A rapid and convenient method for preparing acylhydrazines from acyldiazenes

Article abstract of DOI:10.1002/jccs.200400125

The synthesis of acylhydrazines by using hydrazine hydrate as the reductant to hydrogenate acyldiazenes is reported. Twelve acylhydrazines have been synthesized from acyldiazenes in excellent yields under mild conditions. This method is rapid, convenient, and efficient.

Full text of DOI:10.1002/jccs.200400125

Journal of the Chinese Chemical Society, 2004, 51, 835-837
835
A Rapid and Convenient Method for Preparing Acylhydrazines from
Acyldiazenes
Jian-Ping Li* (
Gui-Rong Qu (
), Shu-Qiang Yu (
) and Yu-Lu Wang (
),
)
College of Chemistry and Environmental Science, Henan Normal University, Xinxiang, 453002, P. R. China
The Key Laboratory of Environmental Science and Technology of High Education of Henan Province,
Xinxiang, 453002, P. R. China
The synthesis of acylhydrazines by using hydrazine hydrate as the reductant to hydrogenate acyldiazenes
is reported. Twelve acylhydrazines have been synthesized from acyldiazenes in excellent yields under mild
conditions. This method is rapid, convenient, and efficient.
Keywords: Acylhydrazines; Acyldiazenes; Hydrazine hydrate.
INTRODUCTION
Acylhydrazine compounds have caused great interest
pensive catalysts and operations are tedious. In this paper, us-
ing hydrazine hydrate without a catalyst as reductant, twelve
acylhydrazines have been synthesized from acyldiazenes in
excellent yields under mild conditions. The structures of
in organic synthesis because of their extensive applied val-
ues. Some acylhydrazines and their derivatives exhibit a
broad spectrum of biological activities such as antifungal,1
antiviral, regulating plant growth,2 restraining the reproduc-
tion of multi-cell parasites and are used as insecticides,3,4 her-
bicides5 and pesticides.6,7 Moreover, as a kind of widely-used
intermediate, their metal [Cu(II), Ni(II), Zn(II), Co(II), Ga,
In, Iron(III), and Ca] complexes possess more effective bio-
logical activities.8-12 Besides, acylhydrazine compounds are
also extensively used in heterocyclic chemistry,13 photo-
graphic technology, paint synthesis, textile fabrics dyes,
chemical luminescence reactions, etc.
1
these products were confirmed by IR, H NMR, 13C NMR,
MS and elemental analysis.
Scheme
.
NH2NH2 H2O
X
CON=N
Y
r.t. ( 5-15min )
1
X
CONHNH
2a-l
Y
In general, acylhydrazines are prepared by substituted
hydrazines or their derivatives’ interactions with ester, acyl
chloride and carboxylic acid. The synthesis of acylhydra-
zines from acyldiazenes directly has seldom been reported. In
the process of our further research on acyldiazenes, we found
that hydrazine hydrate is an efficient reductant to hydroge-
nate acyldiazenes to form acylhydrazines. To our knowledge,
it is the first time for hydrazine hydrate to be used in hydroge-
nating this type of acyldiazenes. This reaction has its pecu-
larities and has potential applied value to some extent.
a: X = H,
c: X = MeO, Y = NO2
e: X = EtO, Y = Cl
g: X = Br,
i: X = EtO, Y = Br
k: X = Br, Y = Br
Y = NO2
b: X = EtO,
d: X = Br,
f: X = MeO, Y = Cl
h: X = H, Y = Br
j: X = MeO, Y = Br
l: X = EtO, Y = H
Y = NO2
Y = NO2
Y = Cl
In the course of the experiments, it is found that the re-
action speed of acyldiazenes with a substitution group of
nitryl(-NO2) on the aromatic rings is much quicker than oth-
ers. The possible reason is that nitryl is a strong electron-
attracting group which is relevant to reaction speed.
RESULTS AND DISCUSSION
This method only needs simple instruments and is easy
to operate. All the reaction periods are only about 5-15 min.
Hydrazine hydrate is a traditional reductant which is
used in a variety of reactions. But its reactions often need ex-

836 J. Chin. Chem. Soc., Vol. 51, No. 4, 2004
Li et al.
In conclusion, it is a rapid and convenient method for the
preparation of acylhydrazines from acyldiazenes with hydra-
zine hydrate as reductant.
1-(p-Methoxybenzoyl)-2-(p-nitrophenyl)hydrazine (2c)
Pale-yellow leaflets; Yield: 96%; mp 245-246 °C (lit.14
248 °C); IR (KBr) n: 3323, 3228, 3084, 3011, 2845, 1625,
1604, 1510 cm-1; 1H NMR d: 3.82 (s, 3H, CH3), 6.82-8.08 (m,
8H, ArH), 9.15 (s, 1H, NH), 10.48 (s, 1H, NH); Anal. calcd.
for C14H13N3O4: C, 58.53; H, 4.56; N, 14.63. Found: C, 58.76;
H, 4.43; N, 14.40.
EXPERIMENTAL SECTION
Melting points were determined with a Kofler micro
melting point apparatus and were uncorrected. IR spectra
1-(p-Bromobenzoyl)-2-(p-nitrophenyl)hydrazine (2d)
Pale-yellow needles; Yield: 83%; mp 243-245 °C (lit.15
247-249 °C); IR (KBr) n: 3322, 3242, 3084, 1633, 1594,
1506 cm-1; 1H NMR d: 6.84-8.10 (m, 8H, ArH), 9.22 (s, 1H,
NH), 10.71 (s, 1H, NH); Anal. calcd. for C13H10BrN3O3: C,
46.45; H, 3.00; N, 12.50. Found: C, 46.71; H, 3.32; N, 12.75.
1
were recorded on a FTS-40 spectrophotometer in KBr. H
NMR and 13C NMR spectra were measured on a Bruker
DPX-400M (13C NMR spectra on DPX-100M) spectrometer
using TMS as internal standard and DMSO-d6 as solvent. MS
were implemented on an HP-5989B mass spectrograph with
acetone as solvent. Elemental analyses were performed on a
PE-2400 CHN elemental analyzer.
1-(p-Ethoxybenzoyl)-2-(p-chlorophenyl)hydrazine (2e)
White leaflets; Yield: 89%; mp 182-183 °C; IR (KBr)
n: 3363, 3262, 3060, 2987, 2944, 1646, 1607, 1491 cm-1; 1H
NMR d: 1.35 (t, 3H, CH3), 4.10 (q, 2H, CH2), 6.76-7.89 (m,
8H, ArH), 8.01 (s, 1H, NH), 10.23 (s, 1H, NH); 13C NMR d:
166.91 (C=O), 162.29, 149.70, 130.22, 129.50, 125.84,
122.96, 115.14, 114.83 (Ar-C), 64.39 (CH3), 15.53 (CH2).
Anal. calcd. for C15H15ClN2O2: C, 61.97; H, 5.20; N,9.64.
Found: C, 61.68; H, 5.04; N, 9.49.
General procedure for the preparation of acylhydrazines
(2a-l)
Acyldiazene (1 mmol) and ethyl ether (10 mL) were
placed in a round bottomed flask. Hydrazine hydrate (1.05
mmol) was added over 5-6 min under stirring at room temper-
ature. The mixture was stirred for 5-15 min. Pale-yellow or
white precipitate came into being. It was filtrated, recrys-
tallized and dried to yield the pure product.
The yields of the reactions are more than 80%. Accord-
ing to the emergence of the N-H absorption in the 1H NMR,
IR and MS spectrum, the reaction was proved to take place
and be carried out completely. All the compounds gave satis-
factory analytical and spectral data.
1-(p-Methoxybenzoyl)-2-(p-chlorophenyl)hydrazine (2f)
White needles; Yield: 93%; mp 194-196 °C; IR (KBr)
n: 3362, 3245, 3070, 2997, 1646, 1606, 1492 cm-1; 1H NMR
d: 3.82 (s, 3H, CH3), 6.76-7.90 (m, 8H, ArH), 8.01 (s, 1H,
NH), 10.23 (s, 1H, NH); 13C NMR d: 166.88 (C=O), 163.00,
149.64, 130.21, 129.51, 125.95, 122.94, 114.87, 114.75
(Ar-C), 56.42 (CH3). MS (EI) m/z: 276 (M+), 135 (B), 107,
92, 77, 51. Anal. calcd. for C14H13ClN2O2: C, 60.77; H, 4.74;
N, 10.12. Found: C, 60.60; H, 4.48; N, 10.25.
1-Benzoyl-2-(p-nitrophenyl)hydrazine (2a)
Yellow needles; Yield: 81%; mp 195-196 °C (lit.14 193
°C); IR (KBr) n: 3321, 3231, 3078, 1631, 1606, 1515 cm-1; 1H
NMR d: 6.82-8.08 (m, 9H, ArH), 9.21 (s, 1H, NH), 10.62 (s,
1H, NH); Anal. calcd. for C13H11N3O3: C, 60.70; H, 4.31; N,
16.33. Found: C, 60.56; H, 4.10; N, 16.11.
1-(p-Bromobenzoyl)-2-(p-chlorophenyl)hydrazine (2g)
White leaflets; Yield: 87%; mp 195-197 °C; IR (KBr)
1
n: 3353, 3244, 3062, 1662, 1589, 1492 cm-1; H NMR d:
1-(p-Ethoxybenzoyl)-2-(p-nitrophenyl)hydrazi-ne (2b)
Pale-yellow needles; Yield: 82%; mp 239-240.5 °C; IR
(KBr) n: 3310, 3230, 3094, 2981, 1628, 1610, 1512 cm-1; 1H
NMR d: 1.35 (t, 3H, CH3), 4.11 (q, 2H, CH2), 6.81-8.09 (m,
8H, ArH), 9.15 (s, 1H, NH), 10.47 (s, 1H, NH); 13C NMR d:
166.73 (C=O), 162.53, 156.20, 139.17, 130.39, 126.93,
125.26, 115.26, 111.76 (Ar-C), 64.46 (CH3), 15.53 (CH2).
Anal. calcd. for C15H15N3O4: C, 59.80; H, 5.02; N, 13.95.
Found: C, 59.62; H, 5.27; N, 13.72.
6.75-7.85 (m, 8H, ArH), 8.07 (s, 1H, NH), 10.44 (s, 1H, NH);
13C NMR d: 166.54 (C=O), 149.27, 132.93, 132.57, 130.45,
129.56, 126.53, 123.16, 114.93 (Ar-C). Anal. calcd. for
C13H10BrClN2O: C, 47.96; H, 3.10; N, 8.60. Found: C, 48.31;
H, 3.41; N, 8.38.
1-Benzoyl-2-(p-bromophenyl)hydrazine (2h)
White leaflets; Yield: 85%; mp 172.5-174.5 °C; IR
(KBr) n: 3354, 3246, 3040, 1652, 1591, 1488 cm-1; 1H NMR

Preparing Acylhydrazines from Acyldiazenes
J. Chin. Chem. Soc., Vol. 51, No. 4, 2004 837
d: 6.74-7.93 (m, 9H, ArH), 8.09 (s, 1H, NH), 10.38 (s, 1H,
NH); 13C NMR d: 167.34 (C=O), 149.92, 133.87, 132.73,
132.38, 129.51, 128.34, 115.37, 110.46 (Ar-C). Anal. calcd.
for C13H11BrN2O: C, 53.63; H, 3.81; N, 9.62. Found: C,
53.40; H, 3.50; N, 9.84.
NMR d: 1.35 (t, 3H, CH3), 4.10 (q, 2H, CH2), 6.77-7.90 (m,
9H, ArH), 7.79 (s, 1H, NH), 10.13 (s, 1H, NH); 13C NMR d:
166.88 (C=O), 162.20, 150.67, 130.16, 129.71, 126.03,
119.64, 115.13, 113.41 (Ar-C), 64.38 (CH3), 15.55 (CH2).
MS (EI) m/z: 256 (M+), 149 (B), 121, 93, 65, 39. Anal. calcd.
for C15H16N2O2: C, 70.29; H, 6.29; N, 10.93. Found: C, 70.60;
H, 6.51; N, 10.76.
1-(p-Ethoxybenzoyl)-2-(p-bromophenyl)hydrazine (2i)
White leaflets; Yield: 88%; mp 175-177 °C; IR (KBr)
n: 3364, 3260, 3063, 2987, 2895, 1646, 1607, 1488 cm-1; 1H
NMR d: 1.35 (t, 3H, CH3), 4.10 (q, 2H, CH2), 6.71-7.88 (m,
8H, ArH), 8.02 (s, 1H, NH), 10.22 (s, 1H, NH); 13C NMR d:
166.83 (C=O), 162.28, 150.10, 132.34, 130.21, 125.83,
115.34, 115.15, 110.33 (Ar-C), 64.39 (CH3), 15.54 (CH2).
MS (EI) m/z: 336, 334 (M+), 171, 149 (B), 121, 93, 65, 39.
Anal. calcd. for C15H15BrN2O2: C, 53.75; H, 4.51; N, 8.36.
Found: C, 53.61; H, 4.63; N, 8.62.
Received October 17, 2003.
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1-(p-Methoxybenzoyl)-2-(p-bromophenyl)hydrazine (2j)
White needles; Yield: 95%; mp 173-175 °C; IR (KBr)
n: 3368, 3245, 3068, 2965, 2836, 1652, 1605, 1508 cm-1; 1H
NMR d: 3.82 (s, 3H, CH3), 6.71-7.91 (m, 8H, ArH), 8.02 (s,
1H, NH), 10.23 (s, 1H, NH); 13C NMR d: 166.86 (C=O),
163.00, 150.04, 132.35, 130.21, 125.98, 115.38, 114.75,
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C, 52.36; H, 4.08; N, 8.72. Found: C, 52.50; H, 4.30; N, 8.84.
1-(p-Bromobenzoyl)-2-(p-bromophenyl)hydrazine (2k)
White powder; Yield: 83%; mp 171-173 °C; IR (KBr)
1
n: 3350, 3244, 3062, 1660, 1590, 1488 cm-1; H NMR d:
6.75-7.89 (m, 8H, ArH), 10.47 (s, 1H, NH), 10.64 (s, 1H,
NH); 13C NMR d: 166.44 (C=O), 149.68, 134.95, 132.57,
132.40, 130.45, 126.54, 115.42, 110.64 (Ar-C). Anal. calcd.
for C13H10Br2N2O: C, 42.20; H, 2.72; N, 7.57. Found: C,
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1-(p-Ethoxybenzoyl)-2-phenylhydrazine (2l)
White leaflets; Yield: 80%; mp 161-163 °C; IR (KBr)
n: 3333, 3300, 3060, 2985, 2895, 1637, 1604, 1479 cm-1; 1H