Reactions of 1-(alk-1-ynyl)-1-chlorocyclopropanes with arenethiols and alkanethiols in dimethyl sulfoxide in the presense of KOH

Article abstract of DOI:10.1007/s11172-009-0340-8

The reaction of 1-(alk-1-ynyl)-1-chlorocyclopropanes with arenethiols in DMSO in the presence of KOH at 90-100°C affords the corresponding 1-(alk-1-ynyl)-2-arylsulfanyl-cyclopropanes in the yields up to 67%. At the same time, [1,2-bis(alkylsulfanylalk-1-e

Full text of DOI:10.1007/s11172-009-0340-8

Russian Chemical Bulletin, International Edition, Vol. 58, No. 12, pp. 2432—2436, December, 2009
2432
Reactions of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocyclopropanes with arenethiols
and alkanethiols in dimethyl sulfoxide in the presense of KOH
K. N. Shavrin, V. D. Gvozdev, and O. M. Nefedov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: vgvozdev2006@yandex.ru
The reaction of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocyclopropanes with arenethiols in DMSO in the
presence of KOH at 90—100 °С affords the corresponding 1ꢀ(alkꢀ1ꢀynyl)ꢀ2ꢀarylsulfanylꢀ
cyclopropanes in the yields up to 67%. At the same time, [1,2ꢀbis(alkylsulfanylalkꢀ
1ꢀenyl]cyclopropanes or mixtures of isomeric 1ꢀ(alkꢀ1ꢀynyl)ꢀ2ꢀalkyltsulfanylcyclopropanes
and (alkylsulfanyl)alkenylidenecyclopropanes are formed in analogous reactions with alkaneꢀ
thiols depending on the substituent at the triple bond of the starting compound.
Key words: cyclopropanes, cyclopropenes, allenes, alkynes, thiols, arenethiols, sulfides,
nucleophilic addition, nucleophilic substitution.
Scheme 1
1ꢀAlkynylꢀ1ꢀhalogenocyclopropanes, first of all,
1ꢀalkynylꢀ1ꢀchlorocyclopropanes are convenient and
available building blocks easily obtainable by [1+2] cycloꢀ
addition of alkynyl(chloro)carbenes to alkenes1,2 or by
the reaction of trichlorovinyl(chloro)cyclopropanes with
BunLi followed by hydrolysis.3 At present, rather numerous
transformations of 1ꢀalkynylꢀ1ꢀchlorocyclopropanes are
known, viz., metallation at the chlorine atom followed by
reactions with various electrophiles,3,4 the Pauson—Khand
cycloaddition.3 They are also used in the synthesis of
nitrogenꢀcontaining heterocycles,5 conjugated alkynylꢀ
and iminoalkylcyclopropenes.6,7
Recently,8 we have found that reactions of 1ꢀalkynylꢀ
1ꢀchlorocyclopropanes with alcohols and phenols in
DMSO in the presence of КОН is a convenient approach
to 1ꢀalkynylꢀ2ꢀalkoxyꢀ and 1ꢀalkynylꢀ2ꢀphenoxycycloꢀ
propanes, which had widely been applied previously in
the synthesis of various carbocyclic compounds.9—11
In continuation of these works, it was of interest to study
the addition of thiols to these substrates.
Easily accessible 1ꢀalkynylꢀ1ꢀchloroꢀ2,2ꢀdimethylꢀ
cyclopropanes 1a,b were chosen as the starting compounds.
The presence of two geminal methyl groups in their molꢀ
ecules unambiguously determines the direction of dehyꢀ
drochlorination and excludes the possibility of isomerizaꢀ
tion of cyclopropene intermediates if formed during the
reaction. It was shown that the addition of cyclopropanes
1a,b to a fivefold excess of benzenethiol or 4ꢀmethylꢀ
benzenethiol and 7.5ꢀfold excess of powdered KOH in
DMSO at 90—100 °С affords the corresponding 1ꢀalkynylꢀ
2ꢀarylsulfanylcyclopropanes 3a—d as a mixture of cisꢀ
and transꢀisomers in 56ꢀ67% yield (Scheme 1, Table 1).
1, 2: R1 = Ph (a), But (b)
3: R1 = R2 = Ph (a); R1 = Ph, R2 = 4ꢀMeC6H4 (b); R1 = But,
R2 = Ph (c); R1 = But, R2 = 4ꢀMeC6H4 (d)
Reagents and conditions: i. KOH, DMSO, 90—100 °C.
As follows from the structures of the products obꢀ
tained, sulfides 3a—d most probably formed from chloroꢀ
cyclopropanes 1a,b according to the elimination—addiꢀ
tion mechanism via alkynylcyclopropenes 2а,b resulting
from dehydrochlorination of the starting chlorocycloꢀ
propanes under the action of the hydroxide anions. Then,
similarly to analogous reactions with alcohols described
by us previously,8 the arenethiolate ions present in the
reaction mixture add to the double bond of the cycloꢀ
propene fragment, exclusively at the unsubstituted carbon
atom, affording cyclopropane sulfides 3a—d.
The nature of the substituent at the triple bond greatly
influences the rate of the reaction under study. Thus,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2354—2358, December, 2009.
1066ꢀ5285/09/5812ꢀ2432 © 2009 Springer Science+Business Media, Inc.

1ꢀ(Alkynyl)ꢀ2ꢀorganylsulfanylcyclopropanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2433
Table 1. Preparation of sulfides 3a—d from 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchloroꢀ2,2ꢀdimethylcyclopropanes 1a,ba
b
Starting compound
RSH
t/h
T/°C
Product
Yield (%)
trans : cis ratio
1a
1a
1b
1b
PhSH
4ꢀMeC6H4SH
PhSH
3
3
8
8
90
90
100
100
3a
3b
3c
3d
67c
56c
64d
59d
1.4 : 1
1.5 : 1
1.7 : 1
1.6 : 1
4ꢀMeC6H4SH
a Fivefold excess of RSH, 7.5ꢀfold excess of KOH, DMSO, 80—100 °C.
b Based on the NMR spectra of isolated products.
c Isolated by column chromatography.
d Isolated by vacuum microdistillation.
chlorocyclopropane 1a containing the phenyl substituent
at the triple bond reacts completely at 90 °С for 3 h, while
heating at 100 °С for 8 h is required for complete conꢀ
version of chloride 1b containing the tertꢀbutyl subꢀ
stituent. Presumably, this is related to a more pronounced
–Iꢀeffect of the phenylethynyl fragment, which favors
easier elimination of HCl from chlorocyclopropane 1а.
In contrast to the reactions with arenethiols, the reacꢀ
tions of alkanethiols with the same alkynyl(chloro)ꢀ
cyclopropanes 1 are more complicated. Thus, in addition
to transꢀcyclopropane 3e isomeric allene 4a formed in the
reaction of 2,2ꢀdimethylꢀ1ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ
1ꢀchlorocyclopropane 1b with butanethiol (fivefold
excess) (the ratio 3e : 4a = 1 : 1.4) (Scheme 2). The total
yield of these two products was 34%, they were characꢀ
terized without separation.
Most probably, the formation of alkenylidenecycloꢀ
propane 4a is the result of addition of the butanethiolate
anion at the triple bond of compound 1b followed by
elimination of the chloride anion. The possibility of proꢀ
ceeding of related processes was described in literature.12,13
The experimental confirmation of this assumption is the
fact that compound 4а was obtained in 30% yield without
admixture of the acetylenic isomer 3e upon heating of
cyclopropane 1b with a fivefold excess of sodium butaneꢀ
thiolate (obtained previously from butanethiol and sodium
hydride) in DMSO at 100 °С for 16 h. On the contrary,
transꢀcyclopropane 3e was obtained in 45% yield upon
reaction of cyclopropene 2b prepared as described previꢀ
ously,8 with butanethiol in DMSO in the presence of
KOH at 100 °С. Hence, product 4а was obtained directly
from chloride 1b.
The reaction of chlorocyclopropane 1a with butaneꢀ
thiol (fivefold excess) and KOH (fivefold excess) as
suspension in DMSO at 90—100 °С afforded olefinic
bissulfide 5a in a yield of 60% (a mixture of Zꢀ and
Eꢀisomers, ratio 9 : 1) (Scheme 3). Probably, in this case
exclusive addition of the thiolate anion followed by elimiꢀ
nation of the chloride anion occurs in the first step rather
than elimination of HCl due to increased electrophilicity
of the triple bond. In contrast to analogous product 4a,
alkenylidenecyclopropane 4b formed primarily adds one
more molecule of butanethiol at the central carbon atom
of the allene system due to activating influence of the
phenyl substituent.
Analogous results were obtained in the reaction of
cyclopropane 1а with 2ꢀaminoethanethiol (see Scheme 3).
In this case, the reaction proceeds exclusively at the SH
group to give vinylcyclopropanes 5b (a mixture of Zꢀ and
Eꢀisomers in a 3.2 : 1 ratio, the yield was 65%); no reacꢀ
Scheme 2
Reagents and conditions: i. KOH, DMSO, BuSH, 80—100 °C; ii. BuSNa, DMSO, 100 °C.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Shavrin et al.
Scheme 3
on the regioꢀ and stereoselection of these processes
were demonstrated. It was shown that arenethiols react
regioselectively to afford hetherto unkown 1ꢀalynylꢀ
2ꢀarylsulfanylcyclopropanes. At the same time, in the case
of alkanethiols the formation of (1,2ꢀbisalkylsulfanylꢀ
alkenyl)cyclopropanes or mixtures of isomeric 1ꢀ(alkꢀ
1ꢀynyl)ꢀ2ꢀalkylsulfanylcyclopropanes and alkylsulfanylꢀ
alkenylidenecyclopropanes is observed, which results
probably from the addition of the thiolate anion present
in the reaction mixture to the triple bond.
Experimental
R1 = Bu (4b, 5a), NH2CH2CH2 (4c, 5b)
The GLC analysis of the starting compounds and
the products obtained was performed on a Hewlett—Packard
5890 Series II instrument equipped with a capillary column
(30 m × 0.153 mm) and a Hewlett—Packard 3396A automatic
integrator. 1H and 13C NMR spectra of solutions in CDCl3
(except for compound 5b) were recorded on a Bruker ACꢀ200p
spectrometer using Me4Si as the internal standard. Mass spectra
were obtained on a Finningan MAT INCOSꢀ50 chromatoꢀmass
spectrometer.
The starting 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocyclopropanes 1 were
synthesized by cycloaddition of (alkꢀ1ꢀynyl)chlorocarbenes
to 2ꢀmethylpropene according to the procedures published
earlier.1,2
Reaction of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchloroꢀ2,2ꢀdimethylcyclopropanes
1a,b with arenethiols in the presence of KOH (general procedure).
Powdered КОН (840 mg, 15 mmol) was added to a solution of
arenethiol (10 mmol) in DMSO (2—3 mL). Then a solution
of (alkꢀ1ꢀynyl)chlorocyclopropane (2 mmol) in DMSO (0.5 mL)
was added and the reaction mixture was heated with vigorous
stirring (conditions are given in Table 1). After completion of
the reaction, water (5 mL) and ether (10 mL) were added, the
organic layer was separated, the aqueous layer was extracted
with ether three times. The combined organic layers were
successively washed with 10% NaOH and water two times, and
dried with MgSO4. The solvent was evaporated, and the product
was isolated from the residue by column chromatography or by
vacuum microdistillation. The yields and isomers ratio of the
products obtained are presented in Table 1.
Reagent and conditions: i. KOH, DMSO, 80—100 °C.
tion products with involvement of the amino group was
observed. Such a chemospecificity could be explained
by formation, under the reaction conditions, of small
amounts of the 2ꢀaminoethanethiolate anion, which is
the true reactive species.
The structure of the products obtained 3—5 was estabꢀ
lished based on data from NMR and mass spectra. The
mass spectra of all compounds show rather abundant peaks
of the molecular ions. In the 13С NMR spectra of sulfides
3a—e, two signals typical of carbon atoms of the acetylene
fragment at δ 74—91 are observed. In the 1Н NMR specꢀ
tra, the expected groups of signals for the substituents at
the triple bond and in the cyclopropane ring, pairs of
douplets for the cyclopropane protons are observed, too.
The vicinal spin—spin coupling constants of these proꢀ
tons (4.6—4.7 Hz for the major isomer and 6.9—7.9 Hz
for the minor isomer) unambiguously point to the preꢀ
valence of transꢀisomer in all the cases.
In the 13C NMR spectra of alkenylidenecyclopropane
4а, typical signals for the allene fragment at δ 95.4, 116.4,
and 179.5 were observed, corresponding to two terminal
1
and one central carbon atoms. In the H NMR spectra
3,3ꢀDimethylꢀ1ꢀphenylsulfanylꢀ2ꢀphenylethynylcyclopropane
(3a) was prepared in 67% yield from chlorocyclopropane 1а and
benzenethiol. It was isolated by column chromatography on
silica gel (eluent, hexane—Et2O, 10 : 1).
of akenylcyclopropanes 5а,b, typical sets of doublets of
doublets corresponding to the protons of 1,1,2ꢀtrisubstiꢀ
tuted cyclopropane ring and a doubled set of signals of the
alkulsulfanyl substituents were observed, which confirmed
the presence of two isomers. The additional confirmation
of the structure is the presence, in the 13C NMR spectra,
of two weak signals at δ 137—139 corresponding to
tetrasubstituted double bond and the absence of signals
for the acetylene fragment. The configuration of the double
bond in cyclopropanes 5a,b was determined based on
NOESYꢀ2D spectra, according to which the cyclopropane
and phenyl substituents in the major isomer are cis.
1
transꢀIsomer. H NMR, δ: 1.48 (s, 3 Н, Me); 1.62 (s, 3 H,
Me); 1.74 (d, 1 H, CHC≡C, J = 4.7 Hz); 2.53 (d, 1 H, CHSPh,
J = 4.7 Hz); 7.20—7.70 (m, 10 H, 2 Ph). 13C NMR, δ: 20.5,
22.6, 23.5 (2 Me + C≡CCH); 27.2 (CMe2); 35.0 (CHSPh);
80.6, 88.4 (C≡C); 123.5 (C(1), C6H5C≡C); 126.2, 127.7, 128.0,
128.2, 128.8, 131.5 (2 Ph); 138.0 (C(1), Ph).
cisꢀIsomer. 1H NMR, δ: 1.45 (s, 3 H, Me); 1.53 (s, 3 H,
Me); 2.07 (d, 1 H, CHC≡C, J = 7.9 Hz); 2.52 (d, 1 H, CHSPh,
J = 7.9 Hz); 7.20—7.70 (m, 10 H, 2 Ph). 13C NMR, δ: 16.8,
21.0, 26.5 (2 Me + C≡CCH); 25.5 (CMe2); 33.2 (CHSPh);
81.5, 85.7 (C≡C); 123.7 (C(1), C6H5C≡C); 124.9, 125.0, 126.9,
127.6, 128.7, 131.7 (2 Ph); 137.7 (C(1), Ph). MS, m/z: 278
[M]+. Found (%): C, 81.82; H, 6.43; S, 11.71. C19H18S.
Calculated (%): C, 81.97; H, 6.52; S, 11.52.
Thus, the ability of 1ꢀ(alkꢀ1ꢀynyl)ꢀ1ꢀchlorocycloꢀ
propanes to react with arenethiols and alkanethiols in a
basic system КОН/DMSO was revealed. Some regulariꢀ
ties of the effect of the structure of the starting compound

1ꢀ(Alkynyl)ꢀ2ꢀorganylsulfanylcyclopropanes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2435
3,3ꢀDimethylꢀ1ꢀ(4ꢀmethylphenylsulfanyl)ꢀ2ꢀphenylethynylꢀ
cyclopropane (3b) was prepared in 56% yield from chlorocycloꢀ
propane 1а and 4ꢀmethylbenzenehiol. It was isolated by column
chromatography on silica gel (eluent, hexane—Et2O, 10 : 1).
(0.5 mL) was added, and the reaction mixture was heated
with vigorous stirring for 4 h at 100 °C. After completion of
the reaction, water (5 mL) and ether (10 mL) were added, the
organic layer was separated, the agueous layer was extracted
with ether three times. The combined organic layers were washed
with water twice and dried with MgSO4. The solvent was
evaporated, and the product was isolated from the residue by
vacuum microdistillation (100—110 °C (bath)/1 Torr). The yield
of the liquid compound was 160 mg (a mixture of transꢀ3e
and 4а in 1 : 1.5 ratio, NMR), which corresponds to 34% overall
yield.
1
transꢀIsomer. H NMR, δ: 1.47 (s, 3 H, Me); 1.59 (s, 3 H,
Me); 1.70 (d, 1 H, CHC≡C, J = 4.7 Hz); 2.51 (d, 1 H, CHS,
J = 4.7 Hz); 7.15—7.6 (m, 9 H, Ph + Tol). 13C NMR, δ:
20.6, 22.7, 23.6 (2 Me + C≡CCH); 21.1 (СH3C6H4); 27.2
(CMe2); 35.6 (CHS); 80.5, 88.5 (C≡C); 123.6 (C(1), C6H5C≡C);
126.7, 127.6, 128.2, 129.6, 131.5 (Ph + Tol); 134.1, 134.7
(C(1) + C(4), Tol).
cisꢀIsomer. 1H NMR, δ: 1.41 (s, 3 Н, Me); 1.51 (s, 3 H,
Me); 2.01 (d, 1 H, CHC≡C, J = 7.9 Hz); 2.51 (d, 1 H, CHS,
J = 7.9 Hz); 7.15—7.60 (m, 9 H, Ph + Tol). 13C NMR, δ: 16.9,
20.9, 26.6 (2 Me + C≡CCH); 21.0 (СH3C6H4); 25.5 (CMe2);
34.0 (CHS); 81.6, 86.9 (C≡C); 123.7 (C(1), C6H5C≡C); 127.5,
127.6, 128.0, 129.5, 131.7 (Ph + Tol); 133.8, 134.9 (C(1) + C(4),
Tol). MS, m/z: 292 [M]+. Found (%): C, 81.98; H, 6.78;
S, 11.01. C20H20S. Calculated (%): C, 82.14; H, 6.89; S, 10.97.
3,3ꢀDimethylꢀ2ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ1ꢀphenylsulfanylꢀ
cyclopropane (3с) was prepared in 64% yield from chloroꢀ
cyclopropane 1b and benzenethiol. It was isolated by vacuum
microdistillation (150—160 °C (bath)/ 0.5 Torr).
transꢀ1ꢀButylsulfanylꢀ3,3ꢀdimethylꢀ2ꢀ(3,3ꢀdimethylbutꢀ
1ꢀynyl)cyclopropane (transꢀ3e). 1H NMR, δ: 0.95 (t, 3 H, Me
in Bu, J = 7.1 Hz); 1.12 (d, 1 H, CHC≡C, J = 4.7 Hz); 1.19 (s,
9 H, But); 1.21 (s, 1 H, Me); 1.22 (s, 1 H, Me); 1.20—1.70 (m,
4 H, CH2CH2Me); 1.80 (d, 1 H, CHSBu, J = 4.7 Hz); 2.55 (t,
2 H, CH2S, J = 6.9). 13C NMR, δ: 14.2 (Me in Bu); 20.7, 22.5,
23.1 (2 Me, C≡CCH); 25.8 (CMe2); 27.5 (CMe3); 31.4 (C(CH3)3);
32.0 (СH2); 32.9 (СH2); 35.8 (CHS); 77.3, 88.5 (C≡C). MS,
m/z: 238 [M]+.
2ꢀ(2ꢀButylsulfanylꢀ3,3ꢀdimethylbutꢀ1ꢀenylidene)ꢀ1,1ꢀ
dimethylcyclopropane (4a). 1H NMR, δ: 0.90 (t, 3 H, Me in Bu,
J = 7.1 Hz); 1.16 (s, 9 H, But); 1.27 (s, 1 H, Me); 1.28 (s, 1 H,
Me); 1.38 (s, 2 H, CH2); 1.20—1.70 (m, 4 H, CH2CH2Me);
2.52 (t, 2 H, CH2S, J = 6.9 Hz); 13C NMR, δ: 13.8 (Me in Bu);
21.4 (CMe2); 22.1 (СH2); 24.3, 24.4 (2 Me); 29.8 (C(CH3)3);
31.1 (CH2 in cycloꢀC3H2); 31.8 (СH2); 32.7 (СH2); 35.9 (CMe3);
95.4 (C= in cycloꢀC3H2); 116.4 (=C(But)SBu); 179.5 (=C=).
MS, m/z: 238 [M]+.
1
transꢀIsomer. H NMR, δ: 1.26 (s, 9 H, But); 1.24 (s, 3 H,
Me); 1.35 (d, 1 H, CHC≡C, J = 4.6 Hz); 1.36 (s, 3 H, Me); 2.17
(d, 1 H, CHS, J = 4.6 Hz); 7.20—7.50 (m, 5 H, Ph). 13C NMR,
δ: 20.5, 20.8, 22.3, (2 Me, C≡CCH); 26.0 (CMe2); 27.2 (CMe3);
31.6 (C(CH3)3); 34.3 (CHS); 76.5, 90.0 (C≡C); 126.1, 127.0,
131.8 (Ph); 137.8 (C(1), Ph).
cisꢀIsomer. 1H NMR, δ: 1.18 (s, 3 H, Me); 1.21 (s, 3 H,
Me); 1.25 (s, 9 H, But); 1.71 (d, 1 H, CHC≡C, J = 7.9 Hz); 2.23
(d, 1 H, CHS, J = 7.9 Hz); 7.2—7.50 (m, 5 H, Ph). 13C NMR, δ:
16.2, 20.2, 26.6 (2 Me, C≡CCH); 27.6 (CMe2); 27.3 (CMe3);
31.2 (C(CH3)3); 32.5 (CHS); 74.9, 90.0 (C≡C); 126.3, 127.4,
131.5 (Ph); 137.7 (C(1), Ph). MS, m/z: 258 [M]+. Found (%):
C, 78.85; H, 8.65; S, 12.33. C17H22S. Calculated (%): C, 79.01;
H, 8.58; S, 12.41.
Reaction of 1ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ2,2ꢀdimethylcycloꢀ
propene 2b with butanethiol in the presence of KOH. Cycloꢀ
propene 2b was synthesized by the action of lithium diethylamide
on chlorocyclopropane 1b according to the procedure published
earlier.8 The product obtained (87 mg, ~85% purity) was added
to a mixture of DMSO (2 mL), BuSH (450 mg, 5 mmol), and
КОН (112 mg, 2 mmol) preheated to 100 °С, and the reaction
mixture was stirred for 15 min. After completion of the reaction,
water (5 mL) and ether (10 mL) were added, the organic layer
was separated, the aqueous layer was extracted with ether three
times. The combined organic extracts were washed with water
twice, and dried with MgSO4. The solvent was evaporated, and
toluene (50 mg) as the internal standard was added to the residue.
The main product in the mixture obtained was sulfide transꢀ3e
(1H NMR data), the yield was 45% (with respect to the starting
chloride 1b) determined by comparison of integral intensities
of the signal for CHS fragment and signals for aromatic protons
of toluene.
Reaction of 1ꢀchloroꢀ1ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ2,2ꢀdiꢀ
methylcyclopropane (1b) with sodium butanethiolate. A 60%
suspension of sodium hydride in mineral oil (400 mg, 10 mmol)
was added to a solution of butanethiol (1.080 g, 12 mmol) in
DMSO (10 mL). After evolution of hydrogen ceased, a solution
of chlorocyclopropane 1b (370 mg, 2 mmol) in DMSO (0.5 mL)
was added and the reaction mixture was vigorously stirred for
16 h at 100 °С. After completion of the reaction, water (5 mL)
and ether (10 mL) were added, the organic layer was separated,
the aqueous layer was extracted with ether three times. The
combined organic layers were washed with water twice, and
dried with MgSO4. The solvent was evaporated, and alkenylꢀ
idenecyclopropane 4а was isolated by vacuum microdistillation
(100—110 °C (bath)/1 Torr). The yield of 4а was 165 mg (35%),
3,3ꢀDimethylꢀ2ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ1ꢀ(4ꢀmethylphenylꢀ
sulfanyl)cyclopropane (3d) was prepared in 59% yield from
chlorocyclopropane 1b and 4ꢀmethylbenzenethiol. It was isolated
by vacuum microdistillation (150—160 °C (bath)/0.5 Torr).
1
transꢀIsomer. H NMR, δ: 1.25 (s, 9 H, But); 1.28 (s, 3 H,
Me); 1.31 (d, 1 H, CHC≡C, J = 4.6 Hz); 1.37 (s, 3 H, Me); 2.15
(d, 1 H, CHS, J = 4.6 Hz); 2.32 (s, 3 H, SC6H4CH3); 7.05—7.30
(m, 4 H, C6H4). 13C NMR, δ: 20.5, 20.8, 22.3, 23.0 (3 Me,
C≡CCH); 25.9 (CMe2); 27.2 (CMe3); 31.3 (C(CH3)3); 34.8
(CHS); 76.8, 89.1 (C≡C); 126.4, 129.5 (Co, Сm, Tol); 134.3,
134.6 (C(1) + C(4), Tol).
cisꢀIsomer. 1H NMR, δ: 1.20 (s, 6 H, 2 Me); 1.25 (s, 9 H,
But); 1.65 (d, 1 H, CHC≡C, J = 7.9 Hz); 2.22 (d, 1 H, CHS,
J = 7.9 Hz); 2.32 (s, 3 H, SC6H4CH3); 7.05—7.30 (m, 4 H,
C6H4). 13C NMR, δ: 16.6, 20.4, 26.5, 31.1 (3 Me, C≡CCH);
27.4 (CMe2); 27.3 (CMe3); 31.2 (C(CH3)3); 32.9 (CHS); 74.8,
90.1 (C≡C); 127.4, 129.3 (Co, Сm, Tol); 134.2, 134.5 (C(1) + C(4),
Tol). MS, m/z: 272 [M]+. Found (%): C, 79.48; H, 8.65;
S, 11.92. C18H24S. Calculated (%): C, 79.35; H, 8.88; S, 11.77.
Reaction of 1ꢀchloroꢀ1ꢀ(3,3ꢀdimethylbutꢀ1ꢀynyl)ꢀ2,2ꢀdimethylꢀ
cyclopropane (1b) with butanethiol in the presence of KOH.
Powdered КОН (560 mg, 10 mmol) was added to a solution of
butanethiol (900 mg,10 mmol) in DMSO (5 mL). Then a
solution of chlorocyclopropane 1b (370mg, 2 mmol) in DMSO

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Shavrin et al.
purity was ~85%, it did not contain acetylene derivative 3е
isomeric to 4а.
(2 CH2NH2); 40.8, 41.6 (2 SCH2); 126.9, 127.6, 129.2 (Ph);
138.3, 138.7, 141.9 (C(1) в Ph, C=C). MS, m/z: 322 [M]+.
Found: C, 63.58; H, 7.95; S, 19.74. C17H26N2S2. Calculꢀ
ated (%): C, 63.31; H, 8.13; S, 19.88.
Reaction of 1ꢀchloroꢀ2,2ꢀdimethylꢀ1ꢀphenylethynylcycloꢀ
propane (1а) with alkanethiols in the presence of KOH. The
reaction was carried out according to the general procedure at
80—90 °С for 4 h. The products were isolated by vacuum
microdistillation (5а) or by passing a solution in a hexane—
ether mixture through a thin layer of silica gel (5b).
This study was financially supported by the Council
on Grants at the President of the Russian Federation
(Programm for State Support of Leading Scientific Schools
of the Russian Federation, Grant NShꢀ3237.2008.3),
by the Russian Foundation for Basic Research (Project
No. 06ꢀ03ꢀ33045ꢀa), and by the Russian Academy of
Sciences (Program OKhꢀ01).
2ꢀ[1,2ꢀDi(butylsulfanyl)ꢀ2ꢀphenylvinyl]ꢀ1,1ꢀdimethylcycloꢀ
propane (5a) was obtained in 60% yield from chlorocyclopropane
1b and butanethiol. It was isolated by the vacuum microdisꢀ
tillation (180—190 °C (bath)/0.5 Torr). 1H NMR, δ: 0.32 (dd,
1 H, 1 H from CH2 in cycloꢀC3H3, J = 5.8 Hz, J = 4.6 Hz); 0.51
(dd, 1 H, 1 H from CH2 in cycloꢀC3H3, J = 8.4 Hz, J = 4.6 Hz);
0.76 (s, 3 H, Me); 0.77 (t, 3 H, Me in Bu, J = 7.2 Hz); 0.84 (s,
3 H, Me); 0.96 (t, 3 H, Me in Bu, J = 7.2 Hz); 1.15—1.75 (m,
9 H, 4 CH2 + CHC=); 2.23 (t, 2 H, SCH2—, J = 7.1 Hz); 2.83
(td, 2 H, SCH2—, J = 7.2 Hz, J = 2.4 Hz); 7.15—7.40 (m, 5 H,
Ph). 13C NMR, δ: 13.6, 13.8 (2 Me in 2 Bu); 20.3, 26.3, 28.9
(2 Me, CHC=C); 20.9 (CMe2); 21.7, 22.2, 22.8, 32.0, 31.9,
32.4, 32.5 (7 CH2); 127.0, 127.7, 130.0 (Ph); 134.8, 137.7, 139.3
(C(1) в Ph, C=C). MS, m/z: 348 [M]+. Found (%): C, 72.12;
H, 9.16; S, 18.67. C21H32S2. Calculated (%) C, 72.35; H, 9.25;
S, 18.40.
References
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2ꢀ[1,2ꢀBis(2ꢀaminoethylsulfanyl)ꢀ2ꢀphenylvinyl]ꢀ1,1ꢀdimethylꢀ
cyclopropane (5b) was obtained in 65% yield from chlorocycloꢀ
propane 1b and 2ꢀaminoethanethiol. It was isolated by passing a
solution in hexane—ether mixture (10 : 1) through a thin layer
of silica gel.
ZꢀIsomer. 1H NMR (DMSOꢀd6), δ: 0.25 (dd, 1 H, 1 H from
CH2 in cycloꢀC3H3, J = 6.0 Hz, J = 4.6 Hz); 0.57 (dd, 1 H, 1 H
from CH2 in cycloꢀC3H3, J = 8.4 Hz, J = 4.6 Hz); 0.68 (s, 3 H,
Me); 0.72 (s, 3 H, Me); 1.48 (dd, 1 H, CH in cycloꢀC3H3,
J = 6.0 Hz, J = 8.4 Hz); 1.70 (br.s, 2 H, 2 NH2); 2.27 (t, 2 H,
SCH2—, J = 6.6 Hz); 2.53 (m, 2 H, SCH2—); 2.75—2.95 (m,
4 H, 2 CH2NH2); 7.15—7.4 (n, 5 H, Ph). 13C NMR, δ: 19.9
(СHC=C); 20.5 (CMe2); 22.3 (CH2); 25.8, 28.2 (2 Me); 36.6
(2 CH2NH2); 41.0, 41.4 (2 SCH2); 126.8, 127.5, 129.4 (Ph);
134.5, 138.0, 138.3 (C(1) в Ph, C=C). MS, m/z: 322 [M]+.
EꢀIsomer. 1H NMR (DMSOꢀd6), δ: 0.81 (dd, 1 H, 1 H from
CH2 in cycloꢀC3H3, J = 6.0 Hz, J = 4.1 Hz); 0.95 (dd, 1 H, 1 H
from CH2 in cycloꢀC3H3, J = 8.2 Hz, J = 4.1 Hz); 1.06 (s, 3 H,
Me); 1.27 (s, 3 H, Me); 1.53 (dd, 1 H, CH in cycloꢀC3H3,
J = 6.0 Hz, J = 8.2 Hz); 1.70 (br.s, 2 H, 2 NH2); 2.27 (t, 2 H,
SCH2—, J = 6.5 Hz); 2.75—2.95 (m, 6 H, 2 CH2NH2, SCH2—);
7.15—7.40 (m, 5 H, Ph). 13C NMR, δ: 19.3 (СHC=C); 20.5
(CMe2); 21.7 (CH2); 26.6, 27.7 (2 Me); 29.2 (CMe2); 36.2, 37.0
Received April 29, 2009;
in revised form September 22, 2009