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J = 154 Hz), À9.24 (d, 1B, B8, J = 165 Hz), À10.75 (d,
1B, B10, J = 180 Hz), À12.32 (d, 2B, B4,7, J = 171 Hz),
À13.56 (d, 2B, B5,11, J = 145 Hz), À14.04 (d, 1B, B6,
J = 138 Hz). Anal. Calc. for C11H19B10NO3: C, 41.12;
H, 5.91; B, 33.67. Found: C, 41.52; H, 5.97; B, 33.98%.
4.2.5. 3-Acetylamino-1-carboxymethyl-2-phenyl-o-
carborane (15)
Obtained from compound 8 (2.77 g, 10 mmol),
NaNH2 (20 mmol) and sodium bromoacetate (3.2 g,
20 mmol) in 100 ml of liquid ammonia. Yield, 3.10 g
(94%). M.p.: 227–224 °C. IR (cmÀ1): 3349 (NH), 3040
(OH), 2603 (BH), 1730 (CO, COOH), 1643 (CO,
CONH). 1H NMR: 7.78–7.49 (m, 5H, Ph), 6.93 (s,
1H, NH), 3.08 (d, 1H, CH2, J = 14.6 Hz), 3.02 (d, 1H,
CH2, J = 14.6 Hz). 11B NMR: À2.85 (s, 1B, B3), À4.30
(d, 1B, B9, J = 142 Hz), À5.32 (d, 1B, B12, J = 141 Hz),
4.2.2. 3-Benzoylamino-l-carboxymethyl-2-methyl-o-
carborane (12)
Obtained from compound
5 (2.8 g, 10 mmol),
NaNH2 (20 mmol) and sodium bromoacetate (3.2 g,
20 mmol) in 100 ml of liquid ammonia. Yield, 3.0 g
(89%). M.p.: 213–214 °C. IR (cmÀ1): 3307 (NH), 2953
(OH), 2601 (BH), 1730 (CO, COOH), 1674 (CO,
CONH). 1H NMR: 8.44 (m, 2H, Ph), 8.31 (s, 1H,
NH), 8.04–7.93 (m, 3H, Ph), 3.52 (d, 1H, CH2,
J = 14.8 Hz), 3.32 (d, 1H, CH2, J = 14.8 Hz). 11B
NMR: À3.11 (s, 1B, B3), À5.14 (d, 1B, B9,
J = 160 Hz), À6.41 (d, 1B, B12, J = 158 Hz), À7.58 (d,
À7.85 (d, 1B, B8, J = 163 Hz), À10.22 (d, 4B,
B10, 4, 7, 5(11), J = 160 Hz), À12.80 (d, 2B, B
,
J = 150 Hz). Anal. Calc. for C12H21B10NO3: C, 42.99;
H, 6.27; B, 32.24. Found: C, 43.24; H, 6.47, B, 31.98%.
11(5), 6
4.2.6. 1-Carboxymethyl-3-formylamino-o-carborane (16)
Obtained from compound 9 (3.74 g, 20 mmol),
NaNH2 (60 mmol) and sodium bromoacetate (9.7 g,
60 mmol) in 100 ml of liquid ammonia. Yield, 4.70 g
(95%). M.p.: 178–179 °C. IR (cmÀ1): 3296 (NH), 3060
(carborane CH), 2940 (OH), 2600 (BH), 1726 (CO,
COOH), 1675 (CO, CONH). 1H NMR: 8.50 (s, 1H,
CHO), 7.25 (s, 1H, NH), 4.23 (s, 1H, carborane CH),
3.06 (d, 1H, CH2, J = 14.5 Hz), 2.93 (d, 1H, CH2,
J = 14.5 Hz). 11B NMR: À3.51 (s, 1B, B3), À5.19 (d,
2B, B9,12, J = 154 Hz), À9.24 (d, 1B, B8, J = 165 Hz),
À10.75 (d, 1B, B10, J = 175 Hz), À12.32 (d, 2B, B4,7
J = 171 Hz), À13.56 (d, 2B, B5,11, J = 145 Hz), À14.04
(d, 1B, B6, J = 143 Hz). Anal. Calc. for C5H15B10NO3:
C, 24.48; H, 6.12; B, 44.13. Found: C, 24.56; H, 6.06,
B, 43.87%.
1B, B8, J = 168 Hz), À9.71 (d, 2B, B10, 4(7)
À12.11 (d, 1B, B11, J = 180 Hz), À13.73 (d, 1B, B6,
J = 159 Hz). Anal. Calc. for C12 H21B10NO3: C, 42.98;
H, 6.27; B, 32.26. Found: C, 43.15; H, 6.29; B, 32.02%.
,
J = 149 Hz), À10.67 (d, 2B, B7(4), 5
, J = 162 Hz),
4.2.3. 3-Acetylamino-1-carboxymethyl-o-carborane (13)
Obtained from compound
6 (2.4 g, 12 mmol),
NaNH2 (36 mmol) and sodium bromoacetate (5.8 g,
36 mmol) in 100 ml of liquid ammonia. Yield, 2.85 g
(92%). M.p.: 210–211 °C. IR (cmÀ1): 3329 (NH), 2940
(OH), 2605 (BH), 1726 (CO, COOH), 1638 (CO,
CONH). 1H NMR: 7.76 (s, 1H, NH), 5.43 (s, 1H, carbo-
rane CH), 3.62 (d, 1H, CH2, J = 15.2 Hz), 3.48 (d, 1H,
CH2, J = 15.2 Hz). 11B NMR: À3.96 (s, 1B, B3), À5.10
(d, 1B, B9, J = 159 Hz), À5.59 (d, 1B, B12, J = 160 Hz),
4.2.7. 1-Carboxymethyl-3-formylamino-2-methyl-o-
carborane (17)
À9.58 (d, 1B, B8, J = 162 Hz), À10.95 (d, 2B, B10, 4(7)
,
J = 165 Hz), À12.54 (d, 2B, B7(4), 5(11), J = 178 Hz),
À13.97 (d, 1B, B11,(5), J = 158 Hz), À14.39 (d, 1B, B6,
J = 142 Hz). Anal. Calc. for C6H17B10NO3: C, 27.80;
H, 6.64; B, 41.70. Found: C, 28.09; H, 6.60, B, 41.37%.
Obtained from compound 10 (2.0 g, 10 mmol),
NaNH2 (20 mmol) and sodium bromoacetate (3.2 g,
20 mmol) in 100 ml of liquid ammonia. Yield, 2.3 g
(90%). M.p.: 181–183 °C. IR (cmÀ1): 3890 (NH), 2925
(OH), 2602 (BH), 1725 (CO, COOH), 1674 (CO,
CONH). 1H NMR: 8.45 (s, 1H, CHO), 7.25 (s, 1H,
NH), 3.03 (d, 1H, CH2, J = 14.6 Hz), 2.96 (d, 1H,
CH2, J = 14.6 Hz). 11B NMR: À3.11 (s, 1B, B3), À5.14
(d, 1B, B9, J = 160 Hz), À6.41 (d, 1B, B12, J = 158 Hz),
4.2.4. 3-Acetylamino-1-carboxymethyl-2-methyl-o-
carborane (14)
Obtained from compound
7 (2.4 g, 11 mmol),
NaNH2 (22 mmol) and sodium bromoacetate (3.5 g,
22 mmol) in 100 ml of liquid ammonia. Yield, 2.70 g
(90%). M.p.: 209–210 °C. IR (cmÀ1): 3329 (NH), 2915
(OH), 2605 (BH), 1726 (CO, COOH), 1650 (CO,
CONH). 1H NMR: 7.38 (s, 1H, NH), 3.32 (d, 1H,
CH2, J = 14.8 Hz), 3.11 (d, 1H, CH2, J = 14.8 Hz). 11B
NMR: À3.24 (s, 1B, B3), À5.17 (d, 1B, B9,
J = 163 Hz), À6.53 (d, 1B, B12, J = 158 Hz), À8.05 (d,
À7.58 (d, 1B, B8, J = 168 Hz), À9.71 (d, 2B, B10,4(7)
,
J = 149 Hz), À10.67 (d, 2B, B7(4),5
, J = 162 Hz),
À12.11 (d, 1B, B11, J = 180 Hz), À13.73 (d, 1B, B6,
J = 159 Hz). Anal. Calc. for C6H17B10NO3: C, 27.80,
H, 6.56, B, 41.70. Found: C, 27.56; H, 6.57, B, 42.04%.
4.2.8. 3-Ammonium-1-carboxymethyl-o-carborane
hydrochloride (18)
3-Acetylamino acid (13) (1.3 g, 5.0 mmol) was heated
in the mixture of AcOH (10 ml) and HC1 (10 ml) for
15 h at 60 °C. The reaction mixture was evaporated to
dryness under reduced pressure. The crude product
1B, B8, J = 165 Hz), À10.14 (d, 3B, B10,4,7
,
J = 170 Hz), À10.87 (d, 1B, B5(11), J = 159 Hz), À12.09
(d, 1B, B11(5)
J = 153 Hz). Anal. Calc. for C7H19B10NO3: C, 30.76;
,
J = 148 Hz), À14.18 (d, 1B, B6,
H, 6.96; B, 39.56. Found: C, 31.04; H, 7.03, B, 39.12%.