Oxidative addition of N-aminophthalimide to cinnamic aldehyde phthaloylhydrazone

Full text of DOI:10.1134/S107042800905025X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 5, pp. 792−793. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.V. Beletskii, M.A. Kuznetsov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 5, pp. 804−805.
SHORT
COMMUNICATIONS
OxidativeAddition of N-Aminophthalimide
to Cinnamic Aldehyde Phthaloylhydrazone
E. V. Beletskii and M. A. Kuznetsov
St. Petersburg State University, St. Petersburg, 198504 Russia
e-mail: mak@mail.wplus.net
Received September 4, 2008
DOI: 10.1134/S107042800905025X
The oxidative addition of a series of N-aminohetero-
cycles, first of all, of N aminophthalimide and various
3-aminoquinazolinones, to olefins proceeds at the π-bond
and serves as a general method of synthesis of N-amino-
aziridine derivatives [1–3]. Under these conditions in the
azo group the unshared electron pair is attacked on one
of the nitrogen atoms leading to the formation of poly-
nitrogen 1,3-dipoles, N-aminoazimines [4]. A question
arises, what path would take this reaction with the C=N
group? No published data exist on such reactions with
imines, and our attempts to carry out the oxidative addition
of N-aminophthalimide to compounds conteining isolated,
conjugated, or cumulated C=N bonds have been
unsuccessful up till now [5]. Moreover, it turned out that
in compounds containing a fragment C=C–C=N in this
reaction did not enter not only the C=N bond, but also
the commonly active conjugated C=C bond [6]. In
particular, the investigation of oxidative aziridination with
phthalimide of conjugated alkenylpyrazolines and
alkenylpyrazoles [6] showed that the taken alkenyl-
pyrazolines did not react, although the similarly substituted
alkenylpyrazoles gave the corresponding aziridines in good
yields. Evidently this result originated from the inclusion
of the C=N bond into an aromatic heterocycle where
this bond considerably lost its individual character.
RNH2
R
R
Ph
N
Ph
N
Pb(OAc)4
N
R
II, 46%
I
O
b
a
c
R =
N
O
structure was proved by 1H and 13C NMR spectra where
the signals of all fragments of the molecule were present
in the corresponding regions and with the expected
multiplicity. In keeping with the 1H NMR spectrum due
to the typical for the N-aminoaziridine derivatives slow
inversion of the endocyclic nitrogen [7] this compound
existed in DMSO in the form of two invertomers in a ratio
~8:1. Inasmuch as in these aziridines the phthalimide
substituent commonly deshielded the syn-located protons,
the main invertomer contained the phthalimide and phenyl
groups on the opposite sides of the plane of the three-
membered ring, in agreement with the steric reasons.
Still on attempt to perform the oxidative addition of
N-aminophthalimide to analogous compounds containing
a C=C–C=N fragment, cinnamic aldehyde phenylimine
(R = Ph) and to its dimethylhydrazone (R = Me2N), we
did not detect in the 1H NMR spectra of the reaction
mixtures the characteristic signals of the aziridine protons.
Yet by an example of hydrazone I we were fortunate
to carry out the first successful aminoaziridination of
a compound containing a fragment C=C–C=N whose
C=N bond was not included in an aromatic system.
The composition of obtained aziridine II was
confirmed by elemental analysis and by the presence in
its mass spectrum of the molecular ion peak, and its
2-{[(1E,2E)-3-Phenylprop-2-en-1-ylidene]-
amino}-1H-isoindole-1,3(2H)-dione (I). To a suspen-
sion of 1.62 g (10 mmol) of N-aminophthalimide [8] in
792

OXIDATIVE ADDITION OF N-AMINOPHTHALIMIDE
793
30 ml of ethanol was added 1.45 g (11 mmol) of cinnamic
aldehyde, and the mixture was boiled at reflux for 2 h.
The precipitate settled on cooling was filtered off and
dried in air. Yield 2.10 g (76%). Light-yellow crystalline
powder, mp 197–198°C (mp 199–200°C [8]). 1H NMR
spectrum (CDCl3), δ, ppm: 7.1–7.2 m (2H, CH=CH),
7.35–7.45 m (3H, Hm + Hï), 7.50–7.57 m (2H, HO), 7.77–
7.82 m (2H, Ht), 7.90–7.96 m (2H, Ht), 9.29 d.d (1H,
CH=N, J 5.5 and 2.7 Hz).
Ci), 157.29 (C=N), 163.99 and 164.65 (2CO). Mass
spectrum, m/z (Irel, %): 436 (1.3) [M]+, 290 (32) [M –
R]+, 289 (79) [M – RH]+, 236 (58), 187 (16), 185 (16),
147 (98) [RH]+, 132 (32), 130 (28), 105 (26), 104 (99)
[C6H4CO]+, 103 (44), 90 (18), 77 (38), 76 (100), 75 (28),
74 (25), 63 (12), 51 (21), 50 (87), 39 (17), 38 (18), 37
(17). Found, %: C 68.71; H 3.73; N 12.80. C25H16N4O4.
Calculated, %: C 68.81; H 3.67; N 12.84. M 436.43.
1H (300 MHz) and 13C (75.4 MHz) NMR spectra
were registered on a spectrometer Bruker DPX-300.
Mass spectrum was measured on an MKh-1321
instrument (energy of ionizing electrons 70 eV). Elemental
analysis was performed on an automatic CHN-analyzer
Hewlett Packard 185B.
2-(2-{(E)-[(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-
yl)imino]methyl-3-phenyl-aziridin-1-yl)-1H-
isoindole-1,3(2H)-dione (II). To a solution of 2.76 g
(10 mmol) of hydrazone I in 50 ml of dichloromethane
cooled to 0°C where was dispersed 5.0 g of potassium
carbonate was added at stirring by small portions within
15 min 1.62 g (10 mmol) of N-aminophthalimide and
4.43 g (10 mmol) of lead tetraacetate. On completion of
addition the mixture was stirred for 10 min more, then it
was filtered, the precipitate of inorganic salts was washed
with 20 ml of dichloromethane. The solution was
evaporated in a vacuum to a volume of ~30 ml, cooled
to–5°C, the separated precipitate was filtered off. Yield
2.00 g (46%). Colorless powder, mp 178–179°C.
According to 1H NMR spectrum the product existed in
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1
the form of two invertomers in a ratio ~8:1. H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz), main invertomer:
3.76 d.d (1H, CHN, J 7.3 and 5.5), 4.50 d (1H, PhCHN,
J 5.5), 7.33–7.45 m (3H, Hm + Hp), 7.51 d (2H, Ho, J 7.3),
7.79–7.83 m (8H, Ht), 8.68 d (CH=N, J 7.3); minor
invertomer: 4.14 d (1H, PhCHN, J 5.5), 4.70 d.d (1H,
CHN, J 7.3 and J 5.5), 7.67–7.95 m (8H, Ht), 8.74 d
(CH=N, J 7.3). 13C NMR spectrum of the main inverto-
mer (DMSODMCO-d6), δ, ppm: 48.53 (CHN), 49.26
(CHN), 122.95 and 123.50 (2CHt, Cb), 127.32 and 128.48
(Ph, Co and Cm), 128.30 (Ph, Cp), 129.61 and 130.06
(2CHt, Ca), 134.51 and 135.00 (2CHt, Cc), 135.18 (Ph,
8. Drew, N.D.K. and Hatt, N.H., J. Chem. Soc., 1937, p. 16.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 5 2009