900
1
(
(
4
C=O), 1 620 and 1 280 (N=O); H-NMR δ 1.20–1.80
4.3.8. Methyl O-(3-nitrooxypivaloyl)-salicylate (SE 136)
1.52 g (10.0 mmol) methyl salicylate were treated with
1.63 g (10.0 mmol) 3c and 1.78 g (11.0 mmol) of CDI as
described for SE 135. The crude product was chromato-
graphed on a silica gel column with petroether/
ethylacetate (5:1). 2.37 g (80%) white powder; m.p. =
m, 16H, 8 × CH ); 2.20 (t, J = 7.8 Hz, 2H, CO-CH );
2
2
.50 (t, J = 7.8 Hz, 2H, CH -ONO ); 12.00 (s, 1H,
2 2
COOH). Anal. C H NO (C, H, N).
11
21
5
4
.3.5. 4-Nitrooxymethylbenzoic acid (3f)
–1
4
1
3
7–50 °C; IR (KBr) cm : 1 750 (C=O), 1 730 (C=O);
5
.38 g 4-bromomethylbenzoic acid in 30 mL of dry
1
625 and 1 280 (N=O); H-NMR δ 1.39 (s, 6H, C-CH ),
3
acetonitrile were added to 4.95 g (29.0 mmol) silver
nitrate in acetonitrile and stirred overnight. The filtrate of
the mixture was poured into 500 mL of icewater. The
precipitated crude product was separated, dried in vacuo
and recrystallized from diisopropylether. 4.12 g (84%)
white powder; m.p. = 165 °C; IR (KBr) cm : 1 690
C=O), 1 670 and 1 270 (N=O); H-NMR δ 5.65 (s, 2H,
.80 (s, 3H, O-CH ), 4.75 (s, 2H, CH -ONO ), 7.20 (dd,
3
2
2
J = 8.1/1.0 Hz, 1H, aromat. H-3), 7.42 (ddd, J = 8.1/1.0
Hz, 1H, aromat. H-5), 7.68 (ddd, J = 8.1/1.5 Hz, 1H,
aromat. H-4), 7.93 (dd, J = 8.1/1.5 Hz, 1H, aromat. H-6).
Anal. C H NO (C, H, N).
13
15
7
–1
1
(
4.3.9. Methyl S-(3-nitrooxypivaloyl)-thiosalicylate (SE
145)
CH -ONO ); 7.58 (d, J = 8.1 Hz, 2H, aromat. H-3,5);
2
2
7
.98 (d, J = 8.1 Hz, 2H, aromat. H-2,4). Anal. C H NO
2.58 g (15.3 mmol) 5a were treated with 2.50 g
(15.3 mmol) 3c and 2.73 g (16.86 mmol) CDI as de-
scribed for SE 135. The crude product was chromato-
graphed on a silica gel column with petrolether/
ethylacetate (5:1). 3.19 g (67%) white crystals; m.p. =
8
7
5
(C, H, N).
4
.3.6. Ethyl S-(11-nitrooxyundecanoyl)-thiosalicylate
(
SE 85)
.0 g (12.1 mmol) of 11-nitrooxyundecanoic acid (3g)
and 2.21 g (12.1 mmol) ethyl thiosalicylate (6b) were
dissolved in 30 mL of dry CH Cl . 2.73 g (13.23 mmol)
3
8–39 °C (crystallized from petrolether in the cold); IR
3
–1
(
KBr) cm : 1 730 (C=O), 1 690 (C=O), 1 630 and 1 275
N=O); H-NMR δ 1.35 (s, 6H, C-CH ), 3.79 (s, 3H,
1
(
3
2
2
O-CH ), 4.66 (s, 2H, CH -ONO ), 7.50–7.70 (m, 3H,
3 2 2
DCC, dissolved in 20 mL CH Cl , were added with
2
2
aromat. H-3,4,5), 7.88 (dd, J = 7.6/2.0 Hz, 1H, aromat.
protection by argon and stirred for 24 h. The solid was
separated, the filtrate washed with 0.1 N hydrochloric
acid (3 × 30 mL) and dried (Na SO ). After evaporation,
the crude product was chromatographed on a silica gel
column with ethylacetate. 0.86 g (17%) yellow paste; IR
H-6). Anal. C H NO S (C, H, N).
13
15
6
4.3.10. Ethyl S-(3-nitrooxypivaloyl)-thiosalicylate (SE
152)
2
4
Synthesized from 2.0 g (10.81 mmol) ethyl thiosalicy-
late (6b), 1.76 g (10.81 mmol) 3c and 1.93 g
(11.89 mmol) CDI as described for SE 135. The crude
product was chromatographed on a silica gel column with
petroleum ether/ethylacetate (4:1). 2.42 g (68%) yellow-
–1
(
NaCl) cm : 1 710 (C=O), 1 630 and 1 725 (N=O);
H-NMR δ 1.25–1.75 (m, 19H, 8 × CH , CH -CH ), 2.65
1
2
2
3
(
2
7
t, J = 7.2 Hz, 2H, CO-CH -(CH ) ), 4.25 (q, J = 7.1 Hz,
H, CH -CH ), 4.50 (t, J = 6.6 Hz, 2H, -CH -ONO ),
2 3 2 2
.50–7.70 (m, 3H, aromat. H-3,4,5); 8.82 (dd, J = 6.8/2.2
2 2 8
–1
ish oil; IR (NaCl) cm : 1 720 (C=O), 1 700 (C=O),
1
Hz, 1H, aromat. H-6). Anal. C H NO S (C, H, N).
1 635 and 1 280 (N=O); H-NMR δ 1.28 (t, J = 7.1 Hz,
20
29
6
2
2
3
H, CH -CH ), 1.35 (s, 6H, C-CH ), 4.26 (q, J = 7.1 Hz,
2 3 3
H, CH -CH ), 4.65 (s, 2H, CH -ONO ), 7.50–7.65 (m,
2
3
2
2
4
.3.7. S-(3-Nitrooxypivaloyl)-thiophenole (SE 135)
H, aromat. H-3,4,5), 7.87 (dd, J = 7.1/2.0 Hz, 1H,
1.63 g (10.0 mmol) of 3c in 50 mL of dry DMF were
aromat. H-6). Anal. C H NO S (C, H, N).
14
17
6
cooled to –10 °C and 1.78 g (11.0 mmol) of CDI were
added. After stirring (argon) for 2 h, 1.10 g (10 mmol) of
thiophenol were added and the reaction mixture was
stirred for another 2 h at –10 °C. 50 mL ethylacetate were
added, the mixture washed with saturated NaCl solution
4.3.11. O-(3-Nitrooxypivaloyl)-salicylic acid dimethyl-
amide (SE 157)
Synthesized from 1.65 g (10.0 mmol) salicylic acid
dimethylamide (7b) [17], 1.63 g (10.0 mmol) 3c and
1.78 g (11.0 mmol) CDI as described for SE 135. The
crude product was chromatographed on a silica gel
column with ethylacetate. 3.0 g (96%) colourless oil; IR
(
3 × 30 mL), dried over Na SO and evaporated. The
2 4
residue was chromatographed on a silica gel column with
petrolether/acetone (7:1). 0.7 g (28%) colourless oil; IR
–1
–1
(
NaCl) cm : 1 690 (C=O), 1 640 and 1 275 (N=O);
H-NMR δ 1.35 (s, 6H, C-CH ), 4.68 (s, 2H, CH -
(NaCl) cm : 1 750 (C=O), 1 650 (C=O), 1 640 and 1 280
(N=O); H-NMR δ 1.32 (s, 6H, C-CH ); 2.76 (s, 3H,
1
1
3
2
3
ONO2), 7.34–7.52 (m, 5H, aromat. H). Anal.
C H NO S(C, H, N).
N-CH ); 2.94 (s, 3H, N-CH ); 4.68 (s, 2H, CH -ONO );
7.19 (d, J = 8.1 Hz, 1H, aromat. H-3); 7.33–7.36 (m, 2H,
3
3
2
2
11
13
4