The Journal of Organic Chemistry
ARTICLE
3-Butyl-4-(phenylselenyl)-1H-isochromen-1-one (2h).
Yield: 0.066 g (74%). 1H NMR (CDCl3, 200 MHz): δ 8.28 (dd, J = 7.8
Hz, J = 1.0 Hz, 1H), 7.97À7.91 (m, 1H), 7.70À7.61 (m, 1H), 7.50À7.42
(m,1H), 7.25À7.15 (m, 5H), 3.04 (t, J = 7.5 Hz, 2H), 1.68 (quint, J = 7.6
Hz, 2H), 1.41 (sext, J = 7.6 Hz, 2H), 0.90 (t, J = 7.2 Hz, 3H). 13C NMR
(CDCl3, 100 MHz): δ 163.8, 162.0, 138.3, 135.2, 131.3, 129.5, 129.4,
128.7, 127.9, 127.3, 126.4, 120.4, 104.1, 34.4, 30.1, 22.3, 13.7. MS
(relative intensity) m/z: 358 ([M + 1] 59), 274 (51), 193 (39), 165
(100), 131 (54), 91 (47), 85 (52), 57 (91). Anal. Calcd for C19H18O2Se:
C 63.87, H 5.08. Found: C 63.65, H 5.02.
100), 282 (37), 240 (19), 202 (25), 197 (67), 159 (60), 85 (71), 57 (49).
HRMS calcd for C17H22O2Se: 361.0682 [M + Na], found 361.0705.
7-Methyl-3-phenyl-4-(phenylselenyl)-1H-isochromen-1-
one (2o). Yield: 0.073 g (75%). 1H NMR (CDCl3, 200 MHz): δ
8.16À8.13 (m, 1H), 7.94À7.90 (m, 1H), 7.68À7.63 (m, 2H), 7.53À7.34
(m, 4H), 7.21À7.16 (m, 5H), 2.47 (s, 3H). 13C NMR (CDCl3, 100 MHz):
δ 161.9, 158.6, 139.1, 136.6, 135.9, 134.0, 131.9, 129.9, 126.3, 125.0, 120.6,
104.6, 21.1. MS (relative intensity) m/z: 392 ([M + 1] 8), 341 (10), 284
(17), 253 (10), 207 (45), 178 (25), 105 (100), 77 (18). Anal. Calcd for
C22H16O2Se: C 67.52, H 4.12. Found: C 67.65, H 4.20.
4-(4-Chlorophenylselenyl)-3-phenyl-1H-isochromen-1-
one (2i). Yield: 0.082 g (80%). 1H NMR (CDCl3, 200 MHz): δ 8.36
(dd, J = 7.8 Hz, J = 1.0 Hz, 1H), 8.02À7.97 (m, 1H), 7.76À7.50 (m, 4H),
7.46À7.35 (m, 3H), 7.18À7.07 (m, 4H). 13C NMR (CDCl3, 100 MHz):
δ 161.5, 159.7, 138.0, 135.4, 133.8, 132.6, 130.2, 130.1, 129.9, 129.8,
129.6, 129.5, 128.8, 127.9, 127.8, 120.8, 104.5. MS (relative intensity)
m/z: 412 ([M + 1] 8), 304 (4), 193 (6), 165 (14), 105 (100), 77 (22).
Anal. Calcd for C21H13ClO2Se: C 61.26, H 3.18. Found: C 61.42,
H 3.22.
4-(4-Chlorophenylsenenyl)-7-methyl-3-phenyl-1H-iso-
chromen-1-one (2p). Yield: 0.076 g (72%). 1H NMR (CDCl3, 200
MHz): δ 8.18À8.15 (m, 1H), 7.90À7.84 (m, 1H), 7.65À7.59 (m, 2H),
7.55À7.50 (m, 1H), 7.47À7.34 (m, 3H), 7.17À7.06 (m, 4H), 2.48
(s, 3H). 13C NMR (CDCl3, 100 MHz): δ 161.5, 159.0, 139.2, 136.5,
135.8, 134.0, 132.7, 130.4, 130.1, 130.0, 129.7, 129.6, 129.5, 127.9, 127.8,
120.1, 104.7, 21.1. MS (relative intensity) m/z: 426 ([M + 1] 8), 318 (5),
207 (7), 178 (14), 105 (100), 77 (20). HRMS calcd for C22H15ClO2Se:
429.0369 [M + Na], found 428.0633 [M À 1].
4-(4-Fluorophenylselenyl)-3-phenyl-1H-isochromen-1-
one (2j). Yield: 0.072 g (73%). 1H NMR (CDCl3, 200 MHz): δ 8.35
(dd, J = 7.8 Hz, J = 1.0 Hz, 1H), 8.07À8.03 (m,1H), 7.77À7.50 (m, 4H),
7.47À7.36 (m, 3H), 7.21À7.10 (m, 1H), 6.96À6.82 (m, 2H). 13C NMR
(CDCl3, 100 MHz): δ 161.9 (d, 1JCF = 246.6 Hz), 161.5, 159.5, 138.2,
135.3, 133.9, 131.2 (d, 3JCF = 8.0 Hz), 130.1, 128.7, 128.0, 127.8, 125.9,
7-Methyl-3-phenyl-4-(p-tolylselenyl)-1H-isochromen-1-
1
one (2q). Yield: 0.075 g (74%). H NMR (CDCl3, 200 MHz): δ
8.17À8.13 (m, 1H), 7.84À7.78 (m, 1H), 7.66À7.62 (m, 2H),
7.51À7.31 (m, 4H), 7.16À6.88 (m, 4H), 2.47 (s, 3H), 2.34 (s, 3H).
13C NMR (CDCl3, 100 MHz): δ 161.7, 158.7, 139.1, 136.5, 136.1,
134.2, 132.7, 130.2, 129.9, 129.6, 129.4, 128.2, 127.7, 126.9, 126.2, 120.8,
104.2, 21.2, 21.1. MS (relative intensity) m/z: 406 ([M + 1] 24), 301 (6),
236 (13), 207 (16), 178 (27), 105 (100), 77 (30). Anal. Calcd for
C23H18O2Se: C 68.15, H 4.48. Found: C 68.33, H 4.52.
4-(Methylthio)-3-phenyl-1H-isochromen-1-one (2r). Yield:
0.043 g (65%). 1H NMR (CDCl3, 200 MHz): δ 8.37 (dd, J = 7.8 Hz, J =
1.0 Hz, 1H), 8.28À8.21 (m, 1H), 7.92À7.74 (m, 3H), 7.62À7.55
(m, 1H), 7.51À7.46 (m, 3H), 2.17 (s, 3H). 13C NMR (CDCl3,100
MHz): δ 161.5, 158.0, 138.0, 135.2, 133.1, 130.0, 129.9, 129.7, 128.4,
127.8, 125.5, 120.9, 110.9,18.9. MS (relative intensity) m/z: 268 (100),
225 (69), 197 (95), 165 (33), 120 (38), 105 (44), 77 (81). Anal. Calcd
for C16H12O2S: C 71.62, H 4.51. Found: C 71.85, H 4.59.
3-Phenyl-4-(phenyltellurenyl)-1H-isochromen-1-one (2s).
Yield: 0.080 g (75%). 1H NMR (CDCl3, 200 MHz): δ 8.38À8.29 (m,
1H), 8.14À8.06 (m, 1H), 7.74À7.66 (m, 1H), 7.57À7.34 (m, 8H),
7.21À7.07 (m, 3H). 13C NMR (CDCl3, 100 MHz): δ 162.1, 161.4,
139.7, 136.3, 135.4, 135.0, 132.7, 130.0, 129.8, 129.7, 129.6, 128.7, 127.7,
127.5, 120.5, 115.5, 93.7. MS (relative intensity) m/z: 428 ([M + 2] 19),
298 (22), 270 (14), 193 (37), 165 (90), 105 (100), 77 (66). HRMS calcd
for C21H14O2Te: 448.9823 [M + Na], found 447.9901 [M À 1].
4-(Butyltellurenyl)-3-phenyl-1H-isochromen-1-one (2t).
Yield: 0.035 g (35%). 1H NMR (CDCl3, 400 MHz): δ 8.35À8.33 (m,
1H), 8.18À8.16 (m, 1H), 7.82À7.78 (m, 1H), 7.60À7.58 (m, 2H),
7.56À7.52 (m, 1H), 7.46À7.41 (m, 3H), 2.58 (t, J = 7.3 Hz, 2H), 1.50
(quint, J = 7.6 Hz, 2H), 1.18 (sext, J = 7.3 Hz, 2H), 0.77 (t, J = 7.3 Hz,
3H). 13C NMR (CDCl3, 100 MHz): δ 162.3, 159.7, 140.3, 136.4, 135.3,
132.7, 130.1, 129.8, 129.7, 128.5, 127.6, 120.3, 90.3, 33.0, 24.6, 13.2, 9.8.
MS (relative intensity) m/z: 406 (23), 222 (59), 193 (100), 165 (52),
105 (13), 77 (20), 57 (5). HRMS calcd for C19H18O2Te: 431.0266 [M +
Na], found 431.0295.
General Procedure for 3-Substituted Isochromen-1-ones.
In a Schlenk tube, under air, containing CH2Cl2 (4 mL) were added
FeCl3 (0.041 g, 1 equiv, 99.99% purity from commercial suppliers) and
2-alkynylaryl esters (0.25 mmol) in CH2Cl2 (1 mL), and the reaction
mixture was stirred overnight at room temperature. After this, the
mixture was diluted with dichlorometane (20 mL) and washed with a
saturated solution of NH4Cl (20 mL). The organic phase was separated,
dried over MgSO4, and concentrated under vacuum. The residue was
purified by flash chromatography and eluted with mixture of hexane/
acetate (95:5).
2
125.2, 120.8, 116.6 (d, JCF = 21.9 Hz), 105.4, 101.7. MS (relative
intensity) m/z: 396 ([M + 1] 12), 288 (8), 193 (7), 165 (16), 105 (100),
77 (23). Anal. Calcd for C21H13FO2Se: C 63.81, H 3.31. Found: C
63.67, H 3.27.
3-Phenyl-4-(p-tolylselenyl)-1H-isochromen-1-one (2k).
Yield: 0.066 g (68%). H NMR (CDCl3, 200 MHz): δ 8.37 (dd, J =
1
7.7 Hz, J = 1.0 Hz, 1H), 7.95À7.91 (m, 1H), 7.73À7.62 (m, 3H),
7.57À7.36 (m, 4H), 7.17À6.92 (m, 4H), 2.35 (s, 3H). 13C NMR
(CDCl3, 100 MHz): δ 161.7, 159.6, 138.4, 136.4, 135.4, 133.9, 130.3,
130.1, 129.6, 129.5, 128.7, 128.2, 127.7, 127.0, 126.1, 120.8, 103.9, 21.2.
MS (relative intensity) m/z: 392 ([M + 1] 24), 284 (5), 222 (9), 193
(13), 165 (27), 105 (100), 77 (30). Anal. Calcd for C22H16O2Se: C
67.52, H 4.12. Found: C 67.60, H 4.20.
4-(Butylselenyl)-3-phenyl-1H-isochromen-1-one (2l).
Yield: 0.067 g (76%). 1H NMR (CDCl3, 200 MHz): δ 8.40À8.31
(m,1H), 8.29À8.21 (m, 1H), 7.88À7.79 (m, 1H), 7.72À7.67 (m, 2H),
7.60À7.52 (m, 1H), 7.48À7.43 (m, 3H), 2.55 (t, J = 7.2 Hz, 2H), 1.40
(quint, J = 7.2 Hz, 2H), 1.16 (sext, J = 7.4 Hz, 2H), 0.74 (t, J = 7.2 Hz,
3H). 13C NMR (CDCl3, 100 MHz): δ 161.8, 157.9, 138.9, 135.1, 134.3,
130.1, 129.8, 129.7, 128.4, 128.1, 127.6, 120.7, 105.0, 31.5, 28.7, 22.4,
13.3. MS (relative intensity) m/z: 358 ([M + 1] 38), 302 (18), 245 (14),
193 (100), 165 (59), 105 (75), 77 (64). HRMS calcd for C19H18O2Se:
358.0472. Found: 358.0491.
4-(Ethylselenyl)-3-phenyl-1H-isochromen-1-one (2m).
Yield: 0.070 g (85%). 1H NMR (CDCl3, 200 MHz): δ 8.35 (dd, J = 7.8
Hz, J = 1.0 Hz, 1H), 8.26À8.22 (m, 1H), 7.86À7.78 (m, 1H), 7.71À7.64
(m, 2H), 7.59À7.51 (m, 1H), 7.48À7.43 (m, 3H), 2.56 (q, J = 7.4 Hz,
2H), 1.16 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, 50 MHz): δ 161.8,
157.9, 138.8, 135.1, 134.2, 130.0, 129.7, 129.6, 128.4, 128.0, 127.6, 120.5,
104.7, 22.3, 14.9. MS (relative intensity) m/z: 330 ([M + 1] 47), 301
(10), 273 (10), 245 (12), 193 (100), 165 (30), 105 (14), 77 (25). Anal.
Calcd for C17H14O2Se: C 62.01, H 4.29. Found: C 62.30, H 4.42.
3-Butyl-4-(butylselenyl)-1H-isochromen-1-one (2n). Yield:
0.056 g (67%). 1H NMR (CDCl3, 200 MHz): δ 8.28 (dd, J = 7.9 Hz, J =
1.1 Hz, 1H), 8.14À8.09 (m, 1H), 7.81À7.72 (m, 1H), 7.52À7.44
(m, 1H), 3.05 (t, J = 7.8 Hz, 2H), 2.68 (t, J = 7.3 Hz, 2H), 1.79À1.25
(m, 8H), 0.99À0.84 (m, 6H). 13C NMR (CDCl3, 100 MHz): δ 162.3,
162.2, 138.8, 134.9, 129.5, 127.6, 127.3, 120.3, 104.1, 34.2, 32.1, 30.2,
28.3, 22.8, 22.3, 13.8, 13.4. MS (relative intensity) m/z: 338 ([M + 1]
6795
dx.doi.org/10.1021/jo201211s |J. Org. Chem. 2011, 76, 6789–6797