1780
P. K. Tiwari, I. S. Aidhen
LETTER
129.4 (ArCH), 130.0 (ArC), 132.9 (ArCH), 134.1 (ArC),
144.2 (ArC), 198.4 (CH2CO). IR (CHCl3): 2401, 1679,
1607, 1579, 1522, 1477, 1423, 1339, 1218 cm–1. HRMS
(ESI): m/z [M + Na]+ calcd for C16H16NaOSe: 327.0264;
found: 327.0255.
MHz, CDCl3): δ = 3.18 (t, J = 6.8 Hz, 2 H, COCH2), 3.30 (t,
J = 6.8 Hz, 2 H, SeCH2), 7.24 (s, 3 H, ArH), 7.48 (d,
J = 6.4 Hz, 3 H, ArH), 7.67 (d, J = 4.4 Hz, 1 H, ArH), 7.92
(s, 1 H, ArH). 13C NMR (100 MHz, CDCl3): δ = 20.9
(COCH2), 39.5 (SeCH2), 127.1 (ArCH), 127.4 (ArCH),
129.3 (ArCH), 129.6 (ArC), 130.1 (ArCH), 130.9 (ArCH),
133.1 (ArCH), 133.5 (ArC), 136.1 (ArC), 138.0 (ArC),
196.5 (CH2CO). IR (CHCl3): 2400, 1693, 1582, 1556, 1523,
1478, 1439, 1390, 1336 cm–1. HRMS (ESI): m/z [M + Na]+
calcd for C15H12Cl2NaOSe: 380.9328; found: 380.9316.
3-(Phenylselanyl)-1-(3,4,5-trimethoxyphenyl)propan-1-
one (9j): Yield: 0.43 g (62%); yellow viscous liquid; Rf =
0.35 (hexane–EtOAc, 9.5:0.5). 1H NMR (400 MHz, CDCl3):
δ = 3.24 (t, J = 6.8 Hz, 2 H, COCH2), 3.36 (t, J = 6.8 Hz,
2 H, SeCH2), 3.88 (s, 6 H, 2 × OCH3), 3.90 (s, 3 H, OCH3),
7.15 (s, 2 H, ArH), 7.25–7.29 (m, 3 H, ArH), 7.51–7.54 (m,
2 H, ArH). 13C NMR (100 MHz, CDCl3): δ = 21.4 (COCH2),
39.1 (SeCH2), 56.3 (OCH3), 61.0 (OCH3), 105.5 (ArCH),
127.2 (ArCH), 129.2 (ArCH), 129.9 (ArC), 131.8 (ArC),
132.8 (ArCH), 142.8 (ArC), 153.1 (ArC), 197.5 (CH2CO).
IR (CHCl3): 2941, 2840, 2401, 1676, 1585, 1505, 1462,
1415, 1345 cm–1. HRMS (ESI): m/z [M + Na]+ calcd for
C18H20NaO4Se: 403.0424; found: 403.0420.
1-(4-Methoxyphenyl)-3-(phenylselanyl)propan-1-one
(9e): Yield: 0.97 g (75%); colourless solid; mp 83–85 °C; Rf
= 0.65 (hexane–EtOAc, 9.5:0.5). 1H NMR (500 MHz,
CDCl3): δ = 3.17 (t, J = 7.0 Hz, 2 H, COCH2), 3.27 (t,
J = 7.0 Hz, 2 H, SeCH2), 3.79 (s, 3 H, OCH3), 6.82–6.85 (m,
2 H, ArH), 7.17–7.22 (m, 3 H, ArH), 7.44–7.46 (m, 2 H,
ArH), 7.80–7.83 (m, 2 H, ArH). 13C NMR (125 MHz,
CDCl3): δ = 21.5 (COCH2), 39.1 (SeCH2), 55.6 (OCH3),
113.9 (ArCH), 127.1 (ArCH), 129.2 (ArCH), 129.7 (ArC),
130.1 (ArC), 130.4 (ArCH), 132.9 (ArCH), 163.7 (ArC),
197.2 (CH2CO). IR (CHCl3): 2401, 1674, 1601, 1577, 1510,
1477, 1420 cm–1. HRMS (ESI): m/z [M + Na]+ calcd for
C16H16NaO2Se: 343.0213; found: 343.0202. Anal. Calcd for
C16H16O2Se: C, 60.19; H, 5.05. Found: 60.76; H, 4.93.
1-(4-Fluorophenyl)-3-(phenylselanyl)propan-1-one (9f):
Yield: 67% (0.68 g); colourless crystalline solid; mp 93–
95 °C; Rf = 0.65 (hexane–EtOAc, 9.5:0.5). 1H NMR (500
MHz, CDCl3): δ = 3.23 (t, J = 7.0 Hz, 2 H, COCH2), 3.36 (t,
J = 7.0 Hz, 2 H, SeCH2), 7.08–7.13 (m, 2 H, ArH), 7.25–
7.29 (m, 3 H, ArH), 7.50–7.53 (m, 2 H, ArH), 7.90–7.94 (m,
2 H, ArH). 13C NMR (125 MHz, CDCl3): δ = 21.1 (COCH2),
39.4 (SeCH2), 115.8 (d, J = 21.7 Hz, ArCH), 127.3 (ArCH),
129.3 (ArCH), 129.8 (ArC), 130.8 (d, J = 9.37 Hz, ArCH),
131.6 (ArC), 133.0 (ArCH), 165.9 (d, J = 253.7 Hz, ArCF),
197.1 (CH2CO). IR (CHCl3): 2400, 2344, 1683, 1600, 1509,
1477, 1420, 1340, 1216 cm–1. HRMS (ESI): m/z [M + Na]+
calcd for C15H13FNaOSe: 331.0013; found: 331.0008.
1-(4-Chlorophenyl)-3-(phenylselanyl)propan-1-one (9g):
Yield: 0.76 g (71%); colourless crystalline solid; mp 95–
97 °C; Rf = 0.65 (hexane–EtOAc, 9.5:0.5). 1H NMR (400
MHz, CDCl3): δ = 3.23 (t, J = 6.8 Hz, 2 H, COCH2), 3.36 (t,
J = 6.8 Hz, 2 H, SeCH2), 7.26–7.28 (m, 3 H, ArH), 7.39–
7.43 (m, 2 H, ArH), 7.50–7.53 (m, 2 H, ArH), 7.81–7.85 (m,
2 H, ArH). 13C NMR (100 MHz, CDCl3): δ = 21.1 (COCH2),
39.5 (SeCH2), 127.3 (ArCH), 129.1 (ArCH), 129.3 (ArCH),
129.5 (ArCH), 129.8 (ArC), 133.0 (ArCH), 134.9 (ArC),
139.8 (ArC), 197.5 (CH2CO). IR (CHCl3): 2400, 1683,
1590, 1524, 1478, 1436, 1402, 1340, 1217 cm–1. HRMS
(ESI): m/z [M + Na]+ calcd for C15H13ClNaOSe: 346.9718;
found: 346.9728.
(14) Preparation of vinyl ketones 1a–l; General procedure:
To a solution of 9a (0.20 g, 0.62 mmol) in THF (3 mL), 30%
H2O2 (0.15 mL, 4.92 mmol) was added at 0 °C. Within
10 min, the reaction mixture became deep-yellow (the
progress of the reaction was monitored by TLC) and after 30
min, aq Na2S2O3 (0.1 M, 3 mL) was added and the solvent
was evaporated under reduced pressure. The residue was
dissolved in CH2Cl2 (15 mL) and washed with H2O (3 × 4
mL) and the organic layer was separated, dried over Na2SO4,
and concentrated. The product was purified by silica gel
column chromatography (EtOAc–hexane, 1%) to afford 1a
(93 mg, 90%) as a yellow liquid. Rf = 0.68 (hexane–EtOAc,
9.5:0.5). 1H NMR (400 MHz, CDCl3): δ = 0.86 (t,
J = 6.8 Hz, 3 H, CH3), 1.26–1.29 (m, 10 H), 1.59–1.64 (m,
2 H, CH2), 2.56 (t, J = 7.2 Hz, 2 H, CH2), 5.79 (d,
J = 10.8 Hz, 1 H, =CHbHc), 6.20 (d, J = 17.6 Hz, 1 H,
=CHbHc), 6.34 (dd, J = 10.8, 17.6 Hz, 1 H, COCHa). 13
C
NMR (100 MHz, CDCl3): δ = 14.2 (CH3), 22.7 (CH2), 24.1
(CH2), 29.2 (CH2), 29.4 (CH2), 29.5 (CH2), 31.9 (CH2), 39.8
(CH2), 127.9 (CH), 136.7 (=CH2), 201.2 (CO). IR (CHCl3):
2931, 2865, 2408, 1686, 1617, 1524, 1456, 1410, 1218 cm–1.
Tetradec-1-en-3-one (1b): Yield: 135 mg (83%); yellow
liquid; Rf = 0.58 (hexane–EtOAc, 9.5:0.5). 1H NMR (400
MHz, CDCl3): δ = 0.87 (t, J = 6.8 Hz, 3 H, CH3), 1.25–1.29
(m, 16 H), 1.59–1.64 (m, 2 H, CH2), 2.57 (t, J = 7.6 Hz, 2 H,
CH2), 5.81 (dd, J = 1.2, 10.4 Hz, 1 H, =CHbHc), 6.21 (dd,
J = 1.2, 17.6, Hz, 1 H, =CHbHc), 6.35 (dd, J = 10.8, 17.6 Hz,
1 H, COCHa). 13C NMR (100 MHz, CDCl3): δ = 14.2 (CH3),
22.8 (CH2), 24.1 (CH2), 29.4 (CH2), 29.47 (CH2), 29.5
(CH2), 29.6 (CH2), 29.7 (CH2), 32.0 (CH2), 39.8 (CH2),
128.0 (=CH), 136.7 (=CH2), 201.3 (CH2CO). IR (CHCl3):
2928, 2855, 2401, 1679, 1614, 1524, 1464, 1405 cm–1.
1H and 13C NMR spectra of synthesized vinyl ketones 1a–l
have been included in the Supporting Information. The
spectral data for vinyl ketones 1c,2b 1d15a and 1e15b were
consistent with those reported in the literature.
3-(Phenylselanyl)-1-(2-thienyl)propan-1-one (9h): Yield:
0.63 g (65%); pink solid; mp 57–59 °C; Rf = 0.65 (hexane–
EtOAc, 9.5:0.5). 1H NMR (400 MHz, CDCl3): δ = 3.24 (t,
J = 6.8 Hz, 2 H, COCH2), 3.31 (t, J = 6.8 Hz, 2 H, SeCH2),
7.10 (t, J = 4.4 Hz, 1 H, ArH), 7.26–7.28 (m, 3 H, ArH),
7.52–7.54 (m, 2 H, ArH), 7.63 (d, J = 4.8 Hz, 2 H, ArH). 13
C
NMR (100 MHz, CDCl3): δ = 21.3 (COCH2), 40.1 (SeCH2),
127.3 (ArCH), 128.2 (ArCH), 129.3 (ArCH), 129.7 (ArC),
132.1 (ArCH), 133.1 (ArCH), 134.0 (ArCH), 143.9 (ArC),
191.5 (CH2CO). IR (CHCl3): 2401, 1661, 1579, 1518, 1477,
1416, 1359, 1336, 1213 cm–1. HRMS (ESI): m/z [M + Na]+
calcd for C13H12NaOSSe: 318.9672; found: 318.9686. Anal.
Calcd for C13H12OSSe: C, 52.88; H, 4.10. Found: 53.09; H,
4.01.
1-(3,4-Dichlorophenyl)-3-(phenylselanyl)propan-1-one
(9i): Yield: 0.80 g (68%); light-yellow crystalline solid; mp
61–63 °C; Rf = 0.65 (hexane–EtOAc, 9.5:0.5). 1H NMR (400
(15) (a) Cai, M.; Zheng, G.; Ding, G. Green Chem. 2009, 11,
1687. (b) Aranha, R. M.; Bowser, A. M.; Madalengoitia, J.
S. Org. Lett. 2009, 11, 575.
Synlett 2013, 24, 1777–1780
© Georg Thieme Verlag Stuttgart · New York