CN107372504B - Application of sulfonamide compound in enhancing plant stress resistance and medicament containing same - Google Patents

Application of sulfonamide compound in enhancing plant stress resistance and medicament containing same Download PDF

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CN107372504B
CN107372504B CN201610325799.0A CN201610325799A CN107372504B CN 107372504 B CN107372504 B CN 107372504B CN 201610325799 A CN201610325799 A CN 201610325799A CN 107372504 B CN107372504 B CN 107372504B
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杨光富
黄志友
郝格非
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Central China Normal University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

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Abstract

The invention relates to the field of pesticides, and discloses application of a sulfonamide compound in enhancing plant stress resistance and a medicament containing the compound, wherein the sulfonamide compound has a structure shown in a formula (1); the active ingredient of the medicament for enhancing the stress resistance of plants provided by the invention is at least one sulfonamide compound shown in a formula (1), and the content of the active ingredient is 0.1-100 wt% based on the total weight of the medicament. The sulfonamide compound can obviously enhance the tolerance of plants to abiotic stress (cold, drought, high temperature, osmotic pressure and the like) which is ubiquitous in the environment.
Figure DDA0000992002500000011

Description

Application of sulfonamide compound in enhancing plant stress resistance and medicament containing same
Technical Field
The invention relates to the field of pesticides, in particular to application of sulfonamide compounds in enhancing plant stress resistance and a medicament containing the sulfonamide compounds and used for enhancing plant stress resistance.
Background
Abscisic acid (ABA) is a five-major phytohormone combined with ethylene and is first discovered in the 60 th of the 19 th century. Until 2009, two independent research groups demonstrated that a family of proteins containing a START characteristic region (PYR/PYL/RCAC) can specifically bind to ABA to form a complex, and the complex further acts with a class a protein phosphatase 2C (PP2C) and inhibits the activity of the protein phosphatase, and then transmits the complex to a negative regulator of SNF 1-related protein kinase 2(SnRK2), which is a key role, so that the regulation of ABA signal transduction is realized. ABA can promote growth and development of organ abscission, seed maturation, dormancy, germination and the like, and can also enhance the tolerance of plants to abiotic stresses (cold, drought, heat, osmotic pressure and the like) which are ubiquitous in the environment. Therefore, it is also called "stress hormone".
Although ABA has good and extensive biological activity, methyl groups at 7', 8' and 9' positions are easy to be subjected to hydroxymethylation, and a cis double bond at 2-position of a side chain is easy to be subjected to photoisomerization, so that the ABA is poor in stability and easy to be activated, and the wide application of the ABA in agriculture is greatly limited. Although much work has been done on structural modification of ABA molecular frameworks, the prior art still fails to overcome the problem of high synthesis cost.
In recent years, research groups have obtained a batch of compounds with higher biological activity, such as representative compounds Pyrabactin and AM1, by computer virtual screening based on receptor proteins PYR/PYL/RCAC. The compounds have novel structures, greatly reduce the synthesis cost, and more importantly, can play a similar function to ABA. Thus, the design and synthesis of ABA functional analogs is one of the hot areas of chemical research.
Disclosure of Invention
According to the systematic research on ABA functional analogues, the invention provides application of N- (2-nitrophenyl) benzene sulfonamide compounds in improving plant stress resistance and a medicament containing the N- (2-nitrophenyl) benzene sulfonamide compounds and used for improving plant stress resistance.
In order to achieve the above object, the present invention provides, in a first aspect, use of a sulfonamide compound represented by formula (1) for enhancing stress resistance of plants,
Figure BDA0000992002480000021
wherein, in formula (1), W is N or
Figure BDA0000992002480000022
R1Selected from H, C1-C4Alkyl of (C)1-C4Alkoxy, substituted or unsubstituted phenyl, acetamido, nitro, cyano, ester, monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, and halogen;
R2、R3、R4、R5、R6、R7、R8、R9and R10Are respectively selected from H, C1-C4Alkyl of (C)1-C4Or a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy group, a nitro group, a cyano group, an ester group, a trifluoromethyl group, a trifluoromethoxy group, and a halogen, or R2And R3、R4And R5And R8And R9Together each optionally forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring containing a N atom;
wherein substituted means with a substituent selected from C1-C4Alkyl of (C)1-C4Is substituted by at least one substituent of alkoxy, nitro, cyano, trifluoromethyl, trifluoromethoxy and halogen.
In a second aspect, the invention provides a medicament for enhancing plant stress resistance, which comprises at least one sulfonamide compound represented by formula (1) as an active ingredient in an amount of 0.1 to 100% by weight based on the total weight of the medicament,
Figure BDA0000992002480000023
wherein R is1-R10As defined above.
The inventor of the invention finds that the sulfonamide compound shown in the formula (1) can obviously enhance the tolerance of plants to abiotic stress (such as cold, drought, high temperature and osmotic pressure) commonly existing in the environment, and has high application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIGS. 1a, 1b and 1c are graphs showing the results of specific binding assay of exemplary compound 9 and compound 37 to receptor protein using ITC means, and control with ABA; wherein,
FIG. 1a is a schematic diagram of the ITC assay of compound (+) ABA with receptor protein PYR 1;
FIG. 1b is a schematic of the ITC assay for Compound 37 and the receptor protein PYR 1.
FIG. 1c is a schematic of the ITC assay for Compound 9 with the receptor protein PYR 1.
FIG. 2 is a graph showing the results of a drought tolerance test for Compound 7 in test example 3.
FIG. 3 is a graph showing the results of a drought tolerance test for Compound 37 in test example 3.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides an application of sulfonamide compound shown in formula (1) in enhancing plant stress resistance,
Figure BDA0000992002480000031
wherein, in formula (1), W is N or
Figure BDA0000992002480000032
R1Selected from H, C1-C4Alkyl of (C)1-C4Alkoxy, substituted or unsubstituted phenyl, acetamido, nitro, cyano, ester, monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, and halogen;
R2、R3、R4、R5、R6、R7、R8、R9and R10Are respectively selected from H, C1-C4Alkyl of (C)1-C4Or a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy group, a nitro group, a cyano group, an ester group, a trifluoromethyl group, a trifluoromethoxy group, and a halogen, or R2And R3、R4And R5And R8And R9Together each optionally forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring containing a N atom;
wherein substituted means with a substituent selected from C1-C4Alkyl of (C)1-C4Is substituted by at least one substituent of alkoxy, nitro, cyano, trifluoromethyl, trifluoromethoxy and halogen.
Said "C1-C4The "alkyl group" of (a) means an alkyl group having 1 to 4 carbon atoms.
Said "C1-C4The "alkoxy group" of (a) means an alkoxy group having 1 to 4 carbon atoms.
Preferably, in formula (1), R1Selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, substituted or unsubstituted phenyl, acetamido, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000041
Monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo; the substituent in the substituted phenyl group is at least one selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, nitro, cyano, fluoro, chloro, bromo, and iodo; more preferably, R1Selected from H, methyl, ethyl, n-propyl, isopropyl, n-butylTert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, substituted or unsubstituted phenyl, acetylamino, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3Monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo; the substituent of the substituted phenyl group is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, nitro, cyano, fluoro, chloro, bromo and iodo.
Preferably, in formula (1), R2、R3、R4、R5、R8、R9Each selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000042
Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo, or R2And R3、R4And R5And R8And R9Together each optionally forming an unsubstituted aromatic ring or an unsubstituted aromatic heterocycle containing N atoms, or R2And R3、R4And R5And R8And R9Together each optionally forming an aromatic ring or a substituted aromatic heterocyclic ring containing an N atom substituted with at least one group selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, N-butyl, tert-butyl, 2-methyl-propyl, nitro, cyano, fluorine, chlorine, bromine and iodine; more preferably, R2、R3、R4、R5、R8、R9Each selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxyNitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo, or R2And R3、R4And R5And R8And R9Together each optionally forming an unsubstituted aromatic ring or an unsubstituted aromatic heterocycle containing N atoms, or R2And R3、R4And R5And R8And R9Together each optionally form an aromatic ring or a substituted aromatic heterocycle containing an N atom substituted with at least one group selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, nitro, cyano, fluorine, chlorine, bromine and iodine.
Said "R" is2And R3、R4And R5And R8And R9Together each optionally forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring containing a N atom means that R2And R3May together form a substituted or unsubstituted aromatic ring, or R2And R3May together form a substituted or unsubstituted aromatic heterocycle containing a N atom; to R4And R5And R8And R9Having the same general formula as R2And R3Similar definitions apply.
Preferably, in formula (1), R6、R7And R10Each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, phenoxy, 2-methyl-phenoxy, 4-ethyl-phenoxy, 2-fluoro-phenoxy, 4-chloro-phenoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000051
Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo, and iodo; more preferably, R6、R7And R10Are respectively provided withSelected from H, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, phenoxy, 2-methyl-phenoxy, 4-ethyl-phenoxy, 2-fluoro-phenoxy, 4-chloro-phenoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo.
The following provides several preferred embodiments of the present invention with respect to the sulfonamide compounds represented by the aforementioned formula (1):
embodiment mode 1:
in the sulfonamide compound represented by the formula (1), W is N or
Figure BDA0000992002480000052
R1Selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, substituted or unsubstituted phenyl, acetamido, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000053
Monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo; the substituent in the substituted phenyl group is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, nitro, cyano, fluorine, chlorine, bromine and iodine;
R2、R3、R4、R5、R8、R9each selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000054
Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo, or R2And R3、R4And R5And R8And R9Together each optionally forming an unsubstituted aromatic ring or an unsubstituted aromatic heterocycle containing N atoms, or R2And R3、R4And R5And R8And R9Together each optionally forming an aromatic ring or a substituted aromatic heterocyclic ring containing an N atom substituted with at least one group selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, N-butyl, tert-butyl, 2-methyl-propyl, nitro, cyano, fluorine, chlorine, bromine and iodine;
R6、R7and R10Each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methyl-propoxy, phenoxy, 2-methyl-phenoxy, 4-ethyl-phenoxy, 2-fluoro-phenoxy, 4-chloro-phenoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3、
Figure BDA0000992002480000061
Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo, and iodo.
Embodiment mode 2:
in the sulfonamide compound represented by the formula (1), W is N or
Figure BDA0000992002480000062
R1Selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, substituted or unsubstituted phenyl, acetamido, nitro, cyano, N-butyl, N,-COOCH3、-COOCH2CH3、-COO(CH2)2CH3Monobromomethyl, monochloromethyl, monofluoromethyl, trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo; the substituent in the substituted phenyl group is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, nitro, cyano, fluorine, chlorine, bromine and iodine;
R2、R3、R4、R5、R8、R9are each selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methyl-propyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo and iodo, or R2And R3、R4And R5And R8And R9Together each optionally forming an unsubstituted aromatic ring or an unsubstituted aromatic heterocycle containing N atoms, or R2And R3、R4And R5And R8And R9Together each optionally forming an aromatic ring or a substituted aromatic heterocycle containing an N atom substituted with at least one group selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, nitro, cyano, fluorine, chlorine, bromine and iodine;
R6、R7and R10Are each selected from H, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, phenoxy, 2-methyl-phenoxy, 4-ethyl-phenoxy, 2-fluoro-phenoxy, 4-chloro-phenoxy, nitro, cyano, -COOCH3、-COOCH2CH3、-COO(CH2)2CH3Trifluoromethyl, trifluoromethoxy, fluoro, chloro, bromo, and iodo;
the substituent of the substituted phenyl group is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, nitro, cyano, fluoro, chloro, bromo and iodo.
Embodiment mode 3: the sulfonamide compound represented by the formula (1) is at least one of the following compounds:
compound 1: r1Is Br; r4Is NO2；R2、R3、R5、R6、R7、R8、R9And R10Are all H; w is C;
compound 2: r4Is NO2；R6Is Br; r1、R2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 3: r1Is OCH3；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 4: r1Is CH3；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 5: r1Is C2H5；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 6: r1Is composed ofnC3H7；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 7: r1And R6Is Br; r4Is NO2；R2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 8: r1Is I; r4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 9: r1And R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 10: r1Is CH3CONH；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 11: r1Is BrCH2；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 12: r3And R4Is NO2；R6Is Br; r1、R2、R5、R7、R8、R9And R10Are all H; w is C;
compound 13: r1And R6Is Br; r3Is F; r4Is NO2；R2、R5、R7、R8、R9And R10Are all H; w is C;
compound 14: r1Is C2H5；R4Is NO2；R6Ph; r2、R3、R5、R7、R8、R9And R10Are all H; w is C;
compound 15: r1Is Cl; r2Is NO2；R6Is Br; r3、R4、R5、R7、R8、R9And R10Are all H; w is C;
compound 16: r1Is Cl; r2Is NO2；R4Is F; r6Is Br; r3、R5、R7、R8、R9And R10Are all H; w is C;
compound 17: r1And R6Is Br; r2Is NO2；R3、R4、R5、R7、R8、R9And R10Are all H; w is C;
compound 18: r1And R6Is Br; r3Is NO2；R2、R4、R5、R7、R8、R9、R10Are all H; w is C;
compound 19: r1And R6Is Br; r4And R5Together form a phenyl group; r7Is NO2；R2、R3、R8、R9、R10Are all H; w is C;
compound 20: r1And R3Is NO2；R4And R5Together form a phenyl group; r6Is Br; r2、R7、R8、R9、R10Are all H; w is C;
compound 21: r1Is Br; r4And R5Together form a phenyl group; r2、R3、R6、R7、R8、R9、R10Are all H; w is C;
compound 22: r1Is Br; r2And R3Together form a phenyl group; r4And R5Are formed together
Figure BDA0000992002480000081
R6、R7、R8、R9、R10Are all H; w is C;
compound 23: r1And R7Is Br; r2And R3Together form a phenyl group; r4Is NO2；R6Is F; r5、R8、R9、R10Are all H; w is C;
compound 24: r1Is Br; r2And R3Together form a phenyl group; r4Is NO2；R6Is F; r5、R7、R8、R9、R10Are all H; w is C;
compound 25: r1Is Br; r2And R3Together form a phenyl group; r4Is NO2；R6Is Cl; r5、R7、R8、R9、R10Are all H; w is C;
compound 26: r1And R6Is Br; r2And R3Together form a phenyl group; r4Is NO2；R5、R7、R8、R9、R10Are all H; w is C;
compound 27: r1Is 4-Br-Ph; r4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 28: r1Is 3-Br-Ph; r4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 29: r1Is Br; r4Is NO2；R6Is CH3；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 30: r1Is COOC2H5；R4Is NO2；R6Is Br; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 31: r1Is Br; r4Is NO2；R6Is composed ofiC3H7；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 32: r1Is Br; r4Is NO2；R6Is composed oftC4H9；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 33: r1Is Br; r4Is NO2；R6Is F; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 34: r1Is Br; r4Is NO2；R6Is Cl; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 35: r1Is Br; r4Is NO2；R6Is I; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 36: r1Is Br; r4Is NO2；R6Is CN; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 37: r1And R6Is Br; r4And R7Is NO2；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 38: r1、R6And R7Is Br; r4Is NO2；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 39: r1And R6Is Br; r4Is NO2；R7Is OPh; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 40: r1And R7Is Br; r4Is NO2；R6Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 41: r1Is Br; r4Is NO2；R6Is Cl; r7Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 42: r1Is Br; r4Is NO2；R6And R7Is CH3；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 43: r1Is Br; r4Is NO2；R6Is CH3；R7Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 44; r1Is Br; r4Is NO2；R6Is F; r7Is CH3；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 45: r1Is Br; r4Is NO2；R6Is COOCH3；R7Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 46: r1Is Br; r4Is NO2；R6Is OCH3；R7Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound (I)47：R1Is Br; r4Is NO2；R6Is CF3；R7Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 48: r1Is Br; r5Is NO2；R6Is F; r2、R3、R4、R7、R8、R9、R10Are all H; w is C;
compound 49: r1Is Br; r5Is NO2；R6Is Cl; r2、R3、R4、R7、R8、R9、R10Are all H; w is C;
compound 50: r1And R6Is Br; r5Is NO2；R2、R3、R4、R7、R8、R9、R10Are all H; w is C;
compound 51: r1And R6Is Br; r4Is NO2；R7、R8Is F; r2、R3、R5、R9、R10Are all H; w is C;
compound 52: r1、R3And R7Is NO2；R4And R5Together form a phenyl group; r6Is Br; r2、R8、R9、R10Are all H; w is C;
compound 53: r1Is Br; r4Is NO2；R6Is CH3；R2、R3、R5、R8、R9、R10Are all H; w is N;
compound 54: r1Is Br; r4Is NO2；R6Is CF3；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 55: r1Is Br; r4Is NO2；R6Is OCF3；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 56: r1Is Br; r4And R7Is NO2；R6Is Cl; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 57: r1Is Br; r4And R7Is NO2；R6Is composed oftC4H9；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 58: r1Is Br; r4And R7Is NO2；R6Is F; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 59: r1Is Br; r4And R7Is NO2；R6Is OCH3；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 60: r1Is Br; r4And R7Is NO2；R6Is CN; r2、R3、R5、R8、R9、R10Are all H; w is C;
compound 61: r1Is Br; r4And R7Is NO2；R6Is CF3；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 62: r1Is Br; r4And R7Is NO2；R6Is OCF3；R2、R3、R5、R8、R9、R10Are all H; w is C;
compound 63: r1Is Br; r6Is CH3；R2、R3、R4、R5、R8、R9、R10Are all H; w is N;
compound 64: r1Is Br; r2And R3Together form a phenyl group; r6Is CH3；R4、R5、R8、R9、R10Are all H; w is N;
compound 65: r1Is C (CH)3)3；R3Is Cl; r4Is NO2；R5Is CH3；R6Is OC2H5；R7Is CN; r2、R8、R9、R10Are all H; w is C;
compound 66: r1Is O (CH)2)3CH3；R2And R6Is CH3；R4Is NO2；R7Is 4-Cl-PhO; r9Is F; r3、R5、R8、R10Are all H; w is C;
compound 67: r1Is Br; r4Is NO2；R2、R3、R5、R6、R8、R9、R10Are all H; w is N;
compound 68: r4Is NO2；R6Is Br; r1、R2、R3、R5、R8、R9、R10Are all H; w is N;
compound 69: r1Is C2H5；R4Is NO2；R6Is Br; r2、R3、R5、R8、R9、R10Are all H; w is N;
compound 70: r1Is BrCH2；R4Is NO2；R6Is Br; r2、R3、R5、R8、R9、R10Are all H; w is N;
compound 71: r1Is Cl; r2Is NO2；R4Is F; r6Is Br; r3、R5、R8、R9、R10Are all H; w is N;
compound 72: r1And R3Is NO2；R4And R5Together form a phenyl group; r6Is Br; r2、R8、R9、R10Are all H; w is N;
compound 73: r1And R6Is Br; r2And R3Together form a phenyl group; r4Is NO2；R5、R8、R9、R10Are all H; w is N.
Preferably, the plant stress resistance comprises at least one of cold tolerance, drought tolerance, heat tolerance and salt and alkali tolerance. The saline-alkali resistance is also understood to be the resistance to osmotic pressure changes.
The plant stress resistance is also manifested by regulating the root growth of the plant. It will be appreciated by those skilled in the art that compounds capable of having root growth inhibitory activity will generally enhance plant stress resistance, and that compounds of the prior art will also generally be investigated for their root growth inhibitory activity when assessing whether they can enhance plant stress resistance.
Particularly preferably, the plant stress resistance is selected from at least one of cold resistance, drought resistance and heat resistance.
In a second aspect, the invention provides a medicament for enhancing plant stress resistance, which comprises at least one sulfonamide compound represented by formula (1) as an active ingredient in an amount of 0.1 to 100% by weight, based on the total weight of the medicament,
Figure BDA0000992002480000121
wherein R is1-R10Limit of (2)As previously defined.
It should be noted that, in the second aspect of the present invention, the definition and the optional range of the sulfonamide compound represented by formula (1) are the same as those of the sulfonamide compound represented by formula (1) in the first aspect, and the present invention is not described in detail in the second aspect in order to avoid redundancy, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the content of the active ingredient is 1 to 98% by weight; more preferably 5 to 90 wt%.
The agent for enhancing plant stress resistance may further comprise various additives and adjuvants or solvents commonly used in the art, and the present invention is not particularly limited thereto.
Preferably, the dosage form of the medicament is selected from the group consisting of hydration agents, powders, emulsions, suspensions and granules.
The sulfonamide compound represented by the formula (1) of the present invention can be produced by a method according to the prior art, or can be commercially available; the present invention is not particularly limited in this regard. Several methods for the preparation of the compounds are provided as examples in the present invention and the skilled person should not be understood as a limitation of the invention.
The present invention will be described in detail below by way of preparation examples and test examples. In the following preparation examples and test examples, various raw materials used were commercially available without specific description.
Preparation example 1: preparation of N- (2-nitro-4-bromophenyl) -4-ethylbenzenesulfonamide (compound 5)
Step 1: 1.720g of 4-bromoaniline was put into a 100mL single-necked flask and 30mL of dichloromethane was added, a dichloromethane solution containing 2.150g of 4-ethylbenzenesulfonyl chloride was slowly added dropwise in an ice-water bath, 1.6g of pyridine was added dropwise after the addition, and the mixture was allowed to stand at room temperature (25 ℃ C., the same applies hereinafter) for 10 hours. After the reaction is finished, adding 1M hydrochloric acid for washing for three times, drying the mixture by anhydrous sodium sulfate, decompressing and drying the filtrate, and carrying out column chromatography, wherein the eluent is a mixture of 20: 3 petroleum ether and acetone. A white solid was obtained with a yield of 88%.
Step 2: 1.370g of N- (4-bromophenyl) -4-ethylbenzenesulfonamide was charged into a 25mL single-necked flask and 10mL of methylene chloride was added, and 0.8mL of fuming nitric acid was slowly added dropwise in an ice-water bath, and the flask was moved to 25 ℃ to react. After TLC monitoring reaction, adding a proper amount of crushed ice, extracting, drying with anhydrous sodium sulfate, decompressing and drying filtrate, and performing column chromatography, wherein the eluent is a mixture of 20: 2 petroleum ether and acetone. A pale yellow solid was obtained in 68% yield.1H NMR(600MHz,CDCl3):δ9.77(s,1H),8.25(s,1H),7.76(m,3H),7.68(d,J＝9.0Hz,1H),7.31(d,J＝6.0Hz,2H),2.70(d,J＝5.4Hz,2H),1.37–1.04(m,3H)。
Preparation example 2: preparation of N- (2-nitro-4-bromophenyl) -4-bromobenzenesulfonamide (Compound 7)
Step 1: 1.720g of 4-bromoaniline was put into a 100mL single-necked flask, 30mL of dichloromethane was added, a dichloromethane solution containing 2.680g of 4-bromobenzenesulfonyl chloride was slowly added dropwise in an ice-water bath, 1.6g of pyridine was added dropwise after the addition, and the mixture was allowed to stand at room temperature (25 ℃ C., the same applies hereinafter) for 10 hours. After the reaction is finished, adding 1M hydrochloric acid for washing for three times, drying the mixture by anhydrous sodium sulfate, decompressing and drying the filtrate, and carrying out column chromatography, wherein the eluent is a mixture of 20: 3 petroleum ether and acetone. White solid N- (4-bromophenyl) -4-bromobenzenesulfonamide was obtained in 90% yield.
Step 2: 1.464g of N- (4-bromophenyl) -4-bromobenzenesulfonamide was added to a 25mL single-necked flask and 12mL of methylene chloride was added, and 1.0mL of fuming nitric acid was slowly added dropwise in an ice-water bath, and the mixture was allowed to warm to room temperature after completion of the addition. After TLC monitoring reaction, adding a proper amount of crushed ice, extracting, drying with anhydrous sodium sulfate, decompressing and drying filtrate, and performing column chromatography, wherein the eluent is a mixture of 20: 2 petroleum ether and acetone. A pale yellow solid was obtained in 81% yield.
Preparation example 3: preparation of N- (3-nitro- [1, 1' -biphenyl ]) -4-ethylbenzenesulfonamide (compound 14)
0.386g of N- (2-nitro-4-bromophenyl) -4-ethylbenzenesulfonamide was coupled with arylboronic acid under the catalysis of tetratriphenylphosphine palladium and irradiated with microwaves at 110 ℃ for 10 min. Cooling to room temperature, decompressing and drying the reaction system, and carrying out column chromatography, wherein the eluent is a mixture of 20: 3 Petroleum ether and acetone. A pale yellow solid was obtained in 86% yield.1H NMR(600MHz,DMSO-d6):δ10.35(s,1H),8.17(d,J＝2.4Hz,1H),7.95(dd,J＝8.4,2.4Hz,1H),7.71(dd,J＝7.8,4.2Hz,4H),7.48(t,J＝7.8Hz,2H),7.43(dd,J＝7.8,3.6Hz,3H),7.35(d,J＝8.4Hz,1H),2.67(q,J＝7.8Hz,2H),1.18(t,J＝7.8Hz,3H)。
Preparation example 4: preparation of N- (4-bromophenyl) -3-nitro-4-chloro-benzenesulfonamide (compound 15)
The method comprises the following steps: 0.344g of 4-bromoaniline was added to a 25mL single-necked flask and 10mL of THF was added, a THF solution containing 0.564g of 3-nitro-4-chloro-benzenesulfonyl chloride was slowly added dropwise in an ice-water bath, 0.475g of pyridine was added dropwise after the addition, and the reaction was refluxed for 10 hours after the addition was completed. After the reaction is finished, decompression drying and column chromatography are carried out, wherein the eluent is a mixture of 20: 3 petroleum ether and acetone. A pale yellow solid was obtained in 71% yield.
Preparation example 5: preparation of N- (2-nitro-4-bromophenyl) -4 '-bromo- [1, 1' -biphenyl ] -4-benzenesulfonamide (compound 27)
Step 1: 1.720g of 4-bromoaniline was reacted with 2.682g of 4-bromobenzenesulfonyl chloride to give N- (4-bromophenyl) -4-bromobenzenesulfonamide as a white solid in 93% yield.
Step 2: 0.391g of N- (4-bromophenyl) -4-bromobenzenesulfonamide is coupled with arylboronic acid under the catalysis of palladium tetratriphenylphosphine and irradiated with microwaves at 110 ℃ for 10 min. Cooling to room temperature, decompressing and drying the reaction system, and carrying out column chromatography, wherein the eluent is a mixture of 20: 3, and acetone to give a white solid with a yield of 46%.
And step 3: using a similar nitration process as in preparation 1, 0.467g of N- (4-bromophenyl) -4 '-bromo- [1, 1' -biphenyl]The nitration reaction of the-4-benzene sulfonamide is carried out to obtain light yellow solid with the yield of 74 percent.1H NMR(600MHz,CDCl3):δ9.84(s,1H),8.26(s,1H),7.90(d,J＝8.4Hz,2H),7.81(d,J＝9.0Hz,1H),7.71(d,J＝9.0Hz,1H),7.65(d,J＝8.4Hz,2H),7.60(d,J＝7.8Hz,2H),7.43(d,J＝8.4Hz,2H)。
Preparation example 6: preparation of N- (2-nitro-4-bromophenyl-6-phenoxy) -4-bromobenzenesulfonamide (compound 39)
Step 1: 2.200g of 2-fluoro-4-bromonitrobenzene and 1.660g of K2CO3The mixture was added to a 100mL single-necked flask and 30mL of DMF, and a DMF solution containing 1.040g of phenol was slowly added dropwise in an ice-water bath, and the mixture was transferred to an oil bath at 60 ℃ for reaction for 12 hours after completion of the addition. After the reaction is finished, adding ethyl acetate for extraction, adding water for washing for three times, drying the anhydrous sodium sulfate, and decompressing and drying the filtrate. A pale yellow solid was obtained in 94% yield.
Step 2: 1.178g of 2-phenoxy-4-bromonitrobenzene were added to a 50mL single-necked flask and 24mL of ethanol and 4mL of water were added, 0.643g of NH was added4Cl and 0.895g of reduced iron powder, and reacting for 10 hours under reflux. After the reaction is finished, adding diatomite for suction filtration, decompressing and drying the filtrate, adding ethyl acetate for extraction, drying sodium sulfate, decompressing and drying the filtrate. A white solid was obtained in 91% yield.
And step 3: 0.528g of 2-phenoxy-4-bromoaniline was reacted with 0.539g of 4-bromobenzenesulfonyl chloride in a similar manner to preparation example 1. A white solid was obtained with a yield of 88%.
And 4, step 4: 0.484g of N- (2-phenoxy-4-bromophenyl) -4-bromobenzenesulfonamide was nitrated in a similar manner to preparation example 1 to give a pale yellow solid in a yield of 63%.1H NMR(600MHz,DMSO-d6):δ10.75(s,1H),8.11(s,1H),7.76(d,J＝8.4Hz,2H),7.69(d,J＝8.4Hz,2H),7.42(t,J＝7.8Hz,2H),7.27(t,J＝7.2Hz,1H),6.95(s,1H),6.77(d,J＝7.8Hz,2H)。
Preparation example 7: preparation of N- (3-nitro-4-bromophenyl) -4-bromo-benzenesulfonamide (compound 50)
The method comprises the following steps: 0.434g of 3-nitro-4-bromoaniline was added to a 25mL single-necked flask and 10mL of THF was added, a solution of THF containing 0.564g of 4-bromo-benzenesulfonyl chloride was slowly added dropwise in an ice-water bath, 0.475g of pyridine was added dropwise after the addition, and the reaction was refluxed for 10 hours after the addition was completed. After the reaction is finished, decompression drying and column chromatography are carried out, wherein the eluent is a mixture of 20: 3 petroleum ether and acetone. A pale yellow solid was obtained in 73% yield.
Other compounds of compounds 1-73 were prepared in a similar manner to the above preparations. And, providing nuclear magnetic data for:
compound 3:1H NMR(600MHz,DMSO-d6):δ10.29(s,1H),8.14(d,J＝2.4Hz,1H),7.83(dd,J＝9.0,2.4Hz,1H),7.68(d,J＝9.0Hz,2H),7.23(d,J＝9.0Hz,1H),7.10(d,J＝9.0Hz,2H)。
compound 6:1H NMR(600MHz,CDCl3):δ9.75(s,1H),8.24(d,J＝2.4Hz,1H),7.75(m,3H),7.68(dd,J＝9.0,2.4Hz,1H),7.28(d,J＝8.4Hz,2H),2.86–2.38(m,2H),1.67–1.59(m,2H),0.92(t,J＝7.2Hz,3H)。
compound 8:1H NMR(600MHz,CDCl3):δ9.80(s,1H),8.27(d,J＝2.4Hz,1H),7.85(d,J＝8.4Hz,2H),7.75(d,J＝9.0Hz,1H),7.70(m,1H),7.55(d,J＝8.4Hz,2H)。
compound 10:1H NMR(600MHz,DMSO-d6):δ10.37(s,1H),10.28(s,1H),8.14(d,J＝2.4Hz,1H),7.83(dd,J＝9.0,2.4Hz,1H),7.74(d,J＝9.0Hz,2H),7.65(d,J＝9.0Hz,2H),7.19(d,J＝9.0Hz,1H),2.08(s,3H)。
compound 11:1H NMR(600MHz,DMSO-d6):δ10.50(s,1H),8.15(d,J＝2.4Hz,1H),7.84(dd,J＝9.0,2.4Hz,1H),7.73(dd,J＝13.8,8.4Hz,2H),7.68–7.59(m,2H),7.20(d,J＝9.0Hz,1H),4.80(s,2H)。
compound 12:1H NMR(600MHz,DMSO-d6):δ8.20(d,J＝2.4Hz,1H),8.02(dd,J＝7.8,1.2Hz,1H),7.95(dd,J＝7.8,1.2Hz,1H),7.94–7.89(m,2H),7.87(dt,J＝7.8,3.6Hz,1H),7.31(d,J＝9.0Hz,1H)。
compound 13:1H NMR(600MHz,DMSO-d6):δ10.85(s,1H),8.15(d,J＝2.4Hz,1H),7.93–7.83(m,2H),7.66–7.61(m,1H),7.60(dd,J＝8.4,1.8Hz,1H),7.33(d,J＝9.0Hz,1H)。
compound 17:1H NMR(600MHz,DMSO-d6):δ10.77(s,1H),8.38(d,J＝2.4Hz,1H),8.14(d,J＝8.4Hz,1H),7.85(dd,J＝8.4,2.4Hz,1H),7.48(d,J＝9.0Hz,2H),7.07(d,J＝9.0Hz,2H)。
compound 18:1H NMR(600MHz,DMSO-d6):δ8.45(s,1H),8.36(s,1H),7.95(d,J＝10.8Hz,1H),7.41–7.29(m,3H),6.93(d,J＝9.0Hz,2H)。
compound 22:1H NMR(600MHz,DMSO-d6):δ10.62(s,1H),8.92(d,J＝8.4Hz,1H),8.71(d,J＝2.4Hz,1H),8.29(d,J＝8.4Hz,1H),8.22(d,J＝8.4Hz,1H),8.17(d,J＝7.8Hz,1H),8.01(d,J＝7.8Hz,1H),7.87–7.72(m,2H),7.70–7.56(m,2H),7.50(dt,J＝16.8,6.0Hz,2H)。
compound 23:1H NMR(600MHz,DMSO-d6):δ11.11(s,1H),8.59(d,J＝8.4Hz,1H),8.33(d,J＝8.4Hz,1H),8.04(dd,J＝7.8,3.0Hz,1H),7.99(d,J＝7.8Hz,1H),7.95(dd,J＝7.8,3.0Hz,1H),7.87–7.75(m,3H)。
compound 24:1H NMR(600MHz,DMSO-d6):δ10.80(s,1H),8.62(d,J＝8.4Hz,1H),8.34(d,J＝8.4Hz,1H),8.02(d,J＝7.8Hz,1H),7.89(d,J＝7.8Hz,1H),7.88–7.84(m,2H),7.81(t,J＝7.8Hz,1H),7.47(td,J＝9.0,3.0Hz,1H),7.11(dd,J＝9.0,5.4Hz,1H)。
compound 25:1H NMR(600MHz,CDCl3):δ10.24(s,1H),8.63(d,J＝8.4Hz,1H),8.38(d,J＝8.4Hz,1H),8.17(d,J＝7.8Hz,1H),8.02(d,J＝2.4Hz,1H),7.87(d,J＝7.8Hz,1H),7.80–7.70(m,3H),7.47(dd,J＝9.0,2.4Hz,1H)。
compound 26:1H NMR(600MHz,CDCl3):δ10.26(s,1H),8.62(d,J＝8.6Hz,1H),8.38(d,J＝8.4Hz,1H),8.22–8.13(m,2H),7.87(d,J＝8.0Hz,1H),7.78(d,J＝7.6Hz,1H),7.73(d,J＝8.1Hz,1H),7.68(d,J＝9.0Hz,1H),7.60(dd,J＝9.0,2.0Hz,1H)。
compound 28:1H NMR(600MHz,CDCl3):δ9.84(s,1H),8.27(s,1H),7.91(d,J＝7.8Hz,2H),7.81(d,J＝9.0Hz,1H),7.71(d,J＝10.2Hz,2H),7.66(d,J＝7.8Hz,2H),7.55(d,J＝7.8Hz,1H),7.48(d,J＝7.8Hz,1H),7.35(d,J＝7.8Hz,1H)。
compound 30:1H NMR(600MHz,DMSO-d6):δ10.67(s,1H),8.15(d,J＝2.4Hz,1H),8.12(d,J＝8.4Hz,2H),7.84(dd,J＝8.4,3.6Hz,3H),7.16(d,J＝8.4Hz,1H),4.35(q,J＝7.2Hz,2H),1.33(t,J＝7.2Hz,3H)。
compound 31:1H NMR(600MHz,DMSO-d6):δ10.38(s,1H),7.80(d,J＝8.4Hz,2H),7.77(d,J＝1.8Hz,1H),7.63(d,J＝8.4Hz,2H),7.53(d,J＝8.4Hz,1H),7.14(d,J＝8.4Hz,1H),2.95(dt,J＝13.8,6.5Hz,1H),1.18(d,J＝7.2Hz,6H)。
compound 32:1H NMR(600MHz,CDCl3):δ9.77(s,1H),8.10(d,J＝2.4Hz,1H),7.72(dd,J＝10.8,9.0Hz,3H),7.63(dd,J＝11.4,5.4Hz,3H),1.30(s,9H)。
compound 35:1H NMR(600MHz,DMSO-d6):δ10.53(s,1H),8.22(d,J＝1.8Hz,1H),7.98(dd,J＝8.4,1.8Hz,1H),7.81(d,J＝8.4Hz,2H),7.63(d,J＝8.4Hz,2H),7.03(d,J＝8.4Hz,1H)。
compound 36:1H NMR(600MHz,DMSO-d6):δ8.46(s,1H),8.02(d,J＝8.4Hz,1H),7.82(d,J＝8.4Hz,2H),7.76(d,J＝9.0Hz,2H),7.49(d,J＝8.4Hz,1H)。
compound 37:1H NMR(600MHz,CDCl3):δ8.33(s,1H),8.30(s,2H),7.64(d,J＝8.4Hz,2H),7.50(d,J＝8.4Hz,2H)。
compound 38:1H NMR(600MHz,DMSO-d6):δ10.89(s,1H),8.29(d,J＝2.4Hz,1H),8.25(d,J＝2.4Hz,1H),7.78(d,J＝8.4Hz,2H),7.54(d,J＝8.4Hz,2H)。
compound 40:1H NMR(600MHz,CDCl3):δ7.66(dd,J＝7.2,3.0Hz,1H),7.63(d,J＝8.4Hz,2H),7.59(dd,J＝7.2,3.0Hz,1H),7.54(d,J＝8.4Hz,2H),7.20(s,1H)。
compound 41:1H NMR(600MHz,CDCl3):δ8.26(s,1H),7.85(s,1H),7.68(q,J＝9.0Hz,4H),7.47(dd,J＝9.6,2.4Hz,1H)。
compound 42:1H NMR(600MHz,CDCl3):δ7.86(d,J＝9.0Hz,2H),7.77(s,1H),7.76–7.74(m,2H),7.51(s,1H),2.51(s,3H),2.49(s,3H)。
compound 43:1H NMR(600MHz,CDCl3):δ8.15(s,1H),7.67–7.60(m,5H),7.26(d,J＝5.4Hz,1H),2.43(s,3H)。
compound 44:1H NMR(600MHz,CDCl3):δ7.58(d,J＝8.4Hz,3H),7.40(d,J＝8.4Hz,2H),7.34(d,J＝7.8Hz,2H),2.65(s,3H)。
compound 45:1H NMR(600MHz,CDCl3):δ7.80(d,J＝8.4Hz,1H),7.71–7.63(m,4H),7.61(d,J＝8.4Hz,2H),7.01(s,1H),3.89(s,3H)。
compound 46:1H NMR(600MHz,CDCl3):δ8.31(d,J＝7.8Hz,1H),7.89(d,J＝8.4Hz,2H),7.76(d,J＝8.4Hz,2H),6.56(d,J＝9.0Hz,1H)。
compound 47:1H NMR(600MHz,CDCl3):δ9.02(s,1H),8.23(s,1H),7.82–7.76(m,2H),7.71(d,J＝8.4Hz,2H),7.68(d,J＝10.2Hz,1H)。
compound 51:1H NMR(600MHz,DMSO-d6):δ11.46–10.62(s,1H),8.35(d,J＝4.8Hz,1H),7.81(d,J＝8.4Hz,2H),7.63(d,J＝8.4Hz,2H)。
compound 52:1H NMR(600MHz,DMSO-d6):δ8.82(s,1H),8.45(dd,J＝9.0,2.4Hz,1H),8.40(s,1H),8.21(d,J＝8.4Hz,1H),7.98(dd,J＝8.4,4.2Hz,2H),7.82(d,J＝7.2Hz,1H),7.60(d,J＝7.8Hz,1H)。
compound 53:1H NMR(400MHz,DMSO-d6)δ10.81(s,1H),8.28(s,2H),7.89(d,J＝8.4Hz,2H),7.81–7.74(m,2H),2.27(s,3H).
compound 57:1H NMR(600MHz,CDCl3):δ8.27(s,1H),8.13(s,2H),7.61(d,J＝8.4Hz,2H),7.50(d,J＝9.0Hz,2H),1.39(s,9H).
compound 58:1H NMR(600MHz,DMSO-d6)δ10.59(s,1H),7.79(d,J＝8.4Hz,2H),7.67(s,1H),7.56(d,J＝8.4Hz,2H),7.47(d,J＝10.2Hz,1H).
compound 59:1H NMR(600MHz,DMSO-d6)δ10.90(s,1H),7.82(s,2H),7.76(d,J＝8.4Hz,2H),7.46(d,J＝8.4Hz,2H),3.92(s,3H).
compound 60:1H NMR(600MHz,DMSO-d6)δ8.63(s,2H),7.71(d,J＝7.8Hz,2H),7.50(d,J＝8.4Hz,2H).
compound 61:1H NMR(600MHz,CDCl3)δ8.93(s,1H),8.48(s,2H),7.68(d,J＝8.4Hz,2H),7.57(d,J＝8.4Hz,2H).
compound 62:1H NMR(600MHz,CDCl3)δ8.41(s,1H),8.05(s,2H),7.65(d,J＝8.4Hz,2H),7.52(d,J＝8.4Hz,2H).
compound 64:1H NMR(600MHz,CDCl3)δ8.41(s,1H),8.05(s,2H),7.65(d,J＝8.4Hz,2H),7.52(d,J＝8.4Hz,2H).
compound 65:1H NMR(600MHz,CDCl3):δ10.77(s,1H),7.93(s,1H),7.72(d,J＝8.4Hz,1H),7.60(d,J＝8.4Hz,1H),7.64(s,1H),4.02(q,J＝5.4Hz,2H),2.34(s,3H),1.32(s,9H),1.08(t,J＝5.4Hz,3H)。
compound 66:1H NMR(600MHz,DMSO-d6):δ10.73(s,1H),7.83(s,1H),7.60(m,3H),7.42(m,3H),7.30(s,1H),7.64(s,1H),4.05(t,J＝5.4Hz,3H),2.32(s,3H),2.10(s,3H),1.72(m,2H),1.38-0.9(m,5H)。
compound 69:1H NMR(600MHz,DMSO-d6):δ10.83(s,1H),8.84(s,1H),8.21(s,1H),7.83(d,J＝7.2Hz,2H),7.73(d,J＝7.2Hz,2H),7.68(t,J＝7.2Hz,1H)。
compound 70:1H NMR(600MHz,DMSO-d6):δ10.84(s,1H),8.81(s,1H),8.21(s,1H),7.84(dd,J＝8.7,2.3Hz,1H),7.73(d,J＝8.4Hz,2H),7.50(d,J＝8.4Hz,1H),2.60(q,J＝5.4Hz,2H),1.26(t,J＝5.4Hz,3H)。
compound 71:1H NMR(600MHz,DMSO-d6):δ10.83(s,1H),8.82(s,1H),8.20(s,1H),7.73(d,J＝8.4Hz,2H),7.50(d,J＝8.4Hz,1H),4.82(s,2H)。
compound 72:1H NMR(600MHz,DMSO-d6):δ10.79(s,1H),8.59(s,1H),8.15(d,J＝8.4Hz,1H),7.95(d,J＝8.4Hz,1H),7.60(s,2H)。
compound 73:1H NMR(600MHz,DMSO-d6):δ11.32(s,1H),8.97(s,1H),8.70(s,1H),8.51(s,1H),8.21(s,1H),8.01(d,J＝7.2Hz,1H),7.81(d,J＝7.2Hz,1H),7.58(m,,2H)。
compound 74:1H NMR(600MHz,CDCl3):δ10.56(s,1H),8.81(m,2H),8.60(d,J＝8.4Hz,1H),8.35(d,J＝8.4Hz,1H),8.22–8.17(m,3H),7.87(d,J＝7.8Hz,1H)。
test example 1
This test example is intended to demonstrate the plant root growth inhibitory activity (% root growth inhibition) of the compound having the structure represented by the formula (I).
Preliminary screening test (MS medium method):
the plant was examined as wild type (Columbia type, Col-0) Arabidopsis thaliana.
The sterilized and vernalized seeds are cultured for about 5 days under the conditions of 23 ℃ of temperature, 16h of illumination and 8h of darkness and long period of sunlight, and can be transplanted for later use when the root of arabidopsis thaliana grows for about 1-2 cm.
Adding each compound in the compounds 1-73 into a culture medium according to a final concentration of 100 mu m for testing, and respectively adding equal amounts of (+) ABA and Pyrabactin into two groups of positive control groups; the blank was 0.5% DMSO in water. After the seedlings are inoculated, sealing, marking the root tip position of each seedling transplanted on the culture medium, vertically placing the seedling into an illumination incubator for culture, setting the growth conditions of 16h illumination, 8h darkness and 23 ℃, and collecting the phase after 7 days of growth.
The elongation of the main root of each arabidopsis seedling was measured using ImageJ-2x software, then the average of the total number of plants on the petri dish was calculated, and finally the inhibition rate (%) of the compound on the root length was calculated according to the following method (root length inhibition calculation method), and the results are shown in table 1. And the root length inhibition rates of (+) ABA and Pyrabactin are 86% and 100%, respectively.
Root length inhibition rate calculation method
Figure BDA0000992002480000201
TABLE 1
Compound numbering Root length growth inhibition/%) Compound numbering Root length growth inhibition/%)
1 100 38 100
2 100 39 60
3 93 40 100
4 100 41 100
5 100 42 100
6 100 43 100
7 100 44 100
8 100 45 100
9 100 46 100
10 66 47 100
11 69 48 100
12 100 49 100
13 100 50 100
14 60 51 100
15 100 52 100
16 100 53 100
17 100 54 100
18 60 55 100
19 67 56 100
20 72 57 100
21 100 58 100
22 100 59 100
23 100 60 100
24 100 61 100
25 100 62 100
26 100 63 100
27 60 64 100
28 60 65 62
29 100 66 61
30 100 67 100
31 100 68 100
32 100 69 63
33 91 70 70
34 100 71 71
35 100 72 100
36 100 73 65
37 100
Test example 2
Isothermal Titration Calorimetry (ITC): typical compound 37 and compound 9 were tested for specific binding to receptor proteins using the ITC approach and compared to ABA, with the results shown in fig. 1a, 1b, and 1 c. The dissociation constant Kd value of compound 37 and receptor protein PYR1 is 1.1 μm (shown in FIG. 1 b), which is significantly better than the binding of ABA to receptor protein PYR1 (shown in FIG. 1a, Kd is 72.5 μm). Meanwhile, the dissociation constant Kd value of the compound 9 and the receptor protein PYR1 is 4.1 mu m (shown in figure 1 c), which is obviously better than the combination of ABA and the receptor protein PYR 1.
Test example 3
Drought tolerance experiment: the arabidopsis Col-0 ecotype seeds are sterilized by NaClO, placed in a refrigerator at 4 ℃ for vernalization for 3 days, and then sown on an MS culture medium, and seedlings with good and consistent growth vigor are selected and transplanted into a culture pot filled with soil after 4 days of growth.
Each pot was filled with the same mass of soil and transferred to the same number (10 columns) of plants, all the pots (5 pots per group) were placed in 23 ℃ sunlight and, 14 days later, watering was stopped for drought treatment, during which 25 μm (+) -ABA was sprayed to the leaves every other day (the experimental group was sprayed with the compound of the present invention, the blank control was sprayed with 0.05% DMSO aqueous solution). The watering was resumed after 14 days. Photographs were taken both before and after rehydration (figure 2 shows plant status before and after rehydration for typical compound 7, and figure 3 shows plant status before and after rehydration for typical compound 37). The results show that after two weeks of drought treatment, the (+) -ABA-sprayed plants recovered water supply and 75% survived, the 0.05% DMSO-sprayed wild-type plants all withered and failed to recover after water supply recovery, and the plant revival rates of the compounds of the present invention are shown in table 2.
The revival rate is the number of plants revived after drought treatment and drug application/total number of plants multiplied by 100%
TABLE 2
Figure BDA0000992002480000211
Figure BDA0000992002480000221
Test example 4
Cold stress experiments: the process of seed vernalization and Arabidopsis growth is the same as the drought-enduring experiment, three weeks old plants are transferred into a 4 ℃ illumination incubator for culture and placed for 5 days, and mixed liquor containing 0.02% of Tween-20 and 50 mu m of the compound of the invention, or mixed liquor (positive control) containing 0.02% of Tween-20 and 50 mu m-ABA or mixed liquor containing 0.02% of Tween-20 and 0.05% of DMSO is sprayed on the leaf surfaces every day. Five days later the incubator was removed and placed in a normal growth environment.
The experimental results are as follows: after 5 days of cold treatment, about 78% of the plants sprayed with ABA survived, the wild type plants sprayed with DMSO control liquid all withered and returned to normal growing environment and could not be recovered, and the revival rate of the plants sprayed with the compound of the present invention is shown in table 3.
The revival rate is the number of plants revived after cold treatment and drug application/total number of plants multiplied by 100%
TABLE 3
Figure BDA0000992002480000222
Figure BDA0000992002480000231
The effects of the test examples show that the sulfonamide compounds provided by the invention can well enhance the stress resistance of plants, and particularly, the sulfonamide compounds have plant root growth inhibitory activity, and the effect of most of the root growth inhibitory activity is obviously better than that of natural product ABA.
In addition, the plants of the present invention were tested for superior drought and cold tolerance. Moreover, it can be seen from the ITC test results that the specific binding ability of the sulfonamide compound of the present invention to the protein associated with plant stress resistance is significantly higher than that of the natural product ABA, thereby demonstrating that the compound of the present invention can have a significant effect in enhancing plant stress resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (6)

1. The application of the sulfonamide compound shown in the formula (1) in enhancing the stress resistance of plants, wherein the stress resistance of the plants is at least one of cold resistance, drought resistance, heat resistance and saline-alkali resistance,
Figure FDA0002425132240000011
wherein, in formula (1), W is N or
Figure FDA0002425132240000012
The sulfonamide compound is at least one of the following compounds:
compound 4: r1Is CH3；R2、R3、R5、R7、R8、R9And R10Are all H; r4Is NO2；R6Is Br; w is C;
compound 7: r1Is Br; r2、R3、R5、R7、R8、R9And R10Are all H; r4Is NO2；R6Is Br; w is C;
compound 9: r1Is NO2；R2、R3、R5、R7、R8、R9And R10Are all H; r4Is NO2；R6Is Br; w is C;
compound 29: r1Is Br; r4Is NO2；R6Is CH3；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
chemical combinationSubstance 34: r1Is Br; r4Is NO2；R6Is Cl; r2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 54: r1Is Br; r4Is NO2；R6Is CF3；R2、R3、R5、R7、R8、R9、R10Are all H; w is C;
compound 56: r1Is Br; r4And R7Is NO2；R6Is Cl; r2、R3、R5、R8、R9、R10Are all H; w is C.
2. The use of claim 1, wherein the plant stress resistance is selected from at least one of cold tolerance, drought tolerance and heat tolerance.
3. A medicament for enhancing plant stress resistance, which is characterized in that the active ingredient of the medicament is at least one sulfonamide compound shown in a formula (1), the content of the active ingredient is 0.1-100 wt% based on the total weight of the medicament,
Figure FDA0002425132240000021
wherein R is1-R10And W is as defined in claim 1.
4. The medicament according to claim 3, wherein the content of the active ingredient is 1-98% by weight.
5. The medicament according to claim 3, wherein the content of the active ingredient is 5-90% by weight.
6. The medicament of any one of claims 3 to 5, wherein the medicament is in a dosage form selected from the group consisting of a hydrating agent, a powder, an emulsion, a suspension, and granules.
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