Reactions of distabilized β-dicarbonyl sulfonium and iodonium ylides with isocyanates

Article abstract of DOI:10.1007/s11172-006-0347-3

The reactions of tosyl isocyanate with diethyl diphenylsulfuranylidenemalonate, 2-dimethylsulfuranylidenedimedone, and 2-dimethylsulfuranylideneindane-1,3-dione afforded 1,3-ditosyl-5,5- diethoxycarbonylimidazolidine-2,4-dione and tosylimination products at the keto groups, respectively. Phenyliodonium ylides derived from diethyl malonate and ethyl acetate react with 3,4-dichlorophenyl isocyanate to form substituted oxazolin-2-ones. Springer Science+Business Media, Inc. 2006.

Full text of DOI:10.1007/s11172-006-0347-3

Russian Chemical Bulletin, International Edition, Vol. 55, No. 5, pp. 883—891, May, 2006
883
Reactions of distabilized βꢀdicarbonyl sulfonium and iodonium
ylides with isocyanates
Yu. G. Gololobov,ꢀ I. R. Golding, M. A. Galkina, B. V. Lokshin, I. A. Garbuzova, P. V. Petrovskii,
Z. A. Starikova, and B. B. Averkiev
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5085. Eꢀmail: Yugol@ineos.ac.ru
The reactions of tosyl isocyanate with diethyl diphenylsulfuranylidenemalonate, 2ꢀdiꢀ
methylsulfuranylidenedimedone, and 2ꢀdimethylsulfuranylideneindaneꢀ1,3ꢀdione afforded
1,3ꢀditosylꢀ5,5ꢀdiethoxycarbonylimidazolidineꢀ2,4ꢀdione and tosylimination products at the
keto groups, respectively. Phenyliodonium ylides derived from diethyl malonate and ethyl
acetate react with 3,4ꢀdichlorophenyl isocyanate to form substituted oxazolinꢀ2ꢀones.
Key words: distabilized βꢀdicarbonyl sulfonium and iodonium ylides, aryl isocyanates, tosyl
isocyanate, tosylimination, 1,3ꢀditosylꢀ5,5ꢀdicarbethoxyimidazolidineꢀ2,4ꢀdione, oxazolinꢀ2ꢀ
one, Xꢀray diffraction study.
Distabilized cycloimmonium, sulfonium, and iodoꢀ
nium ylides derived from βꢀdicarbonyl compounds have
attracted considerable attention as functional nucleophilic
reagents.1—3 The electronic structures of these compounds
give promise that interesting results will be obtained in
comparative studies of the reactions of distabilized ylides
with isocyanates.
atom. Apparently, this type of compounds have the weakꢀ
est C—I bond. Therefore, in summary of the aboveꢀmenꢀ
tioned factors, pyridinium and phenyliodonium ylides
would be expected to exhibit the highest reactivity toward
isocyanates. However, the schemes of their interactions
can be substantially differrent due to the aboveꢀmentioned
structural features.
As part of our research on the reactions of carbanions
with isocyanates,4 we qualitatively correlated the reactiviꢀ
ties of distabilized βꢀdicarbonyl cycloimmonium, iodoꢀ
nium, and sulfonium ylides with the Mulliken charges on
the ylide carbon atoms calculated by the quantum chemiꢀ
cal DFT B3LYP/LanL2DZ method.
Actually, pyridinium ylide 1 reacts with aryl isocyanꢀ
ates at room temperature in a solution in CH2Cl2 providꢀ
ing the C→N migration of the ethoxycarbonyl group in
the second step of the reaction. This rearrangement afꢀ
fords new pyridinium ylide 3 containing the carbamate
function5 (Scheme 1).
The reaction according to Scheme 1 is a special case
of the reactions of carbanions derived from esters with
alkyl and aryl isocyanates giving rise to new types of
carbamates through the insertion of the isocyanate molꢀ
ecule at the C—CO2Alk bond of the starting carbanion.6
Taking into account the aboveꢀmentioned reactivity of
nitrogen ylides toward aryl isocyanates and with the aim
of comparing the reactivities of different distabilized ylides,
we performed the reactions of isocyanates with iodonium
and sulfonium derivatives, for which only scarce examples
were documented.7,8
The reactivity of iodonium ylides 4 toward aryl isoꢀ
cyanates was demonstrated to be comparable to that of
pyridinium ylide 1. The reactions of iodonium ylides with
3,4ꢀdichlorophenyl isocyanate proceed at 0 °C but afford
oxazolinꢀ2ꢀones 7 rather than lead to the insertion of the
isocyanate molecule at the C—C bond (cf. lit. data;7
Scheme 2). In addition, it should be emphasized that
"dimers" 8a and 8b were found among the products of
As can be seen from the above data, the highest negaꢀ
tive charge is concentrated on the carbon atom of
pyridinium ylide, the ylide carbon atom of the iodine
derivative bears a somewhat lower negative charge, and
the anionic charges are delocalized to the greatest extent
in sulfur ylides. The nucleophilic reactivity of the ylides
under consideration can correlate with the negative
charges on the ylide carbon atoms. However, the scheme
of interactions can also be influenced by the strength of
the bond between the ylide carbon atom and the heteroꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 854—861, May, 2006.
1066ꢀ5285/06/5505ꢀ0883 © 2006 Springer Science+Business Media, Inc.

884
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
Gololobov et al.
Scheme 1
these reactions (see Scheme 2). The structure of tetraꢀ
ethyl ethylenetetracarboxylate 8b was established by Xꢀray
diffraction.
C(8)
C(7)
C(14)
C(9)
C(10)
Cl(2)
C(13)
O(1)
C(1)
O(2)
C(12)
C(11)
O(3)
O(5)
Scheme 2
C(2)
N(1)
C(3)
C(4)
Cl(1)
C(5)
O(4)
C(6)
Fig. 1. Molecular structure of compound 7b in the crystal.
dent structurally identical molecules in the crystal strucꢀ
ture of 7b (Fig. 1). In the crystals, molecules 7b are
nonplanar. The dichlorophenyl ring is twisted by 60° about
the N(1)—C(9) bond. The oxazolinone ring, the CO2Et
group, and the O(3) and N(1) atoms are coplanar. The
Et substituent of the ethoxy group is in an orthogonal
orientation.
The structure of tetraethyl ethylenetetracarboxylate 8b
was established by Xꢀray diffraction. The crystal strucꢀ
ture consists of the centrosymmetric isolated molecules
(Fig. 2). The overall molecular conformation is characꢀ
terized by the coplanar arrangement of two carboxylate
substituents and the ethylenic bond, whereas two other
carboxylate substituents are orthogonal to this bond
(Table 1).
Taking into account that the basicity (and, apparꢀ
ently, the nucleophilicity) of distabilized sulfonium ylides
is much lower than that of nitrogen and iodonium anaꢀ
logs,10 the reactivity of distabilized sulfonium ylides toꢀ
ward isocyanates would be expected to be lower. Actually,
ylide 9 reacts with aryl isocyanates only at about 100 °C to
R = Me (a), OEt (b)
Ar = 2,4ꢀCl2C6H3
Since the bond between the iodine and carbon atoms
in the assumed betaine 5 is weak and the formation of the
aromatic system of iodobenzene is energetically favorable
(cf. lit. data9), the C—I bond cleavage in the second
step of the reaction leads, apparently, to αꢀelimination
of iodobenzene and isocyanate and the formation of
carbene 6, which can undergo both dimerization and
transformation into heterocycle 7 occurring as 2+3 cyꢀ
clization.
The structure of oxazolinꢀ2ꢀone 7b was established by
elemental analysis, IR and NMR spectroscopy, and
Xꢀray diffraction. It should be noted that the Raman specꢀ
tra of compounds 7a,b and 8a show intense bands in the
1650—1670 cm–1 region (C=C). There are four indepenꢀ
O(4)
C(6)
C(7)
O(3A)
O(1A)
C(2A)
C(1)
C(5)
C(4)
C(1A)
C(5A)
O(2A)
C(2)
O(1)
O(2)
C(3)
O(3)
O(4A)
Fig. 2. Orientation of the CO2Et groups relative to the ethylenic
bond in molecule 8b.

Reactions of iodine and sulfur ylides with isocyanates Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
885
Scheme 3
form a complex mixture of nonidentified products. By
contrast, the reaction with substantially more electrophilic
tosyl isocyanate (TsNCO) smoothly proceeds in CH2Cl2
at 20 °C to give hydantoin 12 (Scheme 3).
structural asymmetry of the molecule. Actually, Xꢀray
diffraction study showed (Fig. 3) that the hydrogen
atoms of both CH2 groups are in a different intramolecuꢀ
lar environment because the ethoxy groups have a difꢀ
ferent orientation relative to the heterocycle. The
C(11)(=O(12))O(13)C(14)C(15) fragment is planar. The
dihedral angle between this fragment and the plane of the
heterocycle is 90.3°. The C(6)(=O(7))O(8)C(9)C(10)
group is nonplanar (the C(6)O(8)C(9)C(10) torsion angle
is 83.3°). The dihedral angle between the average plane of
this group and the heterocycle is 28.3°. A consequence of
the planar structure of the former ethoxy group is that
both hydrogen atoms of the methylene group form inꢀ
tramolecular contacts with the carbonyl oxygen atom
(O(12)...H(14a), 2.74 Å; O(12)...H(14b), 2.58 Å), whereas
only one hydrogen atom of the nonplanar ethoxy group is
involved in an analogous contact (O(7)...H(9a), 2.45 Å;
O(7)...H(9b), 3.60 Å).
A comparison of the reactivities of distabilized sulfoꢀ
nium ylide (derivative of diethyl malonate) and distabilized
sulfonium ylides containing the keto group at the ylide
carbon atom is of considerable interest. Earlier,12 we have
described a new reaction of keto ylides 13 with tosyl isoꢀ
cyanate, which occurs at the keto group, the latter being
transformed into the tosylimino group (Scheme 4).
Presumably, due to the high electronꢀwithdrawing
ability of the tosyl group, anion 10 generated in the first
step is weakly nucleophilic. As a result, it cannot effiꢀ
ciently attack the carbonyl C atom of the ethoxycarbonyl
group, which could lead to the rearrangement presented
in Scheme 1. At the same time, the nucleophilicity of
Nꢀanion 10 is sufficiently high for this anion to react with
the second tosyl isocyanate molecule to form anion 11.
The latter undergoes cyclization giving rise to hydantoin
12 according to a known scheme.8 The structure of comꢀ
pound 12 was established by elemental analysis, IR and
NMR spectroscopy, and Xꢀray diffraction. According
to the Xꢀray diffraction data (Fig. 3), the central heteroꢀ
cycle is planar (within 0.03 Å) with the C(1) atom deꢀ
viating from the plane through the other four atoms by
only 0.132 Å. The sulfur and oxygen atoms also lie in
this plane. Pairs of the benzene ring and the CO2Et group
are located on the opposite sides of the heterocycle.
The bond lengths and bond angles (Table 2) in the heteroꢀ
1
cycle are typical of hydantoin rings.11 The H NMR
spectroscopic study demonstrated that the methylene
protons of the ethoxy groups in hydantoin 12 are magꢀ
netically nonequivalent, which is evidence for the
Table 2. Bond lengths (d) and bond angles (ω) in molecule 12
Table 1. Selected bond lengths (d), bond angles, and torsion
angles (ω) in molecules 8b
Bond
d/Å
Bond
d/Å
S(1)—N(3)
S(2)—N(5)
S(1)—C(16)
S(2)—C(23)
C(1)—C(2)
C(4)—O(2)
1.717(2)
1.693(3)
1.735(3)
1.737(4)
1.538(4)
1.198(3)
N(5)—C(1)
N(5)—C(4)
C(4)—N(3)
N(3)—C(2)
C(2)—O(1)
1.470(4)
1.385(4)
1.412(4)
1.400(4)
1.191(3)
Bond
d/Å
Angle
ω/deg
C(1)—C(1A) 1.334(4)
C(1)—C(2) 1.513(2)
C(1)—C(5) 1.511(2)
C(2)—O(1) 1.203(2)
C(2)—O(2) 1.320(2)
C(5)—O(3) 1.199(2)
C(5)—O(4) 1.327(2)
O(2)—C(3) 1.471(2)
O(4)—C(6) 1.464(2)
C(3)—C(4) 1.489(3)
C(6)—C(7) 1.506(3)
C(2)—C(1)—C(5)
C(2)—C(1)—C(1A)
C(5)—C(1)—C(1A)
O(1)—C(2)—C(1)—C(1A) 1.6(4)
O(3)—C(5)—C(1)—C(1A) 89.9(3)
115.3(2)
120.3(2)
124.3(2)
Angle
ω/deg
Angle
ω/deg
C(1)—N(5)—C(4) 112.3(2)
C(1)—N(5)—S(2) 124.8(2)
C(4)—N(5)—S(2) 121.9(2)
C(4)—N(3)—S(1) 121.5(2)
N(5)—C(4)—N(3) 107.0(3)
C(4)—N(3)—C(2) 111.2(3)
N(3)—C(2)—C(1) 106.6(3)
N(5)—C(1)—C(2) 101.6(2)
C(2)—N(3)—S(1) 126.8(2)

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Gololobov et al.
C(10)
O(12)
C(9)
O(8)
C(6)
C(14)
C(11)
O(13)
C(15)
O(7)
O(5)
O(1)
C(2)
C(1)
N(5)
O(3)
S(1)
S(2)
N(3)
C(28)
C(21)
C(20)
C(19)
C(4)
C(27)
C(26)
C(23)
C(24)
O(6)
C(16)
C(17)
O(2)
C(22)
O(4)
C(29)
C(25)
C(18)
Fig. 3. Molecular structure of compound 12.
Scheme 4
tive charge resulting in a high negative charge on the
oxygen atom of the keto group. As a result of this charge
distribution, the attack occurs on the O atom. The Xꢀray
diffraction data are consistent with this assumption. We
demonstrated that the structure of keto ylide hemihydrate
13a (see Ref. 13) consists of centrosymmetric Hꢀbonded
dimers formed by two ester molecules, which are linked
together by strong C=O...H—O hydrogen bonds between
the carbonyl groups and the water molecule (Fig. 4).
The hydrogen bond parameters are as follows:
O(3)...O(3A), 2.730(2) Å; O(3)...H(1w), 1.88(2) Å;
R = C(O)Me (a), C(O)OEt (b)
Presumably, such an unusual behavior of keto ylides
13 is partly due to considerable delocalization of the negaꢀ
C(5)
S(1)
C(8)
C(6)
O(3)
O(1)
C(2)
C(7)
H(1W)
O(1W)
H(1WA)
O(3A)
C(1)
C(3)
C(4)
O(2)
S(1A)
Fig. 4. Centrosymmetric Hꢀbonded dimer in the crystal structure of 13a•0.5H2O.

Reactions of iodine and sulfur ylides with isocyanates Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
887
O(3)—H(1W)—O(1W), 169.4(8)°. The geometric paramꢀ
eters of ylide 13a are indicative of high polarization of the
keto group due, evidently, to an efficient delocalization
of the negative charge. The S(1)—C(2) bond length
(1.737(1) Å) is substantially smaller than the typical
S—Csp3 bond length, the C(3)—O(3) bond (1.257(2) Å) is
substantially longer than the typical C=O bond in ketones
and carboxylic acids (1.21 Å),14 and the C(2)—C(3) bond
is stronger that the single C—C bond in ketones.
This distribution of the bond lengths provides evidence
for a substantial contribution of the betaine form
Me2S+—C(COOEt)=C(Me)—O– along with the ylide
form Me2S+—C–(COOEt)C(Me)=O. Apparently, the
betaine form is responsible for the formation of the strong
hydrogen bond between the O(3) atom and the water
molecule in the crystal structure.
The second step of the reaction (Scheme 4) is accomꢀ
panied by the formation of energetically favorable carbon
dioxide, which is the driving force of the process.
With the aim of extending tosylimination of keto ylides
to other sulfonium keto ylides, we performed the reaction
of TsNCO with cyclic diketo ylides 15 and 18. In both
processes, the first step of imination readily occurs to give
monoylides 17 and 19, respectively, in yields of about 70%.
The replacement of the second keto group in keto ylide 16
occurs at high temperature.
the total complex influence of the electronic and steric
factors in the step of the replacement of the second keto
group. The structures of the imination products were conꢀ
firmed by elemental analysis, NMR spectroscopy, and
IR spectroscopy. The threeꢀdimensional structure of
diimine 17 in the crystal structure of the solvate 17•CHCl3
was established by Xꢀray diffraction. The latter conꢀ
tains two crystallographically independent molecules,
each being involved in an S=O...H(CHCl3) hydrogen
bond (O...H, 2.25 Å; CHO, 160°). The independent
molecules are structurally identical (Fig. 5). The central
ring adopts a sofa conformation with the C(3) atom deviꢀ
ating from the mean plane through the other atoms of the
ring by 0.6 Å. The phenyl rings are orthogonal to the
central ring and are located on the opposite sides of this
ring. The geometric parameters of the molecules (Table 3)
are indicative of the ylide structure. The C=N bond lengths
in molecule 17 have typical values.14 The C(6)—C bond
lengths (aver., 1.41 Å) are similar to the bond lengths in
the benzene rings (1.39 Å). The C(6)—S(3) bond lengths
(aver., 1.75 Å) are similar to the corresponding bond
lengths in molecule 13a (1.737(1) Å) and the dication of
bis(2ꢀdimethylsulfoniocyclohexyl) sulfide.15
To summarize, the variety of the aboveꢀdescribed
transformations of isocyanates with nitrogenꢀ, iodineꢀ,
and sulfurꢀsubstituted distabilized ylides is attributed
both to the difference in the nucleophilicity and polarizꢀ
ability of these compounds and the structural features
of the bonds between the heteroatoms and the ylide carꢀ
bon atom.
By contrast, the reaction of cyclic diketo ylide 18 even
with a large excess of TsNCO affords only monoylide.
Apparently, such a large difference in the reactivity of
keto ylides 15 and 18 in tosylimination is associated with
Scheme 5

888
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
Gololobov et al.
C(7)
O(1)
S(1)
C(24)
S(3)
C(6)
C(21)
N(1)
C(8)
C(20)
C(22)
O(2)
C(11)
C(19)
N(2)
C(1)
C(23)
C(16)
C(15)
C(18)
C(5)
C(4)
C(3)
C(2)
C(12)
S(2)
C(10)
C(13)
C(14)
O(3)
O(4)
C(17)
C(9)
Fig. 5. Molecular structure of compound 17.
Table 3. Selected bond lengths (d) and bond angles (ω) in
two independent molecules (17A and 17B) in the crystal
structure of 17•CHCl3
3 H, CH3CH2, J = 7.2 Hz); 2.55 (s, 3 H, CH3C(O)); 4.10 (q,
2 H, CH3CH2, J = 7.2 Hz); 7.32—7.75 (m, 5 H, Harom).
Phenyliodoniodiethoxycarbonylmethanide (4b) was syntheꢀ
sized according to a known procedure.17 1H NMR, δ: 1.31 (t,
6 H, CH3CH2, J = 7.2 Hz); 4.31 (q, 4 H, CH3CH2, J = 7.2 Hz);
7.08—7.70 (m, 5 H, Harom).
Parameter
Value
17A
17B
Ethyl 3ꢀ(3,4ꢀdichlorophenyl)ꢀ5ꢀmethylꢀ2ꢀoxooxazolinꢀ4ꢀ
carboxylate (7a). A solution of 3,4ꢀdichlorophenyl isocyanate
(0.93 g, 4.95 mmol) in CH2Cl2 (20 mL) was added dropwise to a
solution of 4a (0.55 g, 1.65 mmol) in CH2Cl2 (25 mL) at –10 °C.
The reaction mixture was stirred at –10 °C for 1 h and then kept
at 0 °C for 16 h. The precipitate was separated, the filtrate was
concentrated in vacuo, and the residue was successively treated
with hexane and ethyl ether. Diethyl acetylfumarate 8a was
isolated from the hexane solution in a yield of 0.12 g (56.6%),
m.p. 93—95 °C (cf. lit. data18: 94 °C). Found (%): C, 56.19;
H, 6.25. C12H16O6. Calculated (%): C, 56.24; H, 6.29. 1H NMR,
δ: 1.28 (t, 6 H, CH3CH2, J = 7.2 Hz); 2.45 (s, 6 H, CH3C(O));
4.25 (q, 2 H, CH3CH2, J = 7.2 Hz). IR, ν/cm–1: 1644 (C=C);
Bond
d/Å
C(1)—N(1)
C(5)—N(2)
N(1)—S(1)
N(2)—S(2)
C(6)—S(3)
S(3)—C(7)
S(3)—C(8)
C(1)—C(6)
C(1)—C(2)
C(2)—C(3)
C(3)—C(4)
C(4)—C(5)
C(5)—C(6)
1.274(7)
1.313(7)
1.635(6)
1.634(6)
1.767(6)
1.787(7)
1.769(6)
1.411(8)
1.550(8)
1.503(8)
1.525(8)
1.513(8)
1.405(8)
1.316(8)
1.305(8)
1.623(6)
1.627(6)
1.742(6)
1.790(6)
1.758(7)
1.376(8)
1.542(8)
1.500(8)
1.519(8)
1.514(8)
1.413(8)
1713 (C(O)Me); 1724 (C(O)OEt). Raman spectrum, ν/cm–1
:
1646 (C=C). Crystalline colorless product 7a was isolated
from the ethereal solution in a yield of 0.15 g (28.8%), m.p.
136—137 °C. Found (%): C, 49.33; H, 3.41; N, 4.34; Cl, 22.17.
C13H11Cl2NO4. Calculated (%): C, 49.39; H, 3.51; N, 4.43;
Cl, 22.43. IR, ν/cm–1: 1644 (C=C); 1723 (C(O)OEt); 1776
(N—C(O)—O). Raman spectrum, ν/cm–1: 1596 (Ar); 1655
(C=C). 1H NMR, δ: 1.18 (t, 3 H, CH3CH2, J = 7.2 Hz); 2.49 (s,
3 H, CH3); 4.19 (q, 2 H, CH3CH2, 3J = 7.2 Hz); 7.14 (dd, 1 H,
Angle
ω/deg
C(1)—C(6)—C(5)
C(6)—C(5)—C(4)
C(6)—C(1)—C(2)
C(1)—N(1)—S(1)
C(5)—N(2)—S(2)
126.1(6)
117.7(6)
112.9(6)
125.4(5)
120.8(5)
124.7(6)
117.7(6)
114.8(6)
125.0(5)
120.8(6)
Harom
,
3J = 8.8 Hz, 4J = 2.4 Hz); 7.40 (d, 1 H, Harom
,
4J = 2.4 Hz); 7.50 (d, 1 H, Harom, J = 8.8 Hz). 13C NMR, δ:
12.4 (CH3CH2); 13.8 (CH3C—O—); 61.3 (CH3CH2); 115.6
(=C—C(O)OEt); 126.2, 128.9, 130.3, 132.5, 132.6, 133.7
(Carom); 147.9 (=C—Me); 152.4 (OC=O); 158.2 (C(O)OEt).
Ethyl 3ꢀ(3,4ꢀdichlorophenyl)ꢀ5ꢀethoxyꢀ2ꢀoxooxazolinꢀ4ꢀ
carboxylate (7b). A solution of 3,4ꢀdichlorophenyl isocyanate
(2.73 g, 14.5 mmol) was added dropwise to a solution of 4b
(1.75 g, 4.83 mmol) in CH2Cl2 (25 mL) at –10 °C. The reaction
mixture was stirred at –10 °C for 1 h and then stored at 0 °C
for 16 h. The precipitate was separated, the filtrate was concenꢀ
trated, and the residue was successively treated with hexane and
acetone. Ethyl ethylenetetracarboxylate 8b was isolated from
the hexane solution in a yield of 0.39 g (51%), m.p. 44—46 °C
3
Experimental
The NMR spectra were recorded on a Bruker AMXꢀ400
spectrometer (400.26 MHz for H and 100.68 MHz for 13C) in
1
CDCl3. The IR spectra were measured on a MagnaꢀIRꢀ750
(Nicolet) Fourier transform spectrometer (KBr pellets). The
Raman spectra of solid samples were recorded on a LabRAM
laser spectrometer (Jobin Yvou) at λ = 632.8 nm. The reactions
were performed under dry nitrogen. The solvents were purified
and dried before use.
Phenyliodonioacetylethoxycarbonylmethanide (4a) was synꢀ
thesized according to a known procedure.16 1H NMR, δ: 1.19 (t,

Reactions of iodine and sulfur ylides with isocyanates Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
889
(cf. lit. data19: 45—46 °C). Found (%): C, 53.21; H, 6.41;
C14H20O8. Calculated (%): C, 53.16; H, 6.37. 1H NMR, δ: 1.27
(t, 12 H, CH2CH3, J = 7.2 Hz); 4.27 (q, 8 H, CH2CH3, J =
7.2 Hz). IR, ν/cm–1: 1657 (C=C); 1736 (C=O). Crystals of 7b
were isolated from the acetone solution in a yield of 0.4 g (24%),
m.p. 132—134 °C. Found (%): C, 48.65; H, 3.74; N, 4.07;
Cl, 20.59. C14H31Cl2NO5. Calculated (%): C, 48.58; H, 3.78;
N, 4.05; Cl, 20.48. IR, ν/cm–1: 1786 (OC=O); 1723, 1707
(O=C—OEt), 1669 (C=C). Raman spectrum, ν/cm–1: 1667
(C=C). 1H NMR, δ: 1.17 (t, 3 H, CH3CH2, J = 6.8 Hz); 1.48 (t,
C, 57.68; H, 6.64; N, 4.00; S, 17.85. C17H23NO3S2. Calcuꢀ
lated (%): C, 57.77; H, 6.56; N, 3.96; S, 18.14. IR, ν/cm–1
:
1
1605 (C=O). H NMR, δ: 0.97 (s, 6 H, CH3); 2.22 (s, 2 H,
CH2); 2.38 (s, 3 H, MeTs); 2.91 (s, 6 H, Me2S); 2.93 (s, 2 H,
CH2); 7.24 and 7.78 (both d, 2 H each, Harom, 3J = 8 Hz).
2ꢀDimethylsulfuranylideneꢀ5,5ꢀdimethylꢀ1,3ꢀbisꢀtosyliminoꢀ
cyclohexane (17). Ylide 15 (0.26 g, 1.3 mmol) was added to a
solution of TsNCO (0.53 g, 2.6 mmol) in toluene (5 mL). The
reaction was accompanied by extensive elimination of CO2 and
the formation of a precipitate. The reaction mixture was heated
at 100 °C for 5 min and then stirred at 20 °C for 12 h. The
precipitate was separated and recrystallized from toluene. A colꢀ
orless product was obtained in a yield of 0.45 g (68%), m.p.
238—239 °C. Found (%): C, 56.93; H, 6.04; N, 5.41; S, 18.91.
C24H30N2O4S3. Calculated (%): C, 56.89; H, 5.98; N,5.53;
S, 18.98. The IR spectrum shows no absorption bands of the
CO groups in the 1600—1750 cm–1 region. 1H NMR, δ: 0.96 (s,
6 H, Me); 2.39 (s, 6 H, MeTs); 2.89 (s, 6 H, Me2S); 2.94 (s, 4 H,
CH2); 7.25 and 7.76 (both d, 4 H each, Ar, J = 8 Hz). 13C NMR,
δ: 21.36 (MeTs); 25.04 (Me—S); 27.69 (Me); 31.26 (CMe2);
44.29 (CH2); 87.06 (Cylide); 126.28, 129.25, 140.31,142.42
(Carom); 175.95 (C=N).
2ꢀDimethylsulfuranylideneꢀ3ꢀtosyliminoindanone (19). Ylide
18 (0.42 g, 2 mmol) was added to a solution of TsNCO (1 g,
5 mmol) in toluene (10 mL). The reaction mixture was heated at
100 °C for 5 h and then cooled. The crystalline precipitate was
separated and crystallized. Brightꢀyellow crystals were obtained
in a yield of 0.35 g (80%), m.p. 230—232 °C (decomp., from
toluene). Found (%): C, 60.05; H, 4.71; N, 3.68; S, 17.78.
C18H17NO3S2. Calculated (%): C, 60.14; H, 4.77; N, 3.89;
S, 17.84. IR, ν/cm–1: 1649 (C=O), 1605 (Ar); 1523 v.s. 1H NMR,
δ: 2.42 (s, 3 H, MeTs); 3.13 (s, 6 H, Me2S); 7.30—7.94 (m, 8 H,
Ar). 13C NMR, δ: 21.41 (MeTs); 26.73 (Me—S); 75.64 (Cylide);
120.07, 121.46, 128.09, 129.11, 131.38, 131.92, 135.40, 140.34,
141.12, 142.32 (Carom); 168.59 (C=N); 189.96 (C=O).
Quantum chemical calculations. The charges were calculated
with the use of the Gaussianꢀ98 program package.22
Xꢀray diffraction study. The crystallographic data, details of
Xꢀray data collection, and parameters of the structure refineꢀ
ment for compounds 8b, 12, 13b•0.5 H2O, and 17•CHCl3 are
given in Table 4.
The intensities of reflections were integrated and the equivaꢀ
lent reflections were merged using the SAINT23 and SAINTPlus
programs.24 Absorption corrections were applied using the
SADABS program.25
The structures were solved by direct methods. All nonꢀ
hydrogen atoms were located in difference electron density maps
and refined anisotropically against F 2hkl. All hydrogen atoms
were placed in geometrically calculated positions and refined
using a riding model with U(H) = nU(C), where n = 1.2 and 1.5
for the methylene and methyl groups, respectively, and U(C) are
the equivalent thermal parameters of the C atoms to which the
corresponding H atoms are bound. All calculations were carried
out using the SHELXTL PLUS 5 program package.26 For comꢀ
pounds 12, 13a, and 17, semiempirical absorption corrections
were applied based on equivalent reflections.
Colorless plateꢀlike crystals of compound 7b were obtained
as twins. Numerous attempts to find a singleꢀcrystalline fragꢀ
ment (or to perform additional recrystallization) were unꢀ
succesfull. We also failed to separate the Xꢀray intensity data
(14441 reflections), which were collected on a Bruker SMART
3
3 H, CH3CH2O, J = 7.2 Hz); 4.16 (q, 2 H, CH3CH2O, J =
3
7.2 Hz); 4.46 (q, 2 H, CH3CH2, J = 6.8 Hz); 7.17 (dd, 1 H,
3
4
4
H
arom, J = 8.8 Hz, J = 2.4 Hz); 7.40 (d, 1 H, Harom, J =
2.4 Hz); 7.49 (d, 1 H, Harom, 3J = 8.8 Hz).
Diethyl 2ꢀdiphenylsulfuranylidenemalonate (9) was syntheꢀ
sized by analogy with the known procedure.20 A mixture of
diethyl diazomalonate (1.23 g, 6.6 mmol), Ph2S (5 mL), and
CuSO4 (20 mg) was heated at 90 °C for 5 h. Toluene (10 mL)
was added, the precipitate was separated, and the filtrate was
chromatographed on a silica gel column (toluene was used as
the eluent for the separation of impurities, and the product was
eluted with the use of CH2Cl2). The yield of ylide 9 was 0.57 g
(25%), m.p. 106—108 °C. Found (%): C, 66.36; H, 5.76;
S, 9.02. C19H10O4S. Calculated (%): C, 66.25; H, 5.85; S, 9.31.
IR, ν/cm–1: 1672, 1648 (C=O). 1H NMR, δ: 1.15 (t, 6 H,
3
3J = 7.2 Hz); 4.12 (q, 4 H, CH2, J = 7.2 Hz); 7.39—7.60 (m,
10 H, Harom). 13C NMR, δ: 14.37 (CH2CH3); 59.40 (CH2CH3);
59.93 (Cylide); 129.10, 129.23, 130.50, 131.04 (Carom);
166.12 (C=O).
5,5ꢀDiethoxycarbonylꢀ1,3ꢀditosylimidazolidineꢀ2,4ꢀdione
(12). Tosyl isocyanate (0.89 g, 4.5 mmol) was added to a soluꢀ
tion of ylide 9 (0.7 g, 2 mmol) in CH2Cl2 (2 mL). The reaction
mixture was kept at 20 °C for 3 days, and then hexane was
added. The target product was separated and recrystallized from
a 1 : 5 CH2Cl2—hexane mixture. The yield was 0.67 g (62%),
m.p. 168—170 °C. Found (%): C, 50.08; H, 4.57; S, 11.63.
C23H24N2O10S2. Calculated (%): C, 50.00; H, 4.35; S, 11.59.
1
IR, ν/cm–1: 1758, 1764, 1777 (C=O). H NMR, (CDCl3), δ:
1.25 (t, 6 H, CH2CH3, 3J = 7.2 Hz); 2.45 and 2.46 (both s,
3 H each, CH3 in Ts); 4.30 (HA), 4.33 (HB) (CHAHBCH3, 4 H,
3JH
= 3JH ,H = 7.2 Hz, 2JH B = 10.8 Hz); 7.36, 7.38, 7.96,
,H
B A
,H
A
and 8.08 (all d, 4 H, Ts, J = 7.6 Hz). 13C NMR (CDCl3), δ:
13.54 (C(10), C(15)); 21.69, 21.73 (C(22), C(29)); 64.38 (C(9),
C(14)); 73.65 (C(1)); 128.62, 129,35 (C(18), C(20), C(25),
C(27)); 129.99, 130.11 (C(17), C(21), C(24), C(28)); 133.36,
133.87 (C(16), C(23)); 146.38, 146.43 (C(19), C(26)); 147.32
(C(4)); 156.95 (C(2)); 159.99 (C(6), C(11)).*
3
2ꢀDimethylsulfuranylideneꢀ5,5ꢀdimethylcyclohexaneꢀ1,3ꢀ
dione (15) and 2ꢀdimethylsulfuranylideneindaneꢀ1,3ꢀdione (18)
were synthesized according to a known procedure.21
2ꢀDimethylsulfuranylideneꢀ5,5ꢀdimethylꢀ3ꢀtosyliminocycloꢀ
hexanone (16). A solution of ylide 15 (0.4 g, 3 mmol) in CHCl3
(5 mL) was added to a solution of TsNCO (0.6 g, 3 mmol) in
CHCl3 (5 mL). The reaction started immediately and was acꢀ
companied by extensive elimination of CO2. The reaction mixꢀ
ture was stirred at 20 °C for 12 h and then poured into hexane.
The precipitate was separated and recrystallized from a 4 : 1
acetone—CHCl3 mixture. The colorless product was obtained
in a yield of 0.52 g (67%), m.p. 226—227 °C. Found (%):
* The atomic numbering scheme for C atoms is given in Fig. 3.

890
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
Gololobov et al.
Table 4. Crystallographic data and details of the structure refinement for compounds 8b, 12, 13a•0.5H2O, and 17•CHCl3
Compound
8b
12
13a•0.5(H2O)
17•СHСl3
Molecular formula
Molecular weight
Space group
T/K
C14H20O8
316.30
C23H24N2O10S2
552.56
C8H15O3.5
199.26
C2/c
S
C25H31Cl3N2O4S3
626.05
P–1
P–1
P–1
140(2)
293(2)
110(2)
120(2)
a/Å
b/Å
c/Å
α/deg
7.7502(14)
7.9240(15)
8.0293(15)
72.984(4)
67.102(4)
61.963(3)
397.3(1)
1
8.561(2)
10.747(2)
14.376(3)
81.934(5)
80.651(5)
82.212(5)
31283.7(5)
2
11.087(2)
10.484(2)
18.529(3)
—
100.874(4)
—
5.831(2)
22.680(9)
23.077(10)
71.370(10)
82.889(10)
82.645(8)
2857(2)
β/deg
γ/deg
V/Å3
2115.1(7)
8
Z
4
dcalc/g cm–3
Crystal color
and shape
Dimensions/mm
Diffractometer
Radiation
µ/cm–1
Tmin/Tmax
Scanning mode
2θmax/deg
Total number of reflections
Number of independent
1.322
Colorless
prism
1.430
Colorless
plate
1.251
Colorless
plate
1.455
Colorless
plate
0.60×0.40×0.30
0.20×0.15×0.03
0.60×0.45×0.30
0.25×0.20×0.15
Bruker SMART
MoꢀKα (λ = 0.71073 Å)
2.66
0.962/0.677
1.0979
—
2.83
0.3470/1.000
5.75
0.962/0.677
φ/ω
52.00
3076
1347
56.10
13318
6160
60.06
18096
3082
46.52
13840
8069
reflections (Rint
)
(0.0969)
0.0737
(1089 refl.)
0.1419
(0.0625)
0.0554
(2124 refl.)
0.1401
(0.0192)
0.0467
(2801 refl.)
0.1334
(0.0939)
0.0682
(2754 refl.)
0.1078
R1 (based on F for reflections
with I > 2σ(I ))
wR2 (based on F 2 for
all reflections)
Number of parameters
in refinement
Weighing scheme
a
102
408
118
619
2
2
2
w
–1 = σ (Fo ) + (aP)2 + bP, where P = 1/3(Fo2 + 2Fc )
0.0013
0.2500
0.966
168
0.0532
0.0988
0.7839
1.022
856
0.0011
0
0.910
1304
b
0
GOOF
F(000)
0.771
576
diffractometer at 140 К, into singleꢀcrystalline sets with the use
of the GEMINI program.27 Crystals of 7b (C14H13Cl2NO5,
M = 346.15) are triclinic, at 140 К a = 7.921(15) Å, b =
14.47(3) Å, c = 25.78(5) Å, α = 81.94(3)°, β = –85.55(3)°,
γ = 89.67(3)°, V = 2916(9) Å3, space group P1, Z = 8,
dcalc = 1.577. The refinement by the leastꢀsquares method conꢀ
verged to a high R factor (R1 = 0.1981; calculated based on
3339 reflections with I > 2σ(I )); 626 parameters were refined.
All four crystallographically independent molecules are strucꢀ
turally identical. The errors in bond lengths and bond angles
were high (0.01—0.03 Å and 1—2°, respectively) and did not
allow us to compare these parameters. These data should be
considered as preliminary results, which provide a reliable inꢀ
sight into the overall molecular structure of compound 7b.
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Foundation for Basic Research (Project No. 04ꢀ03ꢀ
32489).

Reactions of iodine and sulfur ylides with isocyanates Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
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Received March 14, 2006;
in revised form April 12, 2006