR spectrum, ν,
cm–1: 1140–1070, 650. 1Н NMR spectrum, δ, ppm: 0.97 t
(3Н, СН3), 1.24–1.83 m (12Н, 3СН2 of cycle and 3СН2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

SYNTHESIS OF HIGHER SPIROACETALS
1157
(1Н, Н5, СН), 3.48–3.61 d (4Н, Н2,3, СН2О). Found,
Calculated, %: С 74.29; Н 10.48.
%: С 73.96; Н 12.65. С15Н28О2. Calculated, %: С 75.0;
Н 11.67.
5-(Bicyclo[2.2.1]heptyl)-1,4-dioxaspiro[4.4]-
nonane (ХIIIc) was obtained from 17.8 g of compound
VIc and 12.4 g of compound VIII. Yield 15.9 g (72%),
bp 96–98°C (2 mm Hg), d420 1.1081, nD20 1.5108. IR
5-Pentyl-1,4-dioxaspiro[4.5]decane (ХIIa) was
obtained from 16.8 г of compound Va and 12.4 g of
compound VIII. Yield 14.5 g (69%), bp 103–105°C
1
spectrum, ν, cm–1: 1200–1040. Н NMR spectrum, δ,
(1.2 mm Hg), d4 0.9628, nD20 1.4582. IR spectrum, ν,
20
ppm: 1.22–1.56 d (8Н, 4СН2 Hept), 1.36–1.83 m (6Н,
3СН2 spiro), 1.42 t (1Н, Н2, СН Hept), 1.43–1.45 d
(2Н, Н1,4, 2СН Hept), 2.14 m (1Н, Н5, СН spiro), 3.84–
3.96 d.d (4Н, Н2,3, 2СН2О). Found, %: С 75.64; Н 10.03.
С14Н22О2. Calculated, %: С 75.67; Н 9.91.
cm–1: 1350, 1200–1040, 650. 1Н NMR spectrum, δ, ppm:
0.95 m (3Н, СН3), 1.23–1.77 m (16Н, 4СН2 of cycle and
4СН2 Alk), 2.08 m (1Н, Н5, СН), 3.84– 3.96 d.d (4Н,
Н2,3, 2СН2О). Found %: С 73.86; Н 11.76. С13Н24О2.
Calculated %: С 73.58; Н 11.32.
5-(6-Methylbicyclo[2.2.1]heptyl)-1,4-dioxaspi-
ro[4.4]nonane (ХIIId) was obtained from 19.2 g of
compound VId and 12.4 g of compound VIII. Yield
16.2 g (69%), bp 108–110°C (2 mm Hg), d420 1.0836,
nD20 1.5078. IR spectrum, ν, cm–1: 1200–1040. 1Н NMR
spectrum, δ, ppm: 1.07 d (3Н, СН3), 1.23–1.54 d (6Н,
3СН2 Hept), 1.36–1.83 m (6Н, 3СН2 spiro), 1.41 t (1Н,
Н2, СН), 1.41–1.44 d (2Н, Н1,4, 2СН Hept), 1.62 t (1Н,
Н6, СН), 2.14 (1Н, Н5, СН spiro), 3.84–3.99 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 76.2; Н 10.22. С15Н24О2.
Calculated, %: С 76.27; Н 10.17.
5-Hexyl-1,4-dioxaspiro[4.5]decane (ХIIb) was
obtained from 18.2 g of compound Vb and 12.4 g of
compound VIII. Yield 15 g (67%), bp 119–121°C
(1.2 mm Hg), d4 0.9612, nD20 1.4634. IR spectrum, ν,
20
cm–1: 1340, 1200–1040, 655. 1Н NMR spectrum, δ, ppm:
0.95 m (3Н, СН3), 1.24–1.80 m (18Н, 4СН2 of cycle and
5СН2 Alk), 2.08 m (1Н, Н5, СН), 3.84– 3.96 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 74.28; Н 11.82. С14Н26О2.
Calculated, %: С 74.34; Н 11.50.
5-Heptyl-1,4-dioxaspiro[4.5]decane (ХIIc) was
obtained from 19.6 g of compound Vc and 12.4 g of
compound VIII. Yield 15.7 g (66%), bp 132–134°C
5-Cyclopentyl-1,4-dioxaspiro[4.5]decane (ХIVа)
was obtained from 16.6 g of compound VIIа and 12.4 g
of compound VIII. Yield 17.5 g (83%), bp 157–160°C
(3 mm Hg), d420 1.0564, nD20 1.4910. IR spectrum, ν,
cm–1: 1445, 1420 [δ(СН2 of cycle)], 1200–1040 (С–О–С).
1Н NMR spectrum, δ, ppm: 1.26–1.76 m (8Н, 4СН2
spiro), 1.48 m (1Н, Н1, СН Pent), 1.36–1.61 m (8Н,
4СН2 Pent), 2.14 m (1Н, Н5, СН spiro), 3.84–3.96 d.d
(4Н, 2СН2О). Found, %: С 76.42; Н 10.52. С13Н22О2.
Calculated, %: С 76.36; Н 10.48.
(1.2 mm Hg), d4 0.9582, nD20 1.4657. IR spectrum, ν,
20
cm–1: 1340, 1175–1040, 650. 1Н NMR spectrum, δ, ppm:
0.97 m (3Н, СН3), 1.24–1.80 m (20Н, 4СН2 of cycle
and 6СН2 Alk), 2.06 m (Н5, СН), 3.86–3.98 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 75.64; Н 11.88. С15Н26О2.
Calculated, %: С 75.0; Н 11.67.
5-Cyclopentyl-1,4-dioxaspiro[4.4]nonane (ХIIIa)
was obtained from 15.2 g of compound VIa and 12.4 g
of compound VIII. Yield 15.6 g (79%), bp 144–146°C
5-Cyclohexyl-1,4-dioxaspiro[4.5]decane (ХIVb)
was obtained from 18 g of compound VIIb and 12.4 g
of compound VIII. Yield 16.8 g (75%), bp 149–151°C
(1.2 mm Hg), d420 1.0574, nD20 1.5098. IR spectrum, ν,
(3 mm Hg), d4 1.0474, nD20 1.4884. IR spectrum, ν,
20
1
cm–1: 1200, 1200–1040. Н NMR spectrum, δ, ppm:
1.33–1.84 m (14Н, 3СН2 spiro- and 4СН2 Pent), 1.48 d
(1Н, СН Pent), 2.12 t (1Н, Н5, СН), 3.86–3.94 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 43.42; Н 10.28. С12Н20О2.
Calculated, %: С 73.47; Н 10.2.
1
cm–1: 1040–1200. Н NMR spectrum, δ, ppm: 0.85–
1.64 m (10Н, 5СН2 Hex), 1.30 m (1Н, Н1, СН Hex),
1.32–1.83 m (8Н, 4СН2 spiro), 2.12 m (1Н, Н5, spiro),
3.84–3.96 d.d (4Н, Н2,3, 2СН2О). Found, %: С 74.93;
Н 10.81. С14Н24О2. Calculated, %: С 75.0; Н 10.71.
5-Cyclohexyl-1,4-dioxaspiro[4.4]nonane (ХIIIb)
was obtained from 16.6 g of compound VIb and 12.4 g
of compound VIII. Yield 16.6 g (78%), bp 151–153°C
(3 mm Hg), d420 1.0453, nD20 1.4948. IR spectrum, ν, cm–1:
5-(Bicyclo[2.2.1]heptyl)-1,4-dioxaspiro[4.5]-decane
(ХIVc) was obtained from 19.2 g of compound VIIc
and 12.4 g of compound VIII. Yield 16.2 g (69%),
bp 139–141°C (2 mm Hg), d420 1.003, nD20 1.5140. IR
1
1200–1040. Н NMR spectrum, δ, ppm: 0.82–1.62m
1
spectrum, ν, cm–1: 1200–1055. Н NMR spectrum, δ,
(16Н, 3СН2 spiro- and 5СН2 Hex), 1.28 t (1Н, Н1,
СН Hex), 2.12 m (1Н, Н5, spiro), 3.86–3.94 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 74.25; Н 10.52. С13Н22О2.
ppm: 1.24–1.56 d (8Н, 4СН2 Hept), 1.41 t (1Н, Н2, СН
Hept), 1.43–1.46 d (2Н, Н1,4, 2СН2 Hept), 1.32–1.83 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

ALIMARDANOV, et al.
1158
(8Н, 4СН2 spiro), 2.14 m (1Н, Н5, СН spiro), 3.84–
3.96 d.d (4Н, Н2,3, 2СН2О). Found, %: С 76.25; Н 10.22.
С15Н24О2. Calculated, %: С 76.27; Н 10.17.
%: С 75.0; Н 11.67.
6-Heptyl-2-methyl-1,5-dioxaspiro[4.5]decane
(ХVIа) was obtained from 18.2 g of compound IVe and
18 g of compound X. Yield 15.1 g (59%), bp 134–136°C
(5 mm Hg), d420 0.9575, nD20 1.4638. IR spectrum, ν, cm–1:
1200–1050, 650. 1Н NMR spectrum, δ, ppm: 0.95 t (СН3,
Hept), 1.20 d (3Н, 2-СН3), 1.28–1.55 m (18Н, 3СН2 spiro
and 6СН2 Hept), 1.50–1.72 m (2Н, Н3, СН2), 3.00 m (1Н,
Н6, СН), 3.74–3.93 m (2Н, Н4, СН2О), 4.05 m (1Н, Н2,
СН). Found, %: С 75.72; Н 11.96. С16Н30О2. Calculated,
%: С 75.59; Н 11.81.
5-(6-Methylbicyclo[2.2.1]heptyl)-1,4-dioxaspi-
ro[4.5]decane (ХIVd) was obtained from 20.6 g of
compound VIId and 12.4 g of compound VIII. Yield
15.9 g (64%), bp 137–138°C (1 mm Hg), d420 1.0735,
nD20 1.5165. IR spectrum, ν, cm–1: 1200–1060. 1Н NMR
spectrum, δ, ppm: 1.05 d (3Н, СН3), 1.22–1.58 d (6Н,
3СН2 Hept), 1.36–1.83 m (8Н, 4СН2 spiro), 1.40 t (1Н,
Н2, СН Hept), 1.42–1.44 d (2Н, Н1,4, СН Hept), 2.12 m
(1Н, Н5, СН spiro), 3.86–3.94 d.d (4Н, Н2,3, 2СН2О).
Found, %: С 76.74; Н 10.46. С16Н26О2. Calculated, %:
С 76.8; Н 10.4.
2-Methyl-5-cyclopentyl-1,4-dioxaspiro[4.4]-
nonane (ХVIIа) was obtained from 15.2 g of compound
VIа and 15.2 g of compound IX. Yield 17.3 g (83%),
bp 127–129°C (1.2 mm Hg), d420 1.0523, nD20 1.4971.
5-Methyl-9-(bicyclo[2.2.1]heptyl)-1,4-dioxaspi-
ro[4.5]decane (ХIVe) was obtained from 20.6 g of
compound VIIe and 12.4 g of compound VIII. Yield
14.8 g (59%), bp 130–132°C (1 mm Hg), d420 1.0768,
nD20 1.5112. IR spectrum, ν, cm–1: 2870, 1380 (СН3),
IR spectrum, ν, cm–1: 1200–1040. Н NMR spectrum,
1
δ, ppm: 1.22 t (3Н, СН3), 1.28–1.50 d (4Н, Н6,7, 2СН2
spiro), 1.33–1.62 m (8Н, 4СН2 Pent), 1.81 d (1Н, СН
Pent), 2.83 m (2Н, Н5, СН), 3.32 t (1Н, Н2, ОСН),
3.36–3.61 m (2Н, Н3, СН2О), 3.34–3.36 d (2Н, Н8, СН2).
Found, %: С 74.32; Н 10.64. С13Н22О2. Calculated, %:
С 74.28; Н 10.48.
1
1200–1060 (С–О–С). Н NMR spectrum, δ, ppm:
1.22 d (3Н, СН3С5), 1.23–1.54 m (8Н, 4СН2 Hept),
1.28–1.52 d.d (6Н, 3СН2 spiro), 1.41 t (1Н, Н2, Hept),
1.41–1.43 d (2Н, Н1,4, 2СН Hept), 2.14 m (1Н, Н5, СН
spiro), 3.84–3.96 d.d (4Н, Н2,3, 2СН2О). Found, %:
С 76.75; Н 10.47. С16Н26О2. Calculated, %: С 76.8;
Н 10.4.
2-Methyl-5-cyclohexyl-1,4-dioxaspiro[4.4]-nonane
(ХVIIb) was obtained from 16.6 g of compound VIb and
15.2 g of compound IX. Yield 18 g (80%), bp 147–149°C
(1.2 mm Hg), d420 1.0622, nD20 1.5164. IR spectrum, ν,
1
cm–1: 1200–1040. Н NMR spectrum, δ, ppm: 0.82–
5-Methyl-9-(6-methylbicyclo[2.2.1]heptyl)-1,4-
dioxaspiro[4.5]decane (ХIVf) was obtained from 22 g
of compound VIIf and 12.4 g of compound VIII. Yield
14.4 g (54%), bp 144–145°C (1 mm Hg), d420 1.0525, nD20
1.5068. IR spectrum, ν, cm–1: 2870, 1380, 1360 (СН3),
1200–1050 (С–О–С). 1Н NMR spectrum, δ, ppm: 1.07 d
(3Н, 6-СН3), 1.22 d (3Н, 5-СН3), 1.23–1.54 m (6Н, 3СН2
Hept), 1.26–1.78 m (6Н, 3СН2 spiro) 1.41 t (1Н, Н2, СН
Hept), 1.41–1.43 d (2Н, Н1,4, 2СН Hept), 1.61 t (1Н, Н6,
СН Hept), 2.12 m (1Н, Н5, СН spiro), 3.84–3.96 d.d (4Н,
Н2,3, 2СН2О). Found, %: С 77.27; Н 10.65. С17Н28О2.
Calculated, %: С 77.27; Н 10.6.
1.62 m (10Н, 5СН2 Hex), 1.22 t (3Н, СН3), 1.28 t (1Н,
СН Hex), 2.81 m (1Н, Н5, СН), 3.32 t (1Н, Н2, ОСН),
3.38–3.65 m (2Н, Н3, СН2О), 3.34–3.36 (2Н, Н8, СН2).
Found, %: С 75.24; Н 10.85. С14Н24О2. Calculated, %:
С 75.0; Н 10.71.
2-Methyl-5-(bicyclo[2.2.1]heptyl)-1,4-dioxas-
piro[4.4]nonane (ХVIIc) was obtained from 18 g
of compound VIc and 15.2 g of compound IX. Yield
16.3 g (68%), bp 143–145°C (1.2 mm Hg), d420 1.0478,
nD20 1.5054. IR spectrum, ν, cm–1: 1200–1040. 1Н NMR
spectrum, δ, ppm: 1.22 t (3Н, СН3) 1.22–1.58 d (8Н,
4СН2 Hept), 1.36–1.83 m (6Н, 3СН2 spiro), 1.42 t (1Н,
Н2, СН Hept), 1.43–1.45 d (2Н, Н1,4, 2СН Hept), 2.81
m (1Н, Н5, СН), 3.32 t (1Н, Н2, ОСН), 3.34–3.60 m
(2Н, Н3, СН2О). Found, %: С 76.38; Н 10.23. С15Н24О2.
Calculated, %: С 76.27; Н 10.17.
5-Heptyl-2-methyl-1,4-dioxaspiro[4.4]nonane
(ХVа) was obtained from 18.2 g of compound IVe
and 15.4 g of compound IX. Yield 19.3 g (80%), bp
139–141°C (10 mm Hg), d420 0.9422, nD20 1.4502. IR
spectrum, ν, cm–1: 1170–1050, 660. 1Н NMR spectrum,
δ, ppm: 0.95 t (3Н, СН3, Hept), 1.20 d (3Н, СН3 Ht),
3.04 m (1Н, Н5, СН), 4.05 m (1Н, Н2, СН), 3.73–3.98 m
(2Н, Н3, СН2), 1.28–1.55 m (18Н, 3СН2 spiro and 6СН2
Hept). Found, %: С 74.86; Н 11.73. С15Н28О2. Calculated,
2-Methyl-5-(6-methylbicyclo[2.2.1]heptyl)-1,4-
dioxaspiro[4.4]nonane (ХVIId) was obtained from
19.2 g of compound VId and 15.2 g of compound
IX. Yield 15.8 g (63%), bp 155–157°C (1.2 mm Hg),
d420 1.0467, nD20 1.5102. IR spectrum, ν, cm–1: 1200–
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SYNTHESIS OF HIGHER SPIROACETALS
1159
1
1040. Н NMR spectrum, δ, ppm: 1.07 d (3Н, 6-СН3),
СН2), 3.36–3.61 m (2Н, Н4, СН2О). Found, %: С 75.26;
Н 11.08. С14Н24О2. Calculated, %: С 75.00; Н 10.71.
1.22 d (3Н, 2-СН3), 1.23–1.54 m (6Н, 3СН2 Hept),
1.28–1.52 d.d (4Н, Н6,7, 2СН2), 2.83 d (1Н, Н5, СН),
3.32 d (1Н, Н2, ОСН), 3.35–3.64 d.d (4Н, Н3,8, 2СН2).
Found, %: С 76.65; Н 10.66. С16Н26О2. Calculated, %:
С 76.8; Н 10.4.
2-Methyl-6-cyclohexyl-1,5-dioxaspiro[4.5]dec-
ane (ХIХb) was obtained from 16.6 g of compound
VIb and 18.0 g of compound X. Yield 18.6 g (78%),
bp 147–149°C (1.2 mm Hg), d420 1.0622, nD20 1.5164. IR
1
2-Methyl-5-cyclopentyl-1,4-dioxaspiro[4.5]-decane
(ХVIIIа) was obtained from 16.6 g of compound VIIа
and 15.2 g of compound IX. Yield 18.8 g (84%), bp
134–136°C (1.2 mm Hg), d420 1.0562, nD20 1.5061. IR
spectrum, ν, cm–1: 1460, 1440 (СН2 of cycle), 1380,
spectrum, ν, cm–1: 1200–1040. Н NMR spectrum, δ,
ppm: 0.85–1.64 m (10Н, 5СН2 Hex), 1.22 t (3Н, СН3),
1.30 m (1Н, Н1, СН Hex), 1.32–1.83 m (8Н, 4СН2
spiro), 1.50–1.72 m (2Н, Н3, СН2 Ht), 3.32 t (1Н, Н2,
ОСН), 3.38–3.65 m (2Н, Н4, СН2О). Found, %: С 75.77;
Н 11.11. С15Н26О2. Calculated, %: С 75.63; Н 10.92.
1
1360 (СН3), 1200–1050 (С–О–С). Н NMR spectrum,
δ, ppm: 1.22 t (3Н, СН3), 1.26–1.76 m (8Н, 4СН2 spiro),
1.36–1.61 m (8Н, 4СН2 Pent), 1.48 m (1Н, Н1, СН Pent),
2.81 m (1Н, Н5, СН), 3.32 t (1Н, Н2, ОСН), 3.38–3.65 m
(2Н, Н3, СН2О). Found, %: С 75.34; Н 10.96. С14Н24О2.
Calculated %: С 75.00; Н 10.71.
6-(Bicyclo[2.2.1]heptyl)-2-methyl-1,5-dioxas-
piro[4.5]decane (ХIХc) was obtained from 17.8 g
of compound VIc and 18.0 g of compound X. Yield
16.7 g (67%), bp 159–161°C (1.2 mm Hg), d420 1.0724,
nD20 1.5081. IR spectrum, ν, cm–1: 2870, 1380, 1360
(СН3), 1200–1050 (С–О–С). 1Н NMR spectrum, δ, ppm:
1.20 t (3Н, СН3 Ht), 1.23–1.54 m (6Н, 3СН2 Hept),
1.30–1.53 d (4Н, Н7,8, 2СН2 spiro), 1.43–1.45 d (2Н, Н1,4,
2СН Hept), 2.81 d (1Н, Н6, СН), 3.32 t (1Н, Н2, ОСН),
3.34–3.36 d (2Н, Н9, СН2), 3.36–3.61 m (2Н, Н4, СН2О).
Found, %: С 77.43; Н 11.13. С17Н28О2. Calculated, %:
С 77.27; Н 10.61.
2-Methyl-5-cyclohexyl-1,4-dioxaspiro[4.5]-decane
(ХVIIIb) was obtained from 18 g of compound VIIb
and 15.2 g of compound IX. Yield 18.7 g (79%), bp
150–152°C (1.2 mm Hg), d420 1.0541, nD20 1.5120. IR
spectrum, ν, cm–1: 1460, 1440 (СН2 of cycle), 1380, 1360
(СН3), 1200–1050 (С–О–С). 1Н NMR spectrum, δ, ppm:
0.85–1.64 m (10Н, 5СН2 Hex), 1.22 t (3Н, СН3), 1.30 m
(1Н, Н1, СН Hex), 1.32–1.83 m (8Н, 4СН2 spiro), 3.32 t
(1Н, Н2, ОСН), 3.40–3.68 m (2Н, Н3, СН2О). Найdено,
%: С 75.82; Н 11.12. С15Н26О2. Calculated, %: С 75.63;
Н 10.92.
2-Methyl-6-cyclopentyl-1,5-dioxaspiro[5.5]un-
decane (ХХа) was obtained from 15.6 g of compound
VIIа and 18.0 g of compound X. Yield 20.3 g (85%),
bp 152–154°C (1.2 mm Hg), d420 1.0566, nD20 1.5122.
IR spectrum, ν, cm–1: 2870, 1380 (СН3), 1175–1040
(С–О–С). 1Н NMR spectrum, δ, ppm: 1.22 t (3Н, СН3),
1.28 t (1Н, Н1, СН Pent), 1.33–1.62 m (8Н, 4СН2 Pent),
2.81 m (1Н, Н6, СН), 3.32 t (1Н, Н2, ОСН), 3.34–3.61 m
(4Н, Н4,10, 2СН2). Found, %: С 75.86; Н 11.18. С15Н26О2.
Calculated, %: С 75.63; Н 10.92.
5-(Bicyclo[2.2.1]heptyl)-2-methyl-1,4-
dioxaspiro[4.5]decane (ХVIIIc) was obtained from
19.2 g of compound VIIc and 15.2 g of compound
IX. Yield 17.6 g (70%), bp 161–163°C (1.2 mm Hg),
d420 1.0748, nD20 1.5123. IR spectrum, ν, cm–1: 1200–1050.
1Н NMR spectrum, δ, ppm: 1.22 t (3Н, СН3), 1.24–1.56 d
(8Н, 4СН2 Hept), 1.32–1.83 m (8Н, 4СН2 spiro), 1.41 t
(1Н, Н2, СН Hept), 1.43–1.46 d (2Н, Н1,4, 2СН Hept),
2.14 m (1Н, Н5, СН spiro), 3.32 t (1Н, Н2, ОСН), 3.40–
3.68 m (2Н, Н3, СН2О). Found, %: С 76.86; Н 11.06.
С16Н26О2. Calculated, %: С 76.8; Н 10.4.
2-Methyl-6-cyclohexyl-1,5-dioxaspiro[5.5]
undecane (ХХb) was obtained from 18.0 g of compound
VIIb and 18.0 g of compound X. Yield 18.6 g (74%),
bp 167–169°C (1.2 mm Hg), d420 1.0652, nD20 1.5233.
IR spectrum, ν, cm–1: 2870, 1380 (СН3), 1175–
1040 (С–О–С). 1Н NMR spectrum, δ, ppm: 0.82–1.62 m
(10Н, 5СН2 Hex), 1.22 t (3Н, СН3), 1.28 (1Н, Н1, СН
Hex), 2.81 m (1Н, Н6, СН), 3.32 t (1Н, Н2, ОСН), 3.34–
3.36 d (2Н, Н10, СН2), 3.38–3.61 m (2Н, Н4, 2СН2О).
Found, %: С 76.39; Н 11.24. С16Н28О2. Calculated, %:
С 76.19; Н 11.11.
2-Methyl-6-cyclopentyl-1,5-dioxaspiro[4.5]decane
(ХIХа) was obtained from 15.2 g of compound VIа and
18.0 g of compound X. Yield 18.7 g (84%), bp 132–134°C
(1.2 mm Hg), d420 1.0648, nD20 1.5092. IR spectrum, ν,
cm–1: 1200–1040. 1Н NMR spectrum, δ, ppm: 1.22 t (3Н,
СН3), 1.26–1.76 m (8Н, 4СН2 spiro), 1.28–1.50 d (4Н,
Н7,8, 2СН2), 1.48 m (1Н, Н1, СН Pent), 1.36–1.61 m (8Н,
4СН2 Pent), 1.50–1.72 m (2Н, Н3, СН2 Ht), 2.81 m (1Н,
Н6, СН), 3.32 t (1Н, Н2, ОСН), 3.32–3.36 d (2Н, Н9,
6-(Bicyclo[2.2.1]heptyl)-2-methyl-1,5-dioxas-
piro[5.5]undecane (ХХc) was obtained from 19.2 g
of compound VIIc and 18.0 g of compound X. Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

ALIMARDANOV, et al.
1160
17.1 g (65%), bp 181–183°C (1.2 mm Hg), d420 1.0744,
nD20 1.5184. IR spectrum, ν, cm–1: 2870, 1380, (СН3),
1200–1040 (С–О–С). 1Н NMR spectrum, δ, ppm: 1.22 t
(3Н, СН3), 1.24–1.56 d (8Н, 4СН2 Hept), 1.32–1.83 m
(8Н, 4СН2 spiro), 1.43–1.46 d (2Н, Н1,4, 2СН Hept),
2.14 m (2Н, Н6, СН spiro), 3.32 t (1Н, Н2, ОСН), 3.36–
3.68 m (2Н, Н4, СН2О). Found, %: С 77.45; Н 10.83.
С17Н28О2. Calculated %: С 77.27; Н 10.61.
Shamshurin, A.A. and Primer, M.Z., Fiziko-khimicheskie
svoistva organicheskikh yadokhimikatov i regulyatorov
rosta rastenii. Spravochnik (Physical and Chemical Prop-
erties of Organic Pesticides and Plant Growth Regulators.
Handbook), Moscow: Nauka, 1966; Zumach, G., Kuchle,
E., and Behnenz, W., US Patent 2113454, 1972; Chem.
Abstr., 1972, vol. 77, 164665m.
6. Piter, K. and Erlis, R., Inventor’s Certificate 587839, 1978;
SSSR Byull. Izobr., 1978, no. 1; Shulijin, Y., Wenlong, T.,
Dihai, Ch., and Jutang, S., Rare Metal Mater. Eng., 2005,
vol. 34, p. 157; Ref. Zh. Khim., 2007, no. 10, B4.128.
7. Shulijin, Y., Wenlong, T., and Guojin, Y.J., Univ. Sci. Tech-
nol. Beijing, 2006, vol. 28, p. 278; Ref. Zh. Khim., 2007,
B4.472.
8. Li-ping, Z., J. Shanxy Univ. Natur. Sci. Ed., 2006, vol. 29,
p. 294. Ref. Zh. Khim., 2007, vol. 24, B.4.124.
9. Waller, D.L., Stephenson, C.R.J., and Wipf, P., Org. Biomol.
Chem., 2007, vol. 5, p. 58
2-Methyl-6-(6-methylbicyclo[2.2.1]heptyl)-1,5-di-
oxaspiro[5.5]undecane (ХХd) was obtained from 20.6 g
of compound VIId and 18.0 g of compound X. Yield
17.1 g (62%), bp 193–195°C (1.2 mm Hg). IR spectrum,
ν, cm–1: 2870, 1380, 1355 (СН3), 1200–1050 (С–О–С).
1Н NMR spectrum, δ, ppm: 1.07 d (3Н, СН3 Hept), 1.22 t
(3Н, СН3 Ht), 1.23–1.54 m (6Н, 3СН2 Hept), 1.28–1.53 d
(6Н, 3СН2 spiro), 1.43–1.45 d (2Н, Н1,4, 2СН Hept),
2.81 d (1Н, Н6, СН), 3.32 t (1Н, Н2, ОСН), 3.34–3.36 d
(2Н, Н10, СН2), 3.36–3.61 m (2Н, Н4, СН2О). Found,
%: С 77.85; Н 10.92. С18Н30О2. Calculated, %: С 77.69;
Н 10.79.
10. Sykes, P., A Guidebook to Mechanism in Organic Chem-
istry, 2nd edn., London: Longmans, 1966.
11. Delmal, B., J. Therm. Anal. Calorim., 2007, vol. 90; Ma-
vrov, M.V. and Zlotin, S.G., Khim. Geterotsikl. Soedin.,
2006, p. 677; Sayama, S., Tetrahedron Lett., 2006, p. 4001.
12. Suleimanova, E.T., Mekhtiev, S.D.., Musaev, M.R., Ali-
mardanov, Kh.M., Kasumov, L.I., Abbasov, M.F., and
Mirgasanova, M.I., Neftekhimiya, 1979, 19.815; Abbasov,
M.F., Alimardanov, Kh.M., and Suleimanova, E.T., Zh.
Prikl. Khim., 1997, vol. 70, p. 648.
13. Alimardanov, Kh.M.,Abbasov, M.F., Velieva, F.M., Dzha-
farova, N.A., and Sadygova, R.Sh., Neftekhimiya, 2004,
vol. 44, p. 170.
14. Alimardanov, Kh.M., Abbasov, M.F., Suleimanova, E.T.,
and Dzhafarova, N.A., Protsessy neftekhimii i nefteper-
erabotki (The processes of Petrochemical and Oil Refining),
2002, p. 71; Ref. Zh. Khim., 2004, vol. 3, 19B4.252.
15. Rakhmankulov, D.L., Musavirov, R.S., and Kantor, E.A.,
Khim. Geterotsikl. Soedin, 1970, p. 856.
16. Bellamy, L.J., The Infra-Red Spectra of Complex Molecules,
London: Methuen, 1958.
17. Gordon, A.J. and Ford, R.A., The Chemist’s Companion,
New York: Wiley, 1972.
18. Gasanov,A.I.,Aliev, V.M., Korobov, N.A., Talybov, G.M.,
Gulieva, E.T., Bairamov, R.N., and Alimardanov, Kh.M.,
Inventor’s Certificate 1468585, 1988; SSSR Byull. Izobr.,
1989, no. 12.
19. Sadygov, O.A. and Chalabiev, Ch.A., Inventor’s Certificate
1728250, 1990 SSSR Byull. Izobr., 1991, no. 15.
20. Ionin, B.I. and Ershov, B.A., YaMR spektry v organicheskoi
khimii (NMR Spectra in Organic Chemistry), Moscow:
Khimiya, 1967.
REFERENCES
1. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs), Mos-
cow: 2000, vols. 1, 2; Giller, S.A., Venter, N.K., and Kol-
berga, R.Yu., Ispol’zovanie pentozasoderzhashchego syr’ya
(Application of Pentosa Containinf Raw), Riga: Zinatne,
1976; Nakaguchi, G.M., Wang-Ting-J., and Caseric, F.F.,
US Patent 3832356, 1972. Ref. Zh. Khim., 1975, 13r49P.
2. Kheifits, L.A. and Dashunin, V.M., Dushistye veshchestva i
drugie produkty parfyumerii (Fragrances and Other Perfum-
ery Products), Moscow: Khimiya, 1994; Voitkevich, S.A.
and Kheifits, L.A., Ot drevnikh blagovonii k sovremennym
parfyumerii i kocmetike (FromAncient Incense to Modern
Perfumes and Cosmetics), Moscow: Pishch. Promyshlen-
nost’, 1997; Vyglazov, O.G., Chuiko, V.A., Izotova, L.V.,
Vintarskaya, M.V., and Yudenko, R.A., Zh. Prikl. Khim.,
2001, vol. 74, p. 1829
3. Luknitski, F.L., Chem. Rev., 1975, vol. 75, p. 259.
4. Shrot, V., Khim. Geterotsikl. Soedin., 1985, p. 1443.
5. Kul’nevich, V.G., Zelikman, Z.I., Kalashnikova, V.G.,
Pyatashova, D.N., and Torkler, D., Inventor’s Certificate
702020, 1979; SSSR Byull. Izobr., 1979, no. 45; Cha-
lova, O.B., Kantor, E.A., Maksimova, N.E. Rakhmanku-
lov, D.P., Syrkin, A.M., and Chistoedova, G.P., Inventor’s
Certificate 771098, 1979; SSSR Byull. Izobr., 1980, no. 38;
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