The Journal of Organic Chemistry
Page 8 of 12
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H]+ Calcd for C15H14NO4S 304.0644; Found 304.0648; 1H
g/cm3, F(000) = 696, 2θ range 1.935~27.104o, R indices (all
NMR (400 MHz, CDCl3): δ 7.99 (dd, J = 1.2, 8.4 Hz, 1H),
7.84-7.81 (m, 2H), 7.64-7.60 (m, 1H), 7.58 (dd, J = 1.2, 8.0
Hz, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.50-7.40 (m, 2H), 5.46 (s,
1H), 5.39 (s, 1H), 4.17 (d, J = 0.8 Hz, 2H); 13C NMR (100
MHz, CDCl3): δ 146.94, 138.9, 136.1, 134.9, 133.8, 133.6,
132.7, 129.2 (2x), 129.1, 128.2 (2x), 124.48, 124.47, 62.6.
data) R1 = 0.1205, wR2 = 0.2805.
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1-Methyl-3-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4g).
Yield = 71% (113 mg); Colorless gum; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C16H16NO4S 318.0800; Found 318.0802;
1H NMR (400 MHz, CDCl3): δ 7.96 (dd, J = 1.2, 8.0 Hz, 1H),
7.60-7.54 (m, 3H), 7.46-7.32 (m, 4H), 5.46 (s, 1H), 5.38 (s,
1H), 4.15 (s, 2H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 146.8, 139.4, 138.6, 136.0, 134.9, 134.4, 133.5, 132.7, 129.0
(2x), 128.3, 125.2, 124.4 (2x), 62.5, 21.1.
1-Nitro-2-(3-methylsulfonylprop-1-en-2-yl)benzene
(4c).
o
Yield = 63% (76 mg); Colorless solid; mp = 117-119 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C10H12NO4S 242.0487; Found 242.0486;
1H NMR (400 MHz, CDCl3): δ 8.06 (dd, J = 1.2, 8.4 Hz, 1H),
7.66-7.62 (m, 1H), 7.54-7.49 (m, 2H), 5.70 (s, 1H), 5.48 (s,
1H), 4.11 (s, 2H), 2.89 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 135.8, 135.0, 133.7, 132.6 (2x), 129.3, 124.7, 124.3, 61.3,
40.6. Single-crystal X-Ray diagram: crystal of compound 4c
was grown by slow diffusion of EtOAc into a solution of
compound 4c in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the triclinic crystal system, space group P
- 1, a = 7.1934(7) Å , b = 7.9479(7) Å , c = 9.7888(9) Å , V =
540.42(9) Å 3, Z = 2, dcalcd = 1.483 g/cm3, F(000) = 252, 2θ
range 2.889~26.442o, R indices (all data) R1 = 0.287, wR2 =
0.0674.
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1-Ethyl-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene
(4h).
Yield = 60% (99 mg); Colorless gum; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C17H18NO4S 332.0957; Found 332.0961;
1H NMR (400 MHz, CDCl3): δ 7.97 (dd, J = 1.6, 8.4 Hz, 1H),
7.71 (d, J = 8.4 Hz, 2H), 7.56 (dt, J = 1.2, 7.6 Hz, 1H), 7.44
(dt, J = 1.6, 8.4 Hz, 1H), 7.40 (dd, J = 1.6, 7.6 Hz, 1H), 7.31 (d,
J = 8.4 Hz, 2H), 5.46 (s, 1H), 5.37 (s, 1H), 4.15 (s, 2H), 2.71
(q, J = 7.6 Hz, 2H), 1.25 (t, J = 7.6 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 150.9, 146.9, 136.2, 136.1, 135.0, 133.5,
132.7, 129.0, 128.6 (2x), 128.3 (2x), 124.4, 124.3, 62.6, 28.8,
15.1.
1-Isopropyl-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4i).
Yield = 66% (114 mg); Colorless solid; mp = 94-96 C (re-
o
1-Nitro-2-(3-n-butylsulfonylprop-1-en-2-yl)benzene
(4d).
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C18H20NO4S 346.1113; Found 346.1118;
1H NMR (400 MHz, CDCl3): δ 7.92 (dd, J = 1.2, 8.0 Hz, 1H),
7.68 (d, J = 8.0 Hz, 2H), 7.51 (dt, J = 1.2, 7.6 Hz, 1H), 7.39
(dt, J = 0.8, 7.6 Hz, 1H), 7.34-7.29 (m, 3H), 5.45 (s, 1H), 5.35
(s, 1H), 4.14 (s, 2H), 2.96-2.89 (m, 1H), 1.21 (d, J = 6.8 Hz,
6H); 13C NMR (100 MHz, CDCl3): δ 155.3, 146.7, 135.95,
135.9, 135.0, 133.4, 132.5, 128.8, 128.2 (2x), 127.1 (2x),
124.3, 124.2, 62.4, 34.0, 23.4 (2x).
Yield = 60% (85 mg); Colorless gum; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C13H18NO4S 284.0957; Found 284.0961;
1H NMR (400 MHz, CDCl3): δ 8.04 (dd, J = 1.2, 8.0 Hz, 1H),
7.63 (dt, J = 1.2, 7.6 Hz, 1H), 7.54 (dd, J = 1.2, 8.0 Hz, 1H),
7.49 (dt, J = 1.2, 8.0 Hz, 1H), 5.67 (s, 1H), 5.46 (s, 1H), 4.04
(s, 2H), 2.94 (t, J = 8.0 Hz, 2H), 1.79-1.71 (m, 2H), 1.45-1.36
(m, 2H), 0.90 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 147.1, 136.0, 134.6, 133.6, 132.6, 129.1, 124.5,
124.3, 59.1, 52.6, 23.8, 21.5, 13.4.
1-n-Butyl-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4j).
Yield = 70% (126 mg); Colorless gum; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C19H22NO4S 360.1270; Found 360.1276;
1H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.4 Hz, 1H), 7.70
(d, J = 8.4 Hz, 2H), 7.58-7.54 (m, 1H), 7.48-7.40 (m, 2H),
7.29 (d, J = 8.4 Hz, 2H), 5.47 (s, 1H), 5.38 (s, 1H), 4.15 (s,
2H), 2.67 (t, J = 8.0 Hz, 2H), 1.64-1.56 (m, 2H), 1.39-1.30 (m,
2H), 0.93 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
149.7, 146.9, 136.2, 136.1, 135.0, 133.5, 132.8, 129.2 (2x),
129.0, 128.2 (2x), 124.4, 124.3, 62.7, 35.5, 33.1, 22.2, 13.8.
1-Fluoro-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4e).
Yield = 70% (112 mg); Colorless solid; mp = 107-109 oC (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C15H13FNO4S 322.0549; Found 322.0545;
1H NMR (400 MHz, CDCl3): δ 7.99 (d, J = 8.4 Hz, 1H), 7.86-
7.81 (m, 2H), 7.61-7.57 (m, 1H), 7.49-7.44 (m, 1H), 7.41 (dd,
J = 1.6, 7.6 Hz, 1H), 7.21-7.15 (m, 2H), 5.46 (s, 1H), 5.40 (s,
1H), 4.17 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 165.8 (d, J
= 254.7 Hz), 146.9, 135.9, 134.9 (d, J = 3.1 Hz), 134.8, 133.6,
132.7, 131.1 (d, J = 9.9 Hz, 2x), 129.2, 124.6, 124.5, 116.5 (d,
J = 22.8 Hz, 2x), 62.7.
1-t-Butyl-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4k).
Yield = 71% (127 mg); Colorless gum; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C19H22NO4S 360.1270; Found 360.1274;
1H NMR (400 MHz, CDCl3): δ 7.95 (dd, J = 1.2, 8.0 Hz, 1H),
7.70 (dd, J = 8.4 Hz, 2H), 7.53 (dt, J = 1.6, 7.6 Hz, 1H), 7.48
(d, J = 8.4 Hz, 2H), 7.42 (dt, J = 1.6, 8.0 Hz, 1H), 7.35 (dd, J
= 1.6, 7.6 Hz, 1H), 5.49 (s, 1H), 5.38 (s, 1H), 4.15 (s, 2H),
1.31 (s, 9H); 13C NMR (100 MHz, CDCl3): δ 157.6, 146.8,
139.5, 136.1, 135.8, 135.0, 133.5, 132.7, 128.9, 127.9 (2x),
126.1 (2x), 124.4, 124.3, 62.5, 35.1, 30.9 (3x).
1-Methoxy-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4f).
Yield = 80% (133 mg); Colorless solid; mp = 107-108 oC (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C16H16NO5S 334.0749; Found 334.0753;
1H NMR (400 MHz, CDCl3): δ 7.99 (dd, J = 1.6, 8.4 Hz, 1H),
7.73 (d, J = 9.2 Hz, 2H), 7.60-7.56 (m, 1H), 7.48-7.42 (m, 2H),
6.95 (d, J = 8.8 Hz, 2H), 5.43 (s, 1H), 5.37 (s, 1H), 4.13 (s,
2H), 3.87 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 163.8,
136.3, 135.2, 133.5, 132.8, 130.4 (2x), 129.0, 124.5 (2x),
124.3 (2x), 114.3 (2x), 62.9, 55.7. Single-crystal X-Ray dia-
gram: crystal of compound 4f was grown by slow diffusion of
EtOAc into a solution of compound 4f in CH2Cl2 to yield col-
orless prisms. The compound crystallizes in the triclinic crys-
tal system, space group P 21/c, a = 10.958(3) Å , b = 7.579(2)
Å , c = 18.911(5) Å , V = 1508.8(6) Å 3, Z = 4, dcalcd = 1.467
1-Bromo-4-((2-(2-nitrophenyl)allyl)sulfonyl)benzene (4l).
Yield = 70% (133 mg); Colorless solid; mp = 105-107 oC (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M
+
H]+ Calcd for C15H13BrNO4S 381.9749; Found
1
381.9753; H NMR (400 MHz, CDCl3): δ 7.99 (d, J = 8.0 Hz,
1H), 7.68-7.62 (m, 4H), 7.60-7.56 (m, 1H), 7.46-7.45 (m, 1H),
7.40-7.38 (m, 1H), 5.46 (s, 1H), 5.40 (s, 1H), 4.16 (s, 2H); 13
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