T. Yamamoto et al. / Bioorg. Med. Chem. Lett. 16 (2006) 798–802
801
Table 4. Inhibitory activities of compounds in phase II pain responses
following footpad injection of formalin in the rat
slightly lower N-type activity (IC50 = 1.5 lM). The elec-
tron-donating methyl group at 4-position showed
improved potency for N-type calcium channels
(IC50 = 0.89 lM), but its activity against L-type was also
increased (IC50 = 0.0068 lM). The inhibitory activity
for N-type calcium channels of 4-pyridyl derivative 9d
was lower than that of cilnidipine.
Compound
Rat formalin test (30 mg/kg, po)
Inhibition %
n
Cilnidipine
21b
46
46
5
5
Inhibition % is given by the control and test compound.
The introduction of a b-methyl group (9e) or a naphthyl
group (9g) resulted in increased activities against L-type
channels (IC50 = 0.0028 and 0.014 lM, respectively).
The amide (9f) derivatives showed lower activity against
N-type calcium channel. The diphenylmethyl derivative
9i had an almost equivalent potency for N-type
(IC50 = 1.1 lM) with that of 7h with considerably de-
creased activity against L-type calcium channels
(IC50 = 0.36 lM), which was more than 320-fold lower
than that of cilnidipine. However, the N-type activity
of its diphenylmethylidene (9h) and bipyridylmethyl
(9j) derivatives for N-type channels was decreased.
romethyl-1,4-dihydropyridine-3,5-dicarboxylic acid 5-
(3,3-diphenylpropyl) ester 21b, which had an almost
equipotent activity against N-type calcium channels
but 1600-fold lower activity for L-type than that of ciln-
idipine, showed equivalent oral analgesic activity to ciln-
idipine. This result reemphasized the importance of
inhibitory activity against N-type channels for the treat-
ment of neuropathic pain. Further SAR studies are
under progress and will be reported elsewhere.
Finally, we introduced the trifluoromethyl moiety at the
6-position of the 1,4-dihydropyridine ring and found
that the derivative 21b had a 1600-fold lower activity
against L-type channels (IC50 = 1.8 lM) with an almost
equivalent activity for N-type (IC50 = 1.7 lM) to cilnid-
ipine (Table 3). This considerable decrease of L-type
activity might be ascribed to the inductive effect of triflu-
oromethyl moiety which increases the acidity of carbox-
ylic acid at 3-position of the 1,4-dihydropyridine ring.
References and notes
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Schwartz, A. Trends Pharmacol. Sci. 1995, 16, 43; (e)
Nooney, J. M.; Lambert, R. C.; Feltz, A. Trends
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naga, T.; Ino, M.; Sawada, K.; Niidome, T. Trends
Cardiovasc. Med. 2002, 12, 270.
3. (a) Saegusa, H.; Kurihara, T.; Zong, S.; Kazuno, A.;
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Tanabe, T. EMBO J. 2001, 20, 2349; (b) Takizawa, S.;
Matsushima, K.; Fujita, H.; Nanri, K.; Ogawa, S.;
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Subsequently, the oral analgesic effect of 21b was tested
in vivo using formalin-induced pain model.14 As can be
seen in Table 4, 21b showed equivalent oral activity to
cilnidipine. This result indicated that 21b was an orally
effective N-type calcium channel blocker. Moreover, this
result showed that the activity for N-type calcium chan-
nels is more important than that for L-type to exert the
analgesic efficacy.
In conclusion, the SAR study on 4,5 and 6-position of
series of 1,4-dihydropyridine derivatives starting from
APJ2708 led to the discovery of novel N-type calcium
channel blockers with less effects on cardiovascular sys-
tem than those of cilnidipine and APJ2708. Among
them, promising 4-(3-chloro-phenyl)-2-methyl-6-trifluo-
Table 3. In vitro results of dihydropyridine derivatives
Cl
6. (a) Tomiyama, H.; Kimura, Y.; Kuwabara, Y.; Maruy-
ama, C.; Yoshida, Y.; Kuwata, S.; Kinouchi, T.; Yoshida,
H.; Doba, N. Hypertens. Res. 2001, 24, 679; (b) Takeda,
S.; Ueshiba, H.; Hattori, Y.; Irie, M. Diabetes Res. Clin.
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O
O
R
Ph
HO
O
Ph
N
H
7. (a) Takahara, A.; Konda, T.; Enomoto, A.; Kondo, N.
Biol. Pharm. Bull. 2004, 27, 1388; (b) Konda, T.; Takeda,
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P82 (Abstract).
8. Murakami, M.; Nakagawasai, O.; Fujii, S.; Hosono, M.;
Hozumi, S.; Esashi, A.; Taniguchi, R.; Okamura, T.;
Suzuki, T.; Sasano, H.; Yanagisawa, T.; Tan-no, K.;
Compound
R
N-type IMR-32
IC50 (lM)
L-type Magnus
IC50 (lM)
9i
21b
Me
CF3
1.1
1.7
0.36
1.8
The inhibition against N-type (calcium influx using IMR-32 cells) and
L-type (Magnus method) calcium channels.