Tryptophan derivative, preparation method and application in plant virus control, bactericidal and insecticidal aspects

Abstract

The invention relates to a tryptophan derivative (I), a preparing method of the tryptophan derivative (I), and application of the tryptophan derivative (I) in preventing and treating plant viruses, killing bacteria and killing insects. The formula of the tryptophan derivative (I) is shown in the description, and the meanings of all groups in the formula are shown in the description. The tryptophan derivative expresses especially excellent plant virus resisting activity, and also has broad-spectrum bactericidal activity and insecticidal activity.

Description

technical field

[0001] The invention relates to a tryptophan derivative, a preparation method and an application in plant virus prevention and control, sterilization and insecticide, belonging to the technical field of pesticides. Background technique

[0002] Tryptophan is divided into L-tryptophan and D-tryptophan according to its chirality.

[0003]

[0004] L-Tryptophan has extremely important uses in food, medicine, feed and so on. First, L-tryptophan can be used as a food additive. L-Tryptophan is one of the limiting amino acids necessary for the human body. It is synthesized very little in the body and needs to be taken from the outside. In organisms, bioactive substances such as 5-hydroxytryptamine, indoleacetic acid, nicotinic acid, pigments, alkaloids and coenzymes can be synthesized from L-chromohelium acid. Secondly, L-tryptophan also has important applications in medicine. L-tryptophan can pass through the blood-brain barrier, and is transformed into 5-hy...

Examples

Embodiment 1

[0071] Embodiment 1: Synthesis of (S)-2-amino-3-(1H-indole-3)-propionic acid methyl ester (1)

[0072]

[0073] Add 10g (49.02mmol) of L-tryptophan and 150mL of methanol into a 250mL single-necked round-bottom flask, add 10mL of thionyl chloride dropwise under stirring, and stir for 4 hours under heating and reflux. The reaction was complete as monitored by TLC, and the solution was removed. The obtained solid was washed with saturated aqueous sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, filtered, and removed from the solvent to obtain 9.16 g of a brown solid with a melting point of 90-91° C. and a yield of 86%. 1 H NMR (300MHz, CDCl 3 )δ8.47(s, 1H, Ar-NH), 7.60(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.32(d, 3 J HH =8.1Hz, 1H, Ar-H), 7.18(t, 3 J HH =7.2Hz, 1H, Ar-H), 7.11(t, 3 J HH =7.2Hz, 1H, Ar-H), 7.00(s, 1H, Ar-H), 3.82(dd, 3 J HH = 4.8Hz, 2 J HH 7.5Hz, 1H, CH), 3.71(s, 3H, CH 3 ), 3.28 (dd, 3 J HH = 4.5Hz, 2 J HH =14.4Hz, 1H, CH ...

Embodiment 2

[0077] Example 2: Synthesis of (S)-2-amino-N-butyl-3-(1H-indole-3-)propionamide (I-3)

[0078]

[0079] Add 0.40g (1.83mmol) methyl ester 1 and 10mL n-butylamine to a 25mL single-necked round bottom flask, stir at room temperature for 2 days, remove the solvent, add dichloromethane / water for liquid extraction, dry the organic phase with anhydrous sodium sulfate, filter, remove dissolved and drained to obtain 0.33 g of yellow viscous liquid, yield 70%. 1 H NMR (300MHz, CDCl 3 )δ8.14(s, 1H, Ar-NH), 7.69(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.38(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.21(t, 3 J HH =7.5Hz, 1H, Ar-H), 7.13(t, 3 J HH =7.5Hz, 1H, Ar-H), 7.08(s, 1H, Ar-H), 3.71(dd, 3 J HH =9.0Hz, 3.9Hz, 1H, CH), 3.40(dd, 3 J HH = 3.9Hz, 2 J HH =14.4Hz, 1H, CH 2 ), 3.25(q, 3 J HH =6.6Hz, 1H, CH 2 ), 2.91 (dd, 3 J HH =9.0Hz, 2 J HH =14.4Hz, 1H, CH 2 ), 1.57-1.20 (m, 4H, CH 2 CH 2 ), 0.91(t, 3 J HH =7.5Hz, 3H, CH 3 ); 13 C NMR (100MHz, CDCl 3 )δ174.7, 136.4, 127.5, 123.1,...

Embodiment 3

[0080] Example 3: (S)-1-(2-hydroxyethylamino)-3-(1H-indole-3-)-1-oxopropan-2-ammonium hydrochloride (I-4) synthesis

[0081]

[0082] Add 0.50g (2.29mmol) of methyl ester 1 and 10mL of ethanolamine to a 25mL single-necked round-bottom flask, stir at room temperature for 2.5 days, transfer the reaction solution to a 100mL single-necked flask, add enough ethanol, and dissolve the obtained solid in dichloromethane , HCl gas was passed into this liquid, a yellow solid was precipitated, cooled, filtered, the mother liquor was precipitated, and DCM / MeOH=5:1 (v / v) was used as the eluent for column chromatography to obtain a yellow solid 0.32 g. Yield 49%, melting point 118-120°C. 1 H NMR (400MHz, DMSO-d 6 )δ10.92(s, 1H, NH), 8.03(t, 3 J HH =4.8Hz, 1H, O=C-NH), 7.57(d, 3 J HH =8.0Hz, 1H, Ar-H), 7.34(d, 3 J HH =8.0Hz, 1H, Ar-H), 7.17(d, 4 J HH =1.6Hz, 1H, Ar-H), 7.06(t, 3 J HH =7.6Hz, 1H, Ar-H), 6.97(t, 3 J HH =7.6Hz, 1H, Ar-H), 4.75(br, 1H, OH), 3.49(dd, 3 J HH =8....

technical field

[0001] The invention relates to a tryptophan derivative, a preparation method and an application in plant virus prevention and control, sterilization and insecticide, belonging to the technical field of pesticides. Background technique

[0002] Tryptophan is divided into L-tryptophan and D-tryptophan according to its chirality.

[0003]

[0004] L-Tryptophan has extremely important uses in food, medicine, feed and so on. First, L-tryptophan can be used as a food additive. L-Tryptophan is one of the limiting amino acids necessary for the human body. It is synthesized very little in the body and needs to be taken from the outside. In organisms, bioactive substances such as 5-hydroxytryptamine, indoleacetic acid, nicotinic acid, pigments, alkaloids and coenzymes can be synthesized from L-chromohelium acid. Secondly, L-tryptophan also has important applications in medicine. L-tryptophan can pass through the blood-brain barrier, and is transformed into 5-hy...

Examples

Embodiment 1

[0071] Embodiment 1: Synthesis of (S)-2-amino-3-(1H-indole-3)-propionic acid methyl ester (1)

[0072]

[0073] Add 10g (49.02mmol) of L-tryptophan and 150mL of methanol into a 250mL single-necked round-bottom flask, add 10mL of thionyl chloride dropwise under stirring, and stir for 4 hours under heating and reflux. The reaction was complete as monitored by TLC, and the solution was removed. The obtained solid was washed with saturated aqueous sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, filtered, and removed from the solvent to obtain 9.16 g of a brown solid with a melting point of 90-91° C. and a yield of 86%. 1 H NMR (300MHz, CDCl 3 )δ8.47(s, 1H, Ar-NH), 7.60(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.32(d, 3 J HH =8.1Hz, 1H, Ar-H), 7.18(t, 3 J HH =7.2Hz, 1H, Ar-H), 7.11(t, 3 J HH =7.2Hz, 1H, Ar-H), 7.00(s, 1H, Ar-H), 3.82(dd, 3 J HH = 4.8Hz, 2 J HH 7.5Hz, 1H, CH), 3.71(s, 3H, CH 3 ), 3.28 (dd, 3 J HH = 4.5Hz, 2 J HH =14.4Hz, 1H, CH ...

Embodiment 2

[0077] Example 2: Synthesis of (S)-2-amino-N-butyl-3-(1H-indole-3-)propionamide (I-3)

[0078]

[0079] Add 0.40g (1.83mmol) methyl ester 1 and 10mL n-butylamine to a 25mL single-necked round bottom flask, stir at room temperature for 2 days, remove the solvent, add dichloromethane / water for liquid extraction, dry the organic phase with anhydrous sodium sulfate, filter, remove dissolved and drained to obtain 0.33 g of yellow viscous liquid, yield 70%. 1 H NMR (300MHz, CDCl 3 )δ8.14(s, 1H, Ar-NH), 7.69(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.38(d, 3 J HH =7.8Hz, 1H, Ar-H), 7.21(t, 3 J HH =7.5Hz, 1H, Ar-H), 7.13(t, 3 J HH =7.5Hz, 1H, Ar-H), 7.08(s, 1H, Ar-H), 3.71(dd, 3 J HH =9.0Hz, 3.9Hz, 1H, CH), 3.40(dd, 3 J HH = 3.9Hz, 2 J HH =14.4Hz, 1H, CH 2 ), 3.25(q, 3 J HH =6.6Hz, 1H, CH 2 ), 2.91 (dd, 3 J HH =9.0Hz, 2 J HH =14.4Hz, 1H, CH 2 ), 1.57-1.20 (m, 4H, CH 2 CH 2 ), 0.91(t, 3 J HH =7.5Hz, 3H, CH 3 ); 13 C NMR (100MHz, CDCl 3 )δ174.7, 136.4, 127.5, 123.1,...

Embodiment 3

[0080] Example 3: (S)-1-(2-hydroxyethylamino)-3-(1H-indole-3-)-1-oxopropan-2-ammonium hydrochloride (I-4) synthesis

[0081]

[0082] Add 0.50g (2.29mmol) of methyl ester 1 and 10mL of ethanolamine to a 25mL single-necked round-bottom flask, stir at room temperature for 2.5 days, transfer the reaction solution to a 100mL single-necked flask, add enough ethanol, and dissolve the obtained solid in dichloromethane , HCl gas was passed into this liquid, a yellow solid was precipitated, cooled, filtered, the mother liquor was precipitated, and DCM / MeOH=5:1 (v / v) was used as the eluent for column chromatography to obtain a yellow solid 0.32 g. Yield 49%, melting point 118-120°C. 1 H NMR (400MHz, DMSO-d 6 )δ10.92(s, 1H, NH), 8.03(t, 3 J HH =4.8Hz, 1H, O=C-NH), 7.57(d, 3 J HH =8.0Hz, 1H, Ar-H), 7.34(d, 3 J HH =8.0Hz, 1H, Ar-H), 7.17(d, 4 J HH =1.6Hz, 1H, Ar-H), 7.06(t, 3 J HH =7.6Hz, 1H, Ar-H), 6.97(t, 3 J HH =7.6Hz, 1H, Ar-H), 4.75(br, 1H, OH), 3.49(dd, 3 J HH =8....

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