COMMUNICATIONS
Akbar Heydari, Saied Aslanzadeh
(
m, 2H, CH ), 2.4–2.7 (br, 3H, NHOH, OH), 3.3 (m, 1H,
2
1
3
CHN), 3.6 (dd, J¼4 Hz, J¼10 Hz, 2H, CH OH); C NMR
2
(
6
22.4 MHz, CDCl ): d¼9.8 (CH ), 26 (CH ), 53.9 (CH OH),
3
3
2
2
5.6 (CHN).
2
c: White crystals, mp 158–1598C; IR (KBr): n¼3370, 1727,
ꢀ
1 1
1
432, 1189, 1010 cm ; H NMR (90 MHz, CDCl ): d¼0.86 (d,
3
J¼9 Hz, 3H, CH ), 0.97 (d, J¼9 Hz, 3H, CH ), 2 (m, 1H, CH),
3
3
1
3
3
(
(
.35 (d, J¼7 Hz, 1H, CHN), 3.75 (s, 3H, OCH ); C NMR
3
22.4 MHz, CDCl ): d¼18.2 (CH ), 25.3 (CH ), 31.5 (CH), 52
3
3
3
OCH ), 61 (CHN), 164 (C¼O). The spectra datal of the prod-
3
[5]
uct were identical with those of authentic samples.
2
d: White crystals, mp 65–678C; IR (KBr): n¼3355, 2925,
ꢀ
1 1
1
727, 1431, 1193 cm ; H NMR (90 MHz, CDCl ): d¼0.9 (d,
3
J¼ 2 Hz, 3H, CH ), 0.95 (d, J¼ 2 Hz, 3H, CH ), 1.2–1.6 (m,
3
3
3
(
2
1
H, CH, CH ), 3.4 (dd, J¼5 Hz, J¼13.5 Hz, 1H, CHN), 3.75
2
1
3
s, 3H, OCH ); C NMR (22.4 MHz, CDCl ): d¼21.4 (CH ),
3
3
3
2.6 (CH ), 24.3 (CH), 43.8 (CH ), 51.5 (OCH ), 52.5 (CHN),
3
2
3
77.4 (C¼O).
2
e: White crystals, mp 69–718C; IR (KBr): n¼3000–3500
ꢀ1 1
(
(
7
bs), 3064, 1487, 1439, 1369, 1298, 1154, 1074 cm ; H NMR
90 MHz, CDCl ): d¼1.4 (d, J¼7 Hz, 3H, CH ), 4.1(q, J¼
3
3
Hz, 1H, CH), 5.5–6.0 (br, 2H, NHOH), 7.2–7.5 (s, 5H, Ph).
The spectroscopic data are comparable with those reported
in the literature.
Scheme 1. Oxidation of primary amines using Na WO and
UHP.
[16]
2
4
2
f: Pale yellow crystals, mp 140–1428C; IR (KBr): n¼3210
ꢀ1 1
(
bs), 1726, 1431, 1196, 1008 cm
;
H NMR (90 MHz,
CDCl ): d¼3.7 (s, 3H, OCH ), 4.75 (s, 1H, CHN), 6.2–6.6
3
3
In summary, we have developed a novel methodology
for the direct conversion of primary amines to the corre-
sponding N-monoalkylhydroxylamines by way of oxida-
tion. The present protocol seems to be applicable to a
wide range of primary amines.
1
3
(
br, 2H, NHOH), 7.2–7.7 (s, 5H, Ph); C NMR (22.4 MHz,
CDCl ): d¼52.9 (OCH ), 58.4 (CHN), 127 (CH), 128.4 (CH),
3
3
1
29.6 (CH), 141 (C), 174.5 (C¼O). The spectral data of the
[4c]
product were identical with those of authentic samples.
2g: White crystals, mp 69–718C; IR (KBr): n¼3000–3500
ꢀ
1 1
(
br), 3064, 1487, 1439, 1369, 1298, 1154, 1074 cm ; H NMR
(
1
3
90 MHz, CDCl ): d¼2.2–2.4 (bs, 2H, NHOH), 2.9 (dd, J¼
3
4 Hz, 8 Hz, 1H), 3.04 (dd, J¼13.5 Hz, 5.2 Hz, 1H), 3.68 (s,
13
Experimental Section
H, OCH ), 3.7 (m, 1H, CH), 7.4 (s, 5H, Ar); C NMR
3
(
1
22.4 MHz, CDCl ): d¼40 (CH ), 51.7 (OCH ), 55.5 (CH),
3
2
3
26.6 (CH), 128 (CH), 129 (CH), 136.9 (C), 175(CO). The spec-
Typical Procedure:Preparation of N-
Monoalkylhydroxylamine 2f
tral data of the product were identical with those of authentic
samples.
[5,16a]
To a mixture of Na WO (0.032 g, 0.01 mmol, 10 mol %) and
2
4
2h: Pale yellow crystals, mp 828C; IR (KBr): n¼3340 (br),
ꢀ
1
1
1.2 mmol UHP (the exact concentration of H O in UHP was
2 2
1719, 1430, 1200 cm ; H NMR (90 MHz, CDCl ): d¼1.7–
3
determined by the addition of KI in 15 mL of acidic Et O to
2
2.0 (bs, 2H, NHOH), 3.2 (q, J¼5.5 Hz, J¼7.2 Hz, 2H, CH ),
2
the solution of 0.1 g of UHP in water and then titration with
Na S O ) in 15 mL of ether was added 0.165 g (1 mmol) of phe-
3
.5–4.0 (m, 4H, CH, OCH ), 7.0–7.7 (m, 5H, aryl), 8.5 (br,
3
13
2
2
3
1H, NH); C NMR (22.4 MHz, CDCl ): d¼30.4 (CH ), 51.8
3
2
nylglycine methyl ester. After stirring for 6 h at room temper-
ature, the resulting suspension was filtered through a pad of
Celite, and the filtrate concentrated on arotary evaporator. Pu-
rification of the residue by flash column chromatography on
silica gel (50% ethyl acetate in hexanes) gave the desired N-
(
OCH ), 54.7 (CHN), 110.9 (CH), 111.4 (CH), 118.9 (CH),
3
1
19.6 (CH), 122.3 (CH), 123 (C), 127.6 (C), 136.5 (C), 178
(
C O); The spectral data of the product were identical with
¼
[17]
those of authentic samples.
[14]
monoalkylhydroxylamine 2f; yield: 75%.
Acknowledgements
Product Characterization
Research supported by the National Research Council of I. R.
Iran as a National Research project under the number 984.
2
3
a·HCl: White crystals, mp 176–1808C; IR (KBr): n¼3000–
ꢀ1 1
500 (br), 1430, 1200, 1000 cm ; H NMR (90 MHz, DMSO/
13
CDCl ): d¼1.4 (s, 9H, CH ), 7.8–8.5 (br, 2H, NHOH);
C
3
3
NMR (22.4 MHz, DMSO, CDCl ): d¼26 (CH ), 50 (C). The
3
3
spectral data of the product were identical with those of au- References and Notes
[15]
thentic samples.
b: Oil; IR (KBr): n¼3315 (br), 2905, 1452, 1057 cm ; H
NMR (90 MHz, CDCl ): d¼0.9 (d, J¼8 Hz, 3H, CH ), 1.35
ꢀ
1 1
2
[1] a) H. C. J. Ottenneijm, J. D. M. Herscheid, Chem. Rev.
1986, 86, 697; b) W. R. Bowman, R. J. Marmon, in: Com-
3
3
1224
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2005, 347, 1223–1225