Chemistry of diazocarbonyl compounds: XXVIII. Reaction of acyclic N-arylsulfonylacetamides with Rh(II)-carbenoids as a new synthetic route to alkyl acetimidoates

Article abstract of DOI:10.1134/S1070428006120074

A new procedure was proposed for the synthesis of alkyl acetimidoates via alkylation of the carbonyl group in N-arylsulfonylacetamides with Rh(II)-carbenoids. The procedure ensures preparation in good yield of acetimidoates having a polyfunctionalized O-alkyl group. The obtained alkyl acetimidoates in crystal exist as E isomers with respect to the C=N bond and as s-cis conformers relative to the C-OCHRR' bond. Alkyl N- arylsulfonylacetimidoates react with ammonia and hydrazine hydrate to give in good yield the corresponding carboximidamides(hydrazides) via replacement of the O-alkyl group. Unlike structurally related compounds having simple alkyl or aryl groups on the nitrogen atom, N-arylsulfonylacetimidoates readily undergo hydrolysis in the presence of moisture and traces of acids.

Full text of DOI:10.1134/S1070428006120074

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 12, pp. 1792–1799. © Pleiades Publishing, Inc., 2006.
Original Russian Text © A.V. Selivanova, V.V. Nikolaev, R.R. Kostikov, V.A. Nikolaev, J. Siler, B. Schulze, 2006, published in Zhurnal Organicheskoi
Khimii, 2006, Vol. 42, No. 12, pp. 1804–1810.
Chemistry of Diazocarbonyl Compounds: XXVIII.* Reaction of
Acyclic N-Arylsulfonylacetamides with Rh(II)-Carbenoids
as a New Synthetic Route to Alkyl Acetimidoates
A. V. Selivanovaa, V. V. Nikolaeva, R. R. Kostikova, V. A. Nikolaeva,
J. Silerb, and B. Schulzeb
a St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
e-mail: vnikola@VN6646.spb.edu
b Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, Leipzig, 04103, Germany
e-mail: bschulze@organik.chemie.uni-leipzig.de
Received December 30, 2005
Abstract—A new procedure was proposed for the synthesis of alkyl acetimidoates via alkylation of the
carbonyl group in N-arylsulfonylacetamides with Rh(II)-carbenoids. The procedure ensures preparation in good
yield of acetimidoates having a polyfunctionalized O-alkyl group. The obtained alkyl acetimidoates in crystal
exist as E isomers with respect to the C=N bond and as s-cis conformers relative to the C−OCHRR' bond.
Alkyl N-arylsulfonylacetimidoates react with ammonia and hydrazine hydrate to give in good yield the
corresponding carboximidamides(hydrazides) via replacement of the O-alkyl group. Unlike structurally related
compounds having simple alkyl or aryl groups on the nitrogen atom, N-arylsulfonylacetimidoates readily
undergo hydrolysis in the presence of moisture and traces of acids.
DOI: 10.1134/S1070428006120074
We previously found [2] that catalytic decomposi-
tion of diazo compounds in the presence of saccharin
and its analogs involves exclusively O-alkylation of
the carbonyl group in the heteroring with intermediate
carbenoid species to give 3-oxoisothiazole 1,1-dioxide
enol ethers. We thus discovered a new method for
chemoselective functionalization of the carbonyl group
in the sulfonimide (SO2NHCO) fragment. The examin-
ed 3-oxoisothiazole 1,1-dioxides are cyclic analogs of
known acyclic N-substituted sulfonamide derivatives
which are used as antibacterial agents in medical
practice and as sweeteners [3, 4]. Furthermore, some
N-arylsulfonyl imidoates were reported to be pre-
cursors of drugs having primary sulfonamide and ester
moieties [5]. Reactions of diazo compounds and inter-
mediates derived therefrom with N-arylsulfonylcar-
boxamides were not studied previously [6]. Therefore,
extension of the carbene technique for the transforma-
tion of carboxamide group into carbimidoate to acyclic
N-arylsulfonylcarboxamides and development of a new
synthetic approach to alkyl imidoates on this base
seemed to be quite important and promising.
The present article reports on the results of our
study on the catalytic decomposition of diazocarbonyl
compounds in the presence of N-arylsulfonylacet-
amides, structure of the reaction products, and their
subsequent hydrolysis and reactions with nucleophiles
(ammonia and hydrazine). As substrates we used
N-(p-tolylsulfonyl)- and N-(p-chlorosulfonyl)acet-
amides Ia and Ib. As previously [2], ketocarbenoids
[7] were generated by catalytic decomposition of
dimethyl diazomalonate (IIa), ethyl diazoacetoacetate
(IIb), diazoacetylacetone (IIc), and ethyl diazoacetate
(IId) in the presence of dirhodium tetraacetate. The
reactions were carried out in methylene chloride at 18–
20°C; the rhodium catalyst was taken in an amount of
0.1 to 2 mol %. When the initial diazo compound
disappeared, the mixture was separated by chromatog-
raphy on neutral silica gel, and the products were
1
identified by H and 13C NMR spectroscopy, mass
spectrometry, and X-ray analysis.
Our experiments showed that Rh(II)-ketocarben-
oids generated from diazocarbonyl compounds IIa–IId
reacted with N-sulfonylacetamides Ia and Ib to give
alkyl acetimidoates IIIa–IIIh as the major products
* For communication XXVII, see [1].
1792

CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XXVIII.
1793
Scheme 1.
Me
SO2Ar
RR'CHO
N
O
N2
Rh2(OAc)4
–N2
IIIa–IIIh
+
SO2Ar
Me
N
H
R
R'
O
Ia, Ib
IIa–IId
SO2Ar
Me
N
CHRR'
A
I, Ar = p-MeC6H4 (a), p-ClC6H4 (b); II, R = R' = MeOCO (a), MeCO (c); R = EtOCO, R' = MeCO (b); R = H, R' = EtOCO (d);
III, R = R' = MeOCO, Ar = p-MeC6H4 (a), p-ClC6H4 (b); R = EtOCO, R' = MeCO, Ar = p-MeC6H4 (c), p-ClC6H4 (d); R = R' =
MeCO, Ar = p-MeC6H4 (e), p-ClC6H4 (f); R = H, R' = EtOCO, Ar = p-MeC6H4 (g), p-ClC6H4 (h).
(Scheme 1). No isomeric N-alkyl-N-sulfonylacet-
amides A were detected in the reaction mixtures by
1H NMR spectroscopy.
The reaction with methanol followed a different
pattern: heating of compounds III in methanol resulted
in formation of the corresponding arenesulfonamides
Va and Vb rather than imides I (Scheme 2). In addi-
tion, from the reaction mixtures we isolated 2-hy-
droxy-1,3-dicarbonyl compounds VIa–VIc; compound
VIa was identified by comparison with published data
[9], while VIb and VIc were converted into crystalline
derivatives, 1-phenyl-4-phenylhydrazono-3-methyl-
4,5-dihydro-1H-pyrazol-5-one [10] and 3-hydroxy-
pentane-2,4-dione bis(2,4-dinitrophenylhydrazone)
[11], respectively.
The structure of products IIIa–IIIh was determined
1
on the basis of their H and 13C NMR spectra, as well
as by comparison of their spectral parameters with
those reported in [2] for the corresponding O-alkyl sac-
1
charin derivatives [2]. In the H and 13C NMR spectra
of IIIa and IIIb, signals from the O–CH fragment
appeared at δ 5.4–5.5 and δC 74.6–74.7 ppm, respec-
tively (cf. δ 5.7–5.9 and δC 76–77 ppm for their ana-
logs derived from 3-oxoisothiazole 1,1-dioxides [2]).
The structure of compound IIIa was unambiguously
proved by X-ray analysis. The molecule of adduct IIIa
is shown in figure, and its principal geometric param-
eters (bond lengths and bond and torsion angles) are
listed in table. It is seen that compound IIIa (and
hence its analogs IIIb–IIIh) is characterized by E con-
figuration at the C=N double bond and, like O-alkyl
saccharin derivatives [2], s-cis conformation with
respect to the C−OCHRR' bond.
Insofar as imides I are fairly stable in methanol
solution and they do not undergo hydrolysis even on
prolonged heating, arenesulfonamides V are formed in
the methanolysis of compounds III from other pre-
cursors. It is known that the O-alkyl group in carb-
imidoates may be replaced by another alkyl group on
heating with excess amount of the corresponding
1
13
As follows from the H and C NMR and IR data,
alkyl acetimidoates IIIc–IIIf having an acetyl group
in the 1,3-dicarbonyl fragment exist in solution as
diketone tautomers, in contrast to the corresponding
N-alkyl amides and lactams which exist in solution
exclusively in the enol form [8].
Alkyl N-arylsulfonylacetimidoates III turned out to
be very labile compounds. They readily underwent
hydrolysis in the presence of traces of moisture and
acids; imidoates IIIc–IIIf having an acetyl group in
the OCHRR' fragment were the most sensitive to
hydrolysis. For example, complete hydrolysis of com-
pounds IIIc and IIIf with quantitative regeneration of
initial amides Ia and Ib occurred during separation of
the reaction mixture on silica gel (pH <6).
Structure of the molecule of dimethyl [N-(p-tolylsulfonyl)-
acetimidoyloxy]malonate (IIIa) according to the X-ray dif-
fraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

SELIVANOVA et al.
1794
Bond lengths (d, Å), bond angles (ω, deg), and torsion angles (φ, deg) in the molecule of dimethyl [N-(p-tolylsulfonyl)-
acetimidoyloxy]malonate (IIIa)
Bond
S1–O1
d, Å
Bond
C2–O3
d, Å
Bond
C6–O7
d, Å
Bond
d, Å
1.427(1)
1.435(1)
1.647(1)
1.753(1)
1.280(2)
1.346(2)
1.426(2)
1.316(2)
1.453(2)
1.190(2)
1.193(2)
1.313(2)
1.456(2)
1.488(2)
1.525(2)
1.527(2)
0.949(2)
1.384(2)
C8–C13
C9–C10
C10–C11
C11–C12
C11–C14
C12–C13
1.386(2)
1.382(2)
1.393(2)
1.389(2)
1.498(2)
1.382(2)
S1–O2
S1–N1
S1–C8
C1–N1
C1–O3
C3–O4
C4–O4
C3–O5
C5–O6
C5–O7
C1–C7
C2–C5
C2–C3
C2–H2
C8–C9
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O1S1O2
O1S1N1
O2S1N1
O1S1C8
O2S1C8
N1S1C8
C1N1S1
C1O3C2
Angle
118.1(7)
108.4(6)
110.6(6)
109.2(7)
108.0(6)
101.1(6)
0120.4(10)
0116.8(10)
φ, deg
C3O4C4
C5O7C6
N1C1O3
N1C1C7
O3C2C5
O3C2C3
C5C2C3
116.2(12)
115.8(13)
118.3(12)
130.5(13)
109.7(11)
105.9(10)
110.2(11)
O3C2H2
C5C2H2
C3C2H2
O5C3O4
O5C3C2
O6C5O7
O6C5C2
110.8(10)
113.6(9)0
106.2(9)0
126.6(12)
124.4(13)
126.1(13)
123.2(13)
C9C8C13
C9C8S1
C10C9C8
C9C10C11
C12C11C10
C10C11C14
C12C13C8
120.9(12)
120.3(10)
118.9(12)
121.6(13)
118.1(12)
121.1(13)
119.2(12)
Angle
φ, deg
Angle
φ, deg
Angle
φ, deg
O1S1N1C1
O2S1N1C1
C8S1N1C1
S1N1C1O3
S1N1C1C7
C2O3C1N1
C2O3C1C7
0–77.3(12)
0–53.7(12)
–167.9(10)
–177.1(9)0
00–2.0(2)
C1O3C2C5
C1O3C2C3
C4O4C3O5
C4O4C3C2
O3C2C3O5
C5C2C3O5
O3C2C3O4
0–67.9(14)
–173.2(10)
00–2.0(2)0
–179.2(12)
0–16.7(18)
–101.9(15)
–164.5(10)
C5C2C3O4
C6O7C5O6
C6O7C5C2
O3C2C5O6
C3C2C5O6
O3C2C5O7
O1S1C8C9
0–76.9(13)
00–1.8(2)0
–177.4(13)
–25.6(17)
O2S1C8C9
N1S1C8C9
O1S1C8C13
O2S1C8C13
N1S1C8C13
S1C8C9C10
–151.4(11)
–092.4(11)
–154.7(10)
0–25.0(12)
0–91.2(11)
–176.0(11)
–090.7(16)
–155.2(11)
0–21.8(13)
00–2.1(17)
–177.1(12)
alcohol [12, 13]. Presumably, the process involves
initial transesterification of III with formation of
methyl acetimidoates VII which are then converted
into arenesulfonamides V. In fact, methyl acetimidoate
VIIa (prepared by independent method [14]) reacted
with excess methanol to give p-toluenesulfonamide
(Va) in quantitative yield.
the same series [12, 13, 15]. The hydrolysis of III in
aqueous medium involves tetrahedral intermediate B;
at pH < 3–4, cleavage of the C−OAlk bond usually
occurs with formation of imides I and hydroxy car-
bonyl compounds VI, while the predominant process
in neutral medium (pH > 4–7) is cleavage of the N–C
bond in intermediate B, which leads to arenesulfon-
amides V and the corresponding esters IX (Scheme 3).
The behavior of compounds III having bulky
groups on the oxygen atom in the hydrolysis and
methanolysis is consistent with the known data for
analogous transformations of simpler compounds of
With a view to compare the reactivity of acyclic
imidoates III with that of known analogs we examined
their reactions with p-toluenesulfonyl isocyanate and
Scheme 2.
Me
H+, H2O, SiO2
MeOH, Δ
MeOH, Δ
Ia, Ib
III
ArSO2NH2
SO2Ar
–HOCHRR' (VIa–VIc)
–MeC(OMe)3
MeO
N
94–95%
VIIa, VIIb
Va, Vb (82–93%)
V, VII, p-MeC6H4 (a), p-ClC6H4 (b); VI, R = R' = MeOCO (a), MeCO (c); R = EtOCO, R' = MeCO (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XXVIII.
1795
Scheme 3.
OH
OH
O
H+
H2O
III
ArSO2NH
Me
ArSO2NH
Me
–H+
OCHRR'
pH > 4–7
H
CHRR'
B
pH < 3–4
ArSO2NH2
+
RC(O)OCHRR' ArSO2NHC(O)R
IX
+
HOCHRR'
V
I
VI
nitrogen-centered nucleophiles (ammonia and hydra-
zine), which were repeatedly used as effective reagents
in the chemistry of imidic acid esters [12, 16]. We
anticipated that compounds III should react with
p-toluenesulfonyl isocyanate (as the most active among
the above reagents) to give [2+2]- or [4+2]-cycloaddi-
tion products or other products typical of such reac-
tions [16]. However, compound IIIa failed to react
with p-toluenesulfonyl isocyanate, though analogous
reactions with known N-alkyl imidoates are exo-
thermic. Likewise, no expected product was formed
in the reaction of p-toluenesulfonyl isocyanate with
methyl N-(p-tolylsulfonyl)acetimidoate (VIIa) having
methyl group on the oxygen atom instead of the bulky
O-substituent in IIIa. Presumably, the electron density
on the nitrogen atom in molecules III and VII is con-
siderably reduced due to the presence of a strong elec-
tron-acceptor arylsulfonyl group; therefore, nucleo-
philicity of the nitrogen atom is insufficient to react
with such electrophiles as isocyanates under the given
conditions.
acetamides with Rh(II)-carbenoids; the procedure en-
sures acetimidoates having polyfunctionalized groups
on the oxygen atom to be obtained in good yields.
Products III in solution and in the crystalline state are
E isomers with respect to the C=N bond. Reactions of
compounds III with ammonia and hydrazine hydrate
give the corresponding products of replacement of the
O-alkyl group in good yields. Unlike imidic acid esters
having alkyl or aryl substituents on the nitrogen atom,
N-arylsulfonyl analogs III readily undergo hydrolysis
in the presence of atmospheric moisture and traces
of acids.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
Varian Gemini 200 (200 and 50.3 MHz, respectively),
Gemini 300 (300 and 75.45 MHz), Bruker Spectro-
spin-300 (300 and 75.46 MHz), and Bruker Spectro-
spin-600 (600 and 150.92 MHz) spectrometers using
TMS as internal reference. The mass spectra of com-
pounds IIIa–IIIh (electron impact, 70 eV) were ob-
tained on a VG 12-250 quadrupole mass spectrometer
(VG Instruments GmbH, Manchester Analytical) with
direct sample admission into the ion source. The IR
spectra were measured in KBr on an ATI Mattson
Genesis Series FTIR instrument.
Like simpler analogs [12], compound IIIa reacted
with ammonia and hydrazine hydrate with heat evolu-
tion, and the products were amidine Xa and amidra-
zone Xb, respectively (Scheme 4), which were formed
via replacement of the O-alkyl group. The structure of
compounds Xa and Xb was confirmed by spectral data
(see Experimental).
The X-ray diffraction data for compound IIIa were
obtained at 213(2) K on a Siemens SMART CCD
diffractometer (λ 0.71073 Å) from a 0.3×0.3×0.2-mm
colorless single crystal (from benzene). Monoclinic
Thus we have proposed a new procedure for the
synthesis of acyclic N-arylsulfonylacetimidoates III by
O-alkylation of the carbonyl group in N-arylsulfonyl-
Scheme 4.
Ts
Me
Ts
Me
Ts
Me
TsNCO
RNH2
Cycloaddition
products
N
N
N
N
–AlkOH
O
OAlk
OAlk
NHR
Ts
IIIa, VIIa
Xa, Xb
IIIa, Alk = (MeOCO)2CH; VIIa, Alk = Me; X, R = H (a, 53%), NH2 (b, 91%).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

SELIVANOVA et al.
1796
crystal system; unit cell parameters: a = 8.2096(15),
b = 21.381(4), c = 9.2491(17) Å; β = 90.644°; V =
1623.4(5) Å3; d = 1.405 g/cm3; space group P21/c.
Absorption coefficients were determined with the aid
of SADABS program, and the structure was solved
using SHELXS97 software [17].
General procedure for catalytic decomposition
of ethyl diazoacetoacetate (IIb) and diazoacetyl-
acetone (IIc) in the presence of N-arylsulfonylacet-
amides Ia and Ib. A solution of 2.4 mmol of diazo-
carbonyl compound IIb or IIc in 5 ml of anhydrous
methylene chloride was added to a solution of
2.3 mmol of imide Ia or a suspension of 2.3 mmol of
imide Ib in 10 ml of anhydrous methylene chloride,
10 mg (22 μmol) of Rh2(OAc)4 was added, and the
mixture was stirred for 18–20°C until the diazo com-
pound disappeared completely (20–40 min; TLC). In
the reactions of IIb and IIc with Ia, the mixture was
evaporated to a volume of 2–3 ml and filtered through
a thin layer of silica gel (5 g), and compounds IIIc and
IIIe isolated by removal of the solvent from the main
Initial imides Ia and Ib were prepared by known
procedures [18, 19] and were purified by recrystalliza-
tion from methylene chloride–petroleum ether (2:1);
N-p-tolylsulfonylacetamide (Ia), mp 135–136°C [18];
N-p-chlorophenylsulfonylacetamide (Ib), mp 197–
198°C [19]. Diazodicarbonyl compounds IIa–IIc were
synthesized and purified according to the procedures
described in [2]; ethyl diazoacetate (IId) from Fluka
was distilled just before use, bp 60°C (1 mm).
1
fraction were analyzed by H NMR spectroscopy and
mass spectrometry.
The progress of reactions was monitored by TLC
on Silufol UV-254 plates. Neutral silica gel (Chemapol
L, 40–100 μm, or Merck, 70–230 mesh) was used for
column chromatography.
In the reactions of IIb and IIc with Ib, the mixture
was evaporated to a volume of 3–4 ml, the unreacted
N-p-chlorophenylsulfonylacetamide (Ib) was filtered
off, the filtrate was passed through a layer of silica gel
(5 g), and compounds IIId and IIIf isolated by
removal of the solvent from the main fraction were
analyzed as described above.
General procedure for catalytic decomposition
of dimethyl diazomalonate (IIa) in the presence of
N-arylsulfonylacetamides Ia and Ib. Dirhodium
tetraacetate, 5 mg (11 μmol), was added in one portion
to a solution of 2.1 mmol of imide Ia or Ib and
2.1 mmol of dimethyl diazomalonate (IIa) in 17 ml of
methylene chloride, and the mixture was stirred until
the diazo compound disappeared completely (TLC).
The mixture was then subjected to chromatography on
silica gel, the main fraction was evaporated, and the
residue was additionally recrystallized from benzene
(IIIa) or CH2Cl2–petroleum ether (10:4; IIIb).
Ethyl 3-oxo-2-[N-(p-tolylsulfonyl)acetimidoyl-
oxy]butanoate (IIIc). Yield 0.6 g (78%), oily sub-
1
stance. H NMR spectrum (CDCl3), δ, ppm: 1.13 t
(3H, CH2CH3, J = 7.0 Hz), 2.19 s (3H, CH3), 2.37 s
(3H, CH3), 2.56 s (3H, CH3), 4.08 q (2H, CH2CH3,
J = 7.0 Hz), 5.41 s (1H, OCH), 7.25 d (2H, Harom, J =
8.1 Hz), 7.68 d (2H, Harom, J = 8.1 Hz). Mass spectrum,
m/z (Irel, %): 341 (1.2) [M]+, 326 (1.4), 300 (3.3), 274
(1.9), 258 (12.8), 254 (4.8), 211 (4.8), 198 (4.7), 196
(4.7), 184 (3.2), 171 (7.7), 155 (84.0), 108 (53.8), 91
(100.0), 65 (35.9), 49 (28.2).
Dimethyl [N-(p-tolylsulfonyl)acetimidoyloxy]-
malonate (IIIa). Yield 0.64 g (90%), colorless crystals,
mp 122–123°C (from CH2Cl2–petroleum ether).
13C NMR spectrum (CDCl3), δC, ppm: 20.0 (C6H4CH3);
21.9 (CH3C=N); 53.7 (OCH3); 74.6 (OCH); 127.2,
129.8, 138.3, 144.2 (Carom); 164.3 (C=N); 168.3 (C=O).
Found, %: C 48.97, 49.05; H 4.95, 5.09; N 4.17, 3.99;
S 9.39, 9.29. C14H17NO7S. Calculated, %: C 48.98;
H 4.99; N 4.07; S 9.34.
Ethyl 2-[N-(p-chlorophenylsulfonyl)acetimidoyl-
oxy]-3-oxobutanoate (IIId). Yield 0.56 g (68%),
1
oily substance. H NMR spectrum (CDCl3), δ, ppm:
1.17 t (3H, CH2CH3, J = 7.4 Hz), 2.21 s (3H, CH3),
2.61 s (3H, CH3), 4.11 q (2H, CH2CH3, J = 7.4 Hz),
5.38 s (1H, OCH), 7.46 d (2H, Harom, J = 9.0 Hz),
7.76 d (2H, Harom, J = 9.0 Hz). Mass spectrum, m/z
(Irel, %): 361 (3.5) [M]+, 345 (7.1), 319 (16.4), 296
(7.8), 278 (40.3), 274 (20.2), 211 (77.0), 183 (61.1),
175 (19.7), 171 (22.2), 156 (19.4), 129 (36.1),
111 (25.0), 103 (16.6), 83 (99.3), 67 (66.6), 55 (42.7),
43 (100.0).
Dimethyl [N-(p-chlorophenylsulfonyl)acetimid-
oyloxy]malonate (IIIb). Yield 0.66 g (87%), colorless
crystals, mp 103–104°C (from CH2Cl2–petroleum
ether). 13C NMR spectrum (CDCl3), δC, ppm: 20.2
(CH3C=N); 53.7 (OCH3); 74.7 (OCH); 128.6, 129.5,
139.7, 139.8 (Carom); 164.1 (C=N); 172.3 (C=O).
Found, %: C 43.11, 43.06; H 3.93, 3.94; N 3.85, 3.71;
S 8.91, 8.79. C13H14ClNO7S. Calculated, %: C 42.93;
H 3.87; N 3.84; S 8.81.
1-Acetyl-2-oxopropyl N-(p-tolylsulfonyl)acet-
imidoate (IIIe). Yield 0.55 g (77%), oily substance.
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CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XXVIII.
1797
1H NMR spectrum (CDCl3), δ, ppm: 2.14 s (6H,
COCH3), 2.38 s (3H, CH3), 2.59 s (3H, CH3), 5.40 s
(1H, OCH), 7.28 d (2H, Harom, J = 8.0 Hz), 7.67 d (2H,
Decomposition of diazo compounds IIb and IIc
in the presence of imides Ia and Ib, followed by
methanolysis of imidic acid esters IIIc–IIIf. Di-
rhodium tetraacetate, 15 mg (34 μmol), was added to
a solution of 7.5 mmol of N-arylsulfonylacetamide Ia
or Ib and 7.9 mmol of diazo compound IIb or IIc in
17 ml of methylene chloride, and the mixture was
stirred for 1 h at 15–20°C. When the initial diazo
compound disappeared (TLC), the catalyst was filtered
off through a layer of silica gel (5 g), the solvent was
removed from the filtrate, the residue (a yellow oily
substance) was dissolved in 5 ml of methanol, and the
solution was heated for 5 h under reflux. The solvent
and volatile components were distilled off at 70°C
under reduced pressure (1–2 mm) into a cooled trap,
and the residue was recrystallized from methylene
chloride–diethyl ether (5:1).
H
arom, J = 8.0 Hz). Mass spectrum, m/z (Irel, %): 311
(1.0) [M]+, 279 (1.2), 285 (1.2), 270 (16.0), 253 (2.8),
243 (7.2), 227 (15.2), 214 (15.3), 197 (6.24), 187 (8.3),
173 (12.6), 155 (20.0), 114 (19.5), 108 (13.0), 99 (4.3),
91 (69.5), 72 (32.0), 65 (26.5), 43 (100.0).
1-Acetyl-2-oxopropyl N-(p-chlorophenylsul-
fonyl)acetimidoate (IIIf). Yield 0.35 g (47%), oily
1
substance. H NMR spectrum (CDCl3), δ, ppm: 2.16 s
(3H, CH3), 2.64 s (3H, CH3), 5.40 s (1H, OCH), 7.48 d
(2H, Harom, J = 9.0 Hz), 7.75 d (2H, Harom, J = 9.0 Hz).
Mass spectrum, m/z (Irel, %): 331 (4.1) [M]+, 290 (1.3),
272 (1.1), 253 (3.2), 248 (8.5), 214 (3.2), 175 (47.2),
159 (8.1), 153 (8.5), 141 (7.5), 128 (8.3), 111 (41.6),
75 (13.8), 43 (100.0).
By methanolysis of compounds IIIc–IIIf and sub-
sequent recrystallization of the residue we isolated the
following substances (given are the initial imidic acid
number, resulting sulfonamide, yield, melting point,
and reference): IIIc, p-toluenesulfonamide (Va), 1.05 g
(82%), 135–137°C [20]; IIId, p-chlorobenzenesulfon-
amide (Vb), 0.83 g (58%), 144–145°C [21]; IIIe, Va,
0.92 g (77%), 135–136°C [20]; IIIf, Vb, 0.58 g (93%),
144–145°C [21].
Ethyl [N-(p-tolylsulfonyl)acetimidoyloxy]acetate
(IIIg). A solution of 1.7 g (15 mmol) of ethyl diazo-
acetate (IId) in 30 ml of methylene chloride was added
dropwise over a period of 5 h to a solution of 2.55 g
(12 mmol) of imide Ia and 30 mg (68 μmol) of
dirhodium tetraacetate in 15 ml of methylene chloride.
When the reaction was complete (TLC), the catalyst
was filtered off through a layer of silica gel (7 g). An
analytical sample was isolated by repeated chromatog-
raphy on silica gel (20 g per gram of the reaction
mixture) using petroleum ether–methylene chloride as
eluent. Yield 1.5 g (41%), colorless liquid. 13C NMR
spectrum (CDCl3), δC, ppm: 13.8 (CH3CH2O); 19.6
(CH3C=N); 21.4 (CH3C6H4); 61.3 (CH3CH2O); 63.8
(OCH); 126.6, 129.3, 138.3, 143.4 (Carom); 166.5
(C=N); 172.6 (C=O). Found, %: C 52.21, 52.16; H 5.79,
5.75; N 4.65, 4.61; S 10.81, 10.74. C13H17NO5S. Cal-
culated, %: C 52.17; H 5.72; N 4.67; S 10.71.
The condensate collected in the trap in the metha-
nolysis of compounds IIIc and IIId was dissolved in
15 ml of methanol, 3.9 mmol of selenium(IV) oxide
was added, the mixture was left to stand for 10 h at
room temperature and cooled to 0°C, 15 mmol of
phenylhydrazine in 5 ml of methanol was added, and
the mixture was left to stand for 3 h at 18–20°C. The
solvent was distilled off under reduced pressure (10–
15 mm) to a volume of ~5 ml, and the red–brown
precipitate of 3-methyl-1-phenyl-4-(phenylhydrazono)-
4,5-dihydro-1H-pyrazol-5-one was filtered off. Yield
1.3 g (63%, from IIIc), 1.2 g (58%, from IIId);
mp 155–156°C (from ethanol) [11]. 1H NMR spectrum
(CDCl3), δ, ppm: 2.30 s (3H, CH3), 7.18–7.97 m (10H,
C6H5), 13.58 s (1H, OH).
Ethyl [N-(p-chlorophenylsulfonyl)acetimidoyl-
oxy]acetate (IIIh). A solution of 0.48 g (4.2 mmol) of
ethyl diazoacetate (IId) in 20 ml of methylene chloride
was added dropwise under stirring over a period of 1 h
to a suspension of 0.5 g (2.1 mmol) of imide Ib and
10 mg (22 μmol) of Rh2(OAc)4 in 15 ml of methylene
chloride. When the reaction was complete, the mixture
was treated as described above for compound IIIg.
Yield 0.19 g (28%), colorless liquid. 13C NMR spec-
trum (CDCl3), δC, ppm: 12.9 (CH3CH2O); 19.0
(CH3C=N); 60.5 (CH3CH2O); 63.1 (OCH); 127.2,
128.0, 138.1, 138.7 (Carom); 165.4 (C=N); 172.2
(C=O). Found, %: C 45.19, 44.96; H 4.47, 4.42; N 4.31,
4.29; S 10.07, 10.14. C12H14ClNO5S. Calculated, %:
C 45.08; H 4.41; N 4.37; S 10.02.
The condensate collected in the trap in the metha-
nolysis of compounds IIIe and IIIf was dissolved in
15 ml of methanol, a solution of 15 mmol of 2,4-di-
nitrophenylhydrazine in 15 ml of methanol was added,
the mixture was heated for 4 h under reflux and
cooled, and the precipitate of 3-hydroxypentane-2,4-
dione bis(2,4-dinitrophenylhydrazone) was filtered
through a Schott filter and recrystallized from acetone
or ethanol. Yield, 1.6 g (45%, from IIIe), 1.39 g
(39%, from IIIf); mp 219°C (from acetone), 217°C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

SELIVANOVA et al.
1798
(from ethanol) [10]. 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.15 s (6H, CH3), 4.9 d (1H, OCH, J = 9.0 Hz),
6.3 d (1H, OH, J = 9.0 Hz), 7.94–8.91 m (6H, Harom),
10.9 s (2H, NH).
(acetone-d6), δ, ppm: 2.28 s (3H, Me), 2.40 s (3H, Me),
7.36 d (2H, J = 8.0 Hz), 7.78 d (2H, J = 8.0 Hz),
10.7 br.s. Mass spectrum, m/z (Irel, %): 227 (10) [M]+,
196 (4), 186 (6), 171 (4), 155 (33), 122 (7), 107 (4),
91 (100), 72 (17), 65 (26).
Methyl N-(p-tolylsulfonyl)acetimidoate (VIIa).
A mixture of 1.36 g (8 mmol) of imide Ia and 2.3 g
(19 mmol) of trimethyl orthoacetate was heated for 2 h
at 100°C. It was then cooled, the solvent and excess
trimethyl orthoacetate were distilled off under reduced
pressure (1–2 mm) at 18–20°C, and the residue was
recrystallized from hexane. Yield 1.6 g (88%), mp 74–
75°C (from hexane) [5].
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A solution of 1 g (4.4 mmol) of ester VIIa in 10 ml
of methanol was heated for 2 h under reflux, the
mixture was cooled to room temperature, volatile com-
ponents were distilled off under reduced pressure (1–
2 mm) at 18–20°C, and the residue was recrystallized
from methylene chloride–petroleum ether (4:1). Yield
of sulfonamide Va 0.7 g (93%), mp 135–136°C [20].
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N-(p-Tolylsulfonyl)acetimidamide (Xa). Com-
pound IIIa, 0.206 g (0.6 mmol), was dissolved in 3 ml
of acetone, 0.15 ml of 25% aqueous ammonia was
added, and the mixture was vigorously shaken (the
mixture slightly warmed up). After 15 min, the solvent
and excess ammonia were removed under reduced
pressure, and the solid residue was washed with
diethyl ether and recrystallized from ethanol. Yield
0.05 g (39%), colorless crystals, mp 144–145°C.
1H NMR spectrum (acetone-d6), δ, ppm: 2.10 s (3H,
Me), 2.41 s (3H, Me), 7.30 d (2H, J = 8.0 Hz), 7.77 d
(2H, J = 8.0 Hz), 7.88 br.s (2H, NH2). Mass spectrum,
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The ether washings were evaporated under reduced
pressure (15–20 mm) at room temperature to obtain
a colorless crystalline substance which was identified
as dimethyl 2-hydroxymalonate (VIa). Yield 0.70 g
10. Bome, H. and Schneider, H., Chem. Ber., 1958, vol. 91,
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1
11. Hesse, G. and Stahl, H., Chem. Ber., 1956, vol. 89,
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(79%), mp 50–52°C [9]. H NMR spectrum (CDCl3),
δ, ppm: 3.84 s (6H, OMe), 4.76 s (1H, CH), 5.31 s
(1H, OH).
N-(p-Tolylsulfonyl)acetimidohydrazide (Xb).
A solution of 0.132 g (2.64 mmol) of hydrazine
hydrate in 4 ml of diethyl ether was added under con-
tinuous stirring to a suspension of 0.412 g (1.2 mmol)
of compound IIIa in 6 ml of diethyl ether, and the
mixture was stirred at 18–20°C until ester IIIa disap-
peared (~1 h, TLC). The precipitate was filtered off,
washed with diethyl ether, and dried under reduced
pressure (1–2 mm) at 20–25°C. Yield 0.25 g (91%),
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15. Lee, Y.-N. and Schmir, G.L., J. Am. Chem. Soc., 1979,
1
yellow crystals, mp 164–165°C. H NMR spectrum
vol. 101, p. 6277.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

CHEMISTRY OF DIAZOCARBONYL COMPOUNDS: XXVIII.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006