Reaction of γ-dicarboxylic acids amides and imides with trifluoromethanesulfonamide and formaldehyde

Article abstract of DOI:10.1134/S1070428009110116

Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and succinamide depending on the reaction conditions led alongside bis(trifluoromethanesulfonamido)methane to the formation of a substitution product, bis[(trifluoromethylsulfonyl)aminomethyl]succinamide, or to a cyclization product, N-[trifluoromethylsulfonyl)aminomethyl]succinimide. The attempt to obtain the latter by the reaction of the trifluoromethanesulfonamide sodium salt CF₃SO₂NHNa with N-chloromethylsuccinimide unexpectedly resulted in N,N-bis(succinimidomethyl)-trifluoromethanesulfonamide. Analogously the reaction of CF₃SO₂NHNa with N-chloromethyl-phthalimide gave N,N-bis(phthalimidomethyl)trifluoromethanesulfonamide. The reaction of CF₃SO₂NHNa with succinimide and phthalimide in water and alcohol solution resulted in the ring opening and further transformation of the formed monosubstituted N-(trifluoromethylsulfonyl)amides of succinic and phthalic acids.

Full text of DOI:10.1134/S1070428009110116

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 11, pp. 1644−1650. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.Yu. Moskalik, V.I. Meshcheryakov, B.A. Shainyan, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 11, pp. 1654−1659.
Reaction of γ-Dicarboxylic Acids Amides and Imides
with Trifluoromethanesulfonamide and Formaldehyde
M. Yu. Moskalik, V. I. Meshcheryakov, and B. A. Shainyan
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
Irkutsk, 664033 Russia
e-mail: bagrat@irioch.irk.ru
Received April 9, 2009
Abstract—Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and
succinamide depending on the reaction conditions led alongside bis(trifluoromethanesulfonamido)methane to
the formation of a substitution product, bis[(trifluoromethylsulfonyl)aminomethyl]succinamide, or to a cyclization
product, N-[trifluoromethylsulfonyl)aminomethyl]succinimide. The attempt to obtain the latter by the reaction of
the trifluoromethanesulfonamide sodium salt CF3SO2NHNa with N-chloromethylsuccinimide unexpectedly resulted
in N,N-bis(succinimidomethyl)-trifluoromethanesulfonamide. Analogously the reaction of CF3SO2NHNa with
N-chloromethyl-phthalimide gave N,N-bis(phthalimidomethyl)trifluoromethanesulfonamide. The reaction of
CF3SO2NHNa with succinimide and phthalimide in water and alcohol solution resulted in the ring opening and
further transformation of the formed monosubstituted N-(trifluoromethylsulfonyl)amides of succinic and phthalic
acids.
DOI: 10.1134/S1070428009110116
We showed formerly that the condensation of
trifluoromethanesulfonamide (triflamide) CF3SO2NH2
with paraformaldehyde depending on the reaction
conditions led to the formation of versatile linear and
cyclic products [1, 2].Also the three-component reactions
of triflamide with paraformaldehyde and various amides
were investigated, and in some events mixed condensation
products were obtained [3]. It was shown in particular
that the reaction of triflamide, paraformaldehyde, and
malonamide provided a spirocyclic condensation product
involving both amido groups and the methylene group of
the malonamide, 4,10-bis-(trifluoromethylsulfonyl)-
2,4,8,10-tetraazaspiro-[5,5]undecane-1,7-dione [3]. In
extension of this research the present study consists in
the investigation of the reaction of succinamide,
succinimide, and phthalimide with trifluoromethane-
sulfonamide and formaldehyde under various conditions.
of its condensation with formaldehyde [bis(trifluoro-
methanesulfonamido)methane (II)] the formation was
found of a product of the triple condensation at both amido
groups, bis[(trifluoromethylsulfonyl)aminomethyl]-
succinamide (III) that was isolated after washing the
reaction product II with a mixture ether–hexane and was
recrystallized from dichloromethane.
The same reaction carried out in ethyl acetate in the
presence of sulfuric acid alongside compound II un-
expectedly furnished a cyclic amidomethylation product,
N-[(trifluoromethylsulfonyl)aminomethyl]succinimide
(IV) isolated analogously and recrystallized from chloro-
form.
The structure of compound III was proved by the
1
presence in its H NMR spectrum of a singlet from
CH2CH2 group at 2.36 ppm, a broadened singlet of
NHSO2, a triplrt of NHCO, and a doublet of NCH2N in
the ratio 2:1:1:2, and of the corresponding signals in the
13C NMR spectrum. Unlike that in the 1H NMR spectrum
of compound IV appeared a singlet of CH2CH2 group at
2.68 ppm, and signals of NHSO2 and NCH2N groups in
the ratio 4:1:2, and the corresponding signals in the
The investigation of the transformations in the system
trifluoromethanesulfonamide–formaldehyde−succinamide
(I) revealed the fundamental dependence of the reaction
direction on its conditions. In the medium of concn. H2SO4
alongside the unreacted triflamide and the linear product
1644

REACTION OF γ-DICARBOXYLIC ACIDS AMIDES AND IMIDES
1645
13C NMR spectrum. In the spectrum of compound IV
a spin-spin splitting of the signal from the fragment
CH2NH was not observed.
and it was found that at its heating in ethyl acetate with
sulfuric acid for 24 h (~40°C) the succinimide actually
did not form, as showed the absence of succinimide signals
in the 1H and 13C NMR spectra of the isolated reaction
product. However under these conditions the succinamide
suffered transformations, since in the 1H NMR spectrum
of the product instead of a singlet of the CH2CH2 group
at 2.26 ppm appeared two triplets at 2.32 and 2.44 ppm
(J 6.5 Hz), two broadened singlets of NH at 6.8 and 7.3
ppm, and signals of an ethyl group at 4.02 q and 1.16 t
ppm. In the 13C NMR spectrum signals are observed
from two C=O groups at 172.41 and 172.84 ppm, two
signals from nonequivalent methylene groups of the
fragment CH2CH2 at 28.84 and 20.52 ppm, and ethyl
group signals at 14.06 and 59.75 ppm. These spectra
correspond to the formation of ethyl 4-amino-4-
oxobutanoate C2H5OOCCH2CH2CONH2 due to a partial
The reaction product IV might originate from
triflamidomethylation of the succinimide formed by a
partial hydrolysis and dehydration of succinamide.
However this cyclization is hardly possible at room
temperature, moreover in ethyl acetate and in the
presence of sulfuric acid, namely, in less acid medium
than sulfuric acid proper. Besides this mechanism does
not account for the pronounced dependence of the
reaction direction (Scheme 1) on the nature of the reaction
medium: of the presence of insignificant additive of
compound IV in the reaction along the a pathway and of
compound III as an insignificant impurity in the reaction
by the b pathway. We tested the possibility of succinamide
cyclization under these reaction conditions (Scheme 1),
Scheme 1.
O
NHCH2NHSO2CF3
NHCH2NHSO2CF3
H2SO4
(CF3SO2NH)2CH2 +
II
O
(a)
(b)
O
III
NH2
NH2
CF3SO2NH2 + CH2O +
O
O
I
AcOEt
H2SO4
(CF3SO2NH)2CH2 +
NCH2NHSO2CF3
II
O
IV
Scheme 2.
OH
O
O
+
H+
H+
NCH2NHTf
+
NHCH2NHTf
NHCH2NHTf
NHCH2NHTf
+
NCH2NHTf
NCH2NHTf
OH
O
III
OH
III-H22+
III-H+
O
.
O
O
.
+
NHCH2NHTf
+
NHCH2NHTf
NHCH2NHTf
_TfNHCH2NH2 _H+
NHCH2NHTf
,
HO
NHCH2NHTf
O
IV
OH
III-H+
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

MOSKALIK et al.
1646
difference in the behavior of succinamide and its
alcoholysis of the succinamide.
disubstituted derivative III under the same conditions is
due to the greater nucleofuge ability of the TfNHCH2NH
group compared to the NH2 group owing to the strong
electron-withdrawing effect of the trifluoromethane-
sulfonyl group.
We examined the behavior of bis[(trifluoromethyl-
sulfonyl)aminomethyl]succinamide (III) under the
reaction conditions (Scheme 1) and found that at weak
heating for 16 h in contrast to succinamide it nearly totally
underwent cyclization (to ~90%) in N-[(trifluoromethyl-
sulfonyl)aminomethyl]succinimide (IV)as indicated by
a coincidence of the NMR signals of the obtained
reaction product with the signals of the authentic com-
pound IV. This fact suggests the following mechanism
of compound IV formation.
In order to increase the yield of compound III we
studied various versions of this reaction: the condensation
in 2-propanol in the presence of potassium carbonate, in
dilute and concentrated hydrochloric acid and in 2-propanol
in the presence of hydrochloric acid, the condensation in
sulfuric acid of triflamide with N,N-bis(dihydroxy-
methylene)-succinamide obtained by the reaction of
formaldehyde and succinamide in the presence of
potassium carbonate, and also the condensation of
oxymethyl derivative of triflamide CF3SO2NHCH2OH
with succinamide. However these attempts were
unsuccessful.
Inasmuch as the carboxylic acids amides are
protonated at the oxygen atom (see [4] and references
therein) compound III in acid medium would exist as an
equilibrium mixture of mono- and diprotonated forms
(III-H+) and (III-H22+).
In the pure sulfuric acid (pathway a, Scheme 1) the
basicity of both amide nitrogen atoms in the linear
compound III is suppressed by protonation to (III-H22+),
and the reaction is stopped at the stage of its formation.
Under less acid conditions (pathway b, Scheme 1) the
relative concentration of the form (III-H+) grows, and
the probability of an attack of the nitrogen from the free
amide group on the carbon atom of the protonated amide
group with the ring closure increases (Scheme 2). The
An alternative method for preparation of compound
IV and its analog, N-[(trifluoro-methylsulfonyl)amino-
methyl]phthalimide, by the reaction of triflamidesodium
salt with N-chloromethyl derivatives of imides was tested
by examples of succinimide and phthalimide. N-Oxy-
methyl derivatives of succinimide and phthalimide obtained
in the reaction with formaldehyde water solution were
Scheme 3.
O
O
N
O
O
N
O
DMF
_NaCl
X
NCH2Cl + CF3SO2NHNa
X
X
CH2 N CH2
SO2CF3
VI
O
Và, Vb
VIIà, VIIb
X = CH2CH2 (a), 1,2-C6H4 (b).
Scheme 4.
O
O
O
CF3SO2NHNa
CF3SO2NH2
CF3SO2NHNa
_NaCl
NCH2Cl
NCH2NHSO2CF3
NCH2NNaSO2CF3
O
O
O
O
O
O
NCH2Cl
N
CH2N
NCH2
O
SO2CF3
O
O
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

REACTION OF γ-DICARBOXYLIC ACIDS AMIDES AND IMIDES
1647
chlorinated with PCl5, and thus prepared N-chloromethyl-
succinimide (Va) and N-chloromethylphthalimide (Vb)
were brought into the reaction with triflamide sodium salt
(VI) in DMF. The result was unexpected: In both cases
formed bis-substituted triflamides VIIa and VIIb
(Scheme 3).
We also investigated the ring opening in the
succinimide and the phthalimide molecules in the reaction
with the triflamide sodium salt in water or in alcohol. The
reaction of succinimide in water with excess salt VI
actually resulted in the ring opening, but the only product
of this reaction isolated by the workup of the reaction
mixture followed by recrystallization proved to be
succinamic acid VIIIa.
Compound VIIa formed as the only reaction product
even at the equimolar reagents ratio; the characteristic
doublet signal of NCH2 at 4.8 ppm belonging to the
expected intermediate compound IV did not appear in
The formation of compound VIIIa was proved by
NMR spectra, elemental analysis, and the coincidence
of the melting point with the published finding. The
1H NMR spectrum contains two triplets corresponding
to two nonequivalent CH2C(O) fragments, and two signals
of the nonequivalent protons of the amide group CONH2,
and in the 13C NMR spectrum two signals from CH2
and two signals of carbonyl groups are observed.
Inasmuch as the succinimide proper does not react with
water even at boiling, the reaction evidently proceeds by
the type of nucleophilic catalysis with the intermediate
formation of N-trifluoromethylsulfonylsuccinamide with
a highly nicleofugic group CF3SO2NH that is easily
hydrolyzed by the liberated alkali. We formerly observed
this type nucleophilic catalysis with the elimination of the
residue CF3SO2NH in the form of trifluoromethane-
sulfonamide in the reaction of 2-phenyl-2H-1,2,3-triazole-
1
the H NMR spectrum of the reaction mixture. It may
mean that the intermediately formed monosubstituted
product IV reacted with N-chloromethylsuccinimide far
faster than the triflamide sodium salt. It evidently depends
on its higher NH-acidity and consequently on the shift of
the equilibrium to the right (Scheme 4).
The position of this equilibrium may be estimated by
an example of the phthalimide derivative while comparing
the values of pKa of acetic acid and phthalimidoacetic
acid equal 4.75 and 3.0 respectively [5]. The latter value
is virtually equal to the pKa of bromoacetic acid, therefore
the σ* value of the heterocyclic substituent amounts to
~0.5. The value ΔpKa 1.75 corresponds to the content
of the sodium salt of compound IV >98% , and of
triflamide sodium salt <2% manifesting the reason of the
experimental result.
Scheme 5.
O
O
O
H2O
_CF3SO2NH2
H2O
NH + CF3SO2NHNà
_NaOH
COOH
NH2
NHSO2CF3
NH2
O
O
O
VIIIa
Scheme 6.
O
O
NH2
..
NHSO2CF3
ROH
NH + CF3SO2NHNa
_RONa
O
O
VIIIb
Δ
_CF3SO2NH2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

MOSKALIK et al.
1648
(4 × 40 ml), the extract was dried with MgSO4, the solvent
was removed. The obtained liquid residue was treated
with a mixture ether–hexane, 1:6. The unreacted
triflamide and bis(trifluoro-methanesulfonamido)methane
(II) were soluble in this mixture and were removed; from
the residue after recrystallization from dichloromethane
the target product was isolated as colorless crystals, mp
4-carboxamide with acid chloride CF3SO2Cl in methanol
[6].
The opening of the imide ring occurred also in the
phthalimide molecule in the reaction with the triflamide
sodium salt in the mixture of methanol with 2-propanol.
In the 1H NMR spectrum of the crude reaction product
VIIIb containing a considerable amount of phthalimide
seven signals of equal intensity are observed: two doublets
and two triplets of four nonequivalent aromatic protons,
two nonequivalent signals of amide group CONH2 in the
region ~7.2 ppm. and the signal at 9.1 ppm, i.e., in the
region characteristic of the CF3SO2NH group. In the
1H NMR spectrum of the proper phthalimide the
resonance of all aromatic protons appeared as a singlet
at 7.76 ppm. Therefore it was possible to ascribe to
product VIIIb the structure of N-(trifluoromethyl-
sulfonyl)phthalamide.
1
185–190°C. H NMR spectrum (DMSO-d6), δ, ppm:
2.36 s (4H, CH2), 4.45 d (4H, NCH2N, J 6.0 Hz), 8.82 t
(2H, NHCO, J 6 Hz), 10.13 br.s (2H, NHSO2). 13C NMR
spectrum (DMSO-d6), δ, ppm: 29.83 s (CH2CH2), 47.82
(NCN), 119.42 q (CF3, J 321.8 Hz), 171.97 s (C=O).
19F NMR spectrum (CD3CN), δ, ppm: –79.41. Found,
%: C 21.87; H 2.95; N 12.50; S 14.26. C8H12F6N4O6S2.
Calculated, %: C 21.92; H 2.76; N 12.78; S 14.63.
N-[(Trifluoromethyl-sulfonyl)aminomethyl]-
succinimide (IV). To a dispersion of 6.4 g of triflamide,
2 g of succinamide, and 1.29 g of paraformaldehyde in
35 ml of ethyl acetate was added dropwise within 35 min
12 ml of concn. H2SO4. The reaction mixture was stirred
for 4 h at room temperature, then poured on ice with
NaCl, extracted thrice with ethyl acetate, the extract was
dried with MgSO4, the solvent was removed. The
obtained liquid residue was treated with a mixture ether–
hexane, 1:6, the insoluble solid residue was filtered off
and recrystallized from chloroform to obtain colorless
crystals, mp 105–107°C. 1H NMR spectrum (DMSO-
d6), δ, ppm: 2.68 s (4H, CH2), 4.75 s (2H, NCH2N),
10.55 br.s (1H, NH). 13C NMR spectrum (DMSO-d6),
δ, ppm: 27.88 s (CH2CH2), 45.60 (NCN), 119.57 q (CF3,
J 320.9 Hz), 176.29 s (CO). 19F NMR spectrum
(CD3CN), δ, ppm: –74.95. Mass spectrum, m/z (Irel, %):
191 (6) [M – CF3], 162 (9) [CF3SO2NHCH2], 127 (79)
[M – SO2CF3], 112 (51) [M – NHSO2CF3], 100 (42)
[127 – HCN], 84 (38) [112 – CO], 78 (21) [NSO2], 69
(93) [CF3], 56 (84) [C3H4O], 55 (100) [C3H3O]. Found,
%: C 27.23; H 2.61; F 22.27; N 10.16; S 12.81.
C6H7F3N2O4S. Calculated, %: C 27.70; H 2.71; F 21.91;
N 10.77; S 12.32.
Regretfully, we failed to isolate compound VIIIb in
the pure state for the recrystallization from 2-propanol
of the crude product containing compound VIIIb and
phthalimide in the ratio ~3:2 resulted in the increased
content of phthalimide to the ratio ~1:2, and on the
recrystallization from benzene separated a mixture of
pure phthalimide and triflamide. It means that at heating
of compound VIIIb the reverse cyclization easily
occurred with the elimination of the triflamide.
EXPERIMENTAL
IR spectrum of incomplete internal reflection of
compound VIIIa was recorded on a spectrophotometer
Varian 3100 FT-IR. NMR spectra were registered on a
spectrometer Bruker DPX-400 at operating frequencies
400 (1H), 100 (13C), 376 MHz (19F), the chemical shifts
were measured relative to TMS (1H, 13C) and CCl3F
(19F). Mass spectrum of electron ionization (70 eV) was
obtained on an instrument GCMS-QP5050A Shimadzu
(quadrupol mass analyzer) in the direct admission mode.
The reaction progress was monitored by TLC on plates
with silica gel 60 F-254, eluent hexane–ether, 1:2.
N,N-Bis(succinimidomethyl)trifluoromethane-
sulfonamide (VIIa). N-Hydroxymethylsuccinimide,
obtained by reacting the succinimide with water solution
of formaldehyde in the presence of potassium carbonate,
was converted into N-chloromethylsuccinimide (Va) by
the reaction with PCl5 in chloroform by procedure [7].
To a solution of 2.54 g (15 mmol) of CF3SO2NHNa (VI)
in 13 ml of DMF was added 2.26 g (0.015 mmol) of
N-chloromethylsuccinimide, the mixture was stirred for
N,N'-Bis[(trifluoromethylsulfonyl)aminomethyl]-
succinamide (III). To a solution of 2 g of succinamide
pn 55 ml of concn. H2SO4 was added 6.4 g of triflamide,
1.29 g of paraformaldehyde, and the mixture was stirred
for 2 days at room temperature. The reaction mixture
was poured on ice with NaCl, the separated precipitate
of bis(trifluoromethanesulfonamido)methane (II), was
filtered off, the water solution was extracted with ether
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

REACTION OF γ-DICARBOXYLIC ACIDS AMIDES AND IMIDES
1649
602. 1H NMR spectrum (DMSO-d6), δ, ppm: 2.28 t (2H,
CH2COOH, J 6.6 Hz), 2.39 t (2H, CH2CONH2,
J 6.6 Hz), 6.76 s (1H, CONHA), 7.29 s (1H, CONHB),
12.05 br.s (1H, OH). 13C NMR spectrum (DMSO-d6),
δ, ppm: 29.00 (CH2COOH), 29.70 (CH2CONH2), 173.10
(CONH2), 173.93 (COOH). Found, %: C 40.90; H 6.01;
N 11.32. C4H7NO3..Calculated, %: C 41.03; H 6.03;
N 11.96.
5 h at room temperature and 5 h more at 60°C, DMF
was distilled off in a vacuum, the liquid residue was mixed
with 2-propanol, and on cooling from the mixture separated
dark-red precipitate. After double recrystallization from
2-propanol yield 0.83 g (15%), mp 166–168°C. 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.68 s (8H, CH2CH2),
5.20 s (4H, NCH2N). 13C NMR spectrum (DMSO-d6),
δ, ppm: 27.95 s (CH2CH2), 52.99 (NCN), 118.98 q (CF3,
J 323.6 Hz), 176.94 s (CO). 19F NMR spectrum (DMSO-
d6), δ, ppm: –75.14. Found, %: C 35.55; H 3.38; F 16.39;
N 11.03; S 8.97. C11H12F3N4O6S.. Calculated, %: C 35.58;
H 3.26; F 15.35; N 11.32; S 8.64.
N-(Trifluoromethylsulfonyl)phthalamide (VIIIb).
To a dispersion of 0.5 g (3 mmol) of phthalimide in a mix-
ture of 10 ml of 2-propanol and 2 ml of MeOH was added
by small portions 1.4 g (8 mmol) of triflamide sodium
salt. The reaction mixture was heated for 16 h at 75°C,
then 5 ml of 5% HCl was added, the mixture was
thoroughly stirred, the solvents were evaporated at a
reduced pressure. In the residue (1.7 g, mp 177°C)
N,N-Bis(phthalimidomethyl)trifluoromethane-
sulfonamide (VIIb). N-Hydroxymethylphthalimide,
obtained by reacting the phthalimide with water solution
of formaldehyde in the presence of potassium carbonate
[8], was converted into N-chloromethylphthalimide (Vb)
by the reaction with PCl5 in chloroform by procedure
[9]. To a solution of 0.96 g (5.6 mmol) of CF3SO2NHNa
(VI) in 4 ml of DMF was added by small portions 1 g
(5.1 mmol) of N-chloromethylenephthalimide, the mixture
was stirred for 2 h at room temperature, 4 h at 80°C, 5 h
at 110°C, and 5 h at 140°C, then it was poured on ice
with NaCl, the separated precipitate was filtered off and
recrystallized from acetone. Yield 0.9 g (38%), mp 197–
1
according to H NMR data, ~40% phthalimide was
present. 1H NMR spectrum (DMSO-d6), δ, ppm
(phthalimide signals are omitted): 7.17 s (1H, CONHA),
7.28 t (1H, Hβ, J 7.1 Hz), 7.35 t (1H, H'β J 7.2 Hz),
7.48 d (1H, Hα, J 7.5 Hz), 7.60 d (1H, H'α , J 7.7 Hz),
9.14 s (1H, NHSO2). The signal of proton CONHB
overlapped with triplet signals of protons Hβ and H'β as
showed the integral intensity of this spectral region
overestimated by one proton. 13C NMR spectrum
(DMSO-d6), δ, ppm: 124.06, 126.14, 127.41, 128.89,
129.82, 139.06, 171.04, 173.62. We failed to accumulate
the signal of CF3 group. In the 19F NMR spectrum of
samples obtained after removal of solvent from the
reaction mixture and recrystallization of the residue from
2-propanol only the signal of trifluoromethanesulfonamide
was present.
1
199°C. H NMR spectrum (DMSO-d6), δ, ppm: 5.50 s
(4H, CH2), 7.92 m (8H, Harom). 13C NMR spectrum
(DMSO-d6), δ, ppm: 52.89 (CH2), 119.11 q (CF3,
J 323.8 Hz), 123.70 (C4,7), 131.25 (C8,9), 135.12 (CH5,6),
166.96 (CO). 19F NMR spectrum (DMSO-d6), δ, ppm:
–75.47. Found, %: C 48.83; H 2.89; F 12.19; N 8.99;
S 6.80. C19H12F3N3O6S. Calculated, %: C 48.62; H 3.01;
F 12.14; N 8.95; S 6.84.
The attempts to purify the reaction product by
recrystallization from 2-propanol or benzene resulted in
its reverse cyclization into phthalimide with the triflamide
elimination (see the text).
4-Amino-4-oxobutanoic acid (VIIIa). To a solution
of 0.5 g (5 mmol) of succinimide in 7 ml of water was
added by small portions 1.88 g (11 mmol) of triflamide
sodium salt. The reaction mixture was heated for 6 h at
90°C, water was evaporated on a rotary evaporator at
a reduced pressure. The obtained glassy residue (2 g)
was treated with ethyl acetate removing the soluble in
this solvent unreacted triflamide sodium salt. Insoluble
dark-red precipitate (1.1 g) was treated with 5 ml of 5%
HCl, thoroughly stirred, evaporated at a reduced pressure,
the residue was recrystallized from 2-propanol. Yield
0.55 g (44% ), mp 158–160°C (mp 157°C [10]). IR
spectrum, ν, cm–1: 3364, 3203 (N–H), 2933 (C–H), 2770–
2470 (OH), 1726, 1704 (COOH), 1644 (CONH2), 1581,
1414, 1359, 1269, 1201, 1170, 1125, 966, 923, 797, 660,
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
07-03-00425).
REFERENCES
1. Meshcheryakov, V.I., Albanov, A.I., and Shainyan, B.A.,
Zh. Org.Khim., 2005, vol. 41, p. 1409.
2. Meshcheryakov, V.I., Moskalik, M.Yu., Kelling, A.,
Schilde, U., Ushakov, I.A., and Shainyan, B.A., Zh.
Org.Khim., 2008, vol. 44, p. 313.
3. Meshcheryakov, V.I., Danilevich, Yu.S., Moskalik, M.Yu.,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

MOSKALIK et al.
Stetsyura, N.Yu., Zavodnik, V.E., Bel’skii, V.K., and Shai-
1650
6. Meshcheryakov, V.I., Shainyan, B.A., Tolstikova, L.L., and
Albanov,A.I., Zh. Org.Khim., 2003, vol. 39, p. 1583.
7. Cherbuliez, E. and Sulzer, G., Helv. Chim. Acta, 1925, vol. 8,
p. 567.
8. Zaugg, G. and Martin, V., Organicheskie reaktsii (Organic
Reactions), 1967, vol. 14, p. 65.
9. Bohme, H., Broese, R., and Eiden, F., Chem. Ber., 1959,
vol. 92, p. 1258.
10. Jeffery, G.H. and Vogel,A.I., J. Chem. Soc., 1934, p. 1101.
nyan, B.A., Zh. Org.Khim., 2007, vol. 43, p. 799.
4. Bagno, A., Bujnicki, B., Bertrand, S., Comuzzi, C., Dori-
go, F., Janvier, P., and Scorrano, G., Chem. Eur. J., 1999,
vol. 5, p. 523.
5. Tablitsy konstant skorosti i ravnovesiya geteroliti-
cheskikh organicheskikh reaktsii (Tables of Rate and
Equilibrium Constants of Heterocyclic Organic Reactions),
Pal’m, V.A., Ed., Moscow:VINITI, 1975.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009