PAPER
Direct Arylation of 3-Arylsydnones
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13C NMR (100 MHz, CDCl3): δ = 55.7, 102.9, 113.0 (d, J = 14.5
Hz, 1 C), 114.9 (2 C), 115.1 (d, J = 2.1 Hz, 1 C), 116.2 (d, J = 20.9
Hz, 1 C), 124.9 (2 C), 127.8, 131.2, 131.7 (d, J = 8.2 Hz, 1 C), 159.4
(d, J = 249.9 Hz, 1 C), 162.0, 167.2.
1H NMR (400 MHz, CDCl3): δ = 7.27–7.35 (m, 7 H), 7.51–7.55 (m,
2 H).
13C NMR (100 MHz, CDCl3): δ = 108.0, 114.1, 117.4 (d, J = 23.5
Hz, 2 C), 124.2, 127.0 (d, J = 9.2 Hz, 2 C), 127.5 (2 C), 128.9 (2 C),
130.7 (d, J = 2.9 Hz, 1 C), 164.3 (d, J = 253.3 Hz, 1 C), 167.0.
HRMS: m/z calcd for C15H11FN2O3: 286.0812 [M]+; found:
286.0806.
HRMS: m/z calcd for C14H9FN2O2: 256.0623 [M]+; found:
256.0630.
3-(4-Methoxyphenyl)-4-(3-nitrophenyl)sydnone (3g)
Yield: 75 mg (80%, 0.24 mmol); yellow solid; mp 182.1–182.9 °C.
3-(4-Chlorophenyl)-4-phenylsydnone (3m)
Yield: 49 mg (60%, 0.18 mmol); tan solid; mp 134.0–135.2 °C.
IR (KBr): 3084, 1717, 1636, 1558, 1540, 1507, 1457, 748 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.30–7.40 (m, 5 H), 7.47 (d,
J = 8.8 Hz, 2 H), 7.58 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 108.0, 114.1, 125.1, 126.1 (2 C),
127.3, 127.5 (2 C), 128.9 (2 C), 130.5 (2 C), 138.5, 167.0.
HRMS: m/z calcd for C14H935ClN2O2: 272.0389 [M]+; found:
272.0380.
IR (KBr): 3048, 2951, 2829, 1717, 1616, 1558, 1540, 1507, 1457,
1191, 1011 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.95 (s, 3 H), 7.12 (d, J = 8.8 Hz,
2 H), 7.45 (d, J = 9.2 Hz, 2 H), 7.54 (t, J = 8.2 Hz, 1 H), 7.84 (d,
J = 7.6 Hz, 1 H), 8.06 (s, 1 H), 8.13 (d, J = 8.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 55.9, 105.5, 114.1, 115.7 (2 C),
121.3, 122.8, 126.1 (2 C), 129.9, 132.3, 139.3, 148.3, 162.7, 166.6.
HRMS: m/z calcd for C15H11N3O5: 313.0692 [M]+; found:
313.0687.
3-(3-Chloro-4-fluorophenyl)-4-phenylsydnone (3n)
3-(4-Methoxyphenyl)-4-(naphthalen-1-yl)sydnone (3h)
Yield: 52 mg (59%, 0.18 mmol); brown solid; mp 123.8–124.4 °C.
Yield: 60 mg (63%, 0.19 mmol); tan solid; mp 193.3–194.0 °C.
IR (KBr): 3036, 1734, 1636, 1558, 1540, 1507, 1457, 1395, 766
cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.30–7.34 (m, 2 H), 7.35–7.40 (m,
IR (KBr): 3004, 2950, 2834, 1734, 1699, 1635, 1558, 1540, 1507,
1457, 1188 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.79 (s, 3 H), 6.83 (d, J = 8.8 Hz,
2 H), 7.25–7.28 (m, 2 H), 7.28–7.29 (m, 1 H), 7.37–7.44 (m, 1 H),
7.53–7.56 (m, 2 H), 7.80–7.83 (m, 1 H), 7.89–7.93 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 55.6, 106.9, 114.1, 114.8 (2 C),
121.8, 124.8, 125.3 (2 C), 126.7, 127.4, 128.7, 130.2, 130.5, 131.8,
133.9, 139.3, 161.8, 167.6.
5 H), 7.67–7.70 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 108.2, 118.2 (d, J = 22.9 Hz, 1
C), 119.8, 123.9, 124.0 (d, J = 74.5 Hz, 1 C), 125.0 (d, J = 8.2 Hz,
1 C), 127.5 (2 C), 129.1 (2 C), 129.2, 130.4, 160.0 (d, J = 255.6 Hz,
1 C), 166.8.
HRMS: m/z calcd for C14H835ClFN2O2: 290.0276 [M]+; found:
290.0270.
HRMS: m/z calcd for C19H14N2O3: 318.1022 [M]+; found:
318.1027.
3-(4-Nitrophenyl)-4-phenylsydnone (3o)
4-Phenyl-3-p-tolylsydnone (3i)16
Yield: 25 mg (30%, 0.09 mmol); tan solid; mp 140.0–141.1 °C.
Yield: 59 mg (78%, 0.23 mmol); yellow solid; mp 148.5–149.3 °C.
IR (KBr): 3030, 1734, 1636, 1558, 1540, 1507, 1457 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.29–7.34 (m, 2 H), 7.35–7.39 (m,
3 H), 7.76 (d, J = 8.8 Hz, 2 H), 8.47 (d, J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 115.7, 123.6, 125.6 (2 C), 126.2
(2 C), 127.7 (2 C), 129.2 (2 C), 129.5, 139.0, 149.7, 166.7.
IR (KBr): 3094, 2928, 2858, 1717, 1635, 1558, 1540, 1507, 1457,
1395 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.50 (s, 3 H), 7.30–7.34 (m, 5 H),
7.35–7.40 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ = 21.5, 107.7, 114.1, 124.6 (2 C),
HRMS: m/z calcd for C14H9N3O4: 283.0612 [M]+; found: 283.0618.
127.4 (2 C), 128.7 (2 C), 130.7 (2 C), 132.3, 139.3, 142.8, 167.2.
HRMS: m/z calcd for C15H12N2O2: 252.0916 [M]+; found:
252.0912.
Acknowledgment
4-Phenyl-3-m-tolylsydnone (3j)
The work was supported by Natural Science Foundation of China
(No. 21272174), the Key Projects of Shanghai in Biomedical
(No.08431902700), and the Scientific Research Foundation of State
Education Ministry for the Returned Overseas Chinese Scholars.
We would like to thank the Center for Instrumental Analysis, Tongji
University, China.
Yield: 53 mg (70%, 0.21 mmol); tan solid; mp 132.6–133.5 °C.
IR (KBr): 3081, 2939, 2836, 1734, 1635, 1558, 1540, 1507, 1457,
1395 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.46 (s, 3 H), 7.25–7.28 (m, 1 H),
7.29–7.35 (m, 6 H), 7.43–7.49 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 21.3, 107.8, 122.0, 124.6, 125.2,
127.3 (2 C), 128.6, 128.7 (2 C), 129.9, 132.8, 134.7, 140.8, 167.1.
HRMS: m/z calcd for C15H12N2O2: 252.0876 [M]+; found:
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252.0882.
3,4-Diphenylsydnone (3k)11b
Yield: 48 mg (67%, 0.20 mmol); light yellow solid; mp 179.8–
181.0 °C.
1H NMR (400 MHz, CDCl3): δ = 7.30–7.32 (m, 5 H), 7.51 (d,
J = 7.6 Hz, 2 H), 7.60 (t, J = 7.8 Hz, 2 H), 7.69 (t, J = 7.4 Hz, 1 H).
References
(1) (a) Newton, C. G.; Ramsden, C. A. Tetrahedron 1982, 38,
2965. (b) Stewart, F. H. C. Chem. Rev. 1964, 64, 129.
(2) (a) Robins, P. A.; Walker, J. J. Chem. Soc. 1959, 237.
(b) Ackermann, E. Pharmazie 1967, 22, 537.
(3) Kier, L. B.; Roche, E. B. J. Pharm. Sci. 1967, 56, 149.
(4) McCaustland, D. J.; Burton, W. H.; Cheng, C. C.
J. Heterocycl. Chem. 1971, 8, 89.
3-(4-Fluorophenyl)-4-phenylsydnone (3l)16
Yield: 42 mg (55%, 0.17 mmol); tan solid; mp 180.9–181.6 °C.
IR (KBr): 3023, 1734, 1636, 1558, 1540, 1507, 1457, 1374 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1469–1474