Synthesis of aryl diazonium nitrates from aryl ureas and dioxane-NO2 adduct

Article abstract of DOI:10.1081/SCC-100000520

Aryl urea reacts with dioxane-NO₂ adduct to give dry aryl diazonium nitrate in high purity and yield.

Full text of DOI:10.1081/SCC-100000520

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SYNTHESIS OF ARYL DIAZONIUM NITRATES FROM ARYL
UREAS AND DIOXANE-NO ADDUCT
2
a
b
b
b
c
Zhenrong Zhang , Qingzhi Zhang , Shensong Zhang , Xinming Liu & Gensuo Zhao
a
Fenyang School, Shanxi Medical University , Fenyang, 632200, People's Republic of
China
b
Department of Chemistry , Henan Normal University , Xinxiang, 453002, People's
Republic of China
c
Analytical Center, Henan Chemical Institute , Zhengzhou, 450002, People's Republic of
China
Published online: 09 Nov 2006.
To cite this article: Zhenrong Zhang , Qingzhi Zhang , Shensong Zhang , Xinming Liu & Gensuo Zhao (2001) SYNTHESIS OF
ARYL DIAZONIUM NITRATES FROM ARYL UREAS AND DIOXANE-NO ADDUCT, Synthetic Communications: An International
2
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:3, 329-334, DOI: 10.1081/SCC-100000520
To link to this article: http://dx.doi.org/10.1081/SCC-100000520
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SYNTHETIC COMMUNICATIONS, 31(3), 329–334 (2001)
SYNTHESIS OF ARYL DIAZONIUM
NITRATES FROM ARYL UREAS AND
DIOXANE-NO ADDUCT
2
1
,∗
1,†
Zhenrong Zhang, Qingzhi Zhang, Shensong
1
1
2
Zhang, Xinming Liu, and Gensuo Zhao
1Department of Chemistry, Henan Normal University,
Xinxiang 453002, People’s Republic of China
Analytical Center, Henan Chemical Institute, Zhengzhou
2
450002, People’s Republic of China
ABSTRACT
Aryl urea reacts with dioxane-NO2 adduct to give dry aryl
diazonium nitrate in high purity and yield.
As classic but everlasting synthetic intermediates, diazonium salts have long
been used in dyes and the pharmarceutical industry (1–6). Recently, diazonium
salts have found new application in recording and imaging material science (7–12)
and research into the reactivity of diazonium salts is still active (13–17). The most
frequently employed diazonium salts in these fields are classical aryl diazonium
chlorides, diazonium tetrafluoroborates, diazonium hydrosulfates, and diazonium
dihydrophosphates (1–4). The synthesis and application of aryl diazonium nitrates
are seldom studied, however. The reason is that nitric acid is a strong oxidizing
∗
Present address: Fenyang School, Shanxi Medical University, Fenyang 632200, People’s
Republic of China.
†
Corresponding author.
3
29
Copyright ꢀC 2001 by Marcel Dekker, Inc.
www.dekker.com

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3
30
ZHANG ET AL.
agent; thus, it is difficult to use nitric acid and sodium nitrite to convert aryl amines
into the corresponding diazonium nitrates. To avoid the oxidation of aryl amine by
nitric acid, Kagiyama and Tsurushima (18) once used alkyl nitrites to convert aryl
amines into corresponding diazonium nitrates, while Backman (19) used N2O4
in CHCl3 to react with PhNCO to give phenyldiazonium nitrates, and Hnaupp
and Herrmann (20) used solid aryl amines to react with NO2 gas to give solid
diazonium nitrate salts.
During a recent study on the treatment and utilization of the waste gas
NOx with organic compounds, we separately used TBP (tributyl phosphate), PEG
(polyethylene glycol), and DMF (dimethyl formamide) to absorb NO2 gas and
obtained TBP-NO2, PEG-NO2 and DMF-NO2 adducts. Then dioxane was used as
absorbent to absorb NO2 gas to give a dioxane-NO2 adduct. All of these adducts
were found to be mild oxidizing agents. In attempting to oxidize aryl ureas with
dioxane-NO2, aryl diazonium nitrates were obtained in high yield and high purity.
This result provided a new method for the synthesis of diazonium nitrates and the
utilization of NOx waste.
The reaction schemes are as follows:
O
O + NO2
O
O
NO2 + trace solide
O
O
ArNHCNH2 + 2 O
O
NO2
[ArNHCOH] + N2 + H2O + 2O
O
O
O
NO2
+
−
ArN2 NO3
+
H O
2
ArNH2 + CO2
Compared to the IR spectrum of dioxane, the IR spectrum of the dioxane-
−
1
NO2 absorbent solution indicated the new peaks at 1350, 875, and 890 cm
.
−1
The 1350 cm absorption is due to NO2 in the absorbent solution, which shifted
0 cm to the low-frequency side compared with that of NO2. The 875 and
90 cm signals are due to ring-shaped skeletal vibrations of dioxane in dioxane-
NO2, which shifted correspondingly 45 and 50 cm to the high-frequency side,
compared with that of dioxane. This suggests that the dioxane-NO2 adduct is
formed by the weak attraction between the lone electron pair of oxygen and the
partial positive charge on the nitrogen of NO2.
−
−
1
3
8
1
−
1
When the ratio of NO2 to dioxane was above 2 or locally above 2 during
the process of absorption, crystals formed under room temperature, which was the
adduct of dioxane-N2O4 (25).
Aryl ureas reacted with dioxane-NO2 adduct to give off gases (CO2 and
N2) at room temperature. The aryl urea solids disappeared completely in 5 min.

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SYNTHESIS OF ARYL DIAZONIUM NITRATES
331
Table 1. Diazonium Nitrate from Aryl Urea and Dioxane-NO
2
Entry
1
Aryl Urea
Product
State
Yield (%)
95.4
O
+
−
NHCNH2
N2 NO3
Colorless needle
O
+
−
NHCNH2
N2 NO3
2
Colorless needle
90.2
CH3
CH3
O
+
−
NHCNH2
N2 NO3
3
4
Colorless needle
Colorless needle
94.7
88.4
H3C
H3C
O
+
−
NHCNH2
N2 NO3
Cl
Cl
O
N2+ NO−3
NHCNH2
5
6
Colorless needle
Colorless needle
90.1
94.7
Cl
Cl
Cl
O
+
−
NHCNH2
Cl
N2 NO3
O
+
−
NHCNH2
N2 NO3
7
Colorless needle
94.0
Br
Br
O
+
−
N2 NO3
NHCNH2
8
9
Colorless needle
Colorless needle
94.3
95.0
Br
Br
Br
O
N2+ NO−
3
NHCNH2
Br
About 15 min later, new solids precipitated. The new solids were recrystilized using
−
1
DMF and Et2O and dried in vacuo (see Table 1). The IR peaks at 2252–2295 cm
,
+
−1
indicated the existence of ArN , while the peaks at 1384 and 825–826 cm can
2
be assigned to the absorption of νNO3
−
. These new solids can also be confirmed as
1
diazonium nitrates through microanalysis and H NMR spectroscopy (see Table 2).
Those aryl diazonium nitrates with an electron-poor group were very stable and
could be stored at room temperature in a desiccator for 6 months with no change.
On the other hand, the other diazonium nitrates could be stored at 10–15 C for
months. When the room temperature was higher (e.g., 30 C in summer), these
◦
◦
2
◦
diazonium nitrates gradually darken. When heated to 65 C or hit or ignited, the
dry diazonium nitrates exploded. These diazonium nitrates are expected to be as

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ZHANG ET AL.
Table 2. Spectral Data of Diazonium Nitrate
IR (KBr,
Disc cm
Microanalysis
(%) Found (cal)
1H NMR (δ, ppm)
−1
)
Product
b
a
8
8
7
.49 (d,2H,H
a
)
2295 (m, sharp)
1384 (vs)
825 (w)
C: 43.42 (43.11)
H: 3.17 (3.02)
N: 25.05 (25.15)
+
−
c
N2 NO3
.22 (s,1H,H
.89 (s,2H,H
c
)
b
)
b
d
a
8.40 (s,1H,H
a
)
2261 (w, sharp)
1385 (vs)
844 (w)
C: 46.81 (46.40)
H: 4.02 (3.90)
N: 23.90 (23.20)
c
N2 NO3
+
−
8.07 (d,1H,Hc)
7.69 (m,2H,H
.72 (s,3H,CH
CH3
b
+) H
d
)
2
3
b
a
+
−
8.30 (s,2H,H + H )
2279 (m, sharp)
1384 (vs)
825 (w)
C: 46.72 (46.40)
H: 3.67 (3.90)
N: 23.59 (23.20)
c
N2 NO3
a
c
b
d
d
8.04 (s,1H,H
)
)
H3C
7
2
8
8
8
7
.76 (s,1H,H
.47 (s,3H,CH )
3
.60 (m,1H,H
.20 (m,1H,H
.00 (m,1H,H
.83 (m,1H,H
b
c
a
a
d
c
b
)
)
)
)
2270 (m, sharp)
1384 (vs)
826 (w)
C: 34.92 (35.75)
H: 1.79 (2.00)
N: 20.21 (20.85)
+
−
N2 NO3
d
Cl
b
c
a
8
8
8
.60 (s,1H,H
.49 (d,1H,H
.25 (d,1H,H
d
)
2294 (w)
1384 (vs)
826 (w)
C: 35.90 (35.75)
H: 1.87 (2.00)
N: 20.94 (20.85)
+
−
N2 NO3
a
)
)
d
Cl
c
7
.88 (t,1H,H
b
)
b
a
8
.51 (d,2H,H
a
)
)
2287 (w)
1384 (vs)
C: 35.79 (35.75)
H: 1.91 (2.10)
+
−
Cl
N2 NO3
7
.94 (d,2H,H
b
8
26 (w)
N: 21.04 (20.85)
b
c
a
8
8
7
.61 (d,1H,H
.13 (m,2H,H
a
)
2263 (m, sharp)
1384 (vs)
826 (m)
C: 28.71 (29.29)
H: 1.81 (1.64)
N: 17.31 (17.08)
+
−
N2 NO3
c
d
+ H )
d
Br
.88 (t,1H,H
b
)
b
c
a
8
8
8
7
.73 (s,1H,H
d
)
)
)
2278 (m, sharp)
1384 (vs)
826 (w)
C: 29.48 (29.29)
H: 1.45 (1.64)
N: 17.20 (17.08)
+
−
N2 NO3
.52 (d,1H,H
.40 (d,1H,H
.80 (t,1H,H
a
d
Br
Br
c
b
)
8
.41 (d,2H,H
a
)
)
2273 (s)
1384 (vs)
C: 29.57 (29.29)
H: 1.77 (1.64)
b
a
+
−
8.12 (d,2H,H
b
N2 NO3
8
26 (m)
N: 17.27 (17.08)
reactive as other diazonium salts. As synthetic intermediates, the high yield, dry
state, and high purity of diazonium nitrates achieved by this method render it more
versatile than other diazonium salts. Further studies on the applications of the dry
diazonium nitrates are underway.

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SYNTHESIS OF ARYL DIAZONIUM NITRATES
EXPERIMENTAL
333
All A.R.-grade solvents and reactants were used without further purification.
1
IR spectra were obtained on a FTS-40 infrared spectrophotometer, H NMR spec-
tra were recorded on a Bruker DPX-400 spectrometer, using TMS as an internal
standard. Microanalyses were performed on a PE-2400 microelemental analyzer.
Starting material aryl ureas were prepared according to the published method from
the corresponding aryl amines and ureas (26). The typical procedure is described
here.
Dioxane-Nitrogen Dioxide Adduct. To 35.2 g (0.5 mol) of sodium nitrite
(98%) in a three-neck round bottom flask, 30 g (0.3 mol) of conc. sulfuric acid
(98%) was added dropwise with a constant pressure funnel at room temperature
(after all conc. sulfuric acid had been added, the mixture was heated so that it
reacted completely). The evolved NOx gases were blown by a stream of oxygen
intotheflask, thenthroughacondenserintoadryingtower(packedwiththemixture
of phosphorus pentoxide and quartz sand), then into an oxidizing tower (packed
with quartz sand carrying chromium trioxide) to insure complete oxidation of NO
to NO2, and finally into an absorption tower (height 300 mm, inside diameter
15 mm, packed with glass rings). Through the top of the absorption tower, 44.1 g
(
0.5 mol) dioxane was added dropwise with a constant pressure funnel to induce
counterface absorption. The adding rate of dioxane and conc. sulfuric acid and
the rate of the oxygen stream were controlled to provide a complete absorption.
The liquid dropping from the bottom of the absorption tower was dioxane-NO2
adduct.
Aryl Diazonium Salts. To 1 mmol of aryl urea solids in 2 mL dioxane
◦
were added 0.85 mL (10 mmol) dioxane-NO2 adduct at 15–30 C. Gases evolved.
About 5 min later, the aryl urea solids disappeared completely. About 15 min
later, the diazonium nitrates began to precipitate. The reaction was monitored by
TLC. After the completion of the reaction (about 4 h), the diazonium nitrates were
filtered and washed with Et2O. Pure diazonium nitrates were obtained through
recrystallization by dissolving the crude product in DMF and then adding Et2O
and evaporation in vacuo.
ACKNOWLEDGMENTS
This program is supported by the National Science Foundation of China and
Henan Province Education Committee.

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ZHANG ET AL.
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Received in the UK December 2, 1999

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