A one-pot synthesis of alkynyl sulfides from terminal alkynes

Article abstract of DOI:10.1002/hc.20744

A one-pot synthesis of alkynyl sulfide from terminal alkyne has been reported via lithiation of the alkyne, oxidative addition of sulfur, consecutively followed by the nucleophilic substitution of lithium alkynyl thiolate to various halides.

Full text of DOI:10.1002/hc.20744

Heteroatom Chemistry
Volume 23, Number 1, 2012
A One-Pot Synthesis of Alkynyl Sulfides
from Terminal Alkynes
Weixin Zheng, Fenfen Zheng, Ya Hong, and Linfeng Hu
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, 16 Xuelin
Road, Xiasha, Hangzhou 310036, People’s Republic of China
Received 7 April 2011; revised 19 May 2011
[6], and cross-coupling reactions [7] as well as in the
ABSTRACT: A one-pot synthesis of alkynyl sulfide
preparation of self-assembled monolayers in the pro-
from terminal alkyne has been reported via lithiation
duction of composite materials [8].
of the alkyne, oxidative addition of sulfur, consec-
In this way, some methodologies have been men-
utively followed by the nucleophilic substitution of
tioned for the syntheses of alkynyl sulfides. The
ꢀ
C
lithium alkynyl thiolate to various halides. 2011 Wi-
nucleophilic substitution reactions of the lithium
ley Periodicals, Inc. Heteroatom Chem 23:105–110, 2012;
acetylide to the RSX compounds involving an
View this article online at wileyonlinelibrary.com. DOI
electron-withdrawing X as the leaving groups (X=
10.1002/hc.20744
tosyl [8], chloro [9], bromo [10], cyano [11],) could
give the alkynyl sulfides, in which the sulfur moi-
ety should be generated from odorous thiol. The
INTRODUCTION
alkynyl sulfides are also obtained via the reaction
of terminal alkynes with phenylsulfuryl halides [9b]
or dialkyl disulfides [12] as well as alkynyl bromides
with disulfides [13] in the presence of copper iodide
(I) in polar solvent. These conversions should be car-
ried out in toxic solvent and with the cupric salts
that are necessary. The appointed materials contain-
ing sulfur should be supplied and some of them,
for instance, sulfuryl halides and the precursor thio-
phenol, are stenchy and highly toxic. An alternative
preparation has been reported via the cleavage of
an S S bond of the disulfides by alkynyl metallic
species formed in situ from terminal alkynes. How-
ever, the losing moiety of thiolate should be trapped
by the extra halides to avoid further addition of the
thiolate anion to the formed alkynyl sulfide to give
bisphenylthio alkenes [4b,14]. The generation of the
monosulfide as the byproduct is inevitable. Other
protocols, such as the cleavage of 5-chloro-1, 2, 3-
thiadiazoles, the dehydrobromination of vinyl sul-
fides, and the substitution of the silyl group in the
silyl alkyne, have suffered from astricting the broad
spectrum of the methodologies [15]. Owing to the
Sulfur-containing compounds exist widely in nature
and the sulfur moiety serves as important auxiliary
functional group in synthetic sequences, owing to
which the selective formation of C S bonds have
attached much attention in the organic synthesis
[1].
Among the compounds containing sulfur
groups, the alkynyl sulfides have been found to be es-
sential building blocks in organic synthesis [2]. Be-
cause of the activity of the alkylthio group to the
carbon–carbon triple bonds, alkynyl sulfides have
been involved in hydrostannation [3], [2 + 2] [4] or
[4 + 2] -type [5] cycloaddition, silacyclo-propenation
Correspondence to: Weixin Zheng; e-mail: zhengweixinzwx@
yahoo.com.cn.
Contract grant sponsor: Natural Science Foundation of
Zhejiang Province.
Contract grant number: Y406341.
Contract grant sponsor: National Natural Science Foundation
of China.
Contract grant number: 20702010, 20972037.
2011 Wiley Periodicals, Inc.
c
ꢀ
105

106 Zheng et al.
R1
R1
H
RESULTS AND DISCUSSION
n-BuLi
Our procedure is as follows. To a THF solution
of lithium acetylide prepared in situ and gener-
ated from terminal acetylene and n-BuLi at –78◦C,
one equivalent of sulfur powder was added. The
reaction was gradually warmed from –78◦C to 0◦C
untill the sulfur was consumed completely to af-
ford the red lithium alkynyl thiolate 1. Alkyl bro-
mide at the same temperature. The solution grad-
ually changed to pale orange. Hydrolysis of the
completed reaction mixture with saturated aqueous
ammonium chloride afforded 2 (Scheme 1) in good
yields based on the terminal alkynes.
Ethyl magnesium bromide was used instead of
n-BuLi, and the disappearance of sulfur powder
was also observed. However, the yield of the tar-
get product was poor, owing to the formation of
some byproducts. When the reaction temperature
was higher than 0◦C in the step of the coupling of
lithium alkynyl thiolate 1 and alkyl bromide, we
could not get a good yield of the desired sulfide as
a result of the polymerization of the alkyne. Both
alkynl and aromatic alkyne are receivable in this
protocol. Alkyl halides, which are readily available
commercially are generally more varied and cheaper
than alkyl thiols or disulfides [12–14]. The results are
summarized in Table 1.
8°C
R2
X
R1
S
Sulfur
R1
Li
S
R2
Li
1
2a-r
R1 = C6H5 n-C4H9, n-C6H13
R2 = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, CH2C6H5, CH2COC6H5, CH2COOC2H5
X = Cl, Br, I
SCHEME 1
above, we conceived that the elementary sulfur could
be addressed as the precursor of the thio group to
avoid the use of the toxic and stenchy materials and
to accord with the atomic economics.
Herein, we have developed a one-pot synthesis
of alkyl alkynyl sulfides from various alkyl halides
and terminal alkynes. Although the preparation of
lithium alkynyl thiolate is a classical way [16], there
has been no report on the synthesis of the alkynyl
sulfides via lithium alkynyl thiolate generated in situ
from terminal alkyne and n-BuLi in the presence of
sulfur, to the best of our knowledge. In this study, we
report the ready coupling of lithium alkynyl thiolate
with different alkyl halides to afford various alkynyl
sulfides in good yields (Scheme 1).
TABLE 1 Preparation of Alkynyl Sulfides 2
Entry
R1
R2
X
Product 2
Time (h)
Yielda
1
2
3
4
5
6
7
8
C6H5
C6H5
C6H5
C6H5
C6H5
CH3
C2H5
n-C3H7
i-C3H7
CH2C6H5
CH2COPh
CH2COOEt
CH3
I
2a
2b
2c
2d
2e
2f
3
4
4
4
3
1
1
3
4
5
24
5
4
5
24
4
4
5
4
86
84
79
Br
Br
Br
Br
Br
Br
I
Br
Br
Cl
Br
I
Br
Cl
I
Br
Cl
I
15 (39b)
85
C6H5
C6H5
80
82
88
80
79
—
2g
2h
2i
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C6H13
n-C6H13
n-C6H13
n-C6H13
n-C6H13
9
C2H5
10
11
12
13
14
15
16
17
18
19
20
21
22
23
n-C3H7
n-C3H7
i-C3H7
2j
—
2k
2k
2l
14 (40b)
26 (47b)
77
i-C3H7
n-C4H9
n-C4H9
s-C4H9
CH2C6H5
CH2C6H5
CH3
—
2m
2n
2n
2o
2p
2q
2r
—
33 (40b)
79
56
81
72
78
75
74
C2H5
Br
Br
Br
Br
4
5
5
4
n-C3H7
n-C4H9
CH2C6H5
2s
aIsolated yields based on the alkynes.
b5 mol% of CuCl was added to the reaction.
Heteroatom Chemistry DOI 10.1002/hc

A One-Pot Synthesis of Alkynyl Sulfides from Terminal Alkynes 107
When 2-bromophenylacetone and the 2-
bromoethyl acetate (entries 6 and 7) were used
as reactants, good yields were achieved and the
reactions progressed faster than others. It was
realized that the reaction rate of the bromide with
the electron-withdrawing group was more reactive
than that with the electron-donating group. The
yield of 2f and 2g indicated the favorable chemos-
electivity of nucleophilic substitution of the alkynyl
thiolate to the halides rather than the nucleophilic
addition to the carbonyl group and the abstraction
of the active hydrogen atom in the α-position of the
carbonyl group as well. The reaction of the benzyl
chloride resulted in the moderate yield of benzyl
alkynyl sulfide 2n (entry 18). Yet no reaction could
be detected in the case of entries 11 and 15, chain
alkyl chloride, even in the presence of CuCl. As
the carbon chain in R2 became longer, the yield of
the alkynyl sulfides was slightly lower (entries 1–3,
entries 8–10, entry 14, and entries 19–22). However,
when the Br was attached to a secondary carbon
in the halide, the decline of the yield of the alkynyl
sulfide was observed (entries 4 and 12), which was
caused mainly by the elimination reaction of the
secondary bromide. To decrease the alkalinity of
the organometallic reagent, 5 mol% of CuCl was
added and the yields improved markedly. When
the secondary iodide was involved instead of the
bromide, a better yield was obtained and the copper
catalyst also led to a moderate yield (entries 13
and 16).
line techniques when appropriate. Standard column
chromatography was performed on 300–400 meshes
of silica gel using flash column chromatography
techniques. All glassware, syringes, and needles were
flame dried above 100◦C. 1H and 13C NMR spec-
tra were recorded over Bruker AdvanceDMX 400 in
CDCl3, using Me4Si as the internal standard. Chem-
ical shifts (δ) were reported in parts per million
(ppm). IR spectra were recorded on BrukerTENSOR
27. Low resolution MS were carried out on Bruker
Daltonics Esquire 3000 plus. HRMS were recorded
on GCT Premier. Unless stated otherwise, commer-
cial reagents were used without further purification.
Solvents were purified by distillation under dry ni-
trogen from sodium/benzophenone (THF).
A Typical Procedure for the Preparation of Lithium
Alkynyl Thiolate 1. To a THF (5 mL) solution of ter-
minal alkyne (1.0 mmol) at –78◦C was added n-BuLi
(1.1 mmol, 1.6 M in hexane). The above reaction so-
lution was then stirred for 1 h, to which was added
1.0 mmol of sulfur powder followed by further stir-
ring at −78◦C for 1 h. The mixture was gradually
warmed to 0◦C untill the sulfur was completely con-
sumed to give red lithium alkynyl thiolate 1.
A Typical Procedure for the Synthesis of Alkynyl
Sulfide 2. To the in situ prepared lithium alkynyl
thiolate 1 in THF at 0◦C was added 1.0 mmol of
halide via a syringe and 5 mol% of CuCl if necessary,
which was monitored by TLC. Then the saturated
aqueous NH4Cl was added into the pale orange so-
lution to quench the reaction. The inorganic layer
was extracted with diethyl ether three times. The
combined extract was washed with brine and dried
over MgSO4. After rotary evaporation, the residue
was purified by column chromatograph (silica gel,
petroleum ether) to afford alkynyl sulfide 2. The
reaction time and the yields are listed in Table 1.
The analytical data for the products are shown as
follows.
CONCLUSION
In summary, we have developed a one-pot synthesis
of the alkynyl sulfide from sulfur simple substance,
terminal alkyne, and diverse alkyl halides. All of the
substances are readily and commercially available.
The alkylthio moiety in the product derived from
the sulfur powder and halide, avoiding the prepa-
ration of other sulfur-containing compounds. Con-
sidering both the reactivity and cost, the bromide
is suitable for the primary substance and the iodide
for the secondary. Therefore, this procedure has the
advantages of convenience, safety, and atomic econ-
omy, owing to the avoidance of the loss of alkylthio
moiety.
Methyl(2-phenylethynyl)sulfide (2a) [15a]
Yellow oil, isolated yield 86%; IR cm−1 (neat) v 3060,
2926, 2826, 2167 (C C), 1595, 1500, 1440 (CH3),
1069(C S), 754, 689; 1H NMR (CDCl3, Me4Si) δ
EXPERIMENTAL
General Information
2.46 (s, 3H), 7.26-7.29(m, 3H), 7.38–7.41(m, 2H); 13
C
The thermometer was uncorrected. All reactions
were conducted under a slightly positive pressure
of dry, prepurified nitrogen using standard Schlenk
NMR (CDCl3, Me4Si)19.3, 80.9, 91.8, 123.3, 128.0,
128.2, 131.4; MS (EI 70 ev): m/e 57 (100), 148
(M+, 2).
Heteroatom Chemistry DOI 10.1002/hc

108 Zheng et al.
1486, 1196 (C O C), 1070 (C S), 753, 688; 1H NMR
(CDCl3, Me4Si) δ 1.30 (t, J= 7.2 Hz, 3H), 3.56 (s, 2H),
4.25(q, J= 7.2 Hz, 2H), 7.29–7.31 (m, 3H), 7.40–7.42
(m, 2H);13C NMR (CDCl3, Me4Si)14.1, 37.6, 61.8,
77.3, 94.4, 122.9, 128.2, 128.4, 131.5, 168.2; MS (EI
70 ev): m/e 105 (100), 220 (M+, 5).
Ethyl (2-phenylethynyl) sulfide (2b) [4b]
Yellow oil, isolated yield 84%; IR cm−1 (neat) v 3031,
2964, 2926, 2166 (C C), 1595, 1486, 1442, 1375
(CH3), 1069 (C S), 690, 754; 1H NMR (CDCl3, Me4Si)
δ 1.46 (t, J = 7.2 Hz, 3H), 2.82 (q, J = 7.2 Hz, 2H),
7.26–7.31 (m, 3H), 7.40–7.43 (m, 2H); MS (EI 70 ev):
m/e 91 (100), 162(M+, 3).
Hexa-1-ynyl (methyl) sulfide (2h) [14c]
Yellow oil, isolated yield 88%; IR cm−1 (neat) v 3060,
(2-Phenylethynyl)propyl sulfide (2c)
Yellow oil, isolated yield 79%; IR cm−1 (neat)
v 3061, 2964, 2873, 2167 (C C), 1596, 1487,
1292, 1237, 1069 (C S), 754, 690; 1H NMR
(CDCl3, Me4Si) δ 1.06 (t, J = 7.2 Hz, 3H), 1.81–1.86
(m, 2H), 2.78 (t, J = 7.2 Hz, 2H), 7.25-7.42 (m, 5H);
13C NMR (CDCl3, Me4Si)13.0, 22.7, 37.8, 79.6, 92.8,
123.6, 128.0, 128.3, 131.4; MS (EI 70 ev): m/e 57
(100), 176 (M+, 8). HRMS: m/z for C11H12S, calcd:
176.0660. Found: 176.0669.
2926, 2167 (C C), 1595, 1340 (CH3), 1169 (C S),
1
754; H NMR (CDCl3, Me4Si) δ 0.91 (t, J = 7.4 Hz,
3H), 1.38–1.55 (m, 4H), 2.29 (t, J= 7.0 Hz, 2H),
2.35(s, 3H); 13C NMR (CDCl3, Me4Si)13.6, 19.3, 19.7,
21.9, 30.8, 69.7, 93.3; MS (EI 70 ev): m/e 59 (100),
128(M+, 10).
Ethyl (hexa-1-ynyl) sulfide (2i) [20]
Yellow oil, isolated yield 80%; IR cm−1 (neat) v 2958,
2929, 2871, 1456, 1376(CH3), 1055 (C S), 745; H
NMR (CDCl3, Me4Si) δ 0.91 (t, J = 7.6 Hz, 3H), 1.37
(t, J = 7.2 Hz, 3H), 1.38–1.57 (m, 4H), 2.31 (t, J = 7.2
Hz, 2H), 2.68 (q, J = 7.2 Hz, 2H); 13C NMR (CDCl3,
Me4Si)13.5, 14.6, 19.8, 21.9, 29.5, 30.9, 31.3, 35.1,
67.8, 94.8; MS (EI 70 ev): m/e 57 (100), 142(M+, 1).
Isopropyl(2-phenylethynyl)sulfide (2d) [17]
Yellow oil, isolated yield 39%; IR cm−1 (neat) v 3061,
1
2962, 2926, 2856, 2166 (C C), 1596, 1572, 1486,
1
1367, 1238, 1155, 1069 (C S), 754, 689; H NMR
(CDCl3, Me4Si) δ 1.42 (s, 3H), 1.44 (s, 3H), 3.25 (m,
1H), 7.24–7.42 (m, 5H); 13C NMR (CDCl3, Me4Si)
23.0, 39.9, 77.4, 78.6, 94.8, 123.7, 128.0, 128.3, 131.4;
MS (EI 70 ev): m/e 57 (100), 176 (M+, 1).
Hexa-1-ynyl (propyl) sulfide (2j)
Yellow oil, isolated yield 79%; IR cm−1 (neat) v
Benzyl (2-phenylethynyl) sulfide (2e) [4b]
Yellow oil, isolated yield 85%; IR cm−1 (neat) v 3030,
2927, 2164(C≡C), 1596, 1489, 1447, 1069(C S), 757,
696; 1H NMR (CDCl3, Me4Si) δ 4.01 (s, 2H), 7.25–7.39
(m, 10H); MS (EI 70 ev): m/e 224 (M+, 100); HRMS:
m/z for C15H12S, calcd: 224.0660. Found: 224.0659.
2961, 2933, 2873, 1462(CH3), 1378, 1294, 1237, 1094
1
(C S), 896, 837, 782, 743; H NMR (CDCl3, Me4Si)
δ 0.91 (t, J = 7.2 Hz,3H), 1.01 (t, J = 7.2 Hz, 3H),
1.36–1.45 (m, 2H), 1.46-1.53 (m, 2H), 1.71–1.80 (m,
2H), 2.30 (t, J = 7.2 Hz, 2H), 2.64 (t, J = 7.2Hz, 2H);
13C NMR (CDCl3, Me4Si)12.9, 13.6, 19.8, 21.9, 22.6,
30.9, 37.4, 68.2, 77.0, 94.1; MS (EI 70 ev): m/e 57
(100), 156 (M+, 27); HRMS: m/z for C9H16S, calcd:
156.0973. Found: 156.0982.
Phenyl-2-(2-phenylethynylthio) ethanone
(2f) [18]
Yellow oil, isolated yield 80%; IR cm−1 (neat) v 2982,
2170 (C C), 1736 (C O), 1595, 1571, 1487, 1089
1
(C S), 756, 690; H NMR (CDCl3, Me4Si) δ 4.29 (s,
Hexa-1-ynyl (iso-propyl) sulfide (2k)
2H), 7.25–7.61 (m, 8H), 7.69–7.99 (m, 2H); 13C NMR
(CDCl3, Me4Si)42.3, 77.7, 94.4, 122.9, 128.3, 128.4,
128.7, 128.8, 131.5, 133.8, 135.1, 193.0; MS (EI 70
ev): m/e 105 (100), 262 (M+, 1).
Yellow oil, isolated yield 40%; IR cm−1 (neat) v 2961,
2930, 2864, 1463, 1381 (CH3), 1237, 1052 (C S), 929,
881, 745, 627; 1H NMR (CDCl3, Me4Si) δ 0.91 (t, J=
7.2 Hz, 3H), 1.34 (s, 3H), 1.36 (s, 3H), 1.39–1.47 (m,
2H), 1.48–1.53 (m, 2H), 2.33 (t, J = 7.2 Hz, 3H), 3.10
(m, 1H); 13C NMR (CDCl3, Me4Si)13.6, 19.9, 21.9,
22.8, 30.9, 39.0, 67.1, 77.0, 96.1; MS (EI 70 ev): m/e
57 (100), 156(M+, 9); HRMS: m/z for C9H16S, calcd:
156.0973. Found: 156.0977.
Ethyl 2-(2-phenylenylethynylthio) acetate (2g)
[19]
Yellow oil, isolated yield 82%; IR cm−1 (neat)
v 3060, 2915, 2190 (C C), 1680 (C O), 1596, 1579,
Heteroatom Chemistry DOI 10.1002/hc

A One-Pot Synthesis of Alkynyl Sulfides from Terminal Alkynes 109
2); HRMS: m/z for C10H18S, calcd: 170.1129. Found:
170.1131.
Butyl (hexa-1-ynyl) sulfide (2l) [21]
Yellow oil, isolated yield 77%; IR cm−1 (neat) v 2958,
2858, 1464, 1378 (CH3), 1325, 1224, 1100 (C S), 916,
726; H NMR (CDCl3, Me4Si), δ 0.89–0.95 (m, 6H),
1
Octa-1-ynyl (propyl) sulfide (2q)
Yellow oil, isolated yield 68%; IR cm−1 (neat) v 2961,
2931, 2858, 1460, 1378, 1294, 1237, 1061 (C S), 896,
838, 783, 726; 1H NMR (CDCl3, Me4Si) δ 0.89 (t, J =
6.8 Hz, 3H), 1.02 (t, J = 7.2 Hz, 3H), 1.26–1.41 (m,
6H), 1.51 (m, 2H), 1.71–1.80 (m, 2H), 2.29 (t, J = 7.2
Hz, 2H), 2.64 (t, J = 7.2 Hz, 2H); 13C NMR (CDCl3,
Me4Si) 12.9, 14.1, 16.7, 20.1, 22.6, 28.5, 28.8, 31.3,
37.4, 68.2, 94.2; MS (EI 70 ev): m/e 71 (100), 184
(M+, 13). HRMS: m/z for C11H20S, calcd: 184.1286.
Found: 184.1299.
1.36–1.54 (m, 6H), 1.67–1.74 (m, 2H), 2.30 (t, J= 7.2
Hz, 2H), 2.67 (t, J= 7.2 Hz, 2H); 13C NMR (CDCl3,
Me4Si)13.6, 13.7, 19.8, 21.4, 21.9, 30.9, 31.3, 35.1,
68.3, 94.2; MS (EI 70 ev): m/e 57 (100), 198(M+, 5).
Hexa-1-ynyl (sec-butyl) sulfide (2m)
Yellow oil, isolated yield 40%; IR cm−1 (neat)
v 2962, 2931, 2874, 2361, 1687, 1458, 1378 (CH3),
1293, 1220, 1058 (C S), 999, 956, 793, 745; 1H NMR
(CDCl3, Me4Si) δ 0.91 (t, J= 7.2 Hz, 3H), 0.99 (t, J=
7.6 Hz, 3H), 1.35 (d, J= 6.8 Hz, 3H), 1.39–1.74 (m,
6H), 2.32 (t, J = 6.8 Hz, 2H), 2.82 (q, J = 6.8 Hz,
1H); 13C NMR (CDCl3, Me4Si)11.6, 13.6, 19.9, 20.6,
21.9, 29.2, 31.0, 45.7, 66.9, 95.6; MS (EI 70 ev): m/e
57 (100), 170 (M+, 2). HRMS: m/z for C10H18S, calcd:
170.1127. Found: 170.1130.
Butyl (octa-1-ynyl) sulfide (2r) [22]
Yellow oil, isolated yield 75%; IR cm−1 (neat) v 2959,
2937, 2872, 1486, 1363(CH3), 1074 (C S), 874, 744;
1H NMR (CDCl3, Me4Si) δ 0.87–0.95 (m, 6H), 1.26–
1.54 (m, 10H), 1.67–1.74 (m, 2H), 2.29 (t, J = 7.2
Hz, 2H), 2.67 (t, J = 7.2 Hz, 2H); 13C NMR (CDCl3,
Me4Si)13.6, 14.1, 16.7, 20.1, 21.4, 22.6, 28.5, 28.8,
31.3, 35.1, 68.2, 94.2; MS (EI 70 ev): m/e 57 (100),
198(M+, 1).
Benzyl (hexa-1-ynyl) sulfide (2n)
Yellow oil, isolated yield 79%; IR cm−1 (neat) v 3063,
3030, 2957, 2929, 2987, 1602, 1494, 1454, 1378(CH3),
1070 (C S), 763, 697; 1H NMR (CDCl3, Me4Si) δ 0.88
(t, J = 7.2 Hz, 3H, CH3(CH2)3), 1.29–1.48 (m, 4H),
2.26 (t, J = 6.8 Hz, 2H), 3.87 (s, 2H), 7.24–7.32 (m,
5H); 13C NMR (CDCl3, Me4Si) 13.6, 19.7, 21.8, 30.7,
40.2, 67.9, 96.0, 127.6, 128.4, 129.0, 137.0; MS (EI
70 ev): m/z 91 (100), 113 (4), 204(M+, 2); HRMS: m/z
for C13H16S, calcd: 204.0973. Found: 204.0963.
Benzyl (octa-1-ynyl) sulfide (2s)
Yellow oil, isolated yield 70%; IR cm−1 (neat) v 3063,
2929, 2857, 1602, 1494, 1454, 1446, 1378 (CH3) 1070
1
(C S), 763, 696; H NMR (CDCl3, Me4Si) δ 0.89 (t,
J = 7.2 Hz, 3H), 1.23–1.36 (m, 6H), 1.42–1.47 (m,
2H), 2.26 (t, J = 7.2 Hz, 2H), 3.88 (s, 2H), 7.25–
7.33 (m, 5H); 13C NMR (CDCl3, Me4Si) 14.0, 20.1,
22.5, 28.5, 28.6, 31.3, 40.2, 67.9, 96.1, 127.5, 128.4,
129.0, 137.0; MS (EI 70 ev): m/z 91 (100), 232(M+,
1); HRMS: m/z for C15H20S, calcd: 232.1686. Found:
232.1687.
Methyl (octa-1-ynyl) sulfide (2o)[6]
Yellow oil, isolated yield 81%; IR cm−1 (neat) v 2954,
2922, 2852, 1376(CH3), 1090(C S); 1H NMR (CDCl3,
Me4Si) δ 0.89 (t, J = 7.2 Hz, 3H), 1.26–1.41 (m, 6H),
1.47–1.54 (m, 2H), 2.28 (t, J= 7.2 Hz, 2H), 2.35 (s,
3H); 13C NMR (CDCl3, Me4Si) 14.0, 15.5, 16.7, 23.1,
28.3, 28.8, 31.6, 66.7, 92.5; MS (EI 70 ev): m/z 71
(100), 156(M+, 16).
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