Synthesis of (o-alkylthio)nitrotoluenes
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 2, February, 2001
263
Table 2. 1H NMR spectra and data of elemental analysis of ortho-substituted nitrotoluenes
Com-
pound
Found
Calculated
Molecular
formula
1H NMR (solvent; δ, J/Hz)
(%)
C
H
N
S
2à
2b
55.07
55.26
48.92
48.98
3.73
3.97
3.41
3.42
9.33
9.21
9.61
9.52
10.71
10.53
10.94
10.89
C14H12N2O4S
C12H10N2O5S
Acetone-d6; 2.51 (s, 3 H); 4.51 (s, 2 H); 7.32 (m, 3 H);
7.47 (m, 2 H); 8.38 (d, 1 H, J = 2); 8.42 (d, 1 H, J = 2)
CDCl3; 2.54 (s, 3 H); 4.29 (s, 2 H); 6.26 (dd, 1 H,
J = 3, 1.5); 6.33 (d, 1 H, J = 3); 7.37 (d, 1 H, J = 1.5);
8.37 (d, 1 H, J = 2); 8.42 (d, 1 H, J = 2)
2c
2d
2e
48.59
48.88
5.08
5.22
10.48
10.36
11.98
11.86
C11H14N2O4S
C10H12N2O6S
C13H16N2O4S
CDCl3; 1.15 (d, 6 H, J = 10); 2.04 (nonet, 1 H, J = 10);
2.58 (s, 3 H); 2.88 (d, 2 H, J = 11); 8.21 (d, 1 H, J = 2);
8.34 (d, 1 H, J = 2)
41.45
41.67
4.09
4.20
9.81
9.72
11.22
11.12
Acetone-d6; 2.53 (s, 3 H); 3.27 (dd, 1 H, J = 14, 8);
3.48 (dd, 1 H, J = 14, 6); 3.66 (t, 2 H, J = 10); 3.96 (m, 2 H);
4.38 (d, 1 H, J = 8); 8.40 (d, 1 H, J = 2); 8.52 (d, 1 H, J = 2)
Acetone-d6; 1.49 (m, 6 H); 1.65 (m, 2 H); 1.79 (m, 2 H);
2.56 (s, 3 H); 3.51 (m, 1 H); 8.40 (d, 1 H, J = 2);
8.45 (d, 1 H, J = 2)
52.55
52.69
5.38
5.44
9.51
9.45
10.89
10.82
2f
2g
2h
2i
39.61
39.71
43.89
44.00
41.91
41.96
41.82
41.96
45.69
45.86
2.89
2.96
3.97
4.03
3.49
3.52
3.36
3.52
4.33
4.49
10.35
10.29
9.50
9.33
9.80
9.79
9.91
9.79
9.08
8.91
11.87
11.78
10.71
10.68
11.22
11.20
11.29
11.20
10.32
10.20
C9H8N2O6S
Acetone-d6; 2.51 (s, 3 H); 4.13 (s, 2 H); 8.47 (d, 1 H, J = 2);
8.52 (d, 1 H, J = 2)
Acetone-d6; 1.22 (t, 3 H, J = 9); 2.56 (s, 3 H); 4.12 (s, 2 H);
4.18 (q, 2 H, J = 10); 8.44 (d, 1 H, J = 2); 8.48 (d, 1 H, J = 2)
DMSO-d6; 2.44 (s, 3 H); 3.66 (s, 3 H); 4.28 (s, 2 H);
8.31 (d, 1 H, J = 2); 8.51 (d, 1 H, J = 2)
Acetone-d6; 1.61 (d, 3 H, J = 10); 2.64 (s, 3 H);
4.29 (q, 1 H, J = 9); 8.55 (d, 1 H, J = 2); 8.68 (d, 1 H, J = 2)
CDCl3; 1.25 (t, 3 H, J = 9); 1.65 (d, 3 H, J = 10);
2.63 (s, 3 H); 4.00 (q, 1 H, J = 9); 4.20 (q, 2 H, J = 9);
8.45 (d, 1 H, J = 2); 8.54 (d, 1 H, J = 2)
C11H12N2O6S
C10H10N2O6S
C10H10N2O6S
C12H14N2O6S
2j
3
65.98
66.11
46.03
46.15
4.96
5.02
4.79
4.93
3.72
3.67
9.81
9.78
16.91
16.81
11.29
11.20
C21H19NO2S2
C11H14N2O5S
DMSO-d6; 2.33 (s, 3 H); 4.34 (s, 4 H); 7.32 (m, 10 H);
7.91 (s, 2 H)
CDCl3; 1.14 (d, 3 H, J = 9); 1.26 (d, 3 H, J = 9);
2.42 (nonet, 1 H, J = 6); 2.61 (s, 3 H); 2.792.55 (m, 2 H);
8.80 (d, 1 H, J = 2); 9.08 (d, 1 H, J = 2)
4c
4g
41.63
41.77
3.74
3.82
8.98
8.86
10.22
10.14
C11H12N2O7S
Acetone-d6; 1.20 (t, 3 H, J = 9); 2.67 (s, 3 H); 3.88 (d, 1 H,
J = 18); 4.17 (q, 2 H, J = 10); 4.28 (d, 1 H, J = 18);
8.88 (d, 1 H, J = 2); 8.92 (d, 1 H, J = 2)
5a
5c
49.89
50.00
43.59
43.71
3.53
3.60
4.57
4.67
8.47
8.33
9.33
9.27
9.71
9.53
10.81
10.61
C14H12N2O6S
C11H14N2O6S
Acetone-d6; 2.68 (s, 3 H); 4.80 (s, 2 H); 7.32 (m, 5 H);
8.72 (d, 1 H, J = 2); 8.90 (d, 1 H, J = 2)
CDCl3; 1.15 (d, 6 H, J = 9); 2.42 (nonet, 1 H, J = 10);
2.92 (s, 3 H); 3.15 (d, 2 H, J = 9); 8.70 (d, 1 H, J = 2);
9.12 (d, 1 H, J = 2)
5g
39.78
39.76
3.52
3.64
8.59
8.43
9.33
9.65
C11H12N2O8S
Acetone-d6; 1.14 (t, 3 H, J = 10); 2.93 (s, 3 H);
4.12 (q, 2 H, J = 10); 4.74 (s, 2 H); 9.00 (d, 1 H, J = 2);
9.04 (d, 1 H, J = 2)
5h
5j
37.69
37.74
41.49
41.62
3.09
3.17
4.01
4.07
8.87
8.80
8.13
8.09
10.12
10.07
9.33
C10H10N2O8S
C12H11N2O8S
CDCl3; 2.92 (s, 3 H); 3.73 (s, 3 H); 4.32 (s, 2 H);
8.84 (d, 1 H, J = 2); 9.11 (d, 1 H, J = 2)
Acetone-d6; 1.08 (t, 3 H, J = 9); 1.68 (d, 3 H, J = 10);
2.91 (s, 3 H); 4.08 (q, 2 H, J = 10); 4.76 (q, 1 H, J = 9);
8.96 (d, 1 H, J = 2); 9.05 (d, 1 H, J = 2)
9.26
2-Alkylthio-4,6-dinitrotoluenes (2àj). A solution of TNT
(5.675 g, 0.025 mol) in N-MP (10 mL) was added to a mixture
of the corresponding alkanethiol (0.025 mol), K2CO3 (3.45 g,
0.025 mol), and N-MP (15 mL). The reaction mixture was
stirred under conditions given in Table 1. Then the mixture was
poured into cold water (120 mL). The precipitate that formed
was filtered off, dried, and recrystallized from the corresponding
solvent (see Table 1). Compounds 2à, 2b, 2g, 2h, and 2j were
dissolved in chloroform and filtered through a silica gel layer
(∼20 g) before recrystallization. In the cases of compounds 2f
and 2i, the reaction mixtures were poured into CH2Cl2 (120 mL).
The precipitates that formed were filtered off, dried, and dis-
solved in water and the solution were filtered. The filtrates were
acidified with HCl and the precipitates that formed were filtered
off and recrystallized.
2,6-Bis(benzylthio)-4-nitrotoluene (3). A mixture of com-
pound 2à (6.08 g, 0.02 mol), HMPA (20 mL), PhCH2SH
(2.48 g, 0.02 mol), and K2CO3 (2.76 g, 0.02 mol) was stirred at