Table 3.
Experimental (k 2 exp) and calculated (k 2 eq1) second‐order rate constants for the reactions of iminium ions 1 and 2 a with diazomethanes 4 and 6 a–c (CH2Cl2, 20 °C).
|
R(R1)CN2 [a] |
Iminium ion |
k 2 exp (m −1 s−1) |
k 2 eq1 (m −1 s−1) |
k 2 exp/k 2 eq1 |
|---|---|---|---|---|
|
Ph2CN2 (4) |
1 a |
1.48×10−1 |
1.75×10−2 |
8.5 |
|
N=5.29, s N=0.92 |
1 b |
6.48×10−2 |
1.75×10−2 |
3.7 |
|
|
1 c |
1.76×10−2 |
3.21×10−3 |
5.5 |
|
|
1 d |
4.73×10−1 |
2.75×10−1 |
1.7 |
|
|
2 a |
5.54×10−1 |
6.14×10−1 |
0.90 |
|
|
|
|
|
|
|
PhCHN2 (6 a) |
1 a |
2.07×103 |
6.09×101 |
34 |
|
N=9.35, s N=0.83 |
1 b |
6.11×102 |
6.09×101 |
10 |
|
|
1 c |
1.35×102 |
1.32×101 |
10 |
|
|
|
|
|
|
|
(4‐NC‐C6H4)CHN2 (6 b) |
1 a |
2.69×101 |
2.33 |
12 |
|
N=7.66, s N=0.80 |
1 b |
1.51×101 |
2.33 |
6.5 |
|
|
1 c |
2.94 |
5.35×10−1 |
5.5 |
|
|
|
|
|
|
|
(4‐Br‐C6H4)CHN2 (6 c) |
1 a |
4.56×102 |
2.34×101 |
19 |
|
N=8.87, s N=0.82 |
1 b |
1.98×102 |
2.34×101 |
8.5 |
|
|
1 c |
4.70×101 |
5.17 |
9.1 |