Reaction of endic anhydride with hydrazines and acylhydrazines

Article abstract of DOI:10.1023/B:RUJO.0000045895.04509.2d

Reaction products of bicyclo[2.2.1]hept-2-ene-endo,endo-5,6-dicarboxylic (endic) acid with hydrazines and acylhydrazines were prepared. The features distinguishing of these reactions from those with amines were revealed. The compounds obtained were characterized by ¹H, ¹³C NMR, and IR spectra. The assignment of the signals in NMR spectra was done with the use of quantum-chemical calculations of chemical shifts performed by the density functional method. The structure of one among compounds synthesized, N-(m-hydroxybenzoylamino)-bicyclo[2.2.1]hept-2-ene- endo,endo-5,6-dicarboxamide, was proved by X-ray diffraction analysis.

Full text of DOI:10.1023/B:RUJO.0000045895.04509.2d

Russian Journal of Organic Chemistry, Vol. 40, No. 8, 2004, pp. 1140-1145. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 8, 2004,
pp. 1188-1193.
Original Russian Text Copyright Ó 2004 by Krishchik, Tarabara, A. Kas’yan, Shishkina, Shishkin, Isaev, L. Kas’yan.
Reaction of Endic Anhydride with Hydrazines and Acylhydrazines
O.V. Krishchik1, I.N. Tarabara1, A.O. Kas’yan2, S.V. Shishkina3, O.V. Shishkin3,
A.K. Isaev1, and L.I. Kas’yan1
1Dnepropetrovsk National University Dnepropetrovsk, 49625 Ukraine
e-mail: cf@ff.dsu.dp.ua
2 Organisch-chemische Institut von Rhein-Westfaelische Universitaet, Aachen, BRD
3Institute of Single crystals, Kharkov, Ukraine
Received January 22, 2003
Abstract—Reaction products of bicyclo[2.2.1]hept-2-ene-endo,endo-5,6-dicarboxylic (endic) acid with hydrazines
and acylhydrazines were prepared. The features distinguishing of these reactions from those with amines were
1
revealed. The compounds obtained were characterized by H, 13C NMR, and IR spectra. The assignment of the
signals in NMR spectra was done with the use of quantum-chemical calculations of chemical shifts performed by
the density functional method. The structure of one among compounds synthesized, N-(m-hydroxybenzoylamino)-
bicyclo[2.2.1]hept-2-ene-endo,endo-5,6-dicarboxamide, was proved by X-ray diffraction analysis.
temperature equimolar amounts of endic anhydride (I)
with alkyl-amines, arylamines, amines containing cage-
like norbornene, norbornane, and adamantane frag-
ments. Amido-acids by boiling with acetic acids were
transformed into carboximides III that under similar
conditions were obtained directly from anhydride I and
amines although in lower yields.
Organic hydrazine derivatives are widely applied as
synthons in manufacturing pharmaceuticals possessing
tuberculocidal, antitumor, psychoterapeutic, and other
activity They are used in agriculture as plant growth
regulators and stimulators, and as chemical protecting
agents for plants [1]. Among hydrazine derivatives the
products of their acylation with endic anhydride
[bicyclo[2.2.1]hept-2-ene-endo,endo-5,6-dicarboxylic
acid anhydride (I)] were investigated [2]. Some of them
also function as plant growth regulators [3], herbicides
[4], activators of antitumor drugs [5], and synthons for
preparation of new antibiotics [6].
Unlike the aminolysis of anhydride (I) its reactions
with alkyl- and- arylhydrazines under mild conditions
pre-vailingly afforded compounds with imide fragments.
Reactions products with phenylhydrazine IVa and
3-hydrazinothiolane dioxide IVb formed an exclusion
We report here on investigation of reaction between
endic anhydride (I) with various type hydrazines that
has been compared with reactions involving related
amines. We formerly developed [7, 8] a procedure for
preparation amidoacids II by reacting in benzene at room
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1070-4280/04/4008-1140Ó2004 MAIK “Nauka/Interperiodica”

REACTION OF ENDIC ANHYDRIDE WITH HYDRAZINES AND ACYLHYDRAZINE
1141
are nonequivalent, in particular, H5 and H6, and also H2
and H3 in compound IVa. Secondly, two signals from
protons attached to nitrogen are present whose position
is affected by their environment. In the spectrum of
amidoacid IVa the proton signal from the carboxy group
for they had structures of hydrazidoacids. The latter
compounds were converted into imides Va, b by heating
in acetic acid.
Other hydrazines (1,1-dimethylhydrazine, o-nitro-,
p-nitro-, o,p-dinitrophenylhydrazines, 2-benzothiazolyl-
hydrazine) both under mild conditions (reaction a) and
at boiling the reagents with acetic acid (reaction b)
furnished imides Vc–g.
1
appeared at 11.36 ppm. In the H NMR spectra of
compounds Va–e, g the protons H1 and H4, H2 and H3,
H5 and H6 are equivalent, and their signals are located
downfield with respect to the corresponding signals in
the spectra of amidoacids. The bridge protons (H7s and
H7a) resonate as doublets with a coupling constant 8.7–
9.3 Hz. In all imide spectra save that of compound Vc
one-proton signals are present at 3.50–10.80 ppm belong-
ing to hydrogens linked to nitrogen. The 13C NMR spectra
of aminoimides Vd, e, g demonstrate as well as the proton
spectra the equivalence of skeleton carbon atoms C1 and
C4, C2 and C3, C5 and C6. The signals from carbon atoms
in imide groups appear in a narrow range 173.9–
175.7 ppm. The assignment of signals in the NMR spectra
was done on the strength of quantum-chemical calcula-
2
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2
2
9F
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2
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12
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1
tions of the chemical shifts in the H and 13C NMR
9H
spectra of compound Vb (Table 1). The calculations were
performed by methods GIAO [10] and IGAIM [11] in
PBE1PBE approximation using a set of basis functions
6-31G**(II) physically adapted to the calculation of
magnetic properties[12]. The geometry of hydrazide Vc
was preliminary optimized in the B3LYP/6-311G*
approximation. The calculation results revealed an
important feature of protons shielding in the molecule
of imide Vc: the signals from protons H1 and H4 and
from the corresponding carbons are located downfield
from the signals of H5 and H6 and C5 and C6.
2
2 1
11+
12
2
9I
2
1
11+
6
2
9J
The reactions of endic anhydride with hydrazines
were compared with its reactions with hydrazides of carb-
oxylic acids from the aromatic series (benzoic, o-chloro-,
m-hydroxy-, m-nitro-, p-nitrobenzoic acids), with
The discovered trend to cyclic imide formation in the
reactions of endic anhydride with hydrazines in contrast
to similar reactions with amines affording under the same
conditions amidoacids [7, 8] apparently originates from
increase in the acidity of hydrogens in the NH group at
the carbonyl in the intermediates (hydrazidoacids) caused
by the effect of the adjacent amino group.
Table 1. Chemical shifts (ppm) in 1H and 13C NMR spectra
of compound Vc calculated in PBE1PBE/6-31G**(II)
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In the IR spectrum of amidoacid IVa several bands
of stretching vibrations of carbonyl groups were observed
corresponding to carboxy and carboxamide groups; the
presence of the latter was proved by absorption bands at
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3250 [n(NH)], 2750–2300 [n(OH)], 1500 [d(NH)] cm
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In the 1H NMR spectra of hydrazidoacids IVa, b two
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

KRISHCHIK et al.
1142
Table 2. Coordinates (´ 104) and equivalent isotropic
in alcohol in the presence of catalytic quantity of concn.
sulfuric acid (procedure c). The identity of products
obtained by both methods was demonstrated by an
example of compound Vd. More severe conditions of
reaction between endic anhydride and carboxylic acids
hydrazides are apparently due to the lack of the a-effect
ensuring the supernucleophilicity of hydrazines [13].
thermal parameters (E2 ´103) of nonhydrogen atoms in the
structure of compound VId
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The IR spectra of compounds VIa–g contain no
absorption bands of carboxy groups but appear the bands
of asymmetrical and symmetric stretching vibrations of
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imide carbonyl groups (1790–1770, 1733–1716 cm )
and of a carbonyl group belonging to the amide moiety
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(1680–1660 cm ). The spectra contain absorption bands
from vibrations of N–H bonds in the regions 3475–3265
–1
and 1590–1530 cm [n(NH), d(NH)], and also from
the aromatic fragments of compounds VIb–f.
On comparison of the 1H NMR spectra of compounds
Va and VIb stands out the difference in positions of
proton signals from H2 and H3 (6.20 and 5.95 ppm
respectively). In the 13C NMR spectra of compounds
VIa–g appears a signal from a carbon atom of the
exocyclic carboxy group. In the spectra of compounds
VIb,c these signals are displaced to 132.61 and 131.99
ppm respectively testifying to the existence in solution
of tautomer forms of aminoimides acyl derivatives [NH–
C=ODN=C(OH)].
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Single crystals of compound VId were subjected to
X-ray diffraction study that proved its amide structure
(see figure, Table 2). The five-membered heterocycle
exists in an envelop conformation.
The deviation of atom N1 from the mean-square plane
of the other atoms in the ring is 0.09 . The nitrogen
atom is planar (the sum of bond angles equals to 359.6°).
The bicycloheptene fragment and the five-membered
heterocycle are in a cis-junction (torsion angle H2C2C8H8
is 2.6°).
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1-adamantanecarboxylic acid hydrazide, and with semi-
carbazide hydrochloride. All hydrazides were inert to
endic anhydride in reactions performed by procedure a
and at heating at reflux in benzene, but the process
occurred under conditions of procedure b or at heating
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Atom C10 is in the ac conformation with respect to
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VI, R = NH2 (a), C6H5 (b), o-C6H4Cl (c), m-C6H4OH
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Structure of compound VId according to X-ray diffraction study.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

REACTION OF ENDIC ANHYDRIDE WITH HYDRAZINES AND ACYLHYDRAZINE
1143
–1
Phenyl substituent is in close to ap conformation with
respect to N1–N2 bond [torsion angle N1N2C10C11
1.390 g/cm3, m(MOKa) 0.102 mm , F(000) 624. Unit
cell parameters and intensities of 1783 reflections (1783
independent, Rint 0.00) were measured on an automatic
four-circle diffractometer Siemens P3/PC (MOKa,
graphite monochromator, 2q/q-scanning, 2qmax 56°).
–
173.1(2)°] and is turned relative to N2–C10 bond by
160.5(2)° [torsion angle N2C10C11C12]. The carbonyl
group and aromatic system are acoplanar [torsion angle
O3C10C11C12 –18.5(4)°]. This results in lack of
conjugation between these fragments as revealed in the
length of C10–C11 bond equal to1.491(3) .
The structure was solved by the direct method with
the use of software package SHELX97 [16]. Position of
hydrogen atoms was revealed from the difference
synthesis of electron density and taken into account with
the use of rider model with Uiso = nUeq (n is 1.5 for hydr-
oxy group and 1.2 for the other hydrogen O atoms). The
structure was refined by F2 in full-matrix least-squares
procedure in anisotropic approximation for nonhydrogen
atoms till wR2 0.088 for 1783 reflections (R1 0.033 for
1262 reflections with F > 4s(F), S 1.001). Final values
of atomic coordinates are given in Table 2.
Formation of intermolecular hydrogen bonds N2–
3
...
...
...
H O (x – 1/2, –y + 3/2, z), H O 1.98 , NH O 155.3°
4
1
...
...
...
and O –H O (–x, 1 – y, z – 1/2), H O 2.02 , OH O
159.6° results in elongation of bonds N1–C1 1.385(3)
(Average value 1.372
(1.372) , N2–C10 1.350(3)(1.334) .
[14]), N1–C9 1.401(3)
We demonstrated by an example of one hydrazide
the possibility of their epoxidation. Treating hydrazide
VIb with performic acid in statu nascendi obtained from
98% formic acid and 30–35% solution of hydrogen
peroxide gave the corresponding epoxide VII. The
assumed structure of compound VII is confirmed by the
presence in its IR spectrum by a band in the region
Reaction of endic anhydride with substituted
hydrazines. (a) Equimolar amounts of endic anhydride
and substituted hydrazine were mixed in benzene
solution, and the mixture was left standing till separated
a precipitate. The latter was filtered off, dried, and
subjected to further purification. Compounds IVa, b,
Vc–g were prepared by this procedure.
–1
855 cm characteristic of epoxynorbornanes [15]. In the
1H NMR spectrum the indicative features are the position
of signals from protons H2 and H3 attached to the epoxy
ring (3.12 ppm) and the upfield shift of one of bridge
protons (H7a) (1.05 ppm). This proton is located just over
the plane of the epoxy ring and is subject to magnetic
anisotropic effect thereof.
(b) Equimolar amounts of endic anhydride and
substituted hydrazine were heated at reflux in glacial
acetic acid till completion of reaction (TLC monitoring).
The acetic acid was removed in a vacuum, ice water was
added to the residue, the separated precipitate was filtered
off, dried, and subjected to further purification.
Compounds Vc–g and VId were prepared by this
procedure.
EXPERIMENTAL
(c) Equimolar amounts of endic anhydride and an
appropriate hydrazide were dissolved in ethanol, 2–
3 drops of concn. sulfuric acid were added to the mixture,
and it was heated at reflux till completion of reaction
(TLC monitoring). The ethanol was removed in a
vacuum, ice water was added to the residue, the separated
crystals were filtered off, washed with water on the filter,
dried, and subjected to further purification. Compounds
VIa-g were prepared by this procedure.
Compounds Va, b were prepared by heating at reflux
in the glacial acetic acid of the corresponding amidoacids
IVa, b till completion of reaction (TLC monitoring).
After the usual workup of the reaction mixture the
reaction products were subjected to further purification
IR spectra were recorded on spectrophotometer
Specord IR75 from samples in KBr pellets. H NMR
1
spectra were registered on spectrometers Varian VXR-
300 (operating frequency 300 MHz) and Gemini-BB
(operating frequency 500 MHz) from solutions in
deuterochloroform, deuterodimethyl sulfoxide, or
deuteromethanol using HMDS as internal refernce. 13C
NMR spectra were measured on spectrometer Gemini-
BB (operating frequency 100.58 MHz). The reaction
progress was monitored and the purity of compounds
synthesized was checked by TLC on Silufol UV-254
plates, eluent ethyl ether, development in iodine vapor.
Elemental analysis was performed on a Karlo Erba
analyzer.
Crystals of compouns VId rhombic, at 20°C a
endo-5-(N'-Phenylhydrazinocarbonyl)bicyclo-
[2.2.1]hept-2-ene-endo-6-carboxylic acid (IVa). Yield
3
9.942(3), b 10.942(4), c 13.103(4) E, V 1425.4(8)
,
C16H14N2O4, Mr 298.29, Z 4, space group Pna2i, dcalc
–1
85%, mp 163–165°C. IR spectrum, cm : 3250, 1700,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

KRISHCHIK et al.
1144
1680, 1500, 1350, 1150. 1H NMR spectrum, d, ppm:
9.40 d (1H, NH), 7.24 d (1H, NH), 7.10–6.70 (5H, H
arom), 6.16 d (1H, H2), 5.92 d (1H, H3), 3.24 m (1H,
H1), 3.20 m (1H, H4), 3.00 m (2H, H5, H6), 1.32 m (2H,
H7s, H7a). Found, %: C 66.24; H 5.81; N 10.33.
C15H16N2O3. Calculated, %: C 66.18; H 5.88; N 10.29.
N-(p-Nitrophenylamino)bicyclo[2.2.1]hept-2-ene-
endo,endo-5,6-dicarboximide (Ve). Yield 70%, mp 230–
232°C. IR spectrum, cm : 3359, 3081, 1720, 1602, 1518,
–1
1336, 1193, 752. 1H NMR spectrum, d, ppm: 9.48 s
(1H, NH), 8.09, 6.76 (4H, H arom), 6.26 m (2H, H2, H3),
3.52 m (2H, H1, H4), 3.35 m (2H, H5, H6), 1.64 d (1H,
H7s) 1.60 d (1H, H7a). 13C NMR spectrum, d, ppm:
175.66 (C=O), 126.40, 112.07 (C arom), 139.86 (C2, C3),
52.44 (C7), 45.14 (C1, C4), 44.53 (C5, C6). Found, %:
C 60.26; H 4.41; N 14.03. C15H13N3O4. Calculated, %:
C 60.20; H 4.35; N 14.05.
endo-5-[N'-(1,1-Dioxotetrahydrothiophen-3-yl)-
hydrazinocarbonyl]bicyclo[2.2.1]hept-2-ene-endo-6-
carboxylic acid (IVb). Yield 83%, mp 185–187°C. 1H
NMR spectrum, d, ppm: 5.65 d (1H, NH), 3.78 d.d (1H,
NH), 6.10 m (2H, H2, H3), 3.36 m (1H, H1), 3.33 m (1H,
H4), 3.12 m (2H, H5, H6), 1.65 d (1H, H7s) 1.56 d (1H,
H7a). Found, %: C 49.63; H 5.75; N 8.94. C13H18N2O5S.
Calculated, %: C 49.68; H 5.73; N 8.92.
N-(o,p-Dinitrophenylamino)bicyclo[2.2.1]-hept-2-
ene-endo,endo-5,6-dicarboximide (Vf). Yield 68%, mp
–1
236–238°C. IR spectrum, cm : 3353, 1727, 1610, 1587,
N-(Anilino)bicyclo[2.2.1]hept-2-ene-endo,endo-
5,6-dicarboximide (Va). Yield 69%, mp 180–182°C. IR
1323, 1180, 842, 733. Found, %: C 52.25; H 3.41;
N 16.30. C15H12N4O6. Calculated, %: C 52.32; H 3.49;
N 16.28.
–1
1
spectrum, cm : 3050, 1700, 1500, 1350, 1150, 712. H
NMR spectrum, d, ppm: 7.10–6.70 (5H, H arom), 5.95 s
(1H, NH), 6.20 m (2H, H2, H3), 3.46 m (2H, H1, H4),
3.32 m (2H, H5, H6), 1.75 d (1H, H7s), 1.49 d (1H, H7a).
Found, %: C 70.85; H 5.54; N 11.08. C15H14N2O2.
Calculated, %: C 70.87; H 5.51; N 11.02.
N-(Benzothiazol-2-ylamino)bicyclo[2.2.1]-hept-2-
ene-endo,endo-5,6-dicarboximide (Vg). Yield 93%, mp
1
180–182°C. H NMR spectrum, d, ppm: 10.84 s (1H,
NH), 7.68–7.10 (4H, H arom), 6.18 m (2H, H2, H3), 3.45
m (2H, H1, H4), 3.30 m (2H, H5, H6), 1.58 d (1H, H7s)
1.52 d (1H, H7a). 13C NMR spectrum, d, ppm: 173.92
(C=O), 128.21, 126.13, 122.21, 121.67, 117.18 (C arom),
134.75 (C2, C3), 51.35 (C7), 44.41 (C1, C4), 43.56 (C5,
C6). Found, %: C 61.69; H 4.25; N 13.45. C16H13N3O2S.
Calculated, %: C 61.74; H 4.18; N 13.50.
N-(1,1-Dioxotetrahydrothiophen-3-ylamino)-
bicyclo[2.2.1]hept-2-ene-endo,endo-5,6-dicarb-
oximide (Vb). Yield 73%, mp 185–187°C. IR spectrum,
–1
1
cm : 3250, 1750, 1350, 1250, 1150, 1050, 720. H NMR
spectrum, d, ppm: 4.46 s (1H, NH), 6.15 m (2H, H2,
H3), 3.80 m (2H, H1, H4), 3.26 m (2H, H5, H6), 1.70 d
(1H, H7s) 1.45 d (1H, H7a). Found, %: C 52.73; H 5.44;
N 9.49. C13H16N2O4S. Calculated, %: C 52.70; H 5.40;
N 9.46.
N-Ureidobicyclo[2.2.1]hept-2-ene-endo,endo-5,6-
1
dicarboximide (VIa). Yield 79%, mp 203–205°C. H
NMR spectrum, d, ppm: 9.77 s (1H, NH), 8.11 s (1H,
NH), 7.80 s (1H, NH), 5.99 m (2H, H2, H3), 3.35 m (2H,
H1, H4), 3.25 m (2H, H5, H6), 1.54 m (2H, H7s, H7a). 13C
NMR spectrum, d, ppm: 174.20 (C=O), 134.11 (C2, C3),
50.83 (C7), 44.11 (C1, C4), 43.61 (C5, C6). Found, %:
C 54.26; H 5.02; N 19.05. C10H11N3O3. Calculated, %:
C 54.30; H 4.98; N 19.00.
N-(Dimethylamino)bicyclo[2.2.1]hept-2-ene-
endo,endo-5,6-dicarboximide (Vc). Yield 65%, mp
–1
139–141°C. IR spectrum, cm : 1700, 1450, 1359, 1200,
1
790, 725. H NMR spectrum, d, ppm: 6.09 m (2H, H2,
H3), 3.40 m (2H, H1, H4), 3.12 m (2H, H5, H6), 1.72 d
(1H, H7s) 1.49 d (1H, H7a). Found, %: C 64.01; H 6.83;
N 13.49. C11H14N2O2. Calculated, %: C 64.08; H 6.80;
N 13.59.
N-(Benzoylamino)bicyclo[2.2.1]hept-2-ene-
endo,endo-5,6-dicarboximide (VIb). Yield 96%, mp
–1
106–108°C. IR spectrum, cm : 3450, 1790, 1716, 1668,
1
1552, 1339, 1308, 707. H NMR spectrum, d, ppm: 7.85–
N-(O-Nitrophenylamino)bicyclo[2.2.1]hept-2-ene-
endo,endo-5,6-dicarboximide (Vd). Yield 95%, mp
7.47 (5H, H arom), 5.95 m (2H, H2, H3), 3.46 m (2H, H1,
H4), 3.32 m (2H, H5, H6), 1.75 d (1H, H7s), 1.49 d (1H,
H7a). 13C NMR spectrum, d, ppm: 174.96 (C=O), 132.61
(C=O), 128.57, 127.64 (C arom), 134.58 (C2, C3), 51.57
(C7), 45.10 (C1, C4), 44.36 (C5, C6). Found, %: C 68.03;
H 4.89; N 9.94. C16H14N2O3. Calculated, %: C 68.09;
H 4.96; N 9.93.
1
153–155°C. H NMR spectrum, d, ppm: 8.09, 7.75 (4H,
H arom), 6.15 m (2H, H2, H3), 3.48 m (2H, H1, H4), 3.38
m (2H, H5, H6), 1.72 d (1H, H7s) 1.63 d (1H, H7a). 13C
NMR spectrum, d, ppm: 174.42 (C=O), 133.61, 131.74,
129.52, 124.50 (C arom), 134.59 (C2, C3), 51.46 (C7),
45.13 (C1, C4), 44.40 (C5, C6). Found, %: C 60.25; H
4.29; N 14.11. C15H13N3O4. Calculated, %: C 60.20; H
4.35; N 14.05.
N-(o-Chlorobenzoylamino)bicyclo[2.2.1]hept-2-
ene-endo,endo-5,6-dicarboximide (VIc). Yield 72%,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

REACTION OF ENDIC ANHYDRIDE WITH HYDRAZINES AND ACYLHYDRAZINE
1145
–1
mp 192–194°C. IR spectrum, cm : 3267, 3067, 1786,
1733, 1685, 1591, 1351, 872. 1H NMR spectrum, d,
ppm: 7.58, 7.47, 7.38 (4H, H arom), 6.15 m (2H, H2,
H3), 3.47 m (2H, H1, H4), 3.38 m (2H, H5, H6), 1.71 d
(1H, H7s), 1.62 d (1H, H7a). 13C NMR spectrum, d, ppm:
174.49 (C=O), 131.99 (C=O), 131.52, 130.20, 129.41,
128.13, 126.89 (C arom), 134.58 (C2, C3), 51.48 (C7),
45.13 (C1, C4), 44.41 (C5, C6). Found, %: C 60.72;
H 4.05; N 8.81. C16H13ClN2O3. Calculated, %: C 60.66;
H 4.11; N 8.85.
0.05 ml (0.43 mmol) of 30% hydrogen peroxide solution,
and stirring was continued till completion of the reaction
(TLC monitoring). The formic acid was removed in a
vacuum, ice water was added to the residue, the
precipitated crystals were filtered off, washed with
water on the filter, dried, and recrystallized from 2-
–
propanol. Yield 72%, mp 132–133°C. IR spectrum, cm
1
1: 3410, 1705, 1655, 1540, 1310, 1290, 1190, 855. H
NMR spectrum, d, ppm: 8.05 (NH), 7.80–7.45 (5H, H
arom), 3.45 m (2H, H1, H4), 3.25 m (2H, H5, H6), 3.12 m
(2H, H2, H3), 1.71 d (1H, H7s), 1.05 d (1H, H7a). Found,
%: C 64.54; H 4.79; N 9.31. C16H14N2O4. Calculated,
%: C 64.43; H 4.70; N 9.39.
N-(m-Hydroxybenzoylamino)bicyclo[2.2.1]-hept-
2-ene-endo,endo-5,6-dicarboximide (VId). Yield 88%,
–1
mp 238–240°C. IR spectrum, cm : 3366, 3009, 1792,
1728, 1662, 1584, 1359, 838. 1H NMR spectrum, d,
ppm: 7.29–7.00 (4H, H arom), 6.16 m (2H, H2, H3), 3.45
m (2H, H1, H4), 3.36 m (2H, H5, H6), 1.71 d (1H, H7s),
1.61 d (1H, H7a). 13C NMR spectrum, d, ppm: 174.96
(C=O), 157.75 (C=O), 133.57, 132.98, 130.20, 126.95,
114.48 (C arom), 134.57 (C2, C3), 51.56 (C7), 45.10 (C1,
C4), 44.38 (C5, C6). Found, %: C 64.48; H 4.74; N 9.43.
C16H14N2O4. Calculated, %: C 64.43; H 4.70; N 9.40.
REFERENCES
1. Grekov, A.P., Organicheskaya khimiya gidrazina (Hydr-
azine Organic Chemistry), Kiev: Tekhnika, 1966, 235 p.
2. Onishchenko, A.S., Dienovyi sintez (Diene Synthesis),
Moscow: Izd. Akad. Nauk SSSR, 1963, 314 p.
3. US Patent 3277111, 1966; Ref. Zh. Khim., 1968, 6N729P.
4. Japan Patent 9319 1967; Ref. Zh. Khim., 1968, 21N595;
Furdik, M., Sidoova, E., and Priechradny, S., Acta Fac.
Rerum. Nature. Univ. Com. Chim., 1968, vol. 12, p. 253;
Japan Patent 59-122465, 1984; Ref. Zh. Khim., 1985,
15O39P; Koval, I., Sulfur Reports, 1993, vol. 14, p. 149.
5. Japan Patent 48-2552, 1973; Ref. Zh. Khim., 1973,
23N365P.
N-(m-Nitrobenzoylamino)bicyclo[2.2.1]hept-2-
ene-endo,endo-5,6-dicarboximide (VIe). Yield 92%,
–1
mp 114–116°C. IR spectrum, cm : 3476, 3010, 1783,
1718, 1670, 1534, 1375, 1350, 1304, 740. 1H NMR
spectrum, d, ppm: 8.70, 8.43, 8.21, 7.75 (4H, H arom),
6.18 m (2H, H2, H3), 3.50 m (2H, H1, H4), 3.39 m (2H,
H5, H6), 1.72 d (1H, H7s), 1.63 d (1H, H7a). 13C NMR
spectrum, d, ppm: 174.78 (C=O), 148.44 (C=O), 133.57,
132.98, 130.22, 126.95, 122.54 (C arom), 134.61 (C2,
C3), 51.97 (C7), 45.16 (C1, C4), 44.37 (C5, C6). Found,
%: C 58.77; H 4.05; N 12.89. C16H13N3O5. Calculated,
%: C 58.72; H 3.98; N 12.84.
6. German Patent 295630 1991; Ref. Zh. Khim., 1992,
18O149P.
7. Kas’yan,A.O., Krishchik, O.V., Krasnovskaya, O.Yu., and
Kas’yan, L.I., Zh. Org. Khim., 1998, vol. 34, p. 1802.
8. Kas’yan, L.I., Krishchik, O.V., Umrykhina, L.K., and
Kas’yan, A.O., Vestn. DGU, Khimiya, 1998, p. 87.
9. Nakanisi, K., Infrakrasnye spektry organicheskikh molekul
(IR Spectra of Organic Molecules), Moscow: Mir, 1965,
209 p.
10. Keith, T.A. and Bader, R.F.W., Chem. Phys. Lett., 1992,
vol. 194, p. 1; Keith, T.A. and Bader, R.F.W., Can. J.
Chem., 1996, vol. 74, p. 185.
N-(p-Nitrobenzoylamino)bicyclo[2.2.1]hept-2-ene-
endo,endo-5,6-dicarboximide (VIf). Yield 51%, mp
–1
127–129°C. IR spectrum, cm : 3452, 3010, 1770, 1674,
1606, 1526, 1358, 854, 708. Found, %: C 58.67; H 4.08;
N 12.88. C16H13N3O5. Calculated, %: C 58.72; H 3.98;
N 12.84.
11. Ditchfield, R., Mol. Phys., 1974, vol. 27, p. 789; Wolinski,
K., Hilton, J.F., and Pulay, P.J., J. Am. Chem. Soc., 1990,
vol. 112, p. 8251.
N-(1-Adamantanecarbonylamino)bicyclo-
[2.2.1]hept-2-ene-endo,endo-5,6-dicarboximide (VIg).
Yield 68%, mp 214–216°C. Found, %: C 70.31; H 7.09;
N 8.33. C20H24N2O3. Calculated, %: C 70.59; H 7.06;
N 8.24.
12. Rossikhin, V.V., Okovytyy, S.I., Kasyan, L.I., Voron-
kov, E.O., Umrikhina, L.K., and Leszczynski, J., J. Phys.
Chem., 2002, vol 106, p. 4176.
13. Shustov, G.V., Dokl. Akad. Nauk SSSR, 1985, p. 1378.
14. Burgi, H.-B. and Dunitz, J.D., Structure Correlation, 1994,
vol. 2, p. 741.
N-(Benzoylamino)-exo-2,3-epoxybicyclo-[2.2.1]-
heptane-endo,endo-5,6-dicarboximide (VII). To a
solution of 0.1 g (0.355 mmol) of hydrazide VIb in 3 ml
of 98% formic acid at 35–40°C while stirring was added
15. Kas’yan, L.I., Zh. Org. Khim., 1999, vol. 35, p. 661.
16. Sheldrick, G.M., SHELX97 PC, Version A. System of
computer programs for the crystal structure solution and
refinement, Rev. 2, 1998.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004