CN110003077B - Butyrylphenylhydrazine compound containing pyrrolidine dione and aniline groups, and preparation method and application thereof - Google Patents
Butyrylphenylhydrazine compound containing pyrrolidine dione and aniline groups, and preparation method and application thereof Download PDFInfo
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- CN110003077B CN110003077B CN201810016951.6A CN201810016951A CN110003077B CN 110003077 B CN110003077 B CN 110003077B CN 201810016951 A CN201810016951 A CN 201810016951A CN 110003077 B CN110003077 B CN 110003077B
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- dioxopyrrolidin
- ylidene
- chlorophenyl
- butyrylhydrazine
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- -1 Butyrylphenylhydrazine compound Chemical class 0.000 title claims abstract description 100
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract description 30
- QFYXSLAAXZTRLG-UHFFFAOYSA-N pyrrolidine-2,3-dione Chemical compound O=C1CCNC1=O QFYXSLAAXZTRLG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- QWOSOZMDGKDUJJ-UHFFFAOYSA-N n-phenylbutanehydrazide Chemical class CCCC(=O)N(N)C1=CC=CC=C1 QWOSOZMDGKDUJJ-UHFFFAOYSA-N 0.000 claims description 15
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 12
- 241000209140 Triticum Species 0.000 claims description 11
- 235000021307 Triticum Nutrition 0.000 claims description 11
- 208000031888 Mycoses Diseases 0.000 claims description 10
- 240000007594 Oryza sativa Species 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 10
- 235000009566 rice Nutrition 0.000 claims description 10
- 206010039509 Scab Diseases 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 5
- 235000002566 Capsicum Nutrition 0.000 claims description 4
- 235000016623 Fragaria vesca Nutrition 0.000 claims description 4
- 240000009088 Fragaria x ananassa Species 0.000 claims description 4
- 235000011363 Fragaria x ananassa Nutrition 0.000 claims description 4
- 241000233866 Fungi Species 0.000 claims description 4
- 239000006002 Pepper Substances 0.000 claims description 4
- 235000016761 Piper aduncum Nutrition 0.000 claims description 4
- 235000017804 Piper guineense Nutrition 0.000 claims description 4
- 244000203593 Piper nigrum Species 0.000 claims description 4
- 235000008184 Piper nigrum Nutrition 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 241001361634 Rhizoctonia Species 0.000 claims description 3
- 201000010099 disease Diseases 0.000 claims description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 3
- 241000193738 Bacillus anthracis Species 0.000 claims description 2
- 241000223218 Fusarium Species 0.000 claims description 2
- 241001465180 Botrytis Species 0.000 claims 1
- 230000003032 phytopathogenic effect Effects 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 239000003899 bactericide agent Substances 0.000 abstract description 6
- 244000000004 fungal plant pathogen Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 46
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 12
- 241000123650 Botrytis cinerea Species 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical group 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 241000813090 Rhizoctonia solani Species 0.000 description 3
- 244000000005 bacterial plant pathogen Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940125890 compound Ia Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005887 Chromafenozide Substances 0.000 description 2
- 241000222199 Colletotrichum Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000223195 Fusarium graminearum Species 0.000 description 2
- 239000005917 Methoxyfenozide Substances 0.000 description 2
- IMHBYKMAHXWHRP-UHFFFAOYSA-N anilazine Chemical compound ClC1=CC=CC=C1NC1=NC(Cl)=NC(Cl)=N1 IMHBYKMAHXWHRP-UHFFFAOYSA-N 0.000 description 2
- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 2
- XXNOGQJZAOXWAQ-UHFFFAOYSA-N 4-chlorophenylhydrazine Chemical compound NNC1=CC=C(Cl)C=C1 XXNOGQJZAOXWAQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000002567 Capsicum annuum Nutrition 0.000 description 1
- 241001290235 Ceratobasidium cereale Species 0.000 description 1
- 241000222201 Colletotrichum capsici Species 0.000 description 1
- 241001529387 Colletotrichum gloeosporioides Species 0.000 description 1
- 241000222239 Colletotrichum truncatum Species 0.000 description 1
- 241001344131 Magnaporthe grisea Species 0.000 description 1
- 241000231139 Pyricularia Species 0.000 description 1
- 239000005828 Pyrimethanil Substances 0.000 description 1
- 241000208292 Solanaceae Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- FCCCRBDJBTVFSJ-UHFFFAOYSA-N butanehydrazide Chemical compound CCCC(=O)NN FCCCRBDJBTVFSJ-UHFFFAOYSA-N 0.000 description 1
- 239000001511 capsicum annuum Substances 0.000 description 1
- XSXCZNVKFKNLPR-SDQBBNPISA-N carbazochrome Chemical compound NC(=O)N/N=C/1C(=O)C=C2N(C)CC(O)C2=C\1 XSXCZNVKFKNLPR-SDQBBNPISA-N 0.000 description 1
- 229960002631 carbazochrome Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JFSPBVWPKOEZCB-UHFFFAOYSA-N fenfuram Chemical compound O1C=CC(C(=O)NC=2C=CC=CC=2)=C1C JFSPBVWPKOEZCB-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- CNKHSLKYRMDDNQ-UHFFFAOYSA-N halofenozide Chemical compound C=1C=CC=CC=1C(=O)N(C(C)(C)C)NC(=O)C1=CC=C(Cl)C=C1 CNKHSLKYRMDDNQ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the field of bactericides and discloses a butyrylphenylhydrazine compound containing pyrrolidine dione and aniline groups, a preparation method and application thereof, wherein the structure of the compound is shown as the formula (I):
Description
Technical Field
The invention relates to a butyrylphenylhydrazine compound containing pyrrolidine dione and aniline groups, a preparation method and application thereof in preventing and treating plant pathogenic fungi, and has application in preparing pesticide bactericides.
Background
Hydrazide compounds often show significant biological activity, and have wide application in the field of pesticides, for example, chromafenozide (chromafenozide), methoxyfenozide (methoxyfenozide), chlorfenozide (halofenozide) and the like are all pesticides containing hydrazide groups, and can effectively control agricultural pests. The aniline group is a common active group in the molecular structure of agricultural fungicides, such as pyrimethanil, furoyl aniline (fenfuram), and anilazine (anilazine). In addition, some compounds containing a pyrrolidine dione group can show remarkable bactericidal activity, such as different types of pyrrolidine dione compounds disclosed in the patents ZL201110453110.x and ZL201210524110.9, all have good activity of inhibiting plant pathogenic fungi.
According to the active group splicing principle, hydrazide, aniline and a pyrrolidine diketone group are introduced into the same molecular structure, a series of butyryl phenylhydrazine compounds containing pyrrolidine diketone and aniline groups with novel structures are designed and synthesized, and the compounds are found to have obvious inhibitory activity on plant pathogenic fungi through bactericidal activity determination.
Disclosure of Invention
The invention aims to provide a butyrylphenylhydrazine compound containing pyrrolidine diketone and aniline groups.
The invention also aims to provide a preparation method of the butyrylphenylhydrazine compounds containing the pyrrolidine diketone and the aniline groups.
Another object of the present invention is to provide the use of the above compounds.
The invention provides a butyrylphenylhydrazine compound containing pyrrolidine diketone and aniline groups and having a structure shown in a general formula (I),
in formula (I), the various groups have the definitions set forth below:
X(m)wherein m is a 1-5 substitution, X(m)Selected from the following 1-5 groups: x, R ', OR', NO2Wherein X represents halogen; r' represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens1-6An alkyl group; r' represents hydrogen, C unsubstituted or substituted by 1-6 halogen1-6An alkyl group;
Y(n)wherein n is a 1-5 substitution, Y(n)Selected from the following 1-5 groups: x, R ', OR', NO2Wherein X represents halogen; r' represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens1-6An alkyl group; r' represents hydrogen, C unsubstituted or substituted by 1-6 halogen1-6An alkyl group.
In formula (I), the respective groups have the preferred definitions as described below:
X(m)wherein m is a 1-3 substitution, X(m)Selected from the following 1-3 groups: x, R', OR ", wherein X represents halogen; r' represents hydrogen, C unsubstituted or substituted by 1 to 3 halogens1-3An alkyl group; r' represents C unsubstituted or substituted by 1-3 halogen1-3An alkyl group;
Y(n)wherein n is a 1-3 substitution, Y(n)Selected from the following 1-3 groups: x, R', OR ", wherein X represents halogen; r' represents hydrogen, C unsubstituted or substituted by 1 to 3 halogens1-3An alkyl group; r' represents C unsubstituted or substituted by 1-3 halogen1-3An alkyl group.
In formula (I), the respective groups have further preferred definitions as described below:
X(m)wherein m is a 1 substitution, X(m)Selected from the following 1 group: x, R', OR ", wherein X represents halogen; r' represents hydrogen, methyl unsubstituted or substituted by 1 to 3 halogens; r' represents methyl unsubstituted or substituted by 1-3 halogen;
Y(n)wherein n is a 1-2 substitution, Y(n)Selected from the following 1-2 groups: x, R', OR ", wherein X represents halogen; r' represents hydrogen or methyl; r' represents a methyl group.
In formula (I), the various groups have the further preferred definitions as described below:
X(m)selected from the following groups: H. 4-F, 2-Cl, 3-Cl, 4-Br, 2-CH3、3-CH3、4-CH3、3-OCH3、3-CF3、3-OCF3；
Y(n)Selected from the following groups: H. 2-F, 4-F, 2-Cl, 3-Cl, 4-Br, 2, 4-Cl2、4-CH3、3，4-(CH3)2、4-OCH3。
In formula (I), the individual radicals have the particularly preferred definitions indicated below:
n' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine (Ia),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((4-fluorophenyl) amino) butyryl hydrazine (Ib),
N' - (4-chlorophenyl) -4- ((2-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Ic),
N' - (4-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Id),
N' - (4-chlorophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Ie),
4- ((4-bromophenyl) amino) -N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (If),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((o-tolyl) amino) butyrylhydrazine (Ig),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((m-tolyl) amino) butyryl hydrazine (Ih),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((p-tolyl) amino) butyryl hydrazine (Ii),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3-methoxyphenyl) amino) butyryl hydrazine (Ij),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethyl) phenyl) amino) butyryl hydrazine (Ik),
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethoxy) phenyl) amino) butyryl hydrazine (Il),
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' -phenyl-4- (phenylamino) butyryl-hydrazine (Im),
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (2-fluorophenyl) -4- (phenylamino) butyryl hydrazine (In),
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-fluorophenyl) -4- (phenylamino) butyryl hydrazine (Io),
N' - (2-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl-hydrazine (Ip),
N' - (3-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl-hydrazine (Iq),
N' - (4-bromophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl hydrazine (Ir),
N' - (2, 4-dichlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl hydrazine (Is),
4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) -N' - (p-tolyl) butyrylhydrazine (It),
N' - (3, 4-dimethylphenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl-hydrazine (Iu),
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-methoxyphenyl) -4- (phenylamino) butyrylhydrazine (Iv),
N' - (2-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Iw),
N' - (4-bromophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Ix).
In a second aspect of the present invention, there is provided a method for preparing a pyrrolidinedione and aniline group-containing butyrylphenylhydrazine compound of formula (I), which comprises reacting a compound of formula (II) with a substituted phenylhydrazine of formula (III) to prepare a pyrrolidinedione and aniline group-containing butyrylphenylhydrazine compound of formula (I), wherein the reaction equation is represented by the following general formula (a):
wherein in each of the above structural formulae:
X(m)、Y(n)all have the definitions of the corresponding groups as described above.
The third aspect of the invention relates to the application of the butyrylphenylhydrazine compounds containing the pyrrolidine dione and aniline groups in the formula (I) in the aspect of preventing and treating plant pathogenic fungi, and the butyrylphenylhydrazine compounds can be applied to the field of pesticides and can be used as bactericides.
The pyrrolidinedione and aniline group-containing butyrophenohydrazines of the formula (I) according to the invention can be used in plant protection for controlling fungal diseases in crops caused by the following pathogenic bacteria, but it should not be considered as limiting the invention in any way:
preventing and treating fungal diseases of wheat crops:
fusarium species, such as Fusarium graminearum, cause scab in wheat;
rhizoctonia species, such as Rhizoctonia cerealis, cause sheath blight of wheat;
preventing and treating rice crop fungal diseases:
pyricularia species, such as Pyricularia grisea, cause rice blast;
rhizoctonia species, such as Rhizoctonia solani, cause rice sheath blight;
preventing and treating fungal diseases of fruit crops:
botrytis cinerea, such as Botrytis cinerea, causes gray mold of strawberry and gray mold of grape;
preventing and treating fungal diseases of vegetable crops:
botrytis cinerea, such as Botrytis cinerea, causes gray mold of vegetables of Solanaceae, such as gray mold of Capsicum annuum, gray mold of eggplant;
anthrax, such as Colletotrichum capsici, causes anthracnose of capsicum.
The compound of the invention is particularly suitable for preventing and treating fungal diseases of wheat crops, such as wheat scab; preventing and treating fungal diseases of vegetable crops, such as pepper anthracnose; preventing and treating fungal diseases of rice crops, such as rice sheath blight; preventing and treating fungal diseases of fruit crops, such as strawberry gray mold.
Has the advantages that:
1. the butyrophenohydrazide compound containing pyrrolidine dione and aniline groups in the formula (I) has a novel molecular structure, the structural formula contains a butyrophenohydrazide main chain, a substituted phenyl group is connected to N' of a hydrazine group, and two groups of substituted aniline and pyrrolidine dione are simultaneously connected to a C atom at the 4-position.
2. The preparation method of the butyrylphenylhydrazine compound containing the pyrrolidine dione and aniline groups disclosed by the invention is simple and convenient, and has the advantages of readily available raw materials and high yield.
3. The butyrylphenylhydrazine compound containing the pyrrolidine dione and the aniline group in the formula (I) shows remarkable activity of inhibiting plant pathogenic fungi, can be applied to crop diseases caused by the fungi, and has the application as a pesticide bactericide.
Detailed Description
The essential features of the invention can be seen from the following examples, which should not be construed as limiting the invention in any way.
Preparation examples
Example 1: preparation of butyrylphenylhydrazine compound Ia containing pyrrolidinedione and aniline groups
Adding 10mL of ethanol, 1mmol of intermediate IIa and 1mmol of 4-chlorophenylhydrazine (IIIa) into a 50mL three-necked flask, stirring, reacting at room temperature, monitoring the reaction process by TLC, after about 30min, precipitating a solid, performing suction filtration, washing with ethanol, and drying to obtain the butyrylhydrazine compound Ia containing the pyrrolidine dione and aniline groups, wherein the reaction equation is as follows:
by the method of example 1, compounds Ia to Ix in butyrylphenylhydrazine compounds (I) containing a pyrrolidinedione group and an aniline group were prepared:
n' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine (Ia):
white powder, yield 87.8%; m.p.181.0 ℃, decomposing; IR (KBr, cm)-1)v：3347，3314，3269，3194，3039，2911，1678， 1667，1648，1544，1442，1336，1249，1090，818，751.1H NMR(400MHz，DMSO-dd)δ：E-isomer：11.62(s，1H，C＝CNH)，9.95(s，1H，PhNHNH)，8.53(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.49(s，1H， CH2NH)，7.29(dd，J＝12.4，5.3Hz，4H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)， 3.67(s，2H，CH2NH)，3.28-3.22(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s， 1H，C＝CNH)，9.93(s，1H，PhNHNH)，8.47(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.54(d，J＝7.8Hz， 2H，PhH)，7.29(dd，J＝12.4，5.3Hz，4H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H， PhH)，3.62(s，2H，CH2NH)，3.21-3.12(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)； EI-MS(m/z)398.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((4-fluorophenyl) amino) butyryl hydrazine (Ib):
white powder, yield 92.1%; m.p.266.2 ℃, decomposing; IR (KBr, cm)-1)v：3345，3313，3187，3076，2911，1679，1667， 1647，1548，1489，1222，1091，816，778.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H， C＝CNH)，10.01(s，1H，PhNHNH)，8.52(s，1H，PhNHNH)，7.55(dd，J＝9.0，5.0Hz，2H，PhH)，7.48(s，1H， CH2NH)，7.29(d，J＝8.8Hz，2H，PhH)，7.12(t，J＝8.9Hz，2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.67 (s，2H，CH2NH)，3.28-3.21(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s，1H，C＝CNH)，9.99(s，1H，PhNHNH)，8.46(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.55(dd，J＝9.0，5.0Hz， 2H，PhH)，7.29(d，J＝8.8Hz，2H，PhH)，7.12(t，J＝8.9Hz，2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.62 (s，2H，CH2NH)，3.21-3.12(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)； EI-MS(m/z)416.1[M]+.
N' - (4-chlorophenyl) -4- ((2-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyryl hydrazine (Ic):
white powder, yield 80.5%; m.p.172.4-173.4 ℃; IR (KBr, cm)-1)v：3322，3267，3181，3032，2917，1650，1580，1437，1246，1091，824，745.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H，C＝CNH)，9.52(s， 1H，PhNHNH)，8.53(s，1H，PhNHNH)，7.67(d，J＝6.8Hz，1H，PhH)，7.51-7.44(m，1H，PhH and CH2NH)，7.30(t，J＝7.4Hz，3H，PhH)，7.17(t，J＝7.7Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.68 (s，2H，CH2NH)，3.29-3.22(m，2H，C＝CCH2)，2.72-2.58(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s，1H， C＝CNH)，9.52(s，1H，PhNHNH)，8.47(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.67(d，J＝6.8Hz，1H， PhH)，7.51-7.44(m，1H，PhH)，7.30(t，J＝7.4Hz，3H，PhH)，7.17(t，J＝7.7Hz，1H，PhH)，6.77(d，J＝ 8.8Hz，2H，PhH)，3.63(s，2H，CH2NH)，3.22-3.12(m，2H，C＝CCH2)，2.72-2.58(m，2H，C＝CCH2CH2)； EI-MS(m/z)432.1[M]+.
N' - (4-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Id):
white powder, yield 85.0%; m.p.244.5-246.3 ℃; IR (KBr, cm)-1)v：3330，3185，3076，2903，1667，1645，1534， 1423，1250，1197，1089，820，774.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H，C＝CNH)， 10.15(s，1H，PhNHNH)，8.51(s，1H，PhNHNH)，7.79-7.73(m，1H，PhH)，7.49(s，1H，CH2NH)，7.39(d，J ＝8.1Hz，1H，PhH)，7.34-7.26(m，3H，PhH)，7.08(dd，J＝7.9，1.1Hz，1H，PhH)，6.77(d，J＝8.9Hz，2H， PhH)，3.67(s，2H，CH2NH)，3.29-3.22(m，2H，C＝CCH2)，2.65-2.54(m，2H，C＝CCH2CH2)；Z-isomer： 11.46(s，1H，C＝CNH)，10.13(s，1H，PhNHNH)，8.46(s，1H，PhNHNH)，7.79-7.73(m，2H，PhH and CH2NH)，7.39(d，J＝8.1Hz，1H，PhH)，7.34-7.26(m，3H，PhH)，7.08(dd，J＝7.9，1.1Hz，1H，PhH)， 6.77(d，J＝8.9Hz，2H，PhH)，3.62(s，2H，CH2NH)，3.21-3.14(m，2H，C＝CCH2)，2.65-2.54(m，2H， C＝CCH2CH2)；EI-MS(m/z)432.1[M]+.
N' - (4-chlorophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyryl hydrazine (Ie):
white powder, yield 96.2%; m.p.273.8-275.2 deg.C, decomposing; IR (KBr, cm)-1)v：3345，3309，3192，3072，2906，1679， 1669，1647，1538，1489，1335，1247，1091，816，775.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s， 1H，C＝CNH)，10.10(s，1H，PhNHNH)，8.52(s，1H，PhNHNH)，7.57(d，J＝8.8Hz，2H，PhH)，7.49(s，1H， CH2NH)，7.33(d，J＝8.9Hz，2H，PhH)，7.29(d，J＝8.8Hz，2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.67 (s，2H，CH2NH)，3.29-3.21(m，2H，C＝CCH2)，2.65-2.54(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s，1H， C＝CNH)，10.08(s，1H，PhNHNH)，8.46(s，1H，PhNHNH)，7.77(s，1H，CH2NH)，7.57(d，J＝8.8Hz，2H， PhH)，7.33(d，J＝8.9Hz，2H，PhH)，7.29(d，J＝8.8Hz，2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.62(s， 2H，CH2NH)，3.21-3.12(m，2H，C＝CCH2)，2.65-2.54(m，2H，C＝CCH2CH2)；EI-MS(m/z)432.1[M]+.
4- ((4-bromophenyl) amino) -N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (If):
white powder, yield 93.2%; m.p.278.9 ℃, decomposing; IR (KBr, cm)-1)v：3343，3307，3191，3067，2905，1669，1647， 1537，1487，1335，1246，1092，815，776.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H，C＝CNH)，10.09(s，1H，PhNHNH)，8.51(s，1H，PhNHNH)，7.52(d，J＝9.0Hz，2H，PhH)，7.49(s，1H， CH2NH)，7.46(d，J＝8.9Hz，2H，PhH)，7.28(d，J＝8.8Hz，2H，PhH)，6.76(d，J＝8.8Hz，2H，PhH)，3.67 (s，2H，CH2NH)，3.28-3.21(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；Z-isomer：11.45(s，1H， C＝CNH)，10.08(s，1H，PhNHNH)，8.46(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.52(d，J＝9.0Hz，2H， PhH)，7.46(d，J＝8.9Hz，2H，PhH)，7.28(d，J＝8.8Hz，2H，PhH)，6.76(d，J＝8.8Hz，2H，PhH)，3.61(s， 2H，CH2NH)，3.21-3.12(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；EI-MS(m/z)476.0[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((o-tolyl) amino) butyrylhydrazine (Ig):
white powder, yield 76.3%; m.p.239.9-242.2 ℃, decomposing; IR (KBr, cm)-1)v：3254，3190，3035，2906，1683，1663， 1644，1604，1571，1530，1489，1454，1292，1059，745.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.63 (s，1H，C＝CNH)，9.30(s，1H，PhNHNH)，8.54(s，1H，PhNHNH)，7.49(s，1H，CH2NH)，7.38(t，J＝7.5Hz， 1H，PhH)，7.29(d，J＝8.7Hz，2H，PhH)，7.19(d，J＝7.5Hz，1H，PhH)，7.13(t，J＝7.1Hz，1H，PhH)，7.06 (t，J＝6.9Hz，1H，PhH)，6.78(d，J＝8.7Hz，2H，PhH)，3.68(s，2H，CH2NH)，3.30-3.22(m，2H， C＝CCH2)，2.68-2.54(m，2H，C＝CCH2CH2)，2.16(s，3H，CH3)；Z-isomer：11.47(s，1H，C＝CNH)，9.29(s， 1H，PhNHNH)，8.48(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.38(t，J＝7.5Hz，1H，PhH)，7.29(d，J＝ 8.7Hz，2H，PhH)，7.19(d，J＝7.5Hz，1H，PhH)，7.13(t，J＝7.1Hz，1H，PhH)，7.06(t，J＝6.9Hz，1H， PhH)，6.78(d，J＝8.7Hz，2H，PhH)，3.63(s，2H，CH2NH)，3.22-3.12(m，2H，C＝CCH2)，2.68-2.54(m， 2H，C＝CCH2CH2)，2.16(s，3H，CH3)；EI-MS(m/z)412.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((m-tolyl) amino) butyryl hydrazine (Ih):
white powder, yield 94.6%; m.p.192.3 ℃, decomposing; IR (KBr, cm)-1)v：3345，3297，3185，3036，2918，1680，1647，1546，1440，1334，1249，1090，819，775.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H， C＝CNH)，9.87(s，1H，PhNHNH)，8.52(s，1H，PhNHNH)，7.49(s，1H，CH2NH)，7.37(s，1H，PhH)，7.30(t， J＝10.1Hz，3H，PhH)，7.15(t，J＝7.8Hz，1H，PhH)，6.84(d，J＝7.5Hz，1H，PhH)，6.77(d，J＝8.8Hz， 2H，PhH)，3.67(s，2H，CH2NH)，3.27-3.21(m，2H，C＝CCH2)，2.63-2.53(m，2H，C＝CCH2CH2)，2.25(s， 3H，CH3)；Z-isomer：11.46(s，1H，C＝CNH)，9.85(s，1H，PhNHNH)，8.47(s，1H，PhNHNH)，7.76(s，1H， CH2NH)，7.37(s，1H，PhH)，7.30(t，J＝10.1Hz，3H，PhH)，7.15(t，J＝7.8Hz，1H，PhH)，6.84(d，J＝7.5 Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.62(s，2H，CH2NH)，3.20-3.12(m，2H，C＝CCH2)，2.63- 2.53(m，2H，C＝CCH2CH2)，2.25(s，3H，CH3)；EI-MS(m/z)412.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((p-tolyl) amino) butyryl hydrazine (Ii):
white powder, yield 95.0%; m.p.248.8 ℃, decomposing; IR (KBr, cm)-1)v：3346，3303，3195，3042，2914，1679，1665， 1651，1560，1490，1335，1248，1141，1091，813，777.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s， 1H，C＝CNH)，9.86(s，1H，PhNHNH)，8.52(s，1H，PhNHNH)，7.48(s，1H，CH2NH)，7.42(d，J＝8.3Hz， 2H，PhH)，7.29(d，J＝8.8Hz，2H，PhH)，7.08(d，J＝8.3Hz，2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.67 (s，2H，CH2NH)，3.26-3.21(m，2H，C＝CCH2)，2.61-2.52(m，2H，C＝CCH2CH2)，2.23(s，3H，CH3)；Z-isomer：11.45(s，1H，C＝CNH)，9.84(s，1H，PhNHNH)，8.47(s，1H，PhNHNH)，7.76(s，1H，CH2NH)， 7.42(d，J＝8.3Hz，2H，PhH)，7.29(d，J＝8.8Hz，2H，PhH)，7.08(d，J＝8.3Hz，2H，PhH)，6.77(d，J＝8.8 Hz，2H，PhH)，3.61(s，2H，CH2NH)，3.19-3.12(m，2H，C＝CCH2)，2.61-2.52(m，2H，C＝CCH2CH2)，2.23 (s，3H，CH3)；EI-MS(m/z)412.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3-methoxyphenyl) amino) butyryl hydrazine (Ij):
white powder, yield 84.4%; m.p.166.0-166.9 ℃; IR (KBr, cm)-1)v：3344，3306，3190，3093，2900，1679，1648， 1549，1456，1334，1230，1156，1045，818，777.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H， C＝CNH)，9.94(s，1H，PhNHNH)，8.52(s，1H，PhNHNH)，7.49(s，1H，CH2NH)，7.29(d，J＝8.8Hz，2H， PhH)，7.25(s，1H，PhH)，7.18(t，J＝8.1Hz，1H，PhH)，7.06(d，J＝8.2Hz，1H，PhH)，6.77(d，J＝8.8Hz， 2H，PhH)，6.61(dd，J＝8.0，2.1Hz，1H，PhH)，3.71(s，3H，OCH3)，3.67(s，2H，CH2NH)，3.27-3.20(m， 2H，C＝CCH2)，2.63-2.53(m，2H，C＝CCH2CH2)；Z-isomer：11.45(s，1H，C＝CNH)，9.92(s，1H， PhNHNH)，8.46(s，1H，PhNHNH)，7.76(s，1H，CH2NH)，7.29(d，J＝8.8Hz，2H，PhH)，7.25(s，1H，PhH)， 7.18(t，J＝8.1Hz，1H，PhH)，7.06(d，J＝8.2Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，6.61(dd，J＝ 8.0，2.1Hz，1H，PhH)，3.71(s，3H，OCH3)，3.62(s，2H，CH2NH)，3.19-3.12(m，2H，C＝CCH2)，2.63-2.53 (m，2H，C＝CCH2CH2)；EI-MS(m/z)428.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethyl) phenyl) amino) butyryl hydrazine (Ik):
white powder, yield 55.6%; m.p.180.6 ℃, decomposing; IR (KBr, cm)-1)v：3342，3296，3186，3032，2903，1679，1667， 1647，1556，1445，1331，1248，1117，823，792.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H， C＝CNH)，10.38(s，1H，PhNHNH)，8.60(s，1H，PhNHNH)，7.74(d，J＝8.1Hz，1H，PhH)，7.58-7.47(m， 2H，PhH)，7.37(d，J＝7.7Hz，2H，PhH and CH2NH)，7.27(d，J＝8.7Hz，2H，PhH)，6.77(d，J＝8.8Hz， 2H，PhH)，3.67(s，2H，CH2NH)，3.31-3.23(m，2H，C＝CCH2)，2.68-2.58(m，2H，C＝CCH2CH2)； Z-isomer：11.46(s，1H，C＝CNH)，10.37(s，1H，PhNHNH)，8.55(s，1H，PhNHNH)，7.77(s，1H，CH2NH)， 7.74(d，J＝8.1Hz，1H，PhH)，7.58-7.47(m，2H，PhH)，7.37(d，J＝7.7Hz，1H，PhH)，7.27(d，J＝8.7Hz， 2H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.62(s，2H，CH2NH)，3.23-3.15(m，2H，C＝CCH2)，2.68-2.58 (m，2H，C＝CCH2CH2)；EI-MS(m/z)466.1[M]+.
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethoxy) phenyl) amino) butyryl hydrazine (Il):
white powder, yield 61.0%, m.p.175.4 deg.C; IR (KBr, cm)-1)v：3343，3283，3196，3031，2903，1680， 1668，1648，1547，1441，1371，1272，1092，822，782.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s， 1H，C＝CNH)，10.26(s，1H，C＝CNH)，8.52(s，1H，PhNHNH)，7.73(s，1H，PhH)，7.47-7.39(m，2H，PhH)， 7.28(d，J＝8.8Hz，2H，PhH)，7.01(d，J＝7.0Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.68(s，2H， CH2NH)，3.30-3.23(m，2H，C＝CCH2)，2.66-2.55(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s，1H， C＝CNH)，10.24(s，1H，C＝CNH)，8.46(s，1H，PhNHNH)，7.73(s，1H，PhH)，7.47-7.39(m，2H，PhH)， 7.28(d，J＝8.8Hz，2H，PhH)，7.01(d，J＝7.0Hz，1H，PhH)，6.77(d，J＝8.8Hz，2H，PhH)，3.62(s，2H， CH2NH)，3.23-3.15(m，2H，C＝CCH2)，2.66-2.55(m，2H，C＝CCH2CH2)；EI-MS(m/z)482.1[M]+.
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' -phenyl-4- (phenylamino) butyryl-hydrazine (Im):
white powderThe yield is 94.8%; m.p.189.6-191.3 deg.C, decomposing; IR (KBr, cm)-1)v：3373，3255，3199，3085，2911，1681， 1660，1633，1555，1440，1234，1085，915，788.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.68(s，1H， C＝CNH)，9.96(s，1H，PhNHNH)，8.39(s，1H，PhNHNH)，7.55(d，J＝7.8Hz，2H，PhH)，7.47(s，1H， CH2NH)，7.27(dd，J＝15.5，7.3Hz，4H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.89(t，J＝7.3Hz，1H，PhH)， 6.77(d，J＝7.8Hz，2H，PhH)，3.68(s，2H，CH2NH)，3.31-3.23(m，2H，C＝CCH2)，2.67-2.55(m，2H， C＝CCH2CH2)；Z-isomer：11.49(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.34(s，1H，PhNHNH)，7.74(s， 1H，CH2NH)，7.55(d，J＝7.8Hz，2H，PhH)，7.27(dd，J＝15.5，7.3Hz，4H，PhH)，7.02(t，J＝7.4Hz，1H， PhH)，6.89(t，J＝7.3Hz，1H，PhH)，6.77(d，J＝7.8Hz，2H，PhH)，3.62(s，2H，CH2NH)，3.23-3.14(m， 2H，C＝CCH2)，2.67-2.55(m，2H，C＝CCH2CH2)；EI-MS(m/z)364.2[M]+.
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (2-fluorophenyl) -4- (phenylamino) butyryl hydrazine (In):
white powder, yield 91.1%; m.p.209.0-210.2 deg.C, decomposing; IR (KBr, cm)-1)v：3348，3309，3188，3034，2900，1681， 1668，1649，1597，1549，1444，1253，1092，843，784.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s， 1H，C＝CNH)，9.96(s，1H，PhNHNH)，8.44(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.49(s，1H， CH2NH)，7.28(t，J＝7.9Hz，2H，PhH)，7.19(dd，J＝11.9，8.2Hz，1H，PhH)，7.11(t，J＝7.7Hz，1H，PhH)， 7.02(t，J＝7.4Hz，1H，PhH)，6.90(dd，J＝12.6，7.7Hz，1H，PhH)，6.82(t，J＝8.4Hz，1H，PhH)，3.68(s， 2H，CH2NH)，3.30-3.23(m，2H，C＝CCH2)，2.69-2.57(m，2H，C＝CCH2CH2)；Z-isomer：11.46(s，1H， C＝CNH)，9.95(s，1H，PhNHNH)，8.40(s，1H，PhNHNH)，7.77(s，1H，CH2NH)，7.54(d，J＝7.8Hz，2H， PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.19(dd，J＝11.9，8.2Hz，1H，PhH)，7.11(t，J＝7.7Hz，1H，PhH)， 7.02(t，J＝7.4Hz，1H，PhH)，6.90(dd，J＝12.6，7.7Hz，1H，PhH)，6.82(t，J＝8.4Hz，1H，PhH)，3.63(s， 2H，CH2NH)，3.23-3.14(m，2H，C＝CCH2)，2.69-2.57(m，2H，C＝CCH2CH2)；EI-MS(m/z)382.1[M]+.
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-fluorophenyl) -4- (phenylamino) butyryl hydrazine (Io):
white powder, yield 78.4%; m.p.182.8-184.9 ℃; IR (KBr, cm)-1)v：3346，3313，3272，3185，3037，2914，1679， 1667，1650，1544，1447，1226，1095，823，778.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.65(s，1H， C＝CNH)，9.96(s，1H，PhNHNH)，8.34(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.47(s，1H， CH2NH)，7.28(t，J＝7.9Hz，2H，PhH)，7.10(t，J＝8.8Hz，2H，PhH)，7.02(t，J＝7.3Hz，1H，PhH)，6.83- 6.74(m，2H，PhH)，3.67(s，2H，CH2NH)，3.30-3.24(m，2H，C＝CCH2)，2.65-2.54(m，2H，C＝CCH2CH2)； Z-isomer：11.47(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.29(s，1H，PhNHNH)，7.74(s，1H，CH2NH)， 7.54(d，J＝7.8Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.10(t，J＝8.8Hz，2H，PhH)，7.02(t，J＝7.3 Hz，1H，PhH)，6.83-6.74(m，2H，PhH)，3.61(s，2H，CH2NH)，3.23-3.15(m，2H，C＝CCH2)，2.65-2.54 (m，2H，C＝CCH2CH2)；EI-MS(m/z)382.1[M]+.
N' - (2-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl-hydrazine (Ip):
white powder, yield 95.3%; decomposing at m.p.226.3 ℃; IR (KBr, cm)-1)v：3335，3261，3187，3034，2909，1683，1667， 1644，1545，1443，1300，1155，1035，784.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.67(s，1H， C＝CNH)，9.97(s，1H，PhNHNH)，8.32(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.51(s，1H， CH2NH)，7.39(dd，J＝7.9，1.2Hz，1H，PhH)，7.32-7.23(m，3H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.95 -6.87(m，1H，PhH)，6.82-6.76(m，1H，PhH)，3.69(s，2H，CH2NH)，3.26-3.19(m，2H，C＝CCH2)，2.71- 2.59(m，2H，C＝CCH2CH2)；Z-isomer：11.52(s，1H，C＝CNH)，9.96(s，1H，PhNHNH)，8.29(s，1H， PhNHNH)，7.79(s，1H，CH2NH)，7.54(d，J＝7.8Hz，2H，PhH)，7.39(dd，J＝7.9，1.2Hz，1H，PhH)，7.32- 7.23(m，3H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.95-6.87(m，1H，PhH)，6.82-6.76(m，1H，PhH)，3.64 (s，2H，CH2NH)，3.18-3.10(m，2H，C＝CCH2)，2.71-2.59(m，2H，C＝CCH2CH2)；EI-MS(m/z)398.1 [M]+.
N' - (3-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl-hydrazine (Iq):
white powder, yield 92.5%; m.p.211.2 ℃, decomposing; IR (KBr, cm)-1)v：3342，3295，3192，3036，2903，1679，1665， 1645，1546，1442，1251，1094，863，776.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.61(s，1H， C＝CNH)，9.96(s，1H，PhNHNH)，8.62(s，1H，PhNHNH)，7.54(d，J＝7.7Hz，2H，PhH)，7.50(s，1H， CH2NH)，7.33-7.21(m，3H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.93-6.87(m，1H，PhH)，6.76(s，1H， PhH)，6.72(d，J＝8.2Hz，1H，PhH)，3.68(s，2H，CH2NH)，3.28-3.21(m，2H，C＝CCH2)，2.65-2.54(m， 2H，C＝CCH2CH2)；Z-isomer：11.45(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.57(s，1H，PhNHNH)，7.77 (s，1H，CH2NH)，7.54(d，J＝7.7Hz，2H，PhH)，7.33-7.21(m，3H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)， 6.93-6.87(m，1H，PhH)，6.76(s，1H，PhH)，6.72(d，J＝8.2Hz，1H，PhH)，3.62(s，2H，CH2NH)，3.21- 3.12(m，2H，C＝CCH2)，2.65-2.54(m，2H，C＝CCH2CH2)；EI-MS(m/z)398.1[M]+.
N' - (4-bromophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl hydrazine (Ir):
white powder, yield 91.1%; m.p.200.4 ℃, decomposing; IR (KBr, cm)-1)v：3345，3301，3181，3034，2903，1681，1647， 1544，1442，1368，1072，817，752.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.61(s，1H，C＝CNH)， 9.95(s，1H，PhNHNH)，8.54(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.49(s，1H，CH2NH)，7.41 (d，J＝8.8Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.02(t，J＝7.3Hz，1H，PhH)，6.72(d，J＝8.8Hz， 2H，PhH)，3.67(s，2H，CH2NH)，3.28-3.20(m，2H，C＝CCH2)，2.63-2.53(m，2H，C＝CCH2CH2)； Z-isomer：11.45(s，1H，C＝CNH)，9.93(s，1H，PhNHNH)，8.48(s，1H，PhNHNH)，7.77(s，1H，CH2NH)， 7.54(d，J＝7.8Hz，2H，PhH)，7.41(d，J＝8.8Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.02(t，J＝7.3 Hz，1H，PhH)，6.72(d，J＝8.8Hz，2H，PhH)，3.62(s，2H，CH2NH)，3.20-3.12(m，2H，C＝CCH2)，2.63- 2.53(m，2H，C＝CCH2CH2)；EI-MS(m/z)442.1[M]+.
N' - (2, 4-dichlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl hydrazine (Is):
white powder, yield 95.5%; m.p.230.0 ℃, decomposing; IR (KBr, cm)-1)v：3339，3303，3196，3036，2904，1668，1645， 1547，1443，1252，1049，852，750.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.62(s，1H，C＝CNH)， 9.95(s，1H，PhNHNH)，8.43(s，1H，PhNHNH)，7.53(dd，J＝5.0，2.5Hz，4H，PhH and CH2NH)，7.34- 7.22(m，3H，PhH)，7.02(t，J＝7.3Hz，1H，PhH)，6.79(dd，J＝8.8，3.6Hz，1H，PhH)，3.68(s，2H，CH2NH)， 3.25-3.17(m，2H，C＝CCH2)，2.69-2.57(m，2H，C＝CCH2CH2)；Z-isomer：11.49(s，1H，C＝CNH)，9.94(s， 1H，PhNHNH)，8.40(s，1H，PhNHNH)，7.80(s，1H，CH2NH)，7.53(dd，J＝5.0，2.5Hz，3H，PhH)，7.34- 7.22(m，3H，PhH)，7.02(t，J＝7.3Hz，1H，PhH)，6.79(dd，J＝8.8，3.6Hz，1H，PhH)，3.63(s，2H，CH2NH)， 3.16-3.08(m，2H，C＝CCH2)，2.69-2.57(m，2H，C＝CCH2CH2)；EI-MS(m/z)432.1[M]+.
4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) -N' - (p-tolyl) butyrylhydrazine (It):
white powder, yield 95.9%; m.p.196.1-197.1 ℃; IR (KBr, cm)-1)v：3340，3320，3194，3022，2917，1673，1646，1543，1441，1335，1248，1031，810，749.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.67(s，1H， C＝CNH)，9.95(s，1H，PhNHNH)，8.24(s，1H，PhNHNH)，7.54(d，J＝7.8Hz，2H，PhH)，7.45(s，1H， CH2NH)，7.28(t，J＝7.9Hz，2H，PhH)，7.07(d，J＝8.2Hz，2H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.68 (d，J＝8.3Hz，2H，PhH)，3.67(s，2H，CH2NH)，3.29-3.23(m，2H，C＝CCH2)，2.65-2.53(m，2H， C＝CCH2CH2)，2.21(s，3H，CH3)；Z-isomer：11.47(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.18(s，1H， PhNHNH)，7.72(s，1H，CH2NH)，7.54(d，J＝7.8Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.07(d，J＝8.2Hz，2H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.68(d，J＝8.3Hz，2H，PhH)，3.61(s，2H，CH2NH)，3.22 -3.14(m，2H，C＝CCH2)，2.65-2.53(m，2H，C＝CCH2CH2)，2.21(s，3H，CH3)；EI-MS(m/z)378.2[M]+.
N' - (3, 4-dimethylphenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyryl hydrazine (Iu):
white powder, yield 97.2%; m.p.202.1-204.2 deg.C; IR (KBr, cm)-1)v：3335，3317，3190，3075，2966，1673，1647， 1544，1440，1335，1250，859，748.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.66(s，1H，C＝CNH)， 9.95(s，1H，PhNHNH)，8.17(s，1H，PhNHNH)，7.55(d，J＝7.8Hz，2H，PhH)，7.45(s，1H，CH2NH)，7.28 (t，J＝7.9Hz，2H，PhH)，7.02(t，J＝8.1Hz，2H，PhH)，6.58(s，1H，PhH)，6.49(dd，J＝8.0，2.3Hz，1H， PhH)，3.67(s，2H，CH2NH)，3.30-3.23(m，2H，C＝CCH2)，2.66-2.54(m，2H，C＝CCH2CH2)，2.16(s，3H， CH3)，2.12(s，3H，CH3)；Z-isomer：11.46(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.11(s，1H，PhNHNH)， 7.72(s，1H，CH2NH)，7.55(d，J＝7.8Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.02(t，J＝8.1Hz，2H， PhH)，6.58(s，1H，PhH)，6.49(dd，J＝8.0，2.3Hz，1H，PhH)，3.61(s，2H，CH2NH)，3.23-3.15(m，2H， C＝CCH2)，2.66-2.54(m，2H，C＝CCH2CH2)，2.16(s，3H，CH3)，2.12(s，3H，CH3)；EI-MS(m/z)392.2 [M]+.
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-methoxyphenyl) -4- (phenylamino) butyrylhydrazine (Iv):
white powder, yield 92.0%; m.p.181.3-183.1 deg.C; IR (KBr, cm)-1)v：3343，3313，3199，3070，2911，1671，1647， 1544，1442，1240，1032，817，753.1H NMR(400MHz，DMSO-d6)δ：11.67(s，1H，C＝CNH)，9.96(s，1H， PhNHNH)，8.09(s，1H，PhNHNH)，7.55(d，J＝7.9Hz，2H，PhH)，7.44(s，1H，CH2NH)，7.28(t，J＝7.9Hz， 2H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.87(d，J＝8.9Hz，2H，PhH)，6.74(d，J＝8.9Hz，2H，PhH)，3.69 (s，3H，OCH3)，3.66(s，2H，CH2NH)，3.32-3.26(m，2H，C＝CCH2)，2.66-2.55(m，2H，C＝CCH2CH2)； 11.46(s，1H，C＝CNH)，9.94(s，1H，PhNHNH)，8.03(s，1H，PhNHNH)，7.71(s，1H，CH2NH)，7.55(d，J＝ 7.9Hz，2H，PhH)，7.28(t，J＝7.9Hz，2H，PhH)，7.02(t，J＝7.4Hz，1H，PhH)，6.87(d，J＝8.9Hz，2H，PhH)，6.74(d，J＝8.9Hz，2H，PhH)，3.69(s，3H，OCH3)，3.61(s，2H，CH2NH)，3.25-3.18(m，2H， C＝CCH2)，2.66-2.55(m，2H，C＝CCH2CH2)；EI-MS(m/z)394.2[M]+.
N' - (2-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyryl hydrazine (Iw):
white powder, yield 79.5%; m.p.213.3 ℃, decomposing; IR (KBr, cm)-1)v：3295，3255，3189，3074，2900，1685，1630， 1590，1477，1303，1239，1038，879，736.1H NMR(400MHz，DMSO-d6)δ：E-isomer：11.65(s，1H，C＝CNH)，10.17(s，1H，PhNHNH)，8.28(s，1H，PhNHNH)，7.75(s，1H，PhH)，7.52(s，1H，CH2NH)，7.39 (d，J＝7.8Hz，2H，PhH)，7.31(t，J＝8.1Hz，1H，PhH)，7.26(t，J＝7.8Hz，1H，PhH)，7.08(d，J＝7.9Hz， 1H，PhH)，6.91(t，J＝7.6Hz，1H，PhH)，6.79(d，J＝7.8Hz，1H，PhH)，3.69(s，2H，CH2NH)，3.24(t，J＝ 7.7Hz，2H，C＝CCH2)，2.71-2.59(m，2H，C＝CCH2CH2)；Z-isomer：11.51(s，1H，C＝CNH)，10.16(s，1H， PhNHNH)，8.25(s，1H，PhNHNH)，7.80(s，1H，CH2NH)，7.75(s，1H，PhH)，7.39(d，J＝7.8Hz，2H，PhH)， 7.31(t，J＝8.1Hz，1H，PhH)，7.26(t，J＝7.8Hz，1H，PhH)，7.08(d，J＝7.9Hz，1H，PhH)，6.91(t，J＝7.6 Hz，1H，PhH)，6.79(d，J＝7.8Hz，1H，PhH)，3.63(s，2H，CH2NH)，3.16(t，J＝7.8Hz，2H，C＝CCH2)，2.71 -2.59(m，2H，C＝CCH2CH2)；EI-MS(m/z)432.1[M]+.
N' - (4-bromophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine (Ix):
white powder, yield 95.4%; m.p.275.5 ℃, decomposing; IR (KBr, cm)-1)v：3340，3312，3192，3042，2906，1670， 1645，1596，1487，1299，1090，813，774.1H NMR(400MHz，DMSO-d6)δ(ppm)：E-isomer：11.61(s，1H， C＝CNH)，10.11(s，1H，PhNHNH)，8.54(s，1H，PhNHNH)，7.57(d，J＝8.8Hz，2H，PhH)，7.50(s，1H， CH2NH)，7.40(d，J＝8.7Hz，2H，PhH)，7.34(d，J＝8.8Hz，2H，PhH)，6.72(d，J＝8.7Hz，2H，PhH)，3.67 (s，2H，CH2NH)，3.28-3.20(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；Z-isomer：11.45(s，1H， C＝CNH)，10.09(s，1H，PhNHNH)，8.48(s，1H，PhNHNH)，7.78(s，1H，CH2NH)，7.57(d，J＝8.8Hz，2H， PhH)，7.40(d，J＝8.7Hz，2H，PhH)，7.34(d，J＝8.8Hz，2H，PhH)，6.72(d，J＝8.7Hz，2H，PhH)，3.62(s， 2H，CH2NH)，3.20-3.12(m，2H，C＝CCH2)，2.64-2.53(m，2H，C＝CCH2CH2)；EI-MS(m/z)476.0[M]+.
Examples of the use
Example 2: the butyrylphenylhydrazine compounds (I) containing the pyrrolidine dione and aniline groups have plant diseases
Measurement of fungicidal Activity of Proto fungus
The bactericidal activity of compounds Ia-Ix in butyrylphenylhydrazine compounds (I) containing pyrrolidine dione and aniline groups on 4 test plant pathogenic bacteria of wheat scab (Fusarium graminearum), Botrytis cinerea (Botrytis cinerea), Rhizoctonia solani (Rhizoctonia solani) and Colletotrichum capsulatum (Colletotrichum capsicii) at a concentration of 10 mu g/mL is measured by adopting a hypha growth rate method.
The determination method comprises the following steps: accurately weighing 4.5mg of the compound to be tested (including the control medicament Hydrazoxamine) and dissolving in 2.5mL of methanol, sucking 0.5mL of the methanol, adding into 89.5mL of sterilized PSA culture medium, shaking thoroughly to obtain a drug-containing culture medium with a concentration of 10 mug/mL, and pouring into a sterile culture dish with a diameter of 9 cm. The control was medium prepared by adding equal amount of solvent. Meanwhile, a culture medium prepared by adding the bactericide of hydralazinone and having the concentration of 50 mug/mL is used as a medicament control. The bacterial colony which grows normally is punched by a puncher (with the inner diameter of 0.5cm) to prepare bacterial cake, the bacterial cake is inoculated into the center of the culture medium plate by an inoculating needle, and the bacterial cake is inversely cultured in an incubator at 25 ℃. The diameter of the colonies on the control medium was measured as long as 2/3 on the plate, and the diameter of each colony was measured 2 times by the cross method, and the average value (unit: cm) was calculated. Triplicates were set for each concentration and for each of the three controls. And (3) calculating the growth inhibition rate after medicament treatment, wherein the calculation formula is as follows:
inhibition (%) - (solvent control colony diameter-treated colony diameter) ÷ (solvent control colony diameter-0.5) × 100%
The results of measuring the growth inhibition rate of the butyrylphenylhydrazine compounds (I) containing the pyrrolidinedione and aniline groups on 4 test plant pathogenic bacteria are shown in Table 1.
TABLE 1 inhibition ratio of butyrylphenylhydrazine type compound (I) containing pyrrolidinedione and anilino group against 4 plant pathogenic bacteria (10. mu.g/mL)
Table 1 shows that compounds Ia-Ix in butyrylphenylhydrazine compounds (I) containing pyrrolidine dione and aniline groups have significant inhibitory activity on 4 test plant pathogens of wheat scab, strawberry botrytis cinerea, rice sheath blight germ and pepper anthracnose pathogen at a concentration of 10 mu g/mL. The inhibition rate of each compound on the wheat scab germ is 21.2-99.2%, and the inhibition rate of most compounds is more than 80%, wherein the inhibition rates of the compounds Ia-Il, Io, Ir and Ix are more than 90%, and are superior to 74.1% of that of a contrast medicament, namely hydralazinone. The inhibition rate of each compound on botrytis cinerea is 35.6-83.4%, wherein the In and Ip of the compounds reach more than 80%, and the rest compounds are 60-80%. The inhibition rate of each compound on rice sheath blight bacteria is 58.6-100%, and the inhibition rate of most compounds is more than 90%, wherein the inhibition rates of the compounds Ij, In and Iw are up to 100%, and the inhibition rates are superior to 86.1% of that of carbazochrome. The inhibition rate of each compound on the pepper colletotrichum gloeosporioides is 47.3% -95.9%, and is superior to 38.33% of the inhibition rate of the compound on the hydrazinoketone, wherein the compound Ia, Ib, Id, Ig, Ii, Ij, In and Ix reach more than 90%.
Claims (6)
1. A butyrylphenylhydrazine compound containing pyrrolidine diketone and aniline groups and with a structure shown in a formula (I),
characterized in that it is one of the following compounds:
n' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((4-fluorophenyl) amino) butyryl hydrazine,
N' - (4-chlorophenyl) -4- ((2-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine,
N' - (4-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine,
N' - (4-chlorophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine,
4- ((4-bromophenyl) amino) -N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((o-tolyl) amino) butyrylhydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((m-tolyl) amino) butyrylhydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((p-tolyl) amino) butyrylhydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3-methoxyphenyl) amino) butanoyl hydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethyl) phenyl) amino) butyryl hydrazine,
N' - (4-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- ((3- (trifluoromethoxy) phenyl) amino) butyryl hydrazine,
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' -phenyl-4- (phenylamino) butyrylhydrazine,
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (2-fluorophenyl) -4- (phenylamino) butyryl-hydrazine,
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-fluorophenyl) -4- (phenylamino) butyryl-hydrazine,
N' - (2-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
N' - (3-chlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
N' - (4-bromophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
N' - (2, 4-dichlorophenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) -N' - (p-tolyl) butyrylhydrazine,
N' - (3, 4-dimethylphenyl) -4- (2, 4-dioxopyrrolidin-3-ylidene) -4- (phenylamino) butyrylhydrazine,
4- (2, 4-dioxopyrrolidin-3-ylidene) -N' - (4-methoxyphenyl) -4- (phenylamino) butyrylhydrazine,
N' - (2-chlorophenyl) -4- ((3-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine,
N' - (4-bromophenyl) -4- ((4-chlorophenyl) amino) -4- (2, 4-dioxopyrrolidin-3-ylidene) butyrylhydrazine.
2. A process for producing a butyrylphenylhydrazine compounds containing a pyrrolidinedione and an anilino group as described in claim 1, which comprises the steps of:
wherein in each of the above structural formulae:
X(m)、Y(n)all have the meaning as indicated in claim 1.
3. Use of a butyrophenohydrazide compound containing a pyrrolidinedione and aniline groups according to claim 1 for controlling phytopathogenic fungi.
4. The use according to claim 3, characterized in that the butyrylphenylhydrazine compounds containing pyrrolidinedione and anilino groups according to claim 1 are used for controlling fungal diseases in wheat crops, rice crops, fruit crops and vegetables.
5. The use according to claim 4, characterized in that the butyrylphenylhydrazine compounds containing pyrrolidinedione and anilino groups as claimed in claim 1 are used for controlling diseases in wheat crops caused by Fusarium fungi, rice crops caused by Rhizoctonia fungi, fruit crops caused by Botrytis fungi, vegetable crops caused by anthrax fungi.
6. The use of claim 5, wherein the butyrylphenylhydrazine compounds containing pyrrolidinone and aniline groups in claim 1 are used for preventing and treating wheat scab, strawberry gray mold, rice sheath blight and pepper anthracnose.
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