M. M. Sa´ et al. / Tetrahedron Letters 49 (2008) 1228–1232
1231
6. Srihari, P.; Singh, A. P.; Jain, R.; Yadav, J. S. Synthesis 2006, 2772–
2776.
7. Singh, V.; Pathak, R.; Batra, S. Catal. Commun. 2007, 8, 2054–2058.
easily available S-nucleophiles in aqueous medium. Besides
being obtained in good yield, high purity and excellent
selectivity, the allylic thiocyanates and 1,3-thiazin-4-ones
are multifunctional products that can be explored in
further synthetic manipulations. The reactivity of allylic
bromides towards other functionalized nucleophiles, as
well as their synthetic application and mechanistic
considerations, is under current investigation.
´
8. (a) Sa, M. M.; Meier, L.; Fernandes, L.; Pergher, S. B. C. Catal.
´
Commun. 2007, 8, 1625–1629; (b) Fernandes, L.; Bortoluzzi, A. J.; Sa,
´
M. M. Tetrahedron 2004, 60, 9983–9989; (c) Sa, M. M. J. Braz. Chem.
Soc. 2003, 14, 1005–1010; (d) Nascimento, M. G.; Zanotto, S. P.;
Melegari, S. P.; Fernandes, L.; Sa´, M. M. Tetrahedron: Asymmetry
2003, 14, 3111–3115.
´
9. Sa, M. M.; Ramos, M. D.; Fernandes, L. Tetrahedron 2006, 62,
11652–11656.
Supplementary data
10. Typical procedure for the synthesis of allylic thiocyanates (4): To a
stirred solution of allylic bromide 3 (1.0 mmol) in 4.0 mL of acetone/
H2O (3:1 v/v) at 25 °C was added 2.0 mmol of NaSCN. After stirring
for 1 h, the final mixture was diluted with CH2Cl2 and washed with
H2O and brine. The organic extract was dried over Na2SO4, filtered
and concentrated under reduced pressure. The resulting residue was
purified by chromatography (hexane/ethyl acetate 9:1) to give the
corresponding (Z)-2-(thiocyanomethyl)alkenoates 4. Spectral and
analytical data of selected compounds are as follows:
Full crystallographic tables (excluding structure factors)
for compounds 4j and 7a have been deposited with the
Cambridge Crystallographic Data Centre as supplemen-
tary publication number CCDC 666027 (4j) and CCDC
666028 (7a). Copies of the data can be obtained, free of
charge, on application to CCDC, 12 Union Road, Cam-
bridge CB2 lEZ, UK [fax: +44 (0) 1223 336033 or e-mail:
Methyl (Z)-3-(2-chlorophenyl)-2-(thiocyanomethyl)propenoate (4d):
84%; white solid, mp 77.6–78.0 °C; IR (KBr): m 3089, 3009, 2951,
2145, 1713, 1635 cmÀ1 1H NMR (400 MHz, CDCl3): d 3.89 (s, 3H),
;
3.94 (s, 2H), 7.36–7.46 (m, 4H), 8.01 (s, 1H); 13C NMR (100 MHz,
CDCl3): d 31.4, 53.0, 112.1, 127.4, 128.4, 130.1, 130.2, 131.1, 132.6,
134.3, 141.8, 166.0. Anal. Calcd for C12H10ClNO2S: C, 53.83; H, 3.76;
N, 5.23; S, 11.98. Found: C, 54.06; H, 3.60; N, 5.36; S, 11.68.
Methyl (Z)-3-(4-nitrophenyl)-2-(thiocyanomethyl)propenoate (4f):
91%; white solid, mp 101.1–101.7 °C; IR (KBr): m 3106, 2955, 2148,
Acknowledgements
´
The authors wish to thank Central de Analises
´
´
(Departamento de Quımica, UFSC, Florianopolis) for
spectroscopic analysis. L.F. and M.F. are grateful to
CAPES and CNPq (Brazil) for fellowships. M.M.S. and
A.J.B. are grateful to CNPq for research fellowships.
Financial support by MCT/CNPq (Brazilian Research
Council), FAPESC (Santa Catarina State Research Coun-
cil, Brazil) and PRONEX-2003 (CNPq/FAPESC) is also
gratefully acknowledged.
1718, 1606, 1593, 1344, 1273 cmÀ1 1H NMR (400 MHz, CDCl3): d
;
3.90 (s, 3H), 4.01 (s, 2H), 7.57 (d, J = 8.8 Hz, 2H), 8.01 (s, 1H), 8.29
(d, J = 8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): d 30.4, 52.8, 111.3,
124.0 (2 Â CH), 129.0, 129.8 (2 Â CH), 139.9, 141.6, 147.9, 165.3.
Anal. Calcd for C12H10N2O4S: C, 51.79; H, 3.62; N, 10.07; S, 11.52.
Found: C, 52.02; H, 3.57; N, 10.08; S, 11.19.
Methyl (Z)-3-(3,4-methylenedioxyphenyl)-2-(thiocyanomethyl)pro-
penoate (4j): 81%; white solid, mp 74.2–74.9 °C; IR (KBr): m 2903,
2144, 1712, 1594, 1482, 1344, 1241 cmÀ1 1H NMR (400 MHz,
;
CDCl3): d 3.86 (s, 3H), 4.16 (s, 2H), 6.02 (s, 2H), 6.86–6.97 (m, 3H),
7.86 (s, 1H); 13C NMR (100 MHz, CDCl3): d 31.7, 52.9, 102.0, 109.1,
109.4, 112.1, 123.9, 125.1, 127.7, 144.9, 148.6, 149.5, 166.8. Anal.
Calcd for C13H11NO4S: C, 56.31; H, 4.00; N, 5.05; S, 11.56. Found: C,
56.64; H, 3.96; N, 4.96; S, 11.29.
References and notes
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-
ꢀ
˚
˚
NO4S, space group P1, FW 277.29, a = 6.635(2) A, b = 8.968(1) A,
˚
c = 10.838(2) A, a = 83.52(1)°, b = 88.64(2)°, c = 80.60(1)°, V =
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3
˚
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ꢀ
˚
˚
space group P1, FW 218.27, a = 7.273(1) A, b = 10.921(1) A, c =
˚
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,
3
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