Study of induced hypohalogenation of 1-alkyl(4-methylcyclohex-1-enyl) alkanones, and chemical transformations of the obtained compounds

Article abstract of DOI:10.1134/S1070363209080180

Induced hydroxyhalogenation of alkyl cyclohexenyl ketones in the systems [MHlg-HX or HHlg]-H₂O₂ or (NaClO) was performed and the optimal conditions of this reaction were elucidated. It is established that in the system in situ is induced a hypohaloid acid HClO or HBrO is produced that then enters into electrophilic addition at the ring double bond affording hydroxyhalo derivatives of the cycloaliphatic ketones. The alkyl cyclohexenyl ketone chloro(bromo)hydrines and the oxiranes obtained from them are very reactive compounds and can be used as initial compounds for the synthesis of many individual organic compounds.

Full text of DOI:10.1134/S1070363209080180

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1691–1697. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © O.A. Sadygov, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 8, pp. 1331–1337.
Study of Induced Hypohalogenation
of 1-Alkyl(4-methylcyclohex-1-enyl)alkanones,
and Chemical Transformations of the Obtained Compounds
O. A. Sadygov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Republic Azerbaidjan,
pr. Khodzhaly 30, Baku, AZ 1025 Azerbaidjan
e-mail: omar.sadıqov@gmail.com
Received December 4, 2008
Abstract—Induced hydroxyhalogenation of alkyl cyclohexenyl ketones in the systems [MHlg–HX or HHlg]–
H2O2 or (NaClО) was performed and the optimal conditions of this reaction were elucidated. It is established
that in the system in situ is induced a hypohaloid acid HClO or HBrO is produced that then enters into
electrophilic addition at the ring double bond affording hydroxyhalo derivatives of the cycloaliphatic ketones.
The alkyl cyclohexenyl ketone chloro(bromo)hydrines and the oxiranes obtained from them are very reactive
compounds and can be used as initial compounds for the synthesis of many individual organic compounds
DOI: 10.1134/S1070363209080180
Ketones possessing halogen atoms are synthons in
organic syntheses and find application in producing
medicine preparations and biologically active
substances [1, 2].
work is aimed at the study of the reaction of hydroxy-
halogenation of alkyl(4-methylcyclohexene-1-yl)
ketones under the conditions of a system that induces
hypohaloid acids HOHlg. For this purpose [МHlg +
HX] + Н2О2 or NaClO were used .
The reaction of electrophilic addition of the
fragments of hypohaloid acids to unsaturated
compounds has been considered in details in
monography [3]. According to [4], solvohalogenation
of unsaturated compounds with N-chloro- and N-
bromosuccinimide in aqueous medium follows an
electrophilic mechanism and leads to the formation of
the corresponding chloro(bromo)hydrines. Hydroxyhalo-
genation is applied widely in the chemistry of natural
compounds [5, 7], with the use of solvents like acetone
[8], acetonitrile [9] and dimethylsulfoxide [10–12]. As
the sources of halogen the synthesized preliminary N-
chloro- and N-bromo-succinimides commonly are
used.
The synthesis of initial compounds was carried out
along the commonly used procedure [13, 14].
Application to this reaction as a catalyst of highly
disperse SnCl4 on a solid carier НNa–modernit instead
of commonly used soluble salts allowed to carry out
this reaction selectively at higher temperature, –10 to
0°C against –32 to –25°C that was commonly applied,
along Scheme 1:
Scheme 1.
O
catalyst
C−R
H3C
H3C
+ RCOCl
_HCl
Iа_Ig
It should be noted that in the literature are
practically no data on the hydroxyhalogenation of
alkyl cyclohexenyl ketone under the conditions of
induction of electrophilic reagents. Now the search of
more effecttive oxidation systems allowing to produce
electrophilic reagents (HOHlg) is actual for realization
of low temperature liquid phase hydroxyhalogenation
of unsaturated compounds for practical purposes. This
R =CH3 (а); C2H5 (b); C3H7 (c); C4H9 (d); C5H11 (e); C6H13 (f);
C7H15 (g).
Physicochemical constants of the synthesized alkyl
(4-methylcyclohexene-1-yl) ketones (Table 1) are con-
sistent with the published data [14], the results of
elemental analysis confirm the composition of products.
1691

1692
SADYGOV
Earlier we have shown that NaBr (or KBr) and
found that the yield of chloro(bromo)hydrines depends
on the concentration of hydrohalogenic acids and
temperature (Tables 2 and 3).
hypochlorous (hypobromous) acids in the presence of
oxidizers Н2О2 or NаОCl are effective halogenating
agents of butenylbenzenes both at the aromatic ring
and at the multiple bond of the side chain [15], while
their low concentration solutions are effective
hydroxyhalogenating agents for vinyl- and allyl-
acetylene com-pounds [16].
The data of Table 2 show that sufficiently high
yield of chlorohydrines (up to 92%) is provided at the
use of 6–10% aqueous solution of hydrochloric acid.
Increase in the acid concentration to 15–36% results in
decrease in the yield of chlorohydrines to 39%. Similar
results were obtained with hydrobromic acid and its
salts (NaBr, CoBr2). A high yield (up to 90%) of
bromohydrines can be obtained with 8% solution of
HBr (NaBr). Increase in the acid concentration above
8% leads to a decrease in the yield of the bromohydrines
by approximately 48%, probably owing to intensifica-
tion of formation of molecular halogen (Cl2 or Br2).
Electrophilic addition of the latter at the double bond
of cyclohexene fragment of ketone molecule leads to
formation of the alkyl cyclohexyl ketone dichloro or
dibromo derivatives, respectively.
We found that with low concentration solutions of
halides in the presence of oxidizers the alkyl (4-
methylcyclohexene-1-yl) ketones form in a sufficiently
high yield the respective products of hydroxy-
halogenation along the Scheme 2:
Scheme 2.
R_C=O
H3C
The data of Table 3 show that the increase in
temperature from 20°C to 40°C enhances the yield of
chloro- and bromohydrines by 10–12%, while the
increase in the temperature to 50°C (and over)
decreases the yield of the target compound by
approximately 5–6% due to the inten-sification of non-
productive decomposition of hypo-halogenic acids.
Iа_Ig
R_C=O
H
6
+[MHlg + HX + H2O2 ] or NaOCl
1
Hlg
5
3
2
4
H
H
H3C
OH
Structures of the synthesized alkyl cyclohexyl
ketone chloro- and bromohydrines (IIа–IIg, IIIа–IIIg)
are confirmed by the elemental analyses, physico-
IIа_IIg, IIIа_IIg
Hlg = Cl (IIа–IIg); Br (IIIа–IIIg), Х = НSO4–, NO3–, RSO3–,Cl–,
Br–, Me = Na, K, Co.
1
chemical constants, IR and Н and 13С NMR spectral
data. In the IR spectra of the synthesized halohydrines
besides the bands of stretching vibrations of CH, CH2,
and CH3 appear the absorption bands at 3615, 1725,
and 800–650 cm–1 characteristic of O–H, C=O, C–Cl,
and C–Br bonds respectively. The bands of stretching
vibrations of С=С bond in the region of 1630–
For estimating the relative reactivity of 1-(4-methyl-
cyclohexen-1-yl)alkanones in the reactions of induced
hypohalogenation and elucidating optimal conditions
of the process of the halohydrine synthesis we studied
the effect of various parameters on the yield of the
chloro(bromo)hydrines. By these experiments we
1
1650 cm–1 were not observed. In the Н NMR spectra
Table 1. Yields, physicochemical constants and elemental analyses of 4-methyl cyclohexenyl ketones
Found, %
Calculated, %
C H
Comp.
no.
Yield,
%
bp, °С
d420
n820
Formula
(3 mm Hg)
С
78.41
78.74
79.35
79.85
80.36
80.48
81.25
H
72.6
66.4
54.6
46.5
40.6
35.8
32.6
57–59
65–67
1.4841
1.4762
1.4743
1.4726
1.4687
1.4662
1.4643
0.9686
0.9543
0.9385
0.9324
0.9232
0.9116
0.9886
10.33
10.85
10.36
11.28
11.42
11.66
11.92
С9Н14О
С10Н16О
С11Н18О
С12Н20О
С13Н22О
С14Н24О
С15Н26О
78.26
78.95
79.52
80.01
80.41
80.54
81.08
10.14
10.53
10.84
11.14
11.34
11.54
11.71
Iа
Ib
Ic
Id
Ie
If
75–77
83–85
96–98
110–112
123–125
Ig
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

STUDY OF INDUCED HYPOHALOGENATION
1693
Table 2. Dependence of chloro(bromo)hydrine yield on the concentration of chloro(bromo)hydrygen acid (4-methyl-
cyclohexenylketone : HHlg : Н2О2 = 0.2:0.24:0.24, temperature 30°C, rate of feeding H2O2 10 g h–1 , τ 6 h)
Yield of halohydrines, %
chlorohydrines
bromohydrines
а
b
c
d
e
f
g
а
b
c
d
e
f
g
6
10
15
25
36
82.6
92.5
75.6
53.8
46.7
80.5
88.6
73.2
51.6
44.6
76.6
85.4
71.4
50.4
43.2
73.4
83.6
70.6
49.5
42.6
70.8
81.4
68.7
49
70
68.6
85.6
90.6
73.6
52.4
48.6
42.6
82.5
87.8
70.5
50.6
46.5
38.4
78.6
86.5
68.4
48.4
43.8
36.7
75.4
86.0
67.6
48.6
43.2
35.8
72.6
82.8
67
72
70
6
8
80.6 78.8
80
77.6
67
68
48
66
66.4
48.3
44.8
31.8
15
47.6
50.2
45.4
33.6
46.8 25
42.6 33
30.4 46
40.6
40.6 40
Table 3. Effect of temperqature on the yield of chloro(bromo)hydrines (ratio alkyl cyclohexenyl ketone : MHlg(HHlg) : H2O2
(NaОCl) = 0.2 : 0.24 : 0.24; concentration of solutions: 10% HCl, 8% HBr, 10% NaBr or 10% CoBr2; reaction duration 6 h,
rate of feeding H2O2 10 g h–1 (NaOCl 25 g h–1)
Yield of halohydrines, % a
Temperature,
°С
а
b
c
d
e
f
g
20
30
40
50
75.6/79.5
80.4/82.6
92.5/90.8
86.7/84.6
73.4/76.6
77.6/78.5
88.6/86.5
82.5/83.8
71.6/73.5
74.5/76.3
84.6/85.4
78.7/82.4
69.5/74.7
72.8/73.6
81.6/83.8
75.8/80.7
67.7/75.3
71.4/69.8
80.4/82.6
73.6/81.3
65.6/69.8
68.7/68.4
78.4/80.6
72.3/78.7
64.8/67.5
66.8/67.9
75.6/78.6
70.5/73.6
a (Clorohydrine/bromohydrine).
of compounds IIа–IIg and IIIа–IIIg there are the
signals at δ 3.70 and 3.81 ppm assignable to the geminal
protons in a-position to Cl or Br atom and to the
oxygen atom of hydroxy group. The protons of
hydroxy groups are characterized by the signals at δ
2.1 and 4.81 ppm. These spectral data show that the
alkyl cyclohexenyl ketone chloro(bromo)hydrines
contain in approximately equal amounts of two
sifficultly separable isomers, 1-oxoalkyl(е)-trans-1-
Hlg(а)-cyclohexan-2-ol(а) and 1-oxoalkyl(е)-trans-2-
Hlg(а)-cyclohexan-1-ol(а)-1 differ by the positions of
the halogen and the hydroxy group.
spectra, as well as by the independent synthesis:
epoxidation of 4-methyl cyclohexenyl alkanols Iа–Ig
with 30% dioxane solution of Н2О2 and СН3СООН in
the presence of chlorine-containing acid cationite KU-
2×8 or KU-2×8p at the mole ratio substrate : Н2О2 :
СН3СООН = 1:1.2:0.5, followed by hydrolysis of the
obtained oxiranes in the presence of acid catalysts
(RSO3H, KU-2) into the corresponding diols Va–Vg.
Thus, we showed that the synthesized methylcyclo-
hexenylalkanone chloro- and bromohydrines IIа–IIg,
IIIа–IIIg can be widely used not only for obtaining
epoxides but also for the synthesis of various poly-
functional alicyclic ketones.
We found that both chloro- and bromohydrines
IIа–IIg and IIIа–IIIg at treatment with powdered
potassium hydroxide readily suffer dehydrohalo-
genation affording respective oxiranes (85.3–96.5%)
while at the action of aqueous alkali they are
transformed into trans-diols (78.6–92.4%) (Scheme 3).
EXPERIMENTAL
The IR spectra of the synthesized compounds were
1
taken on a UR-20 spectrometer, the Н and 13С NMR
spectra on the spectrometer BS-487C with operating
frequency for protons 80 MHz. Internal reference
HMDS, solvent CCl4.
Composition and structure of the oxiranes IVa–
IVg and diols Va–Vg are confirmed by the data of
elemental analysis and by the IR and 1Н and 13С NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1694
SADYGOV
Scheme 3.
R−C
=O
H
6
1
5
solid KOH, 30_60oС
3
O
2
4
anhydrous Et2O
H
H3C
H
IVа_IVg
H+ HOH
IIа_IIg + IIIа_IIIg
OH
H
H
C_R
O
6
1
5
3
15_20% KOH (NaOH)
boiling
2
4
H
H3C
HO
Vа_Vg
The composition and purity of initial and
synthesized compounds were tested by TLC on Silufol
UV-254 plates (eluent benzene–diethyl ether, 3–5:1 by
volume, developing with iodine) and GLC on a
chromatograph LKhM-8MD, column 0.3×200 cm,
stationary phase Chromaton N-AW DMCS with 5% of
silicon XE-60, carrier gas helium, flow rate 40 ml min–1.
For the signal assignment in the 13C NMR spectra were
used the data of [17].
adding 15–20% solution of potassium (sodium) hyd-
roxide. Yields, elemental compositions and physico-
chemical constants of chloro(bromo)hydrines are listed
in Tables 2–4.
4-Methyl-1-acetyl-1,2-epoxycyclohexane (IVa) was
obtained from 8.7 g (0.05 mol) of IIа or 11 g (0.05
mol) of IIIа. Yield from IIа 6.5 g (83.6%) and from
IIIа, 7.0 g (90. 8%), bp 81–83°C (5 mm Hg). IR
spectrum, ν, cm–1: 920, 1250, 1260 (oxirane), 1723,
1
1730 (С=О). H NMR spectrum, δ, ppm: 1.07 d (3Н,
4-Methyl cyclohexyl ketone halohydrines (IIа–
IIg, IIIа–IIIg). To a flask at the studied temperature
was loaded 0.15–0.2 mol of 6–10% HCl solution for
the synthesis of chlorohydrine or 6–8% HBr, (MBr +
HBr) solution for the synthesis of bromohydrine, and
0.1 mol of a compound Iа–Ig. From a dropping funnel
at vigorous stirring of reaction mixture was added
0.15–0.22 mol of hydrogen peroxide as 26–30%
aqueous solution (feeding rate 10 g h–1) or 124.2 g of
18.5% solution of sodium hypochlorite (0.2 mol,
content of active chlorine 110 g-ion l–1). Stirring was
continued for 5–6 h. The reaction was stopped after
complete consumption of oxidizer (test by
permanganatometry or iodometry [18]). Then organic
layer was separated from aqueous layer, the aqueous
layer was extracted with ether (2×50 ml). Etheral
extracts were combined with organic layer, neutralized
with 10% aqueous Na2CO3, dried over magnesium
sulfate and after distilling ether off the mixture of
halohydrine isomers was separated. The chloro- and
bromohydrines obtained were then used for
preparation of respective 1-(4-methyl-7-oxabicyclo-
[4.1.0]hept-1-yl)alkanones IVa–IVg by adding to the
reaction mixture of potassium hydroxide, and 1-(1,2-
dihydroxy-4-methylcyclohexyl)alkanols Va–Vg by
СН3), 2.1 s (3Н, СН3), 1.62 d (1Н, СН), 1.28–1.92 d
(6Н, СН2), 3.1 t (1Н, СН). 13C NMR spectrum, δ,
ppm: 210.5 (С7), 61.3 (С1), 57.5 (С2), 35.6 (С3), 30.2
(С4), 29.2 (С5), 26.2 (С6), 22.5(С8), 20.4 (С9). Found,
%: С 70.53, Н 9.32. С9Н14О2. Calculated, % : С 70.13,
Н 9, 09.
4-Methyl-1-propanoyl-1,2-epoxycyclohexane (IVb)
was obtained from 9.5 g (0.05 mol) of IIb or 11.7 g
(0.05 mol) of IIIb. Yield from IIb 6.9 g (82.6%) and
from IIIb, 7.4 g (87.4%), bp 108–110°C (5 mm Hg).
IR spectrum, ν, cm–1: 863, 920, 1260 (oxirane), 1730,
1
1722, 1704 (С=О). H NMR spectrum, δ, ppm: 1.07 d
(6Н, 2СН3), 1.62 d (1Н, СН), 1.28–1.92 d (6Н, 3СН2),
3.1 t (1Н, СН), 2.50 d.d (2Н, СН2С=О). 13C NMR
spectrum, δ, ppm: 215.9 (С7), 61.2 (С1), 57.7 (С2),
35.6 (С3), 30.2 (С4), 29 (С5), 28.7 (С8), 26.5 (С6), 20.4
(С10), 8.6 (С9). Found, % : С 71.78, Н 9.85. С10Н16О2.
Calculated, % : С 71.43, Н 9.52.
4-Methyl-1-butanoyl-1,2-epoxycyclohexane (IVc)
was obtained from 10.2 g (0.05 mol) of IIc or 12.4 g
(0.05 mol) of IIIc. Yield from IIc 7.3 g (80%) and
from IIIc 7.7 g (84.7%), bp 122–124°C (5 mm Hg). IR
spectrum, ν, cm–1: 920, 1250, 1260 (oxirane), 1704,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

STUDY OF INDUCED HYPOHALOGENATION
1695
Table 4. Physicochemical constants and elemental composition of the synthesized alkyl cyclohexyl ketone chloro(bromo)-
hydrines
bp, °С
Found, %
H
Calculated, %
H
Comp.
no.a
(mm Hg),
mp, °С
Formula
C
Cl(Br)
C
Cl(Br)
74–76
62.06
63.82
65.34
66.76
67.88
69.05
69.86
49.64
51.83
53.76
55.42
56.92
58.41
59.67
8.83
9.32
20.65
19.06
17.85
16.67
15.84
14.87
13.96
36.86
34.67
32.65
30.86
29.36
28.05
26.78
C9H15OCl
C10H17OCl
C11H19OCl
C12H21OCl
C13H23OCl
C14H25OCl
C15H27OCl
C9H15OBr
C10H17OBr
C11H19OBr
C12H21OBr
C13H23OBr
C14H25OBr
C15H27OBr
61.89
63.66
65.19
66.51
67.69
68.71
69.63
49.32
51.50
53.44
55.17
56.73
58.13
59.41
8.60
9.02
9.38
9.70
9.98
10.22
10.44
6.85
6.44
7.69
8.05
8.36
8.65
8.91
20.34
18.83
17.53
16.39
15.40
14.52
13.73
36.53
34.33
32.39
30.65
29.09
27.68
26.40
IIа
89–91
IIb
IIc
101–102
112–114
127–128
136–138
149–151
113–114
122–124
135–137
146–147
156–158
167–169
180–181
9.57
10.08
10.14
10.43
10.75
7.03
IId
IIe
IIf
IIg
IIIа
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
6.75
7.92
8.37
8.64
8.93
9.06
a IIа–IIg chlorohydrins, IIIa–IIIg bromohydrines.
1
1723, 1730 (С=О). H NMR spectrum, δ, ppm:0.97 t
(3Н, СН3), 1.06 d (3Н, СН3), 1.61 d (2Н, 2СН), 1.28–
1.92 d (8Н, 4СН2), 2.47 d.d (2Н, СН2С=О). 13C NMR
spectrum, δ, ppm: 215.9 (С7), 61, 0 (С1), 57.8(С2),
36.5 (С8), 35.4 (С3), 30.1 (С4), 29.1 (С5), 26.6 (С6),
20.5 (С11), 17.5 (С9), 13.6(С10). Found, %: С 72.83, Н
9.13. С11Н18О2. Calculated, %: С 72.53, Н 8.89.
4-Methyl-1-heptanoyl-1,2-epoxycyclohexane (IVf)
was obtained from 12.2 g (0.05 mol) of IIf or 14.5 g
(0.05 mol) of IIIf. Yield from IIf 7.8 g (77.5%) and
from IIIf 8 g (79.9%), mp 102–104°C. Found, %: С
75.42, Н 11.22. С14Н24О2. Calculated, %: С 75.0, Н
10.71.
4-Methyl-1-octanoyl-1,2-epoxycyclohexane (IVg)
was obtained from 13 g (0.05 mol) of IIg or 15.2 g
(0.05 mol) of IIIg. Yield from IIg 9.2 g (77%), mp
113–115°C. Found, %: С 75.92, Н 11.08. С15Н26О2.
Calculated, %: С 75.63, Н 10.92.
4-Methyl-1-pentanoyl-1,2-epoxycyclohexane (IVd)
was obtained from 10.8 g (0.05 mol) of IIg or 13.1 g
(0.05 mol) of IIId. Yield from IId 7.4 g (74.5%) and
from IIId 8.1 g (82.6%), mp 81–83°C. IR spectrum, ν,
cm–1: 863, 920, 1260 (oxirane), 1704, 1723, 1730
Diols Va–Vg from halohydrines and from
oxiranes IVа–IVg. To a solution of 2.2 g of NaOH (or
КОН) in 15 g of water was added 0.05 mol of
respective compound IIа–IIg or IIIа–IIIg, and after
stirring for 4 h at 50–60°C the solution was saturated
with potassium carbonate and by extraction with ether
were isolated diols Va–Vg. The ether solutions were
dried over calcined potassium carbonate, ether was
removed and the products were distilled in a vacuum.
The diols formed crystallized in the receiver.
1
(С=О). H NMR spectrum, δ, ppm: 0.97т (3Н, СН3),
1.05 d (3Н, СН3), 1.27–1.93 d (10Н, 5СН2), 2.46 d.d
(2Н, СН2С=О), 3.1 t (1Н, СН), 13C NMR spectrum, δ,
ppm: 216 (С7), 61.2 (С1), 57.8 (С2), 35.6 (С3), 34 (С8),
30.2(С4), 29.1 (С5), 26.5 (С6), 26.3 (С9), 22.2 (С10),
20.4 (С12), 13.8 (С11). Found, %: С 73.67, Н 10.6.
С12Н20О2. Calculated, %: С 73.47, Н 10.2.
Identical spectral characteristics are obtained for
compounds IVe–IVg.
For the synthesis of diols Va–Vg from oxiranes, to
0.05 mol of a compound IVa–IVg was added 2 g of
water and 2–3 g of catalyst (RSO3H, KU-2), the
mixture was stirred at 50–60°C for 3.5–4.5 h, and then
after crystallizadion according to the procedure in [19]
the respective diol was isolated.
4-Methyl-1-hexanoyl-1,2-epoxycyclohexane (IVe)
was obtained from 11.5 g (0.05 mol) of IIe or 13.8 g
(0.05 mol) of IIIe. Yield from IIe 7.8 g (74.6%) and
from IIIe 11.3 g (81.5%), mp 90–93°C. Found, %: С
74.61, Н 10.67. С13Н22О2. Calculated, %: С 74.29, Н 10.48.
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SADYGOV
1,2-Dihydroxy-4-methyl-1-acetylcyclohexane (Va)
Yield 9.8 g (80.8%), mp 166–167°C. Found, %:
С69.83, Н 11.12. С14Н26О3. Calculated, %: С 69.42, Н
10.74.
was obtained from 11 g (0.05 mol) of IIIа or 7.7 g
(0.05 mol) of IVa. Yield from IIIа 7.9 g (83%) and
from IVa 7.9 g (92%), mp 110–112°C. IR spectrum, ν,
1,2-Dihydroxy-4-methyl-1-octanoylcyclohexane
(Vg), was obtained from 12 g (0.05 mol) of IVg. Yield
10.1 g (78.6%), mp 176–178°C. Found, %: С 70.82, Н
11.08. С15Н28О3. Calculated, %: С 70.31, Н 10.94.
1
cm–1: 974, 1100, 3615, 3625 (ОН), 1723 (С=О). H
NMR spectrum, δ, ppm: 1.07 d (3Н, СН3), 1.60 d (1Н,
СН), 1.27–1.97 d (6Н, 3СН2), 2.02 d (1Н, ОН), 2.1 s
(3Н, СН3), 4.81 br.s (1Н, ОН). 13C NMR spectrum,
210 (С7), 94.2 (С1), 70.3 (С2), 36 (С3), 27.3 (С5), 26.8
(С6), 23(С8), 21 (С9). Found, % : С 63.12, Н 9.75.
С9Н16О3. Calculated, % : С 62.79, Н 9.3.
REFERENCES
1. Pilgram, K. and Kendall Hass, D., J. Med. Chem., 1975,
vol. 18, p. 1204.
1,2-Dihydroxy-4-methyl-1-propanoylcyclohexane
(Vb) was obtained from 11.7 g (0.05 mol) of IIIb or
9.3 g (0.05 mol) of IVb. Yield from IIIb 7.5 g (80%)
and from IVb 8.3 g (89%), mp 122–124°C. IR
spectrum, ν cm–1: 818, 974, 1100, 3615, 3625 (ОН),
2. Kalyagina, G.F., Glazunova, N.I., Meshcheryakov, V.M.,
Govrilov, L.K., and Vereshchagin, L.I., Khim-Farm.
Zh., 1981, no. 2, p. 46.
3. de la Maar, P. and Bolton, R., Elektrofil’noe prisoedi-
nenie
k nenasyshchennym sistemam (Electrophilic
1
1723 (С=О). Н NMR spectrum, δ, ppm: 1.07 d (6Н,
Addition to Ansaturated Systems), Moscow: Mir, 1968.
2СН3), 1.62 d (1Н, СН), 2.01 d (1Н, ОН), 2.46 d.d
(2Н, СН2С=О), 3.48 t (1Н, СН), 4.81 br.s (1Н, ОН),
13C NMR spectrum, 215.8 (С7), 94.2 (С1), 70.2 (С2),
36 (С3), 29 (С8), 28.4 (С4), 27.2 (С5), 26.9 (С6), 21
(С10), 8.6 (С9). Found, %: С 65.08, Н 10.06. С10Н18О3.
Calculated, %: С 64.52, Н 9.68.
4. Kovalov, I.V., Zh. Org. Khim., 2002, vol. 38, no. 3,
p. 327.
5. Kzishnaswamy, R.N. and Vilaya, K.K., Indian J.
Chem., B, 1989, vol. 28, no. 8, p. 664.
6. Yamauchi, S. and Taniguchi, E., Biosci., Biotechnol.,
Biochem., 1992, vol. 56, no. 11, p. 1751.
1,2-Dihydroxy-4-methyl-1-butanoylcyclohexane
(Vc) was obtained from 9.1 g (0.05 mol) of IVc. Yield
8.7 g (86.6%), mp 134–136°C. IR spectrum, ν, cm–1:
7. Tsubuki, M., Kanai, K., and Konda, T., Chem.
Commun., 1992, no. 22, p. 1640.
8. Cotterill, C.I., Dorman, G., Faber, K., Jaouhari, R.,
Roberts, M.S., Scheinmann, F., Spreitz, J., Suther-
land, G.A., Winders, A.J., and Wakefield, J.B., Chem.
Commun., 1990, no. 23, p. 1661.
9. Knapp, S. and Kukkola, J.P., J. Org. Chem., 1990,
vol. 55, p. 1632.
10. Xong, R.J., Codtes, C., Luna, E., Lee, H., and Har-
vey, R.G., J. Org. Chem., 1993, vol. 58, no. 2, p. 356.
1
3615, 3625 (ОН), 1723 (С=О). H NMR spectrum, δ,
ppm: 0.97 t (3Н, СН3), 1.07 d (3Н, СН3), 1.62 d (1Н,
СН), 1.27–1.98 d (6Н, 3СН2), 2.02 d (1Н, ОН), 2.46
d.d (2Н, СН2С=О), 3.48 t (1Н, СН), 4.81 br.s (1Н,
13
ОН), C NMR spectrum, δ, ppm: 216 (С7), 94.2 (С1),
70.4 (С2), 36 (С3), 34.3 (С8), 28.4 (С4), 27.3 (С5), 27
(С6), 26.4 (С9), 22.3 (С10), 21.3 (С12), 13.9 (С11) [20–
1
11. Dalton, D.R. and Jones, D.G., Tetrahedron Lett., 1967,
no. 38, p. 2875.
12. Saicho, K., Khashimoto, Yu., and Sudo, A., Zh. Org.
Khim., 1996, vol. 32, no. 2, p. 249.
22]. Found, %: С 66.42, Н 10.39. C1 H20O3.
Calculated, %: С 66, Н 10.
Identical spectral characteristics are obtained for
compounds IVd–IVg.
13. Reaktsii
i
metody issledovaniya organicheskikh
soedinenii (Reactions and Methods of Investigations of
Organic Compounds), Moscow: Mir, 1958, vol. 7.
14. Pishnamaz-zade, B.F. and Guseinov, I.A., Az. Neftyanoe
Khozyaistvo, 1969, no. 1, p. 30.
15. Sadygov, O.A. and Alimardanov, Kh.M., Zh. Org.
Khim., 2007, vol. 43, no. 11, p. 1664.
16. Veliev, M.G., Sadygov, O.A., Alimardanov, Kh.M., and
Shatirov, M.I., Zh. Org. Khim., 2007, vol. 43, no. 11,
p. 1609.
17. Khalilov, L.I., Sultanov, V.S., Panasenko, A.A.,
Khusnutdinov, R.I., Galleev, R.K., Tolstikov, G.A., and
Dzhemilov, U.M., Izv. Akad. Nauk SSSR, Ser. Khim.,
1987, no. 5, p. 1018.
1,2-Dihydroxy-4-methyl-1-pentanoylcyclohexane
(Vd) was obtained from 9.8 g (0.05 mol) of IVd. Yield
9.1 g (85.2%), mp 142–144°C. Found, %: С 67.83, Н
10.65. С12Н22О3. Calculated, %: С 67.29, Н 10.28.
1,2-Dihydroxy-4-methyl-1-hexanoylcyclohexane
(Ve) was obtained from 10.5 g (0.05 mol) of IVe.
Yield 9.3 g (81.6%), mp 153–155°C. Found, %: С
68.76, Н 10.85. С13Н24О3. Calculated, %: С 68.42, Н
10.53.
1,2-Dihydroxy-4-methyl-1-heptanoylcyclohexane
(Vf), was obtained from 11.2 g (0.05 mol) of IVf.
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STUDY OF INDUCED HYPOHALOGENATION
1697
18. Babko, A.K. and Pyatnitskii, I.V., Kolichestvennyi
(Infrared Spectra of Complex), Moscow, 1963.
21. Ionin, B.I. and Ershov, B.A., YaMR spektry
analiz (Quantitative Analysis), Moscow: Vysshaya
Shkola, 1962.
v
organicheskoi khimii (NMR Spectroscopy in Organic
19. Malinovskii, M.S., Okisi olefinov and ikh proizvodnye
(Oxides of Olefins and Their Derivatives), Moscow:
Goskhimizdat, 1961.
Chemistry), Leningrad: Khimiya, 1967.
22. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion. A Handbook of Practical Data, Techniques and
References, New York: Wiley, 1972.
20. Bellami, L., Infrakrasnye spektry slozhnykh molekul
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009