Thio derivatives of cyclopentanone and cyclohexanone

Article abstract of DOI:10.1134/S0965544108050101

Mono-and bis(methylthiomethyl) substituted derivatives of cyclopentanone and cyclohexanone were obtained on the basis of natural methylmercaptan via the alkylthiomethylation of ketones, and these derivatives were converted into the corresponding γ-hydroxy

Full text of DOI:10.1134/S0965544108050101

ISSN 0965-5441, Petroleum Chemistry, 2008, Vol. 48, No. 5, pp. 393–397. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © L.A. Baeva, A.D. Ulendeeva, D.D. Arslanova, O.V. Shitikova, E.G. Galkin, N.K. Lyapina, 2008, published in Neftekhimiya, 2008, Vol. 48, No. 5, pp. 390–394.
Thio Derivatives of Cyclopentanone and Cyclohexanone
L. A. Baeva, A. D. Ulendeeva, D. D. Arslanova, O. V. Shitikova, E. G. Galkin, and N. K. Lyapina
Institute of Organic Chemistry, pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: sulfur@anrb.ru
Received July 30, 2007
Abstract—Mono- and bis(methylthiomethyl) substituted derivatives of cyclopentanone and cyclohexanone
were obtained on the basis of natural methylmercaptan via the alkylthiomethylation of ketones, and these deriv-
atives were converted into the corresponding γ-hydroxysulfides and ketosulfones via reduction with sodium
borohydride and oxidation with hydrogen peroxide, respectively.
DOI: 10.1134/S0965544108050101
The rational use of mercaptans, sulfides, and
To synthesize thio derivatives of cyclopentanone (1)
thiophenes present in hydrocarbon feedstock is one of and cyclohexanone (2), we used a sulfide–alkaline
the most important tasks of the gas-processing and oil- waste liquor (SAL) from the Orenburg gas-processing
refining industries. Thus, the alkylthiomethylation plant containing 0.038 wt % sulfide and 3.20 wt % mer-
(ATM) of ketones with sulfide–alkaline waste liquor captide sulfur represented mainly by sodium methylm-
(SAW) [1, 2], which contains reactive sodium sulfide ercaptide (95%).
and sodium mercaptides, makes it possible to obtain
Synthesis of 2-(methylthiomethyl)cyclopentan-1-
various γ-ketosulfides differing in structure and proper-
one (3) and 2-(methylthiomethyl)cyclohexan-1-one
ties [3–6] as products promising for practical applica-
(4). Equimolar amounts of formaldehyde (46 ml of a
tion and to simultaneously regenerate sodium hydroxide.
30% solution) and cyclopentanone (45 ml) or cyclohex-
anone (52 ml) were successively added with stirring to
500 g of SAL containing 16 g (0.5 mol) of mercaptide
sulfur. The resultant mixture was stirred at room tem-
perature for 6 and 2 h, respectively, and, then, extracted
with chloroform (3 × 50 ml). The extracts were washed
with a 10% HCl solution, water (1 : 1 by volume), and
dried with MgSO4. Chloroform was evaporated, and
the residue was distilled in vacuum. The yield of 3 was
In this work, we studied the alkylthiomethylation of
cyclopentanone and cyclohexanone with a mixture of
formaldehyde and sodium methylmercaptide, which is
present in SAW, and obtained mono- and bis(methylth-
iomethyl) substituted ketones and their derivatives.
EXPERIMENTAL
54.7 g (76%), bp 80°ë (4 mmHg), d240 1.051, nD20
1.5085, MRD 40.94 (calculated 40.41). IR, ν, cm–1:
The IR spectra of the compounds were recorded on
a Specord M-80 instrument (in film or vaseline oil), and
1
the H and 13C NMR spectra were measured on a
1
1738 (C=O). ç NMR, δ, ppm: 1.65–1.85 m (2ç,
ë3ça, ë4ç‡), 1.96–2.20 m (2ç, ë3çe, ë4çe), 2.09 s
(3ç, SCH3), 2.15–2.40 m (3ç, ë2ç, ë5ç2), 2.50 dd
(1H, C1'HaS, Jgem 12.9 Hz, J1'‡, 2 8.4 Hz), 2.90 dd (1H,
C1'H‚S, Jgem 12.9 Hz, J1'‚, 2 3.7 Hz). 13ë NMR, δ, ppm:
16.26 (CH3S), 20.42 (ë4ç2), 28.99 (C3H2), 34.16
Brucker AM-300 spectrometer operating at frequencies
of 75 and 300 MHz, respectively, in ëDël3 using TMS
as an internal standard. Gas-chromatographic analysis
was carried out on a Chrom-5 chromatograph using a
flame-ionization detector and a 1.2 m × 3 mm column
packed with SE-30 (5%)-coated Chromaton N-AW-
DMCS (0.16–0.20 mm) at a column temperature of
50−300°ë; the carrier gas was helium. Gas chromato-
graphic–mass spectrometric (GC–MS) determinations
were performed with a Thermo Finnigan MAT 95 XP
instrument. The chromatographic separation conditions
were as follows: an HP-5MS column (5% dimethyl
phenyl methyl silicone, 95% dimethyl silicone) and
temperature programming from 50°ë (5 min) to 280°ë
(10 min) at a rate of 7°C/min. The sulfide and mercap-
tan sulfur contents were determined by means of poten-
tiometric titration with potassium iodate and diam-
minesilver nitrate, respectively [7].
(ëç2S), 38.10 (ë5ç2), 49.00 (ë2ç), 219.28 (C=O).
Found, %: C 58.30, H 8.35, S 23.66. Calculated for
C7H12OS, %: C 58.29, H 8.38, S 23.23.
The yield of 4 was 56.1 g (71%), bp 91–93°ë
(4 mmHg), d240 1.056, nD20 1.5090, MRD 44.75 (calcu-
1
lated, 45.03). IR, ν, cm–1: 1708 (C=O). ç NMR, δ,
ppm: 1.30 m (1ç, ë3ç‡), 1.60 m (2ç, ë4ç‡, ë5ç‡),
1.80 m (1ç, ë5çÂ), 1.95–2.05 m (1ç, ë4çÂ), 2.12 s
(3ç, CH3S), 2.15–2.40 m (4ç, C1'H‚S, ë3çÂ, ë6ç2);
2.40–2.60 m (1ç, ë2ç‡), 2.95 dd (1H, C1'HaS, Jgem 13.2
393

394
BAEVA et al.
Hz, J1'‡, 2 4.8 Hz). 13ë NMR, δ, ppm: 16.02 (CH3S),
24.59 (ë4ç2), 27.56 (C5H2), 33.02 (C3H2), 33.68
S 29.60. Calculated for C10H18OS2, %: C 55.00, H 8.31,
S 29.37.
(ëç2S), 41.61 (ë6ç2), 50.17 (ë2ç), 211.09 (C=O).
Found, %: C 60.90, H 8.85, S 19.76. Calculated for
C8H14OS, %: C 60.72, H 8.91, S 20.26.
Synthesis of g-hydroxysulfides (7–9). A solution
of 0.01 mol of ketosulfide 3, 4, or 6 in 15 ml of ethanol
was added gradually to a mixture of 0.38 g (0.01 mol)
of NaBH4, 26.7 ml of ethanol, 13.3 ml of water, and
0.2 ml of 10% NaOH solution heated to 50°ë. The
resultant mixture was stirred at 50°ë for 3 h, cooled,
diluted with 100 ml of water, and extracted with chlo-
roform (3 × 50 ml). The extract was dried with MgSO4,
and chloroform was evaporated.
Synthesis of 2,5-bis(methylthiomethyl)cyclopen-
tan-1-one (5) and 2,6-bis(methylthiomethyl)cyclo-
hexan-1-one (6). Equimolar amounts of formaldehyde
(46 ml of a 30% solution) and 0.25 mol of cyclopen-
tanone (22.5 ml) or cyclohexanone (26 ml) were suc-
cessively added with stirring to 500 g of SAL contain-
ing 16 g (0.5 g-at) of mercaptide sulfur. The resultant
mixtures were stirred at 50°ë for 1 and 0.5 h, respec-
tively, cooled, and extracted with chloroform (3 ×
50 ml). The extracts were washed with a 10% HCl solu-
tion, water (1 : 1 by volume), and dried with MgSO4.
Chloroform was evaporated, and the residue of 5(19)
was chromatographed on a column packed with SiO2 (a
1 : 4 ethyl acetate–petroleum ether solvent blend
(40−70°ë)). The yield of 5 was 0.49 g (49%). IR, ν,
2-(Methylthiomethyl)cyclopentan-1-ol (7). The
yield 1.37 g (94%), d240 1.044, nD20 1.5170, MRD 42.38
(calc. 41.92). IR, ν, cm–1: 3392 (OH). 1ç NMR, δ, ppm:
trans-isomer, 1.15–1.35 m (1ç, ë3ç‡), 2.15 s (3ç,
CH3S), 2.20–2.70 br.s (2ç, éç, ë2ç), 2.53 dd (1H,
ë1'ç‡S, Jgem 12.9 Hz, J1'‡, 2 7.9 Hz), 2.62 dd (1H,
ë1'ç‚S, Jgem 12.9 Hz, J1'‚, 2 5.7 Hz), 3.95 q (1H, C1H, J
6.2 Hz), cis-isomer, 2.15 s (3ç, CH3S), 2.20–2.70 br.s
(2ç, éç, ë2ç), 2.55–2.72 m (2ç, ë1'ç‡S, ë1'ç‚S);
4.30 dd (1H, C1H, J 6.2 Hz, J 4.8 Hz); trans- and cis-
isomers, 1.50–2.00 m (5H + 6H, ë3ç + ë3ç2, ë4ç2,
ë5ç2). The 13ë NMR spectrum, δ, ppm: trans-isomer,
15.70 (CH3S), 21.49 (ë4ç2), 30.12 (C3H2), 34.14
(C5H2), 38.41 (ëç2S), 46.35 (ë2ç), 79.08 (ë1ç); cis-
isomer, 15.95 (CH3S), 22.21 (C4H2), 29.31 (C3H2),
34.31 (C5H2), 34.51 (ëç2S), 44.53 (ë2ç), 73.74
1
cm–1: 1726 (C=O). ç NMR, δ, ppm: 2.10 s, 2.08 s
(6ç, 2CH3S), 2.20–2.34 m (4ç, ë3ç2, ë4ç2), 2.60 m
(4ç, ë2ç, ë5ç, ë1'ç‚S, ë1''ç‚S), 2.73 dd (2H, ë1'ç‡S,
13
ë1''ç‡S, Jgem 12.1, J1'‡, 2 = J1''‡, 5 4.2 Hz). ë NMR, δ,
ppm: cis-isomer, 17.74 (2CH3S), 27.08 (C3H2, C4H2),
37.88 (2ëç2S), 56.59 (ë2ç, ë5ç); 222.49 (C=O);
trans-isomer, 17.63 (2CH3S), 27.14 (C3H2, C4H2),
37.41 (2ëç2S), 56.68 (ë2ç, ë5ç), 222.50 (C=O).
Found, %: C 52.77, H 7.75, S 31.66. Calculated for
C9H16OS2, %: C 52.90, H 7.89, S 31.38.
(ë1ç). Found, %: C 57.45, H 9.48, S 21.01. Calculated
for C7H14OS, %: C 57.49, H 9.65, S 21.92.
The yield of 6 was 50.7 g (93%), d240 1.095, nD20
1.5425, MRD 62.81 (calculated, 62.33). IR, ν, cm–1:
2-(Methylthiomethyl)cyclohexan-1-ol (8). The
yield of 8 was 1.57 g (98%), d240 1.040, nD20 1.5171,
1
1714 (C=O). ç NMR, δ, ppm: cis-isomer, 1.39 dq
1
MRD 46.63 (calc. 46.54). IR, ν, cm–1: 3384 (OH). ç
(2H, ë3ç‡, ë5ç‡, Jgem = J3‡, 4‡ = J3‡, 2‡ 13.2 Hz, J3‡, 4Â
4.0 Hz), 1.78 dtt (1H, ë4ç‡, Jgem 13.8 Hz, J4‡, 3‡ = J4‡, 5‡
13.2 Hz, J4‡, 3 = J4‡, 5 3.7 Hz), 1.94 dtt (1H, ë4ç Jgem
13.8 Hz, J4Â, 3‡ = J4Â, 5‡ 4.0 Hz, J4Â, 3Â = J4Â, 5Â 3.0 Hz),
2.12 s (6ç, 2CH3S), 2.37–2.45 m (2ç, ë5çÂ, ë3çÂ),
NMR, δ, ppm: trans-isomer, 1.05 dq (1H, ë3ç‡, Jgem
12.5 Hz, J3‡, 4Â 3.3 Hz), 2.15 s (3ç, ëç3S), 2.52 dd (1H,
ë1'ç‡S, Jgem 13.0 Hz, J1'‡, 2 6.7 Hz), 2.78 dd (1H, ë1'ç‚S,
Jgem 13.0 Hz, J1'‚, 2 5.6 Hz), 3.40 dt (1H, ë1ç‡, J1, 6‡
=
J1, 2 = 9.8 Hz, J1, 6Â 4,4 Hz); cis-isomer, 2.08 s (3ç,
ëç3S), 2.48 dd (1H, ë1'ç‡S, Jgem 12.8 Hz, J1'‡, 2 6.5 Hz),
2.62.dd (1H, ë1'ç‚S, Jgem 12.8 Hz, J1'‚, 2 8.0 Hz), 4.08
2.37 dd (2H, ë1'ç‚S, ë1''ç‚S, Jgem 13.2 Hz, J1'‚, 2‡
J1''‚, 6‡ 7.8 Hz), 2.57 dddd (2H, ë2ç‡, ë6ç‡, J2‡, 1'‚
=
=
J6‡, 1''‚ 7.8 Hz, J2‡, 1'‡ = J6‡, 1''‡ 5.0 Hz, J2‡, 3‡ = J6‡, 5‡ 13.2
br.s (1H, C1H); trans- and cis-isomers, 1.20–1.35 m,
1.40–.60 m, 1.60–1.75 m, 1.75–2.00 m (9H + 10H,
ë2ç, ë3ç + ë3ç2, ë4ç2, ë5ç2, ë6ç2, OH). 13ë
NMR, δ, ppm: trans-isomer, 16.45 (CH3S), 24.76
Hz, J2‡, 3 = J6‡, 5 3.5 Hz), 2.95 dd (2H, ë1'ç‡S, ë1''ç‡S,
Jgem 13.2 Hz, J1'‡, 2 = J1''‡, 6 5.0 Hz); trans-isomer, 1.62
br.s (2ç, ë4ç2), 1.70–1.80 m (2ç, ë5ç‡, ë3ç‡), 2.09 s
(6ç, CH3S), 2.50–2.60 m (4ç, ë1'ç‚S, ë1''ç‚S, ë3çÂ,
ë5çÂ); 2.70 dq (2H, ë2ç, ë6ç, J2,3 ‡ = J2, 1'‡ = J2, 1'‚
6.0 Hz, J2, 3 1.5 Hz), 2.89 dd (2H, ë1'ç‡S, ë1''ç‡S, Jgem
12.8 Hz, J1'‡, 2 = J1''‡, 6 6.0 Hz). 13ë NMR, δ, ppm: cis-iso-
mer, 16.22 (2CH3S); 24.82 (ë4ç2); 33.57 (C3H2,
C5H2); 34.37 (2ëç2S); 50.70 (ë2ç, ë6ç); 211.01
(C=O); trans-isomer, 15.58 (2CH3S), 19.92 (ë4ç2),
31.70 (2ëç2S), 34.02 (C3H2, C5H2), 48.09 (ë2ç,
ë5ç), 212.34 (C=O). Found, %: C 54.25, H 8.28,
(C5H2), 25.58 (ë4ç2), 35.54 (C3H2), 37.27 (C6H2),
38.63 (ëç2S), 44.15 (ë2ç), 74.85 (ë1ç); cis-isomer,
16.18 (CH3S), 25.20 (C5H2), 26.62 (ë4ç2), 30.81
(C3H2), 33.08 (ëç2S), 38.63 (C6H2), 40.71 (ë2ç),
68.19 (ë1ç). Found, %: C 59.20, H 10.10, S 19.91.
Calculated for C8H16OS, %: C 59.95, H 10.06, S 20.01.
2,6-Bis(methylthiomethyl)cyclohexan-1-ol (9).
The yield of 9 was 2.14 g (97%), d240 1.105, nD20
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THIO DERIVATIVES OF CYCLOPENTANONE AND CYCLOHEXANONE
395
29.94 (C3H2), 36.56 (C5H2), 41.87 (CH3Sé2), 43.73
(ë2ç), 54.63 (ëç2Sé2), 216.89 (C=O). Found, %: C
47.80, H 6.40, S 18.21. Calculated for C7H12O3S, %: C
47.71, H 6.86, S 18.19.
1.5492, MRD 63.46 (calc. 63.85). IR, ν, cm–1: 3424
1
(OH). ç NMR, δ, ppm: trans, trans-isomer, 1.10 dq
(2H, ë3ç‡, ë5ç‡, J3‡, 4 3.4 Hz, Jgem = J3‡, 4‡ = J3‡, 2‡
13.0 Hz), 2.10 s (6ç, 2ëç3S), 2.48 dd (2H, ë1'ç‡S,
ë1''ç‡S, Jgem 13.0 Hz, J1'‡, 2 = J1''‡, 6 7.1 Hz), 2.62 dd (2H,
ë1'ç‚S, ë1''ç‚S, Jgem 13.0 Hz, J1'‚, 2 = J1''‚, 6 7.9 Hz), 3.24
t (1H, C1H, J 9.6 Hz), 4.12 br.s (1H, OH); trans,cis-iso-
mer, 2.18 s (6ç, 2ëç3S), 2.50 dd (2H, ë1'ç‡S, ë1''ç‡S,
2-(Methylsulfonylmethyl)cyclohexan-1-one (11).
The yield of 11 was 3.69 g (97%), mp 50–51°ë. IR, ν,
1
cm–1: 1712 (C=O), 1304, 1132 (SO2). ç NMR, δ,
ppm: 1.51 dq (1H, ë3ç‡, J3‡, 4 3.8 Hz, Jgem 12.8 Hz),
1.60–1.90 m (3ç, ë4ç‡, ë5ç2), 1.95–2.00 m (1ç,
ë4çÂ), 2.10–2.20 m (1ç, ë3çÂ), 2.35–2.55 m (2ç,
ë6ç2), 2.75 dd (1H, ë1'ç‚, Jgem 14.4 Hz, J1'‚, 2 5.6 Hz),
2.95 s (3ç, ëç3SO2), 3.10 dddd (1H, ë2ç‡, J2, 1'‚
5.2 Hz, J2, 1'‡ 5.6 Hz, J2, 3‡ 12.8 Hz, J2, 3Â 5.9 Hz), 3.85 dd
J
gem 13.0 Hz, J1'‡, 2 = J1''‚, 6 6.8 Hz), 2.80 dd (2H, ë1'ç‚S,
ë1''ç‚S, Jgem 13.0 Hz, J1'‚, 2 = J1''‚, 6 5.1 Hz), 3.80 dd (1H,
ë1ç, J1, 6Â 3.4 Hz, J1, 2‡ 6.4 Hz), 4.12 br.s (1H, OH);
trans,trans- and trans,cis-isomers, 1.25–1.40 m, 1.40–
1.50 m, 1.50–1.65 m, 1.65–2.00 m (6H + 8H, ë3ç +
13
(1H, ë1'ç‡, Jgem 14.4 Hz, J1'‡, 2 5.6 Hz). ë NMR, δ,
ppm: 25.16 (ë4ç2), 27.81 (C5H2), 35.05 (C3H2), 41.94
(C6H2), 42.49 (ë2ç), 45.51 (CH3Sé2), 54.34
(ëç2Sé2), 209.15 (C=O). Found, %: C 50.70, H 7.39,
S 16.21. Calculated for C8H14O3S, %: C 50.51 H 7.41,
S 16.85.
13
ë3ç2, ë5ç + ë5ç2, ë4ç2, ë2ç, ë6ç). ë NMR, δ,
ppm: trans,trans-isomer, 16.10 (2CH3S), 25.95 (C3H2,
C5H2), 30.71 (ë4ç2), 37.84 (2ëç2S), 41.60 (ë2ç,
C6H), 68.99 (ë1ç); trans,cis-isomer, 16.43 (2CH3S),
25.04 (ë4ç2), 25.47 (C3H2, C5H2), 38.45 (2ëç2S),
43.99 (ë2ç, C6H), 77.96 (ë1ç); cis,cis-isomer, 15.97
(2CH3S), 19.94 (C3H2, C5H2), 34.40 (ë4ç2), 37.06
(2ëç2S), 39.19 (ë2ç, C6H), 73.57 (ë1ç). Found, %: C
55.80, H 9.15, S 29.47. Calculated for C10H20OS2, %: C
54.50, H 9.15, S 29.10.
2,6-bis(Methylsulfonylmethyl)cyclohexan-1-one
(12). The yield of 12 was 4.86 g (86%), mp 146–148°ë.
IR, ν, cm–1: 1712 (C=O), 1300, 1136 (SO2). 1ç NMR,
δ, ppm: cis-isomer, 1.50 m (2ç, ë3ç‡, ë5ç‡), 1.95 m
(2H, ë4ç2, Jgem 10.5 Hz), 2.50 m (2ç, ë3çÂ, ë5çÂ),
2.80 dd (2H, ë1'ç‚, ë1''ç‚, Jgem 14.4 Hz, J1'‚, 2 5.1 Hz),
2.98 s (6ç, 2ëç3SO2), 3.30 dddd (2H, ë2ç‡, ë6ç‡,
J2, 1'‡ 6.4 Hz, J2, 1'‚ 5.1 Hz, J2, 3‡ 12.0 Hz, J2, 3Â 6.0 Hz),
3.85 dd (2H,ë1'ç‡, ë1''ç‡, Jgem 14.4 Hz, J1'‡, 2 6.4 Hz).
13ë NMR, δ, ppm: cis-isomer, 24.82 (ë4ç2), 35.64
(C3H2, C5H2), 42.36 (ë2ç, C6H), 45.64 (CH3Sé2), 53.99
(ëç2Sé2), 207.30 (C=O). Found, %: C 42.80, H 6.67,
S 22.80. Calculated for C10H18O5S2, %: C 42.54, H
6.42, S 22.71.
Synthesis of g-ketosulfones (10–12). A mixture of
4.7 and 9.4 ml (0.046 and 0.092 mol, respectively) of
33% hydrogen peroxide and five drops of concentrated
sulfuric acid were successively added with stirring to a
cooled (ice bath) solution of 0.02 mol of ketosulfide 3,
4, or 6 in 10 ml of acetic acid. The resultant mixture was
stirred at room temperature for 9 h and allowed to stand
overnight, then diluted with water (50 ml), and
extracted with chloroform (2 × 45 ml). The extract was
successively washed with NaHCO3 and NaCl solutions
and water (1 : 1 by volume) and dried with MgSO4.
Chloroform was evaporated, and the residue was
recrystallized from ethanol.
RESULTS AND DISCUSSION
The mono methylthiomethylated cyclic ketones
2-(methylthiomethyl)cyclopentan-1-one
(3)
and
2-(Methylsulfonylmethyl)cyclopentan-1-one (10). 2-(methylthiomethyl)cyclohexan-1-one (4) or the bis
The yield of 10 was 2.93 g (83%), mp 60–62°ë. IR, ν, methylthiomethylated
substituted
ketones
cm–1: 1740 (C=O), 1292, 1136 (SO2). ç NMR, δ, 2,5-bis(methylthiomethyl)cyclopentan-1-one (5) and
ppm: 1.70 dq (1H, ë3ç‡, Jgem = J3‡, 2‡ = J3‡, 4‡ 11.4 Hz, 2,6-bis(methylthiomethyl)cyclohexan-1-one (6) were
J3‡, 4 6.1 Hz), 1.83–1.92 m (1ç, ë4ç‡), 2.08–2.20 m obtained with 76, 71, 49, and 93% yields, respectively,
(2ç, ë3çÂ, ë4çÂ), 2.33–2.50 m (1ç, ë2ç‡), 2.50– via the alkylthiomethylation of cyclopentanone 1 and
2.75 m (2ç, ë5ç2), 2.90 dd (1H, ë1'ç‚, Jgem 14.0 Hz, cyclohexanone 2 with equimolar amounts or two molar
J1'‚, 2 9.0 Hz), 2.97 s (CH3Sé2), 3.57 dd (1H, ë1'ç‡, Jgem equivalents of formaldehyde and SAL sodium meth-
14.0 Hz, J1'‡, 2 3.0 Hz). 13ë NMR, δ, ppm: 20.46 (ë4ç2), ylmercaptide.
1
O
O
O
O
2CH2O, 2CH3SNa
CH2O, CH3SNa
+
50°
S
S
S
S
S
20°
n
n
n
n
5, 6
1, 2
3, 4
6
where n = 1 for 1, 3, and 5 and n = 2 for 2, 4, and 6.
PETROLEUM CHEMISTRY Vol. 48 No. 5 2008

396
CH3SNa conversion, rel. %
BAEVA et al.
methylthiomethylated mixture. The reactivity of 4 is
100
80
60
40
20
higher than that of 3: the yield of 2,6-bis(methylthiom-
ethyl)cyclohexan-1-one 6 is 1.9 times that of
2,5-bis(methylthiomethyl)cyclopentan-1-one 5.
The yield of mono(methylthiomethyl) substituted
cyclohexanone 4 decreases (from 71 to 65%) with an
increase in the reaction time of more than 2 h owing to
its transformation to 2,6-bis(methylthiomethyl)cyclo-
hexan-1-one 6.
The yield of mono- and bis(methylthiomethyl) sub-
stituted cyclohexanones 4 and 6 significantly depends
on the reagents ratio. For example, the use of a 1.7-fold
excess of ketone and formaldehyde (over the stoichio-
metric amounts) decreases the yields of compounds 4
and 6 to 51 and 35%, respectively.
d
e
‡
c
b
The alkylthiomethylation of cyclopentanone is
accelerated by a sodium hydroxide admixture (1 mole
per mole of Smer) (figure); however, the yield of desired
product 3 decreases from 71 to 61% because of the side
process of the formation of 2-(cyclopentylidene)cyclo-
pentan-1-one identified by GC–MS analysis. The mass
spectrum of the compound was identical to that pub-
lished in [8].
The structure of γ-ketosulfides 3–6 was established
on the basis of spectral data. The IR spectra of 3–6
exhibit carbonyl absorption bands at 1708–1738 cm–1.
The 13C NMR spectra of 3–6 contain methyl (δ 15.58–
17.74 ppm) and methylene (δ 31.70–37.88 ppm) signals
of methylthiomethyl carbon atoms along with the sig-
nals from the carbon atoms of the cycle. The 1H NMR
spectra contain a singlet of thiomethyl protons (δ 2.09–
2.17 ppm). Bis(methylthiomethyl) substituted ketones
5 and 6 are represented by a mixture of the cis- and
trans-isomers in ratios of 2 : 1 and 4 : 1, respectively.
0
1
2
3
4
5
6
τ, h
Dependence of the sodium methanethiolate conversion on
the time of alkylthiomethylation of (a, b, d) cyclopentanone
and (c, e) cyclohexanone at (a, b, c) the equimolar reactant
ratio, 20°C; (b) in the presence of sodium hydroxide (1 mol
per mole of S ); and (d, e) at a ketone : CH O : S molar
mer
2
mer
ratio of 1 : 2 : 2, 50°C.
The ATM reactivity of cyclohexanone is higher than
that of cyclopentanone (figure); however, the yield of
2-(methylthiomethyl)cyclohexan-1-one 4 (71%) is
below that of 2-(methylthiomethyl)cyclopentan-1-one
3 (76%), a difference that is due to the subsequent
transformation of 4 to 2,6-bis(methylthiomethyl)cyclo-
hexan-1-one 6. The introduction of the ëç3SCH2 group
into the molecule of 4 occurs at room temperature and
the equimolar ratio of the reactants, whereas the reac-
The reduction of the carbonyl group of γ-ketosul-
fides 3, 4, and 6 with sodium borohydride (50°ë, 3 h)
results in the formation of γ-hydroxysulfides 7–9 with
tion with 3 proceeds at 50°ë and a twofold excess of the yields of 94, 98, and 97%, respectively.
O
O
OH
NaBH4,
C2H5OH–H2O
2H2O2,
CH3COOH
R
R
R
S
S
S
O
O
n
n
n
7–9
3, 4, 6
10–12
3, 7, 10 – n = 1, R = H; 4, 8, 11 – n = 2, R = H;
6, 9 – n = 2, R = CH2SCH3; 12 – n = 2, R = CH2SO2CH3.
The IR spectra of γ-hydroxysulfides 7–9 exhibit
hydroxyl absorption bands at 3384–3424 cm–1. The 1H
and 13C NMR spectra contain proton (δ 3.24–4.30 ppm)
and carbon (δ 68.19–79.08 ppm) signals, respectively,
of the methine group with an attached hydroxyl group.
γ-Hydroxysulfides 7 and 8 are represented by mixtures
of their trans- and cis-isomers (1.3 : 1 and 1.5 : 1,
respectively); 9 is a mixture of the trans,trans-,
trans,cis-, and cis,cis-isomers (7 : 4 : 1).
The oxidation of γ-ketosulfides 3, 4, and 6 with two
and four equivalents of hydrogen peroxide (20°ë, 9 h),
respectively, results in the formation of γ-ketosulfones
10–12 with yields of 83, 97, and 86%, respectively.
The IR spectra of γ-ketosulfones 10–12 exhibit
intense absorption bands due to the carbonyl (1712–
1740 cm–1) and sulfonyl (1132–1136, 1292–1304 cm–1)
groups. In the 13C NMR spectra, the signals of methyl
(δ 41.87–45.51 ppm) and methylene (δ 53.99–
PETROLEUM CHEMISTRY Vol. 48 No. 5 2008

THIO DERIVATIVES OF CYCLOPENTANONE AND CYCLOHEXANONE
397
2. A. D. Ulendeeva, L. A. Baeva, O. R. Valiullin, et al.,
Neftekhimiya 46, 139 (2006) [Pet. Chem. 46, 122
(2006)].
54.63 ppm) carbon atoms bearing the sulfonyl group
are downfield shifted relative to those of the same car-
bon atoms in ketosulfides.
3. A. D. Ulendeeva, L. A. Baeva, T. S. Nikitina, et al., in
Proceedings of III All-Russia Scientific INTERNET Con-
ference “Integration of Science and Higher Education in
the Field of Bioorganic and Organic Chemistry and
Mechanics of Multiphase Systems”, Ufa, 2004, p. 60.
2-(Methylthiomethyl)cyclohexan-1-one 4 thus pre-
pared was tested as a corrosion inhibitor for Steel 20
(a grade of structural steel) using model hydrogen sul-
fide-containing mineralized media. It was shown that
the addition of 100 mg/l of γ-ketosulfide 4 to the corro-
sive medium increases the degree of protection against
general corrosion to 90.8%.
4. V. V. Potapov, R. A. Khisamutdinov, Yu. I. Murinov,
et al., Zh. Prikl. Khim. (St. Petersburg) 74, 1070 (2001).
5. N. K. Algebraistova, N. V. Gudkova, E. A. Alekseeva,
et al., RU Patent No. 2 185 249, Byull. Izobret., No. 20
(2002).
In summary, the use of the sulfide–alkaline liquor
from the Orenburg gas-processing plant as a source of
sodium methylmercaptide in the ATM of cyclopen-
tanone and cyclohexanone makes it possible to prepare
the mono- and bis(methylthiomethyl) substituted
ketones and to reduce them to γ-hydroxysulfides or to
oxidize to γ-ketosulfones. The results of this work
extend the range of practically useful compounds syn-
thesized from natural mercaptans. The obtained keto-
sulfides can be used as corrosion inhibitors, extracting
agents for noble metals [9], and intermediaries in
organic synthesis [10, 11].
6. N. A. Gafarov, V. M. Kushnarenko, D. E. Bugai, et al.,
Corrosion Inhibitors (Khimiya, Moscow, 2002) [in Rus-
sian].
7. I. A. Rubinshtein, Z. A. Kleimenova, and E. P. Sobolev,
in Methods for Analysis of Petroleum Organic Com-
pounds, Their Mixtures and Derivatives (Moscow,
1960), p. 74.
8. Z. Jedlinski, A. Misiotek, W. Glowkowski, et al., Tetra-
hedron 46, 3547 (1990).
9. V. P. Krivonogov, N. G. Afzaletdinova, Yu. I. Murinov,
et al., Zh. Prikl. Khim. (St. Petersburg) 71, 828 (1998).
REFERENCES
10. I. Paterson and I. Fleming, Tetrahedron Lett., No. 11,
995 (1979).
1. A. D. Ulendeeva, L. A. Baeva, E. G. Galkin, et al.,
Neftekhimiya 38, 214 (1998) [Pet. Chem. 38, 197
(1998)].
11. I. Paterson, Tetrahedron 44, 4207 (1988).
PETROLEUM CHEMISTRY Vol. 48 No. 5 2008