Month 2013
Optical Activity 1,5-Substituted-1,3,5-hexahydrotriazine-2-N-nitroimines:
Synthesis and Insecticidal Activity
Table 1
Insecticidal activities of compounds 3a–3l against Nilaparvata lugen.
Concentration (mg/L)a
100
Compound
n
R1
R2
500
10
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
1
1
1
1
2
1
1
1
1
1
1
2
–
H
CH3
CH3
CH3
CH3
CH3
CH2CH3
CH2CH3
CH2CH3
CH2CH3
CH2CH3
CH2CH3
CH2CH3
–
+++++
++++++
+++++
+++++
++++++
++++++
+++++
+++++
+++++
+++++
+++++
++++++
++++++
+++
++++++
+++
++
+++++
++
(CH3)2CHCH2
CH3
PhCH2
++
nt
H
(CH3)2CHCH2
CH3S·CH2CH2
PhCH2
p‐Cl‐C6H4
(CH3)2CH
H
++++++
++++++
++
++
+++
++
+++
++++++
++++++
+++++
+++++
++
nt
–
++
++
+++++
++++++
H
–
Imidacloprid
aRating system for the mortality percentage: ++++++, 100%; +++++, ≥90%; ++++, ≥80%; +++, ≥70%; ++, ≥60%; +, ≥50%; ꢀ, ≤50%.
135–136°C. 1H NMR (ppm, CDCl3), δ 9.69 (s, 1H, N–H), 7.37
(s, 1H, furan-H), 6.41–6.36 (m, 2H, furan-H), 4.65(s, 2H,
furan-CH2), 4.50 (s, 4H, triazine-H), 3.75 (s, 3H, CH3), 3.42
(s, 2H, NCH2C¼O). IR (KBr, cmꢀ1) ν: 3286, 1742, 1588,
1054; Anal. calcd for C11H15N5O5: C, 44.44; H, 5.09; N,
23.56. Found: C, 44.40; H, 5.11; N, 23.60.
1-(2-Furfuryl)-5-(3-methyl-1-methoxycarbonyl)butyl-1,3,5-
hexahydrotriazine-2-N-nitroimine (3b). Yield: 58.2%. Yellow
solid. m.p. 83–84°C. [α]2D0 = +17.662° (C = 0.01 g/mL
CH3CH2OH). 1H NMR (ppm, CDCl3), δ 9.61 (s, 1H, N–H),
7.39 (s, 1H, furan-H), 6.41–6.36 (m, 2H, furan-H), 4.80–4.74
(m, 6H), 3.66 (s, 3H, OCH3), 3.53 (t, J = 8 Hz, 1H,
NHCHC¼O), 1.60–1.49 (m, 2H, CHCH2), 1.43 (t, J = 8 Hz,
1H, CH(CH3)2), 0.92–0.89 (m, 6H, 2CH3). IR (KBr, cmꢀ1) ν:
3278, 1733, 1600, 1058; Anal. calcd for C15H23N5O5: C, 50.98;
H, 6.56; N, 19.82. Found: C, 51.00; H, 6.54; N, 19.72.
1-(2-Furfuryl)-5-(1-methoxycarbonyl)ethyl-1,3,5-hexahydro-
triazine-2-N-nitroimine (3c). Yield: 60.5%. White solid. m.p.
72–73°C. [α]2D0 = +25.886° (C = 0.01 g/mL CH3CH2OH). 1H
NMR (ppm, CDCl3), δ 9.63 (s, 1H, N–H), 7.39 (s, 1H, furan-H),
6.42–6.36 (m, 2H, furan-H), 4.69–4.58 (m, 2H, furan-CH2),
4.57–4.46 (m, 4H, triazine-H), 3.75–3.68 (m, 6H, 2CH3), 3.55–
3.48 (q, 1H, NCH(CH3)C¼O). IR (KBr, cmꢀ1) ν: 3277, 1738,
1599, 1062; Anal. calcd for C12H17N5O5: C, 46.30; H, 5.50; N,
22.50. Found: C, 46.23; H, 5.45; N, 22.61.
1-(2-Furfuryl)-5-(2-benyl-1-methoxycarbonyl)ethyl-1,3,5-
hexahydrotriazine-2-N-nitroimine (3d). Yield: 50.2%. Yellow
solid. m.p. 82–83°C. [α]2D0 = +17.201° (C = 0.01 g/mL
CH3CH2OH). 1H NMR (ppm, CDCl3), δ 9.59 (s, 1H, N–H),
7.39 (s, 1H, furan-H), 7.32–7.23 (m, 3H, ph-H), 7.14–7.12
(m, 2H, ph-H), 6.42–6.36 (m, 2H, furan-H), 4.72–4.45 (m, 6H),
1560, 1060; Anal. calcd for C12H17N5O5: C,46.30; H, 5.50; N,
22.50. Found: C, 46.20; H, 5.48; N, 22.58.
1-(2-Furfuryl)-5-(3-methyl-1-ethoxycarbonyl)butyl-1,3,5-
hexahydrotriazine-2-N-nitroimine (3f). Yield: 62.6%. White
solid. m.p. 68–69°C. [α]2D0 = +18.550° (C = 0.01 g/mL
CH3CH2OH). 1H NMR (ppm, CDCl3), δ 9.65 (s, 1H, N–H),
7.38 (s, 1H, furan-H), 6.41–6.36 (m, 2H, furan-H), 4.82–4.53
(m, 2H, furan-CH2), 4.49–4.44 (m, 4H, triazine-H), 4.18–4.07
(m, 2H, OCH2), 3.56 (t, J = 8 Hz, 1H, NHCHC¼O), 1.66–1.56
(m, 2H, CHCH2), 1.54–1.49 (m, 1H, CH(CH3)2), 1.26 (t, J =
8 Hz, 3H, OCH2CH3), 0.93–0.90 (q, 6H, 2CH3). IR (KBr,
cmꢀ1) ν: 3276, 1729, 1597, 1050; Anal. calcd for C16H25N5O5:
C, 52.31; H, 6.86; N, 19.06. Found: C, 52.29; H, 6.90; N, 18.96.
1-(2-Furfuryl)-5-(3-methylsulfanyl-1-ethoxycarbonyl)propyl-
1,3,5-hexahydrotriazine-2-N-nitroimine (3g). Yield: 55.8%.
White solid. m.p. 106–107°C. [α]2D0 = +36.228° (C = 0.01 g/mL
CH3CH2OH). 1H NMR (ppm, CDCl3), δ 9.63 (s, 1H, N–H), 7.38
(s, 1H, furan-H), 6.39–6.34 (m, 2H, furan-H), 4.81–4.55 (m, 2H,
furan-CH2), 4.53–4.42 (m, 4H, triazine-H), 4.21–4.03 (m, 2H,
OCH2), 3.66 (t, J = 8 Hz, 1H, NHCHC¼O), 2.52–2.47 (m, 2H,
CHCH2), 2.08 (s, 3H, SCH3), 2.00–1.95 (m, 2H, SCH2), 1.25
(t, J = 8 Hz, 3H, CH2CH3). IR (KBr, cmꢀ1) ν: 3280, 1733, 1585,
1056; Anal. calcd for C15H23N5O5S: C, 46.74; H, 6.01; N, 18.17.
Found: C, 46.77; H, 6.05; N, 18.10.
1-(2-Furfuryl)-5-(2-benyl-1-ethoxycarbonyl)ethyl-1,3,5-hexahy-
drotriazine-2-N-nitroimine (3h). Yield: 56.3%. White solid. m.p.
79–80°C. [α]2D0 = +16.238° (C = 0.01 g/mL CH3CH2OH). 1H
NMR (ppm, CDCl3), δ 9.62 (s, 1H, N–H), 7.39 (s, 1H, furan-H),
7.32–7.13 (m, 5H, ph-H), 6.41 (s, 1H, furan-H), 6.36 (s, 1H, furan-
H), 4.80–4.51 (m, 2H, furan-CH2), 4.51–4.42 (m, 4H, triazine-H),
4.07–3.93 (m, 2H, OCH2), 3.74 (t, J = 8 Hz, 1H, NHCHC¼O),
3.05–2.94 (m, 2H, ph-CH2), 1.10–1.06 (m, 3H, CH3). IR (KBr,
cmꢀ1) ν: 3285, 1731, 1591, 1054; Anal. calcd for C19H23N5O5: C,
56.85; H, 5.78; N, 17.45. Found: C, 56.83; H, 5.73; N, 17.50.
1-(2-Furfuryl)-5-(1-(4-chloro)benyl-1-ethoxycarbonyl)methyl-
1,3,5-hexahydrotriazine-2-N-nitroimine (3i). Yield: 58.0%.
White solid. m.p. 120–121°C. [α]2D0 = +21.228° (C = 0.01 g/mL
CH3CH2OH). 1H NMR (ppm, CDCl3), δ 9.53 (s, 1H, N–H), 7.38
(s, 1H, furan-H), 7.35–7.30 (m, 4H, Cl-ph-H), 6.34 (s, 2H, furan-
H), 4.69–4.65 (m, 1H), 4.51–4.46 (m, 3H), 4.41–4.31 (m, 3H),
4.14–4.09 (m, 2H, OCH2CH3), 1.18–1.15 (m, 3H, CH2CH3). IR
4.77–4.73 (m, 1H, NCH), 3.54 (s, 3H, OCH3), 3.00 (q, J1
=
8 Hz, J2 = 16 Hz, 2H, ph-CH2). IR (KBr, cmꢀ1) ν: 3286, 1729,
1590, 1054; Anal. calcd for C18H21N5O5: C, 55.81; H, 5.46; N,
18.08. Found: C, 55.90; H, 5.42; N, 18.12.
1-(2-Furfuryl)-5-(2-methoxycarbonyl)ethyl-1,3,5-hexahydro-
triazine-2-N-nitroimine (3e). Yield: 72.5%. White solid. m.p. 78–
1
79°C. H NMR (ppm, CDCl3), δ 9.65 (s, 1H, N–H), 7.35 (s, 1H,
furan-H), 6.40–6.33 (m, 2H, furan-H), 4.60–4.58 (s, 2H, furan-
CH2), 4.44–4.37 (m, 4H, triazine-H), 3.60 (s, 3H, OCH3), 2.90–
2.88 (m, 2H), 2.44–2.41 (m, 2H). IR (KBr, cmꢀ1) ν: 3279, 1737,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet