2-Benzothiazolyl-N-(arenesulfonyl)-sulfinimidoyl Fluorides 355
residue was treated with 10 mL ether; the formed
General Procedure for the Synthesis of 4a,b
crystals of 7 were filtered and dried in vacuum. Yield,
The solution of amine in 10 mL of benzene was
added during 0.5 h to the solution of 3b (0.50 g,
1.41 mmol) in 25 mL of benzene. The reaction mix-
ture was stirred at room temperature during 12 h.
The precipitate was filtered, washed with 10 mL of
benzene, dried in vacuum, washed with 50 mL of
water and dried in vacuum. The residue is 4a,b.
1
0.30 g (38%); mp 125–126◦C (decomp.); H NMR
(CDCl3): δ = 2.41 (s, 6H, CH3), 7.14–7.23 (m, 10H,
Ar H), 7.47 (d, 4H, J(HH) = 7.50 Hz, Ar H), 7.79
(d, 4H, J(HH) = 8, 10 Hz, Ar H); 13C NMR (CDCl3):
δ = 21.61 (CH3), 127.65 (Ar C), 128.93 (Ar C),
129.54 (Ar C), 131.00 (Ar C), 134.50 (Ar C),
137.27 (Ar C), 144.04 (Ar C); MS: (m/z, %) =
279 (M+/2, 23), 124 [C6H5SN+, 100]. Anal. Calcd for
C26H24N2O4S4 (556.7): C, 56.09, H, 4.34; N, 5.03; S,
23.03%. Found: C, 56.28; H, 4.29; N, 5.09; S, 23.00%.
2-Benzothiazolyl-N-(p-toluenesulfonyl)-sulfinimi-
doyl tert-Butylamide (4a). The solution of tert-butyl-
amine (0.20 g, 2.73 mmol) was added to the so-
lution of 3b. Yield, 0.45 g (80%); mp 181–183◦C
1
The Reaction of 3b* with
S-Trimethylsilylbenzenethiol
(decomp.). H NMR (CDCl3): δ = 1.49 (s, 9H, CH3),
2.30 (s, 3H, CH3), 5.56 (s, 1H, NH), 7.07 (d, 2H,
J(HH) = 8.10 Hz, Ar H), 7.46–7.56 (m, 2H, Ar H),
7.63 (d, 2H, J(HH) = 8.10 Hz, Ar H), 7.91 (d,
2H, J(HH) = 7.81 Hz, Ar H); MS: (m/z, %) = 321
[M+ C4H9N CH3, 5], 166 [(C7H4NS2)+, 6], 155
[(4-CH3C6H4SO2)+, 39], 135 [(C7H4NS)+, 24], 91
[(4-CH3C6H4)+, 100]. Anal. Calcd for C18H21N3O2S3.
(407.6): C, 53.04; H, 5.19; N, 10.31; S, 23.60%.
Found: C, 52.86; H, 5.25; N, 10.14; S, 23.45%.
S-Trimethylsilylbenzenethiol (0.35 g, 19.19 mmol)
was added dropwise with stirring to the solution of
3b* (0.70 g, 1.97 mmol) in 15 mL of benzene at
room temperature. The reaction mixture was stirred
at room temperature during 12 h. The precipitate
of 2 was filtered, washed with 5 mL of benzene,
and dried in vacuum. Yield, 0.25 g (78%); mp 177–
178◦C (Lit. [26], 178–180◦C). The filtrate was evapo-
rated in vacuum. 0.58 g of oily residue was treated
with 5 mL of ether; the formed crystals of 7* were
filtered and dried in vacuum. Yield, 0.13 g (24%);
mp 125–127◦C (decomp.); 1H NMR (CDCl3): δ = 2.41
(s, 6H, CH3), 7.14–7.23 (m, 10H, Ar H), 7.47 (d,
4H, J(HH) = 7.50 Hz, Ar H), 7.79 (d, 4H, J(HH) =
8, 10 Hz, Ar H); 15N NMR (DMSO): δ = 330.00; MS:
(m/z, %) = 280 (M+/2, 17), 124 [C6H5SN+, 100]. Anal.
Calcd for C26H2415N2O4S4 (558.7): C, 55.89; H, 4.33;
N, 5.37; S, 22.95%. Found: C, 55.65; H, 4.02; N, 5.56;
S, 23.01%.
2-Benzothiazolyl-N-(p-toluenesulfonyl)-sulfinimi-
doyl Morpholide (4b). The solution of morpholine
(0.25 g, 2.87 mmol) was added to the solution of 3b.
Yield, 0.53 g (90%); mp 154–155◦C (from methanol);
1H NMR (CDCl3): δ = 2.39 (s, 3H, CH3), 3.06 (dt,
2H, J(HH)ꢀ = 12.00 Hz, J(HH)ꢀꢀ = 4.50 Hz, CH2),
3.39 (dt, 2H, J(HH)ꢀ = 12.00 Hz, J(HH)ꢀꢀ = 4.50 Hz,
CH2), 3.71 (t, 4H, J(HH)ꢀꢀ = 4.50 Hz, CH2), 7.27
(d, 2H, J(HH) = 6.90 Hz, Ar H), 7.50–7.61 (m,
2H, Ar H), 7.87 (d, 2H, J(HH) = 8, 40 Hz, Ar H),
7.96 (d, 1H, J(HH) = 7.20 Hz, Ar H), 8.12 (d,
1H, J(HH) = 8.40 Hz, Ar H); MS: (m/z, %) = 336
[M+ C4H8NO, 8], 155 [(4-CH3C6H4SO2)+, 20], 91
[(4-CH3C6H4)+, 65], 86 [(C4H8NO)+, 100]. Anal.
Calcd for C18H19N3O3S3. (421.6): C, 51.28; H, 4.54;
N, 9.97; S, 22.82%. Found: C, 51.30; H, 4.55; N,
10.14; S, 22.83%.
REFERENCES
[1] Markovsky, L. N.; Penkovsky, V. V.; Shermolovich,
Yu. G. Rev Heteroatom Chem 1993, 9, 21–46.
[2] Levchenko, E. S.; Markovsky, L. N.; Shermolovich,
Yu. G. Zh Org Khim 2000, 36, 167–181 (in Russian).
[3] Markovsky, L. N.; Timoshenko, V. M.; Shermolovich,
Yu. G. Zh Org Khim 1995, 31, 161–178 (in Russian).
[4] Zibarev, A. V.; Yakobson, G. G. Usp Khim 1985, 54,
1706–1737 (in Russian).
[5] Levchenko, E. S.; Markovsky, L. N.; Shermolovich,
Yu. G. Zh Org Khim 1996, 32, 1447–1459 (in Russian).
[6] Koval, I. V. Sulfur Rep. 1993, 14, 149–221.
[7] Zefirov, N. S.; Zyk, N. V.; Kutateladze, A. G.;
Ignatenko, E. S.; Denisko, O. V. Zh Org Khim 1989,
25, 1576–1577 (in Russian).
[8] Dresdner, R. D.; Johar, J. S.; Merritt, G.; Peterson,
C. S. Inorg Chem 1965, 4, 678–681.
[9] Bludssus, W.; Mews, R. Chem Commun 1979, 1,
35–36.
[10] Bielfeldt, D.; Haas, A. Chem Ber 1983, 116, 1257–
1260.
The Reaction of 3b with
S-Trimethylsilylbenzenethiol
The solution of S-trimethylsilylbenzenethiol (0.52 g,
2.86 mmol) in 5 mL acetonitrile was added dropwise
with stirring to the solution of 3b (1.00 g, 2.83 mmol)
in 15 mL acetonitrile at room temperature. The reac-
tion mixture was stirred at room temperature during
12 h. The precipitate of 2 was filtered, washed with
15 mL of acetonitrile, and dried in vacuum. Yield,
0.39 g (83%); mp 177–178◦C [Lit. [26], 178–180◦C].
The filtrate was evaporated in vacuum. 0.95 g of oily