Reaction of unsaturated compounds with ethyl benzenesulfenate and trimethylsilyl isothiocyanate

Article abstract of DOI:10.1007/s11172-010-0311-0

A new method for the synthesis of thiocyanato- and isothiocyanatoalkyl phenyl sulfides by the reaction of unsaturated compounds with ethyl benzenesulfenate and trimethylsilyl isothiocyanate has been suggested. Regio- and stereoselectivity of the reaction

Full text of DOI:10.1007/s11172-010-0311-0

Russian Chemical Bulletin, International Edition, Vol. 59, No. 9, pp. 1771—1780, September, 2010
1771
Reaction of unsaturated compounds with ethyl benzenesulfenate
and trimethylsilyl isothiocyanate
N. V. Zyk, A. Yu. Gavrilova, O. A. Mukhina, A. A. Borisenko, O. B. Bondarenko, and N. S. Zefirov
M. V. Lomonosov Moscow State University, Department of Chemistry,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: gavrilova@org.chem.msu.ru
A new method for the synthesis of thiocyanatoꢀ and isothiocyanatoalkyl phenyl sulfides by
the reaction of unsaturated compounds with ethyl benzenesulfenate and trimethylsilyl isothioꢀ
cyanate has been suggested. Regioꢀ and stereoselectivity of the reaction was studied, having
taken alkenes, dienes, and alkynes as examples.
Key words: ethyl benzenesulfenate, trimethylsilyl isothiocyanate, alkenes, alkynes, sulfenyꢀ
lation, thiocyanates, electrophilic addition.
Addition of sulfenic acid derivatives (RS—X) to unsatꢀ
urated compounds is one of the principal methods for the
functionalization of multiple bonds, which furnishes
βꢀsubstituted sulfides. Earlier,1 we have suggested a new
method for the halosulfenylation of olefins and dienes with
the ethyl benzenesulfenate—trimethylsilyl halides system.
In continuation of our studies in this field, we investigated
a possibility of sulfenylation of unsaturated compounds
with the ethyl benzenesulfenate—trimethylsilyl isothiocyꢀ
anate system in order to prepare thiocyanate or isothiocyꢀ
anateꢀcontaining sulfides. There are only two examples of
the formation of thiocyanatoalkyl aryl sulfides,2,3 in which
sulfenethiocyanates were used. At fist glance, this is the
simplest approach. However, it should be noted that the
yields in these reactions are moderate, in some cases no
reaction occurs, since the rate of a competing process,
viz., disproportionation of the reagent with the formation
of the corresponding disulfide, turned out to be higher
than the rate of addition at the double bond. At the same
time, the importance of accomplishing such transformaꢀ
tions is obvious, since an introduction of thiocyanate or
isothiocyanate group into a molecule opens a possibility
for the preparation of a wide variety of biologically active
compounds and heterocycles.4—6
δ = 0.34. The 13C and 29Si NMR spectra exhibited a spinꢀ
spin interaction of the carbon 13C and silicon 29Si nuclei
with the nitrogen 14N nucleus. For instance, the 13C NMR
spectrum, together with a singlet for the trimethylsilyl
group at δ = 1.78, contains a triplet of lines of equal intenꢀ
sities for the isothiocyanate group δ = 141.26 and the
1
spinꢀspin coupling constant J (13C—14N) = 25.6 Hz. In
the 29Si NMR spectrum, the signal for the silicon is found
as a triplet of lines of equal intensities with δ = 5.53 (see
Refs 7 and 8) and 1J (29Si—14N) = 7.9 Hz, that is an
evidence that the nitrogen and silicon nuclei in the moleꢀ
cule are bound directly to each other. The 14N NMR specꢀ
trum of the reagent obtained in situ is characterized by
a singlet at δ = –263.7 characteristic of isothiocyanates9
and unusually narrow line halfꢀwidths, which is only
5.3 Hz, that is an evidence of a high symmetry in the
charge distribution at the nitrogen nucleus and a small
contribution of the quadrupole relaxation into the overall
time of the spinꢀlattice relaxation. The high symmetry of
the charge distribution at the nitrogen nucleus in trimethꢀ
ylsilyl isothiocyanate is apparently due to the delocalizaꢀ
tion of the lone pair of electrons on the nitrogen atom to
the vacant dꢀorbitals of the silicon atom.8 A broad absorpꢀ
tion band at 2100 cm–1 characteristic of isothiocyanates10
was observed in the IR spectrum of the reagent.
Trimethylsilyl isothiocyanate was obtained in situ from
sodium isothiocyanate and trimethylsilyl chloride in chloꢀ
roform (or dichloromethane) with stirring for 1 h.* The
formation of trimethylsilyl isothiocyanate in the reaction
To synthesize βꢀsubstituted sulfides (Scheme 1), a soluꢀ
tion of olefin and ethyl benzenesulfenate in chloroform
(or dichloromethane) was slowly added to trimethylsilyl
isothiocyanate obtained in situ and the mixture was stirred
at room temperature until the reaction was completed
(30—40 min).
1
mixture was confirmed spectroscopically: the H NMR
spectrum exhibited a singlet for the methyl groups with
The structures of the thiocyanatoꢀ and isothiocyanaꢀ
toalkyl phenyl sulfides obtained were established by IR
and 1H and 13C NMR spectroscopy. Compositions of the
* If the stirring time is shorter, βꢀchlorophenylthioalkanes are
formed as the side reaction products upon subsequent addition
of an olefin.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1724—1733, September, 2010.
1066ꢀ5285/10/5909ꢀ1771 © 2010 Springer Science+Business Media, Inc.

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Zyk et al.
Scheme 1
Table 1. Yields of the reaction products of ethyl
benzenesulfenate with unsaturated compounds in the
presence of Me3SiNCS
Substrate
Product (ratio of
isomers (%))
Yield
(%)
1
2
5
7
3
4
6
99
99
99
37
19
36
99
99
99
85
99
99
99
99
8a + 8b (67 : 33)
9a + 9b (75 : 25)
10a + 10b (75 : 25)
12
14a + 14b (25 : 75)
16
new compounds were confirmed by the elemental analysis
and mass spectrometric data. The formation of thiocyanꢀ
ates is confirmed by the presence in the 13C NMR spectra
of the signal characteristic of the thiocyanate carbon
(—SCN) in the region δ 111.50—116.0, as well as by the
presence in the IR spectrum of a narrow absorption band
of medium intensity in the region 2170 cm–1 (see Ref. 10).
Despite the available literature data11,12 on the fact that
chemical shift for the carbon atom of an isothiocyanate
group (—NCS) is in the region δ 128.0—137.0, we in most
cases failed in the registration of the signal for the quaterꢀ
nary isothiocyanate carbon atom, apparently, because of
the broadening due to the spinꢀspin interaction with the
nitrogen atom. Nevertheless, the formation of isothioꢀ
cyanates is unambiguously confirmed by the IR and
14N NMR spectroscopic data. For instance, the IR specꢀ
tra of isothiocyanates exhibit a broad intensive band at
2050—2200 cm–1 (see Ref. 10). In the 14N NMR spectra,
the signals for the nitrogen atom of the isothiocyanate
group is found in the region δ –(260—290), whereas the
signals for the nitrogen atom of the thiocyanate group, in
the narrow region δ ~100 (see Ref. 9).
11
13
15
18
19
22
23
26
20
21
24a + 24b (90 : 10)
25a + 25b (83 : 17)
27a + 27b (87 : 13)
The transꢀarrangement of substituents was inferred
from the spinꢀspin coupling constants of the protons on
substituents: for compound 3, the signals are two triplets
of doublets with the spinꢀspin coupling constants 10.1 Hz
and 4.0 Hz, that corresponds to the diequatorial arrangeꢀ
1
ment of the substituents.13 In the H NMR spectrum of
compound 4, the signals for the protons HCSCN and
HCSPh have the shape of doublet of doublets of doublets
at δ 3.53 and 2.80 with the following set of spinꢀspin couꢀ
pling constants: J2,3 = 5.0, J2,1 = 4.3, J2,6exo = 2.2 and
J3,7anti = 2.4, J3,2 = 5.0, respectively. The vicinal constant
value 3J3,2 = 5.0 Hz corresponds to the transꢀarrangement
of the substituents. The exoꢀarrangement of the HCSCN
proton is indicated by the presence of the spinꢀspin couꢀ
pling constant J2,1 = 4.3 Hz. The HCSPh proton has no
spinꢀspin coupling constant with the bridgehead proton
(H(4)), but is characterized by the interaction with the
bridge proton H(7) (J3,7anti = 2.4, the W constant).13
The absence of the Wagner—Meerwein rearrangement
products in the case of norbornene indicates, that effective
electrophilicity of the reagent is low enough.14 Neverꢀ
theless, the reaction of ethyl benzenesulfenate with
3,6ꢀdimethoxybenzonorbornadiene (5) in the presence of
trimethylsilyl isothiocyanate exclusively affords the reꢀ
arranged thiocyanate 6 (Scheme 3).
Using alkenes of different structures as examples, regioꢀ
and stereoselectivity of the addition reaction of ethyl benꢀ
zenesulfenate to them in the presence of Me3SiNCS were
studied. Thus, the reaction with cyclohexene (1) and norꢀ
bornene (2) (Scheme 2) proceeds chemoꢀ and stereospeciꢀ
fically with the formation of transꢀβꢀthiocyanatoalkyl phenyl
sulfides 3 and 4 in the yields close to quantitative (Table 1).
Scheme 2
Scheme 3

Thiocyanatoalkyl phenyl sulfides
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1773
The rearranged character of product 6 is indicated by
the presence in the 1H NMR spectrum of this compound
of two vicinal spinꢀspin coupling constants of the HCSCN
proton with the protons of neighboring H2C(10) methylꢀ
ene group (J9,10endo = 8.6, J9,10exo = 4.5 Hz). The endoꢀ
arrangement of the HCSCN proton was confirmed by the
absence of a large constant of the spinꢀspin interaction of
the HCSCN proton with the bridgehead proton H(8).
The reaction with norbornadiene (7) led to a complex
mixture of substituted alkyl phenyl sulfides 8—10 (Scheme 4)
with predominance of products of the exoꢀattack of the
electrophile, that is more favorable from the point of view
of steric factors. Using chromatographic separation, we
successfully isolated three pairs of isomers: 6ꢀphenylthioꢀ
5ꢀthiocyanatobicyclo[2.2.1]heptꢀ2ꢀenes 8a,b and nortriꢀ
cyclane products 9a,b and 10a,b, which resulted from the
homoallylic participation by the second double bond in
the reaction, with isothiocyanates 10a,b being predomiꢀ
nant among the nortricyclane products (cf. Table 1).
To establish structure of the nortricyclane products,
the data on the effect of substituents on the 1H nuclei
chemical shifts and the data on the nuclear Overhauser
effect (NOE) were used. Analysis of the literature data15
allowed us to exclude from our consideration 5ꢀendoꢀ
phenylthioꢀ3ꢀexoꢀthiocyanatotricyclo[2.2.1.02,6]heptane
and 3ꢀexoꢀisothiocyanatoꢀ5ꢀendoꢀphenylthiotricycloꢀ
[2.2.1.02,6]heptane, since the calculated* chemical shifts
for the protons H(3) of these compounds were δ 4.14 and
4.48, respectively, that was considerably higher than the
chemical shifts for the protons observed experimentally
(Table 2).
Isothiocyanateꢀcontaining isomers 10a,b were isolatꢀ
ed as a mixture. The 14N NMR spectrum of the mixture of
isomers contains a signal with the chemical shift δ –277.1
1
characteristic of isothiocyanates.9 In the H NMR specꢀ
trum, two sets of signals are observed, with the ratio of
their intensities being 3 : 1. Signals for the protons on the
substituent are found as singlets, whose chemical shifts
are δ 3.81 and 3.83 for the predominant and δ 3.22 and
3.64 for the minor isomers, respectively. As it has been
shown earlier,15 a considerable downfield shift of the sigꢀ
nal for the H(5) is due to the change in the orientation of
substituent on the C(3) atom (exo→endo). This allowed us
to suggest that compound 10a has the structure of 3ꢀendoꢀ
isothiocyanatoꢀ5ꢀexoꢀphenylthiotricyclo[2.2.1.02,6]heptꢀ
ane, whereas compound 10b is 3ꢀexoꢀisothiocyanatoꢀ5ꢀ
exoꢀphenylthiotricyclo[2.2.1.02,6]heptane. Our suggestion
was confirmed when the NOE experiment was performed.
When the signal for the H(3)CNCS proton (δ 3.64) of the
minor isomer 10b was irradiated, the Overhauser effect
was observed on the proton H(5)CSPh (η = 3.6%) (Table 3).
For the predominant isomer 10a, the NOE was observed
upon irradiation of the bridge proton H(7´) (δ 1.44): the
intensity of the signal at δ 3.83 (H(3)) increased by 2.6%.
To sum up, the structure of exoꢀexoꢀadduct can be asꢀ
signed to the minor isomer 10b, whereas to the predomiꢀ
nant isomer 10a, the structure of exoꢀendoꢀadduct.
Scheme 4
The structures of isomers 9a,b were established simiꢀ
larly. In the case of product 9a, the Overhauser effect on
the orthoꢀproton of the phenylthio group (η = 2.0%) upon
irradiation of the proton at δ 3.81 allowed us to assign the
latter to the proton H—C—SPh. At the same time, the
absence of the NOE on the bridge protons allows us to
draw a conclusion on the exoꢀarrangement of the arylthio
group. The endoꢀarrangement of the thiocyanate group
* The calculation was performed using the following formula
δ = δ + Δ + Δde, where δ is the chemical shift for the proton
3
0
s
3
HCSCN or HCNCS in 3,5ꢀdisubstituted nortricyclane, δ is the
chemical shift for the proton C(3) in 3ꢀnortricyclane system
0
The structures of the reaction products 8—10 were esꢀ
tablished by 1H and 13C NMR spectroscopy. The 1H NMR
spectra of compounds 8a and 8b exhibit signals for the olefin
protons. The spinꢀspin coupling constant value of the proꢀ
tons on the substituents (J5,6 3.8 Hz) indicate the transꢀ
arrangement of the phenylthio and thiocyanate groups.
(δ (HCSCN) = 3.28, δ (HCNCS) = 3.62), Δ is the change
0
0
s
in the chemical shift for the proton H(3) due to the substituꢀ
ent at position 5 (endo or exo) (for HCSCN and HCNCS
Δ = 0.0 ppm), and Δde is a deshielding effect of the endoꢀsubstitꢀ
s
uent at position 5 (Δde(HCSPh) = 0.86 + 0.02 ppm).15

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Zyk et al.
Table 2. 1H NMR spectra of compounds 8—10 (in CDCl3)
Comꢀ
pound
δ (JH,H/Hz)a
Н(1)
Н(2)
Н(3)
Н(4)
Н(5)
Н(6)
Н(7)
Н(7´)
1.80 (dm,
8a
2.95 (m)
6.28 (dd,
J2,3 = 5.7,
J2,1 = 2.8)
6.35b (m)
2.83 (ddd,
J4,5 = 3.9,
J4,3 = 2.4,
J = 0.5)
3.64 (dd,
J5,4 = 3.9,
J5,6 = 3.7)
3.30 (m)
1.95 (dm,
7,7´ = 9.5)
J
J7,7´ = 9.5)
8b
9a
9аf
3.05 (dd,
J1,6 = 3.8,
J1,2 = 2.1)
6.32—6.39b (m, 2 Н)
3.19 (m, 2 Н)
3.28 (t, J6,1
≈ J6,5 = 3.8)
≈
1.85c (dm)
2.22 (dd,
J7,7´ = 11.6, J7´,7 = 11.6)
J = 1.5)
1.94 (dt,
J7,7´ = 11.2, J7´,7 = 11.2)
J7,1 = J7,4 =
1.80c (dm)
1.56—1.64d
3.60 (t,
J3,2 ≈ J3,4
= 1.4)
2.72 (t,
J3,2 ≈ J3,4
= 1.5)
2.32 (br.s)
1.87 (m)
3.81 (br.s) 1.60d,е
1.54 (d,
=
=
0.89 (tq,
J1,2 ≈ J1,6
= 5.1, J1,7
0.80g
3.71 (br.s) 1.11 (tt,
0.80g (d,
=
≈
J6,1 ≈ J6,2
= 5.1, J6,5
=
≈
≈ J1,7´
≈ J1,4 = 1.1)
1.56—1.64d
≈
≈ J6,4 = 1.1)
= 1.1)
9b
3.47 (br.s)
2.72i
2.30 (br.s)
1.78 (m)
3.28 (br.s) 1.62d,е
2.17 (d,
1.86 (d,
J
7,7´ = 11.9) J7´,7 = 11.9)
9bf
0.95 (tq,
0.90h
2.57 (br.s) 1.02 (tt,
1.91j
1.48 (d,
J1,2 ≈ J1,6
=
J6,1 ≈ J6,2
=
J7´,7 = 12.0)
= 5.1, J1,7
≈
= 5.1, J6,5
≈
≈ J1,7´
≈
≈ J6,4 = 1.1)
≈ J1,4 = 1.1)
10a
10b
1.52 (tddd,
1.63 (tt,
J2,1 ≈ J2,6
= 5.2, J2,3
≈ J2,4 = 1.6)
3.83 (t,
J3,2 ≈ J3,4
= 1.6)
2.22 (m)
3.81 (br.s) 1.60 (tt,
J6,1 ≈ J6,2
= 5.2, J6,5
2.06 (ddd,
J7,7´ = 11.4, J7´,7 = 11.4,
J7,4 = 1.8,
J7,1 = 1.4)
1.44 (ddd,
J1,2 ≈ J1,6
=
=
≈
=
=
≈
= 5.2, J1,7
=
J7´,4 = 1.6,
J7´,1 = 1.2)
= 1.4, J1,7´
= 1.2, J1,4
= 1.0)
=
≈ J6,4 = 1.0)
=
1.50—1.66k
3.64 (t,
J3,2 ≈ J3,4
= 1.6)
2.27 (br.s)
3.22 (br.s) 1.50—1.66k
2.14 (dt,
1.88 (dt,
=
J
7,7´ = 11.4, J7´,7 = 11.4,
J7,1 = J7,4
= 1.1)
=
J7´,1 = J7´,4 =
= 1.4)
a The signals for the protons of the PhS group are found in the region δ 7.20—7.40.
b The signals for the olefin protons of compounds 8a and 8b overlap.
c The signal for the proton overlaps with the signal for the proton H(7´) of compound 8a.
d The signals for the protons H(1), H(2), H(6) of compounds 9a and 9b overlap and are found in the region δ 1.56—1.64.
e Position of the signal was inferred from the NOE experimental data.
f C6D6 was the solvent
g The signals for the protons H(2) and H(7´) overlap.
h The signal overlaps with the signal for the proton H(1) of compound 9a.
i The signal overlaps with the signal for the proton H(3) of compound 9a.
j The signal overlaps with the signals for compound 9a.
k The signal overlaps with the signals for compound 10a.
was confirmed by the presence of the NOE on the bridge
proton H(7´) (η = 2.6%) upon irradiation of the signal at δ
3.60 (H(3)CSCN). Thus, the exoꢀendoꢀconfiguration of
adduct 9a was confirmed. In the case of minor isomer 9b
upon irradiation of the signal at δ 3.28 (H(5)CSPh), the
Overhauser effect (η = 6.6%) was observed on the proton
at the second substituent, that unambiguously confirms
the exoꢀexoꢀarrangement of the phenylthio and thiocyanꢀ
ate groups.
In the case of 1,5ꢀcyclooctadiene (11), the 1,2ꢀadꢀ
dition product, thiocyanate 12, is formed in quantitaꢀ
tive yield, with the second double bond remained inꢀ
tact (Scheme 5). Moreover, when the reaction is carried
out with a twoꢀfold excess of the reagent, the addiꢀ
tion involves exclusively one bond. In the 1H NMR specꢀ
trum of compound 12, the signals for the protons on
substituents are two triplets of doublets with the spinꢀ
spin coupling constants 3J ≈ 8.1 Hz and 3J ≈ 3.5 Hz,

Thiocyanatoalkyl phenyl sulfides
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1775
Table 3. The NOE (η) data for compounds 9a,b and 10a,b
(in CDCl3)
group. Therefore, the major product is the antiꢀMarkovꢀ
nikov addition product, i.e., the reaction is kinetically conꢀ
trolled.17
Comꢀ
pound
Irradiated
protons
η (%)
The reaction of styrene with ethyl benzenesulfenate in
the presence of trimethylsilyl isothiocyanate yields the
Markovnikov addition product, thiocyanate 16 (Scheme 7).
To establish its structure, the 13C NMR spectrum was
recorded without proton decoupling: the signal for the
SCN carbon atom is a doublet with 3J = 4.0 Hz, therefore,
the SCN group is bound to the CH, rather than the
CH2 group.
Н(3) Н(4) Н(5) Н(6) Н(7) Н(7´) C6Н5
9a
Н(5)СSPh
Н(3)СSCN
Н(5)СSPh 6.6 3.6
Н(7)
Н(7´)
Н(3)СNCS
—
—
1.0
1.0
—
—
—
—
—
2.0
—
4.1
—
—
—
—
—
—
—
11.7
—
—
2.6
—
13.0
—
2.0
—
—*
—
—
—
9b
10a
—
2.6
—
—
—
—
10b
3.6
—
* No NOE was detected for the minor isomer in the mixture.
Scheme 7
that is an evidence of the transꢀarrangement of the subꢀ
stituents.16
Scheme 5
The formation of Markovnikov addition product is
characteristic of the sulfenylation reaction of styrene.1 It
should be noted that if thiocyanate 16 is kept in chloroꢀ
form for 1 week at room temperature, its partial isomerꢀ
ization to the thermodynamically more stable isothiocyꢀ
anate 17 takes place (the ratio 16 : 17 = 59 : 41) (see
Scheme 7).
Regioselectivity of the addition was studied using the
reaction of ethyl benzenesulfenate with terminal olefin,
hexꢀ1ꢀene (13), as an example (Scheme 6). Based on the
1H NMR spectrum of the reaction mixture, it was found
that the reaction proceeds with the formation of a mixture
of βꢀthiocyanatoalkyl phenyl sulfides 14a and 14b in the
ratio 1 : 3.
The formation of isothiocyanates 20 and 21 is the only
direction of the reaction in the case of Eꢀ1ꢀphenylpropene
(18) and Eꢀ1ꢀ(4ꢀmethoxyphenyl)propene (19) (Scheme 8).
1
Scheme 6
In the H NMR spectrum, the spinꢀspin coupling conꢀ
stants for the protons HCS and HCN in compounds 20
and 21 are 3.5 Hz and 3.8 Hz, that indicates formation of
the 1R*,2R*ꢀisomers in both cases. This agrees with
the data obtained earlier for the selenothiocyanation of
Eꢀ1ꢀphenylpropene.12,18—20
It should be noted that it is difficult to assign signals to
this or that isomer based only on the 1H NMR spectrum,
since chemical shifts for the protons on substituents are
close. However, the 13C NMR spectrum exhibits two sets
of signals of different intensities. To establish structures of
the isomers obtained, the 13C NMR spectrum was recordꢀ
ed without proton decoupling. The signal for the SCN
carbon atom of the predominant isomer with the chemical
Scheme 8
3
shift δ 110.7 is a doublet of doublets with J = 4.4 and
R = H (18, 20), MeO (19, 21)
3J = 7.3 Hz, whereas the signal for the SCN carbon atom
of the minor isomer is found at δ 109.3 as a doublet with
3J = 6.6 Hz. This indicates that the SCN group in the
predominant isomer 14b is bound to the CH2 group, whereꢀ
as the SCN group in the minor isomer 14a, to the CH
To sum up, as it was noted earlier12,21 an increase in
stability of the intermediately formed carbocation leads to
the increase in the amount of the isothiocyanateꢀsubstiꢀ
tuted adducts in the reaction. It is obvious that the formaꢀ

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Zyk et al.
tion of the allylic carbocation in the course of the reaction
should also favor an increase in the yield of isothiocyanꢀ
ates. In fact, we have found that cyclopentadiene (22) and
cyclohexaꢀ1,3ꢀdiene (23) react with ethyl benzeneꢀ
sulfenate and trimethylsilyl isothiocyanate with the forꢀ
mation of isothiocyanates 24 and 25 (Scheme 9), with the
products of 1,4ꢀaddition being predominant (24a and 25a).
constant with the proton H(5) (3Jcis = 8.2 Hz), and, third,
has two constants Jtrans with the protons H—CNCS and
H(5´) (J4,3 = 4.5 Hz and J4,5 = 3.8 Hz). Therefore, comꢀ
pound 24b is the transꢀ3ꢀisothiocyanatoꢀ4ꢀphenylthioꢀ
cyclopentꢀ1ꢀene.
Based on the 1H—1H homonuclear double resonance
in the study of compounds 25a and 25b, it was established
that in the first case both protons on the substituents have
a mutual spinꢀspin coupling constant with the protons at
the double bond, which confirms the structure of the
1,4ꢀadduct, whereas in the second case only the HCNCS
proton has a mutual spinꢀspin coupling constant with one
of the olefin protons, i.e. compound 25b is the 1,2ꢀadduct.
In the 1H NMR spectrum of compound 25a, all four spinꢀ
spin coupling constants for the protons on the substituents
3
Scheme 9
with the protons of neighboring CH2 groups (J3,4, J3,4´
,
J6,5, and J6,5´) are equal to 5.0 Hz, therefore, the protons
HCN and HCS have the pseudoequatorial arrangeꢀ
ment,25,26 i.e. isothiocyanate 25a is the transꢀisomer. In
compound 25b, the proton HCSPh is found as a doublet
of doublets of doublets and has two large spinꢀspin couꢀ
pling constants with the protons HCNCS and H(5´)
3
(3J4,3 = 6.9 Hz and J4,5´ = 9.6 Hz), as well as one small
spinꢀspin coupling constant with the proton H(5) (3J4,5
=
= 2.9 Hz), which indicates the diequatorial arrangement
of the substituents.25 Therefore, compound 25b is the
transꢀ3ꢀisothiocyanatoꢀ4ꢀphenylthiocyclohexꢀ1ꢀene.
The reaction of terminal alkynes (pentyne and hepꢀ
tyne) with ethyl benzenesulfenate and trimethylsilyl isoꢀ
thiocyanate, in addition to the products of electrophilic
addition to the triple bond, would give significant amounts
of diphenyl disulfide and rearranged products, which is
characteristic of the halosulfenylation of alkynes.27,28 The
reaction with nonterminal hexꢀ3ꢀyne led to the vinyl sulꢀ
fides 27a,b in quantitative yields (Scheme 10). A considꢀ
erable increase in the rate of sulfenylation of internal
alkynes as compared to terminal alkynes has been noted
earlier.29
The structures of the products were established by
1H NMR spectroscopy. Configurational assignments for
the compounds were made based on the analysis of the
spinꢀspin coupling constant values similarly to the haloꢀ
substituted cyclopentadienes and cyclohexadienes.1,22—24
To establish the structure of compound 24a, the
1H—1H homonuclear double resonance was used, which
allowed us to make full analysis of the 1H NMR spectrum
and determine all the spinꢀspin coupling constant values
(see Experimental). It was shown that both protons on the
substituents (H—CSPh and H—CNCS) have the spinꢀ
spin coupling constants with the protons at the double
bond equal to 2.1—2.3 Hz, which confirms the structure
of the 1,4ꢀadduct. In addition, according to the literature
data22—24 in substituted cyclopentenes 3Jtrans = 3.0—4.0 Hz,
Scheme 10
3
whereas Jcis = 6.0—8.0 Hz. Therefore, the H(4´) proton
has the cisꢀarrangement with respect to the H—CNCS
proton and transꢀarrangement with respect to the H—CSPh
proton. Configurational relation of the H(4) proton to the
protons on the substituents is reverse. Thus, compound
24a is the transꢀisomer of 3ꢀisothiocyanatoꢀ5ꢀphenylthioꢀ
cyclopentꢀ1ꢀene.
The structures of isomers 27a,b were established based
on the fact that the signals for the protons of the CH2
group in the 1H NMR spectrum, as well as the signals for
the carbon atoms of the CH2 groups in the 13C NMR
spectrum of the Zꢀisomer, are found more upfield as comꢀ
pared to analogous signals for the Eꢀisomer.29
In conclusion, a new method has been suggested for
the synthesis of thiocyanatoꢀ and isothiocyanatoalkyl pheꢀ
nyl sulfides based on the activation of ethyl benzeneꢀ
1
In the H NMR spectrum of compound 24b, the sigꢀ
nals for the protons H—CNCS and H(5´) overlap with the
corresponding signals for the predominant isomer. However,
it was established that the signal for the proton H—CSPh,
first, has no mutual spinꢀspin coupling constant with the
olefin protons, second, has a mutual spinꢀspin coupling

Thiocyanatoalkyl phenyl sulfides
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1777
C(6)); 51.5, 52.2 (CSPh, CSCN); 111.6 (SCN); 128.4, 129.2,
132.9, 134.1 (CAr).
sulfenate with trimethylsilyl isothiocyanate. The method
is simple in accomplishing and characterized by high yields
the target products. It was shown that linear and cyclic
alkenes, dienes, and alkynes can be involved into the reacꢀ
tion. Isothiocyanates are the thermodynamically conꢀ
trolled products and they were isolated in those cases,
when stable carbocations have been formed in the course
of the reaction (benzylic and allylic type, or stabilization
of carbocation due to the homoallylic involvement of
a double bond (as in the case of norbornadiene)), as well
as a result of isomerization of thiocyanates.
exoꢀ3ꢀPhenylthioꢀendoꢀ2ꢀthiocyanatobicyclo[2.2.1]heptane
(4). 1H NMR (CDCl3), δ: 1.30 (m, 1 H, endoꢀH(5)); 1.55 (ddt, 1 H,
2
antiꢀH(7), J7,7 = 10.6 Hz, J7,3 = 2.4 Hz, J7,1 = J7,4 = 1.7 Hz);
2
1.58 (ddtd, 1 H, exoꢀH(6), J6,6 = 12.9 Hz, J6,5exo = 12.4 Hz,
J6,5endo J6,1 = 4.3 Hz, J6,2 = 2.2 Hz); 1.73 (tt, 1 H, exoꢀH(5),
2J5,5 J5,6exo = 12.4 Hz, J5,4 J5,6endo = 4.3 Hz); 1.86 (dddd, 1 H,
2
endoꢀH(6), J6,6 = 12.9 Hz, J6,5endo = 6.4 Hz, J6,5exo = 4.3 Hz,
J6,7syn = 2.4 Hz); 1.89 (dm, 1 H, synꢀH(7), 2J7,7 = 10.6 Hz); 2.39
(d, 1 H, H(4), J4,5exo = 4.3 Hz); 2.62 (m, 1 H, H(1)); 2.80 (dd, 1 H,
HCSPh, J3,2 = 5.0 Hz, J3,7anti = 2.4 Hz); 3.53 (ddd, 1 H,
HCSCN, J2,3 = 5.0 Hz, J2,1 = 4.3 Hz, J2,6exo = 2.2 Hz); 7.25
(tm, 1 H, Ar, J = 7.3 Hz); 7.33 (t, 2 H, Ar, J = 7.3 Hz); 7.44
(t, 2 H, Ar, J = 7.3 Hz). 13C NMR (CDCl3, δ: 22.5, 28.6 (C(5),
C(6)); 36.5 (C(7)); 42.7, 43.9 (C(1), C(4)); 56.2, 56.4 (CSPh,
CSCN); 111.5 (SCN); 127.6 (CAr(4)); 129.2, 131.8 (CAr(2),
CAr(3), CAr(5), CAr(6)); 134.4 (CAr(1)).
Experimental
1
H, 13C, 29Si, and 14N NMR spectra were recorded on
a Bruker Avance 400 spectrometer (400, 100.6, 79.5, and
28.9 MHz, respectively). Chemical shifts are given relatively to
Me4Si as an internal standard for the 1H, 13C, and 29Si nuclei
and relatively to nitromethane as an external standard for the
14N nucleus. The NOE was measured in the regime of differenꢀ
tial spectroscopy (the NOEDIF program). IR spectra were reꢀ
corded on a URꢀ20 spectrometer (neat). Mass spectra were reꢀ
corded on a Finnigan MIAT TSQ 7000 GLCꢀMS spectrometer
(70 eV). Monitoring of the reaction progress and individuality of
compounds synthesized was made by TLC on a fixed layer of
silica gel (Silufol UV254).
3,6ꢀDimethoxyꢀsynꢀ11ꢀphenylthioꢀexoꢀ9ꢀthiocyanatotriꢀ
1
cyclo[6.2.1.02,7]undecaꢀ2(7),3,5ꢀtriene (6). H NMR (CDCl3),
δ: 2.16 (ddd, 1 H, endoꢀH(10), 2J10,10 = 13.3 Hz, J10,9 = 8.6 Hz,
2
J = 0.6 Hz); 2.47 (dt, 1 H, exoꢀH(10), J10,10 = 13.3 Hz,
J10,9 = 4.5 Hz, J10,1 = 4.0 Hz); 3.29 (ddd, 1 H, HCSCN,
J9,10endo = 8.6 Hz, J9,10exo = 4.5 Hz, J = 1.1 Hz); 3.60 (m, 1 H,
HCSPh or H(8)); 3.68 (m, 1 H, H(1)); 3.76 (s, 3 H, OMe); 3.82
(s, 3 H, OMe); 3.92 (t, 1 H, H(8) or HCSPh, J = 1.4 Hz); 6.60
(d, 1 H, H(4) or H(5), 3J = 8.9 Hz); 6.64 (d, 1 H, H(5) or H(4),
3
3J = 8.9 Hz); 7.23 (t, 1 H, Ar, J = 7.2 Hz); 7.31 (t, 2 H, Ar,
Solvents were purified according to the standard proceꢀ
dures.13 Ethyl benzenesulfenate was synthesized according to
the known procedure.30
3J = 7.2 Hz); 7.47 (d, 2 H, Ar, 3J = 7.2 Hz). 13C NMR (CDCl3),
δ: 34.2 (C(10)); 45.0, 47.8 (C(1), C(8)); 50.8 (CSCN); 55.4, 55.6
(OCH3); 63.2 (CSPh); 109.9, 110.3 (C(4), C(5)); 112.4 (SCN);
127.1 (CAr(4)); 129.1, 131.0 (CAr(2), CAr(3), CAr(5), CAr(6));
133.1 (C(2), C(7)); 134.2 (CAr); 147.5 (C(3), C(6)).
A mixture of 6ꢀexoꢀphenylthioꢀ5ꢀendoꢀthiocyanatobicycloꢀ
[2.2.1]heptꢀ2ꢀene (8a) and 6ꢀendoꢀphenylthioꢀ5ꢀexoꢀthiocyanꢀ
atobicyclo[2.2.1]heptꢀ2ꢀene (8b). 13C NMR of compound 8a
(CDCl3), δ: 46.6, 48.1, 49.1 (C(1), C(4), C(7)); 54.0, 54.3 (CSPh,
CSCN); 111.6 (SCN); 127.7 (CAr(4)); 129.3, 132.0 (CAr(2),
CAr(3), CAr(5) CAr(6)); 134.4 (CAr(1)); 135.0, 138.4 (C(2), C(3)).
13C NMR of compound 8b (CDCl3), δ: 46.3, 48.1, 50.0 (C(1),
C(4), C(7)); 53.7, 55.4 (CSPh, CSCN); 111.7 (SCN); 127.8
(CAr(4)); 129.3, 132.2 (CAr(2), CAr(3), CAr(5), CAr(6)); 134.7
(CAr(1)); 135.8, 137.0 (C(2), C(3)).
A mixture of 5ꢀexoꢀphenylthioꢀ3ꢀendoꢀthiocyanatotricycloꢀ
[2.2.1.02,6]heptane (9a) and 5ꢀexoꢀphenylthioꢀ3ꢀexoꢀthiocyanꢀ
atotricyclo[2.2.1.02,6]heptane (9b). 13C NMR of compound 9a
(CDCl3), δ: 14.3, 16.5, 17.6 (C(1), C(2), C(6)); 30.4 (C(7)); 40.4
(C (4)); 50.2, 54.1 (CSPh, CSCN); 111.5 (SCN); 126.6 (CAr(4));
129.1, 130.1 (CAr(2), CAr(3), CAr(5) CAr(6)); 135.5 (CAr(1)).
13C NMR of compound 9b (CDCl3), δ: 12.0, 17.8, 18.7 (C(1),
C(2), C(6)); 27.3 (C(7)); 40.7 (C(4)); 52.5, 52.7 (CSPh, CSCN);
127.2 (CAr(4)); 129.1, 131.2 (CAr(2), CAr(3), CAr(5), CAr(6));
135.5 (CAr(1)).
Reaction of unsaturated compounds with ethyl benzeneꢀ
sulfenate and trimethylsilyl isothiocyanate (general procedure).
A solution of trimethylsilyl chloride in anhydrous CHCl3
(or CH2Cl2) (2 mL) was added to sodium isothiocyanate (the
molar ratio sodium isothiocyanate : trimethylsilyl chloride ≈ 3 : 1)
with vigorous stirring at room temperature and the stirring
was continued for 1 h, followed by a slow dropwise addition
of a solution of a mixture of ethyl benzenesulfenate and olefin
in the same solvent (the ratio olefin : sulfenate : trimethylꢀ
silyl isothiocyanate = 1 : 1 : 2). The stirring was continued until
the reaction reached completion (TLC monitoring). Then,
the reaction mixture was hydrolyzed with water, the organic
phase was separated, the aqueous phase was thrice extracted
with dichloromethane or chloroform, the organic extracts were
combined and dried with Na2SO4. The solvent was evaporated
in vacuo. Preparative column chromatographic separation of
the reaction products was performed on silica gel Lancaster
(0.04—0.063).
The yields of the reaction products are given in Table 1,
chromatographic, elemental analysis, and IR spectroscopic data,
in Table 4, mass spectrometric characteristics of compounds
1
obtained, in Table 5. The H NMR spectroscopic data of comꢀ
pounds 8—10 are given in Table 2.
A mixture of 3ꢀendoꢀisothiocyanatoꢀ5ꢀexoꢀphenylthiotriꢀ
cyclo[2.2.1.02,6]heptane (10a) and 3ꢀexoꢀisothiocyanatoꢀ5ꢀexoꢀ
phenylthiotricyclo[2.2.1.02,6]heptane (10b). 13C NMR of comꢀ
pound 10a (CDCl3), δ: 13.2, 16.0, 18.7 C(1), C(2), C(6)); 28.5
(C(7)); 40.7 (C(4)); 50.3, 61.4 (CSPh, CNCS); 126.5 (CAr(4));
129.1, 130.2 (CAr(2), CAr(3), CAr(5), CAr(6)); 135.5 (CAr(1)).
13C NMR of compound 10b (CDCl3), δ: 11.5, 17.6, 18.9 C(1),
C(2), C(6)); 27.7 (C(7)); 41.1(C(4)); 50.9, 59.8 (CSPh, CNCS);
transꢀ2ꢀPhenylthioꢀ1ꢀthiocyanatocyclohexane (3). 1H NMR
(CDCl3), δ: 1.35 (m, 2 H, CHꢀframework); 1.53 (m, 1 H,
CHꢀframework); 1.78 (m, 3 H, CHꢀframework); 2.22, 2.48
(both m, 1 H each, CHꢀframework); 3.05 (td, HCSPh or HCSCN,
J = 10.1 Hz, J = 4.0 Hz); 3.24 (td, 1 H, HCSCN or HCSPh,
J = 10.1 Hz, J = 4.0 Hz); 7.34—7.39 (m, 3 H, Ar); 7.50 (m, 2 H, Ar).
13C NMR (CDCl3), δ: 25.0, 25.1 (C(4), C(5)); 33.3, 33.5 (C(3),

1778
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
Zyk et al.
Table 4. Chromatographic data, elemental analysis data, and characteristic absorption bands in the IR spectra
of compounds 3, 4, 6, 8—10, 14, 16, 17, 24, 25, 27
Comꢀ
pound
Found
Calculated
Molecular
formula
Rf
IR
(ν/cm–1
)
(%)
(EtOAc : LPa)
C
H
N
3
62.57
62.65
64.21
64.37
65.17
65.04
64.94
64.86
64.94
64.86
64.94
64.86
65.04
65.45
62.35
62.15
66.21
66.42
66.21
66.42
62.00
61.80
63.79
63.16
62.54
62.65
5.92
6.02
5.65
5.74
5.22
5.15
5.22
5.02
5.22
5.02
5.22
5.02
6.20
6.18
6.73
6.77
4.81
4.80
4.81
4.80
4.88
4.72
5.31
5.26
6.08
6.02
5.58
5.62
5.30
5.36
3.49
3.79
5.17
5.40
5.17
5.40
5.17
5.40
5.27
5.09
5.42
5.58
5.01
5.17
5.01
5.17
6.20
6.01
5.71
5.67
5.52
5.62
C13H15NS2
C14H15NS2
C20H19NS2О2
C14H13NS2
C14H13NS2
C14H13NS2
C15H17NS2
C13H17NS2
C15H13NS2
C15H13NS2
C12H11NS2
C13H13NS2
C13H15NS2
0.71 (1 : 3)
0.67 (1 : 3)
0.63 (1 : 3)
0.72 (1 : 5)
0.63 (1 : 5)
0.80 (1 : 5)
0.63 (1 : 3)
0.76 (1 : 3)
0.40 (1 : 3)
0.40 (1 : 5)
0.73 (1 : 3)
0.78 (1 : 3)
0.63 (1 : 3)
2165 (SCN)
2170 (SCN)
2165 (SCN)
2170 (SCN)
2165 (SCN)
2110 (NCS)
2165 (SCN)
2170 (SCN)
2170 (SCN)
2080 (NCS)
2100 (NCS)
2100 (NCS)
2170 (SCN)
4
6b
8a + 8bс
9a + 9bс
10a + 10bс
12d
14a + 14be
16f
17f
24a + 24b
25a + 25b
27a + 27bg
a LP stands for light petroleum.
b Found (%): S, 17.11. C20H19NS2O2. Calculated (%): S, 17.34.
c For the mixture of isomers 8—10.
d Found (%): S, 23.39. C15H17NS2. Calculated (%): S, 23.27.
e Found (%): S, 25.38. C13H17NS2. Calculated (%): S, 25.49.
f For the mixture of isomers 14a and 14b.
g Found (%): S, 25.50. C13H15NS2. Calculated (%): S, 25.70.
127.0 (CAr(4)); 129.1, 130.2 (CAr(2), CAr(3), CAr(5), CAr(6));
135.5 (CAr(1)). 14N NMR of compounds 10a and 10b (CDCl3),
δ: –277.1.
the protons H2(4), H2(5), and aromatic protons overlap with
signals for compound 14b. 1H NMR of compound 14b (CDCl3),
δ: 0.97 (t, 3 H, CH3, J = 7.2 Hz); 1.30—1.67 (m, 5 H, H(3),
H2(4), H2(5),); 1.88 (m, 1 H, H(3)); 3.06 (dd, 1 H, HCSCN,
2J1,1 = 12.7 Hz, J1,2 = 7.6 Hz); 3.29 (dd, 1 H, HCSCN,
2J1,1 = 12.7 Hz, J1,2 = 4.9 Hz); 3.34 (m, 1 H, HCSPh); 7.2—7.6
(m, 5 H, Ar). 13C NMR of compound 14a (CDCl3+CCl4), δ:
13.8 (C(6)); 22.1 (C(5)); 28.8 (C(4)); 33.1 (C(3)); 40.2 (C(1));
50.3 (C(2)); 109.3 (SCN); 127.3 (CAr(4)); 129.4 (CAr(2), CAr(6));
130.7 (CAr(3), CAr(5)); 134.3 (CAr(1)). 13C NMR of compound
14b (CDCl3+CCl4), δ: 13.9 (C(6)); 22.4 (C(5)); 28.9 (C(4));
32.0 (C(3)); 39.3 (C(1)); 48.6 (C(2)); 110.7 (SCN); 128.2
(CAr(4)); 129.4 (CAr(2), CAr(6)); 133.1 (CAr(3), CAr(5)); 132.7
(CAr(1)).
transꢀ6ꢀPhenylthioꢀ5ꢀthiocyanatocyclooctene (12). 1H NMR
(CDCl3), δ: 1.94 (m, 1 H, CHꢀframework); 2.06—2.66 (m, 7 H,
CHꢀframework); 3.58 (td, 1 H, HCSPh or HCSCN, J = 8.4 Hz,
J = 3.5 Hz); 3.91 (td, 1 H, HCSCN or HCSPh, J = 8.1 Hz,
J = 3.7 Hz); 5.72 (m, 2 H, H(1), H(2)); 7.25—7.35 (m, 5 H, Ar).
13C NMR (CDCl3), δ: 24.3, 24.5, 33.3, 34.4 (C(3), C(4), C(7),
C(8)); 51.7, 54.8 (CSPh, CSCN); 113.4 (SCN); 128.0 (CAr(4));
129.2 (C(1) or C(2)); 129.3 (CAr(2), CAr(6)); 130.2 (C(2) or C(1));
132.4 (CAr(3), CAr(5)); 134.0 (CAr(1)).
A mixture of 1ꢀphenylthioꢀ2ꢀthiocyanatohexane (14a) and
2ꢀphenylthioꢀ1ꢀthiocyanatohexane (14b). 1H NMR of compound
14a (CDCl3), δ: 0.94 (t, 3 H, CH3, J = 7.2 Hz); 1.75, 2.08 (both
m, 1 H each, H2(3)); 3.21 (m, 1 H, HCSCN); 3.23 (dd, 1 H,
CHSPh, 2J1,1 = 13.2 Hz, J1,2 = 8.0 Hz); 3.40 (dd, 1 H, CHSPh,
2J1,1 = 13.2 Hz, J1,2 = 4.6 Hz); 7.2—7.6 (m, 5 H, Ar). Signals for
1ꢀPhenylꢀ2ꢀphenylthioꢀ1ꢀthiocyanatoethane (16). 1H NMR
2
(CDCl3), δ: 3.62 (dd, HCSPh, J2,2 = 14.0 Hz, J2,1 = 9.0 Hz);
2
3.70 (dd, HCSPh, J2,2 = 14.0 Hz, J2,1 = 6.6 Hz); 4.48 (dd,
HCSCN, J1,2 = 9.0 Hz, J1,2 = 6.6 Hz); 7.25—7.50 (m, 10 H, Ar).

Thiocyanatoalkyl phenyl sulfides
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1779
Table 5. Mass spectrometric characteristics of compounds 8—10, 14, 16, 17, 20, 21, 24, 25
Comꢀ
pound
Principal peaks in the MS, m/z (Irel (%))
8a + 8b
9a + 9b
261 [M + 2]+ (1.2); 260 [M + 1]+ (2.2); 259 [M]+ (12.5); 202 (21); 201 (100); 194 (22); 193 (100); 135 (85);
134 (33); 123 (27); 116 (54); 109 (44); 92 (22); 91 (100); 77 (28); 66 (41); 65 (65); 51 (27); 45 (22); 39 (37)
261 [M + 2]+ (10); 260 [M + 1]+ (18); 259 [M]+ (97); 201 (94); 136 (20); 135 (28); 123 (34); 117 (23); 110 (21);
109 (35); 92 (37); 91 (100); 77 (27); 72 (53); 66 (22); 65 (71); 51 (27)
261 [M + 2]+ (8); 260 [M + 1]+ (14); 259 [M]+ (78); 202 (21); 201 (100); 168 (11); 135 (21); 123 (52); 117 (38);
116 (24); 110 (31); 109 (34); 92 (41); 91 (100); 77 (26); 66 (22); 65 (72); 51 (25); 45 (27); 39 (37)
10a + 10b 261 [M + 2]+ (13); 260 [M + 1]+ (21); 259 [M]+ (100); 258 (16); 193 (18); 181 (18); 150 (25); 136 (29); 117 (45);
116 (25); 110 (20); 91 (85); 72 (58); 65 (25)
14а + 14b 253 [M + 2]+ (8); 252 [M + 1]+ (13); 251 [M]+ (77); 193 (28); 179 (52); 135 (12); 123 (100); 110 (54); 109 (31);
83 (30); 69 (16); 55 (25)
253 [M + 2]+ (5); 252 [M + 1]+ (8); 251 [M]+ (54); 193 (23); 179 (18); 123 (100); 110 (23); 109 (21); 83 (35);
55 (19)
16
273 (2) [M + 2]+; 272 (4) [M + 1]+; 271 [M]+•(20); 148 (51); 135 (13); 123 (100); 121 (12); 109 (15); 104 (18);
103 (17); 78 (12); 77 (21)
17
20
21
273 (2) [M + 2]+; 272 (2) [M + 1]+; 271 [M]+•(18); 148 (51); 123 (100); 109 (17); 104 (20); 103 (20); 77 (25)
287 [M + 2]+ (0.7); 286 [M + 1]+ (1.2); 285 [M]+ (6.5); 199 (24); 137 (100); 117 (14); 115 (10); 109 (13)
317 [M + 2]+ (0.1); 316 [M + 1]+ (0.2); 315 [M]+ (1.2); 257 (4.5); 256 (21.5); 255 (5); 230 (16); 229 (100); 207
(11); 206 (67); 178 (17); 172 (12); 148 (62); 147 (28,5); 137 (30); 121 (17); 109 (19); 91 (17); 77 (22); 65 (15)
24а + 24b 235 [M + 2]+ (0.4); 234 [M + 1]+ (0.9); 233 [M]+ (6.2); 174 (100); 173 (69); 147 (27); 140 (32); 109 (23); 97 (25)
25a
249 [M + 2]+ (4); 248 [M + 1]+ (6); 247 [M]+ (39); 188 (38); 161 (31); 155 (10); 137 (28); 110 (100); 109 (46);
84 (22); 79 (90); 78 (68); 77 (62)
249 [M + 2]+ (3); 248 [M + 1]+ (4,5); 247 [M]+ (31); 188 (24); 137 (36); 136 (51); 135 (31); 111 (25); 110 (100);
109 (40); 79 (94); 78 (48); 77 (59)
25b
13C NMR (CDCl3), δ: 39.9 (C(1)); 52.4 (C(2)); 111.3 (SCN);
127.6 (C(4) SPh group); 127.9 (C(3), C(5) Ph group); 129.2,
129.4 (C(2), C(6) SPh group and Ph group); 129.5 (C(4)
Ph group); 131.2 (C(3), C(5) SPh group); 133.6 (C(1) SPh
group); 136.4 (C(1) Ph group).
J3,4 = 5.7 Hz, J3,1 J3,2 J3,5 = 2.1 Hz); 5.84 (ddd, 1 H, H(2),
J2,1 = 5.5 Hz, J2,3 = 2.1 Hz, J2,5 = 1.7 Hz); 6.08 (ddd, 1 H, H(1),
J1,2 = 5.5 Hz, J1,5 = 2.3 Hz, J1,3 = 2.1 Hz); 7.20—7.45 (m, 5 H,
Ar). 1H NMR of compound 24b (CDCl3), δ: 3.07 (ddq, 1 H,
2
H(5), J5,5´ = 17.8 Hz, J5,4 = 8.2 Hz, J5,1 J5,2 J5,3 2.2 Hz); 3.91
(1R*,2R*)ꢀ1ꢀIsothiocyanatoꢀ1ꢀphenylꢀ2ꢀphenylthiopropane
(20). Rf 0.30 (light petroleum—ethyl acetate (5 : 1)). 1H NMR
(CDCl3), δ: 1.28 (d, 3 H, CH3, J3,2 = 6.9 Hz); 3.57 (qd, 1 H,
HCSPh, J2,3 = 6.9 Hz, J2,1 = 3.5 Hz); 4.98 (d, 1 H, HCNCS,
J1,2 = 3.5 Hz); 7.20—7.50 (m, 10 H, Ar). 13C NMR (CDCl3), δ:
14.3 (C(3); 51.1 (CSPh); 64.6 (CNCS); 126.2, 127.2, 127.5,
128.7, 129.1, 129.4, 132.5, 133.3 (Ar). IR, ν/cm–1: 2100 (NCS).
(1R*,2R*)ꢀ1ꢀIsothiocyanatoꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀ2ꢀpheꢀ
nylthiopropane (21). Rf 0.83 (light petroleum—ethyl acetate
(3 : 1)). 1H NMR (CDCl3), δ: 1.28 (d, 3 H, CH3, J3,2 = 6.9 Hz);
3.49 (qd, 1 H, HCSPh, J2,3 = 6.9 Hz, J2,1 = 3.8 Hz); 3.82 (s, 3 H,
OCH3); 4.87 (d, 1 H, HCNCS, J1,2 = 3.8 Hz); 6.85 (d, 2 H, Ar,
J = 6.7 Hz); 7.11 (d, 2 H, Ar, J = 6.7 Hz); 7.30—7.40 (m, 3 H,
Ar); 7.52 (m, 2 H, Ar). 13C NMR (CDCl3), δ: 14.5 (CH3); 51.2
(CSPh); 55.2 (OCH3); 64.2 (CNCS); 114.0 (C(3), C(5) Ar
group); 127.5 (C(2), C(6) Ar group); 128.0 (C(4) SPh group);
129.2 (C(2), C(6) SPh group); 133.3 (C(3), C(5) SPh group);
133.8 (C(1) Ar group); 134.4 (C(1) SPh group); 159.5 (C(4) Ar
group). IR, ν/cm–1: 2090 (NCS).
(ddd, 1 H, HCSPh, J4,5 = 8.2 Hz, J4,3 = 4.5 Hz, J4,5´ = 3.8 Hz);
5.75 (dq, 1 H, H(2), J2,1 = 5.7 Hz, J2,3 = J2,5 = J2,5´ = 2.2 Hz);
6.04 (dtd, 1 H, H(1), J1,2 = 5.7 Hz, J1,5 = J1,5´ = 2.2 Hz,
J1,3 = 1.6 Hz). The signal for the protons H(5´) (δ 2.45) and
HCNSC (δ 4.65), as well as the signals for the aromatic protons
overlap with signals for compound 24a. 13C NMR of compound
24a (CDCl3), δ: 39.9 (C(4)); 51.1 (CSPh); 60.8 (CNCS); 127.7
(CAr(4)); 129.1 (CAr(2), CAr(6)); 131.1 (C(1) or C(2)); 132.6
(CAr(3), CAr(5)); 133.7 (CAr(1)); 136.5 (C(2) or C(1)). 14N NMR
of compounds 23a and 23b (CDCl3), δ: –274.4.
A mixture of transꢀ3ꢀisothiocyanatoꢀ6ꢀphenylthiocyclohexene
(25a) and transꢀ3ꢀisothiocyanatoꢀ4ꢀphenylthiocyclohexene (25b).
1H NMR of compound 25a (CDCl3), δ: 1.78 (dddd, 1 H, H(5),
2J5,5´ = 13.0 Hz, J5,4´ = 7.3 Hz, J5,6 = 5.0 Hz, J5,4 = 2.5 Hz);
2
1.89 (dddd, 1 H, H(4´), J4,4´ = 13.1 Hz, J4´,5 = 7.3 Hz,
J4´,3 = 5.0 Hz, J4´,5´ = 2.5 Hz); 2.17 (dddd, 1 H, H(5´),
2J5´,5 = 13.0 Hz, J5´,4 = 10.6 Hz, J5´,6 = 5.0 Hz, J5´,4´ = 2.5 Hz);
2
2.26 (dddd, 1 H, H(4), J4,4´ = 13.1 Hz, J4,5´ = 10.6 Hz,
J4,3 = 5.0 Hz, J4,5 = 2.5 Hz); 3.87 (tdt, 1 H, HCSPh, J6,5 J6,5´
= 5.0 Hz, J6,1 = 4.0 Hz, J6,2 = J6,3 = 1.5 Hz); 4.24 (tdt, 1 H,
HCNCS, J3,4 3,4´ = 5.0 Hz, J3,2 = 3.9 Hz, J3,1 = J3,6 = 1.5 Hz);
=
A mixture of transꢀ3ꢀisothiocyanatoꢀ5ꢀphenylthiocyclopentene
(24a) and transꢀ3ꢀisothiocyanatoꢀ4ꢀphenylthiocyclopentene (24b).
1H NMR of compound 23a (CDCl3), δ: 2.44 (ddd, 1 H, H(4´),
2J4´,4 =14.1 Hz, J4´,3 = 7.3 Hz, J4´,5 = 4.5 Hz); 2.48 (ddd, 1 H,
H(4), 2J4,4´ = 14.1 Hz, J4,5 = 6.9 Hz, J4,3 = 5.7 Hz); 4.38 (ddddd,
1 H, HCSPh, J5,4 = 6.9 Hz, J5,4´ = 4.5 Hz, J5,1 = 2.3 Hz,
J5,3 = 2.1 Hz, J5,2 = 1.7 Hz); 4.65 (ddq, 1 H, HCNSC, J3,4´ = 7.3 Hz,
J
5.84 (ddd, 1 H, H(2), J1,2 = 9.8 Hz, J1,3 = 3.9 Hz, J2,6 = 1.5 Hz);
6.03 (ddd, 1 H, H(1), J1,2 = 9.8 Hz, J1,6 = 4.0 Hz, J1,3 = 1.5 Hz);
1
7.3—7.5 (m, 5 H, Ar). H NMR of compound 25b (CDCl3), δ:
3.36 (ddd, 1 H, HCSPh, J4,5´ = 9.6 Hz, J4,3 = 6.9 Hz, J4,5 = 2.9 Hz);
4.18 (ddq, 1 H, HCNCS, J3,4 = 6.9 Hz, J3,2 = 3.2 Hz, J3,1 J3,6

1780
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
Zyk et al.
J
3,6´ = 1.8 Hz); 5.67 (ddt, 1 H, H(2), J2,1 = 9.9 Hz, J2,3 = 3.2 Hz,
4. A. K. Mukerjee, R. Ashare, Chem. Rev., 1991, 91, 1.
J2,6 J2,6´ = 2.0 Hz); 5.92 (dtd, 1 H, H(1), J1,2 = 9.9 Hz, J1,6
=
5. G. H. Posner, Ch.ꢀG. Cho, J. V. Green, J. Med. Chem.,
1994, 37, 170.
= J1,6´ = 3.8 Hz, J1,3 = 1.8 Hz). The signals for the protons
H2C(5), H2C(6), and aromatic protons overlap with signals for
the protons of compound 25b. 13C NMR of compound 25a
(CDCl3), δ: 25.0, 27.1 (C(4), C(5)); 42.9, 51.5 (CSPh, CNCS);
126.7 (CAr(4)); 127.5 (C(1) or C(2)); 129.1 (CAr(2), CAr(6));
131.4 (C(2) or C(1)); 132.1 (CAr(3), CAr(5)); 134.3 (CAr(1)).
13C NMR of compound 25b (CDCl3), δ: 23.8, 27.0 (C(5), C(6));
49.2 (CSPh); 56.9 (CNCS); 123.8 (C(1) or C(2)); 128.1 (CAr(4));
129.2 (CAr(2), CAr(6)); 130.9 (C(2) or C(1)); 133.6 (CAr(3),
CAr(5)).
6. E. Elhalem, B. N. Bailey, R. Docampo, I. Ujváry, S. H.
Szajnman, J. B. Rodriguez, J. Med. Chem., 2002, 45, 3984.
7. T. Marsman, Chem. Zeitung, 1972, 96, 288.
8. E. V. Van Der Berghe, G. P. Van Der Kelen, J. Organomet.
Chem., 1974, 82, 345.
9. M. Witanowski, L. Stefaniak, G. A. Webb, in Annual Reports
on NMR Spectroscopy, 7, Ed. G. A. Webb, Academic Press,
London, 1977, 117.
10. L. J. Bellamy, The InfraꢀRed Spectra of Complex Molecules,
J. Wiley and Sons, NewꢀYork, 1957.
A mixture of Eꢀ4ꢀphenylthioꢀ3ꢀthiocyanatohexꢀ3ꢀene (27a)
1
and Zꢀ4ꢀphenylthioꢀ3ꢀthiocyanatohexꢀ3ꢀene (27b). H NMR of
11. G. C. Levy, G. L. Nelson, Carbonꢀ13 Nuclear Magnetic
Resonance for Organic Chemists, J. Wiley and Sons, Chichesꢀ
ter—New York—London—Sydney—Toronto, 1972.
12. D. G. Garrat, Can. J. Chem., 1979, 57, 2180.
13. A. J. Gordon, R. A. Ford, The Chemist´s companion,
A WileyꢀInterscience publication, John Wiley and Sons,
New York—London—Sydney—Toronto, 1972.
14. N. S. Zefirov, I. V. Bodrikov, Zh. Org. Khim., 1983, 19, 2225
[J. Org. Chem. USSR (Engl. Transl.), 1983, 19].
15. A. O. Chizhov, N. S. Zefirov, N. V. Zyk, T. C. Morrill,
J. Org. Chem., 1987, 52, 5647.
16. H. Gunter, NMR Spectroscopy. An Introduction, J. Wiley and
Sons, Chichester—New York—Brisbane—Toronto, 1980.
17. I. V. Koval´, Usp. Khim., 1995, 64, 781 [Russ. Chem. Rev.
(Engl. Transl.), 1995, 64].
18. G. H. Schmid, V. M. Csizmadia, V. J. Nowlan, D. G. Garꢀ
ratt, Can. J. Chem., 1972, 50, 2457.
19. G. H. Schmid, D. G. Garratt, Tetrahedron, 1978, 34, 2869.
20. B. M. Trost, S. D. Ziman, J. Org. Chem., 1973, 38, 932.
21. D. G. Garratt, M. D. Ryan, M. Ujjainwalla, Can. J. Chem.,
1979, 57, 2145.
22. F. G. Cocu, G. Wolczunowicz, L. Bors, Th. Posternak, Helv.
Chim. Acta, 1970, 53, 739.
23. K. Hartke, H.ꢀU. Gleim, Liebigs Ann. Chem., 1976, 716.
24. E. K. Beloglazkina, M. A. Belova, R. L. Antipin, N. V. Zyk,
A. K. Buryak, Zh. Org. Khim., 2003, 39, 549 [Russ. J. Org.
Chem. (Engl. Transl.), 2003, 39].
25. H. Gunter, G. Jikeli, Chem. Rev., 1977, 77, 599.
26. O. Korver, T. L. Kwa, C. Boelhouwer, Tetrahedron, 1968,
24, 1025.
compound 27a (CDCl3), δ: 1.02 (t, 3 H, CH3, J = 7.4 Hz); 1.24
(t, 3 H, CH3, J = 7.4 Hz); 2.35 (q, 2 H, CH2, J = 7.4 Hz); 2.90
(q, 2 H, CH2, J = 7.4 Hz); 7.25—7.40 (m, 5 H, Ar). 1H NMR of
compound 27b (CDCl3), δ: 1.03 (t, 3 H, CH3, J = 7.4 Hz); 1.15
(t, 3 H, CH3, J = 7.4 Hz); 2.30 (q, 2 H, CH2, J = 7.4 Hz); 2.66
(q, 2 H, CH2, J = 7.4 Hz). The signals for the aromatic protons
overlap with signals for the protons of compound 27a. 13C NMR
of compound 27a (CDCl3), δ: 12.9, 13.0 (C(1), C(6)); 27.9, 29.1
(C(2), C(5)); 110.1 (SCN); 127.0 (C(3)); 127.7 (CAr(4)); 129.3
(CAr(2), CAr(6)); 131.6 (CAr(3), CAr(5)); 133.0 (CAr(1)); 143.0
(C(4)). 13C NMR of compound 27b (CDCl3), δ: 12.1, 13.1 (C(1),
C(6)); 26.5, 27.7 (C(2), C(5)); 127.1; 129.1; 130.1; 144.8.
Isomerization of 1ꢀphenylꢀ2ꢀphenylthioꢀ1ꢀthiocyanatoethane
(16). Compound 16 (0.2 g, 0.7 mmol) was dissolved in CHCl3
(5 mL) and kept at room temperature for 7 days. The solvent was
evaporated on a rotary evaporator to obtain a mixture of the
starting 16 (59%) and 1ꢀisothiocyanatoꢀ1ꢀphenylꢀ2ꢀphenylthioꢀ
ethane (17) (41%). 1H NMR of compound 17 (CDCl3), δ: 3.34
(dd, CHSPh, 2J2,2 = 13.9 Hz, J2,1 = 7.9 Hz); 3.38 (dd, CHSPh,
2J2,2 = 13.9 Hz, J2.1 = 5.8 Hz); 4.84 (dd, CHNCS, J1,2 = 7.9 Hz,
J1,2 = 5.8 Hz); 7.25—7.63 (m, 10 H, Ar). 13C NMR of comꢀ
pound 17 (CDCl3), δ: 43.4 (C(1)); 61.1 (C(2)); 126.1 (C(3), C(5)
Ph group); 127.4 (C(4) SPh group); 128.8 (C(4) Ph group); 129.0
(C(2), C(6) SPh group); 129.4 (C(2), C(6) Ph group); 131.1
(C(3), C(5) SPh group); 133.2 (NCS); 134.2 (C(1) SPh group);
137.6 (C(1) Ph group). Compound 17 was not isolated in the
individual state and was characterized in the mixture with comꢀ
pound 16.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00707ꢀa)
and the Russian Academy of Sciences (the Program of
RAS "Theoretical and Experimental Study of the Nature
of Chemical Bond and Chemical Processes").
27. N. V. Zyk, E. K. Beloglazkina, M. A. Belova, N. S. Zefirov,
Izv. Akad. Nauk, Ser. Khim., 2000, 1874 [Russ. Chem. Bull.,
Int. Ed., 2000, 49, 1846].
28. N. V. Zyk, E. K. Beloglazkina, M. A. Belova, S. V. Zatonsky,
N. S. Zefirov, Phosphorus, Sulfur, Silicon, Relat. Elem., 2002,
177, 555.
29. G. H. Schmid, A. Modro, F. Lenz, D. G. Garratt, K. Yates,
J. Org. Chem., 1976, 41, 2331.
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Received October 22, 2009;
in revised form May 14, 2010