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Organic & Biomolecular Chemistry
Page 8 of 10
ARTICLE
Journal Name
2,2-Difluoro-6-methyl-5-(4-methylphenyl)-2H-1,3λ3,2λ4-
dioxaborinin-4-amine (2i)
C11H12BF2NO3Na+ ([M + Na]+): 278.0771, fDoOunI:d10:.2107389./0C777O4B.01356F
Colorless crystals, m.p. 138–142 oC. Yield: 110 mg, 92 %. 1H
NMR (400 MHz, CDCl3) δ: 7.28 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 5-(2-Chlorophenyl)-2,2-difluoro-6-methyl-2H-1,3λ3,2λ4-
Hz, 2H), 6.23 (s, 1H), 5.62 (s, 1H), 2.40 (s, 3H), 1.95 (s, 3H). 13C dioxaborinin-4-amine (2n)
NMR (100 MHz, CDCl3) δ: 178.5, 170.5, 139.2, 131.0, 130.5,
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Colorless crystals, m.p. 175–178 C. Yield: 96 mg, 74 %. H
128.3, 100.7, 21.5, 76.7. 19F NMR (376 MHz, CDCl3) δ: -142.48, - NMR (400 MHz, CDCl3) δ: 7.58–7.56 (m, 1H), 7.46–7.42 (m, 1H),
142.50, -142.5, -142.6. IR (KBr) ν (cm-1): 820, 998, 1041, 1110, 7.42–7.38 (m, 1H), 7.34–7.31 (m, 1H), 6.03 (s, 1H), 5.39 (s, 1H),
1292, 1332, 1376, 1425, 1503, 1596, 1637, 2850, 2921, 3357, 1.93 (s, 3H). 13C NMR (100 MHz, CDCl3) δ: 180.1, 169.6, 136.2,
3482. HRMS (ESI, m/z) calcd. for C11H12BF2NO2Na+ ([M + Na]+): 133.4, 131.2, 130.7, 130.0, 128.2, 98.4, 21.5. 19F NMR (376 MHz,
262.0821, found: 262.0820.
CDCl3) δ: -142.3, -142.4, -142.5, -142.6, -143.5, -143.6, -143.7, -
143.8; . IR (KBr) ν (cm-1): 761, 1040, 1074, 1142, 1180, 1250,
1301, 1335, 1382, 1431, 1505, 1589, 1604, 1643, 2853, 2924,
3358, 3454. HRMS (ESI, m/z) calcd. for C10H9BClF2NO2Na+ ([M +
2,2-Difluoro-5-(4-fluorophenyl)-6-methyl-2H-1,3λ3,2λ4-
dioxaborinin-4-amine (2j)
Colorless crystals, m.p. 181–184 C. Yield: 93 mg, 77 %. H Na]+): 282.0275, found: 282.0278.
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NMR (400 MHz, DMSO-d6) δ: 9.14 (s, 1H), 7.88 (s, 1H), 7.32–7.25
(m, 4H), 1.80 (s, 3H). 13C NMR (100 MHz, DMSO-d6) δ: 174.7, 5-(3,5-Dimethylphenyl)-2,2-difluoro-6-methyl-2H-1,3λ3,2λ4-
169.2, 163.3, 160.9, 133.7, 133.6, 128.39, 128.36, 116.2, 116.0, dioxaborinin-4-amine (2o)
100.2, 21.0. 19F NMR (376 MHz, DMSO-d6) δ: -134.0, -140.8, -
Colorless crystals, m.p. 164–168 oC. Yield: 100 mg, 79 %. 1H
140.9. IR (KBr) ν (cm-1): 740, 1044, 1075, 1116, 1141, 1292, 1383, NMR (400 MHz, CDCl3) δ: 7.06 (s, 1H), 6.85 (s, 2H), 6.04 (s, 1H),
1406, 1458, 1508, 1560, 1594, 1618, 1647, 1655, 1686, 1719, 5.61 (s, 1H), 2.34 (s, 6H), 1.96 (s, 3H). 13C NMR (100 MHz, CDCl3)
2924, 3358. HRMS (ESI, m/z) calcd. for C10H9BF3NO2Na+ ([M + δ: 178.6, 170.5, 139.6, 131.3, 130.8, 128.7, 101.0, 21.6, 21.2. 19
F
Na]+): 266.0571, found: 266.0565.
NMR (376 MHz, CDCl3) δ: -142.9, -143.0. IR (KBr) ν (cm-1): 711,
853, 997, 1042, 1148, 1208, 1326, 1378, 1423, 1505, 1603, 1640,
2924, 3356, 3453. HRMS (ESI, m/z) calcd. for C12H14BF2NO2Na+
([M + Na]+): 276.0978, found: 276.0978.
5-(4-Chlorophenyl)-2,2-difluoro-6-methyl-2H-1,3λ3,2λ4-
dioxaborinin-4-amine (2k)
Colorless crystals, m.p. 134–136 oC. Yield: 119 mg, 92 %. 1H
NMR (400 MHz, CDCl3) δ: 7.49–7.46 (m, 2H), 7.24–7.20 (m, 2H), 2,2-Difluoro-6-phenyl-2H-1,3λ3,2λ4-dioxaborinin-4-amine (2p)
6.29 (s, 1H), 5.60 (s, 1H), 1.96 (s, 1H). 13C NMR (100 MHz, CDCl3)
Colorless crystals, m.p. 176–178 oC, Lit[4b] 183–184 oC. Yield:
δ: 179.0, 170.2, 135.6, 132.6, 130.2, 129.9, 99.8, 21.7. 19F NMR 81 mg, 77 %. 1H NMR (400 MHz, DMSO-d6) δ: 9.24 (s, 1H), 9.21
(376 MHz, CDCl3) δ: -142.4, -142.5. IR (KBr) ν (cm-1): 772, 831, (s, 1H), 7.84–7.82 (m, 2H), 7.60–7.51 (m, 3H), 6.06 (s, 1H). 13C
999, 1018, 1043, 1092, 1289, 1333, 1384, 1397, 1427, 1456, NMR (100 MHz, DMSO-d6) δ: 170.7, 170.3, 132.7, 132.3, 129.0,
1505, 1538, 1557, 1591, 1606, 1644, 1651, 2920, 3357, 3459. 126.6, 84.6. 19F NMR (376 MHz, DMSO-d6) δ: -141.7, -141.8, -
HRMS (ESI, m/z) calcd. for C10H9BClF2NO2Na+ ([M + Na]+): 148.2, -148.3. IR (KBr) ν (cm-1): 687, 770, 800, 1045, 1367, 1459,
282.0275, found: 282.0268.
1489, 1523, 1577, 1607, 1654, 3362. HRMS (ESI, m/z) calcd. for
C9H9BF2NO2+ ([M + H]+): 212.0689, found: 212.0685.
5-(4-Bromophenyl)-2,2-difluoro-6-methyl-2H-1,3λ3,2λ4-
dioxaborinin-4-amine (2l)
2,2-Difluoro-6-(4-methylphenyl)-2H-1,3λ3,2λ4-dioxaborinin-4-
Colorless crystals, m.p. 150–153 oC. Yield: 142 mg, 94 %. 1H amine (2q)
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NMR (400 MHz, CDCl3) δ: 7.63 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.0
Hz, 2H), 6.37 (s, 1H), 5.63 (s, 1H), 1.96 (s, 3H). 13C NMR (100 MHz, NMR (400 MHz, DMSO-d6) δ: 9.16 (s, 1H), 9.13 (s, 1H), 7.73 (d, J
CDCl3) δ: 178.8, 170.1, 133.2, 132.9, 130.4, 123.7, 99.9, 21.6. 19
= 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 6.01 (s, 1H), 2.37 (s, 3H).
Colorless crystals, m.p. 203–205 C. Yield: 71 mg, 63 %. H
F
NMR (376 MHz, CDCl3) δ: -142.36, -142.42. IR (KBr) ν (cm-1): 998, 13C NMR (100 MHz, DMSO-d6) δ: 170.8, 170.3, 142.6, 130.0,
1043, 1074, 1099, 1142, 1180, 1290, 1332, 1400, 1459, 1502, 129.5, 126.5, 83.8, 21.1. 19F NMR (376 MHz, DMSO-d6) δ: -
1560, 1585, 1603, 1618, 1647, 1686, 2850, 2922, 3137, 3360, 141.70, -141.76. IR (KBr) ν (cm-1): 790, 1048, 1244, 1374, 1523,
3448. HRMS (ESI, m/z) calcd. for C10H9BBrF2NO2Na+ ([M + Na]+): 1571, 1605, 1646, 1743, 2985, 3361, 3453. HRMS (ESI, m/z)
325.9770, found: 325.9767.
calcd. for C10H10BF2NO2Na+ ([M + Na]+): 248.0665, found:
248.0668.
2,2-Difluoro-5-(4-methoxyphenyl)-6-methyl-2H-1,3λ3,2λ4-
dioxaborinin-4-amine (2m)
Colorless crystals, m.p. 175–179 C. Yield: 43 mg, 34 %. H amine (2r)
NMR (400 MHz, DMSO-d6) δ: 9.09 (s, 1H), 7.78 (s, 1H), 7.16 (d, J
2,2-Difluoro-6-(4-fluorophenyl)-2H-1,3λ3,2λ4-dioxaborinin-4-
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Colorless crystals, m.p. 213–215 C. Yield: 78 mg, 68 %. H
= 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz, 1H), 3.79 (s, 3H), 1.79 (s, 3H) . NMR (400 MHz, DMSO-d6) δ: 9.25 (s, 1H), 9.22 (s, 1H), 7.90 (dd,
13C NMR (100 MHz, DMSO-d6) δ: 174.5, 169.5, 159.1, 132.5, J = 8.8, 5.6 Hz, 2H), 7.36 (m, 2H), 6.03 (s, 1H). 13C NMR (100 MHz,
124.0, 114.6, 100.7, 55.1, 21.0. 19F NMR (376 MHz, DMSO-d6) δ: DMSO-d6) δ: 170.2, 169.5, 164.4 (d, J = 249 Hz), 129.2 (d, J = 9
-140.9, -141.0. IR (KBr) ν (cm-1): 739, 774, 835, 882, 996, 1044, Hz), 116.0 (d, J = 22 Hz), 84.44. 19F NMR (376 MHz, DMSO-d6) δ:
1095, 1179, 1247, 1266, 1295, 1332, 1377, 1412, 1469, 1506, -107.37, -141.79, -141.85. IR (KBr) ν (cm-1): 607, 791, 846, 1046,
8 | J. Name., 2012, 00, 1-3
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