Journal of Agricultural and Food Chemistry
Article
1
Table 2. H NMR of Compounds 8−23
compound
1H NMR (CDCl3, δ)
8
9
1.21 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 2.25 (s, 3H, Me), 3.98 (s, 3H, NCH3), 7.50 (q, 4H, Ar−H)
1.25 (t, J = 7.5 Hz, 3H, Me), 1.28 (s, 9H, t-Bu), 1.36 (s, 9H, t-Bu), 2.63 (q, J = 7.5 Hz, 2H, CH2), 3.29 (s, 3H, NCH3), 7.06 (d, J = 8.4 Hz, 2H, Ar−H),
7.32 (d, J = 8.4 Hz, 2H, Ar−H)
10
11
12
1.21 (s, 9H, t-Bu), 1.30 (d, J = 6.9 Hz, 6H, CH(CH3)2), 1.34 (s, 9H, t-Bu), 3.00−3.10 (m, 1H, CH), 3.99 (s, 3H, NCH3), 7.50 (q, 4H, Ar−H)
1.21 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.39 (s, 9H, t-Bu), 3.98 (s, 3H, Me), 7.46 (d, J = 8.4 Hz, 2H, Ar−H), 7.55 (d, J = 8.4 Hz, 2H, Ar−H)
0.94 (d, J = 6.9 Hz, 6H, CH(CH3)2), 1.21 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 2.00−2.10 (m, 1H, CH), 2.50 (d, 2H, CH2), 4.00 (s, 3H, NCH3), 7.51 (q, 4H,
Ar−H)
13
0.939 (d, J = 7.5 Hz, 4H, CH2CH2), 1.21 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.80−1.90 (m, 1H, CH), 3.94 (s, 3H, NCH3), 7.46 (d, J = 8.4 Hz, 2H, Ar−H),
7.54 (d, J = 8.4 Hz, 2H, Ar−H)
14
15
1.20 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.55 (t, J = 7.5 Hz, 3H, Me), 2.27 (s, 3H, Me), 4.21 (q, J = 7.2 Hz, 2H, CH2), 7.50 (q, 4H, Ar−H)
0.96 (t, J = 6.6 Hz, 3H, Me), 1.20 (s, 9H, t-Bu), 1.35 (s, 9H, t-Bu), 1.90−2.10 (br, 2H, CH2), 2.29 (s, 3H, Me), 4.09 (t, J = 7.5 Hz, 2H, CH2), 7.55 (d, J =
8.6 Hz, 2H, Ar−H), 7.65 (d, J = 8.6 Hz, 2H, Ar−H)
16
17
18
19
20
21
22
23
1.22 (s, 9H, t-Bu), 1.37 (s, 9H, t-Bu), 1.57 (m, 6H, CH(CH3)2), 2.31 (s, 3H, Me), 4.63 (q, 1H, CH(CH3)2), 7.48 (d, J = 8.4 Hz, 2H, Ar−H), 7.56 (d, J =
8.4 Hz, 2H, Ar−H)
1.20 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 2.32 (s, 3H, Me), 4.97 (d, J = 8.1 Hz, 1H, CH), 5.82 (d, J = 15.9 Hz, 1H, CH), 7.04 (q, J = 6.3 Hz, 1H, CH), 7.50
(dd, J1 = 8.7 Hz, J2 = 8.7 Hz, 4H, Ar−H)
1.14 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.54 (t, J = 7.2 Hz, 3H, Me), 2.31 (s, 3H, Me), 4.25 (q, J = 7.2 Hz, 2H, CH2), 6.36 (s, 1H, Ar−H), 7.45 (d, J = 8.4
Hz, 2H, Ar−H), 7.46 (d, J = 8.4 Hz, 2H, Ar−H)
1.01 (t, J = 7.2 Hz, 3H, Me), 1.27 (s, 9H, t-Bu), 1.36 (s, 9H, t-Bu), 2.28 (s, 3H, Me), 3.57 (q, J = 7.2 Hz, 2H, CH2), 6.18 (s, 1H, Ar−H), 7.07 (d, J = 8.4
Hz, 2H, Ar−H),7.32 (d, J = 8.4 Hz, 2H, Ar−H)
1.15 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.48 (t, J = 7.2 Hz, 3H, Me), 2.12 (s, 3H, Me), 2.23 (s, 3H, Me), 4.20−4.10 (m, 2H, CH2), 7.46 (d, J = 8.4 Hz, 2H,
Ar−H), 7.48 (d, J = 8.4 Hz, 2H, Ar−H)
1.18 (s, 9H, t-Bu), 1.36 (s, 9H, t-Bu), 1.51 (t, J = 7.2 Hz, 3H, Me), 2.26 (s, 3H, Me), 4.18 (q, J = 7.2 Hz, 2H, CH2), 7.46 (d, J = 8.4 Hz, 2H, Ar−H), 7.49
(d, J = 8.4 Hz, 2H, Ar−H)
1.20 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.56 (t, J = 7.2 Hz, 3H, Me), 2.28 (s, 3H, Me), 4.24 (q, J = 7.2 Hz, 2H, CH2), 7.46 (d, J = 8.4 Hz, 2H, Ar−H), 7.54
(d, J = 8.4 Hz, 2H, Ar−H)
1.25 (s, 9H, t-Bu), 1.35 (s, 9H, t-Bu), 1.61 (t, J = 7.2 Hz, 3H, Me), 2.42 (s, 3H, Me), 4.30 (q, J = 7.2 Hz, 2H, CH2), 7.46 (d, J = 8.4 Hz, 2H, Ar−H), 7.55
(d, J = 8.4 Hz, 2H, Ar−H)
Table 3. 13C NMR (CDCl3, δ) and MS of Compounds 14 and 18−22
compound
13C NMR (CDCl3, δ)
MS (EI)
14
11.03, 14.30, 26.58, 29.46, 34.64, 39.17, 45.93, 110.29, 111.29, 115.81 (CN), 125.42, 125.63, 126.53, 127.99, 128.12,
132.00, 145.22, 146.83, 153.40, 174.77
m/z 429.1 ([M + 1]+, 40)
18
19
20
21
22
13.34, 14.87, 26.41, 30.96, 34.61, 38.92, 45.36, 107.73, 109.10, 116.49 (CN), 125.46, 125.62, 126.99, 127.90, 128.13,
135.30, 147.82, 149.29, 153.02, 174.62
m/z 394.2 ([M + 1]+, 100)
m/z 394.2 ([M + 1]+, 100)
m/z 408.2 ([M + 1]+, 100)
m/z 412.1 ([M + 1]+, 100)
m/z 473.1 ([M + 1]+, 100)
13.47, 13.79, 26.69, 30.96, 34.63, 38.92, 44.71, 106.97, 108.40, 115.33 (CN), 125.96, 126.75, 127.80, 127.81, 127.84,
134.53, 148.49, 148.81, 152.87, 175.43
11.10, 13.31, 26.80, 30.98, 34.67, 39.25, 45.36, 110.14, 110.73, 114.93 (CN), 126.02, 126.39, 127.68, 130.99, 145.63,
146.79, 153.26, 174.48
11.94, 14.23, 26.61, 30.87, 34.58, 39.11, 45.93, 95.99, 111.55, 115.71 (CN), 125.45, 125.54, 126.45, 128.01, 128.12,
133.79, 146.83, 147.27, 153.35, 174.73
11.99, 13.21, 26.78, 31.34, 34.61, 39.19, 45.31, 95.68, 110.77, 114.85 (CN), 125.86, 125.99, 126.11, 126.33, 128.15,
132.77, 147.26, 147.32, 153.19, 175.45
Figure 4. Synthetic route of compounds 8−23. Reagents and conditions: (a) MeONa, ethylene glycol ether, heptane; (b) 2,2-dimethylpropionyl
chloride, Et3N, THF or 2,2-dimethylpropionyl chloride, K2CO3, toluene.
activities such as compounds 18 and 19, which have a better
acaricidal activity when compared to the commercialized
compound cyenopyrafen. A summary of results against adults of
T. cinnabarinus is outlined in Figure 6. With regard to the
substitution at the 3-position of the pyrazole ring (R2), the methyl
group was intrinsic for the activity. Elongation of the alkyl chain
and replacement of the methyl group by ethyl (9), isopropyl (10),
tert-butyl (11), isobutyl (12), or cyclopropyl (13) caused an
obvious decrease of activity. Compounds with ethyl at the
1-position of the pyrazole ring (R1) (14) exhibited a better
acaricidal activity compared with the corresponding methyl
substitution (compound 8). Propyl (15) and isopropyl (16)
derivatives showed no activity, and replacement of the ethyl (14)
by a vinyl group (17) caused a clear decrease of activity. Com-
pounds with H (18) and Cl (14) groups at the 4-position of the
pyrazole ring (R3) exhibited acaricidal activity similar to that of the
compound with a methyl (20) group. Replacement of H (18) by
Br (22) or a cyano group (23) clearly diminished the activity.
C
J. Agric. Food Chem. XXXX, XXX, XXX−XXX