New method of synthesis of β-haloalkyl alkynyl sulfides: Reaction of alkynesulfenamides with olefins in the presence of phosphoryl halides

Article abstract of DOI:10.1007/s11178-005-0276-x

Reactions of alkynelsufenamides with olefins (such as cyclohexene, norbornene, 1-hexene, 1-octene, allylbenzene, and styrene) in the presence of phosphoryl halides (POCl₃, POBr₃) afforded 70-95% of β-halo-substituted alkyl alkynyl sulfides. The reactions with cyclohexene and norbornene are characterized by trans stereoselectivity. Alkynylsulfenylation of terminal alkyl- and benzylacetylenes occurs in a regioselective fashion with predominant formation of the corresponding anti-Markownikoff adducts, while the addition to styrene yields halogen-containing sulfides according to the Markownikoff rule.

Full text of DOI:10.1007/s11178-005-0276-x

Russian Journal of Organic Chemistry, Vol. 41, No. 7, 2005, pp. 956–961. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005,
pp. 977–982.
Original Russian Text Copyright © 2005 by Beloglazkina, Belova, Dubinina, Garkusha, Buryak, Zyk.
New Method of Synthesis of β-Haloalkyl Alkynyl Sulfides:
Reaction of Alkynesulfenamides with Olefins
in the Presence of Phosphoryl Halides
E. K. Beloglazkina1, M. A. Belova1, N. S. Dubinina1, I. A. Garkusha1,
A. K. Buryak2, and N. V. Zyk1
1 Faculty of Chemistry, Lomonosov Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
fax: +7(095)9390290; e-mail: bel@org.chem.msu.su
2 Institute of Physical Chemistry, Russian Academy of Sciences, Leninskii prospect, Moscow, 119991 Russia
Received September 24, 2003
Abstract—Reactions of alkynelsufenamides with olefins (such as cyclohexene, norbornene, 1-hexene,
1-octene, allylbenzene, and styrene) in the presence of phosphoryl halides (POCl3, POBr3) afforded 70–95% of
β-halo-substituted alkyl alkynyl sulfides. The reactions with cyclohexene and norbornene are characterized by
trans stereoselectivity. Alkynylsulfenylation of terminal alkyl- and benzylacetylenes occurs in a regioselective
fashion with predominant formation of the corresponding anti-Markownikoff adducts, while the addition to
styrene yields halogen-containing sulfides according to the Markownikoff rule.
At present, the most thoroughly studied and widely
used method for halosulfenylation of unsaturated com-
pounds is classical addition of sulfenyl halides (see,
e.g., reviews [1, 2]). However, a considerable disad-
vantage of this procedure is very low stability of
sulfenyl chlorides and especially sulfenyl bromides.
Arenesulfenyl chlorides usually add to alkenes to give
the corresponding products in preparative yields, reac-
tions with alkanesulfenyl halides result mainly in
decomposition of the reagent, while compounds like
ethene- and alkynesulfenyl chlorides were not reported
previously. Therefore, the application of direct chloro-
and bromosulfenylation of alkenes and alkynes for
preparative purposes is limited almost exclusively to
arenesulfenylation reactions.
as sulfenamides are considerably more stable that the
corresponding sulfenyl chlorides, the initial reactants
do not undergo decomposition during the process, and
the desired halogen-containing aryl, alkyl, and vinyl
sulfides can be obtained in high yields under mild
conditions.
In the present work we made an attempt to extend
the developed approach to the synthesis of β-halo-
substituted alkyl alkynyl sulfides. These compounds
attract interest from the viewpoint of their further
chemical modification at various functional groups
present therein. For example, the sulfur(II) atom
readily undergo oxidation, the triple C≡C bond may be
involved in electrophilic, nucleophilic, and radical ad-
dition reactions, and the halogen atom in the β-position
with respect to the alkynylsulfanyl group can be re-
placed by various nucleophiles.
We previously developed new procedures for elec-
trophilic aryl- [3], alkyl- [4], and vinylsulfenylation [5]
of unsaturated compounds with sulfenamides in the
presence of phosphoryl halides (POCl3, POBr3). As far
The known synthetic approaches to alkynyl sulfides
include the following ones: elimination of HX or XX
Scheme 1.
R
X
H
R
X
X
RS
H
SR
H
Base
(1) BuLi; (2) R'Hlg
or
a
c
SR'
SR'
R
SR'
(1) S8; (2) R'Hlg
R
C
C
Hlg
+
R'S–
R
C
C–
b
d
1070-4280/05/4107-0956 © 2005 Pleiades Publishing, Inc.

NEW METHOD OF SYNTHESIS OF β-HALOALKYL ALKYNYL SULFIDES:
957
species from halo-substituted sulfides (Scheme 1,
path a; see, e.g., [6–10]); nucleophilic substitution at
sp-hybridized carbon atom by the action of sulfur-con-
taining nucleophiles (path b) [11]; splitting of 1,2-bis-
(organylsulfanyl)ethylenes with butyllithium (path c)
[12, 13]; and reactions of metal acetylides with
elemental sulfur or sulfur-containing compounds (d)
[14, 15]. Some specific syntheses of optically active
alkynyl sulfides [16] and those possessing unusual
electronic properties [17] or used as ligands for the
preparation of metal complexes [18] have also been
reported. We can conclude that all known methods
for building up an S–C≡C fragment are based on
elimination processes or substitution reactions leading
to formation of a bond between sulfur atom and sp-
hybridized carbon atom. Therefore, the procedure
proposed by us for electrophilic introduction of
a R–C≡C–S fragment may be regarded as a new ap-
proach to alkynyl sulfides.
(phosphoryl halide) at the sulfur atom, generation of
electrophilic species (sulfonium salt) by replacement
of one halogen atom at the phosphorus, electrophilic
addition of this species at the double C=C bond, and
nucleophilic attack by halide ion (abstracted from the
phosphoryl halide) to give trans-1,2-halosulfenylation
product (Scheme 4).
Scheme 4.
R
C
C
SNR2'
+
POHlg3
R
C
C
SNR2'
Hlg
Hlg
Hlg
I, II
P
O
R
C
C
Hlg
S
P
NR2' Hlg–
O
Hlg
III–XVII
'
–Hlg2P(O)NR2
We examined reactions of alkynesulfenamides I
and II with olefins in the presence of phosphoryl
halides. The reactions were carried out under mild
conditions (CH2Cl2, –40°C), and in most cases the
products were the corresponding β-haloalkyl alkynyl
sulfides which were formed in high yields (Scheme 2).
The structure of the products was confirmed by the
1H NMR and mass spectra. Using the reactions with
norbornene and cyclohexene as examples (Scheme 5),
we showed that the process is characterized by trans
stereoselectivity. The trans configuration of com-
pounds VI–VIII directly follows from the coupling
constant between the HCS and HCHlg protons (3J =
3.7–4.2 Hz), which corresponds to trans interaction
[21]. The configuration of cyclohexane derivatives
III–V was proved by broadening of signals from both
Scheme 2.
R
C
C
SNR2'
+
POHlg3
+
I, II
Hlg
CH2Cl2, –40°C
Scheme 5.
R
C
C
S
I, II
+
POHlg3
+
I, R = Ph; II, R = Bu; Hlg = Cl, Br.
S
Initial N-(2-phenylethynylsulfanyl)morpholine (I)
and N-(1-hexynylsulfanyl)morpholine (II) were pre-
pared by addition of N-(chlorosulfanyl)morpholine to
the corresponding lithium acetylide by analogy with
the procedure described in [19] (Scheme 3).
CH2Cl2, –40°C
C
CR
Hlg
III–V
Scheme 3.
I, II
+
POHlg3
+
O
N
SCl
+
R
C
C
Li
I, II
S
CH2Cl2, –40°C
C
CR
Sulfenamides are weak electrophiles which are in-
capable of adding at multiple bonds without additional
activation. Presumably, the reaction mechanism is
analogous to that proposed previously for arenesul-
fenamides [20]; it includes coordination of Lewis acid
Hlg
VI–VIII
III, VI, R = Ph, Hlg = Cl; IV, VII, R = Bu, Hlg = Cl;
V, VIII, R = Bu, Hlg = Br.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

BELOGLAZKINA et al.
958
protons in positions 1 and 2 in going from more polar
solvent (CDCl3) to less polar (C6D6) (W-criterion [22]).
power of phosphoryl halides with those of thio-
phosphoryl chloride and phosphorus(III) bromide
(Scheme 8). In the presence of PSCl3 and PBr3, the
products were chloro- and bromo-substituted sulfides
VII and VIII, respectively, but their yields were lower
than in the reactions activated by POCl3 and POBr3.
Different regioselectivities were observed in the
addition to alkyl- and arylethenes. The major products
obtained from alkylethenes (1-hexene, 1-octene, and
allylbenzene) were the corresponding anti-Markowni-
koff adducts IXb–XIVb (Scheme 6). Presumably, the
reaction direction is determined by steric factors
operating in the second stage of the AdE reaction, i.e.,
Scheme 8.
II, PSCl3
II, PBr3
1
VII, 40%
VIII, 47%
addition of halide ion. According to the H NMR
spectra of the products recorded in CDCl3 in 1, 7, and
30 days after isolation, the ratio a:b decreases. This
means that Markownikoff adducts IXa–XIVa undergo
partial isomerization into anti-Markownikoff adducts
IXb–XIVb. Obviously, as in the arylsulfenylation
reactions [23–25], compounds IXb–XIVb are thermo-
dynamically controlled products (the a:b ratios given
in Scheme 6 refer to the products immediately after
isolation).
The structure of compounds III, IV, VII–XIV, and
XVI was confirmed by mass spectrometry. All these
compounds showed in the mass spectra the molecular
ion peak with a relative intensity of 11 to 100%. The
molecular ion was the most abundant for phenyl-
ethynyl sulfides. Primary fragmentation of the molec-
ular ion of halogenated sulfides III, IV, VII–XIV, and
XVI includes mainly elimination of the R–C≡C–SH
molecule or R–C≡C–S fragment (R = Ph, Bu) with
formation of ions with m/z 113 (IV), 114 (VII–XI, R =
Bu), 133 (XII, XIII), or 134 (III, R = Ph). In the mass
spectra of some compounds (VII, VIII, XIII), [M –
R–C≡C–S]+ ion peaks were observed; but in most
cases, this ion undergoes further fragmentation to give
smaller hydrocarbon ions (C3H5, C5H9, C5H11, C6H5,
C7H7). Bromine-containing sulfide VIII also showed
a fairly intense [M – R–C≡C–S – H]+ ion peak with
m/z 173. The isotope peak ratios were consistent with
the assumed structures.
Scheme 6.
I, II
+
POHlg3
+
R'CH=CH2
R
R'
Hlg
CH2Cl2, –40°C
R'
S
+
S
Hlg
IXa–XIVa
R
IXb–XIVb
IX, XIII, R = Ph, R' = Bu, Hlg = Cl; X, R = Ph, R' = C6H13,
Hlg = Cl; XI, R = Bu, R' = C6H13, Hlg = Cl; XII, R = Bu,
R' = C6H13, Hlg = Br; XIV, R = Bu, R' = Bu, Hlg = Cl.
IXa:IXb = 1:6, Xa:Xb = 1:5, XIa:XIb = 1:2, XIIa:XIIb =
2:5, XIIIa:XIIIb = 1:3, XIVa:XIVb = 1:2.
Thus alkynylsulfenylation of alkenes by the action
of alkynesulfenamides in the presence of phosphoryl
halides provides a convenient method for the prepara-
tion of β-halo-substituted alkyl alkynyl sulfides. Phos-
phoryl halide-activated sulfenylation of unsaturated
compounds may be regarded as general synthetic
approach to substituted aryl, alkyl, vinyl, and alkynyl
sulfides.
By contrast, the reactions of I and II with styrene
afforded almost exclusively the corresponding Mar-
kownikoff adducts XV–XVII (Scheme 7), i.e., in this
case the regioselectivity of the process is determined
by stabilization of intermediate cation.
Using the reaction of sulfenamide II with nor-
bornene as an example, we compared the activating
EXPERIMENTAL
Scheme 7.
The NMR spectra were recorded on a Varian VXR-
400 spectrometer from solutions in CDCl3. The prog-
ress of reactions and the purity of products were
monitored by chromatography. The mass spectra were
obtained on a JMS-D300 mass spectrometer coupled
with a JMA-2000 computer and an HP 5890 gas
chromatograph; the scan rate was varied from 1 to 2 s
in the mass range from 10 to 300 a.m.u or from 40
to 450 a.m.u.; total ion current chromatograms were
I, II
+
POHlg3
+
PhCH=CH2
R
CH2Cl2, –40°C
Ph
S
Hlg
XV–XVII
XV, R = Ph, Hlg = Cl; XVI, R = Bu, Hlg = Cl;
XVII, R = Bu, Hlg = Br.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

NEW METHOD OF SYNTHESIS OF β-HALOALKYL ALKYNYL SULFIDES:
959
recorded; ion source temperature 150°C, energy of
ionizing electrons 70 eV, accelerating voltage 3 kV.
230 (100) M+, 113 (96) [BuC≡CS]+, 80 (98) [C4H4]+,
71 (98) [C5H11]+, 55 (89) [C4H7]+, 41 (100) [C3H5]+.
trans-1-Bromo-2-(1-hexynylsulfanyl)cyclo-
hexane (V). Yield 85%, Rf 0.85. H NMR spectrum,
N-(Chlorosulfanyl)morpholine was prepared from
N,N'-disulfanyldimorpholine and sulfuryl chloride by
the procedure described in [26]; lithium acetylides
were prepared from phenylacetylene or 1-hexyne and
n-butyllithium as described in [27]. Alkynesulfen-
amides were synthesized by adding at –10°C a freshly
prepared suspension of the corresponding lithium
acetylide to a solution of N-(chlorosulfanyl)morpho-
line in dry hexane (cf. [19]).
1
δ, ppm: 4.33 d.d (HCHlg, J1 = 9.2, J2 = 5.7 Hz),
3.58 d.d (HCS, J1 = 10.2, J2 = 5.7 Hz), 2.23 t (2H,
CH2C≡, J = 7.4 Hz), 1.95–1.20 m (12H), 0.90 t (3H,
CH3, J = 7.2 Hz).
endo-2-Chloro-exo-3-(2-phenylethynylsulfanyl)-
bicyclo[2.2.1]heptane (VI). Yield 80%, Rf 0.82.
1H NMR spectrum, δ, ppm: 7.43–7.24 m (Harom),
4.18 d.d.d (HCHlg, J1,2 = 4.0, J2,3 = 4.0, J2,exo-6
=
N-(2-Phenylethynylsulfanyl)morpholine (I).
1H NMR spectrum, δ, ppm: 7.43 m (2H), 7.30 m (3H),
3.73 m (4H, CH2O), 3.00 m (4H, CH2N). 13C NMR
spectrum, δC, ppm: 131.39, 128.60, 128.33 (Carom);
112.72, 107.97 (C≡); 67.27 (C–O); 55.53 (C–N).
1.8 Hz), 3.02 d.d (HCS, J2,3 = 3.7, J3,anti-7 = 2.7 Hz),
2.40 d (J4,5 = 4.2 Hz), 2.1 t (J1,2 = 4.0, J1,6 = 4.0 Hz),
2.00 d.d.d.d (endo-6-H, J1 = 13.1, J2 = 8.8, J3 = 4.0,
J4 = 2.5 Hz), 1.90 d.d.d (syn-7-H, J1 = 11.0, J2 = 2.5,
J3 = 2.5 Hz), 1.72 d.d.d (exo-6-H, J1 = 13.1, J2 = 6.4,
J3 = 4.6), 1.53–1.33 m (3H).
1
N-(1-Hexynylsulfanyl)morpholine (II). H NMR
spectrum, δ, ppm: 3.72 m (4H, CH2O), 2.91 m (4H,
CH2N), 2.45 t (2H, CH2C≡, J = 6.8 Hz), 1.60–1.26 m
(4H), 0.86 m (3H, CH3, J = 7.0 Hz). 13C NMR spec-
trum, δC, ppm: 110.07, 99.53 (C≡), 69.53 (C–O), 54.13
(C–N), 30.80, 21.94, 20.08, 13.54.
endo-2-Chloro-exo-3-(1-hexynylsulfanyl)bicyclo-
[2.2.1]heptane (VII). Yield 84%, Rf 0.86. H NMR
1
spectrum, δ, ppm: 4.07 d.d.d (HCHlg, J2,1 = 4.0, J2,3
=
4.0, J2,exo-6 = 1.9 Hz), 3.02 d.d (HCS, J2,3 = 4.0,
J3,anti-7 = 2.7 Hz), 2.47 br.s and 2.32 br.s, 2.30 t
(CH2C≡, J = 7.0 Hz), 1.95 m (2H, endo-5-H, endo-
6-H), 1.85 d.d.d (syn-7-H, J1 = 10.5, J2 = 2.5, J3 =
2.5 Hz), 1.69 m (2H, exo-5-H, exo-6-H), 1.55–1.35 m
(5H), 0.90 t (3H, CH3, J = 7.0 Hz). Mass spectrum, m/z
(Irel, %): 242 (50) M+, 129 (89) [M – BuC≡CS]+, 114
(61) [BuC≡CSH]+, 93 (90) [C7H9]+, 81 (99) [C6H9]+,
67 (100) [C5H7]+, 41 (99) [C3H5]+.
Addition of alkynesulfenamides to olefins in the
presence of phosphoryl halides (general procedure).
A solution of 1 mmol of alkynesulfenamide I or II in
10 ml of dry methylene chloride was cooled to –40°C,
1.5 mmol of the corresponding alkene was added, and
a solution of 1 mmol phosphoryl halide in 5 ml of
methylene chloride was slowly added under stirring at
–40°C. The mixture was allowed to warm up to room
temperature and was stirred until initial sulfenamide
I or II disappeared completely (5–10 h, TLC). The
solvent was removed under reduced pressure, and the
product was purified by chromatography on silica gel
using petroleum ether–chloroform (7:1) as eluent.
endo-2-Bromo-exo-3-(1-hexynylsulfanyl)bicyclo-
1
[2.2.1]heptane (VIII). Yield 95%, Rf 0.85. H NMR
spectrum, δ, ppm: 3.99 d.d.d (HCHlg, J2,1 = 4.2, J2,3
=
4.2, J2,exo-6 = 1.8 Hz), 3.19 d.d (HCS, J2,3 = 4.2,
J3,anti-7 = 3.0 Hz), 2.49 br.s, 2.28 br.s, 2.30 t (CH2C≡,
J = 7.0 Hz), 2.04 m (2H, endo-5-H, endo-6-H),
1.76 d.d.d (syn-7-H, J1 = 10.6, J2 = 2.0, J3 = 2.0 Hz),
1.68 m (2H, exo-5-H, exo-6-H), 1.58–1.47 m (5H),
0.90 t (3H, CH3, J = 7.1 Hz). Mass spectrum, m/z
(Irel, %): 288 (12) M+, 173 (20) [M – BuC≡CS – 2H]+,
114 (19) [BuC≡CSH]+, 93 (100) [C7H9]+, 77 (28)
[C6H5]+, 67 (37) [C5H7]+, 41 (19) [C3H5]+.
2-Chloro-1-(2-phenylethynylsulfanyl)hexane
(IXa) and 1-Chloro-2-(2-phenylethynylsulfanyl)-
hexane (IXb) (mixture of isomers). Yield 83%,
Rf 0.93. 1H NMR spectrum, δ, ppm: IXa: 7.43–7.23 m
(5H, Ph), 4.19 m (HCHlg), 3.19 d.d (HCS, J1 = 13.5,
J2 = 6.1 Hz), 3.02 d.d (HCS, J1 = 13.5, J2 = 7.6 Hz),
2.19–1.06 m (C4H9); IXb: 7.43–7.23 m (5H, Ph),
3.94 d.d (HCHlg, J1 = 11.1, J2 = 4.8 Hz), 3.69 d.d
(HCHlg, J1 = 11.1, J2 = 8.4 Hz), 3.06 m (HCS).
trans-1-Chloro-2-(2-phenylethynylsulfanyl)cyclo-
1
hexane (III). Yield 84%, Rf 0.92. H NMR spectrum,
δ, ppm: 7.20–7.25 (Harom), 4.08 d.d.d (HCHlg, J1 = 9.2,
J2 = 9.2, J3 = 4.2 Hz), 3.04 d.d.d (HCS, J1 = 9.2, J2 =
9.2, J3 = 4.1 Hz), 2.30–1.50 [(CH2)4]. Mass spectrum,
m/z, (Irel, %): 250 (39) M+, 134 (100) [PhC≡CSH]+,
89 (61) [C4H9S]+, 81 (100) [C6H9]+, 53 (24) [C4H5]+,
39 (25) [C3H3]+.
trans-1-Chloro-2-(1-hexynylsulfanyl)cyclohexane
1
(IV). Yield 70%, Rf 0.90. H NMR spectrum, δ, ppm:
4.05 d.d.d (HCHlg, J1 = 13.1, J2 = 13.1, J3 = 8.9 Hz),
2.95 d.d.d (HCS, J1 = 13.0, J2 = 8.9, J3 = 4.2 Hz), 2.30 t
(2H, CH2C≡, J = 6.7 Hz), 1.82–1.23 m (12H); 0.90 t
(3H, CH3, J = 6.6 Hz). Mass spectrum, m/z (Irel, %):
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

BELOGLAZKINA et al.
960
2-Chloro-1-(2-phenylethynylsulfanyl)octane (Xa)
2-Chloro-1-(1-hexynylsulfanyl)-3-phenylpropane
(XIVa) and 1-chloro-2-(1-hexynylsulfanyl)-3-phen-
ylpropane (XIVb) (mixture of isomers). Yield 60%,
and 1-chloro-2-(2-phenylethynylsulfanyl)octane (Xb)
1
(mixture of isomers). Yield 93%, Rf 0.92. H NMR
1
spectrum, δ, ppm: Xa: 7.42–7.26 m (5H, Ph), 4.20 m
(HCHlg), 3.19 d.d (HCS, J1 = 13.4, J2 = 6.3 Hz),
3.03 d.d (HCS, J1 = 13.4, J2 = 7.4 Hz), 2.19–1.06 m
(C4H9); Xb: 7.42–7.26 m (5H, Ph), 3.95 d.d (HCHlg,
J1 = 11.0, J2 = 4.5 Hz), 3.70 d.d (HCHlg, J1 = 11.0,
J2 = 8.4 Hz), 3.09 m (HCS), 2.19–1.06 m (C4H9).
Rf 0.94. H NMR spectrum, δ, ppm: XIVa: 7.50–
7.00 m (Ph), 4.20 m (HCHlg), 3.60 d.d (HCS, J1 =
11.4, J2 = 4.6 Hz), 3.47 d.d (HCS, J1 = 11.4, J2 =
6.3 Hz), 2.35 t (J = 7.0 Hz), 3.17 d.d (J1 = 13.2, J2 =
5.0 Hz), 3.04 d.d (J1 = 13.2, J2 = 7.3 Hz), 2.0–1.0 m
(C3H7); XIVb: 7.50–7.00 m (Ph), 3.85 d.d (HCHlg,
J1 = 11.4, J2 = 4.4 Hz), 3.68 d.d (HCHlg, J1 = 11.4,
J2 = 3.2 Hz), 3.35 m (HCS), 2.32 t (J = 7.0 Hz),
3.35 d.d (J1 = 13.7, J2 = 7.6 Hz), 3.12 d.d (J1 = 13.7,
J2 = 5.8 Hz), 2.0–1.0 m (C3H7). Mass spectrum, m/z
(Irel, %): 266 (32) M+, 117 (79) [C6H5C3H4]+, 91 (100)
[C7H7]+, 81 (29) [C6H9]+, 71 (28) [C5H11]+, 41 (15)
[C3H5]+.
2-Chloro-1-(1-hexynylsulfanyl)octane (XIa) and
1-chloro-2-(1-hexynylsulfanyl)octane (XIb) (mixture
of isomers). Yield 77%, Rf 0.93. 1H NMR spectrum, δ,
ppm: XIa: 3.96 m (HCHlg), 3.29 d.d (HCS, J1 = 13.4,
J2 = 5.9 Hz), 3.03 d.d (HCS, J1 = 13.4, J2 = 6.0 Hz),
2.32 t (J = 6.7 Hz), 2.0–1.1 m (CH2), 0.93 t (CH3, J =
6.9 Hz); XIb: 3.95 d.d (HCHlg, J1 = 11.1, J2 = 4.7 Hz),
3.61 d.d (HCHlg, J1 = 11.1, J2 = 8.7 Hz), 3.38 m
(HCS), 2.30 t (J = 6.7 Hz), 2.0–1.1 m (CH2), 0.90 t
(CH3, J = 6.9 Hz). Mass spectrum, m/z (Irel, %): 260
(11) M+, 114 (29) [BuC≡CSH]+, 81 (100) [C6H5]+, 71
(33) [C5H11]+, 55 (34) [C4H7]+, 41 (44) [C3H5]+.
1-Chloro-1-phenyl-2-(2-phenylethynylsulfanyl)-
1
ethane (XV). Yield 78%, Rf 0.96. H NMR spectrum,
δ, ppm: 7.50–7.20 m (Ph), 4.80 d.d (HCHlg, J1 = 8.6,
J2 = 8.0 Hz), 4.75 d.d (HCHlg, J1 = 8.6, J2 = 6.5 Hz),
5.17 d.d (HCS, J1 = 8.0, J2 = 6.5 Hz). According to the
1H NMR data, the reaction mixture contained about
5% of the corresponding anti-Markownikoff adduct.
2-Bromo-1-(1-hexynylsulfanyl)octane (XIIa) and
1-bromo-2-(1-hexynylsulfanyl)octane (XIIb) (mix-
1
1-Chloro-2-(1-hexynylsulfanyl)-1-phenylethane
(XVI). Yield 91%, Rf 0.93. 1H NMR spectrum, δ, ppm:
7.40–7.19 m (Ph), 4.79 d.d (HCHlg, J1 = 8.4, J2 =
6.9 Hz), 4.50 d.d (HCHlg, J1 = 8.4, J2 = 6.5 Hz),
5.10 d.d (HCS, J1 = 6.9, J2 = 6.5 Hz), 2.25 t (J =
6.9 Hz), 1.50–1.30 (CH2), 0.95 t (J = 6.9 Hz). Mass
spectrum, m/z (Irel, %): 252 (11) M+ 139 (100) [M –
BuC≡CS]+, 103 (46) [C6H5C2H2]+, 71 (19) [C5H11]+,
51 (10) [C4H3]+, 41 (10) [C3H5]+. According to the
1H NMR data, the reaction mixture contained about
5% of the corresponding anti-Markownikoff adduct.
ture of isomers). Yield 80%, Rf 0.92. H NMR spec-
trum, δ, ppm: XIIa: 4.05 m (HCHlg), 3.34 d.d (HCS,
J1 = 14.0, J2 = 5.2 Hz), 3.16 d.d (HCS, J1 = 14.0, J2 =
8.1 Hz), 2.24 t (J = 6.7 Hz), 2.05–1.2 m (CH2), 0.90 t
(CH3, J = 6.9 Hz); XIIb: 3.75 d.d (HCS, J1 = 9.6, J2 =
3.0 Hz), 3.65 d.d (HCS, J1 = 9.6, J2 = 6.4 Hz), 3.16 m
(HCS), 2.21 t (J = 6.7 Hz), 2.05–1.2 m (CH2), 0.90 t
(CH3, J = 6.9 Hz). Mass spectrum, m/z (Irel, %): 266
(32) M+, 133 (95) [PhC≡CS]+, 117 (79) [C6H5C3H4]+,
91 (100) [C7H7]+, 81 (29) [C6H9]+, 71 (28) [C5H11]+, 41
(15) [C3H5]+.
1-Bromo-2-(1-hexynylsulfanyl)-1-phenylethane
(XVII). Yield 94%, Rf 0.92. H NMR spectrum, δ,
ppm: 7.35–7.20 m (Ph), 5.09 d.d (HCS, J1 = 9.8, J2 =
6.2 Hz), 4.99 d.d (HCHlg, J1 = 9.5, J2 = 6.2 Hz),
4.54 m (HCHlg), 2.35 t (J = 7.0 Hz), 1.60–1.20 (CH2),
0.90 t (J = 7.0 Hz).
2-Chloro-3-phenyl-1-(2-phenylethynylsulfanyl)-
propane (XIIIa) and 1-chloro-3-phenyl-2-(2-phenyl-
ethynylsulfanyl)propane (XIIIb) (mixture of
1
1
isomers). Yield 88%, Rf 0.91. H NMR spectrum, δ,
ppm: XIIIa: 7.50–7.00 m (Ph), 3.92 m (HCHlg),
3.60 d.d (HCS, J1 = 11.2, J2 = 4.7 Hz), 3.48 d.d (HCS,
J1 = 11.2, J2 = 8.1 Hz), 3.19 d.d (J1 = 13.4, J2 =
5.8 Hz), 3.04 d.d (J1 = 13.4, J2 = 7.3 Hz); XIIIb: 7.50–
7.00 m (Ph), 3.85 d.d (HCHlg, J1 = 11.2, J2 = 4.3 Hz),
3.74 d.d (HCHlg, J1 = 11.2, J2 = 3.7 Hz), 3.33 m
(HCS), 3.33 d.d (J1 = 14.1, J2 = 7.6 Hz), 3.07 d.d (J1 =
14.1, J2 = 7.9 Hz). Mass spectrum, m/z (Irel, %): 280
(80) M+, 251 (10) [M – Cl]+, 223 (34) [M – Cl – C2H4]+,
133 (92) [PhC≡CS]+, 117 (100) [C6H5C3H4]+, 103 (25)
[C6H5C2H2]+, 91 (100) [C7H7]+, 77 (16) [C6H5]+, 63
(42) [C5H3]+, 39 (29) [C3H3]+.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 02-03-33347a) and by the Ministry of Education
of the Russian Federation, “Universities of Russia”
program (project no. 05.03.047).
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