Full text of DOI:10.1002/jhet.5570380412

Jul-Aug 2001
Synthesis and Characterization of New Heterocyclic
Derivatives by Oxidation of 1-Amino-2-methylindoline
L. Peyrot, M. Elkhatib, J. R. Vignalou, R. Metz, F. Elomar and H. Delalu*
885
Laboratoire Hydrazines et Procédés FRE CNRS-2397, Université Claude Bernard Lyon I,
43 boulevard du 11 novembre 1918, Bâtiment 731, F-69622 Villeurbanne cedex, FRANCE
Received November 10, 1999
1-Amino-2-methylindoline is a precursor used in the synthesis of antihypertension drugs. It reacts with
monochloramine to lead to the formation of 1-amino-2-methylindole and azo(2-methyl)indoline. These new
1
13
products have been isolated and characterized by microanalysis, uv, gc/ms, ir, and H/ C nmr. The reaction
leads to the transient formation of an indolic aminonitrene. 1-Amino-2-methylindole formation proceeds in
strongly alkaline medium by rearrangement of a diaziridine intermediate. In neutral or slightly alkaline
medium, one obtains a precipitate of tetrazene type (-N-N=N-N-), the azo(2-methyl)indoline. The study of
the thermochemical properties shows that tetrazene decomposes towards 150 °C to give the 1,1'-bi(2-
methyl)indoline. The stability of the starting reagents and products was the subject of a systematic
investigation. A reaction mechanism is proposed.
J. Heterocyclic Chem., 38, 885 (2001).
Introduction.
This more environmentally sound route involves
numerous secondary products due principally to the
oxidizing power of the haloamine upon hydrazine. In
addition, the physicochemical analyses show that the
aqueous solutions of 1 and 2 undergo a decomposition of
these compounds according to time. A preliminary know-
ledge of their stability is thus necessary. The realization of
this process requires a systematic study of the reactions
that occur during the synthesis.
This work relates to the stability of 1 and 2 in aqueous
solution, the identification of the reaction mechanisms and
the characterization of the products formed during the
oxidation of 1-amino-2-methylindoline by chloramine.
This interaction has not been the object of any former
study.
1
-Amino-2-methylindoline 2 (NAMI) is used in the
pharmaceutical industry as a precursor of antihypertensive
drugs whose common international name is Indapamide.
At present, it is prepared by nitrosation of 2-methyl-
indoline 1 (MI) followed by a reduction of nitrosamine
with LiAlH [1].
4
Results and Discussion.
Stability of Indolic Derivatives in Aqueous Medium.
The dissolution of 1 and 2 in water, at different pH,
shows an alteration of these compounds, which proceeds
visually in a series of colors changes of the solution. No
study on the behavior of these products in aqueous
medium was published. It is however indicated that the
solutions of 2 are stable in concentrated sulphuric acid [2]
without bringing more qualitative or quantitative
information.
To avoid the nitrosated intermediates, we have
undertaken the study of the amination of 2-methylindoline
by chloramine in aqueous medium.
Stability of 2-Methylindoline.
The oxidation of 1 by dissolved oxygen was carried out
in aqueous solution saturated by O under atmospheric
2
pressure ([MI] = 10 × 10-3 M, [O ] = 8 × 10 M). The
-4
2
decomposition is very slow at room temperature. The
chromatographic analysis (gc) shows a new product at t =
R
2
.13 minutes whose gc/ms analysis attributes this to a
-1
molar weight M = 131 g mol . The fragmentary study as

8
86
L. Peyrot, M. Elkhatib, J. R. Vignalou, R. Metz, F. Elomar and H. Delalu
Vol. 38
that the degradation remains superficial and the
principal oxidation product is the 1-amino-2-methylin-
dole 4 (table 1) .
Various tests are performed by dissolving 2 (0.015 M) in
acidic ([HCl] = 0.1 M), neutral (pH = 7) and basic
([NaOH] = 0.1 M) media. Figure 1 shows a chromatogram
obtained for the three zones of pH. Whereas in alkaline
medium the principal product is 4, one obtains in acid
medium a mixture of products corresponding to t = 1.52,
R
2
.13, 2.37 and 2.88 minutes.
pA
1
3
A
6
1
0000
well as a comparison with a reference spectrum [3] prove
that it is 2-methylindole 3, which corresponds to the above
reaction.
8
6
4
2
000
000
000
000
0
In alkaline medium ([NaOH] = 0.1 M), the MI is more
quickly decomposed and that results in successive changes
of colors from green to the yellow-brown. Both gc and hplc
analyses confirm the disappearance of 1 without appearance
of a new peak. The extraction by organic solvents (hexane,
ethylether, chlorobenzene) proves that the totality of the
products remains in aqueous layer. Acidification of the
medium until pH = 6 causes the precipitation of a product
which was isolated and analyzed by mass spectrometry. The
molecular ion is located at m/z = 264, which corresponds to
a dimerized form of 1. This result is in agreement with the
literature, which indicates stable polymer formation starting
from indoles and indolines [4-10].
2
0.5
1
1.5
2
2.5
3
3.5
min.
B
3
pA
1
10000
2
8
6
4
2
000
000
000
000
0
6
4
5
0
.5
1
1.5
2
2.5
3
3.5
min.
C
pA
0000
3
1
1
Stability of 1-Amino-2-methylindoline.
8
6
4
2
000
000
000
000
0
Exposed to atmospheric oxygen, the crystals of 2 are
unstable and one observes the appearance of a pink-
brown color. However, chromatographic analysis shows
4
2
5
0
.5
1
1.5
2
2.5
3
3.5
min.
Figure 1. Stability of NAMI in aqueous solution at different pH. A pH 13,
B pH 7, C pH 1 (1 toluene, 2 MI, 3 NAMI, 4 2-methylindole, 5 3-methyl-
cinnoline, 6 1-amino-2-methylindole).
The principal results of gc/ms analyses are consigned in
table 2. The peaks of mass m/z = 131, 133 and 146 confirm
the presence of 1, 2 and 3. The signal located at t = 2.37 is
R
characterized by a molecular ion m/z = 144. A study of the
reactions of fragmentation in mass spectrometry
associated to a comparison with the data libraries converge
towards the 3-methylcinnoline 5. This result is described
in the literature, which indicates the existence of an indole-
cinnoline rearrangement in acid medium [11,12]. The
formation of 5 is described in scheme 5.
In order to avoid any interference, the MI and the NAMI
were stored under nitrogen cover, then dissolved in water
deprived of oxygen. In particular, the hydrazine crystals
are immediately prepared before use and purified by
fusion and distillation under vacuum.
Table 1
Degradation of 1-Amino-2-methylindoline by Atmospheric Oxygen.
Analysis of Oxidation Products
Purity (%)
NAMI
freshly distilled
NAMI
one month later
1
1
-amino-2-methylindoline
-amino-2-methylindole
99.54
0.33
0.13
97.9
1.70
0.40
2
-methylindole

Jul-Aug 2001
Synthesis and Characterization of New Heterocyclic Derivatives
887
Table 2
Analyses by gc of reaction medium NAMI-O at different pH.
2
-1
t
(min)
Molar weight (g mol )
Compound
R
1
.52
.86
.13
.37
.88
133
148
131
144
146
2-methylindoline
1-amino-2-methylindoline
2-methylindole
3-methylcinnoline
1-amino-2-methylindole
1
2
2
2
DEPT 135
C10
C6
C5
C7
C3
C8
1
30
120
110
100
90
80
70
60
50
40
30
20
10
Figure 2. 13C DEPT sequence of 1-amino-2-methylindole.
Oxidation of 1-Amino-2-methylindoline by Chloramine.
In order to isolate and characterize this product, a
complementary experiment was realized in more
Reaction between 1 and NH Cl led to the formation of 2
2
concentrated medium ([NH Cl] = [NAMI] = 0.05 M). The
2
and other products. In particular, the coexistence of an
oxidant (chloramine) and a reducer (hydrazine) causes the
partial destruction of 2 and the formation of products
whose nature depends on the pH.
brown precipitate formed was filtered, washed, recrystallized
in hexane, dried under reduced pressure, and stored under
nitrogen atmosphere. Its purity reaches 99.8% (gc). The
microanalysis confirms the established formula.
Synthesis of 1-Amino-2-methylindole.
The identification of the product was carried out by
comparison with the spectroscopic data of 2. The ir spectra
show in both cases two intense bands at ν 3271 and 3343
The reaction carried out at pH = 12.89 and T = 25 °C,
-3
under stoichiometric conditions (3 to 10 × 10 M), shows the
formation of a new compound, which exhibits two strong
absorption at λ 220 and 280 nm. Analyses by gc indicate the
formation of a single product whose instantaneous concen-
tration is proportional to that of the reagents. One observes
the decrease of 2 and correlatively the appearance of a signal
at 2.88 minutes. Analysis by gc/ms attributes this to a molar
weight MW = 146 and an isotopic study of the ions frag-
-
1
cm corresponding to vibrations of the NH group.
2
Discrimination between the carbon atoms of pair (CH ) and
2
odd (CH, CH3) multiplicities was accomplished by using the
13
standard C DEPT sequence [13]. The chemical shifts of the
C and H nuclei are given in the experimental section.
1
3
Figure 2 presents C DEPT sequence of the oxidation
product of the NAMI. One remarks a change of parity of
ments leads to the molecular formula C H N .
C3 carbon (CH type) compared to 2 (CH type). Moreover,
9
10
2
2

8
88
L. Peyrot, M. Elkhatib, J. R. Vignalou, R. Metz, F. Elomar and H. Delalu
Vol. 38
the spectrum shows the disappearance of the C2 signal
quaternary carbon) and the presence of six lines of CH
type.
These phenomena prove the appearance of a C2-C3
(
double bond. Aromatic character of the product is
3
confirmed by the long distance coupling J observed in the
1
H nmr spectrum. The results associated with ir and ms
data show that it corresponds to 4. The stoichiometry of
the reaction is unit and the equation is written :
Synthesis of Azo(2-methyl)indoline.
The progressive acidification of the medium induces a
decrease in the formation of 1-amino-2-methylindole in
favor of a new compound which precipitates and becomes
preponderant at pH below 9. At the end of the reaction, the
brown solid is filtered, washed, dried under vacuum and
characterized by microanalysis, ms, ir, nmr and uv.
Figure 3 presents the 13C DEPT spectrum. One
observes a splitting of the 9 lines, which imply the exis-
tence of two identical fragments with a centro-
symmetrical formula unit. This fact can be explained by
a very close electronic environments linked to the
cis-trans isomerism of the azo group. The DEPT
sequence (C3 of CH type) and the absence of ν band
exclude a simple dimerisation of 4. These results lead to
a tetrazene structure (-N-N=N-N-), the azo(2-methyl)-
indoline 6.
The mass spectrum realized by direct introduction
+
(
70 eV) exhibits a molecular ion M = 292. An isotopic
analysis reveals the presence of a peak at m/z = 132
relative to the formation of two half-fragments C H N
2
NH
9
10
with release of a nitrogen molecule. The elementary
analysis confirms the established formula C H N .
1
8 20 4
C5
C5'
C10
C10'
C7
C7'
C2
C2'
C8
C8'
C6
C6'
C3
C3'
1
50
140
130
120
110
100
90
80
70
60
50
40
30
20
10
PPM
Figure 3. 13C DEPT spectrum of azo(2-methyl)indoline.

Jul-Aug 2001
Synthesis and Characterization of New Heterocyclic Derivatives
889
Synthesis of 1,1'-Bi(2-methyl)indoline.
The first at 80 °C is weakly endothermic (8.37 kJ mol-1)
and perfectly reversible between 25 and 100 °C, which cor-
The determination of the thermochemical properties of
the oxidation products show in the case of 6 a thermal
decomposition and the formation of a red-black liquid. The
thermal preparation conditions of the last product were
studied by coupling differential scanning calorimetry/-
thermogravimetric (dsc/tg). Three thermal effects are
observed (figure 4).
responds, taking into account the low value of ∆ H, to a mol-
r
ecular transition. The second begins at 110 °C and is vio-
-1
lently exothermic (∆rH = - 236.8 kJ mol ). The last peak,
which corresponds to an endothermic process, is very broad
-
1
and start at 150 °C (∆ H = 53.2 kJ mol ). The corresponding
r
mass variations are schematized in the figure 5.
∧
exo
Tetrazene 12.0600 mg
Heating rate 5.00 °C/min
2
0
mW
0-20-30
100
150
°C
0
50
200
250
1
0
20
30
40
50
60
70 min
METTLER-TOLEDO TA8000
Figure 4. dsc spectrum of azo(2-methyl)indoline.
Figure 5. Thermogravimetric analysis of azo(2-methyl)indoline.

8
90
L. Peyrot, M. Elkhatib, J. R. Vignalou, R. Metz, F. Elomar and H. Delalu
Vol. 38
transformation of the tetrazene is incomplete. Indeed, this
can result from a solubilization of 6 in the hydrazine
formed during the thermal decomposition. The reaction
leads to 1,1'-bi(2-methyl)indoline 7 and the microanalysis
show the presence of 8% approximately of tetrazene in the
final product. The preparative liquid chromatography
appears the most suitable to obtain a purity of 7 higher than
92%.
Reaction Mechanisms
Starting from 110 °C, the weight loss is carried out in
By analogy with the phenomena observed in the oxida-
tion of unsymmetrical dialkylhydrazines [14], the first ele-
mentary step corresponds to the formation of a diazene
two steps. The first represents a 10% weight loss and
corresponds to the exothermic effect. The second extends
from 130 °C to 275 °C (∆m/m = 55%) and corresponds to
a complete pyrolysis of the initial product 6. The ∆m/m
ratio relative to the first signal shows a release of a
nitrogen molecule with the formation of an intermediate
symmetrical hydrazine, according to the above reaction.
The experimental conditions used by the dsc/tg analysis
lead to small amounts of the end product, which are
insufficient to a subsequent characterization. Experiments
were carried out in thermostatic medium (T = 150 °C)
starting from higher quantities of tetrazene. To control the
progress of the reaction as a function of time, samples have
been analysed by differential scanning calorimetry (dsc).
After cooling at 25 °C, a red-black liquid is obtained.
Analyses accomplished on the liquid show that the
(aminonitrene) [15,16]. The overall two redox half-reac-
tions are described in scheme 8.
Formation of 3-methylcinnoline from 1-amino-2-
methylindole under acidic conditions begins with a proton
addition on the double bond. Addition of a water is fol-
lowed by a series of rearragements which, after aromatiza-
tion, lead to 5 as shown in scheme 9.
Formation of 1-amino-2-methylindole and azo(2-
methyl)indoline from NAMI and chloramine at pH 13 and
9
proceed via a nitrene intermediate. The type of product
formed is dependent on the pH and the concentration of the
nitrene.
At a high pH ([NaOH] = 0.1 M), nitrene generation is
efficient. Intramolecular C-H insertion proceeds to give
the diaziridine intermediate that suffers base-mediated loss
of the C3 hydrogen to produce 1-amino-2-methylindole.
Aromatization is the driving force behind this event.
At pH 9, the conversion of the corresponding nitrene is
probably slower and incomplete. Unreacted NAMI would
be available to trap the nitrene, which would result in a
hydrazine derivative. Further oxidation of the hydrazine by
chloramine would give the azo(2-methyl)indoline.
This study is in agreement with the major facts observed
on the reactivity of the aminonitrenes [16-21]. A mixture
of two species 4 and 6 is obtained at intermediate pH
values. The present work has allowed us to characterize
the products of the reaction between chloramine and
+
-
NH + Cl
4

Jul-Aug 2001
Synthesis and Characterization of New Heterocyclic Derivatives
891
1
-amino-2-methylindoline and to demonstrate the
µm). The gc/ms spectra were acquired with a Delsi Nermag mass
fundamental role of pH in the chemistry of the indolic
amines and hydrazines.
spectrometer with a BP 20 capillar column (50 m) and ion source of
7
8
1
0 eV. Thermodynamic data have been determinated using a TA
000 Mettler system equipped by a DSC 820 modulus acting from -
70 to 200 °C under argon sweeping. The trials were carried out by
EXPERIMENTAL
-1
heating (5 °C min ) using aluminium crucibles and starting from 20
mg of the raw material. The thermogravimetric analyses are
performed by means of a Labsys Setaram TG-DSC unit.
Apparatus.
Chloramine.
The nmr spectra were obtained with a high resolution Bruker AM
00 spectrometer operating at 300 MHz for H and 75 MHz for C.
1
13
3
Unstable in water, monochloramine is therefore prepared at
-10 °C extemporaneously by reacting 25 mL of sodium
hypochlorite 2 M and 20 mL of an aqueous NH -NH Cl solution
Samples were recorded in CDCl solution with Si(CH ) as the
3
3 4
internal standard. The ir and uv spectra were measured with a
Beckman 842 instrument (CsI cells) and a Cary IE double beam
spectrophotometer, respectively. Analyses by gc were carried out on
a HP 6890 chromatograph equipped with EPC modules allowing the
control and the measure of the gas flows and the pressures at
different levels of the apparatus. The separation was done on a 30 m
3
4
([NH ] = 3.6 M, [NH Cl] = 2.3 M) in the presence of diethylether
3
4
(40 mL). The organic layer (0.8 to 1 M in NH Cl) was shaken and
2
washed several times with aliquots of distilled water.
Monochloramine in aqueous solution was obtained by re-extrac-
tion from the ethereal phase. Its content was determinated by uv
spectroscopy at λ 243 nm (ε = 458 M- cm ) [22].
1
-1
long HP1 column (100% dimethylpolysiloxane, 530 µm i.d., d = 1.5
f

8
92
L. Peyrot, M. Elkhatib, J. R. Vignalou, R. Metz, F. Elomar and H. Delalu
Azo(2-methyl)indoline.
Vol. 38
1-Amino-2-methylindoline.
This product is not commercially available. It is provided
It was synthesized at 5 °C and pH 9 by reacting 1-amino-2-
by ORIL INDUSTRIE in the mesylate form after treatment by
methane sulphonic acid. Extraction of the hydrazine from the
mesylate and its purification was effected according to the
following procedure: 60 g of the pink-powder (mesylate) are
dissolved in 500 mL of water then neutralized by addition of
methylindoline and chloramine in stoichiometric conditions
(10 × 10-3 M). The solid obtained was filtered, washed, recrys-
tallized in hexane and dried under vacuum. Its purity is close
to 99.2%; ms (70 eV): m/z 292 (M+, 6.4), 264 (22.7), 262
42.7), 261 (17.3), 249 (22.7), 247 (47.3), 232 (10.8), 160
18.6), 146 (50.2), 143 (15.2), 133 (38.4), 132 (48.9), 131
66.9), 130 (50.8), 118 (100), 117 (45.8), 104 (14.3), 103
(
(
(
(
6
0 g of sodium hydroxide. Mixture is then extracted with 120
mL of hexane. Evaporation of the organic solvent yields to a
red-brown solid which titrates about 91% with respect to the
mesylate. Analysis by gc indicates that the principal impuri-
ties are the 2-methylindoline, the 2-methylindole and the
-amino-2-methylindole. To obtain a high purity product, the
crystals are melted and distilled under reduced pressure taking
into account the high boiling point of the NAMI (255 °C at
60 Torr). Distillation is carried out under a pressure of 5 Torr.
The melting point of the hydrazine is 45 °C. After elimination
of the light fractions, the temperature of the boiler reaches
75 °C whereas that of the head of column is established to
30 °C. The temperature of the refrigerant is maintained at
5 °C, which permit to the vapour to condense without crys-
tallisation. NAMI obtained in liquid state is then collected at
the room temperature where it crystallizes in the form of white
solid. Both gc and elementary analyses show a purity higher
than 99%. The principal impurities still present are the MI and
the 1-amino-2-methylindole. Because of the instability of the
NAMI, the procedure were repeated before each use. This
compound being not previously studied, a complete character-
14.7), 102 (12.9), 91 (44.7), 90 (19.4), 89 (17.7), 77 (23.4),
1
6
5 (18.2), 63 (13.4); H nmr (CDCl ): δ 1.50 (3H, d, 1.86,
3
H10/H10'), 1.52 (3H, d, 1.88, H10/H10'), 2.77-2.88 (2H, q, 5.75,
H /H ), 3.42-3.54 (2H, m, H /H ), 4.65-4.72 (2H, m,
1
3
3'
3
3'
H /H ), 6.85-6.96 (2H, m, H /H ), 7.14-7.26 (2H, m,
2
2'
6
6'
H /H ), 7.14-7.26 (2H, m, H /H ), 7.14-7.26 (2H, m,
5
5'
7
7'
7
1
3
H /H ); C nmr (CDCl ): δ 19.64/20.69 (C10/C10'),
8
8'
3
3
(
1
6.61/36.76 (C /C ), 57.30/57.67 (C /C ), 109.23/109.42
3 3' 2 2'
C /C ), 120.57/120.75 (C /C ), 125.00/125.05 (C /C ),
8 8' 6 6' 5 5'
1
1
4
27.10 (C /C ), 127.74/127.78 (C /C ), 146.7 (C /C ).
4 4' 7 7' 9 9'
Anal. Calc. for C H N (292): C, 73.94; H, 6.89; N, 19.16.
1
8 20 4
Found: C, 73.87; H, 6.92; N, 19.21.
1,1'-Bi(2-methyl)indoline.
It is obtained by pyrolysis of the tetrazene at 150 °C during
several hours. One forms a red-black liquid of which the purity
does not exceed 95%. The principal impurity is the azo(2-
methyl)indoline.
-
1
Anal. Calc. for 92% C H N (264) + 8% C H N (292): C,
ization was performed; mp 45 °C, ∆H 24.45 kJ mol ; bp
18 20
2
18 20 4
f
-
1
-1
81.15; H, 7.52; N, 11.33. Found: C, 81.15; H, 7.57; N, 11.28.
2
2
(
(
(
55 °C, ∆Hv 75.48 kJ mol ; ir: ν NH 3303, 3165 cm ; uv: λ
39 (7150 L mol cm ), 284 (2060 L mol cm ) nm; ms
70 eV): m/z 148 (M , 56), 133 (100), 130 (16), 117 (32), 116
48), 106 (16), 91 (24), 89 (16), 77 (16), 65 (16), 63 (12), 51
12), 39 (16) 18 (52); H nmr (CDCl ): δ 1.43 (3H, d, 6.13,
H10), 2.5 (1H, q, 11.02, H ), 3.1 (1H, q, 7.73, H ), 3.3 (1H, m,
H ), 6.65-6.75 (2H, m, H -H ), 7-7.05 (2H, m, H -H );
2
-
1
-1
-1
-1
+
REFERENCES AND NOTES
1
3
[
1] J. B. Wright and R. E. Willette, J. Med. and Pharm. Chem., 5,
19 (1962).
[2] G. Jacob, Thèse de Docteur-Ingénieur n° 81-131, Université
Rennes I, 1981.
[3] C. J. Pouchert, The Aldrich Librairy of NMR Spectra, 2nd ed.,
Aldrich Chemical, Milwaukee, WI, 1983 ; C. J. Pouchert and J. Behnke,
3
3
8
1
3
C
2
6
8
5
7
nmr (CDCl ): δ 17.9 (C ), 33.8 (C ), 66.77 (C ), 109.2 (C ),
3
10
3
2
8
1
18.5 (C ), 123.5 (C ), 126.8 (C ), 127.1 (C ), 155.1 (C ).
6 5 7 4 9
Anal. Calc. for C H N (148): C, 72.94; H, 8.16; N, 18.90.
9
12 2
Found: C, 72.74; H, 8.15; N, 18.90.
13
1
The Aldrich Library of C and H FT-NMR Spectra, Aldrich Chemical,
Milwaukee, WI, 1992.
1
-Amino-2-methylindole.
[4] E. B. Maarouf, D. Billaud and E. Hannecart, Mat. Res. Bull.,
By dissolving oxygen in a solution of 1-amino-2-methyl-
29(6), 637 (1994).
indoline at 15 × 10-3 M, one observes in basic medium (pH 13)
[5]
G. Zotti, S. Zecchim, G. Schiavon, R. Seraglia, A. Berlin and
the precipitation of fine needles of 1-amino-2-methylindole. The
crystals obtained were filtered, washed, recrystallized in hexane
and dried under vacuum. Analysis by gc provides a titre close to
A. Canavesi, Chem. Mater., 6, 1742 (1994).
[
[
6] R. Holze and C. H. Hamann, Tetrahedron, 47(4), 737 (1991).
7] K. M. Choi, C. Y. Kim and K. H. Kim, J. Phys. Chem., 96,
3
782 (1992).
9
2
3
9.8% and the principal impurity is the NAMI; mp 111.4 °C, ∆Hf
[
[
8] J. Lippe and R. Holze, J. Electroanal. Chem., 339, 411 (1992).
9] D. Billaud, E. B. Maarouf and E. Hannecart, Mat. Res. Bull.,
-
1
-1
5.55 kJ mol ; bp 300.5 °C, ∆H 79.55 kJ mol ; ir: ν NH2 3343,
v
-1
-1
-1
-1
271 cm ; uv: λ 220 (33909 L mol cm ), 280 (6871 L mol
cm ) nm; ms (70 eV): m/z 146 (M , 100), 145 (26.4), 131 (47),
30 (37), 129 (22.4), 128 (15.2), 118 (34.2), 117 (12.5), 105
2
9
5
9(12), 1239 (1994).
10] E. B. Maarouf, D. Billaud and E. Hannecart, J. Chim. Phys.,
2, 1803 (1995).
-1
+
[
1
(
(
37.6), 104 (79.2), 103 (18.8), 102 (15.3), 91 (15.7), 89 (12.1), 78
[11] D. I. Haddlesey, P. A. Mayor and S. S. Szinaï, J. Chem. Soc.,
1
17.9), 77 (29.3), 71 (9.1), 65 (10.9), 63 (16.4); H nmr (CDCl3):
269 (1964).
δ 2.41 (3H, s, H ), 6.21 (1H, s, H ), 7.18 (1H, d, 7.56, H ), 7.22
10
3
8
[12] M. Somei and K. Ura, Chem. Lett., 707 (1978).
[13] D. M. Dodrell, D. T. Pegg and M. R. Bendall, J. Mag. Res.,
48, 323 (1982).
[14] H. Delalu and A. Marchand, J. Chim. Phys., 81(3), 149 (1984).
(
(
(
1H, m, H ), 7.22 (1H, m, H ), 7.60 (1H, d, 7.33, H ); 13C nmr
6 7 5
CDCl ): δ 11.6 (C ), 96.7 (C ), 107.8 (C ), 119.4 (C ), 119.4
3
10
3
8
6
C7), 120.4 (C ), 125.6 (C ), 136.9 (C ), 137.8 (C ).
5
4
2
9
Anal. Calc. for C H N (146): C, 73.94; H, 6.89; N, 19.16.
Found: C, 73.90; H, 6.90; N, 19.20.
[15] E. W. Schmidt, Hydrazine and its derivatives, preparation,
properties, application, Wiley, New York, 1984.
9
10 2

Jul-Aug 2001
Synthesis and Characterization of New Heterocyclic Derivatives
893
[
16] D. M. Lemal in W. Lwowski ed., Nitrenes, Interscience, New
[20] C. G. Overberger and L. P. Herin, J. Org. Chem., 27, 417
(1962).
York, 1970.
[
17] D. M. Lemal and T. W. Rave, J. Am. Chem. Soc., 87, 393 (1965).
[21] C. G. Overberger, J. P. Anselme and J. G. Lombardino,
Organic compounds with nitrogen-nitrogen bonds, Ronald press
company, New York, 1966.
[18] M. Elkhatib, Thèse de doctorat ès sciences n° 89-94,
Université Lyon I, 1994.
[
19] W. R. McBride and E. M. Bens, J. Am. Chem. Soc., 81, 5546
[22] H. Delalu, Thèse de doctorat d'état ès sciences n°77-29,
Université Lyon I, 1977.
(
1959).