A new route to allyl thiols and allyl thiocarbamates from Baylis-Hillman adducts

Article abstract of DOI:10.1002/jhet.3

A facile synthesis of trisubstituted allyl thiols and allyl thiocarbamates has been accomplished from Baylis-Hillman adducts through bromination, thiocyanation, and acid-assisted hydrolysis reaction.

Full text of DOI:10.1002/jhet.3

January 2009
A New Route to Allyl Thiols and Allyl Thiocarbamates from
Baylis-Hillman Adducts
23
Young-Gi Kim, Hee Nam Lim, and Kee-Jung Lee*
Organic Synthesis Laboratory, Department of Chemical Engineering, Hanyang University, Seoul
133-791, Korea
*E-mail: leekj@hanyang.ac.kr
Received June 23, 2008
DOI 10.1002/jhet.3
Published online 4 February 2009 in Wiley InterScience (www.interscience.wiley.com).
A facile synthesis of trisubstituted allyl thiols and allyl thiocarbamates has been accomplished from
Baylis-Hillman adducts through bromination, thiocyanation, and acid-assisted hydrolysis reaction.
J. Heterocyclic Chem., 46, 23 (2009).
INTRODUCTION
nificance in organic synthesis, it is still necessary to
extend the scope of the allyl thiol and thiocarbamate
families and develop new and convenient synthetic
routes. Here the Baylis-Hillman (BH) chemistry [25]
has been applied for the synthesis of these compounds.
Thiols have attained significant importance as syn-
thetic intermediates for valuable sulfur-containing com-
pounds [1]. A number of reports have appeared on the
potential applications of thiol functionality in various
scientific disciplines such as pharmaceutical chemistry
[2], self-assembled monolayers [3], nanoparticles [4],
and conducting polymers [5]. Also, S-alkyl thiocarba-
mates are an important class of compounds that have
received considerable attention [6,7] because of their
numerous biological effects including anesthetic [8],
fungicidal [9], bactericidal [9,10], pesticidal [11,12], and
antiviral [13]. Despite the aforementioned reasons, thio-
carbamates are most noted for their use as commercial
herbicides [14].
RESULTS AND DISCUSSION
The BH reaction is well known as a powerful car-
bon–carbon bond forming methods in organic synthesis
[26]. Nucleophilic displacement of BH acetates or bro-
mides is an important protocol for the synthesis of tri-
substituted alkenes. Although there exist several meth-
ods for the nucleophilic displacement of BH acetates or
bromides with various reagents [27], displacement with
sulfur nucleophiles is limited [28].
Generally, thiols have been synthesized mainly from
alkyl halides with thioacetate ion followed by deacetyla-
tion with base [15], disulfides via reduction [16],
alkenes via anti-Markovnikov addition of thiolacetic
acid, followed by deacetylation with strong base [17],
alcohols via refluxing with hydrobromic acid and thiou-
rea, followed by hydrolysis with strong base [18], thio-
cyanates via reduction [19], and thiocarbamates via hy-
drolysis [20]. The most widely used method for the
preparation of thiocarbamates makes use of gaseous car-
bonyl sulfides and an amine, followed by subsequent
treatment with base and alkyl halide [12,21], condensa-
tion of a thiol with an isocyanate [10], nucleophilic
substitution of trichloroacetyl chloride with a thiol, fol-
lowed by treatment of an amine [22], and the hydration
of an organic thiocyanate [23,24]. In view of their sig-
Recently, we reported substitution reaction of BH
acetates 1 with thiolacetic acid followed by deacetyla-
tion with base [29], and with sodium sulfide [30] to give
the symmetric diallyl disulfides 2, respectively, as
shown in Scheme 1. No traces of the intended allyl thi-
ols were produced. Although the literature has reported
some interesting schemes to obtain allyl thiols, we felt
that thiols can be obtained from allyl thiocyanates.
The known allyl thiocyanates 4 were obtained in high
yields by displacement of 2-(bromomethyl)alkenoates
with sodium thiocyanate [31], derived from BH adducts
with N-bromosuccinimide-dimethyl sulfide [32]. Treat-
ment of allyl thiocyanates 4 with 95% sulfuric acid–ace-
tic acid (9:1, v/v) at ꢀ5 to 0ꢁC produced allyl thiocarba-
mates 5 in 54–96% yields. On hydrolysis reaction of 5
C
V
2009 HeteroCorporation

24
Y.-G. Kim, H. N. Lim, and K.-J. Lee
Vol 46
Scheme 1
chromatography (TLC) was performed on Merck silica gel 60
F254 TLC plates. Melting points were measured by an Electro-
thermal melting point apparatus and were uncorrected. Micro-
analysis was obtained using a Thermo Electron Corporation
Flash EA 1112 element analyzer. Infrared spectra were
recorded with a Nicolet Magna 550 FTIR spectrometer. The
1H and 13C NMR spectra were measured on a Gemini 300
spectrometer using deuteriochloroform. All chemical shifts are
reported in parts per million relative to tetramethylsilane. The
coupling constants (J) are expressed in Hertz.
with one equivalent of p-toluenesulfonic acid monohy-
drate (PTSA) in toluene and dichloromethane (9:1, v/v)
reflux temperature, allyl thiols 6 were obtained in 75–
94% yields (Scheme 2, Table 1). When using 0.1 equiv-
alent of PTSA, the reaction was sluggish and the yield
was low (Entries 1, 2, 7). Direct one-pot transformation
of thiocyanate 4 to thiol 6 was unsuccessful with PTSA
in refluxing toluene. All the products are unambiguously
The known methyl 3-aryl-2-(thiocyanatomethyl)propenoates
4 were prepared according to the literature procedure [31].
General procedure for the preparation of methyl (Z)-3-
aryl-2-(carbamoylthiomethyl)propenoates 5. To an ice-cold
mixture of 95% sulfuric acid (9 mL) and acetic acid (1 mL),
allyl thiocyanate 4 (2 mmoles) was added in small portions for
15 min under stirring at ꢀ5 to 0ꢁC. After dissolution of 4, the
mixture was stirred at room temperature for 0.5–2.5 h and
then poured onto crushed ice. The white precipitate was col-
lected by suction filtration, dried, and crystallized from
dichloromethane and petroleum ether to give compound 5.
The physical and spectral data of 5 prepared by this general
method are as follows.
1
characterized using infrared spectra, H and 13C NMR
1
data. In the H NMR spectra, the characteristic chemical
shift of the thiol protons of 6 were found at d ¼ 2.05–
2.12 as a triplet (J ¼ 7.6–8.3 Hz), the methylene protons
were observed at d ¼ 3.33–3.60 as a doublet (J ¼ 7.6–
8.3 Hz), and the methine protons resonated at d¼ 7.63–
7.92 as a singlet. Their infrared spectra showed absorp-
tion at 2557–2593 cmꢀ1 for the thiol band.
Methyl
(Z)-2-carbamoylthiomethyl-3-phenylpropenoate
(5a). Reaction time: 1 h; white solid; yield: 75%; mp: 99–
100ꢁC; ir (potassium bromide): 3419, 3327, 3182, 1707, 1675,
1597 cmꢀ1 1H NMR (deuteriochloroform): d 3.85 (s, 3 H,
;
OCH3), 4.11 (s, 2 H, CH2), 5.58 (s, 2 H, NH2), 7.37–7.47 (m,
5 H, aromatic), 7.82 (s, 1 H, CH); 13C NMR (deuteriochloro-
form): d 27.8, 52.4, 127.1, 128.7, 129.3, 129.5, 134.4, 142.5,
167.6, 168.4. Anal. Calcd. for C12H13NO3S: C, 57.35; H, 5.21;
N, 5.57; S, 12.76. Found: C, 57.20; H, 5.07; N, 5.39; S, 12.53.
Methyl (Z)-2-carbamoylthiomethyl-3-(4-chlorophenyl)pro-
penoate (5b). Reaction time: 1 h; white solid; yield: 84%; mp:
108–109ꢁC; ir (potassium bromide): 3396, 3298, 3202, 1707,
CONCLUSION
In conclusion, a new method for the synthesis of tri-
substituted allyl thiols from BH adducts has been devel-
oped through bromination, thiocyanation, and acid-
assisted hydrolysis reaction.
1
1655, 1619, 1592 cmꢀ1; H NMR (deuteriochloroform): d 3.85
(s, 3 H, OCH3), 4.07 (s, 2 H, CH2), 5.50 (s, 2 H, NH2), 7.40
(s, 4 H, aromatic), 7.75 (s, 1 H, CH); 13C NMR (deuterio-
chloroform): d 27.7, 52.4, 127.7, 129.0, 130.9, 132.8, 135.3,
141.0, 167.4, 168.2. Anal. Calcd. for C12H12ClNO3S: C, 50.44;
H, 4.23; N, 4.90; S, 11.22. Found: C, 50.19; H, 4.08; N, 5.20;
S, 10.96.
EXPERIMENTAL
Silica gel 60 (70–230 mesh ASTM) used for column chro-
matography was supplied by E. Merck. Analytical thin-layer
Scheme 2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

January 2009 A New Route to Allyl Thiols and Allyl Thiocarbamates from Baylis-Hillman Adducts
25
Table 1
Allyl thiocarbamates 5 and allyl thiols 6.
Entry
1
X
H
Reactant
Time (h)
1
Product
Yield (%)
75
Timea (h)
Product
Yielda (%)
4a
5a
7
(32)
4
6a
94
(82)
89
2
4-Cl
4b
1
5b
84
6b
(56)
10
5
(77)
83
3
4
5
6
7
2-Cl
2-Br
2-F
4-NO2
2-NO2
4c
4d
4e
4f
2.5
2
1
5c
5d
5e
5f
85
86
87
96
89
6c
6d
6e
6f
77
78
5
1
0.5
6
4
85
94
4g
5g
6g
(26)
7
(68)
75
8
4-Me
4h
1
5h
54
6h
aValues in parentheses indicate when 0.1 equivalent of PTSA was used.
1
1712, 1680, 1606, 1522, 1437, 1344 cmꢀ1; H NMR (deuterio-
chloroform): d 3.79 (s, 2 H, CH2), 3.87 (s, 3 H, OCH3), 5.37
(s, 2 H, NH2), 7.37–7.73 (m, 3 H, aromatic), 8.06 (s, 1 H,
CH), 8.21–8.24 (m, 1 H, aromatic); 13C NMR (deuteriochloro-
form): d 27.3, 52.5, 124.9, 129.4, 129.5, 130.9, 131.2, 133.7,
139.2, 147.3, 166.7, 167.8. Anal. Calcd. for C12H12N2O5S: C,
48.64; H, 4.08; N, 9.45; S, 10.82. Found: C, 48.40; H, 3.88;
N, 9.20; S, 10.59.
Methyl (Z)-2-carbamoylthiomethyl-3-(2-chlorophenyl)pro-
penoate (5c). Reaction time: 2.5 h; white solid; yield: 85%;
mp: 102–103ꢁC; ir (potassium bromide): 3419, 3326, 3308,
1
1698, 1662, 1607, 1438 cmꢀ1; H NMR (deuteriochloroform):
d 3.87 (s, 3 H, OCH3), 3.97 (s, 2 H, CH2), 5.42 (s, 2 H, NH2),
7.30–7.46 (m, 4 H, aromatic), 7.89 (s, 1 H, CH); 13C NMR
(deuteriochloroform): d 27.7, 52.5, 126.8, 129.5, 129.6, 130.1,
130.2, 133.2, 134.1, 139.3, 167.0, 168.1. Anal. Calcd. for
C12H12ClNO3S: C, 50.44; H, 4.23; N, 4.90; S, 11.22. Found:
C, 50.22; H, 4.12; N, 4.76; S, 11.03.
Methyl (Z)-3-(2-bromophenyl)-2-(carbamoylthiomethyl)pro-
penoate (5d). Reaction time: 2 h; white solid; yield: 86%; mp:
93–95ꢁC; ir (potassium bromide): 3418, 3334, 1712, 1673, 1465,
1435 cmꢀ1 1H NMR (deuteriochloroform): d 3.87 (s, 3 H,
;
OCH3), 3.94 (s, 2 H, CH2), 5.47 (s, 2 H, NH2), 7.20–7.39 (m, 3
H, aromatic), 7.62–7.64 (m, 1 H, aromatic), 7.82 (s, 1 H, CH);
13C NMR (deuteriochloroform): d 27.6, 52.5, 124.0, 127.4,
129.3, 130.2, 130.3, 132.8, 135.1, 141.4, 167.0, 168.0. Anal.
Calcd. for C12H12BrNO3S: C, 43.65; H, 3.66; N, 4.24; S, 9.71.
Found: C, 43.42; H, 3.40; N, 4.38; S, 9.52.
Methyl (Z)-2-(carbamoylthiomethyl)-3-(4-methylphenyl)pro-
penoate (5h). Reaction time: 1 h; white solid; yield: 54%; mp:
119–120ꢁC; ir (potassium bromide): 3376, 3298, 1699, 1678,
1616, 1436 cmꢀ1; H NMR (deuteriochloroform): d 2.38 (s, 3
1
H, CH3), 3.84 (s, 3 H, OCH3), 4.13 (s, 2 H, CH2), 5.49 (s, 2
H, NH2), 7.23 (d, 2 H, J ¼ 7.9 Hz, aromatic), 7.37 (d, 2 H, J
¼ 7.9 Hz, aromatic), 7.80 (s, 1 H, CH); 13C NMR (deuterio-
chloroform): d 21.4, 28.0, 52.3, 126.0, 129.5, 129.7, 131.5,
139.6, 142.6, 167.8, 168.6. Anal. Calcd. for C13H15NO3S: C,
58.85; H, 5.70; N, 5.28; S, 12.09. Found: C, 58.61; H, 5.43;
N, 5.03; S, 12.31.
General procedure for the preparation of methyl (Z)-3-
aryl-2-(mercaptomethyl)propenoates 6. A stirred solution of
thiocarbamate 5 (1 mmole) and PTSA (0.19 g, 1 mmole) in a
mixture of toluene (9 mL) and dichloromethane (1 mL) was
heated at reflux temperature for 4–10 h. After cooling to room
temperature, the mixture was diluted with saturated aqueous so-
dium bicarbonate solution (5 mL) and extracted with dichloro-
methane (3 ꢂ 10 mL). The combined organic layers were dried
over anhydrous magnesium sulfate and the solvent was evapo-
rated in vacuo. The resulting mixture was chromatographed on
silica gel eluting with hexane/ethyl acetate (15:1) to produce 6.
The physical and spectral data of 6 prepared by this general
method are as follows.
Methyl (Z)-2-(carbamoylthiomethyl)-3-(2-fluorophenyl)pro-
penoate (5e). Reaction time: 1 h; white solid; yield: 87%;
mp: 102–104ꢁC; ir (potassium bromide): 3421, 3323, 3310,
1
3193, 1701, 1662, 1610, 1485, 1438 cmꢀ1; H NMR (deuter-
iochloroform): d 3.86 (s, 3 H, OCH3), 4.04 (s, 2 H, CH2),
5.42 (s, 2 H, NH2), 7.09–7.49 (m, 4 H, aromatic), 7.85 (s, 1
H, CH); 13C NMR (deuteriochloroform): d 27.8, 52.4, 115.6
(J ¼ 22.0 Hz), 122.5 (J ¼ 13.4 Hz), 124.2, 129.6, 130.2,
131.0, 134.7, 160.4 (J ¼ 250 Hz), 167.0, 168.3. Anal. Calcd.
for C12H12FNO3S: C, 53.52; H, 4.49; N, 5.20; S, 11.91.
Found: C, 53.70; H, 4.37; N, 5.02; S, 11.76.
Methyl (Z)-2-(carbamoylthiomethyl)-3-(4-nitrophenyl)pro-
penoate (5f). Reaction time: 1 h; white solid; yield: 96%; mp:
144–145ꢁC; ir (potassium bromide): 3401, 3324, 1717, 1633,
1592, 1517, 1345 cmꢀ1 1H NMR (dimethyl sulfoxide-d6): d
;
Methyl
(Z)-2-(mercaptomethyl)-3-phenylpropenoate
(6a). Reaction time: 7 h; colorless oil; yield: 94%; ir (neat):
1
2571, 1712, 1628, 1493, 1447, 1434 cmꢀ1; H NMR (deuterio-
3.78 (s, 3 H, OCH3), 3.90 (s, 2 H, CH2), 7.66 (s, 2 H, NH2),
7.73 (s, 1H, CH), 7.76 (d, 2 H, J ¼ 8.8 Hz, aromatic), 8.27 (d,
2 H, J ¼ 8.8 Hz, aromatic); 13C NMR (dimethyl sulfoxide-d6):
d 26.2, 52.4, 123.6, 130.6, 131.6, 137.9, 141.1, 147.2, 165.7,
166.6. Anal. Calcd. for C12H12N2O5S: C, 48.64; H, 4.08; N,
9.45; S, 10.82. Found: C, 48.39; H, 4.27; N, 9.28; S, 10.63.
Methyl (Z)-2-(carbamoylthiomethyl)-3-(2-nitrophenyl)pro-
penoate (5g). Reaction time: 0.5 h; white solid; yield: 89%;
mp: 113–114ꢁC; ir (potassium bromide): 3436, 3335, 3175,
chloroform): d 2.06 (t, 1 H, J ¼ 7.9 Hz, SH), 3.60 (d, 2 H, J
¼ 7.9 Hz, CH2), 3.87 (s, 3 H, OCH3), 7.35–7.45 (m, 5 H, aro-
matic), 7.70 (s, 1 H, CH); 13C NMR (deuteriochloroform): d
21.2, 52.2, 128.7, 129.0, 129.3, 131.8, 134.8, 139.7, 167.4.
Anal. Calcd. for C11H12O2S: C, 63.43; H, 5.81; S, 15.40.
Found: C, 63.19; H, 5.75; S, 15.27.
Methyl
noate (6b). Reaction time: 4 h; colorless oil; yield: 89%; ir
(neat): 2573, 1712, 1630, 1591, 1489, 1435 cmꢀ1 1H NMR
(Z)-3-(4-chlorophenyl)-2-(mercaptomethyl)prope-
;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

26
Y.-G. Kim, H. N. Lim, and K.-J. Lee
Vol 46
(deuteriochloroform): d 2.06 (t, 1 H, J ¼ 7.6 Hz, SH), 3.55 (d,
2 H, J ¼ 7.6 Hz, CH2), 3.86 (s, 3 H, OCH3), 7.36–7.41 (m, 4
H, aromatic), 7.63 (s, 1 H, CH); 13C NMR (deuteriochloro-
form): d 21.1, 52.3, 129.0, 130.7, 132.3, 133.2, 135.0, 138.3,
167.1. Anal. Calcd. for C11H11ClO2S: C, 54.43; H, 4.57; S,
13.21. Found: C, 54.22; H, 4.29; S, 12.90.
OCH3), 7.23 (d, 2 H, J ¼ 7.9 Hz, aromatic), 7.35 (d, 2 H, J ¼
7.9 Hz, aromatic), 7.67 (s, 1 H, CH); 13C NMR (deuterio-
chloroform): d 21.3, 21.4, 52.2, 129.4, 129.5, 130.9, 131.9,
139.3, 139.8, 167.5. Anal. Calcd. for C12H14O2S: C, 64.83; H,
6.35; S, 14.42. Found: C, 64.61; H, 6.22; S, 14.28.
Methyl
noate (6c). Reaction time: 10 h; colorless oil; yield: 83%; ir
(Z)-3-(2-chlorophenyl)-2-(mercaptomethyl)prope-
Acknowledgment. This study was supported by a grant of Uni-
versity IT Research Center Project, Republic of Korea.
1
(neat): 2582, 1714, 1633, 1468, 1436 cmꢀ1; H NMR (deuter-
iochloroform): d2.08 (t, 1 H, J ¼ 8.3 Hz, SH), 3.45 (d, 2 H, J
¼ 8.3 Hz, CH2), 3.88 (s, 3 H, OCH3), 7.31–7.48 (m, 4 H, aro-
matic), 7.76 (s, 1 H, CH); 13C NMR (deuteriochloroform): d
21.3, 52.4, 126.9, 129.7, 129.9, 130.0, 133.5, 133.6, 134.1,
136.5, 166.8. Anal. Calcd. for C11H11ClO2S: C, 54.43; H,
4.57; S, 13.21. Found: C, 54.31; H, 4.40; S, 13.03.
REFERENCES AND NOTES
[1] Patai, S., Ed. The Chemistry of the Thiol Group; Wiley:
New York, 1974, Part 1 and 2.
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nandes, B. P.; Lartery, P. A.; Pernet, A. G. J Med Chem 1989, 32,
151.
Methyl
noate (6d). Reaction time: 5 h; colorless oil; yield: 77%; ir
(Z)-3-(2-bromophenyl)-2-(mercaptomethyl)prope-
[3] Yeager, L. J.; Amirsakis, D. G.; Newmann, E.; Garrell, R.
L. Tetrahedron Lett 1998, 39, 8409.
1
(neat): 2574, 1714, 1633, 1464, 1434 cmꢀ1; H NMR (deuter-
[4] Huang, D.; Liao, F.; Molesa, S.; Redinger, D.; Subrama-
nian, V. J Electrochem Soc 2003, 150, G412.
iochloroform): d 2.07 (t, 1 H, J ¼ 8.0 Hz, SH), 3.43 (d, 2 H, J
¼ 8.0 Hz, CH2), 3.89 (s, 3 H, OCH3), 7.23–7.65 (m, 4 H, aro-
matic), 7.70 (s, 1 H, CH); 13C NMR (deuteriochloroform): d
21.2, 52.4, 124.0, 127.5, 130.0, 130.2, 132.9, 133.3, 135.4,
138.7, 166.8. Anal. Calcd. for C11H11BrO2S: C, 46.01; H,
3.86; S, 11.17. Found: C, 45.88; H, 3.60; S, 11.31.
[5] Han, C. C.; Hong, S. P.; Yang, K. F.; Bai, M. Y.; Huang,
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Methyl
noate (6e). Reaction time: 5 h; white solid; yield: 78%; mp
(Z)-3-(2-fluorophenyl)-2-(mercaptomethyl)prope-
32–34ꢁC; ir (potassium bromide): 2557, 1708, 1632, 1608,
1
1482, 1461, 1434 cmꢀ1; H NMR (deuteriochloroform): d 2.08
[10] Beji, M.; Sbihi, H.; Baklouti, A.; Cambon, A. J Fluorine
Chem 1999, 99, 17.
(t, 1 H, J ¼ 7.9 Hz, SH), 3.52 (d, 2 H, J ¼ 7.9 Hz, CH2), 3.87
(s, 3 H, OCH3), 7.08–7.51 (m, 4 H, aromatic), 7.72 (s, 1 H,
CH); 13C NMR (deuteriochloroform): d 21.4, 52.3, 115.8 (J ¼
22.0 Hz), 122.8 (J ¼ 13.4 Hz), 130.1, 130.8, 130.9, 132.1,
[11] Worthing, C. R., Ed. The Pesticide Manual, 9th ed.; British
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[12] Chen-Hsien, W. Synthesis 1981, 622.
133.8, 160.4 (J
C11H11FO2S: C, 58.39; H, 4.90; S, 14.17. Found: C, 58.52; H,
4.72; S, 14.02.
¼
250 Hz), 166.8. Anal. Calcd. for
[13] Goel, A.; Mazur, S. J.; Fattah, R. J.; Hartman, T. L.; Tur-
pin, J. A.; Huang, M.; Rice, W. G.; Appella, E.; Inman, J. K. Bioorg
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Casida, J. E. J Agric Food Chem 1979, 27, 709.
Methyl (Z)-2-(mercaptomethyl)-3-(4-nitrophenyl)propenoate
(6f). Reaction time: 6 h; yellowish solid; yield: 85%; mp 78–
80ꢁC; ir (potassium bromide): 2593, 1717, 1633, 1592, 1517,
1
1434, 1345 cmꢀ1; H NMR (deuteriochloroform): d 2.12 (t, 1
[15] (a) Zheng, T.-C.; Burkart, M.; Richardson, E. D. Tetrahe-
dron Lett 1999, 40, 603; (b) Gryko, T. D.; Clausen, C.; Roth, K. M.;
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H, J ¼ 7.7 Hz, SH), 3.53 (d, 2 H, J ¼ 7.7 Hz, CH2), 3.90 (s,
3 H, OCH3), 7.60 (d, 2 H, J ¼ 8.3 Hz, aromatic), 7.70 (s, 1 H,
CH), 8.28 (d, 2 H, J ¼ 8.8 Hz, aromatic); 13C NMR (deuterio-
chloroform): d 21.0, 52.6, 123.9, 130.0, 134.9, 136.8, 141.3,
147.6, 166.5. Anal. Calcd. for C11H11NO4S: C, 52.16; H, 4.38;
N, 5.53; S, 12.66. Found: C, 51.90; H, 4.02; N, 5.32; S, 12.37.
Methyl (Z)-2-(mercaptomethyl)-3-(2-nitrophenyl)propenoate
(6g). Reaction time: 4 h; yellowish solid; yield: 94%; mp 48–
49ꢁC; ir (potassium bromide): 2569, 1721, 1635, 1605, 1569,
[16] Kim, S.; Ahn, K. H. J Org Chem 1984, 49, 1717.
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2749.
1
1513, 1429, 1337 cmꢀ1; H NMR (deuteriochloroform): d 2.08
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CH), 8.18–8.21 (m, 1 H, aromatic); 13C NMR (deuteriochloro-
form): d 21.2, 52.4, 125.1, 129.6, 130.8, 131.0, 133.1, 133.8,
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

January 2009 A New Route to Allyl Thiols and Allyl Thiocarbamates from Baylis-Hillman Adducts
27
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet