O-acyl derivatives of cyclopentanone and cycloheptanone oximes

Article abstract of DOI:10.1134/S1070428010020065

By acylation of cyclopentanone and cycloheptanone oximes with carboxylic acids anhydrides or chlorides new esters were obtained of cyclopentanone and cycloheptanone oximes and their spectral characteristics were investigated.

Full text of DOI:10.1134/S1070428010020065

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 2, pp. 180−185. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.A. Zhukovskaya, E.A. Dikusar, 2009, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 2, pp. 188−192.
O-Acyl Derivatives of Cyclopentanone
and Cycloheptanone Oximes
N.A. Zhukovskaya and E. A. Dikusar
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus
Minsk, 220072 Belarus
e-mail: dikusar@ifoch.bas-net.by
Received January 28, 2009
Abstract—By acylation of cyclopentanone and cycloheptanone oximes with carboxylic acids anhydrides or
chlorides new esters were obtained of cyclopentanone and cycloheptanone oximes and their spectral characteristics
were investigated.
DOI: 10.1134/S1070428010020065
esters IIIa–IIIq and cycloheptanone oxime esters IVa–
IVq were synthesized from cyclopentanone and
cycloheptanone oximes (IIa and IIb) by treating with
alkylcarboxylic acids anhydrides in the presence of
catalytic quantity of perchloric acid (esters IIIa–IIId,
IVa–IVd), or by chlorides of alkyl-, cycloalkyl-, and
arylcarboxylic acids in the presence of pyridine (esters
IIIe–IIIq, IVe–IVq) (Scheme 1). Yields of
cyclopentanone and cycloheptanone oxime esters IIIa–
IIIq and IVa–IVq attained 80–91%.
Oximes of some aldehydes and ketones can serve as
convenient and available synthons for preparation of
fragrant substances and perfumes, and also of biologically
active compounds. We formerly reported on the synthesis
of oxime esters of vanillin and vanillal [1], menthone [2],
D,L-, D-(+) and L-(–)-camphor [3], jasmorange [4], citral
and veratraldehyde [5, 6], cyclo-hexanone [7]. It was
established that just the presence of methyl, dimethyl,
and isopropyl groups in the molecules of fragrant
substances obtained from oximes of menthone , camphor,
jasmorange, citral, and veratraldehyde ensured the
interaction with the olfactory and taste receptors and led
to the feeling of odor or taste [2–6]. The oxime esters of
cyclohexanone analogous to oxime esters of menthone
[2] did not exhibit promising perfume or taste [7].
The composition and structure of obtained compounds
IIIa–IIIq and IVa–IVq were confirmed by elemental
1
analysis, IR, UV, H NMR spectroscopy, cryoscopic
measurements of molecular weight. According to
1H spectroscopy the purity of compounds obtained was
94 ± 1%. The results of analysis and of the measurements
of molecular weight of compounds synthesized are
consistent with the calculated data. The attempts to
The aim of this study consisted in the preparation of
a series of new esters of cyclopentanone and cyclo-
heptanone oximes (IIa and IIb). Cyclopentanone oxime
Scheme 1.
O
NOH
NOC(O)R
NH2OH
(RCO)2O or RCOCl
(CH2)n
Ia, Ib
(CH2)n
(CH2)n
IIIa_IIIq, IVa_IVq
IIa, IIb
n= 1 (Ia, IIa, IIIa–IIIq); 3 (Ib, IIb, IVa–IVq); R = Me (a), Et (b), Pr (c), i-Pr (d), Bu (e), s-Bu(f), t-Bu (g), C5H11 (h), C6H13 (i), C7H15
(j), C8H17 (k), C9H19 (l), cyclo-C6H11 (m), 1-Ad (n), Ph (o), MeO (p), EtO (q).
180

O-ACYLDERIVATIVES OF CYCLOPENTANONE AND CYCLOHEPTANONE OXIMES
181
determine the molecular weight from the mass of the
molecular ion in the mass spectra failed due to low heat
resistance of esters IIIa–IIIq and IVa–IVq.
Cyclopentanone and cycloheptanone oxime
esters IIIa–IIId, IVa–IVd. General procedure. In
30 ml of anhydrous hexane was dissolved 0.01 mol of
oxime IIa or IIb and 0.011 mol of an appropriate
carboxylic acid anhydride. To the solution obtained 1 drop
of 47% HClO4 was added. The mixture was shaken and
left standing at 20–23°C for 24 h. Then the reaction
mixture was diluted with water, and the products were
extracted into hexane, the extract was washed with water,
5% NaHCO3 solution, and dried with CaCl2. The solvent
was distilled off at a reduced pressure (10–15 mm Hg)
avoiding heating over 25–30°C. The final purification
was performed by column chromatography on silica gel
L5/40 μm (eluent benzene–hexane, 1:1).
Cyclopentanone and cycloheptanone oxime
esters IIIe–IIIq, IVe–IVq. General procedure. In
50 ml of anhydrous hexane was dissolved 0.01 mol of
oxime IIa or IIb and to the solution obtained was added
0.01 mol of anhydrous pyridine. To this solution while
stirring was added at 15°C 0.01 mol of an appropriate
carboxylic acid chloride. The mixture was kept at 20–
23°C for 24–36 h. Then the reaction mixture was diluted
with water, and the products were extracted into hexane,
the extract was washed with water, 5% NaHCO3
solution, and dried with CaCl2. The solvent was distilled
off at a reduced pressure (10–15 mm Hg) avoiding heating
over 25–30°C. The final purification was performed by
column chromatography on silica gel L5/40 μm (eluent
benzene–hexane, 1 : 1).
Oxime esters IIIa–IIIq and IVa–IVq may possess
a high biological activity [8].
EXPERIMENTAL
IR spectra were recorded on an IR Fourier spectro-
photometer Nicolet Protege-460 from thin film or KBr
pellets, UV spectra, on a spectrometer Specord UV
Vis from 1 × 10–3 M solutions of compounds in MeOH.
1H NMR spectra were registered on a spectrometer Tesla
BS-587A (operating frequency 100 MHz) from 5%
solutions in CDCl3, chemical shifts were determined from
the internal reference TMS. Elemental analysis was
carried out on a C, H, N, O, S-analyzer Elementar Vario
EL-III, the measurement error 0.1%. The molecular
weight was determined by cryoscopy in benzene.
Physicochemical characteristics of cyclopentanone
and cycloheptanone oximes (IIa and IIb) prepared from
cyclopentanone and cycloheptanone (Ia and Ib) by
procedure [4] were in agreement with the published data
[9].
Cyclopentanone and cycloheptanone oximes (IIa
and IIb). General procedure. A mixture of 0.5 mol of
cyclopentanone (Ia) or cycloheptanone (Ib), 0.65 mol of
hydroxylamine hydrochloride, and 0.58 mol of sodium
hydrogen carbonate in 200 ml of 96% ethanol was boiled
for 1 h. The reaction mixture was cooled to room
temperature, diluted with water to 1 l volume, oximes
(IIa and IIb) were extracted into ethyl ether (IIa, (3 ×
150 ml). The combined ether extracts were dried with
MgSO4, the solvent was distilled off.
Cyclopentanone O-ethanoyloxime (IIIa). Yield
20
80%, colorless fluid, d 1.0356, nD20 1.4718. IR spectrum,
20
ν, cm–1: 2963, 2930, 2889, 2874, 2840 (CHaliph), 1764
(C=O), 1658 (C=N), 1468, 1453, 1427 (CH2), 1225, 1197,
1002, 969, 936 (C–O). UV spectrum, λmax, nm (log ε):
195 (3.95). 1H NMR spectrum, δ, ppm: 1.55–1.95 m (4H),
2.20–2.70 m [4H, (CH2)4], 2.12 s (3H, Me). Found, %:
C 59.93; H 7.94; N 9.55. M 133. C7H11NO2. Calculated,
%: C 59.56; H 7.85; N 9.92. M 141.17.
Cyclopentanone oxime (IIa). Yield 76%, colorless
crystalline substance, mp56–57°C. IR spectrum, ν, cm–1:
3223, 3127 (OH), 2965, 2940, 2906, 2890, 2870 (CHaliph),
1676 (C=N), 1480, 1452, 1428 (CH2). UV spectrum,
λ
max, nm (log ε): 196 (3.70). 1H NMR spectrum, δ, ppm:
Cyclopentanone O-propanoyloxime (IIIb). Yield
1.35–1.95 m (4H), 2.25–2.70 m [4H, (CH2)4], 8.90 br.s
(1H, OH).
20
82%, colorless fluid, d 0.9824, nD20 1.4720. IR spec-
20
trum, ν, cm–1: 2968, 2944, 2928, 2878 (CHaliph), 1763
Cycloheptanone oxime (IIb). Yield 88%, color-
less crystalline substance, mp 22–23°C. IR spectrum,
ν, cm–1: 3226, 3096 (OH), 2924, 2853 (CHaliph), 1650
(C=O), 1655 (C=N), 1461, 1455, 1425 (CH2), 1218, 1138,
1072, 1008, 986, 922 (C–O). UV spectrum, λmax, nm
1
(log ε): 195 (3.95). H NMR spectrum, δ, ppm: 1.07 t
(C=N), 1455, 1444, 1431 (CH2). UV spectrum, λmax
,
(3H, Me, J 7.3 Hz), 1.40–1.85 m (4H), 2.05–2.65 m [6H,
CH2 and (CH2)4]. Found, %: C 62.18; H 8.53; N 8.76.
M 146. C8H13NO2. Calculated, %: C 61.91; H 8.44;
N 9.03. M 155.19.
nm (log ε): 197 (3.70). 1H NMR spectrum, δ, ppm: 1.35–
1.85 m (8H), 2.25–2.70 m [4H, (CH2)6], 8.05 br.s (1H,
OH).
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ZHUKOVSKAYA, DIKUSAR
182
Cyclopentanone O-butanoyloxime (IIIc). Yield
Cyclopentanone O-hexanoyloxime (IIIh). Yield
20
84%, colorless fluid, d 0.9714, nD20 1.4712. IR spectrum,
20
85%, colorless fluid, d 0.9508, nD20 1.4678. IR spectrum,
20
20
ν, cm–1: 2965, 2940, 2875, 2838 (CHaliph), 1762 (C=O),
ν, cm–1: 2959, 2933, 2872 (CHaliph), 1763 (C=O), 1656
1658 (C=N), 1455, 1420 (CH2), 1247, 1214, 1148, 1092,
(C=N), 1467, 1455, 1418 (CH2), 1240, 1219, 1139, 1092,
940 (C–O). UV spectrum, λmax, nm (log ε): 196 (3.95).
1H NMR spectrum, δ, ppm: 0.81 t (3H, Me, J 6.2 Hz),
1.00–2.55 m [16H, (CH2)4 and (CH2)4]. Found, %:
C 67.18; H 9.95; N 6.85. M 186. C11H19NO2. Calculated,
%: C 66.97; H 9.71; N 7.10. M 197.27.
1080, 937 (C–O). UV spectrum, λmax, nm (log ε): 195
1
(3.95). H NMR spectrum, δ, ppm: 0.88 t (3H, Me,
J 6.8 Hz), 1.35–1.95 m (6H), 2.05–2.60 m [6H, (CH2)2
and (CH2)4]. Found, %: C 64.23; H 9.08; N 7.88. M 160.
C9H15NO2. Calculated, %: C 63.88; H 8.93; N 8.28.
M 169.22.
Cyclopentanone O-heptanoyloxime (IIIi). Yield
Cyclopentanone O-3-methylpropanoyloxime
20
88%, colorless fluid, d 0.9367, nD20 1.4698. IR spectrum,
20
20
(IIId). Yield 85%, colorless fluid, d 0.9842, nD20 1.4685.
ν, cm–1: 2958, 2931, 2871, 2860 (CHaliph), 1763 (C=O),
1658 (C=N), 1467, 1455, 1418 (CH2), 1219, 1139, 1096,
935 (C–O). UV spectrum, λmax, nm (log ε): 195 (3.95).
1H NMR spectrum, δ, ppm: 0.86 t (3H, Me, J 6.1 Hz),
1.05–2.65 m [18H, (CH2)4 and (CH2)5]. Found, %: C 68.60;
H 10.14; N 6.37. M204. C12H21NO2. Calculated, %: C 68.21;
H 10.02; N 6.63. M 211.30.
20
IR spectrum, ν, cm–1: 2971, 2940, 2876, 2830 (CHaliph),
1762 (C=O), 1661 (C=N), 1470, 1456, 1426, 1418 (CH2),
1240, 1216, 1181, 1126, 1101, 1042, 932 (C–O). UV
1
spectrum, λmax, nm (log ε): 195 (3.95). H NMR
spectrum, δ, ppm: 1.17 d (6H, Me2C, J 6.9 Hz), 1.55–
1.90 m (4H), 2.35–2.85 m [5H, CH and (CH2)4]. Found,
%: C 64.07; H 9.01; N 7.95. M 158. C9H15NO2.
Calculated, %: C 63.88; H 8.93; N 8.28. M 169.22.
Cyclopentanone O-octanoyloxime (IIIj). Yield
20
85%, colorless fluid, d 1.0167, nD20 1.4690. IR spectrum,
20
Cyclopentanone O-pentanoyloxime (IIIe). Yield
ν, cm–1: 2957, 2928, 2871, 2857 (CHaliph), 1763 (C=O),
20
84%, colorless fluid, d 0.9666, nD20 1.4705. IR spectrum,
20
1657 (C=N), 1467, 1455, 1418 (CH2), 1219, 1139, 1098,
935 (C–O). UV spectrum, λmax, nm (log ε): 195 (3.90).
1H NMR spectrum, δ, ppm: 0.85 t (3H, Me, J 6.1 Hz),
1.05–2.60 m [20H, (CH2)4 and (CH2)6]. Found, %:
C 69.58; H 10.37; N 6.04. M 214. C13H23NO2. Calculat-
ed, %: C 69.29; H 10.29; N 6.22. M 225.33.
ν, cm–1: 2961, 2935, 2873 (CHaliph), 1763 (C=O), 1657
(C=N), 1467, 1454, 1418 (CH2), 1240, 1221, 1140, 1092,
936 (C–O). UV spectrum, λmax, nm (log ε): 195 (3.95).
1H NMR spectrum, δ, ppm: 0.92 t (3H, Me, J 6.0 Hz),
1.10–1.95 m (8H), 2.20–2.70 m [6H, (CH2)3 and (CH2)4].
Found, %: C 65.84; H 9.41; N 7.24. M 174. C10H17NO2.
Calculated, %: C 65.54; H 9.35; N 7.64. M 183.25.
Cyclopentanone O-nonanoyloxime (IIIk). Yield
20
87%, colorless fluid, d 1.0642, nD20 1.4802. IR spectrum,
Cyclopentanone O-4-methylbutanoyloxime
20
ν, cm–1: 2956, 2926, 2870, 2855 (CHaliph), 1764 (C=O),
20
(IIIf). Yield 88%, colorless fluid, d 1.0791, nD20 1.4715.
20
1658 (C=N), 1467, 1455, 1418 (CH2), 1218, 1138, 1099,
938 (C–O). UV spectrum, λmax, nm (log ε): 195 (4.00).
1H NMR spectrum, δ, ppm: 0.83 t (3H, Me, J 6.1 Hz),
1.05–2.55 m [22H, (CH2)4 and (CH2)7]. Found, %:
C 70.58; H 10.76; N 5.46. M 227. C14H25NO2.
Calculated, %: C 70.25; H 10.53; N 5.85. M 239.35.
IR spectrum, ν, cm–1: 2963, 2940, 2874 (CHaliph), 1759
(C=O), 1657 (C=N), 1467, 1455, 1426, 1418 (CH2), 1292,
1247, 1159, 1091, 958, 934 (C–O). UV spectrum, λmax
,
nm (log e): 195 (3.95). 1H NMR spectrum, δ, ppm:
0.94 d (6H, Me2C, J 6.5 Hz), 1.55–1.85 m (6H), 2.05–
2.65 m [5H, CH, CH2 and (CH2)4]. Found, %: C 65.90;
H 9.48; N 7.35. M 175. C10H17NO2. Calculated, %:
C 65.54; H 9.35; N 7.64. M 183.25.
Cyclopentanone O-decanoyloxime (IIIl). Yield
20
85%, colorless fluid, d 0.9820, nD20 1.4682. IR spectrum,
20
ν, cm–1: 2956, 2925, 2865, 2855 (CHaliph), 1764 (C=O),
Cyclopentanone O-tert-pentanoyloxime (IIIg).
1658 (C=N), 1466, 1456, 1418 (CH2), 1240, 1218, 1138,
20
Yield 89%, colorless fluid, d 0.9657, nD20 1.4642. IR
20
1101, 940 (C–O). UV spectrum, λmax, nm (log ε): 195
spectrum, ν, cm–1: 2969, 2938, 2907, 2873 (CHaliph), 1755
1
(3.95). H NMR spectrum, δ, ppm: 0.80 t (3H, Me,
(C=O), 1656 (C=N), 1481, 1460, 1456, 1417 (CH2), 1272,
1214, 1116, 1028 (C–O). UV spectrum, λmax, nm (log ε):
195 (3.95). 1H NMR spectrum, δ, ppm: 1.18 c (9H,
Me3C), 1.60–1.88 m (4H), 2.33–2.64 m [4H, (CH2)4].
Found, %: C 65.83; H 9.42; N 7.30. M 174. C10H17NO2.
Calculated, %: C 65.54; H 9.35; N 7.64. M 183.25.
J 6.0 Hz), 0.95–2.65 m [24H, (CH2)4 and (CH2)8]. Found,
%: C 71.52; H 10.93; N 5.14. M 242. C15H27NO2.
Calculated, %: C 71.10; H 10.74; N 5.53. M 253.38.
Cyclopentanone O-cyclohexylcarbonyloxime
20
(IIIm). Yield 91%, colorless fluid, d 1.1090, nD20 1.4958.
20
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O-ACYLDERIVATIVES OF CYCLOPENTANONE AND CYCLOHEPTANONE OXIMES
183
20
85%, colorless fluid, d 0.9591 , nD20 1.4884. IR
IR spectrum, ν, cm–1: 2932, 2855 (CHaliph), 1757 (C=O),
1658 (C=N), 1451, 1422, 1418 (CH2), 1245, 1216, 1194,
1150, 1108, 1019 (C–O). UV spectrum, λmax, nm (log ε):
196 (3.95). 1H NMR spectrum, δ, ppm: 1.00–2.65 m (19H,
CHaliph). Found, %: C 69.06; H 9.27; N 6.43. M 198.
C12H19NO2. Calculated, %: C 68.87; H 9.15; N 6.69.
M 209.28.
20
spectrum, ν, cm–1: 2928, 2855 (CHaliph), 1764 (C=O),
1625 (C=N), 1455, 1444, 1414 (CH2), 1279, 997, 963,
927, 887 (C–O). UV spectrum, λmax, nm (log ε): 195
1
(3.95). H NMR spectrum, δ, ppm: 1.35–1.80 m (8H),
2.35–2.70 m [4H, (CH2)6], 2.12 s (3H, Me). Found, %:
C 64.00; H 9.08; N 7.91. M 159. C9H15NO2. Calculated,
%: C 63.88; H 8.93; N 8.28. M 169.22.
Cyclopentanone O-(1-adamantyl)carbonyloxime
(IIIn). Yield 90%, colorless crystalline substance, mp 63–
64°C. IR spectrum, ν, cm–1: 2970, 2940, 2907, 2851
(CHaliph), 1750 (C=O), 1652 (C=N), 1452, 1416 (CH2),
Cycloheptanone O-propanoyloxime (IVb). Yield
20
88%, colorless fluid, d
0.9644, nD20 1.4840. IR
20
spectrum, ν, cm–1: 2979, 2928, 2855 (CHaliph), 1766
(C=O), 1624 (C=N), 1459, 1444, 1414 (CH2), 1154, 1138,
1071, 985, 923 (C–O). UV spectrum, λmax, nm (log ε):
1221, 1198, 1178, 1101, 1055 (C–O). UV spectrum, λmax
,
nm (log ε): 197 (3.90). 1H NMR spectrum, δ, ppm:
1.55–2.15 m (19H), 2.40–2.70 m (4H, CHaliph). Found,
%: C 73.92; H 9.01; N 5.07. M 250. C16H23NO2.
Calculated, %: C 73.53; H 8.87; N 5.36. M 261.36.
1
195 (3.95). H NMR spectrum, δ, ppm: 1.16 t (3H, Me,
J 7.3 Hz), 1.32–1.85 m (8H), 2.25–2.70 m [4H, (CH2)6],
2.40 q (2H, CH2, J 7.3 Hz). Found, %: C 65.92; H 9.48;
N 7.34. M 173. C10H17NO2. Calculated, %: C 65.54;
H 9.35; N 7.64. M 183.25.
Cyclopentanone O-benzoyloxime (IIIo). Yield
89%, colorless crystalline substance, mp 54–55°C. IR
spectrum, ν, cm–1: 3083, 3070, 3060, 3031, 3003 (CHarom),
2966, 2920, 2878 (CHaliph), 1736 (C=O), 1660 (C=N),
1460, 1420 (CH2), 1598, 1451 (C=Carom), 1261, 1173, 1089,
1064, 1026, 960 (C–O), 863, 825, 802, 709 (CHarom). UV
Cycloheptanone O-butanoyloxime (IVc). Yield
86%, colorless fluid, d 1.0852, nD20 1.4810. IR spectrum,
20
20
ν, cm–1: 2963, 2929, 2874, 2856 (CHaliph), 1763 (C=O),
1625 (C=N), 1456, 1444, 1415 (CH2), 1154, 1142, 1091,
963, 934 (C–O). UV spectrum, λmax, nm (log ε): 195
(3.95). H NMR spectrum, δ, ppm: 0.96 t (3H, Me,
J 6.8 Hz), 1.35–1.80 m (10H), 2.10–2.75 m [6H, (CH2)2
and (CH2)6]. Found, %: C 67.32; H 9.86; N 6.82. M 188.
C11H19NO2. Calculated, %: C 66.97; H 9.71; N 7.10.
M 197.27.
1
spectrum, λmax, nm (log e): 198 (4.53), 233 (4.20). H
1
NMR spectrum, δ, ppm: 1.65–2.05 m (4H), 2.40–2.85 m
[4H, (CH2)4], 7.25–7.55 m (3H), 7.90–8.15 m (2H, Ph).
Found, %: C 71.19; H 6.63; N 6.72. M 191. C12H13NO2.
Calculated, %: C 70.92; H 6.45; N 6.89. M 203.24.
Cyclopentanone O-methoxycarbonyloxime
(IIIp). Yield 85%, colorless fluid, d2200 0.9855, nD20 1.4752.
IR spectrum, ν, cm–1: 2961, 2930, 2890, 2876 (CHaliph),
1774 (C=O), 1660 (C=N), 1441, 1418 (CH2), 1248, 1212,
946 (C–O). UV spectrum, λmax, nm (log ε): 195 (3.95).
1H NMR spectrum, δ, ppm: 1.55–1.98 m (4H), 2.20–
2.70 m [4H, (CH2)4], 3.80 s (3H, MeO). Found, %: C
53.90; H 7.18; N 8.57. M 142. C7H11NO3. Calculated,
%: C 53.49; H 7.05; N 8.91. M 157.17.
Cycloheptanone O-3-methylpropanoyloxime
(IVd). Yield 83%, colorless fluid, d2200 1.0018, nD20 1.4832.
IR spectrum, ν, cm–1: 2973, 2927, 2855 (CHaliph), 1761
(C=O), 1623 (C=N), 1469, 1456, 1444, 1415 (CH2), 1127,
1100, 1057, 963, 933 (C–O). UV spectrum, λmax, nm
1
(log ε): 196 (3.95). H NMR spectrum, δ, ppm: 1.21 d
(6H, Me2C, J 6.9 Hz), 1.45–1.90 m (9H), 2.30–2.85 m
[4H, CH and (CH2)6]. Found, %: C 67.26; H 9.80;
N 6.84. M 189. C11H19NO2. Calculated, %: C 66.97; H
9.71; N 7.10. M 197.27.
Cyclopentanone O-ethoxycarbonyloxime (IIIq).
20
Yield 91%, colorless fluid, d 1.0453, nD20 1.4666. IR
Cycloheptanone O-pentanoyloxime (IVe). Yield
85%, colorless fluid, d2200 0.9130, nD20 1.4754. IR spectrum,
ν, cm–1: 2957, 2930, 2860 (CHaliph), 1763 (C=O), 1625
(C=N), 1456, 1444, 1416 (CH2), 1229, 1153, 1141, 1092,
963, 936, 889 (C–O). UV spectrum, λmax, nm (log ε):
20
spectrum, ν, cm–1: 2970, 2941, 2922, 2876 (CHaliph), 1772
(C=O), 1660 (C=N), 1467, 1455, 1418 (CH2), 1243, 1209,
1004, 952 (C–O). UV spectrum, λmax, nm (log ε): 195
(3.95). 1H NMR spectrum, δ, ppm: 1.30 t (3H, Me,
J 7.1 Hz), 1.55–1.98 m (4H), 2.20–2.70 m [4H, (CH2)4],
4.24 q (2H, CH2O, J 7.1 Hz). Found, %: C 56.43; H
7.82; N 7.78. M 165. C8H13NO3. Calculated, %: C 56.13;
H 7.65; N 8.18. M 171.19.
1
195 (3.95). H NMR spectrum, δ, ppm: 0.85 t (3H, Me,
J 6.0 Hz), 1.10–1.84 m (12H), 2.10–2.70 m [6H, (CH2)3
and (CH2)6]. Found, %: C 68.56; H 10.19; N 6.32. M 201.
C12H21NO2. Calculated, %: C 68.21; H 10.02; N 6.63.
M 211.30.
Cycloheptanone O-ethanoyloxime (IVa). Yield
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ZHUKOVSKAYA, DIKUSAR
184
M 244. C15H27NO2. Calculated, %: C 71.10; H 10.74;
N 5.53. M 253.38.
Cycloheptanone O-4-methylbutanoyloxime (IVf).
20
Yield 82%, colorless fluid, d 0.9727, nD20 1.4778. IR
20
spectrum, ν, cm–1: 2958, 2929, 2670, 2857 (CHaliph), 1763
Cycloheptanone O-nonanoyloxime (IVk). Yield
20
88%, colorless fluid, d 0.9758, nD20 1.4748. IR spectrum,
(C=O), 1625 (C=N), 1456, 1445, 1415 (CH2), 1292, 1158,
20
ν, cm–1: 2852, 2926, 2855 (CHaliph), 1764 (C=O), 1624
(C=N), 1457, 1444, 1415 (CH2), 1140, 1099, 1057, 963,
936 (C–O). UV spectrum, λmax, nm (log ε): 195 (3.95).
1H NMR spectrum, δ, ppm: 0.84 t (3H, Me, J 6.1 Hz),
1.02–2.72 m [26H, (CH2)6 and (CH2)7]. Found, %:
C 72.09; H 11.12; N 4.96. M 257. C16H29NO2. Calculat-
ed, %: C 71.86; H 10.93; N 5.24. M 267.41.
1091, 1060, 967, 902 (C–O). UV spectrum, λmax, nm
1
(log e): 195 (3.95). H NMR spectrum, δ, ppm: 0.95 d
(6H, Me2C, J 6.4 Hz), 1.35–2.70 m [15H, CH, CH2 and
(CH2)6]. Found, %: C 68.49; H 10.16; N 6.27. M 202.
C12H21NO2. Calculated, %: C 68.21; H 10.02; N 6.63.
M 211.30.
Cycloheptanone O-tert-pentanoyloxime (IVg).
20
Yield 84%, colorless fluid, d 1.0084, nD20 1.4772. IR
Cycloheptanone O-decanoyloxime (IVl). Yield
20
spectrum, ν, cm–1: 2971, 2929, 2857 (CHaliph), 1755
20
82%, colorless fluid, d 0.9380, nD20 1.4750. IR spectrum,
20
ν, cm–1: 2952, 2925, 2854 (CHaliph), 1764 (C=O), 1623
(C=O), 1621 (C=N), 1480, 1458, 1444, 1415 (CH2), 1274,
1149, 1116, 1058, 1028, 965, 930, 901 (C–O). UV
(C=N), 1457, 1444, 1415 (CH2), 1140, 1100, 1050, 960,
940, 901 (C–O). UV spectrum, λmax, nm (log e): 196 (3.95).
1H NMR spectrum, δ, ppm: 0.80 t (3H, Me, J 6.0 Hz),
1.05–2.72 m [28H, (CH2)6 and (CH2)8]. Found, %:
C 72.89; H 11.23; N 4.56. M 270. C17H31NO2. Calculat-
ed, %: C 72.55; H 11.10; N 4.98. M 281.43.
1
spectrum, λmax, nm (log ε): 195 (4.00). H NMR
spectrum, δ, ppm: 1.18 c (9H, Me3C), 1.36–1.80 m (8H),
2.35–2.70 m [4H, (CH2)6]. Found, %: C 68.53; H 10.11;
N 6.32. M 201. C12H21NO2. Calculated, %: C 68.21;
H 10.02; N 6.63. M 211.30.
Cycloheptanone O-hexanoyloxime (IVh). Yield
Cycloheptanone O-cyclohexylcarbonyloxime
20
91%, colorless fluid, d 0.8853, nD20 1.4774. IR spectrum,
20
(IVm). Yield 87%, colorless fluid, d 1.0611, nD20 1.5030.
20
20
ν, cm–1: 2955, 2929, 2858 (CHaliph), 1764 (C=O), 1625
IR spectrum, ν, cm–1: 2929, 2855 (CHaliph), 1759 (C=O),
(C=N), 1456, 1444, 1414 (CH2), 1226, 1152, 1141, 1093,
1623 (C=N), 1451, 1415 (CH2), 1243, 1202, 1153, 1108,
1019, 902 (C–O). UV spectrum, λmax, nm (log ε): 195
(3.95). 1H NMR spectrum, δ, ppm: 1.00–2.70 m (23H,
CHaliph). Found, %: C 71.18; H 9.84; N 5.64. M 228.
C14H23NO2. Calculated, %: C 70.85; H 9.77; N 5.90.
M 237.34.
963, 901 (C–O). UV spectrum, λmax, nm (log ε): 195
1
(3.95). H NMR spectrum, δ, ppm: 0.87 t (3H, Me,
J 6.2 Hz), 1.10–2.70 m [20H, (CH2)4 and (CH2)6].
Found, %: C 69.63; H 10.42; N 5.96. M 216. C13H23NO2.
Calculated, %: C 69.29; H 10.29; N 6.22. M 225.33.
Cycloheptanone O-heptanoyloxime (IVi). Yield
Cycloheptanone O-(1-adamantyl)carbonyloxime
(IVn). Yield 91%, colorless crystalline substance, mp 93–
94°C. IR spectrum, ν, cm–1: 2923, 2851 (CHaliph), 1744
(C=O), 1620 (C=N), 1453, 1418, 1414 (CH2), 1210, 1177,
1101, 1063, 1051, 979, 937, 891 (C–O). UV spectrum,
20
90%, colorless fluid, d 1.0861, nD20 1.4788. IR spectrum,
20
ν, cm–1: 2955, 2928, 2857 (CHaliph), 1764 (C=O), 1625
(C=N), 1456, 1444, 1415 (CH2), 1227, 1203, 1151, 1141,
1095, 963, 930, 901 (C–O). UV spectrum, λmax, nm
1
(log ε): 195 (3.95). H NMR spectrum, δ, ppm: 0.81 t
λ
max, nm (log ε): 197 (3.90). 1H NMR spectrum, δ,
(3H, Me, J 6.1 Hz), 1.07–2.70 m [22H, (CH2)5 and
(CH2)6]. Found, %: C 70.66; H 10.72; N 5.53. M 228.
C14H25NO2. Calculated, %: C 70.25; H 10.53; N 5.85.
M 239.35.
ppm: 1.45–2.75 m (27H, CHaliph). Found, %: C 74.92;
H 9.46; N 4.47. M 278. C18H27NO2. Calculated, %:
C 74.70; H 9.40; N 4.84. M 289.41.
Cycloheptanone O-benzoyloxime (IVo). Yield
20
Cycloheptanone O-octanoyloxime (IVj). Yield
85%, colorless fluid,d 1.3640, nD20 1.5615. IR spectrum,
20
20
20
85%, colorless fluid, d20 0.9305, nD 1.4770. IR
spectrum, ν, cm–1: 2952, 2927, 2856 (CHaliph), 1764
(C=O), 1625 (C=N), 1456, 1444, 1415 (CH2), 1223, 1201,
ν, cm–1: 3090, 3070, 3026 (CHarom), 2928, 2855 (CHaliph),
1754 (C=O), 1624 (C=N), 1470, 1454, 1417 (CH2), 1591,
1436 (C=Carom), 1288, 1238, 1100, 913, 898 (CO); 863,
831, 800, 747 (CHarom). UV spectrum, λmax, nm (log ε):
1141, 1097, 1058, 963, 933 (C–O). UV spectrum, λmax
,
nm (log ε): 195 (3.95). 1H NMR spectrum, δ, ppm:
0.81 t (3H, Me, J 6.1 Hz), 1.00–2.70 m [24H, (CH2)6
and (CH2)6]. Found, %: C 71.42; H 10.75; N 5.26.
197 (4.54), 234 (4.20). H NMR spectrum, δ, ppm: 1.35–
1
1.95 m (8H), 2.40–2.80 m [4H, (CH2)6], 7.10–7.85 m
(5H, Ph). Found, %: C 72.99; H 7.44; N 5.76. M 222.
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REFERENCES
C14H17NO2. Calculated, %: C 72.70; H 7.41; N 6.06.
M 231.29.
1. Dikusar, E.A., Kozlov, N.G., Zhukovskaya, N.A., and
Moiseichuk, , K.L., Khim. Polim. Soedin., 2004, p. 154.
2. Zhukovskaya, N.A., Dikusar, , E.A., Moiseichuk, , K.L., and
Vyglazov, O.G., Zh. Prikl. Khim., 2006, vol. 79, p. 642.
3. Dikusar, E.A., Zhukovskaya, N.A., and Vyglazov, O.G. , Zh.
Prikl. Khim., 2006, vol. 79, p. 2007.
4. Dikusar, , E.A., Zhukovskaya, N.A., Moiseichuk, K.L., and
Vyglazov, O.G., Khim. Polim. Soedin., 2007, p. 307.
5. Dikusar, E.A., Zhukovskaya, N.A., Moiseichuk, K.L.,
Zalesckaya, E.G., Vyglazov, O.G., and Kurman, P.V., Khim.
Polim. Soedin., 2008, p. 65.
Cycloheptanone O-methoxycarbonyloxime
(IVp). Yield 86%, colorless fluid, d 1.0048, nD20 1.4790.
20
20
IR spectrum, ν, cm–1: 2928, 2855 (CHaliph), 1775 (C=O),
1628 (C=N), 1460, 1441, 1414 (CH2), 1270, 1236, 1190,
1147, 1060 (C–O). UV spectrum, λmax, nm (log ε): 196
1
(3.95). H NMR spectrum, δ, ppm: 1.45–1.90 m (8H),
2.40–2.75 m [4H, (CH2)6], 3.83 s (3H, Me). Found, %:
C 58.75; H 8.36; N 7.71. M 179. C9H15NO3. Calculated,
%: C 58.36; H 8.16; N 7.56. M 185.22.
Cycloheptanone O-ethoxycarbonyloxime (IVq).
6. Dikusar, E.A., Zhukovskaya, N.A., Moiseichyk, K.L.,
Zalesskaya, E.G., Kurman, P.V., andVyglazov, O.G., Zh. Prikl.
Khim., 2008, vol. 81, p. 606.
Yield 88%, colorless fluid, d 1.0989, nD20 1.4760. IR
20
20
spectrum, ν, cm-1: 2982, 2929, 2856 (CHaliph), 1774
(C=O), 1628 (C=N), 1456, 1445, 1415 (CH2), 1267, 1232,
1189, 1002, 925 (C–O). UV spectrum, λmax, nm (log ε):
196 (3.95). 1H NMR spectrum, δ, ppm: 1.23 t (3H, Me,
J 7.2 Hz), 1.35–1.85 m (8H), 2.30–2.70 m [4H, (CH2)6],
4.18 q (2H, CH2O, J 7.2 Hz). Found, %: C 60.71; H 8.65;
N 6.78. M 187. C10H17NO3. Calculated, %: C 60.28;
H 8.60; N 7.03. M 199.25.
7. Dikusar, E.A. and Zhukovskaya, N.A., Zh. Org. Khim., 2008,
vol. 44, p. 1406.
8. Mikhaleva, A.I., Zaitsev, A.B., and Trofimov, B.A., Usp.
Khim., 2006, vol. 75, p. 884.
9. Dictionary of Organic Compounds, Heilbron, J. and
Bunbury, H. M., Eds., London: Eyre and Spottswoode, 1953,
vols. 1–3.
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