Synthesis and Herbicidal Activity of N-Arylmethyl-2-(4-arylxoyphenoxy)propionamide†

doi:10.7503/cjcu20130625

Abstract

Abstract:

Aryloxyphenoxypropionic acid(APP) herbicides inhibiting acetyl-CoA carboxylase(ACCase) have been identified as one of the most important herbicides. As part of continuous efforts to search for new herbicides with high efficacy, broad-spectrum activity and safety to crops, the commercialized APP herbicide metamifop was used as lead compounds for further optimization. Sixteen new N-arylmethyl 2-(4-arylxoy-phenoxy) propionamide compounds were designed and prepared by multistep synthetic procedures starting from(R)-(+)2-(4-hydroxyphenoxy) propanoic acid, and their structures were characterized by ¹H NMR, ¹³C NMR, LC/MS, IR and elemental analysis. Steric configuration was confirmed by chiral column liquid chromatography. The bioassay results indicated that all compounds exhibited >90% activity against crabgrass(Digitaria sanguinalis L.), barnyard grass(Echinochloa crus-galliL.) and green foxtail(Setaria Viridis L.) at 2250 g/ha. Further herbicidal activity and phytotoxicit to crops results indicated that(R)-(+)-N-[(6-chloropyridin-3-yl)methyl]- 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)-propanamide(2b) was more effective against Digitaria sanguinalis (IC₅₀=15.4 g/ha) and Echinochloa crus-galli (IC₅₀=22.8 g/ha) than metamifop(IC₅₀=31.9 g/ha and 25.0 g/ha). In particular, compound 2b was safe to rice(Xiang zao xian 24) and more effective against Leptochloa than commercial cyhalofop-butyl. The herbicidal activity is related to steric configuration that the compounds of R configuration have more effective activity.

Key words: N-Arylmethyl 2-(4-arylxoyphenoxy) propionamide, Herbicidal activity, Crop selectivity

CLC Number:

O626

TrendMD:

LIU Qixing, HU Aixi, WANG Xiaoguang, LEI Manxiang, OU Xiaoming, REN Yeguo, HUANG Lu, LIU Aiping. Synthesis and Herbicidal Activity of N-Arylmethyl-2-(4-arylxoyphenoxy)propionamide^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 262.

Figures/Tables 8

Scheme 1 Synthetic routes of compounds 2a—2p

Table 1 Appearance, yields, melting points, optical rotation and elemental analysis for compounds 2a—2p

Compd.	Appearance	Yield^*(%)	m.p./℃	[α $] D 20$ /(°) (c 1, acetone)	Elemental analysis(%, calcd.)
Compd.	Appearance	Yield^*(%)	m.p./℃	[α $] D 20$ /(°) (c 1, acetone)	C	H	N
2a	White solid	66.7	134.4—135.4	+24.0	54.85(55.06)	3.62(3.70)	9.72(9.63)
2b	White solid	62.5	109.6—112.0	+19.4	52.01(51.87)	3.38(3.32)	8.56(8.64)
2c	Pale yellow solid	57.3	78.8—80.1	+20.2	55.60(55.82)	3.68(3.79)	9.25(9.30)
2d	White solid	77.5	130.7—131.3	+25.4	62.25(62.05)	4.09(4.02)	9.80(9.87)
2e	White solid	68.2	143.0—144.1	+24.9	57.63(57.66)	3.72(3.74)	9.13(9.17)
2f	White solid	53.4	171.8—172.5	+17.4	58.81(58.86)	3.84(3.87)	11.87(11.94)
2g	Yellow solid	25.0	100.1—100.9	+30.4	49.01(48.88)	3.15(3.19)	9.44(9.50)
2h	Pale yellow solid	22.6	113.9—115.0	+25.8	46.45(46.35)	2.91(2.87)	8.50(8.54)
2i	Pale yellow oil	34.1		+24.9	49.88(49.84)	3.37(3.30)	9.11(9.18)
2j	White solid	59.7	95.2—96.6	+27.2	55.70(55.62)	3.44(3.50)	9.70(9.73)
2k	White solid	43.9	152.5—153.0	+32.0	51.70(51.73)	3.31(3.26)	9.10(9.05)
2l	White solid	25.9	165.2—165.4	+27.8	53.12(53.06)	3.45(3.39)	11.88(11.79)
2m	Pale yellow oil	48.0		+19.0	49.91(50.01)	3.49(3.53)	9.28(9.21)
2n	Pale yellow solid	43.4	42.6—54.0	+7.3	47.51(47.44)	3.23(3.19)	8.40(8.30)
2o	Yellow solid	59.5	39.9—40.0	+10.9	51.22(51.07)	3.82(3.86)	8.89(8.93)
2p	Pale yellow oil	40.5		+20.0	48.65(48.47)	3.52(3.49)	8.14(8.08)

Table 1 Appearance, yields, melting points, optical rotation and elemental analysis for compounds 2a—2p

Compd.	Appearance	Yield^*(%)	m.p./℃	[α $] D 20$ /(°) (c 1, acetone)	Elemental analysis(%, calcd.)
Compd.	Appearance	Yield^*(%)	m.p./℃	[α $] D 20$ /(°) (c 1, acetone)	C	H	N
2a	White solid	66.7	134.4—135.4	+24.0	54.85(55.06)	3.62(3.70)	9.72(9.63)
2b	White solid	62.5	109.6—112.0	+19.4	52.01(51.87)	3.38(3.32)	8.56(8.64)
2c	Pale yellow solid	57.3	78.8—80.1	+20.2	55.60(55.82)	3.68(3.79)	9.25(9.30)
2d	White solid	77.5	130.7—131.3	+25.4	62.25(62.05)	4.09(4.02)	9.80(9.87)
2e	White solid	68.2	143.0—144.1	+24.9	57.63(57.66)	3.72(3.74)	9.13(9.17)
2f	White solid	53.4	171.8—172.5	+17.4	58.81(58.86)	3.84(3.87)	11.87(11.94)
2g	Yellow solid	25.0	100.1—100.9	+30.4	49.01(48.88)	3.15(3.19)	9.44(9.50)
2h	Pale yellow solid	22.6	113.9—115.0	+25.8	46.45(46.35)	2.91(2.87)	8.50(8.54)
2i	Pale yellow oil	34.1		+24.9	49.88(49.84)	3.37(3.30)	9.11(9.18)
2j	White solid	59.7	95.2—96.6	+27.2	55.70(55.62)	3.44(3.50)	9.70(9.73)
2k	White solid	43.9	152.5—153.0	+32.0	51.70(51.73)	3.31(3.26)	9.10(9.05)
2l	White solid	25.9	165.2—165.4	+27.8	53.12(53.06)	3.45(3.39)	11.88(11.79)
2m	Pale yellow oil	48.0		+19.0	49.91(50.01)	3.49(3.53)	9.28(9.21)
2n	Pale yellow solid	43.4	42.6—54.0	+7.3	47.51(47.44)	3.23(3.19)	8.40(8.30)
2o	Yellow solid	59.5	39.9—40.0	+10.9	51.22(51.07)	3.82(3.86)	8.89(8.93)
2p	Pale yellow oil	40.5		+20.0	48.65(48.47)	3.52(3.49)	8.14(8.08)

Table 2 1H NMR, 13C NMR, LC-MS and IR data for compounds 2a—2p

Compd.	¹H NMR(300 MHz, CDCl₃), δ	¹³C NMR (75 MHz, CDCl₃), δ	LC-MS ([M+H]⁺), m/z	IR(KBr), $ν ˙$ /cm^-1
2a	1.61(d, J=6.9 Hz, 3H, CH₃), 4.49(d, J=6.6 Hz, 2H, CH₂), 4.74(q, J=6.9 Hz, 1H, CH), 6.88—6.94(m, 3H, PhH+NH), 7.08(d, J=9.0 Hz, 2H, PhH), 7.29(d, J=8.1 Hz, 1H, PyH), 7.49—7.53(m, 2H, PyH), 7.87(d, J=2.1 Hz, 1H, PyH), 8.29(d, J=2.4 Hz, 1H, PyH)		436.0 [M+H]⁺
2b	1.63(d, J=6.6 Hz, 3H, CH₃), 4.49(d, J=6.3 Hz, 2H, CH₂), 4.73(q, J=6.6 Hz, 1H, CH), 6.88(brs, 1H, NH), 6.96(d, J=9.0 Hz, 2H, PhH), 7.10(d, J=9.0 Hz, 2H, PhH), 7.27(d, J=8.1 Hz, 1H, PyH), 7.51(dd, J=8.1, 2.4 Hz, 1H, PyH), 7.99(d, J=2.4 Hz, 1H, PyH), 8.27—8.30(m, 2H, PyH)	18.71, 39.65, 75.39, 116.29, 119.15, 122.18, 122.63, 122.93, 124.28, 132.64, 136.31, 138.21, 142.45, 147.17, 148.69, 150.56, 154.25, 161.17, 172.25	486.0 [M+H]⁺	3295, 3064, 2985, 1675, 1654, 1613, 1507, 1403, 1391, 1234, 840
2c	1.62(d, J=6.9 Hz, 3H, CH₃), 4.49(d, J=6.6 Hz, 2H, CH₂), 4.75(q, J=6.9 Hz, 1H, CH), 6.88—7.12(m, 6H, PhH+NH+PyH), 7.30(d, J=8.4 Hz, 1H, PyH), 7.50(dd, J=8.4, 2.4 Hz, 1H, PyH), 7.90(dd, J=8.7, 2.4 Hz, 1H, PyH), 8.27(d, J=2.4 Hz, 1H, PyH), 8.42—8.44(m, 1H, PyH)		451.9 [M+H]⁺
2d	1.60(d, J=6.9 Hz, 3H, CH₃), 4.40—4.58(m, 2H, CH₂), 4.74(q, J=6.9 Hz, 1H, CH), 6.87—7.04(m, 6H, 4PhH+NH+PyH), 7.04(d, J=6.6 Hz, 1H, PyH), 7.27(d, J=6.3 Hz, 1H, PyH), 7.37—7.56(m, 3H, PhH), 8.22(d, J=1.8 Hz, 1H, PyH)		426.1 [M+H]⁺
2e	1.60(d, J=6.9 Hz, 3H, CH₃), 4.47—4.50(m, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.86—6.99(m, 3H, 2PhH+NH), 7.24—7.54(m, 8H, PyH+benzoxazole-H+PhH)		458.0 [M+H]⁺
2f	1.62(d, J=6.9 Hz, 3H, CH₃), 4.50(s, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.92—6.98(m, 3H, 2PhH+NH), 7.19(d, J=9.0 Hz, 2H, PhH), 7.30(d, J=8.1 Hz, 1H, PyH), 7.52(d, J=8.1 Hz, 1H, PyH), 7.62(dd, J=8.7, 2.7 Hz, 1H, quinoxalin-H), 7.66(d, J=8.7 Hz, 1H, quinoxalin-H), 8.06(d, J=2.7 Hz, 1H, quinoxalin-H), 8.30(s, 1H, PyH), 8.69(s, 1H, quinoxalin-H)	18.74, 39.72, 75.42, 116.29, 122.76, 124.30, 127.93, 128.71, 131.18, 132.64, 132.91, 138.21, 138.36, 139.76, 140.06, 146.95, 148.73, 150.62, 154.05, 157.00, 172.27	469.0 [M+H]⁺
2g	1.58(d, J=6.9 Hz, 3H, CH₃), 4.57(t, J=6.3 Hz, 2H, CH₂), 4.69(q, J=6.9 Hz, 1H, CH), 6.90—6.93(m, 3H, PhH+NH), 7.11(d, J=9.3 Hz, 2H, PhH), 7.38(s, 1H, Thia-H), 7.50(dd, J=9.0, 2.1 Hz, 1H, PyH), 7.87(d, J=2.1 Hz, 1H, PyH)	18.55, 35.44, 75.31, 116.31, 122.50, 124.85, 125.08, 139.36, 140.09, 145.08, 147.37, 148.62, 151.15, 152.10, 153.85, 172.20	442.0 [M+H]⁺
2h	1.59(d, J=6.9 Hz, 3H, CH₃), 4.56—4.59(m, 2H, CH₂), 4.71(q, J=6.9 Hz, 1H, CH), 6.92—6.97(m, 3H, PhH+NH), 7.09(d, J=9.0 Hz, 2H, PhH), 7.38(s, 1H, Thia-H), 7.99(d, J=2.1 Hz, 1H, PyH), 8.26(s, 1H, PyH)		492.0 [M+H]⁺
2i	1.61(d, J=6.9 Hz, 3H, CH₃), 4.56—4.59(m, 2H, CH₂), 4.72(q, J=6.9 Hz, 1H, CH), 6.90—6.95(m, 3H, PhH+NH), 7.03(d, J=8.7 Hz, 1H, PyH), 7.07(d, J=9.0 Hz, 2H, PhH), 7.37(s, 1H, Thia—H), 7.92(dd, J=8.7, 2.4 Hz, 1H, PyH), 8.42—8.43(m, 1H, PyH)		457.8 [M+H]⁺
2j	1.60(d, J=6.6 Hz, 3H, CH₃), 4.40—4.58(m, 2H, CH₂), 4.69(q, J=6.6 Hz, 1H, CH), 6.86—6.93(m, 3H, 2PhH+NH), 7.00(d, J=9.3 Hz, 2H, PhH), 7.27(s, 1H, Thia-H), 7.35—7.49(m, 3H, PhH)		432.0 [M+H]⁺
2k	1.61(d, J=6.6 Hz, 3H, CH₃), 4.54—4.60(m, 2H, CH₂), 4.73(q, J=6.6 Hz, 1H, CH), 6.92—6.98(m, 3H, 2PhH+NH), 7.23—7.45(m, 6H, Thia-H+benzoxazole-H+2PhH)		464.0 [M+H]⁺
2l	1.63(d, J=6.9 Hz, 3H, CH₃), 4.59(d, J=6.0 Hz, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.930—6.98(m, 3H, 2PhH+NH), 7.20(d, J=9.0 Hz, 2H, PhH), 7.39(s, 1H, Thia-H), 7.59(dd, J₁=8.7 Hz, J₂=2.1 Hz, 1H, quinoxalin-H), 7.67(d, J=8.7 Hz, 1H, quinoxalin-H), 8.07(d, J=2.1 Hz, 1H, quinoxalin-H), 8.69(s, 1H, quinoxalin-H)	18.57, 35.49, 75.33, 116.29, 122.70, 127.87, 128.68, 131.10, 132.85, 137.56, 138.33, 139.36, 139.70, 140.00, 146.93, 152.12, 153.99, 156.96, 172.20	475.0 [M+H]⁺	3345, 1655, 1608, 1580, 1535, 1505, 1420, 1239, 822
2m	1.59(d, J=6.9 Hz, 3H, CH₃), 3.12(s, 3H, CH₃), 4.51(dd, J=15, 40.2 Hz, 2H, CH₂), 4.93(q, J=6.9 Hz, 1H, CH), 6.92(d, J=9.0 Hz, 2H, PhH), 7.09(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.49(dd, J=9.0, 2.4 Hz, 1H, PyH), 7.87(d, J=2.4 Hz, 1H, PyH)		456.0 [M+H]⁺
2n	1.61(d, J=6.6 Hz, 3H, CH₃), 3.13(s, 3H, CH₃), 4.53(dd, J=15, 33 Hz, 2H, CH₂), 4.97(q, J=6.6 Hz, 1H, CH), 6.94(d, J=9.0 Hz, 2H, PhH), 7.07(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.98(d, J=2.4 Hz, 1H, PyH), 7.27(s, 1H, PyH)		506.0 [M+H]⁺
2o	1.10(t, J=7.2 Hz, 3H, CH₃), 1.53(d, J=6.6 Hz, 3H, CH₃), 3.38—3.49(m, 2H, CH₂), 4.48(m, 2H, CH₂), 4.88(q, J=6.6 Hz, 1H, CH), 6.84(d, J=9.3 Hz, 2H, PhH), 6.97(d, J=9.3 Hz, 2H, PhH), 7.33(s, 1H, Thia-H), 7.40(dd, J=9.0, 2.4 Hz, 1H, PyH), 7.78(d, J=2.4 Hz, 1H, PyH)		470.0 [M+H]⁺
2p	1.18(t, J=7.2 Hz, 3H, CH₃), 1.58(d, J=6.9 Hz, 3H, CH₃), 3.36—3.64(m, 2H, CH₂), 4.55(dd, J=15, 20.4 Hz, 2H, CH₂), 4.95(q, J=6.9 Hz, 1H, CH), 6.95(d, J=9.0 Hz, 2H, PhH), 7.10(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.98(d, J=2.1 Hz,, 1H, PyH), 8.27(s, 1H, PyH)		520.0 [M+H]⁺

Table 2 1H NMR, 13C NMR, LC-MS and IR data for compounds 2a—2p

Compd.	¹H NMR(300 MHz, CDCl₃), δ	¹³C NMR (75 MHz, CDCl₃), δ	LC-MS ([M+H]⁺), m/z	IR(KBr), $ν ˙$ /cm^-1
2a	1.61(d, J=6.9 Hz, 3H, CH₃), 4.49(d, J=6.6 Hz, 2H, CH₂), 4.74(q, J=6.9 Hz, 1H, CH), 6.88—6.94(m, 3H, PhH+NH), 7.08(d, J=9.0 Hz, 2H, PhH), 7.29(d, J=8.1 Hz, 1H, PyH), 7.49—7.53(m, 2H, PyH), 7.87(d, J=2.1 Hz, 1H, PyH), 8.29(d, J=2.4 Hz, 1H, PyH)		436.0 [M+H]⁺
2b	1.63(d, J=6.6 Hz, 3H, CH₃), 4.49(d, J=6.3 Hz, 2H, CH₂), 4.73(q, J=6.6 Hz, 1H, CH), 6.88(brs, 1H, NH), 6.96(d, J=9.0 Hz, 2H, PhH), 7.10(d, J=9.0 Hz, 2H, PhH), 7.27(d, J=8.1 Hz, 1H, PyH), 7.51(dd, J=8.1, 2.4 Hz, 1H, PyH), 7.99(d, J=2.4 Hz, 1H, PyH), 8.27—8.30(m, 2H, PyH)	18.71, 39.65, 75.39, 116.29, 119.15, 122.18, 122.63, 122.93, 124.28, 132.64, 136.31, 138.21, 142.45, 147.17, 148.69, 150.56, 154.25, 161.17, 172.25	486.0 [M+H]⁺	3295, 3064, 2985, 1675, 1654, 1613, 1507, 1403, 1391, 1234, 840
2c	1.62(d, J=6.9 Hz, 3H, CH₃), 4.49(d, J=6.6 Hz, 2H, CH₂), 4.75(q, J=6.9 Hz, 1H, CH), 6.88—7.12(m, 6H, PhH+NH+PyH), 7.30(d, J=8.4 Hz, 1H, PyH), 7.50(dd, J=8.4, 2.4 Hz, 1H, PyH), 7.90(dd, J=8.7, 2.4 Hz, 1H, PyH), 8.27(d, J=2.4 Hz, 1H, PyH), 8.42—8.44(m, 1H, PyH)		451.9 [M+H]⁺
2d	1.60(d, J=6.9 Hz, 3H, CH₃), 4.40—4.58(m, 2H, CH₂), 4.74(q, J=6.9 Hz, 1H, CH), 6.87—7.04(m, 6H, 4PhH+NH+PyH), 7.04(d, J=6.6 Hz, 1H, PyH), 7.27(d, J=6.3 Hz, 1H, PyH), 7.37—7.56(m, 3H, PhH), 8.22(d, J=1.8 Hz, 1H, PyH)		426.1 [M+H]⁺
2e	1.60(d, J=6.9 Hz, 3H, CH₃), 4.47—4.50(m, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.86—6.99(m, 3H, 2PhH+NH), 7.24—7.54(m, 8H, PyH+benzoxazole-H+PhH)		458.0 [M+H]⁺
2f	1.62(d, J=6.9 Hz, 3H, CH₃), 4.50(s, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.92—6.98(m, 3H, 2PhH+NH), 7.19(d, J=9.0 Hz, 2H, PhH), 7.30(d, J=8.1 Hz, 1H, PyH), 7.52(d, J=8.1 Hz, 1H, PyH), 7.62(dd, J=8.7, 2.7 Hz, 1H, quinoxalin-H), 7.66(d, J=8.7 Hz, 1H, quinoxalin-H), 8.06(d, J=2.7 Hz, 1H, quinoxalin-H), 8.30(s, 1H, PyH), 8.69(s, 1H, quinoxalin-H)	18.74, 39.72, 75.42, 116.29, 122.76, 124.30, 127.93, 128.71, 131.18, 132.64, 132.91, 138.21, 138.36, 139.76, 140.06, 146.95, 148.73, 150.62, 154.05, 157.00, 172.27	469.0 [M+H]⁺
2g	1.58(d, J=6.9 Hz, 3H, CH₃), 4.57(t, J=6.3 Hz, 2H, CH₂), 4.69(q, J=6.9 Hz, 1H, CH), 6.90—6.93(m, 3H, PhH+NH), 7.11(d, J=9.3 Hz, 2H, PhH), 7.38(s, 1H, Thia-H), 7.50(dd, J=9.0, 2.1 Hz, 1H, PyH), 7.87(d, J=2.1 Hz, 1H, PyH)	18.55, 35.44, 75.31, 116.31, 122.50, 124.85, 125.08, 139.36, 140.09, 145.08, 147.37, 148.62, 151.15, 152.10, 153.85, 172.20	442.0 [M+H]⁺
2h	1.59(d, J=6.9 Hz, 3H, CH₃), 4.56—4.59(m, 2H, CH₂), 4.71(q, J=6.9 Hz, 1H, CH), 6.92—6.97(m, 3H, PhH+NH), 7.09(d, J=9.0 Hz, 2H, PhH), 7.38(s, 1H, Thia-H), 7.99(d, J=2.1 Hz, 1H, PyH), 8.26(s, 1H, PyH)		492.0 [M+H]⁺
2i	1.61(d, J=6.9 Hz, 3H, CH₃), 4.56—4.59(m, 2H, CH₂), 4.72(q, J=6.9 Hz, 1H, CH), 6.90—6.95(m, 3H, PhH+NH), 7.03(d, J=8.7 Hz, 1H, PyH), 7.07(d, J=9.0 Hz, 2H, PhH), 7.37(s, 1H, Thia—H), 7.92(dd, J=8.7, 2.4 Hz, 1H, PyH), 8.42—8.43(m, 1H, PyH)		457.8 [M+H]⁺
2j	1.60(d, J=6.6 Hz, 3H, CH₃), 4.40—4.58(m, 2H, CH₂), 4.69(q, J=6.6 Hz, 1H, CH), 6.86—6.93(m, 3H, 2PhH+NH), 7.00(d, J=9.3 Hz, 2H, PhH), 7.27(s, 1H, Thia-H), 7.35—7.49(m, 3H, PhH)		432.0 [M+H]⁺
2k	1.61(d, J=6.6 Hz, 3H, CH₃), 4.54—4.60(m, 2H, CH₂), 4.73(q, J=6.6 Hz, 1H, CH), 6.92—6.98(m, 3H, 2PhH+NH), 7.23—7.45(m, 6H, Thia-H+benzoxazole-H+2PhH)		464.0 [M+H]⁺
2l	1.63(d, J=6.9 Hz, 3H, CH₃), 4.59(d, J=6.0 Hz, 2H, CH₂), 4.76(q, J=6.9 Hz, 1H, CH), 6.930—6.98(m, 3H, 2PhH+NH), 7.20(d, J=9.0 Hz, 2H, PhH), 7.39(s, 1H, Thia-H), 7.59(dd, J₁=8.7 Hz, J₂=2.1 Hz, 1H, quinoxalin-H), 7.67(d, J=8.7 Hz, 1H, quinoxalin-H), 8.07(d, J=2.1 Hz, 1H, quinoxalin-H), 8.69(s, 1H, quinoxalin-H)	18.57, 35.49, 75.33, 116.29, 122.70, 127.87, 128.68, 131.10, 132.85, 137.56, 138.33, 139.36, 139.70, 140.00, 146.93, 152.12, 153.99, 156.96, 172.20	475.0 [M+H]⁺	3345, 1655, 1608, 1580, 1535, 1505, 1420, 1239, 822
2m	1.59(d, J=6.9 Hz, 3H, CH₃), 3.12(s, 3H, CH₃), 4.51(dd, J=15, 40.2 Hz, 2H, CH₂), 4.93(q, J=6.9 Hz, 1H, CH), 6.92(d, J=9.0 Hz, 2H, PhH), 7.09(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.49(dd, J=9.0, 2.4 Hz, 1H, PyH), 7.87(d, J=2.4 Hz, 1H, PyH)		456.0 [M+H]⁺
2n	1.61(d, J=6.6 Hz, 3H, CH₃), 3.13(s, 3H, CH₃), 4.53(dd, J=15, 33 Hz, 2H, CH₂), 4.97(q, J=6.6 Hz, 1H, CH), 6.94(d, J=9.0 Hz, 2H, PhH), 7.07(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.98(d, J=2.4 Hz, 1H, PyH), 7.27(s, 1H, PyH)		506.0 [M+H]⁺
2o	1.10(t, J=7.2 Hz, 3H, CH₃), 1.53(d, J=6.6 Hz, 3H, CH₃), 3.38—3.49(m, 2H, CH₂), 4.48(m, 2H, CH₂), 4.88(q, J=6.6 Hz, 1H, CH), 6.84(d, J=9.3 Hz, 2H, PhH), 6.97(d, J=9.3 Hz, 2H, PhH), 7.33(s, 1H, Thia-H), 7.40(dd, J=9.0, 2.4 Hz, 1H, PyH), 7.78(d, J=2.4 Hz, 1H, PyH)		470.0 [M+H]⁺
2p	1.18(t, J=7.2 Hz, 3H, CH₃), 1.58(d, J=6.9 Hz, 3H, CH₃), 3.36—3.64(m, 2H, CH₂), 4.55(dd, J=15, 20.4 Hz, 2H, CH₂), 4.95(q, J=6.9 Hz, 1H, CH), 6.95(d, J=9.0 Hz, 2H, PhH), 7.10(d, J=9.0 Hz, 2H, PhH), 7.41(s, 1H, Thia-H), 7.98(d, J=2.1 Hz,, 1H, PyH), 8.27(s, 1H, PyH)		520.0 [M+H]⁺

Table 3 Herbicidal activities of compounds 2a—2p at dosage of 2.25×103 g/ha*

Compd.	Postemergence treatment						Preemergence treatment
Compd.	A.T.	A.A.	C.A.	D.S.	E.C.	S.V.	A.T.	A.A.	C.A.	D.S.	E.C.	S.V.
2a	0	0	0	100	100	100	0	0	0	100	100	100
2b	0	0	0	100	100	100	0	0	0	100	100	100
2c	0	0	0	100	100	100	0	0	0	100	100	100
2d	0	0	0	90	90	90	0	0	0	90	90	90
2e	0	0	0	100	100	100	0	0	0	100	95	95
2f	0	0	0	100	100	100	0	0	0	100	100	100
2g	0	0	0	100	90	100	0	0	0	100	100	100
2h	0	0	0	100	100	95	0	0	0	100	100	100
2i	0	0	0	100	100	100	0	0	0	100	98	100
2j	0	0	0	90	90	90	0	0	0	90	90	90
2k	0	0	0	100	100	100	0	0	0	100	100	90
2l	0	0	0	100	100	100	0	0	0	100	100	100
2m	0	0	0	60	40	50	0	0	0	100	50	100
2n	0	0	0	90	30	80	0	0	0	90	90	90
2o	0	0	0	90	80	85	0	0	0	100	100	100
2p	0	0	0	100	100	90	0	0	0	100	100	100
Metamifop	0	0	0	100	100	100	0	0	0	100	100	100
Clodinafop-propargyl	0	0	0	100	100	100	0	0	0	100	100	100

Table 4 Preliminary herbicidal activities at dosage of 75 g/ha

Compd.	Postemergence treatment			Preemergence treatment			Compd.	Postemergence treatment			Preemergence treatment
Compd.	D.S.	E.C.		S.V.	D.S.	E.C.	S.V.	D.S.	E.C.	S.V.	D.S.	E.C.	S.V.
2a	90	100	100	70	40	80	2j	30	30	30	0	0	0
2b	100	100	100	100	100	100	2k	90	80	90	0	0	0
2c	90	85	85	70	60	70	2l	90	85	100	90	90	90
2d	30	30	30	0	0	0	2m	0	0	0	0	0	0
2e	90	50	90	0	0	0	2n	0	0	0	50	0	0
2f	90	50	100	30	30	0	2o	0	0	0	0	0	0
2g	100	100	100	100	100	100	2p	50	40	50	70	40	70
2h	95	95	95	100	100	100	Metamifop	95	80	80	0	0	0
2i	100	100	100	50	0	0	Clodinafop-	100	100	100	100	100	100
							propargyl

Table 5 Further herbicidal activities and IC50 values against D.S. and E.C. in postemergence treatments

Compd.	D.S./(g·ha^-1)				E.C./(g·ha^-1)				I $C 50 *$ /(g·ha^-1)
Compd.	30	15	7.5	3.75	30	15	7.5	3.75	D.S.	E.C.
2b	70	50	30	10	70	30	0	0	15.4	22.8
2g	40	30	20	10	50	30	20	10	46.5	21.8
2h	50	40	30	10	50	30	0	0	25.2	25.0
Metamifop	50	30	20	10	50	30	0	0	31.9	25.0
Clodinafop-propargyl	40	30	20	10	70	50	30	20	46.5	14.6

Table 5 Further herbicidal activities and IC50 values against D.S. and E.C. in postemergence treatments

Compd.	D.S./(g·ha^-1)				E.C./(g·ha^-1)				I $C 50 *$ /(g·ha^-1)
Compd.	30	15	7.5	3.75	30	15	7.5	3.75	D.S.	E.C.
2b	70	50	30	10	70	30	0	0	15.4	22.8
2g	40	30	20	10	50	30	20	10	46.5	21.8
2h	50	40	30	10	50	30	0	0	25.2	25.0
Metamifop	50	30	20	10	50	30	0	0	31.9	25.0
Clodinafop-propargyl	40	30	20	10	70	50	30	20	46.5	14.6

Table 6 Comparative herbicidal activities of compounds 2b and(±)-2b

Compd.	Dosage/(g·ha^-1)	Postemergence treatment			IC₅₀(g·ha^-1)
Compd.	Dosage/(g·ha^-1)	D.S.	E.C.	S.V.	D.S.	E.C.	S.V.
2b	3.75	40	0	20	5.2	13.9	6.5
	7.5	60	10	50	(3.1—8.8)	(11.1—17.5)	(3.9—11.0)
	15	95	80	80
	30	100	95	100
	60	100	100	100
(±)-2b	3.75	40	0	20	6.4	28.0	10.1
	7.5	50	0	40	(4.9—8.5)	(18.7—42.0)	(7.2—14.1)
	15	70	30	50
	30	90	50	90
	60	98	98	90

Table 7 Phytotoxicit of compound 2b to Xiang zao xian 24 in postemergence treatments*

Compd.	Dosage/ (g·ha^-1)	Xiang zao xian 24	Dosage/ (g·ha^-1)	E. C.	Leptochloa
2b	15	3.79	3.75	3.20	50
	30	7.21	7.5	76.38	90
	60	13.77	15	89.74	98
	120	27.43	30	94.65	100
	240	63.52	60	100.00	100
Metamifop	15	-45.04	3.75	24.18
	30	-15.34	7.5	37.10
	60	-57.94	15	49.39
	120	-14.58	30	99.00
	240	-34.15	60	100.00
Cyhalofop-butyl	15	-11.38	3.75	35.02	0
	30	-9.00	7.5	41.10	0
	60	-9.38	15	47.97	0
	120	-10.73	30	55.02	30
	240	8.78	60	64.14	50

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