A kind of thiopyran [4,3-b] indole compound and its preparation method and application

Abstract

The invention discloses a thiopyran [4,3-b] indole compound, a preparation method and application thereof. The structure of the compound is shown in formula (I):; where R 1 ~R 5 Not all are hydrogen at the same time. The compound of the present invention has excellent mycelia growth inhibitory activity, isolated leaf protection activity, in vivo protection activity and in vivo therapeutic activity against rice sheath blight, and its effect is even better than that of the positive control drug. It is effective for the prevention of rice sheath blight And / or treatment has great application value.

Description

technical field

[0001] The invention belongs to the technical field of pesticides. More specifically, it relates to a thiopyran [4,3-b] indole compound and its preparation method and application. Background technique

[0002] Due to the diversity and complexity of structure, biodegradability, environmental friendliness, pest specificity and low toxicity to mammals, natural active molecules have gradually become a research hotspot in the field of pesticides ((1) Dayan et al., Bioorganic & Medicinal Chemistry , 2009, 17, 4022-4034; (2) Rosell et al. Journal of Pesticide Science, 2008, 33, 103-121; (3) Petroski. Journal of Agricultural and Food Chemistry, 2009, 57, 8171-8179; (4) Crombie, Pesticide Science, 1999, 55, 761-774), is expected to replace chemical pesticides, thereby reducing the harm to the environment and human health. In recent years, research on natural source fungicides has received much attention at home and abroad. So far, many natural products have been re...

Examples

Embodiment 1

[0045] Embodiment 1: the synthesis of β-carboline

[0046] For the preparation method of β-carboline, refer to the literature method (Hagen T.J., et al. Journal of Medicinal Chemistry, 1987, 30, 750-753).

Embodiment 2

[0047] Example 2: Synthesis of 2-methyl-2,3,4,5-tetrahydro-1H-pyridin[4,3-b]indole (1)

[0048] Synthetic route 1:

[0049]

[0050] Compounds 1-3 were all prepared by Synthetic Route 1.

[0051] For the preparation method of compound 1, refer to the literature method (Raoul M., et al. Journal of Enzyme Inhibition and Medicinal Chemistry, 2006, 21, 251-260). Add phenylhydrazine hydrochloride (1.45g, 10mmol) into a 100mL round bottom flask, add 50mL of absolute ethanol to dissolve, then add 1-methyl-4-piperidone (1.13g, 10mmol), and heat to reflux for 3h. TLC monitoring completion of the reaction, concentrated under reduced pressure, added 40mL of distilled water to the residue, adjusted to pH 12-13 with 10% NaOH, then extracted 3 times with dichloromethane, combined the extracts, washed with water, dried over anhydrous MgSO4, filtered, Concentrate under reduced pressure to obtain the target compound.

Embodiment 3

[0052] Example 3: Synthesis of 2-ethoxycarbonyl-2,3,4,5-tetrahydro-1H-pyridin[4,3-b]indole (2)

[0053] The operation is the same as in Example 2, except that 1-methyl-4-piperidone is replaced by 1-ethoxycarbonyl-4-piperidone. The detection data of the product are as follows: gray solid, yield 74%. 1 H-NMR (400MHz, CDCl 3 )δ: 7.92(s, 1H, 5-NH), 7.46(d, J=7.8Hz, 1H, 6-H), 7.31(d, J=7.9Hz, 1H, 9-H), 7.16(t, J=7.5Hz, 1H, 8-H), 7.10(t, J=7.4Hz, 1H, 7-H), 4.70(s, 2H, 1-CH 2 -),4.21(q,J=7.1Hz,2H,-O CH 2 CH 3 ),3.88(s,2H,3-CH 2 -),2.85(s,2H,4-CH 2 -), 1.31(t, J=7.1Hz, 3H, -OCH 2 CH 3 ); anal.calcd for C 14 h 16 N 2 o 2 : C, 68.83; H, 6.60; N, 11.47; found: C, 68.69; H, 6.62; N, 11.32.

technical field

[0001] The invention belongs to the technical field of pesticides. More specifically, it relates to a thiopyran [4,3-b] indole compound and its preparation method and application. Background technique

[0002] Due to the diversity and complexity of structure, biodegradability, environmental friendliness, pest specificity and low toxicity to mammals, natural active molecules have gradually become a research hotspot in the field of pesticides ((1) Dayan et al., Bioorganic & Medicinal Chemistry , 2009, 17, 4022-4034; (2) Rosell et al. Journal of Pesticide Science, 2008, 33, 103-121; (3) Petroski. Journal of Agricultural and Food Chemistry, 2009, 57, 8171-8179; (4) Crombie, Pesticide Science, 1999, 55, 761-774), is expected to replace chemical pesticides, thereby reducing the harm to the environment and human health. In recent years, research on natural source fungicides has received much attention at home and abroad. So far, many natural products have been re...

Examples

Embodiment 1

[0045] Embodiment 1: the synthesis of β-carboline

[0046] For the preparation method of β-carboline, refer to the literature method (Hagen T.J., et al. Journal of Medicinal Chemistry, 1987, 30, 750-753).

Embodiment 2

[0047] Example 2: Synthesis of 2-methyl-2,3,4,5-tetrahydro-1H-pyridin[4,3-b]indole (1)

[0048] Synthetic route 1:

[0049]

[0050] Compounds 1-3 were all prepared by Synthetic Route 1.

[0051] For the preparation method of compound 1, refer to the literature method (Raoul M., et al. Journal of Enzyme Inhibition and Medicinal Chemistry, 2006, 21, 251-260). Add phenylhydrazine hydrochloride (1.45g, 10mmol) into a 100mL round bottom flask, add 50mL of absolute ethanol to dissolve, then add 1-methyl-4-piperidone (1.13g, 10mmol), and heat to reflux for 3h. TLC monitoring completion of the reaction, concentrated under reduced pressure, added 40mL of distilled water to the residue, adjusted to pH 12-13 with 10% NaOH, then extracted 3 times with dichloromethane, combined the extracts, washed with water, dried over anhydrous MgSO4, filtered, Concentrate under reduced pressure to obtain the target compound.

Embodiment 3

[0052] Example 3: Synthesis of 2-ethoxycarbonyl-2,3,4,5-tetrahydro-1H-pyridin[4,3-b]indole (2)

[0053] The operation is the same as in Example 2, except that 1-methyl-4-piperidone is replaced by 1-ethoxycarbonyl-4-piperidone. The detection data of the product are as follows: gray solid, yield 74%. 1 H-NMR (400MHz, CDCl 3 )δ: 7.92(s, 1H, 5-NH), 7.46(d, J=7.8Hz, 1H, 6-H), 7.31(d, J=7.9Hz, 1H, 9-H), 7.16(t, J=7.5Hz, 1H, 8-H), 7.10(t, J=7.4Hz, 1H, 7-H), 4.70(s, 2H, 1-CH 2 -),4.21(q,J=7.1Hz,2H,-O CH 2 CH 3 ),3.88(s,2H,3-CH 2 -),2.85(s,2H,4-CH 2 -), 1.31(t, J=7.1Hz, 3H, -OCH 2 CH 3 ); anal.calcd for C 14 h 16 N 2 o 2 : C, 68.83; H, 6.60; N, 11.47; found: C, 68.69; H, 6.62; N, 11.32.

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