4-trifluoromethyl-7-hydroxycoumarin derivative as well as preparation method and application thereof

Abstract

The invention discloses a 4-trifluoromethyl-7-hydroxycoumarin derivative as well as a preparation method and application thereof. The yield of the preparation method is high. The invention also discloses application of the 4-trifluoromethyl-7-hydroxycoumarin derivative to an agricultural anti-fungal aspect. An inventor detects the toxicity effect on rice sheath blight disease, colletotrichum lagenarium, fusarium graminearum, strawberry botrytis cinerea, apple spot germs and alternaria solani by a growth rate method; certain lateral reactivity is realized on the 4-trifluoromethyl-7-hydroxycoumarin derivative; the activity of individual compounds is superior to that of contrast medicine; the effect of the compound in the aspect of inhibiting the rice sheath blight disease is prominent; or the compound can become a lead compound molecule for developing and creating new pesticide.

Description

technical field

[0001] The invention belongs to the technical field of pesticides, and specifically relates to 4-trifluoromethyl 7-hydroxycoumarin derivatives and a preparation method and application thereof. Background technique

[0002] The resistance of harmful organisms caused by the long-term use of pesticides is unavoidable, so researchers need to constantly explore new varieties of pesticides with new sites of action and mechanisms of action. In recent years, many researchers have been devoting themselves to the development of new, efficient, and environmentally friendly botanical fungicides. This is because on the one hand, many natural products have excellent biological activity, but on the other hand, the extraction of natural products is relatively difficult. It is difficult to meet the needs of human life and production in terms of quantity and quality. Therefore, artificially synthesizing natural products or further optimizing the structure of natural products ...

Examples

Embodiment 1

[0055] Embodiment 1: Preparation of 4-trifluoromethyl-7-hydroxycoumarin (a-1)

[0056] 1. Put 30mL of concentrated sulfuric acid in a three-necked flask and cool to 0°C in an ice-salt bath.

[0057] 2. 11.0 g of resorcinol and 12 mL of ethyl trifluoroacetoacetate were uniformly mixed under ultrasonic to obtain a mixed solution of the two.

[0058] 3. Drop the mixed solution into concentrated sulfuric acid under rapid stirring, and the dropping speed is kept at one drop every two seconds to ensure that the system temperature does not exceed 0°C. After the mixed solution was dripped, the stirring was continued for 12h.

[0059] 4. After the reaction, pour the reaction solution into a large beaker filled with 500mL ice water under rapid stirring, fully dilute the concentrated sulfuric acid in it until the solution is weakly acidic, and a large number of pink flocs will appear in it, filter it.

[0060] 5. Recrystallize the solid obtained by filtration with ethanol / water to obta...

Embodiment 2

[0077] Embodiment 2: Preparation of 4-trifluoromethyl-7-allyloxycoumarin (b-1~4)

[0078] 1. Take 2.3g (0.01mol) 4-trifluoromethyl-7-hydroxycoumarin (a-1) in a round bottom flask, add 3.5g (0.025mol) K 2 CO 3 , 0.33g (0.001mol) tetrabutylammonium bromide, and 30mL acetone, make it mix evenly under magnetic stirring, then add 0.02g KI as catalyst;

[0079] 2. The temperature of the mixed solution was raised to 60° C. under stirring, and 1.3 mL (0.015 mol) of allyl bromide was added after 15 minutes, and then stirred and refluxed for 6 hours, and the progress of the reaction was monitored by TCL.

[0080] 3. After the reaction is completed, filter to remove insoluble matter such as potassium carbonate, spin and concentrate to obtain crude product b-1, and recrystallize with ethanol / water to obtain compound b-1, 4-trifluoromethyl-7-allyloxy incense Soybean.

[0081]

[0082] White crystal m.p.: 120.4-121.5°C; yield: 87.4%.

[0083] IR(KBr)ν / cm -1 :2933,1719,1612,1390,1286...

Embodiment 3

[0097] Example 3: Synthesis of 4-trifluoromethyl-7-prenyloxycoumarin derivatives (c-1~4)

[0098] 1. Take 2.3g (0.01mol) 4-trifluoromethyl-7-hydroxycoumarin in a round bottom flask, add 3.5g (0.025mol) K 2 CO 3 , 0.33g (0.001mol) tetrabutylammonium bromide, and 30mL acetone, make it mix evenly under magnetic stirring, then add 0.02g KI as catalyst;

[0099] 2. The temperature of the mixed solution was raised to 60°C under stirring, and 1.7 mL (0.015 mol) of bromoisoamylene was added after 15 minutes, and then stirred and refluxed for 6 hours, and the progress of the reaction was monitored by TCL.

[0100] 3. After the reaction is completed, filter to remove insoluble matter such as potassium carbonate, spin and concentrate to obtain crude product c-1, and recrystallize with ethanol / water to obtain compound c-1,4-trifluoromethyl-7-prenyloxy Coumarin.

[0101] Compounds c-2~4 are synthesized according to the method similar to c-1, the difference is that 4-trifluoromethyl-7-hy...

technical field

[0001] The invention belongs to the technical field of pesticides, and specifically relates to 4-trifluoromethyl 7-hydroxycoumarin derivatives and a preparation method and application thereof. Background technique

[0002] The resistance of harmful organisms caused by the long-term use of pesticides is unavoidable, so researchers need to constantly explore new varieties of pesticides with new sites of action and mechanisms of action. In recent years, many researchers have been devoting themselves to the development of new, efficient, and environmentally friendly botanical fungicides. This is because on the one hand, many natural products have excellent biological activity, but on the other hand, the extraction of natural products is relatively difficult. It is difficult to meet the needs of human life and production in terms of quantity and quality. Therefore, artificially synthesizing natural products or further optimizing the structure of natural products ...

Examples

Embodiment 1

[0055] Embodiment 1: Preparation of 4-trifluoromethyl-7-hydroxycoumarin (a-1)

[0056] 1. Put 30mL of concentrated sulfuric acid in a three-necked flask and cool to 0°C in an ice-salt bath.

[0057] 2. 11.0 g of resorcinol and 12 mL of ethyl trifluoroacetoacetate were uniformly mixed under ultrasonic to obtain a mixed solution of the two.

[0058] 3. Drop the mixed solution into concentrated sulfuric acid under rapid stirring, and the dropping speed is kept at one drop every two seconds to ensure that the system temperature does not exceed 0°C. After the mixed solution was dripped, the stirring was continued for 12h.

[0059] 4. After the reaction, pour the reaction solution into a large beaker filled with 500mL ice water under rapid stirring, fully dilute the concentrated sulfuric acid in it until the solution is weakly acidic, and a large number of pink flocs will appear in it, filter it.

[0060] 5. Recrystallize the solid obtained by filtration with ethanol / water to obta...

Embodiment 2

[0077] Embodiment 2: Preparation of 4-trifluoromethyl-7-allyloxycoumarin (b-1~4)

[0078] 1. Take 2.3g (0.01mol) 4-trifluoromethyl-7-hydroxycoumarin (a-1) in a round bottom flask, add 3.5g (0.025mol) K 2 CO 3 , 0.33g (0.001mol) tetrabutylammonium bromide, and 30mL acetone, make it mix evenly under magnetic stirring, then add 0.02g KI as catalyst;

[0079] 2. The temperature of the mixed solution was raised to 60° C. under stirring, and 1.3 mL (0.015 mol) of allyl bromide was added after 15 minutes, and then stirred and refluxed for 6 hours, and the progress of the reaction was monitored by TCL.

[0080] 3. After the reaction is completed, filter to remove insoluble matter such as potassium carbonate, spin and concentrate to obtain crude product b-1, and recrystallize with ethanol / water to obtain compound b-1, 4-trifluoromethyl-7-allyloxy incense Soybean.

[0081]

[0082] White crystal m.p.: 120.4-121.5°C; yield: 87.4%.

[0083] IR(KBr)ν / cm -1 :2933,1719,1612,1390,1286...

Embodiment 3

[0097] Example 3: Synthesis of 4-trifluoromethyl-7-prenyloxycoumarin derivatives (c-1~4)

[0098] 1. Take 2.3g (0.01mol) 4-trifluoromethyl-7-hydroxycoumarin in a round bottom flask, add 3.5g (0.025mol) K 2 CO 3 , 0.33g (0.001mol) tetrabutylammonium bromide, and 30mL acetone, make it mix evenly under magnetic stirring, then add 0.02g KI as catalyst;

[0099] 2. The temperature of the mixed solution was raised to 60°C under stirring, and 1.7 mL (0.015 mol) of bromoisoamylene was added after 15 minutes, and then stirred and refluxed for 6 hours, and the progress of the reaction was monitored by TCL.

[0100] 3. After the reaction is completed, filter to remove insoluble matter such as potassium carbonate, spin and concentrate to obtain crude product c-1, and recrystallize with ethanol / water to obtain compound c-1,4-trifluoromethyl-7-prenyloxy Coumarin.

[0101] Compounds c-2~4 are synthesized according to the method similar to c-1, the difference is that 4-trifluoromethyl-7-hy...

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