Pronounced catalytic effect of a micellar solution of sodium dodecyl sulfate (SDS) on the efficient C-S bond formation via an odorless thia-michael addition reaction through the in situ generation of S-alkylisothiouronium salts

Article abstract of DOI:10.1002/adsc.200800690

A pronounced catalytic effect of sodium dodecyl sulfate (SDS) was observed on the in situ production of 5-alkylisothiouronium salts via the reaction of primary, allyl and benzyl halides with thiourea in SDS droplets .Hydrolysis of the generated Salkylisot

Full text of DOI:10.1002/adsc.200800690

FULL PAPERS
DOI: 10.1002/adsc.200800690
Pronounced Catalytic Effect of a Micellar Solution of Sodium
Dodecyl Sulfate (SDS) on the Efficient C-S Bond Formation via
an Odorless Thia-Michael Addition Reaction through the in situ
Generation of S-Alkylisothiouronium Salts
Habib Firouzabadi,a,* Nasser Iranpoor,a,* and Mohammad Abbasia
a
Department of Chemistry, Shiraz University, Shiraz 71454, Iran
Fax : (+98)-711-228-0926; phone: (+98)-711-228-4822; e-mail: firouzabadi@chem.susc.ac.ir or iranpoor@chem.susc.ac.ir
Received: November 9, 2008; Published online: March 12, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200800690.
Abstract: A pronounced catalytic effect of sodium produce the thia-Michael adducts. The entire route is
dodecyl sulfate (SDS) was observed on the in situ an almost odorless process. The yields of the prod-
production of S-alkylisothiouronium salts via the re- ucts are good to excellent and the method is applica-
action of primary, allyl and benzyl halides with thio- ble to large-scale operation without any problem.
urea in SDS droplets .Hydrolysis of the generated S-
alkylisothiouronium salts in the palisade layer of the
droplets produces the corresponding thiol moieties Keywords: alkyl halides; S-alkylisothiouronium salts;
which are immediately added to the electron-defi- sodium dodecyl sulfate; thia-Michael addition; thio-
cient olefins that are present in the micellar core to ureas; water
Introduction
methods, the use of highly volatile and foul-smelling
thiols leads to serious environmental and safety prob-
The thia-Michael addition is one of the most versatile lems and also limits the use of these methods for
À
and practical reactions for C S bond formation in or- large-scale operations. In order to minimize or elimi-
ganic synthesis.[1] Conversion of a,b-unsaturated car- nate the encountered problems, a range of odorless
bonyl compounds to the corresponding b-sulfido car- protocols has also been reported. The use of long-
bonyl derivatives provides a strategy for the chemose- chain alkyl thiols or substituted thiophenols with a tri-
lective protection of C=C bonds. Regeneration of the methylsilyl moiety as odorless substrates have been
olefinic double bond is easily achieved by oxidative reported for this purpose.[12] The use of 3-[bis(alkyl-
elimination[2] or induced by Cu+.[3] In addition, these
thio)methylene]pentane-2,4-diones,[13] dialkyl disul-
ACHTUNGTRENNUNG
compounds are starting materials for the generation fides,[14] 4,4-bis(alkylthio)but-3-en-2-ones[15] and S-al-
of b-acylvinyl cations[4] and homoenolate anion equiv- kylisothiouronium salts[16] as thiol equivalent precur-
alents.[5] For these and other reasons, the thia-Michael sors is also reported. However, these odorless proce-
addition is an important reaction in organic synthesis dures encounter disadvantages, such as that most of
and plays a crucial role in biosynthesis and the syn- the reagents should be prepared from thiols, unavaila-
thesis of bioactive compounds.[6] The reported meth- bility and cost of some catalysts, long reaction times
ods for thia-Micheal addition are mainly focused on and use of strong alkaline media.
the use of acidic and basic catalysts for the direct ad-
Disposing of organic solvents in industry is a major
dition of thiols to Michael acceptors in organic sol- problem and around 80% of the wastes are composed
vents. However, efforts have been made constantly to of these solvents.[17,18] The replacement of expensive,
introduce new methodologies which are efficient and toxic, flammable, not recyclable organic solvents with
more compatible with the environment. For this goal, water is thus an important practical achievement.
the reactions conducted under solvent-free condi- Water is a cheap, abundant, non-toxic, non-flammable
tions,[7,8] in ionic liquids[9] and using water as the and relatively green solvent.[19,20] On the other hand,
medium[10,11] have been reported. In all the reported water with its chemical and physical properties impos-
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Habib Firouzabadi et al.
FULL PAPERS
es selectivity and reactivity in reactions conducted in both primary alkyl bromides and iodides in the pres-
aqueous media which cannot be gained using organic ence of thiourea and Michael acceptors such as a,b-
solvents.[21–23] However, dissolving many organic com- unsaturated ketones, esters and acrylonitrile with
pounds in water is difficult and for this reason, reac- good to excellent yields. Secondary and tertiary hal-
tions cannot proceed easily in aqueous media.[24] One ides remained unreacted in the reaction mixture
way to improve the solubility of substrates in water is under such conditions.
the use of surface-active reagents that can form mi-
Moreover, we have also found that the reaction of
celles or vesicular cavities. Due to the applicability more reactive primary benzylic and allylic halides
and practicability of the surfactant-aided reactions, with thiourea and Michael acceptors was efficiently
the use of micellar and vesicle-forming surfactants as catalyzed by the SDS micellar solution at room tem-
catalysts is widespread and has been studied for dif- perature in the presence of Na2CO3. The correspond-
ferent synthetic transformation in water.[25–28]
ing thia-Michael adducts were obtained in good to ex-
Using water as the reaction media has been one of cellent yields. These results are presented in Table 2.
our interests in recent years. Along this line, we have In order to show the merit of the SDS micellar so-
successfully used water and micellar solutions for Mi- lution, the reaction of benzyl chloride, thiourea, and
chael and some other synthetic transformations.[11,29–33] n-butyl acrylate was studied in the absence of SDS
Now, herein we report a pronounced catalytic effect under similar reaction conditions as mentioned in the
of a micellar solution of sodium dodecyl sulfate preceding paragraph. It was observed that the reac-
(SDS) for the in situ generation of the thiol moiety to tion proceeded very slowly and only 40% (GC analy-
perform an efficient and odorless addition to elec- sis) of the desired Michael adduct (5l) was produced
tron-deficient alkenes via the thia-Michael reaction. after 24 h.
For this purpose, commercially available and cheap
Then we applied the above-mentioned optimized
thiourea, alkyl, benzyl and allyl halides and electron- conditions to the reaction of acrylamide with different
deficient a,b-unsaturated olefins were reacted in a halides. Under such reaction conditions, no Michael
vessel under mild basic (NaHCO3 or Na2CO3) condi- adduct were formed at all. Then we decided to per-
tions.
form the reactions in two consecutive steps. For this
purpose, in the first step, thiourea (1.3 mmol) was
added to the alkyl halides (1.2 mmol) in 0.2 mL aque-
ous solution of 0.5 molar SDS and the resulting mix-
ture was heated at 80–908C for the appropriate times
Results and Discussion
À
As a part of our interest in C S bond forming reac- as indicated in Table 3. Then acrylamide (1 mmol),
tions,[7,11] we have initiated an investigation on the use Na2CO3 (1.5 mmol) in H2O (1 mL) were added to the
À
of non-thiolic precursors for C S bond formation via reaction mixture at 80–908C with stirring for 1 h. By
the thia-Michael addition reaction.
this protocol, the reactions proceeded to completion
In this regard, we have studied the reaction of n- and the resulting thia-Michael adducts were isolated
butyl acrylate with 1-bromooctane and thiourea as in 85–92% yields (Table 3).
the source for the in situ generation of thiol in a mi-
The catalytic effect of the micellar solution of SDS
cellar solution of sodium dodecyl sulfate in the pres- may be explained as follows. Alkyl halides are hydro-
ence of NaHCO3. We observed that the optimized phobic molecules thus they are not soluble in aqueous
conditions for completion of the reaction were n- media, and this could be the reason why no reaction
butyl acrylate (1 mmol), 1-bromooctane (1.2 mmol), occurs between alkyl halides and thiourea in the ab-
thiourea (1.3 mmol) and NaHCO3 (1.5 mmol) in sence of SDS. Moreover, in the micellar solution, hy-
0.5 mL of a 0.2 molar (25 CMC, 1 CMC=8.1ꢁ drophobic alkyl halides are pushed by water mole-
10À3 M) solution of SDS in water at 80–908C. More cules towards the hydrophobic core of the micelle
studies showed that the presence of SDS in this reac- droplets. In the droplets, efficient collisions between
tion is crucial, such that the similar reaction in the ab- alkyl halides and thiourea take place more effectively
sence of SDS completely failed and both n-butyl acry- to enhance the reaction rates for the formation of S-
late and 1-bromooctane were isolated intact from the alkylisothiouronium salts. This salt is an amphiphilic
reaction mixture after 8 h. This finding shows the pro- molecule containing both an apolar hydrocarbon tail
nounced catalytic effect of SDS for the generation of moiety and a polar head group. The apolar hydrocar-
the thiol moiety under applied conditions. Then the bon tail moiety of the salt dissolves in the hydropho-
above optimized conditions were applied for the bic core of the micelle, while the polar head group is
preparation of thia-Michael adducts using structurally located at the hydrophilic micellar core (palisade and
diverse primary alkyl halides and electron-deficient Gouy–Chapman layers) in contact with and hydrated
olefins. The results of this study are summarized in by a number of water molecules in the layers. Simul-
Table 1. As the results show, this method is general taneous hydrolysis of the salt followed by the genera-
and applicable for the preparation of thioethers from tion of the thiol moiety and its addition to the alkene
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Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate
FULL PAPERS
Table 1. One-pot thia-Michael addition using RX (X=Br, I), thiourea and electron-deficient alkenes catalyzed by SDS mi-
cellar solution.
Entry
1
RX
Product
Time [h]
3.5
Isolated Yield [%]
73
Ref.
[34]
1a
2a
3a
2
3
4
1a
1a
1a
2b
2c
2d
3b
3c
3d
3.5
3.5
3.5
70
84
87
[35]
[36]
5
6
7
1a
1a
1a
2e
2f
2g
3e
3f
3g
3.5
3.5
3.5
83
83
80
[37]
8
1b
2a
3h
3
75
[34]
[38]
9
1b
1b
2c
3i
3j
3
3
87
87
10
2d
11
1b
2g
3k
3
88
12
13
14
15
1c
1c
1c
1c
2a
2c
2d
2g
3h
3i
3j
8
8
8
8
73
85
86
84
3k
16
1d
2a
3l
1
80
ACHTUNGTRENNUNG[14a]
17
18
1d
1d
2c
3m
3n
1
1
88
90
[9a]
[16]
2d
19
20
1d
1d
2f
2g
3o
3p
1
88
ACHTUNGTRENNUNG
1
87
21
22
23
1e
1e
1e
2a
2c
2d
3l
3m
3n
5
5
5
73
87
91
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Habib Firouzabadi et al.
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Table 1. (Continued)
Entry
RX
Product
Time [h]
Isolated Yield [%]
Ref.
24
25
1e
1e
2f
2g
3o
3p
5
5
84
88
26
1f
2a
3q
0.75
75
[40]
27
28
29
1f
1f
1f
2b
2c
2d
3r
3s
3t
0.75
0.75
0.75
70
87
92
[40]
[41]
[42]
30
1g
2a
3u
1
81[a]
[16]
31
32
33
34
1g
1h
1h
1h
1h
2d
2b
2c
2d
2g
3v
3w
3x
3y
3z
1
6
6
6
6
92[a]
71
[43]
[44]
88
84
35
83
[a]
The reaction was carried out in the sealed tube.
Table 2. One-pot thia-Michael addition using allyl and benzyl halides, thiourea and electron-deficient alkenes catalyzed by
SDS micellar solution at room temperature.
Entry
1
RX
Product
Time [h]
2
Isolated Yield [%]
82
Ref.
[16]
4a
2a
5a
2
3
4
4a
4a
4a
2b
2c
2e
5b
5c
5d
2
2
2
75
90
92
[16]
[16]
[45]
5
6
4a
4b
2g
2a
5e
5a
2
92
80
10
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Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate
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Table 2. (Continued)
Entry
RX
Product
Time [h]
Isolated Yield [%]
Ref.
7
8
9
10
4b
4b
4b
4b
2b
2c
2e
2g
5b
5c
5d
5e
10
10
10
10
72
90
90
90
11
12
13
4c
4c
4c
2b
2c
2d
5f
5g
5h
10
10
10
75
90
90
[46]
14
4c
2g
5i
10
88
15
16
17
4d
4d
4d
2b
2c
2d
5j
5k
5l
2
2
2
76
91
92
[16]
[16]
[47]
18
19
4d
4d
2e
2g
5m
5n
2
2
91
85
[12]
[12]
20
21
22
23
24
4e
4e
4e
4e
4e
2b
2c
2d
2e
2g
5j
5k
5l
5m
5n
4
4
4
4
4
70
90
90
91
85
25
26
27
4f
4f
4f
2b
2c
2d
5o
5p
5q
3
3
3
72
91
89
[48]
28
4f
2g
5r
3
85
29
30
31
32
4g
4g
4g
4g
2b
2c
2d
2g
5s
5t
48
48
48
48
70
89
89
80
[49]
5u
5v
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Table 3. Thia-Michael addition at acrylamide using alkyl halides and thiourea in the presence of Na2CO3 in SDS micellar so-
lution.
Entry
1
RX
Product
t [h]
Isolated Yield [%]
90
Ref.
[50]
n-decyl iodide
6a
2.5
2
3
4
5
6
n-octyl iodide
n-octyl bromide
n-butyl iodide
n-butyl bromide
n-propyl iodide
6b
6b
6c
6c
6d
2
87
85
90
87
92
5
1
2.5
0.7
7
8
benzyl bromide
benzyl chloride
6e
6e
0.5
0.5
91
90
[51]
molecule which is present in the hydrophobic micellar Experimental Section
core results in the formation of the Michael adduct.
The role of SDS droplets for the formation of S-al- General Procedure for the Synthesis of Thia-Michael
kylisothiouronium salt and its consecutive reactions Adducts with Alkyl Halides (1a–1h), Thiourea and
for the formation of thia-Michael adducts are sche- Electron-Deficient Alkenes (2a–2g) in a Micellar
ACHTUNGTRENNUNG
matically presented by Figure 1.
Solution of SDS at 80–908C
To a micellar solution of SDS (0.5 mL, 0.2M), was added an
electron-deficient alkene (2a–2g) (1 mmol), alkyl halide
(1a–1h) (1.2 mmol), thiourea (1.3 mmol) and NaHCO3
(1.5 mmol). The resulting mixture was heated at 80–908C
with stirring. The progress of the reaction was monitored by
TLC or GC until the starting materials were consumed
(Table 1, entries 1–35). Then the reaction mixture was ex-
tracted with ethyl acetate (5ꢁ2 mL), dried over Na2SO4,
and concentrated. Purification by silica gel chromatography
using petroleum ether/EtOAc (20/1) as eluent afforded the
desired products in 70–92% yields.
Conclusions
We have introduced a new, one-pot, odorless proce-
À
dure for C S bond formation via a conjugate addition
reaction using alkyl halides, thiourea and electron-de-
ficient olefins in the SDS micellar solution. In this
procedure, water is employed as the reaction media,
non-thiolic precursors are used for the in situ genera-
tion of thiol moiety, which makes the reaction an
odorless process and, more importantly, makes the
synthesis of structurally diverse thia-Michael adducts
possible. Because structurally different thiols are not
usually commercially available compounds for the
previously used protocol, this limitation has been
eliminated for the preparation of more versatile thia-
Michael products. By this method, we have shown an-
other important catalytic role of the micellar solution
of SDS in organic synthesis. The yields of the ob-
tained thia-Michael adducts are high to excellent and
the work-up of the reaction mixture is very conven-
ient, which could be applied easily for large-scale op-
erations.
General Procedure for the Synthesis of Thia-Michael
Adducts with Allylic and Benzylic Halides (4a–4g),
Thiourea and Electron-Deficient Alkenes (2a–2g) in
a Micellar Solution of SDS at Room Temperature
An allylic or benzylic halide (4a–4g) (1.2 mmol) was added
to a micellar solution of SDS (1 mL, 0.1M), electron defi-
cient alkene (2b–2g) (1 mmol), thiourea (1.33 mmol), and
Na2CO3 (1.5 mmol) and the mixture was stirred magnetical-
ly at room temperature. Monitoring of the reaction by TLC
or GC showed the completion of the reaction within 2–48 h
(Table 2). The product was then extracted with ethyl acetate
(5ꢁ2 mL), dried over Na2SO4, and concentrated. Silica gel
chromatography using petroleum ether/EtOAc (20/1) as
eluent afforded the pure product in 70–92% yields.
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Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate
FULL PAPERS
Figure 1. The proposed role of micellar SDS droplets for thia-Michael adduct formation.
ture was heated at 80–908C with stirring. The progress of
the reaction was monitored by GC until the starting n-butyl
acrylate was consumed. The reaction was completed in 5 h.
Then the reaction mixture was extracted with ethyl acetate
(5ꢁ10 mL), dried over Na2SO4, and concentrated. Purifica-
tion by silica gel chromatography using petroleum ether/
EtOAc (20/1) as eluent afforded the desired product; yield:
3.8 g (87%).
General Procedure for Thia-Michael Addition to
Acrylamide in a Micellar Solution of SDS using Alkyl
Halides, Thiourea and Na2CO3 at 908C
A micellar solution of SDS (0.2 mL, 0.5M), alkyl halide
(1.2 mmol) and thiourea (1.3 mmol) was stirred at 80–908C
for the appropriate times as indicated in Table 3. Then a
mixture of acrylamide (1 mmol), and Na2CO3 (1.5 mmol) in
water (1 mL) was added to the reaction mixture while being
magnetically stirred at 80–908C for 1 h. Then, the mixture
was diluted with water (5 mL) and extracted with EtOAc
(5ꢁ10 mL). Organic phase was washed with water (3ꢁ
10 mL), dried over anhydrous Na2SO4 and evaporated. Re-
crystallization of the crude products in ethyl acetate afford-
ed the purified products in excellent yields.
3-Decylsulfanylcyclohexanone
(3a):
Colorless
oil;
1H NMR (250 MHz, CDCl3): d=3.00–2.94 (m, 1H), 2.64
(dd, J=14.2, 4.4 Hz, 1H), 2.47 (t, J=7.3 Hz, 2H), 2.35–2.24
(m, 3H), 2.13–2.03 (m, 2H), 1.72–1.50 (m, 2H), 1.55–1.44
(m, 2H), 1.28–1.19 (m, 14H), 0.83–0.78 (m, 3H); 13C NMR
(62.5 MHz, CDCl3): d=208.88, 48.22, 42.72, 40.92, 31.84,
31.63, 30.51, 29.68, 29.50, 29.46, 29.26, 29.17, 28.91, 24.23,
22.63, 14.07; IR (neat): n=1717 cmÀ1 (C=O); anal. calcd. for
(C16H30OS): C 71.05, H 11.18, S 11.86; found: C 71.01, H
11.10, S 11.91.
Typical Procedure for Large-Scale Preparation of
Thia-Michael Adduct using n-Butyl Acrylate,
Thiourea, n-Butyl Bromide and NaHCO3 in SDS
Micellar Solution
4-Decylsulfanylbutan-2-one (3b): Colorless oil; 1H NMR
(250 MHz, CDCl3): d=2.66 (s, 4H), 2.44 (t, J=7.3 Hz, 2H),
2.10 (s, 3H), 1.56–1.44 (m, 2H), 1.28–1.19 (m, 14H), 0.81–
0.78 (m, 3H); 13C NMR (62.5 MHz, CDCl3): d=207.01,
43.72, 32.42, 31.87, 30.07, 29.55, 29.53, 29.51, 29.29, 29.21,
28.86, 25.74, 22.66, 14.10; IR: n=1717 cmÀ1 (C=O); anal.
To a micellar solution of SDS (10 mL, 0.2M), was added n-
butyl acrylate (20 mmol), n-butyl bromide (24 mmol), thio-
urea (26 mmol) and NaHCO3 (30 mmol). The resulting mix-
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Habib Firouzabadi et al.
FULL PAPERS
calcd. for (C14H28OS): C 68.79, H 11.55, S 13.12; found: C
68.71, H 11.59, S, 13.17.
3-Decylsulfanylpropionitrile (3c): Colorless oil; H NMR
(250 MHz, CDCl3): d=2.79–2.71 (m, 2H), 2.65–2.49 (m,
4H), 1.61–1.47 (m, 2H), 1.30–1.05 (m, 14H), 0.84–0.78 (m,
3H); 13C NMR (62.5 MHz, CDCl3): d=118.40, 32.25, 31.86,
29.51, 29.47, 29.42, 29.27, 29.16, 28.75, 27.59, 22.65, 18.89,
14.09; IR: n=2249 cmÀ1 (CN); anal. calcd. for (C13H25NS):
C 68.66, H 11.08, N 6.16, S 14.10; found: C 68.60, H 11.06,
N 6.19, S 14.15.
3-Octylsulfanylpropionic acid butyl ester (3j): Colorless
oil; 1H NMR (250 MHz, CDCl3): d=4.03 (t, J=6.63 Hz,
2H), 2.74–2.68 (m, 2H), 2.56–2.43 (m, 4H), 1.61–1.45 (m,
4H), 1.39–1.20 (m, 12H), 0.90–0.78 (m, 6H); 13C NMR
(62.5 MHz, CDCl3): d=172.13, 64.54, 34.96, 32.14, 31.79,
30.61, 29.55, 29.17, 28.86, 27.01, 22.63, 19.11, 14.07, 13.68; IR
(neat): n=1736 cmÀ1 (C=O); anal. calcd. for (C15H30O2S): C
65.64, H 11.02, S 11.68; found: C 65.66, H 11.06, S 11.62.
3-Octylsulfanylbutyric acid ethyl ester (3k): Colorless oil;
1H NMR (250 MHz, CDCl3): d=4.09 (q, J=7.1 Hz, 2H),
3.19–3.06 (m, 1H), 2.59–2.31 (m, 4H), 1.56–1.45 (m, 2H),
1.29–1.17 (m, 16H), 0.83–0.78 (m, 3H); 13C NMR
(62.5 MHz, CDCl3): d=171.53, 60.49, 42.39, 36.13, 31.78,
30.63, 29.68, 29.16, 28.97, 22.61, 21.40, 14.20, 14.06; IR
(neat): n=1736 cmÀ1 (C=O); anal. calcd. for (C14H28O2S): C
64.56, H 10.84, S 12.31; found: C 64.63, H 10.80, S 12.33.
1
3-Decylsulfanylpropionic acid butyl ester (3d): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=4.03 (t, J=6.7 Hz, 2H),
2.74–2.68 (m, 2H), 2.59–2.45 (m, 4H), 1.64–1.45 (m, 4H),
1.39–1.19 (m, 16H), 0.89–0.78 (m, 6H); 13C NMR
(62.5 MHz, CDCl3): d=172.09, 64.51, 34.94, 32.12, 31.86,
30.60, 29.53, 29.50, 29.28, 29.20, 28.85, 26.99, 22.65, 19.10,
14.08, 13.67; IR (neat): n=1736 cmÀ1 (C=O); anal. calcd. for
(C17H34O2S): C 67.49, H 11.33, S 10.60; found: C 67.53, H
11.27, S 10.65.
3-Decylsulfanylpropionic acid ethyl ester (3e): Colorless
oil; 1H NMR (250 MHz, CDCl3): d=4.09 (q, J=7.1 Hz,
2H), 2.73–2.68 (m, 2H), 2.55–2.43 (m, 4H), 1.54–1.47 (m,
2H), 1.29–1.17 (m, 17H), 0.83–0.78 (m, 3H); 13C NMR
(62.5 MHz, CDCl3): d=170.78, 44.81, 31.75, 30.39, 30.18,
29.10, 29.04, 28.82, 28.79, 22.60, 14.05; IR (neat): n=
1736 cmÀ1 (C=O); anal. calcd. for (C15H30O2S): C 65.64, H
11.02, S 11.68; found: C 65.58, H 11.06, S 11.75.
1
3-Butylsulfanylcyclohexanone (3l): Colorless oil; H NMR
(250 MHz, CDCl3): d=3.15–2.98 (m, 1H), 2.70 (dd, J=14.1,
4.5 Hz, 1H), 2.54 (t, J=7.3 Hz, 2H), 2.42–2.30 (m, 3H),
2.17–2.10 (m, 2H), 1.58–1.50 (m, 2H), 1.44–1.35 (m, 2H),
0.91 (t, J=7.2, 3H); 13C NMR (62.5 MHz, CDCl3): d=
208.96, 48.27, 42.74, 40.96, 31.76, 31.67, 30.21, 24.28, 22.04,
13.64; IR (neat): n=1717 cmÀ1 (C=O); anal. calcd. for
(C10H18OS): C 64.46, H 9.74, S 17.21; found: C 64.53, H 9.70,
S 17.19.
3-Butylsulfanyl-2-methylpropionic acid ethyl ester (3o):
1
Colorless oil; H NMR (250 MHz, CDCl3): d=4.07 (q, J=
3-Decylsulfanyl-2-methylpropionic acid ethyl ester (3f):
Colorless oil; H NMR (250 MHz, CDCl3): d=4.09 (q, J=
7.1 Hz, 2H), 2.78–2.71 (m, 1H), 2.67–2.40 (m, 4H), 1.53–
1.42 (m, 2H), 1.39–1.24 (m, 2H), 1.18 (t, J=7.1 Hz, 3H),
1.16 (d, J=6.7 Hz, 3H); 13C NMR (62.5 MHz, CDCl3): d=
175.08, 60.38, 40.16, 35.40, 32.19, 31.60, 21.83, 16.70, 14.10,
13.54; IR (neat): n=1736 cmÀ1 (C=O); anal. calcd. for
(C10H20O2S): C 58.78, H 9.87, S 15.69; found: C 58.87, H
9.82, S 15.73.
3-Butylsulfanylbutyric acid ethyl ester (3p): Colorless oil;
1H NMR (250 MHz, CDCl3): d=4.04 (q, J=7.1 Hz, 2H),
3.15–3.01 (m, 1H), 2.55–2.70 (m, 4H), 1.52–1.40 (m, 2H),
1.37–1.28 (m, 2H), 1.22–1.13 (m, 6H), 0.81 (t, J=7.2 Hz,
3H); 13C NMR (62.5 MHz, CDCl3): d=171.38, 60.36, 42.29,
36.02, 31.67, 30.17, 21.94, 21.32, 14.11, 13.55; IR (neat): n=
1736 cmÀ1 (C=O); anal. calcd. for (C10H20O2S): C 58.78, H
9.87, S 15.69; found: C 58.70, H 9.91, S 15.72.
3-Methylsulfanylcyclohexanone (3u): Colorless oil;
1H NMR (250 MHz, CDCl3): d=2.93–2.85 (m, 1H), 2.65
(dd, J=14.1, 4.2 Hz, 1H), 2.36–2.19 (m, 3H), 2.08–2.05 (m,
5H), 1.73–1.57 (m, 2H); 13C NMR (62.5 MHz, CDCl3): d=
208.85, 47.57, 44.17, 40.91, 31.00, 24.12, 13.53; IR (neat): n=
1713 cmÀ1 (C=O); anal. calcd. for (C7H12OS): C 58.29, H
8.39, S 22.23; found: C 58.22, H 8.42, S 22.20.
1
7.1 Hz, 2H), 2.80–2.73 (m, 1H), 2.62–2.44 (m, 4H), 1.56–
1.44 (m, 2H), 1.22–1.16 (m, 20H), 0.83–0.78 (m, 3H);
13C NMR (62.5 MHz, CDCl3): d=175.23, 60.50, 40.23, 35.47,
32.62, 31.86, 29.60, 29.53, 29.50, 29.28, 29.20, 28.83, 22.65,
16.80, 14.18, 14.09; IR (neat): n=1736 cmÀ1 (C=O); MS:
m/e=288 [M+]; anal. calcd. for (C16H32O2S): C 66.61, H
11.18, S 11.11; found: C 66.66, H 11.16, S 11.14.
3-Decylsulfanylbutyric acid ethyl ester (3g): Colorless oil;
1H NMR (250 MHz, CDCl3): d=4.09 (q, J=7.1 Hz, 2H),
3.19–3.06 (m, 1H), 2.59–2.31 (m, 4H), 1.56–1.45 (m, 2H),
1.32–1.17 (m, 20H), 0.83–0.78 (m, 3H); 13C NMR
(62.5 MHz, CDCl3): d=171.54, 60.49, 42.38, 36.20, 31.87,
30.63, 29.68, 29.53, 29.50, 29.28, 29.21, 28.97, 22.65, 21.41,
14.20, 14.08; IR (neat): n=1736 cmÀ1 (C=O); MS: m/e=288
[M+]; anal. calcd. for (C16H32O2S): C 66.61, H 11.18, S 11.11;
found: C 66.65, H 11.12, S 11.13.
3-Octylsulfanylcyclohexanone
(3h):
Colorless
oil;
1H NMR (250 MHz, CDCl3): d=2.99–2.94 (m, 1H), 2.65
(dd, J=14.2, 4.5 Hz, 1H), 2.47 (t, J=7.5 Hz, 2H), 2.35–2.24
(m, 3H), 2.10–2.03 (m, 2H), 1.68–1.59 (m, 2H), 1.53–1.44
(m, 2H), 1.32–1.20 (m, 10H), 0.83–0.78 (m, 3H); 13C NMR
(62.5 MHz, CDCl3): d=208.96, 48.26, 42.75, 40.95, 31.76,
31.67, 30.54, 29.70, 29.14, 28.93, 24.26, 22.61, 14.06; IR
(neat): n=1717 cmÀ1 (C=O); anal. calcd. for (C14H26OS): C
69.36, H 10.81, S 13.23; found: C 69.33, H 10.75, S 13.29.
3-Octylsulfanylpropionitrile (3i): Colorless oil; 1H NMR
(250 MHz, CDCl3): d=2.66–2.60 (m, 2H), 2.50–2.40 (m,
4H), 1.53–1.38 (m, 2H), 1.25–1.12 (m, 10H), 0.75–0.65 (m,
3H); 13C NMR (62.5 MHz, CDCl3): d=118.43, 32.24, 31.76,
29.41, 29.12, 28.75, 27.57, 22.61, 18.90, 14.09; IR (neat): n=
2249 cmÀ1 (CN); anal. calcd. for (C11H21NS): C 66.27, H
10.62, N 7.03, S 16.08: found: C 66.33, H 10.67, N 7.01, S
15.99.
3-Methylsulfanylpropionic acid butyl ester (3v): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=4.03 (t, J=6.6 Hz, 2H),
2.72–2.67 (m, 2H), 2.57–2.51 (m, 2H), 2.05 (s, 3H), 1.61–
1.50 (m, 2H), 1.39–1.24 (m, 2H), 0.87 (t, J=7.3 Hz, 3H);
13C NMR (62.5 MHz, CDCl3): d=171.90, 64.42, 34.40, 30.55,
29.03, 19.04, 15.34, 13.59; IR (neat): n=1736 cmÀ1 (C=O);
anal. calcd for (C8H16O2S): C 54.51, H 9.15, S 18.19; found:
C 54.57, H 9.10, S, 18.12.
4-Phenethylsulfanylbutan-2-one (3w): Colorless oil;
1H NMR (250 MHz, CDCl3): d=7.33–7.19 (m, 5H), 2.81–
2.65 (m, 8H), 2.15 (s, 3H); 13C NMR (62.5 MHz, CDCl3):
d=206.84, 140.40, 128.49, 126.38, 43.66, 36.22, 33.99, 30.08,
25.90; IR (neat): n=1717 (C=O), 1605, 1496 cmÀ1 (aromatic
762
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Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate
FULL PAPERS
C=C); anal. calcd. for (C12H16OS): C 69.19, H 7.74, S 15.39;
found: C 69.14, H 7.80, S 15.34.
3-Allylsulfanylbutyric acid ethyl ester (5e): Colorless oil;
1H NMR (250 MHz, CDCl3): d=5.83–5.67 (m, 1H), 5.11–
5.00 (m, 2H), 4.08 (q, J=7.1 Hz, 2H), 3.17–3.03 (m, 3H),
2.55 (dd, J=15.4, 6.1 Hz, 1H), 2.35 (dd, J=15.4, 8.3 Hz,
1H), 1.25–1.16 (m, 6H); 13C NMR (62.5 MHz, CDCl3): d=
171.31, 134.43, 116.93, 60.44, 42.03, 35.13, 33.87, 21.13, 14.17;
IR (neat): n=1736 (C=O), 1636 cmÀ1 (C=C); anal. calcd. for
(C9H16O2S): C 57.41, H 8.57, S 17.03, found: C 57.44, H 8.50,
S 17.06.
4-(2-Methylallylsulfanyl)-butan-2-one (5f): Colorless oil;
1H NMR (250 MHz, CDCl3): d=4.69 (s, 2H), 2.96 (s, 2H),
2.59–2.41 (m, 4H), 2.01 (s, 3H), 1.58 (s, 3H); 13C NMR
(62.5 MHz, CDCl3): d=206.96, 141.12, 113.63, 43.26, 39.65,
30.04, 24.68, 20.56; IR (neat): n=1717 (C=O), 1647 cmÀ1
(C=C); anal. calcd. for (C8H14OS): C 60.71, H 8.92, S 20.26;
found: C 60.66, H 8.99, S 20.25.
3-(2-Methylallylsulfanyl)-propionitrile (5g): Colorless oil;
1H NMR (250 MHz, CDCl3): d=4.75–4.72 (m, 2H), 3.04 (s,
2H), 2.61–2.44 (m, 4H), 1.67 (s, 3H); 13C NMR (62.5 MHz,
CDCl3): d=140.57, 118.53, 114.35, 39.20, 26.05, 20.34, 18.39;
IR (neat): n=2249 (CN), 1647 cmÀ1 (C=C); anal. calcd. for
(C7H11NS): C 59.53, H 7.85, N, 9.92, S 22.70; found: C 59.55,
H 7.81, N 9.86, S 22.78.
3-Phenethylsulfanylpropionitrile (3x): Colorless oil;
1H NMR (250 MHz, CDCl3): d=7.34–7.22 (m, 5H), 2.91–
2.84 (m, 4H), 2.76–2.70 (m, 2H), 2.58–2.53 (m, 2H);
13C NMR (62.5 MHz, CDCl3): d=142.28, 128.61, 126.62,
118.59, 36.13, 33.78, 27.82, 18.89; IR (neat): n=2249 (CN),
1601, 1497 cmÀ1 (aromatic C=C); anal. calcd. for
(C11H13NS): C 69.07, H 6.85, N, 7.32, S 16.76; found: C
69.10, H 6.82, N 7.29, S 16.79.
3-Phenethylsulfanylpropionic acid butyl ester (3y): Color-
1
less oil; H NMR (250 MHz, CDCl3): d=7.17–7.06 (m, 5H),
3.99 (t, J=6.6 Hz, 2H), 2.77–2.63 (m, 6H), 2.47 (t, J=
7.2 Hz, 2H), 1.58–1.42 (m, 2H), 1.32–1.15 (m, 2H), 0.83 (t,
J=7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3): d=171.92,
140.42, 128.47, 126.37, 64.50, 36.25, 34.92, 33.66, 30.66, 27.18,
19.15, 13.74; IR (neat): n=1736 (C=O), 1605, 1497 cmÀ1 (ar-
omatic C=C); anal. calcd. for (C15H22O2S): C 67.63, H 8.32,
S 12.04; found: C 67.59, H 8.33, S 12.06.
3-Phenethylsulfanylbutyric acid ethyl ester (3z): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=7.13–7.06 (m, 5H), 4.04
(q, J=7.1 Hz, 2H), 3.22–3.13 (m, 1H), 2.83–2.64 (m, 4H),
2.51 (dd, J=15.4, 6.3 Hz, 1H), 2.33 (dd, J=.15.4, 8.1 Hz,
1H), 1.23 (d, J=6.8 Hz, 3H), 1.15 (t, J=7.1 Hz, 3H);
13C NMR (62.5 MHz, CDCl3): d=171.26, 138.79, 128.47,
128.45, 126.34, 60.44, 42.34, 36.33, 32.17, 21.47, 14.27; IR
(neat): n=1736 (C=O), 1605, 1497 cmÀ1 (aromatic C=C);
anal. calcd for (C14H20O2S): C 66.63, H 7.99, S 12.71; found:
C 66.67, H 8.03, S 12.67.
3-(2-Methylallylsulfanyl)-propionic acid butyl ester (5h):
1
Colorless oil; H NMR (250 MHz, CDCl3): d=4.78–4.77 (m,
2H), 4.03 (t, J=6.6 Hz, 2H), 3.06 (s, 2H), 2.65–2.59 (m,
2H), 2.53–2.46 (m, 2H), 1.75 (s, 3H), 1.60–1.49 (m, 2H),
1.39–1.27 (m, 2H), 0.86 (t, J=7.3 Hz, 3H); 13C NMR
(62.5 MHz, CDCl3): d=171.99, 141.02, 113.64, 64.46, 39.30,
34.41, 30.59, 25.77, 20.49, 19.08, 13.65; IR (neat): n=1736
(C=O), 1647 cmÀ1 (C=C); anal. calcd. for (C11H20O2S): C
61.07, H 9.32, S 14.82; found: C 61.01, H 9.35, S 14.87.
3-(2-Methyl-allylsulfanyl)-butyric acid ethyl ester (5i):
1
3-Allylsulfanylcyclohexanone (5a): Colorless oil; H NMR
(250 MHz, CDCl3): d=5.69–5.53 (m, 1H), 5.00–4.88 (m,
2H), 3.00 (d, J=7.0 Hz, 2H), 2.87–2.81 (m, 1H), 2.50 (dd,
J=14.3, 4.5 Hz, 1H), 2.24–2.12 (m, 3H), 1.98–1.90 (m, 2H),
1.57–1.43 (m, 2H); 13C NMR (62.5 MHz, CDCl3): d=208.75,
134.20, 117.18, 47.88, 41.39, 40.92, 33.54, 31.32, 24.16; IR
(neat): n=1716 (C=O), 1634 cmÀ1 (C=C); anal. calcd. for
(C9H14OS): C 63.48, H 8.29, S 18.83; found: C 63.55, H 8.35,
S 18.76.
1
Colorless oil; H NMR (250 MHz, CDCl3): d=4.59–4.55 (m,
2H), 3.88 (q, J=7.0 Hz, 2H), 2.88 (s, 2H), 2.83–2.74 (m,
1H), 2.32 (dd, J=15.3, 6.3 Hz, 1H), 2.13 (dd, J=15.3,
8.2 Hz, 1H), 1.53 (s, 3H), 1.03–0.94 (m, 6H); 13C NMR
(62.5 MHz, CDCl3): d=171.21, 141.33, 113.31, 60.29, 41.87,
38.37, 20.96, 20.82, 20.55, 14.12; IR (neat): n=1736 (C=O),
1647 cmÀ1 (C=C); anal. calcd. for (C10H18O2S): C 59.37, H
8.97, S 15.85; found: C 59.41, H 8.90, S 15.89.
4-Allylsulfanylbutan-2-one (5b): Colorless oil; 1H NMR
(250 MHz, CDCl3): d=5.77–5.63 (m, 1H), 5.08–5.01 (m,
2H), 3.07 (d, J=7.1 Hz, 2H), 2.66–2.58 (m, 4H), 2.10 (s,
3H); 13C NMR (62.5 MHz, CDCl3): d=206.78, 134.20,
117.16, 43.42, 35.09, 30.04, 24.44; IR (neat): n=1716 (C=O),
1634 cmÀ1 (C=C); anal. calcd. for (C7H12OS): C 58.29, H
8.39, S 22.23; found: C 58.35, H 8.33, S 22.27.
3-Benzylsulfanylpropionic acid butyl ester (5l): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=7.16–7.04 (m, 5H), 3.92
(t, J=6.6 Hz, 2H), 3.53 (s, 2H), 2.53–2.47 (m, 2H), 2.39–
2.32 (m, 2H), 1.49–1.38 (m, 2H), 1.28–1.14 (m, 2H), 0.77 (t,
J=7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3): d=171.55,
138.21, 128.81, 128.41, 126.92, 64.24, 36.08, 34.45, 30.63,
26.21, 19.11, 13.69; IR (neat): n=1736 (C=O), 1601,
1493 cmÀ1 (aromatic C=C); anal. calcd. for (C14H20O2S): C
66.63, H 7.99, S 12.71; found: C 66.69, H 7.95, S 12.85.
3-Allylsulfanylpropionitrile (5c): Colorless oil; 1H NMR
(250 MHz, CDCl3): d=5.82–5.64 (m, 1H), 5.15–5.08 (m,
2H), 3.17 (d, J=7.2 Hz, 2H), 2.71–2.66 (m, 2H), 2.60–2.54
(m, 2H); 13C NMR (62.5 MHz, CDCl3): d=133.60, 118.44,
117.99, 34.69, 25.81, 18.63; IR (neat): n=2249 (CN),
1634 cmÀ1 (C=C); anal. calcd. for (C6H9NS): C 56.65, H
7.13, N 11.01, S 25.21; found: C 56.59, H 7.09, N 11.07, S
25.25.
3-Allylsulfanylpropionic acid ethyl ester (5d): Colorless
oil; 1H NMR (250 MHz, CDCl3): d=5.86–5.69 (m, 1H),
5.14–5.07 (m, 2H), 4.14 (q, J=7.1 Hz, 2H), 3.14 (d, J=
7.1 Hz, 2H), 2.75–2.69 (m, 2H), 2.59–2.53 (m, 2H), 1.25 (t,
J=7.1 Hz, 3H); 13C NMR (62.5 MHz, CDCl3): d=171.89,
134.12, 117.20, 60.61, 34.74, 34.58, 25.50, 14.18; IR (neat):
n=1732 (C=O), 1634 cmÀ1 (C=C); anal. calcd. for
(C8H14O2S): C 55.14, H 8.10, S 18.40; found: C 55.20, H
8.02, S 18.42.
3-Benzylsulfanylpropionic acid ethyl ester (5m): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=7.18–7.04 (m, 5H), 3.99
(q, J=7.1 Hz, 2H), 3.58 (s, 2H), 2.57–2.51 (m, 2H), 2.42–
2.36 (m, 2H), 1.11 (t, J=7.1 Hz, 3H); 13C NMR (62.5 MHz,
CDCl3): d=171.80, 138.14, 128.84, 128.18, 127.05, 60.57,
36.24, 34.52, 26.23, 14.22; IR (neat): n=1732 (C=O), 1601,
1493 cmÀ1 (aromatic C=C); anal. calcd. for (C12H16O2S): C
64.25, H 7.19, S 14.29; found: C 64.30, H 7.17, S 14.24.
3-Benzylsulfanylbutyric acid ethyl ester (5n): Colorless
1
oil; H NMR (250 MHz, CDCl3): d=7.28–7.06 (m, 5H), 4.02
(q, J=7.1 Hz, 2H), 3.65 (s, 2H), 3.08–2.94 (m, 1H), 2.50
(dd, J=15.3, 6.1 Hz, 1H), 2.31 (dd, J=15.3, 8.2 Hz, 1H),
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FULL PAPERS
1.19 (d, J=6.8 Hz, 3H), 1.13 (t, J=7.1 Hz, 3H); 13C NMR
(62.5 MHz, CDCl3): d=171.27, 138.23, 129.00, 128.82,
126.98, 60.48, 42.10, 36.17, 35.92, 21.20, 14.22; IR (neat): n=
1736 (C=O), 1601, 1493 cmÀ1 (aromatic C=C); anal. calcd.
for (C13H18O2S): C 65.51, H 7.61, S 13.45; found: C 65.55, H
7.56, S 13.50.
3-(4-Nitrobenzylsulfanyl)-propionic acid butyl ester (5u):
Colorless oil; H NMR (250 MHz, CDCl3): d=7.96 (d, J=
1
8.4 Hz, 2H), 7.32 (d, J=8.4 Hz, 2H), 3.89 (t, J=6.7 Hz,
2H), 3.71 (s, 2H), 2.54–2.48 (m, 2H), 2.40–2.34 (m, 2H),
1.46–1.35 (m, 2H), 1.24–1.12 (m, 2H), 0.75–0.69 (m, 3H);
13C NMR (62.5 MHz, CDCl3): d=171.63, 146.90, 146.10,
129.64, 124.09, 64.57, 35.68, 34.35, 30.52, 26.91, 19.04, 13.62;
IR (neat): n=1732 (C=O), 1601 (aromatic C=C), 1520,
1346 cmÀ1 (NO2); MS: m/e=297 [M+]; anal. calcd. for
(C14H19NO4S): C 56.55, H 6.44, N 4.71, S 10.78; found: C
56.60, H 6.40, N 4.73, S 10.72.
4-(4-Methylbenzylsulfanyl)-butan-2-one (5o): Colorless
oil; 1H NMR (250 MHz, CDCl3): d=7.07 (d, J=8.0 Hz,
2H), 6.98 (d, J=8.0 Hz, 2H), 3.53 (s, 2H), 2.48 (s, 4H), 2.17
(s, 3H), 1.95 (s, 3H); 13C NMR (62.5 MHz, CDCl3); d=
206.58, 136.52, 135.19, 129.19, 128.89, 43.54, 36.23, 29.90,
25.13, 21.07; IR (neat): n=1717 (C=O), 1582 cmÀ1 (aromatic
C=C); MS: m/e=208 [M+]; anal. calcd. for (C12H16OS): C
69.19, H 7.74, S 15.39; found: C 69.25, H 7.80, S 15.32.
3-(4-Methylbenzylsulfanyl)-propionitrile (5p) Colorless
oil; 1H NMR (250 MHz, CDCl3): d=7.07 (d, J=8.0 Hz,
2H), 6.99 (d, J=8.0 Hz, 2H), 3.61 (s, 2H), 2.52–2.46 (m,
2H), 2.38–2.31 (m, 2H), 2.19 (s, 3H); 13C NMR (62.5 MHz,
CDCl3): d=137.00, 134.26, 129.34, 128.73, 118.42, 35.85,
26.50, 20.99, 18.49; IR (neat): n=2249 (CN), 1512 cmÀ1 (aro-
matic C=C); MS: m/e=191 [M+]; anal. calcd. for
(C11H13NS): C 69.07, H 6.85, N 7.32, S 16.76; found: C 69.01,
H 6.80, N 7.37, S 16.82.
3-(4-Nitrobenzylsulfanyl)-butyric acid ethyl ester (5v):
1
Colorless oil; H NMR (250 MHz, CDCl3): d=8.09 (d, J=
8.7 Hz, 2H), 7.44 (d, J=8.7 Hz, 2H), 4.03 (q, J=7.1 Hz,
2H), 3.77 (s, 2H), 3.1–2.96 (m, 1H), 2.53 (dd, J=15.5,
6.5 Hz, 1H), 2.36 (dd, J=15.5, 7.8 Hz, 1H), 1.24–1.13 (m,
6H); 13C NMR (62.5 MHz, CDCl3): d=171.08, 146.95,
146.18, 129.66, 123.75, 60.66, 42.02, 36.21, 34.75, 21.26, 14.18;
IR (neat): n=1732 (C=O), 1601 (aromatic C=C), 1520,
1346 cmÀ1 (NO2); MS: m/e=283 [M+]; anal. calcd. for
(C13H17NO4S): C 55.11, H 6.05, N 4.94, S 11.32; found: C
55.17, H 6.02, N 5.01, S 11.37.
3-Decylsulfanylpropionamide (Table 3, entry 1): white
1
solid; mp 97–988C; H NMR (250 MHz, DMSO-d6): d=7.19
3-(4-Methylbenzylsulfanyl)-propionic acid butyl ester
1
(S, b, 1H), 6.67 (s, b, 1H), 2.52–2.46 (m, 2H), 2.35–2.29 (m,
2H), 2.19–2.13 (m, 2H), 1.34–1.29 (m, 2H), 1.09 (s, b,14H),
0.73–0.67 (m, 3H); 13C NMR (62.5 MHz, DMSO-d6): d=
172.64, 35.49, 31.27, 30.97, 30.22, 29.03, 28.96, 28.68, 28.62,
28.22, 26.87, 22.06, 13.84; IR (KBr): n (cmÀ1)=1659 cmÀ1
(C=O); MS: m/e=245 [M+]; anal. calcd. for (C13H27NOS): C
63.62, H 11.09, N 5.71, S 13.07; found: C 63.66, H 11.06, N
5.75, S 13.03.
(5q): Colorless oil; H NMR (250 MHz, CDCl3): d=7.11 (d,
J=8.0 Hz, 2H), 7.03 (d, J=8.0 Hz, 2H), 4 (t, J=6.6 Hz,
2H), 3.61 (s, 2H), 2.62–2.56 (m, 2H), 2.48–2.42 (m, 2H),
2.24 (s, 3H), 1.55–1.46 (m, 2H), 1.33–1.24 (m, 2H), 0.85 (t,
J=7.3 Hz, 3H); 13C NMR (62.5 MHz, CDCl3): d=171.99,
136.67, 134.95, 129.21, 128.72, 64.52, 35.92, 34.53, 30.61,
26.21, 21.07, 19.12, 13.70; IR (neat): n=1736 (C=O),
1589 cmÀ1 (aromatic C=C); MS: m/e=266 [M+]; anal. calcd.
for (C15H22O2S): C 67.63, H 8.32, S 12.04; found: C 67.70, H
8.25, S 12.07.
3-Octylsulfanylpropionamide (Table 3, entries 2, 3): white
1
solid; mp 92–938C; H NMR (250 MHz, DMSO-d6): d=7.32
(s, b, 1H), 6.81 (s, b, 1H), 2.64–2.58 (m, 2H), 2.48–2.42 (m,
2H), 2.31–2.25 (m, 2H), 1.47–1.44 (m, 2H), 1.22 (s, b, 10H),
0.84–0.80 (m, 3H); 13C NMR (62.5 MHz, DMSO-d6): d=
172.60, 35.50, 31.19, 30.94, 29.02, 28.59, 28.54, 28.20, 26.86,
22.03, 13.88; IR (KBr): n=1651 cmÀ1 (C=O); MS: m/e=217
[M+]; anal. calcd. for (C11H23NOS): C 60.78, H 10.66, N
6.44, S 14.75; found: C 60.72, H 10.71, N 6.47, S 14.70.
3-Propylsulfanylpropionamide (Table 3, entry 6): white
solid; mp 59–61 8C; 1H NMR (250 MHz, DMSO-d6): d=
7.35 (s, b, 1H), 6.83 (s, b, 1H), 2.64–2.58 (m, 2H), 2.47–2.39
(m, 2H), 2.32–2.25 (m, 2H), 1.57–1.42 (m, 2H), 0.92–0.85
(m, 3H); 13C NMR (62.5 MHz, DMSO-d6): d=172.76, 35.49,
32.99, 26.78, 22.31, 13.16; IR (KBr): n=1659 cmÀ1 (C=O);
anal. calcd. for (C6H13NOS): C 48.94, H 8.90, N 9.51, S
21.78; found: C 48.88, H 8.84, N 9.59, S, 21.83.
3-(4-Methylbenzylsulfanyl)-butyric acid ethyl ester (5r):
Colorless oil; H NMR (250 MHz, CDCl3): d=7.13 (d, J=
1
7.9 Hz, 2H), 7.03 (d, J=7.9 Hz, 2H), 4.05 (q, J=7.2 Hz,
2H), 3.65 (s, 2H), 3.10–2.97 (m, 1H), 2.53 (dd, J=15.3,
6.0 Hz, 1H), 2.34 (dd, J=15.3, 8.4 Hz, 1H), 2.24 (s, 3H),
1.23–1.14 (m, 6H); 13C NMR (62.5 MHz, CDCl3): d=171.38,
136.59, 135.06, 129.19, 128.71, 60.51, 42.11, 35.85, 35.00,
21.18, 21.09, 14.21; IR (neat): n=1736 (C=O), 1512 cmÀ1 (ar-
omatic C=C); MS: m/e=252 [M+]; anal. calcd for
(C14H20O2S): C 66.63, H 7.99, S 12.71; found: C 66.66, H
7.92, S 12.79.
4-(4-Nitrobenzylsulfanyl)-butan-2-one (5s): Colorless oil;
1H NMR (250 MHz, CDCl3): d=8.09 (d, J=8.5 Hz, 2H),
7.42 (d, J=8.5 Hz, 2H), 3.72 (s, 2H), 2.86–2.53 (m, 4H),
2.07 (s, 3H); 13C NMR (62.5 MHz, CDCl3): d=206.44,
146.94, 146.21, 129.76, 123.75, 43.12, 36.17, 30.02, 25.20; IR
3-Benzylsulfanylpropionamide (Table 3, entries 7, 8):
1
white solid; mp 104–1058C; H NMR (250 MHz, DMSO-d6):
(neat): n=1713ACHTUNGTRENNUNG(C=O), 1601 (aromatic C=C), 1520,
d=7.29 (s, b, 1H), 7.19–7.02 (m, 5H), 6.80 (s, b, 1H), 3.60
(s, 2H), 2.45 (t, J=7.2 Hz, 2H), 2.23 (t, J=7.2 Hz, 2H);
13C NMR (62.5 MHz, DMSO-d6): d=172.59, 138.54, 129.03,
128.29, 126.69, 34.97, 34.88, 26.43; IR (KBr): n=1659 (C=
O), 1495 cmÀ1 (aromatic C=C); MS: m/e=195 [M+]; anal.
calcd. for (C10H13NOS): C 61.50, H 6.71, N 7.17, S 16.42;
found: C 61.42, H 6.74, N 7.21, S 16.36.
1346 cmÀ1 (NO2); MS: m/e=239 [M+]; anal. calcd. for
(C11H13NO3S): C 55.21, H 5.48, N 5.85, S 13.40; found: C
55.25, H 5.56, N 5.78, S 13.43.
3-(4-Nitrobenzylsulfanyl)-propionitrile (5t): Colorless oil;
1H NMR (250 MHz, CDCl3): d=8.06 (d, J=8.4 Hz, 2H),
7.46 (d, J=8.4 Hz, 2H), 3.83 (s, 2H), 2.66–2.52 (m, 4H);
13C NMR (62.5 MHz, CDCl3): d=147.11, 145.31, 129.32,
123.91, 118.36, 35.65, 26.82, 18.66; IR (neat): n=2249 (CN),
1601 (aromatic C=C), 1520, 1346 cmÀ1 (NO2); MS: m/e=222
[M+]; anal. calcd. for (C10H10N2O2S): C 54.04, H 4.53, N
12.60, S 14.43; found: C 53.98, H 4.50, N 12.65, S 14.41.
764
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Adv. Synth. Catal. 2009, 351, 755 – 766

Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate
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