782
H. NISHIWAKI et al.
evaporated, and the resulting residue was purified by column
chromatography (hexane:ethyl acetate ¼ 1:1) to afford 10 (0.39 g,
analysis. Calcd. for C11H13N4O2Cl; C, 49.17; H, 4.88; N, 20.85.
2
5
Found: C, 49.11; H, 4.58; N, 20.76. ½ꢀꢁD ꢂ7:5 (c 1.18, CHCl3). NMR
ꢁH (CDCl3): 1.36 (3H, d, J ¼ 6 Hz, CH3), 3.12 (1H, dd, J1 ¼ 10 Hz,
J2 ¼ 7 Hz, CH), 3.67 (1H, t, J ¼ 10 Hz, CH), 4.21 (1H, m, CH), 4.31
(2H, d, J ¼ 4 Hz, PyCH2), 6.64 (1H, s, CHNO2), 7.36 (1H, d,
J ¼ 8 Hz, Py), 7.56 (1H, dd, J1 ¼ 8 Hz, J2 ¼ 3 Hz, Py), 8.29 (1H,
d, J ¼ 3 Hz, Py), 8.77 (1H, br, NH). NMR ꢁC (CDCl3): 21, 47, 50, 51,
55, 96, 125, 129, 138, 149, 152, 159. >99% ee (DAICEL chiral
column OD-H, 254 nm, mobile phase of hexane:2-propanol ¼ 1:1,
tR ¼ 94 min).
25
2
0% in 2 steps). ½ꢀꢁD ꢂ29:1 (c 1.1, CHCl3). NMR ꢁH (CDCl3): 1.04
(
3H, d, J ¼ 7 Hz, CH3), 2.94 (1H, m, CH3CH), 3.52 (2H, m,
PhthalCH2), 3.67 (1H, d, J ¼ 12 Hz, PyCH2), 3.76 (1H, d,
J ¼ 12 Hz, PyCH2), 7.01 (1H, d, J ¼ 8 Hz, Py), 7.46 (1H, dd,
J1 ¼ 8 Hz, J2 ¼ 2 Hz, Py), 7.60 (2H, m, Ph), 7.69 (2H, m, Ph), 8.13
(1H, d, J ¼ 2 Hz, Py).
(
5R)-1-(6-Chloro-3-pyridylmethyl)-5-methyl-2-nitromethylene-imi-
dazolidine (3, steps C-i and -ii). To an ethanol solution containing
.39 g (1.2 mmol) of 10, 0.33 mL (5.8 mmol) of hydrazine monohy-
0
(4S)-1-(6-Chloro-3-pyridylmethyl)-4-methyl-2-nitromethylene-imi-
ꢀ
drate was added, and the mixture was refluxed for 6 h while stirring.
After the insoluble residue had been filtered, the resulting filtrate was
evaporated to afford 11 which was used for the subsequent reaction
without further purification. After diaminopropane 11 had been
dissolved in 20 mL of ethanol, 0.20 g (1.2 mmol) of 1,1-bis(methylth-
io)-2-nitroethylene and 0.16 g (1.2 mmol) of K2CO3 were added to the
solution, and the mixture was refluxed overnight. After removing
K2CO3 by filtration, the filtrate was evaporated in vacuo, and the
resulting residue was purified by column chromatography (ethyl
dazolidine (6). Mp 139–141 C. Elemental analysis. Calcd. for
C11H13N4O2Cl: C, 49.17; H, 4.88; N, 20.85. Found: C, 49.09; H,
2
5
4.83; N, 20.83. ½ꢀꢁD þ7:8 (c 1.14, CHCl3). >99% ee (DAICEL
OD-H, 254nm, mobile phase hexane:2-propanol ¼ 1:1, tR ¼ 102 min).
Acknowledgments
We are grateful to Professor Toru Miyamoto of Tokyo
Agriculture University and to Professor Hisashi
Miyagawa and Professor Yoshiaki Nakagawa of Kyoto
University for respectively presenting the houseflies and
radiolabeled imidacloprid. Part of this study was
performed at INCS (Johoku and Tarumi stations) of
Ehime University.
ꢀ
acetate) to afford 3 (0.22 g, 67% in two steps). Mp 139–141 C.
Elemental analysis. Calcd. for C11H13N4O2Cl: C, 49.17; H, 4.88; N,
2
5
2
0.85. Found: C, 48.94; H, 4.91; N, 20.66. ½ꢀꢁD þ9:9 (c 1.54,
CHCl3). NMR ꢁH (CDCl3): 1.33 (3H, d, J ¼ 6 Hz, CH3), 3.39 (1H, m,
CH), 3.93 (2H, m, CH2), 4.30 (1H, d, J ¼ 17 Hz, PyCH2), 4.37 (1H, d,
J ¼ 17 Hz, PyCH2), 6.56 (1H, s, CHNO2), 7.35 (1H, d, J ¼ 8 Hz, Py),
7
.55 (1H, dd, J ¼ 8 Hz, J ¼ 2 Hz, Py), 8.29 (1H, d, J ¼ 2 Hz, Py), 8.70
(
1H, br, NH). NMR ꢁC (CDCl3): 18, 44, 50, 56, 97, 125, 130, 138, 148,
52, 159. >99% ee [confirmed by a 1H-NMR chemical shift of the
CHNO2 group by the shift reagent, Chirabite].
1
References
(
5S)-1-(6-Chloro-3-pyridylmethyl)-5-methyl-2-nitromethylene-imi-
ꢀ
1) Elbert A, Overbeck H, Iwaya K, and Tsuboi S, ‘‘Proc Brighton
Crop Protect Conf—Pests & Diseases,’’ BCPC, Farnham,
pp. 21–28 (1990).
dazolidine (4). Mp 140–142 C. Elemental analysis. Calcd. for
C11H13N4O2Cl: C, 49.17; H, 4.88; N, 20.85. Found: C, 49.12; H,
2
5
4
.86; N, 20.85. ½ꢀꢁD ꢂ9:5 (c 1.58, CHCl3). The NMR spectral data
2) Kagabu S, J. Agric. Food Chem., 59, 2887–2896 (2011).
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Food Chem., 58, 3415–3421 (2010).
agreed with those of its enantiomer. >99% ee (confirmed by the same
procedure as that for determining the chirality of 3).
0
(2R)-N-(6-Chloro-3-pyridylmethyl)-N -t-butoxycarbonyl-1,2-diami-
nopropane (13, steps D-i and -ii). Hydrazine monohydrate (3 mL,
4) Nishiwaki H, Nakagawa Y, Takeda DY, Okazawa A, Akamatsu
M, Miyagawa H, Ueno T, and Nishimura K, Pest Manag. Sci.,
56, 875–881 (2000).
5
1
3
3 mmol) was added dropwise to ethanol containing 8 (3.23 g,
0 mmol) while stirring at ambient temperature. After refluxing for
h, the reactant was filtered, and the resulting filtrate was evaporated
5) Nishiwaki H, Nakagawa Y, Ueno T, Kagabu S, and Nishimura
K, Pest Manag. Sci., 57, 810–814 (2001).
to afford 12. The residue was dissolved in 20 mL of acetonitrile, to
which 5 mL of triethylamine and 1.26 g (8 mmol) of 2-chloro-5-
chloromethylpyridine hydrochloride was added, and the mixture was
refluxed overnight. After the solvent had been evaporated, the residue
was dissolved in distilled water, and the pH was adjusted to 8.0 with
6) Kagabu S, Nishiwaki H, Sato K, Hibi M, Yamaoka N, and
Nakagawa Y, Pest Manag. Sci., 58, 483–490 (2002).
7) Nishiwaki H, Sato K, Nakagawa Y, Miyashita M, and
Miyagawa H, J. Pestic. Sci., 29, 110–116 (2004).
8) Liu M, Lanford J, and Casida JE, Pestic. Biochem. Physiol., 46,
200–206 (1993).
1
M of aqueous NaOH. The solution was extracted three times with
dichloromethane, and the organic phase was dried over sodium sulfate.
The solvent was evaporated, and the resulting residue was purified by
column chromatography (ethyl acetate:ethanol ¼ 9:1) to afford 13
9) Nishimura K, Kanda Y, Okazawa A, and Ueno T, Pestic.
Biochem. Physiol., 50, 51–59 (1994).
10) Yamamoto I, Tomizawa M, Saito T, Miyamoto T, Walcott EC,
and Sumikawa K, Arch. Insect Biochem. Physiol., 37, 24–32
(1998).
25
(
(
(
1.07 g, 36% in two steps). ½ꢀꢁD ꢂ61:1 (c 1.8, CHCl3). NMR ꢁH
CDCl3): 1.08 (3H, d, J ¼ 7 Hz, CH3), 1.39 (9H, s, (CH3)3C), 2.12
1H, m, CH), 3.69 (2H, m, CH2), 4.74 (1H, br, NH), 7.22 (1H, d,
11) Nishiwaki H, Nakagawa Y, Kuwamura M, Sato K, Akamatsu
M, Matsuda K, Komai K, and Miyagawa H, Pest Manag. Sci.,
59, 1023–1030 (2003).
J ¼ 8 Hz, Py), 7.62 (1H, d, J ¼ 8 Hz, Py), 8.27 (1H, s, Py).
4R)-1-(6-Chloro-3-pyridylmethyl)-4-methyl-2-nitromethylene-imi-
dazolidine (5, steps E-i and -ii). After deprotecting the Boc group of
.07 g (3.6 mmol) of 13 by concentrated HCl to obtain 14, 2.31 g
14 mmol) of 1,1-bis(methylthio)-2-nitroethylene and 1.93 g (14 mmol)
(
12) Soliman SA, J. Toxicol. Environ. Health, 10, 907–920 (1982).
13) Liu M, Latli B, and Casida JE, Pestic. Biochem. Physiol., 50,
171–182 (1994).
1
(
of K2CO3 were added to 20 mL of an ethanol solution containing 14,
and the mixture was refluxed overnight. After filtering to remove
K2CO3, the resulting filtrate was evaporated, and the residue was
purified by column chromatography (ethyl acetate:ethanol ¼ 9:1) to
14) Finney DJ, ‘‘Probit Analysis’’ 2nd ed., Cambridge University
Press, London (1952).
15) Nishiwaki H, Nakagawa Y, Ueno T, and Nishimura K, J. Pestic.
Sci., 26, 91–92 (2001).
ꢀ
afford 5 (0.13 g, 13% in two steps). Mp 139–141 C. Elemental