Synthesis and Herbicidal Activity of 2‐Cyano‐3‐methylthio‐3‐substituted Methylaminoacrylates

Abstract

A series of 2-cyano-3-methylthio-3-substituted methylaminoacrylates were synthesized as herbicidal inhibitors of photosystem II (PSII) electron transport, in order to estimate the effect of fluorine atom, pyridyl group, chirality and ester chain on activity. The important intermediate 2-fluoro-5-aminomethylpyridine was synthesized with high yield. The bioassay results showed that most of title compounds had high herbicidal activity in postemergence treatment. The introduction of an α-methyl into the 3-substituted methylamino could improve the activity notably. The replacement of hydrogen by chlorine or fluorine group and phenyl by pyridyl group showed different effects, and at the same time, the ester chain affected the activity too.

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“…The reaction mixture was filtered through diatomite and washed with MeOH (5 mL × 2). The filtrate was concentrated in vacuo and purified by silica gel column chromatography (CH 2 Cl 2 :MeOH = 100:2) to give intermediate 8 (R 1 = F, R 2 = H, 0.264 g, 85%) as a white–yellow oil …”

“…The filtrate was concentrated in vacuo and purified by silica gel column chromatography (CH 2 Cl 2 :MeOH = 100:2) to give intermediate 8 (R 1 = F, R 2 = H, 0.264 g, 85%) as a white−yellow oil. 48 A solution of compound 8 (R 1 = F, R 2 = H, 133 mg, 1.06 mmol) and 10 (X = S, 189 mg, 1.06 mmol) in dry THF (10 mL) was stirred at room temperature for 12 h. Then the mixture was concentrated in vacuo to give product 11a (0.26 g, 81%) as a yellow solid. 1 To a solution of compound 11a (90 mg, 0.30 mmol), HBTU (114 mg, 0.30 mmol), and Et 3 N (41 μL, 0.30 mmol) in DMF (5 mL) was added o-phenylenediamine (32 mg, 0.30 mmol), and the mixture was stirred at room temperature for 3 h. The reaction solution was diluted with water (40 mL) and filtered.…”

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“…Thus, they further designed a series of 2-cyanoacrylates focusing on the substituents on both nitrogen and the ester group (general structure XIII in Figure ). , The bioassay data indicated that, when ethoxyethyl in the ester part was replaced by a phenoxyethyl or tetrahedrofuranmethyl group, the compounds also had herbicidal activity but a little lower than ethoxyethyl derivatives. The replacement of hydrogen by a chlorine or fluorine group and phenyl by a pyridyl group showed different effects. , The introduction of α-methyl into 3-substituted benzylamino could improve the activity notably. , Among the α-methyl compounds, H-0306 ( 40 ) had excellent herbicidal activity against both dicotyledonous and monocotyledonous weeds in a corn field at a dosage of 30–120 g ha –1 and was selected as a candidate herbicide but finally gave up further development probably as a result of the cost issue.…”

“…Thus, they further designed a series of 2-cyanoacrylates focusing on the substituents on both nitrogen and the ester group (general structure XIII in Figure 13). 48,49 The bioassay data indicated that, when ethoxyethyl in the ester part was replaced by a phenoxyethyl or tetrahedrofuranmethyl group, the compounds also had herbicidal activity but a little lower than ethoxyethyl derivatives. The replacement of hydrogen by a chlorine or fluorine group and phenyl by a pyridyl group showed different effects.…”

“…50,51 The introduction of α-methyl into 3-substituted benzylamino could improve the activity notably. 45,48 Among the α-methyl compounds, H-0306 (40) had excellent herbicidal activity against both dicotyledonous and monocotyledonous weeds in a corn field at a dosage of 30−120 g ha −1 and was selected as a candidate herbicide 52 but finally gave up further development probably as a result of the cost issue. The Hu and Yang group (Nankai University) also reported a new type of 2-cyanoacylate that contained a 3-alkoxy group (general structure XIV in Figure 14).…”