30
W. Przychodze n´ , L. Doszczak and J. Rachon
50.7 MHz ( N) in deuterochloroform. 15N spectra were mea-
15
were prepared by thionation of the respective amides 5
using Lawesson reagent.
sured in CDCl solutions at 0.14 M concentration in standard
3
Ring-substituted THAs 3 and benzohydroxamic acids 4
are new compounds.
NMR tubes (5 mm o.d.). Chemical shifts are referenced to
external CH NO .
3
2
15N long-range gHMQC spectra were acquired with
N-Isopropyl-4-methoxybenzothiohydroxamic acid (3a):
ꢀ
1
yield 10%; ꢀmax ꢁcm ꢂ 3439 (OH), 1222, 1180, 1167; υ
H
1.37
), 4.53 (1H, spt, CHCH ),
.92 (2H, d, J D 9, H-3/5), 7.34 (2H, d, J D 9, H-2/6), 10.7 (1H,
19.9 ꢁCH CHꢂ, 55.4 (CH CH), 55.4 (OCH ), 114.0
C-3/5), 130.5 (C-1), 128.2 (C-2/6), 160.6 (C-4), 180.8 (C S);
HRMS: calcd for C11 S, 225.08235; found, 225.08170.
N-Isopropyl-4-tert-butylbenzothiohydroxamic acid (3b):
yield 15%; υ 1.34 (9H, s, CCH ), 1.38 (6H, d, CHCH ), 4.51
1H, spt, CHCH
), 7.30 (2H, d, J D 9, H-2/6), 7.42 (2H, d,
J D 9, H-3/5), 9.0 (1H, br s, OH); υ 20.2 ꢁCH CHꢂ, 31.4
CCH ), 35.0 (CCH ), 55.6 (CH CH), 125.9 and 126.5 (C-2/6
and C-3/5), 135.5 (C-1), 153.2 (C-4), 181.0 (C S). HRMS:
calcd for C14 21NOS, 251.13439; found, 251.13371.
N-Isopropyl-4-chlorobenzothiohydroxamic acid (3d):-
yield 37%; m.p. 104–109 °C; υ
1.37 (6H, d, CHCH ), 4.41
1H, spt, CHCH
), 7.26–7.47 (4H, 2 ð d, J D 9, Ar-H), 9.8 (1H,
br s, OH); υ 19.9 ꢁCH CHꢂ, 55.6 (CH CH), 127.8 and 129.0 (C-
/6 and C-3/5), 131.4 (C-1), 136.3 (C-4), 179.2 (C S). HRMS:
pulse field gradients in absolute value mode. The spectral
1
15
(
6H, d, CHCH
3
), 3.85 (3H, s, OCH
3
3
windows for H and N domains were 6643 and 14 690 Hz,
respectively. The multiple-bond delay was set to 90 ms.
The data were collected in a 2048 ð 150 matrix with 24
6
br s, OH); υ
C
3
3
3
(
transients per t increment. The recycle period was 1.4 s.
1
H15NO
2
Sine-bell window functions were applied before Fourier
transformation in a 2K ð 1K matrix.
H
3
3
Chosen 2-D spectra slices were subjected to inverse
Fourier transformation (FT), zero-filling to 4K real points
and repeated FT of the resulting 1-D spectra in a digital
resolution of 2.5–3.5 Hz per point.
(
3
C
3
(
3
3
3
Standard procedures of the spectrometer software
(VNMR 5.1) were used. A comparison was made between the
results of the analysis for a central slice cutting the center of
each correlation peak and two additional neighboring slices
which gave the accuracy of š0.1 ppm. The reproducibility of
H
H
3
(
3
1
5
C
3
3
the N chemical shifts values for three spectra recorded at
different times of each compound was 0.3–0.4 ppm.
2
3
5
calcd for C10
N-Isopropyl-3-methoxybenzothiohydroxamic acid (3e):
yield 28%; υ 1.36 (6H, d, CHCH ), 4.45 (1H, spt, CHCH ),
.89 (1H, s, H-2), 6.90 (2H, d, J D 9, H-4 and H-6), 7.30 (1H,
t, J D 9, H-5), 10.8 (1H, br s, OH); υ 20.2 ꢁCH CHꢂ, 55.6
CH CH), 55.8 (OCH ), 112.3 (C-2), 115.6 (C-6), 118.7 (C-6),
30.1 (C-5), 139.6 (C-1), 159.9 (C-3) 180.3 (C S). HRMS: calcd
for C11 S, 225.08235; found, 225.08219.
N-Isopropyl-4-nitrobenzothiohydroxamic acid (3f): yield
8%; m.p. 153–155 °C; υ
1.40 (6H, d, CHCH ), 4.29 (1H, spt,
CHCH
), 7.54 (2H, d, J D 9, H-2/6), 8.28 (2H, d, J D 9, H-3/5),
0.8 (1H, br s, OH); υ 19.9 ꢁCH CHꢂ, 56.0 (CH CH), 124.1
C-3/5), 127.5 (C-2/6), 144.0 (C-1), 148.1 (C-4), 177.7 (C S).
HRMS: calcd for C10 S, 240.05686; found, 240.05717.
N-Isopropyl-4-methoxybenzohydroxamic acid (4a): yield
0%; m.p. 121–122 °C (ethyl acetate); υ
1.29 (6H, d, CHCH ),
.84 (3H, s, OCH ), 4.26 (1H, spt, CHCH
), 6.93 (2H, d, J D 9,
19.0
), 113.2 (C-3/5), 124.3
C-1), 128.8 (C-2/6), 160.9 (C-4), 166.6 (C O). Elemental
analysis: calcd for C11 , C 63.14, H 7.23, N 6.69; found,
C 63.41, H 7.48, N 6.69%.
N-Isopropyl-4-nitrobenzohydroxamic acid (4f): yield
0%; m.p. 107–110 °C (benzene–cyclohexane); υ
1.32 (6H,
d, CHCH ), 4.12 (1H, spt, CHCH
), 7.67 (2H, d, J D 9, H-
/6), 8.30 (2H, d, J D 9, H-3/5), 8.25 (1H, br s, OH); υ 19.6
CH CHꢂ, 52.4 (CH CH), 123.8 (C-3/5), 128.6 (C-2/6), 138.9
C-1), 148.9 (C-4), 164.4 (C O). Elemental analysis: calcd for
, C 53.57, H 5.39, N 12.49; found, C 53.55, H 5.34,
H12NOS Cl, 229.03281; found, 229.03224.
Acknowledgements
Financial support was provided by the Polish State Committee for
Scientific Research (KBN) (grant No. T09A 06116). We thank Dr P.
Sowi n´ ski for his help in measuring the NMR spectra.
H
3
3
6
C
3
(
3
3
REFERENCES
1
H15NO
2
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2
3
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3
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1
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(
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1
5
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3
H
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3
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CH CHꢂ, 52.0 (CH CH), 54.7 (OCH
3
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(
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3
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1
1
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3
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(
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1
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2
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NMR spectra
All spectra were recorded on a Varian Unity 500 Plus spec-
trometer operating at 500 MHz ( H), 125.7 MHz ( C) and
1
1
13
Copyright 2004 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2005; 43: 27–30