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γ-KETOSULFIDES AND HYDROXYSULFIDES
617
2
(d, 6H, C1,5H3, J = 6.9 Hz); 2.08 (s, 6H, 2CH3S); 1Н NMR (CDCl3), δ, ppm: 0.93 (d, 3H, 2J = 6.7 Hz)
2.45 (dd, 2Н, 2CH'S, 2J = 12.4, 3J1',2= 3J1'',4 = 2.7 Hz);
2.75−2.98 (4Н, m, 2CH''S, C2,4H); minor isomer:
2.09 (s, 6H, 2CH3S); 2.43 (dd, 2Н, 2CH'S, 2J = 12.7,
3J1',2= 3J1'',4 = 3.6 Hz). 13С NMR, δ, ppm, major iso-
mer: 16.28, 16.51 (2СH3S, C1,5); 36.67 (2CH2S); 45.23
(C2,4); 215.01 (C3); minor isomer: 16.28 (C1,5); 16.41
(2СH3S); 36.98 (2CH2S); 45.36 (C2,4); 214.53 (C3).
Mass spectrum (EI, 70 eV), m/z (Irel, %): 208
and 0.94 (d, 3H, C5H3, CH3C4, 2J = 6.7 Hz); 2.10 (s,
3Н) and 2.11 (s, 3Н, 2CH3S); 2.12−2.22 (m, 1Н, С4);
2.37−3.00 (m, 7Н, С1H, С3H2, 2CH2S). 13С NMR, δ,
ppm: 16.39 (2CH3S); 22.69 (С5, CH3C4); 23.89 (C4);
35.09 (2CH2S); 51.02 (C1); 53.03 (С3); 210.97 (C2).
Found, %: С 54.61; Н 9.08; S 29.07. Calculated for
С10Н20ОS2, %: С 54.50; Н 9.15; S 29.10.
5-Methyl-2-[(methylsulfanyl)methyl]hexan-3-one (IIе).
[С9H18O34S2]+•(4.5),
206
[M]+•(49.7),
159
20
Yield 9.86 g (63%), bp 70οС (1 mmHg), 20 1.4670,
[M−SCH3]+ (54.3), 117 [M−CH(CH3)CH2SCH3]+
(26.5), 111 [M−SCH3−HSCH3]+ (26.0), 89
[CH(CH3)CH2SCH3]+ (100), 61 [CH2SCH3]+ (61.5),
47 [SCH3]+ (6.5), 41 (40.0). Found, %: С 52.63;
Н 8.82; S 31.19. Calculated for С9Н18ОS2, %: С 52.38;
Н 8.79; S 31.08.
nD
d4
0.934. IR, ν, cm−1: 2959 (СH3, νasym), 2919 (СH2,
ν
δ
asym), 2872 (СH3, νsym), 1712 (C=O, ν), 1457 (СH3,
asym), 1429 (СH2, δasym), 1406, 1366 (СH3, δsym),
1295, 1245, 1169, 1143, 1036, 924. Isomer ratio 1 : 0.9.
1Н NMR (CDCl3), δ, ppm, major isomer: 0.88 (d,
3H, 2J = 6.5 Hz) and 0.90 (d, 3H, C6H3, CH3C5, 2J =
6.5 Hz); 1.12 (d, 3H, C1H3, 2J = 6.7 Hz); 2.07 (s, 3H,
CH3S); 2.33 (d, 2H, C4H2,2J = 7.2 Hz); minor isomer:
3-[(Methylsulfanyl)methyl]hexan-2-one (IIc) Yield
nD20
d420
1.4702,
10.65 g (74%), bp 62οС (1 mmHg),
0.947. IR, ν, cm−1: 2956 (СH3, νasym), 2929 (СH2,
2
0.87 (d, 3H, J = 6.5 Hz) and 0.89 (d, 3H, C6H3,
ν
asym), 2872 (СH3, νsym), 1708 (C=O, ν), 1456 (СH3,
CH3C5, 2J = 6.5 Hz); 1.11 (d, 3H, C1H3, 2J = 6.7 Hz);
2.06 (s, 3H, CH3S); 2.33 (d, 2H, C4H2, 2J = 7.2 Hz);
both isomers: 2.08−2.22 (m, 1H, С5H); 2.38−2.46
(m, 1Н) and 2.66−2.82 (m, 2Н, C2H, CH2S). 13С
NMR, δ, ppm: 16.06, 16.30 (СH3S, C1); 22.38, 22.44
(C6, CH3C5); 23.94 (C5); 36.64 (CH2S); 45.98 (С2);
δ
asym), 1425 (СH2, δasym), 1355 (СH3, δsym), 1240, 1188,
1
1159, 960. Н NMR (CDCl3), δ, ppm: 0.89 (t, 3H,
C6H3, J5,6 = 7.2 Hz); 1.27 (sextet, 2H, C5H2,3J5,4
=
3
3J5,6= 7.2 Hz); 1.41−1.67 (m, 2Н, C4H2); 2.08 (s, 3H,
CH3S); 2.17 (s, 3H, C1H3); 2.50−2.59 (m, 1Н, CH'S);
2.66−2.72 (m, 1Н, CH''S); 2.70−2.77 (1Н, m, C3H).
13С NMR, δ, ppm: 14.01 (C6); 16.08 (СH3S); 20.24
(C5); 29.66 (C1); 33.69 (C4); 35.29 (SСH2); 52.10 (C3);
50.66 (C4); 212.46 (C3). Found, %: С 62.20; Н 10.48;
S 18.46. Calculated for С9Н18ОS, %: С 62.02; Н 10.41;
S 18.40.
211.02 (C2). Found, %: С 59.87; Н 10.11; S 20.13. Cal-
culated for С8Н16ОS, %: С 59.95; Н 10.06; S 20.01.
5-Methyl-2,4-bis[(methylsulfanyl)methyl]hexan-3-one
20
(IIIе). Yield 1.47 g (14%), bp 123οС (1 mmHg),
4-Methyl-3-[(methylsulfanyl)methyl]pentan-2-one
nD
20
(IId). Yield 8.06 g (56%), bp 69−70οС (4 mmHg),
1.4970, 20 0.990. IR, ν, cm−1: 2963 (СH3, νasym), 2916
nD
d4
1.4740, 20 0.943. IR, ν, cm−1: 2960 (СH3, νasym), 2916
(СH2, νasym), 2873 (СH3, νsym), 1709 (C=O, ν), 1455
(СH3, δasym), 1427 (СH2, δasym), 1388 (СH3, δsym), 1371
(СH3, δsym), 1291, 1244, 1171, 1038, 960. Isomer ratio
1 : 0.9. 1Н NMR (CDCl3), δ, ppm, major isomer: 0.83
d4
(СH2, νasym), 2872 (СH3, νsym), 1710 (C=O, ν), 1465
(СH3, δasym), 1425 (СH2, δasym), 1369 (СH3, δsym),
1355 (СH3, δsym), 1273, 1155, 958. 1Н NMR (CDCl3),
2
(d, 3H, J = 7.0 Hz) and 0.86 (d, 3H, C6H3, CH3C5,
2
δ, ppm: 0.91 (d, 3H, J = 6.7 Hz) and 0.93 (d, 3H,
C5H3, CH3C4, 2J = 6.7 Hz); 1.86−1.98 (m, 1H, С4H),
2.06 (s, 3Н, CH3S); 2.19 (s, 3Н, С1H3); 2.50−2.78
(3Н, m, CH2S, С3Н). 13С NMR, δ, ppm: 15.92
(CH3S); 19.49, 20.60 (С5, CH3C4); 30.12, 31.02 (C1,
2J = 7.0 Hz); 1.13 (d, 3H, C1H3, 2J = 6.7 Hz); 2.03 (s,
3Н) and 2.05 (s, 3Н, 2CH3S); minor isomer: 0.90 (d,
3H, 2J = 6.8 Hz) and 0.95 (d, 3H, C6H3, CH3C5, 2J =
6.8 Hz); 1.15 (d, 3H, C1H3, 2J = 6.7 Hz); 2.04 (3Н, s)
and 2.07 (3Н, s, 2CH3S); both isomers: 1.84−2.00 (m,
1Н, C5H); 2.30−2.60 (m, 2Н) and 2.67−3.00 (m, 4Н,
С2H, С4H, 2CH2S). 13С NMR, δ, ppm, major isomer:
16.33, 16.54 (C1, 2CH3S); 18.44, 21.04 (С6, CH3C5);
29.70 (C5); 31.17 (C4CH2S); 36.23 (C2СH2S); 46.38
(C2); 56.57 (С4); 213.40 (C3); minor isomer: 15.44,
16.54 (2CH3S, C1); 19.19, 21.04 (С6, CH3C5); 29.45
(C5); 32.49 (C4CH2S); 36.99 (C2CH2S); 46.72 (C2);
C4); 32.63 (CH2S); 58.73 (С3); 210.91 (C2). Found, %:
С 59.94; Н 10.25; S 20.28. Calculated for
С8Н16ОS, %: С 59.95; Н 10.06; S 20.01.
4-Methyl-1,1-bis[(methylsulfanyl)methyl]pentan-
2-one (IIId). Yield 3.96 g (40%), bp 110οС (4 mmHg),
20
nD20
d4
1.5140,
1.033. IR, ν, cm−1: 2956 (СH3, νasym),
2916 (СH2, νasym), 2870 (СH3, νsym), 1712 (C=O, ν),
1465 (СH3, δasym), 1427 (СH2, δasym), 1365 (СH3,
δ
sym), 1307, 1219, 1170, 1141, 1068, 1043, 956. 57.25 (С4); 214.37 (C3). Found, %: С 56.50; Н 9.56; S
PETROLEUM CHEMISTRY Vol. 59 No. 6 2019