Synthesis of [2-(alkylarylthio)ethyl]pyridines
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 3, March, 2001
565
2-{2-[4-(Adamant-1-yl)phenylthio]ethyl}pyridine (5). A solu-
hydroxythiophenol (2.38 g, 10 mmol). The yield of compound 9
tion of 4-(adamant-1-yl)thiophenol (2.88 g, 11.78 mmol) in 5 mL
of benzene was added in one portion to 2-vinylpyridine (1.24 g,
11.78 mmol) in 0.5 mL of benzene. The reaction mixture was
heated at 60 °C for 3 h, cooled, and concentrated in vacuo. The
residue was purified by low-temperature recrystallization from
was 2.29 g (67%), m.p. 4446 °C (from MeOH). IR (KBr),
ν/cm1: 3280 (OH); 1600 (Ar); 1568 (Py); 1480 (CH2); 1240
(But). 1H NMR (DMSO-d6), δ: 1.26 (s, 9 H, But); 1.38 (s, 9 H,
3
But); 2.93 (t, 2 H, CH2, J = 16.8 Hz); 3.09 (t, 2 H, CH2,
3J = 16.8 Hz); 7.197.30 (4 H, Ar, Py); 7.73 (t, 1 H, Py,
3
etherlight petroleum (1 : 4) to give compound 5
(
3.35 g, 81.3%),
3J = 16.8 Hz); 8.51 (d, 1 H, Py, J = 4.6 Hz); 8.70 (s, 1 H,
20
n
1.5979. IR (thin film), ν/cm1: 2906 (Ad); 2856 (CH2);
OH). Found (%): C, 73.52; H, 8.51; S, 9.58; N, 4.11. C21H29NS.
Calculated (%): C, 73.42; H, 8.51; S, 9.33; N, 4.08.
4-[2-(3,5-Di-tert-butyl-2-hydroxyphenylthio)ethyl]pyridine
D
1592 (Ar); 1568 (Py); 1474 (CH2); 1450 (Ad); 1346 (Ad); 1098
(Ad). 1H NMR (CDCl3), δ: 1.78 (br.s, 6 H, Ad); 1.90 (br.s, 6 H,
Ad); 2.10 (br.s, 3 H, Ad); 3.11 (t, 2 H, CH2
,
3J = 16.0 Hz); 3.33
(10) was obtained by analogy with compound 5 from
(t, 2 H, CH2, 3J = 16.0 Hz); 7.127.37 (6 H, Ar, Py); 7.60 (t,
1 H, Py, 3J = 16.0 Hz); 8.53 (d, 1 H, Py, 3J = 5.3 Hz).
Found (%): C, 78.77; H, 7.75; S, 9.23; N, 3.94. C23H27NS.
Calculated (%): C, 79.03; H, 7.79; S, 9.17; N, 4.01.
4-vinylpyridine (0.87 g, 8.25 mmol) and 3,5-di-tert-butyl-2-
hydroxythiophenol (1.97 g, 8.25 mmol). The yield of sulfide 10
was 2.00 g (71%), m.p. 7173 °C (etherlight petroleum,
1 : 3). IR (KBr), ν/cm1: 3240 (OH); 1604 (Ar); 1564 (Py);
1440 (CH2); 1248 (But). 1H NMR (CDCl3), δ: 1.31 (s, 9 H,
But); 1.43 (s, 9 H, But); 2.85 (t, 2 H, CH2, 3J = 16.8 Hz); 2.99
(t, 2 H, CH2, 3J = 16.8 Hz); 6.98 (s, 1 H, OH); 7.10 (d, 2 H,
Py, 3J = 5.5 Hz); 7.33 (s, 2 H, Ar); 8.52 (d, 2 H, Py,
3J = 5.5 Hz). Found (%): C, 73.64; H, 8.45; S, 9.43; N, 3.86.
4-{2-[4-(Adamant-1-yl)phenylthio]ethyl}pyridine (6) was
obtained by analogy with compound 5 from 4-vinylpyridine
(1.39 g, 13.2 mmol) and 4-(adamant-1-yl)thiophenol (3.22 g,
13.2 mmol). The yield of sulfide 6 was 3.48 g (75.5%),
m.p. 4446 °C (from ether). IR (thin film), ν/cm1: 2902 (Ad);
2854 (CH2); 1600 (Ar); 1562 (Py); 1472 (CH2); 1448 (Ad);
C
21H29NS. Calculated (%): C, 73.42; H, 8.51; S, 9.33; N, 4.08.
1345 (Ad); 1102 (Ad). 1H NMR (CDCl3),
δ: 1.78 (br.s, 6 H,
Ad); 1.90 (br.s, 6 H, Ad); 2.10 (br.s, 3 H, Ad); 2.91 (t, 2 H,
CH2, 3J = 17.3 Hz); 3.17 (t, 2 H, CH2, 3J = 17.3 Hz); 7.11 (d,
2 H, Py, 3J = 6.5 Hz); 7.257.35 (4 H, Ar, Py); 8.51 (d, 2 H,
Py, 3J = 6.5 Hz). Found (%): C, 78.81; H, 7.79; S, 8.93;
N, 3.81. C23H27NS. Calculated (%): C, 79.03; H, 7.79;
S, 9.17; N, 4.01.
References
1. V. I. Laba, A. V. Sviridova, S. A. Bol´shakova, T. N.
Tuzhilkova, and V. P. Litvinov, Khim.-Farm. Zh., 1991, 25,
27 [Pharm. Chem. J., 1991, 25 (Engl. Transl.)].
2. A. Sviridova, V. Laba, I. Baskin, G. Ivanova, and
N. Rozhkova, IX Int. Congress Pesticide Chemistry. The Food-
Environment Challenge. Book of Abstracts, London (27 Au-
gust), 1998, 1, 1D-022.
3. F. Haviv, R. DeNet, R. J. Michaels, J. D. Ratajczyk, G. W.
Carter, and P. R. Young, J. Med. Chem., 1983, 26, 218.
4. US Pat. 4371696; Chem. Abstr., 1983, 98, 198035.
5. V. I. Laba, A. V. Sviridova, O. Yu. Rastegaev, and V. P.
Litvinov, Abstrs., XVI Mendeleev Congress on General and
Applied Chemistry, St.-Petersburg (2630 May), Moscow,
1998, 1, 148.
6. V. I. Laba, A. V. Sviridova, S. V. Vasil´ev, and V. P.
Litvinov, Khimiya i komp´yuternoe modelirovanie. Butlerovskie
soobshcheniya [Computer-Assistant Modeling in Chemistry.
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7. Organikum. Organisch-chemisches Grundpraktikum, Ed.
K. Schwetrich, Berlin, 1976, 1, 2.
8. USSR Author's Certificate 1 719 396; Chem. Abstr., 1992,
117, 212137.
2-[2-(4-tert-Butyl-2,6-dimethylphenylthio)ethyl]pyridine (7)
was obtained by analogy with compound 5 from 2-vinylpyridine
(
4.21 g, 40 mmol) and 4-tert-butyl-2,6-dimethylthiophenol (7.77 g,
40 mmol). The yield of sulfide 7 was 7.05 g (59%), m.p. 4648 °C
(from ether). IR (KBr), ν/cm1: 2956 (Me); 2862 (CH2); 1592
(Ar); 1570 (Py); 1474 (CH2); 1232 (But). 1H NMR (DMSO-d6),
δ: 1.26 (s, 9 H, But); 2.45 (s, 6 H, Me); 2.90 (t, 2 H, CH2
3J = 16.8 Hz); 3.02 (t, 2 H, CH2 3J = 16.8 Hz); 7.13 (s, 2 H, Ar);
,
,
7.167.26 (2 H, Py); 7.68 (t, 1 H, Py, 3J = 12.7 Hz); 8.45 (d,
1 H, Py, 3J = 4.2 Hz). Found (%): C, 76.31; H, 8.45; S, 10.60;
N, 4.71. C19H25NS. Calculated (%): C, 76.20; H, 8.41;
S, 10.71; N, 4.68.
4-[2-(4-tert-Butyl-2,6-dimethylphenylthio)ethyl]pyridine (8)
was obtained by analogy with compound 5 from 4-vinylpyridine
(1.56 g, 14.9 mmol) and 4-tert-butyl-2,6-dimethylthiophenol
(2.90 g, 14.9 mmol). The yield of sulfide 8 was 2.73 g (61.2%),
m.p. 8384 °C (from ether). IR (KBr), ν/cm1: 2956 (Me);
2862 (CH2); 1602 (Ar); 1562 (Py); 1480 (CH2); 1232
(But).1H NMR (CDCl3), δ: 1.32 (s, 9 H, But); 2.52 (s, 6 H,
Me); 2.812.95 (m, 4 H, CH2); 7.10 (d, 2 H, Py, 3J = 4.2 Hz);
7.12 (s, 2 H, Ar); 8.50 (d, 2 H, Py, 3J = 4.2 Hz). Found (%):
C, 76.33; H, 8.35; S, 10.45; N, 4.71. C19H25NS. Calculated (%):
C, 76.20; H, 8.41; S, 10.71; N, 4.68.
9. E. A. Bartkus, E. B. Hotelling, and M. B. Neuworth, J. Org.
Chem., 1960, 25, 232.
2-[2-(3,5-Di-tert-butyl-2-hydroxyphenylthio)ethyl]pyri-
dine (9) was obtained by analogy with compound 5 from
2-vinylpyridine (1.05 g, 10 mmol) and 3,5-di-tert-butyl-2-
Received October 11, 2000;
in revised form December 22, 2000