2662 J. Agric. Food Chem., Vol. 55, No. 7, 2007
Chen et al.
Table 3. 1H NMR of Compounds IIa
−v
δ
(ppm)
IIa
2.32 (s, 3H, CH3), 2.42 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 6.92 (t, 2H, 3JHH
)
8.4 Hz, Ph),
7.35 (m, 1H, Ph), 7.42 (d, 2H, 3JHH
11.19 (s, 1H, NH)
) ) 8.1 Hz, Ph),
8.4 Hz, Ph), 7.67 (d, 2H, 3JHH
IIb
IIc
IId
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.20 (s, 3H, NCH3), 6.89 (t, 2H, 3JHH
)
8.1 Hz, Ph),
8.4 Hz, Ph),
8.4 Hz, Ph),
7.28
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 6.89 (t, 2H, 3JHH
7.06 (d, 2H, 3JHH
9.0 Hz, Ph), 7.19 7.38 (m, 3H, Ph), 11.05 (s, 1H, NH)
− ) 9.0 Hz, Ph), 11.07 (s, 1H, NH)
7.38 (m, 3H, Ph), 7.35 (d, 2H, 3JHH
)
)
−
2.31 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.17 (s, 3H, NCH3), 6.91 (t, 2H, 3JHH
)
7.35 (m, 1H, Ph), 7.42 (d, 2H, 3JHH
11.25 (s, 1H, NH)
)
8.4 Hz, Ph), 7.69 (d, 2H, 3JHH
)
8.1 Hz, Ph),
IIe
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.23 (s, 3H, NCH3), 6.91 (t, 2H, 3JHH
) 8.4 Hz, Ph),
)
7.31
11.12 (s, 1H, NH)
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 6.90 (t, 2H, 3JHH
7.20 7.38 (m, 5H, Ph), 11.12 (s, 1H, NH)
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 6.89 (t, 2H, 3JHH
7.13 (d, 1H, 3JHH
9.0 Hz, Ph), 7.28
11.07 (s, 1H, NH)
2.30 (s, 3H, CH3), 2.40 (s, 3H, SCH3), 3.23 (s, 3H, NCH3), 6.91 (t, 2H, 3JHH
7.28
7.40 (m, 2H, Ph), 7.60 (d, 1H, 4JHH 2.4 Hz, Ph), 7.72 (d, 1H, 3JHH
11.15 (s, 1H, NH)
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.19 (s, 3H, NCH3), 7.28
7.52 8.4 Hz, Ph), 11.04 (s, 1H, NH)
7.55 (m, 1H, Ph), 7.65 (d, 2H, 3JHH
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.20 (s, 3H, NCH3), 7.39 (d, 2H, 3JHH
7.30 7.38 (m, 5H, Ph), 7.52 7.54 (m, 1H, Ph), 10.96 (s, 1H, NH)
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 7.06 (t, 2H, 3JHH
7.20 7.36 (m, 5H, Ph), 7.52 7.55 (m, 1H, Ph), 10.99 (s, 1H, NH)
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 7.21 7.36 (m, 7H, Ph),
7.51 7.54 (m, 1H, Ph), 10.99 (s, 1H, NH)
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 7.14 (d, 2H, 3JHH
7.30 7.54 (m, 6H, Ph), 10.99 (s, 1H, NH)
2.29 (s, 3H, CH3), 2.39 (s, 3H, SCH3), 3.23 (s, 3H, NCH3), 7.28
7.53 2.1 Hz, Ph),
7.55 (m, 1H, Ph), 7.60 (d, 1H, 4JHH
7.72 (d, 1H, 3JHH
8.1 Hz, Ph), 11.04 (s, 1H, NH)
2.32 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.21 (s, 3H, NCH3), 7.17
7.38 (d, 2H, 3JHH 8.1 Hz, Ph), 7.63 (d, 2H, 3JHH
2.32 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.22 (s, 3H, NCH3), 7.16
7.33 (d, 2H, 3JHH
9.0 Hz, Ph), 11.02 (s, 1H, NH)
2.32 (s, 3H, CH3), 2.42 (s, 3H, SCH3), 3.22 (s, 3H, NCH3), 7.05 (t, 2H, 3JHH
7.16 7.26 (m, 5H, Ph), 11.02 (s, 1H, NH)
2.32 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.23 (s, 3H, NCH3), 7.17
2.32 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.22 (s, 3H, NCH3), 7.12 (d, 2H, 3JHH
7.16 9.0 Hz, Ph), 11.02 (s, 1H, NH)
7.24 (m, 3H, Ph), 7.49 (d, 2H, 3JHH
2.31 (s, 3H, CH3), 2.41 (s, 3H, SCH3), 3.25 (s, 3H, NCH3), 7.19 7.29 (m, 4H, Ph),
7.58 (d, 1H, 4JHH 3.0 Hz, Ph), 7.70 (d, 1H, 3JHH
8.4 Hz, Ph), 11.07 (s, 1H, NH)
1.50 [s, 6H, (CH3)2], 2.17 (s, 3H, SCH3), 3.19 (s, 3H, NCH3), 6.90 (t, 2H, 3JHH
7.5 Hz, Ph),
7.21 7.39 (m, 5H, Ph), 7.64 (s, 1H, CH), 10.90 (s, 1H, NH)
2.39 (s, 3H, CH3), 3.32 (s, 3H, NCH3), 6.83
6.92 (m, 4H, Ph), 7.09 (d, 1H, 3JHH
7.25 8.4 Hz, Ph),
7.37 (m, 2H, Ph), 7.47 (d, 2H, 3JHH
7.70 (d, 2H, 3JHH
9.0 Hz, Ph), 11.34 (s, 1H, NH)
−
7.40 (m, 2H, Ph), 7.52 (d, 1H, 3JHH
)
9.0 Hz, Ph), 7.61 (d, 1H, 4JHH
2.1 Hz, Ph),
8.4 Hz, Ph),
8.4 Hz, Ph),
IIf
)
)
−
IIg
)
−
7.38 (m, 1H, Ph), 7.50 (d, 2H, 3JHH
)
8.4 Hz, Ph),
IIh
) 8.4 Hz, Ph),
)
−
)
8.4 Hz, Ph),
IIi
−7.42 (m, 5H, Ph),
−
)
IIj
)
9.0 Hz, Ph),
−
−
IIk
IIl
) 9.0 Hz, Ph),
−
−
−
−
IIm
IIn
) 8.4 Hz, Ph),
−
−7.38 (m, 4H, Ph),
−
)
)
IIo
IIp
IIq
−7.28 (m, 3H, Ph),
)
)
9.0 Hz, Ph), 11.12 (s, 1H, NH)
7.26 (m, 5H, Ph),
−
)
)
9.0 Hz, Ph),
−
IIr
IIs
−7.32 (m, 7H, Ph), 11.02 (s, 1H, NH)
)
8.4 Hz, Ph),
−
)
IIt
−
)
)
IIu
IIv
)
−
d
−
) 7.5 Hz, Ph),
−
)
)
activities against Oriental armyworm, which are parallel to those
of the parent BPUs. For example, the larvicidal activity of the
title compounds IIf was equal to the parent diftrifmeouron. The
mode of action of the title compounds IIa-v is very interesting.
Toxicity assays indicate that at higher concentrations (for
example, 50 mg L-1) the title compounds IIa-v have the
knockdown activities and kill armyworm in 2 h, i.e., as fast as
the parent N-methylcarbamates, whereas at lower concentrations
(below 10 mg L-1) the title compounds IIa-v can interfere with
chitin biosynthesis of armyworm, like the parent BPUs, and
symptoms of toxicity include discoloration, weight loss, ces-
sation of feeding, and death.
Systemic LarVicidal ActiVities against Oriental Armyworm.
The results of systemic larvicidal activities against Oriental
armyworm of some compounds and the parent compounds are
summarized in Table 5. The title compounds IIb, IIf, IIi, and
IIl exhibit good systemic larvicidal activities against Oriental
armyworm. Toxicity assays indicate that the title compounds
IIb, IIf, IIi, and IIl, like the parent compound methomyl, can
cause armyworm convulsion and vomit water as the main poison
symptom within 20 min and kill armyworms within 1 h. Hence,
we have found that the title compounds have systemic properties,
being absorbed from a plant’s roots and effectively transferred
to other parts of the plant such as leaves. This property is
especially advantageous when combating sucking pests, for a
systemic insecticide can spread all through a plant and kill any
targeted insects that feed on it.
The insecticidal activities of the title compounds IIb and IIf
at 200 mg L-1 against A. laburni Kaltenbach were 54 and 36%,
respectively, as compared with 100% mortality of methomyl at
the same concentration. The larvicidal activity of the title
compound IIf against mosquito was 100% at 5 mg L-1
.
In summary, new propesticides with two effects of both BPUs
and carbamates were designed and synthesized by the key