CN111377844B - Dioxopyrrolidine acetic acid derivative, preparation method and application thereof - Google Patents
Dioxopyrrolidine acetic acid derivative, preparation method and application thereof Download PDFInfo
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- CN111377844B CN111377844B CN201811616788.3A CN201811616788A CN111377844B CN 111377844 B CN111377844 B CN 111377844B CN 201811616788 A CN201811616788 A CN 201811616788A CN 111377844 B CN111377844 B CN 111377844B
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- acetic acid
- dioxopyrrolidin
- hydrazino
- chlorophenyl
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- WJDHXIKUICNIKU-UHFFFAOYSA-N acetic acid pyrrolidine-2,3-dione Chemical class CC(O)=O.O=C1CCNC1=O WJDHXIKUICNIKU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- -1 N' - (2-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide Chemical compound 0.000 claims description 35
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 230000002401 inhibitory effect Effects 0.000 claims description 7
- IPXNXMNCBXHYLQ-UHFFFAOYSA-N 2-pyrrolidin-1-ylacetic acid Chemical compound OC(=O)CN1CCCC1 IPXNXMNCBXHYLQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 208000031888 Mycoses Diseases 0.000 claims description 4
- 241000813090 Rhizoctonia solani Species 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 201000010099 disease Diseases 0.000 claims description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 235000016623 Fragaria vesca Nutrition 0.000 claims description 3
- 240000009088 Fragaria x ananassa Species 0.000 claims description 3
- 235000011363 Fragaria x ananassa Nutrition 0.000 claims description 3
- 241000223195 Fusarium graminearum Species 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- AOGGYIVDWGCMSW-UHFFFAOYSA-N acetic acid;1,3-dioxolane Chemical class CC(O)=O.C1COCO1 AOGGYIVDWGCMSW-UHFFFAOYSA-N 0.000 claims 4
- 241001465180 Botrytis Species 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 244000000004 fungal plant pathogen Species 0.000 abstract description 8
- 239000003899 bactericide agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 24
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000004896 high resolution mass spectrometry Methods 0.000 description 8
- 239000001963 growth medium Substances 0.000 description 7
- 239000005740 Boscalid Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 6
- 229940118790 boscalid Drugs 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000005794 Hymexazol Substances 0.000 description 5
- 230000009036 growth inhibition Effects 0.000 description 5
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical group NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 241000123650 Botrytis cinerea Species 0.000 description 3
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 239000006013 carbendazim Substances 0.000 description 3
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- QFYXSLAAXZTRLG-UHFFFAOYSA-N pyrrolidine-2,3-dione Chemical compound O=C1CCNC1=O QFYXSLAAXZTRLG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005887 Chromafenozide Substances 0.000 description 2
- 239000005788 Fluxapyroxad Substances 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- 239000012317 TBTU Substances 0.000 description 2
- CLZISMQKJZCZDN-UHFFFAOYSA-N [benzotriazol-1-yloxy(dimethylamino)methylidene]-dimethylazanium Chemical compound C1=CC=C2N(OC(N(C)C)=[N+](C)C)N=NC2=C1 CLZISMQKJZCZDN-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 244000000005 bacterial plant pathogen Species 0.000 description 2
- 238000004364 calculation method Methods 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
- SXSGXWCSHSVPGB-UHFFFAOYSA-N fluxapyroxad Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1=CC(F)=C(F)C(F)=C1 SXSGXWCSHSVPGB-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GHGPIPTUDQZJJS-UHFFFAOYSA-N (2-chlorophenyl)hydrazine Chemical compound NNC1=CC=CC=C1Cl GHGPIPTUDQZJJS-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 235000021186 dishes Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008103 glucose 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
- 230000028644 hyphal growth Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention belongs to the field of bactericides and discloses a derivative of dioxopyrrolidine acetic acid, 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 derivative of dioxypyrrolidine acetic acid, a preparation method and application thereof in preventing and treating plant fungal diseases, and the derivative has application as a pesticide bactericide.
Background
The pyrrolidine dione is a five-membered heterocycle containing nitrogen, is usually found in the structures of some natural compounds, and the compounds containing the pyrrolidine dione often show various biological activities such as anti-tumor, sterilization, weeding and the like, and are often used as lead compounds for researching and developing novel medicines, particularly pesticides. Pyrrolidine dione compounds as disclosed in patents ZL201210524110.9 and ZL201510204812.2 have good activity in inhibiting plant pathogenic fungi. Hydrazine group is an important active group, people often introduce the hydrazine group into the molecular structure of pesticides, such as chromafenozide (chromafenozide) and chlorfenozide (halofenozide) which belong to pesticides containing hydrazine groups, and the hydrazine group is widely applied to the aspect of controlling agricultural pests. Patent ZL201110453110.X discloses pyrrolidine diketone compounds containing phenylhydrazine groups, and has obvious inhibitory activity on plant pathogenic fungi. WO9962335A1 discloses a class of hydrazide compounds having antifungal activity. In addition, compounds containing amide groups often also have good biological activity. For example, boscalid (boscalid) and fluxapyroxad (fluxapyroxad) are typical amide fungicides.
According to the invention, a substituted phenylhydrazine group is introduced into the position 4 of the dioxypyrrolidine acetic acid, and the position 2 is linked with aniline or a phenylhydrazine group through an acetyl group, so that a dioxypyrrolidine acetic acid derivative is designed and synthesized, and the biological activity test result shows that the compound has the activity of obviously inhibiting plant pathogenic fungi.
Disclosure of Invention
The invention aims to provide a derivative of dioxy pyrrolidine acetic acid.
The second purpose of the invention is to provide a preparation method of the derivative of the dioxy pyrrolidine acetic acid.
The third purpose of the invention is to provide the application of the derivative.
The first aspect of the invention provides a derivative of dioxypyrrolidine acetic acid with a structure shown in a general formula (I),
in formula (I), the respective groups have the definitions as described below:
Y (m) wherein m =1-5 substitution, Y (m) Selected from the following 1-5 groups: x, R, wherein X represents halogen; r represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens 1-6 An alkyl group;
Z (n) wherein n =1-5 substitution, Z (n) Selected from the following 1-5 groups: x, R, wherein X represents halogen; r represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens 1-6 An alkyl group;
k is selected from 0 and 1.
In formula (I), the respective groups have the preferred definitions as described below:
Y (m) wherein m =1-2 substitution, Y (m) 1-2 groups selected from: x, R, wherein X represents halogen; r represents C 1-3 An alkyl group;
Z (n) wherein n =1-2 substitution, Z (n) Selected from 1-2 halogens;
k is selected from 0 and 1.
In formula (I), the respective groups have further preferred definitions as described below:
Y (m) wherein m =1 substitution, Y (m) Selected from the following 1 group: 4-X, 4-CH 3 Wherein X represents F, cl, br;
Z (n) wherein n =1-2 substitution, Z (n) Selected from 1-2F, cl, br;
k is selected from 0 and 1.
In formula (I), the various groups have the further preferred definitions as described below:
Y (m) selected from 4-Cl, 4-CH 3 ；
Z (n) Selected from 2-Cl, 4-Cl, 2,4- (Cl) 2 、4-Br；
k is selected from 0 and 1.
In formula (I), the individual radicals have the particularly preferred definitions indicated below:
n- (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-a),
N- (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-b),
N- (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-c),
N- (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-d),
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-e),
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-f),
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-g),
N' - (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-h),
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-I),
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-j),
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-k),
N' - (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide (I-l).
In a second aspect, the present invention provides a process for preparing a derivative of dioxopyrrolidine acetic acid of formula (I) by reacting a compound of formula (II) with a compound of formula (III) to prepare a derivative of dioxopyrrolidine acetic acid of formula (I) whose reaction formula can be represented by the following general formula (a):
wherein in each of the above structural formulae:
Y (m) 、Z (n) and k each have the definitions of the corresponding groups as described above.
The third aspect of the invention relates to the application of the derivative of dioxy pyrrolidine acetic acid in the aspects of inhibiting plant pathogenic fungi and preventing and treating plant fungal diseases, which is suitable for being used as a bactericide and applied in the field of pesticides.
The compound of the invention is suitable for inhibiting plant pathogenic fungi, such as rice sheath blight fungus, wheat gibberellic disease, strawberry gray mold fungus.
The compound of the invention is suitable for preventing and treating plant fungal diseases, such as rice sheath blight disease, wheat scab and strawberry gray mold.
Has the advantages that:
1. the chemical structure of the derivative of dioxy pyrrolidine acetic acid in formula (I) is novel, the structural formula of the compound contains a pyrrolidine diketone core heterocycle, wherein ethylene on the 4-position is linked with a substituted phenylhydrazine group, and acetyl on the 2-position is linked with substituted aniline or substituted phenylhydrazine.
2. The preparation method of the derivative of dioxypyrrolidine acetic acid shown in formula (I) is simple and easy, and raw materials are easy to obtain.
3. The derivative of dioxypyrrolidine acetic acid shown in formula (I) has practicability, has obvious activity of inhibiting plant pathogenic fungi, can be applied to control plant diseases caused by fungi, and has 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: the invention relates to a preparation method of a derivative I-a of dioxopyrrolidine acetic acid
Adding a compound II-a (3 mmol), p-chloroaniline III-a (3 mmol), TBTU (3 mmol), triethylamine (3 mmol) and 20mL of dichloromethane into a 50mL single-neck flask, stirring at normal temperature for 10h, separating out a solid, performing suction filtration, and washing with petroleum ether to obtain a yellow powdery solid, namely a derivative I-a of dioxypyrrolidine acetic acid, wherein the reaction equation is as follows:
example 2: the invention relates to a preparation method of a derivative I-I of dioxopyrrolidine acetic acid
Adding a compound II-I (3 mmol), 2-chlorophenylhydrazine III-I (3 mmol), TBTU (3 mmol), triethylamine (3 mmol) and 20mL of dichloromethane into a 50mL single-neck flask, stirring at normal temperature for reaction for 10h, separating out a solid, performing suction filtration, and washing with petroleum ether to obtain a white powdery solid, namely a derivative I-I of dioxy pyrrolidine acetic acid, wherein the reaction equation is as follows:
the method of example 1 and example 2 is adopted to prepare the compounds I-a to I-l in the derivatives (I) of the dioxypyrrolidine acetic acid:
n- (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-a)
Yellow powder; the yield is 53.3%; m.p.:229.6 to 230.9 ℃; IR (KBr): v =3280, 3195, 3116, 1676, 1641, 1605, 1569, 1533, 1491, 1399, 1356, 1312, 1248, 1093, 1012, 950, 901cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.49(s，1H，CH 3 CNHNH)，10.17(s，1H，NHC＝O)，8.49(s，1H，CH 3 CNHNH)，7.93(s，1H，CHNH)，7.65-7.62(m，2H，ArH)，7.38-7.36(m，2H，ArH)，7.31-7.29(m，2H，ArH)，6.75-6.73(m，2H，ArH)，4.06-4.03(m，1H，CH)，2.74-2.73(m，1H，CH 2 )，2.46(s，3H，CH 3 )，2.43-2.41(m，1H，CH 2 )ppm；trans-isomer：δ＝11.56(s，1H，CH 3 CNHNH)，10.17(s，1H，NHC＝O)，8.53(s，1H，CH 3 CNHNH)，7.65-7.62(m，3H，CHNH and ArH)，7.38-7.36(m，2H，ArH)，7.31-7.29(m，2H，ArH)，6.75-6.73(m，2H，ArH)，4.12-4.09(m，1H，CH)，2.78-2.77(m，1H，CH 2 )，2.49(s，3H，CH 3 )，2.43-2.41(m，1H，CH 2 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.59(s，pyrrolidine-5-C)，174.51(s，pyrrolidine-3-C)，169.99(s，CONH)，169.04(s，＝CNH)，146.79(s，ArC)，138.50(s，ArC)，129.55(s，ArC)，129.00(s，ArC)，127.18(s，ArC)，124.29(s，ArC)，121.21(s，ArC)，114.58(s，ArC)，94.17(s，pyrrolidine-4-C)，58.45(s，CH)，40.04(s，CH 2 )，13.03(s，CH 3 )ppm；trans-isomer：δ＝198.41(s，pyrrolidine-5-C)，171.37(s，pyrrolidine-3-C)，170.32(s，CONH)，168.84(s，＝CNH)，146.79(s，ArC)，138.50(s，ArC)，129.55(s，ArC)，129.00(s，ArC)，127.18(s，ArC)，124.29(s，ArC)，121.21(s，ArC)，114.58(s，ArC)，95.90(s，pyrrolidine-4-C)，56.16(s，CH)，40.04(s，CH 2 )，12.32(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 20 H 18 Cl 2 N 4 NaO 3 ([M+Na] + )455.0648，found 455.0642.
N- (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-b)
A white powder; the yield is 56.3%; m.p.:223.1 to 224.9 ℃; IR (KBr): v =3649, 3527, 34340, 3285, 3207, 1676, 1646, 1599, 1573, 1532, 1489, 1396, 1307, 1241, 1008, 893cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.48(s，1H，CH 3 CNHNH)，10.16(s，1H，NHC＝O)，8.49(s，1H，CH 3 CNHNH)，7.93(s，1H，CHNH)，7.60-7.57(m，2H，ArH)，7.50-7.48(m，2H，ArH)，7.31-7.28(m，2H，ArH)，6.75-6.73(m，2H，ArH)，4.05-4.02(m，1H，CH)，2.74-2.73(m，1H，CH 2 )，2.46(s，3H，CH 3 )，2.43-2.41(m，1H，CH 2 )ppm；trans-isomer：δ＝11.56(s，1H，CH 3 CNHNH)，10.16(s，1H，NHC＝O)，8.52(s，1H，CH 3 CNHNH)，7.61(s，1H，CHNH)，7.60-7.57(m，2H，ArH)，7.50-7.48(m，2H，ArH)，7.31-7.28(m，2H，ArH)，6.75-6.73(m，2H，ArH)，4.11-4.08(m，1H，CH)，2.77-2.76(m，1H，CH 2 )，2.49(s，3H，CH 3 )，2.43-2.41(m，1H，CH 2 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.59(s，pyrrolidine-5-C)，174.51(s，pyrrolidine-3-C)，169.99(s，CONH)，169.07(s，＝CNH)，146.67(s，ArC)，138.91(s，ArC)，131.91(s，ArC)，129.56(s，ArC)，124.30(s，ArC)，121.60(s，ArC)，115.20(s，ArC)，114.58(s，ArC)，94.18(s，pyrrolidine-4-C)，58.44(s，CH)，39.80(s，CH 2 )，13.04(s，CH 3 )ppm；trans-isomer：δ＝198.42(s，pyrrolidine-5-C)，171.37(s，pyrrolidine-3-C)，170.32(s，CONH)，168.89(s，＝CNH)，146.67(s，ArC)，138.91(s，ArC)，131.92(s，ArC)，129.56(s，ArC)，124.30(s，ArC)，121.60(s，ArC)，115.20(s，ArC)，114.58(s，ArC)，95.90(s，pyrrolidine-4-C)，56.17(s，CH)，39.80(s，CH 2 )，12.33(s，CH 3 )ppm；HRMS(ESI + )：m/z calcd for C 20 H 18 BrClN 4 NaO 3 ([M+Na] + )501.0122，found 501.0125.
N- (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-c)
A white powder; the yield is 56.3%; m.p.:228.3 to 229.9 ℃; IR (KBr): v =3441, 3324, 3269, 1668, 1635, 1599, 1574, 1531, 1511, 1491, 1357, 1250, 1082, 947, 813cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.50(s，1H，CH 3 CNHNH)，10.30(s，1H，NHNHC＝O)，9.67(s，1H，CH 3 CNHNH)，8.27(s，1H，NHNHC＝O)，7.85(s，1H，CHNH)，7.69-7.65(m，1H，ArH)，7.36-7.64(m，1H，ArH)，7.07-7.05(m，2H，ArH)，6.94-6.93(m，1H，ArH)，6.68-6.64(m，3H，ArH)，4.02-3.95(m，1H，CH)，2.78-2.69(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.36-2.31(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.62(s，1H，CH 3 CNHNH)，10.30(s，1H，NHNHC＝O)，9.67(s，1H，CH 3 CNHNH)，8.33(s，1H，NHNHC＝O)，7.53(s，1H，CHNH)，7.69-7.65(m，1H，ArH)，7.36-7.64(m，1H，ArH)，7.07-7.05(m，2H，ArH)，6.94-6.93(m，1H，ArH)，6.68-6.64(m，3H，ArH)，4.11-4.07(m，1H，CH)，2.78-2.69(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.36-2.31(m，1H，CH 2 )，2.17(s，3H，ArCH 3 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.45(s，pyrrolidine-5-C)，174.82(s，pyrrolidine-3-C)，169.83(s，CONH)，169.20(s，＝CNH)，147.38(s，ArC)，145.38(s，ArC)，138.67(s，ArC)，130.17(s，ArC)，128.94(s，ArC)，127.13(s，ArC)，121.28(s，ArC)，113.34(s，ArC)，93.78(s，pyrrolidine-4-C)，58.42(s，CH)，36.89(s，CH 2 )，20.64(s，ArCH 3 )，13.10(s，CH 3 )ppm；trans-isomer：δ＝198.37(s，pyrrolidine-5-C)，171.57(s，pyrrolidine-3-C)，170.21(s，CONH)，169.02(s，＝CNH)，147.38(s，ArC)，145.28(s，ArC)，138.67(s，ArC)，129.72(s，ArC)，129.52(s，ArC)，127.55(s，ArC)，121.28(s，ArC)，113.09(s，ArC)，95.58(s，pyrrolidine-4-C)，56.19(s，CH)，36.89(s，CH 2 )，20.64(s，ArCH 3 )，12.41(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 21 H 22 ClN 4 O 3 ([M+H] + )413.1375，found 413.1374.
N- (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide (I-d)
Yellow powder; the yield is 60.1%; m.p.:229.9-231.9 ℃; IR (KBr): v =3442, 3292, 1677, 1639, 1581, 1532, 1509, 1488, 1396, 1357, 1305, 1246, 1214, 1073, 1008, 951, 901, 812cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.50(s，1H，CH 3 CNHNH)，10.47(s，1H，NHC＝O)，8.40(s，1H，CH 3 CNHNH)，7.86(s，1H，CHNH)，7.65-7.63(m，2H，ArH)，7.49-7.46(m，2H，ArH)，7.07-7.05(m，2H，ArH)，6.67-6.65(m，2H，ArH)，4.04-4.01(m，1H，CH)，2.79-2.75(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.34-2.30(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.63(s，1H，CH 3 CNHNH)，10.47(s，1H，NHC＝O)，8.45(s，1H，CH 3 CNHNH)，7.53(s，1H，CHNH)，7.65-7.63(m，2H，ArH)，7.49-7.46(m，2H，ArH)，7.07-7.05(m，2H，ArH)，6.67-6.65(m，2H，ArH)，4.11-4.08(m，1H，CH)，2.79-2.75(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.34-2.30(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.44(s，pyrrolidine-5-C)，174.80(s，pyrrolidine-3-C)，169.84(s，CONH)，169.19(s，＝CNH)，145.35(s，ArC)，139.08(s，ArC)，131.85(s，ArC)，130.17(s，ArC)，129.72(s，ArC)，121.65(s，ArC)，115.11(s，ArC)，113.32(s，ArC)，93.76(s，pyrrolidine-4-C)，58.36(s，CH)，45.79(s，CH 2 )，20.64(s，ArCH 3 )，13.09(s，CH 3 )ppm；trans-isomer：δ＝198.26(s，pyrrolidine-5-C)，171.48(s，pyrrolidine-3-C)，170.21(s，CONH)，169.01(s，＝CNH)，145.35(s，ArC)，139.08(s，ArC)，131.85(s，ArC)，130.17(s，ArC)，129.72(s，ArC)，121.65(s，ArC)，115.11(s，ArC)，113.32(s，ArC)，93.76(s，pyrrolidine-4-C)，56.12(s，CH)，45.79(s，CH 2 )，20.64(s，ArCH 3 )，12.40(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 21 H 21 BrN 4 NaO 3 ([M+Na] + )479.0689，found 479.0689.
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-e)
A white powder; the yield is 48.8%; m.p.:231.9-232.9 ℃; IR (KBr): v =3551, 3477, 3415, 3275, 3035, 1680, 1635, 158, 1521, 1492, 1383, 1357, 1223, 1095, 1036, 1008, 819cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.46(s，1H，CH 3 CNHNH)，9.89(s，1H，NHNHC＝O)，8.48(s，1H，CH 3 CNHNH)，7.79(s，1H，CHNH)，7.30-7.25(m，4H，NHNHC＝O and ArH)，7.17-7.13(m，1H，ArH)，6.92-6.88(m，1H，ArH)，6.77-6.72(m，3H，ArH)，4.00-3.97(m，1H，CH)，2.66-2.59(m，1H，CH 2 )，2.46(s，3H，CH 3 )，2.40-2.29(m，1H，CH 2 )ppm；trans-isomer：δ＝11.56(s，1H，CH 3 CNHNH)，9.89(s，1H，NHNHC＝O)，8.53(s，1H，CH 3 CNHNH)，7.48(s，1H，CHNH)，7.30-7.25(m，4H，NHNHC＝O and ArH)，7.17-7.13(m，1H，ArH)，6.92-6.88(m，1H，ArH)，6.77-6.72(m，3H，ArH)，4.06-4.03(m，1H，CH)，2.66-2.59(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.40-2.29(m，1H，CH 2 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.38(s，pyrrolidine-5-C)，174.43(s，pyrrolidine-3-C)，170.02(s，CONH)，169.98(s，＝CNH)，146.80(s，ArC)，144.97(s，ArC)，129.56(s，ArC)，128.24(s，ArC)，124.28(s，ArC)，119.97(s，ArC)，117.50(s，ArC)，114.60(s，ArC)，113.76(s，ArC)，94.12(s，pyrrolidine-4-C)，58.43(s，CH)，37.02(s，CH 2 )，13.04(s，CH 3 )ppm；trans-isomer：δ＝198.21(s，pyrrolidine-5-C)，171.25(s，pyrrolidine-3-C)，170.36(s，CONH)，169.86(s，＝CNH)，146.80(s，ArC)，144.97(s，ArC)，129.45(s，ArC)，128.24(s，ArC)，124.28(s，ArC)，119.97(s，ArC)，117.50(s，ArC)，114.55(s，ArC)，113.76(s，ArC)，95.85(s，pyrrolidine-4-C)，56.19(s，CH)，37.02(s，CH 2 )，12.31(s，CH 3 )ppm；HRMS(ESI + )：m/z calcd for C 20 H 20 Cl 2 N 5 O 3 ([M+H] + )448.0938，found 448.0934.
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-f)
Yield 70.0％；yellow solid；m.p.：234.2-235.1℃；IR(KBr)：v＝3551，3475，3414，3283，1678，1635，1580，1516，1401，1359，1251，1224，1172，1096，823cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.45(s，1H，CH 3 CNHNH)，9.72(s，1H，NHNHC＝O)，8.47(s，1H，CH 3 CNHNH)，7.85(s，1H，NHNHC＝O)，7.79(s，1H，CHNH)，7.30-7.28(m，2H，ArH)，7.23-7.14(m，2H，ArH)，6.78-6.72(m，4H，ArH)，3.98-3.95(m，1H，CH)，2.64-2.57(m，1H，CH 2 )，2.45(s，3H，CH 3 )，2.40-2.33(m，1H，CH 2 )ppm；trans-isomer：δ＝11.56(s，1H，CH 3 CNHNH)，9.72(s，1H，NHNHC＝O)，8.53(s，1H，CH 3 CNHNH)，7.85(s，1H，NHNHC＝O)，7.47(s，1H，CHNH)，7.30-7.28(m，2H，ArH)，7.23-7.14(m，2H，ArH)，6.78-6.72(m，4H，ArH)，4.05-4.02(m，1H，CH)，2.64-2.57(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.40-2.33(m，1H，CH 2 )ppm； 13 C NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝195.59(s，pyrrolidine-5-C)，174.55(s，pyrrolidine-3-C)，169.91(s，CONH)，169.73(s，＝CNH)，148.60(s，ArC)，146.82(s，ArC)，129.56(s，ArC)，128.86(s，ArC)，124.26(s，ArC)，122.18(s，ArC)，114.58(s，ArC)，114.24(s，ArC)，94.25(s，pyrrolidine-4-C)，58.17(s，CH)，36.76(s，CH 2 )，13.01(s，CH 3 )ppm；trans-isomer：δ＝198.43(s，pyrrolidine-5-C)，171.41(s，pyrrolidine-3-C)，170.24(s，CONH)，169.60(s，＝CNH)，148.60(s，ArC)，146.82(s，ArC)，129.56(s，ArC)，128.86(s，ArC)，124.26(s，ArC)，122.18(s，ArC)，114.58(s，ArC)，114.24(s，ArC)，94.25(s，pyrrolidine-4-C)，55.91(s，CH)，36.76(s，CH 2 )，12.31(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 20 H 20 Cl 2 N 5 O 3 ([M+H] + )448.0938，found 448.0939.
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide (I-g)
Yield 40.4％；yellow solid；m.p.：229.0-231.0℃；IR(KBr)：v＝3564，3473，3415，3270，3165，1682，1633，1580，1522，1492，1405，1357，1258，1222，1097，996，816cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.46(s，1H，CH 3 CNHNH)，9.94(s，1H，NHNHC＝O)，8.49(s，1H，CH 3 CNHNH)，7.85(s，1H，NHNHC＝O)，7.81(s，1H，CHNH)，7.51(s，1H，ArH)，7.42(s，1H，ArH)，7.30-7.28(m，2H，ArH)，7.20-7.18(m，1H，ArH)，6.94-6.90(m，1H，ArH)，6.75-6.72(m，ArH，2H)，4.00-3.97(m，1H，CH)，2.63-2.59(m，1H，CH 2 )，2.46(s，3H，CH 3 )，2.41-2.30(m，1H，CH 2 )ppm；trans-isomer：δ＝11.56(s，1H，CH 3 CNHNH)，9.94(s，1H，NHNHC＝O)，8.54(s，1H，CH 3 CNHNH)，7.85(s，1H，NHNHC＝O)，7.81(s，1H，CHNH)，7.52(s，1H，ArH)，7.42(s，1H，ArH)，7.30-7.28(m，2H，ArH)，7.20-7.18(m，1H，ArH)，6.94-6.90(m，1H，ArH)，6.75-6.72(m，ArH，2H)，4.07-4.04(m，1H，CH)，2.63-2.59(m，1H，CH 2 )，2.49(s，3H，CH 3 )，2.41-2.30(m，1H，CH 2 )ppm； 13 C NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝195.38(s pyrrolidine-5-C)，174.44(s，pyrrolidine-3-C)，170.03(s，CONH)，170.01(s，＝CNH)，146.80(s，ArC)，144.21(s，ArC)，129.57(s，ArC)，128.73(s，ArC)，128.14(s，ArC)，124.27(s，ArC)，122.40(s，ArC)，117.89(s，ArC)，114.86(s，ArC)，114.60(s，ArC)，94.10(s，pyrrolidine-4-C)，58.37(s，CH)，36.99(s，CH 2 )，13.04(s，CH 3 )ppm；trans-isomer：δ＝198.19(s，pyrrolidine-5-C)，171.26(s，pyrrolidine-3-C)，170.36(s，CONH)，169.89(s，＝CNH)，146.80(s，ArC)，144.21(s，ArC)，129.57(s，ArC)，128.73(s，ArC)，128.14(s，ArC)，124.27(s，ArC)，122.40(s，ArC)，117.89(s，ArC)，114.86(s，ArC)，114，53(s，ArC)，95.74(s，pyrrolidine-4-C)，56.12(s，CH)，36.99(s，CH 2 )，12.32(s，CH 3 )ppm；HRMS(ESI + )：m/z calcd for C 20 H 18 Cl 3 N 5 NaO 3 ([M+Na] + )504.0367，found 504.0371.
N' - (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide (I-h)
A yellow powder; the yield is 75.4%; m.p.:231.1-230.0 ℃; IR (KBr): v =3282, 3184, 1686, 1623, 1606, 1573, 1515, 1486, 1384, 1358, 1223, 1100, 1005, 820cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.45(s，1H，CH 3 CNHNH)，9.73(s，1H，NHNHC＝O)，8.47(s，1H，CH 3 CNHNH)，7.88(s，1H，NHNHC＝O)，7.80(s，1H，CHNH)，7.30-7.26(m，4H，ArH)，6.74-6.71(m，4H，ArH)，3.98-3.95(m，1H，CH)，2.58-2.57(m，1H，CH 2 )，2.45(s，3H，CH 3 )，2.40-2.33(m，1H，CH 2 )ppm；trans-isomer.：δ＝11.55(s，1H，CH 3 CNHNH)，9.73(s，1H，NHNHC＝O)，8.58(s，1H，CH 3 CNHNH)，7.88(s，1H，NHNHC＝O)，7.48(s，1H，CHNH)，7.30-7.26(m，4H，ArH)，6.74-6.71(m，4H，ArH)，4.05-4.03(m，1H，CH)，2.62-2.61(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.40-2.33(m，1H，CH 2 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.88(s，pyrrolidine-5-C)，174.56(s，pyrrolidine-3-C)，169.93(s，CONH)，169.77(s，＝CNH)，148.99(s，ArC)，146.81(s，ArC)，131.69(s，ArC)，129.55(s，ArC)，124.29(s，ArC)，114.77(s，ArC)，114.57(s，ArC)，109.73(s，ArC)，94.27(s，pyrrolidine-4-C)，58.18(s，CH)，36.77(s，CH 2 )，13.03(s，CH 3 )ppm；trans-isomer：δ＝195.58(s，pyrrolidine-5-C)，171.42(s，pyrrolidine-3-C)，170.27(s，CONH)，169.61(s，＝CNH)，148.99(s，ArC)，146.81(s，ArC)，131.69(s，ArC)，129.55(s，ArC)，124.29(s，ArC)，114.77(s，ArC)，114.57(s，ArC)，109.73(s，ArC)，95.99(s，pyrrolidine-4-C)，55.91(s，CH)，36.77(s，CH 2 )，12.31(s，CH 3 )ppm；HRMS(ESI + )：m/z calcd for C 20 H 19 BrClN 5 NaO 3 ([M+Na] + )516.0231，found 516.0231.
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-I)
White powder; the yield is 65.3%; m.p.:231.1-230.0 ℃; IR (KBr): v =3392, 3320, 3273, 1679, 1641, 1612, 1576, 1500, 1406, 1387, 1253, 1229, 1036, 966, 815cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.48(s，1H，CH 3 CNHNH)，9.93(s，1H，NHNHC＝O)，8.25(s，1H，CH 3 CNHNH)，7.74(s，1H，CHNH)，7.31-7.25(m，2H，NHNHC＝O and ArH)，7.17-7.12(m，1H，ArH)，7.07-7.03(m，2H，ArH)，6.95-6.87(m，1H，ArH)，6.78-6.73(m，1H，ArH)，6.68-6.62(m，2H，ArH)，3.99-3.96(m，1H，CH)，2.66-2.59(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.37-2.29(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.63(s，1H，CH 3 CNHNH)，9.93(s，1H，NHNHC＝O)，8.32(s，1H，CH 3 CNHNH)，7.42(s，1H，CHNH)，7.31-7.25(m，2H，NHNHC＝O and ArH)，7.17-7.12(m，1H，ArH)，7.07-7.03(m，2H，ArH)，6.95-6.87(m，1H，ArH)，6.78-6.73(m，1H，ArH)，6.68-6.62(m，2H，ArH)，4.06-4.03(m，1H，CH)，2.66-2.59(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.37-2.29(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.21(s，pyrrolidine-5-C)，174.72(s，pyrrolidine-3-C)，170.11(s，CONH)，169.90(s，＝CNH)，145.36(s，ArC)，144.97(s，ArC)，145.02(s，ArC)，130.17(s，ArC)，129.72(s，ArC)，129.43(s，ArC)，128.25(s，ArC)，120.00(s，ArC)，113.88(s，ArC)，113.29(s，ArC)，93.68(s，pyrrolidine-4-C)，58.42(s，CH)，37.08(s，CH 2 )，20.65(s，ArCH 3 )，13.13(s，CH 3 )ppm；trans-isomer：δ＝198.13(s，pyrrolidine-5-C)，171.44(s，pyrrolidine-3-C)，170.25(s，CONH)，169.96(s，＝CNH)，145.23(s，ArC)，145.02(s，ArC)，130.17(s，ArC)，129.77(s，ArC)，129.51(s，ArC)，128.25(s，ArC)，120.00(s，ArC)，117.57(s，ArC)，113.35(s，ArC)，113.07(s，ArC)，95.48(s，pyrrolidine-4-C)，56.19(s，CH)，37.08(s，CH 2 )，20.65(s，ArCH 3 )，12.42(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 21 H 23 ClN 5 O 3 ([M+H] + )428.1484，found 428.1482.
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide (I-j)
White powder; the yield is 80.3%; n.p.:231.1-230.0 ℃; IR (KBr): v =3444, 3340, 3289, 3024, 1678, 1632, 1583, 1513, 1492, 1404, 1385, 1359, 1253, 1225, 1116, 1093, 943, 904, 812cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.48(s，1H，CH 3 CNHNH)，9.75(s，1H，NHNHC＝O)，8.25(s，1H，CH 3 CNHNH)，7.73(s，1H，NHNHC＝O)，7.43(s，1H，CHNH)，7.23-6.93(m，4H，ArH)，6.78-6.63(m，4H，ArH)，3.97-3.94(m，1H，CH)，2.64-2.58(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.39-2.33(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.63(s，1H，CH 3 CNHNH)，9.66(s，1H，NHNHC＝O)，8.32(s，1H，CH 3 CNHNH)，7.69(s，1H，NHNHC＝O)，7.40(s，1H，CHNH)，7.23-6.93(m，4H，ArH)，6.78-6.63(m，4H，ArH)，4.04-4.01(m，1H，CH)，2.64-2.58(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.39-2.33(m，1H，CH 2 )，2.17(s，3H，ArCH 3 )ppm； 13 C NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝195.40(s，pyrrolidine-5-C)，174.82(s，pyrrolidine-3-C)，169.85(s，CONH)，169.81(s，＝CNH)，148.65(s，ArC)，145.38(s，ArC)，130.18(s，ArC)，128.84(s，ArC)，122.16(s，ArC)，114.29(s，ArC)，113.33(s，ArC)，113.06(s，ArC)，93.81(s，pyrrolidine-4-C)，58.16(s，CH)，36.85(s，CH 2 )，20.64(s，ArCH 3 )，13.08(s，CH 3 )ppm；trans-isomer：δ＝198.34(s，pyrrolidine-5-C)，171.55(s，pyrrolidine-3-C)，170.15(s，CONH)，169.76(s，＝CNH)，147.38(s，ArC)，145.26(s，ArC)，129.72(s，ArC)，129.51(s，ArC)，127.52(s，ArC)，114.29(s，ArC)，113.33(s，ArC)，113.06(s，ArC)，95.61(s，pyrrolidine-4-C)，55.95(s，CH)，20.64(s，ArCH 3 )，36.85(s，CH 2 )，12.38(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 21 H 22 ClN 5 NaO 3 ([M+Na] + )450.1303，found 450.1303.
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide (I-k)
A white powder; the yield is 66.9%; m.p.:231.1-230.0 ℃; IR (KBr): v =3390, 3317, 3275, 1682, 1640, 1613, 1580, 1498, 1407, 1390, 1356, 1253, 1228, 1105, 1047, 982, 939, 814cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.48(s，1H，CH 3 CNHNH)，10.03(s，1H，NHNHC＝O)，8.35(s，1H，CH 3 CNHNH)，7.75(s，1H，CHNH)，7.48-7.41(m，2H，NHNHC＝O and ArH)，7.20-7.16(m，1H，ArH)，7.07-7.05(m，2H，ArH)，6.94-6.91(m，1H，ArH)，6.67-6.64(m，2H，ArH)，3.99-3.96(m，1H，CH），2.66-2.60(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.39-2.41(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.64(s，1H，CH 3 CNHNH)，10.03(s，1H，NHNHC＝O)，8.44(s，1H，CH 3 CNHNH)，7.45(s，1H，CHNH)，7.48-7.41(m，2H，NHNHC＝O and ArH)，7.20-7.16(m，1H，ArH)，7.07-7.05(m，2H，ArH)，6.94-6.91(m，1H，ArH)，6.67-6.64(m，2H，ArH)，4.06-4.03(m，1H，CH)，2.66-2.60(m，1H，CH 2 )，2.48(s，3H，CH 3 )，2.39-2.41(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm； 13 C NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝195.20(s pyrrolidine-5-C)，174.74(s，pyrrolidine-3-C)，170.18(s，CONH)，169.93(s，＝CNH)，145.34(s，ArC)，144.34(s，ArC)，130.16(s，ArC)，129.72(s，ArC)，128.69(s，ArC)，128.14(s，ArC)，122.47(s，ArC)，117.98(s，ArC)，114.97(s，ArC)，113.34(s，ArC)，93.68(s，pyrrolidine-4-C)，58.37(s，CH)，37.05(s，CH 2 )，20.64(s，ArCH 3 )，13.13(s，CH 3 )ppm；trans-isomer：δ＝198.10(s，pyrrolidine-5-C)，171.49(s，pyrrolidine-3-C)，170.26(s，CONH)，170.02(s，＝CNH)，144.97(s，ArC)，144.34(s，ArC)，130.16(s，ArC)，129.78(s，ArC)，128.69(s，ArC)，128.14(s，ArC)，122.47(s，ArC)，117.98(s，ArC)，114.97(s，ArC)，113.29(s，ArC)，95.47(s，pyrrolidine-4-C)，56.15(s，CH)，37.05(s，CH 2 )，20.64(s，ArCH 3 )，12.42(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcdfor C 21 H 21 Cl2N 5 NaO 3 ([M+Na] + )484.0914，found 484.0912.
N' - (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide (I-l)
A white powder; the yield is 66.9%; m.p.:231.1-230.0 ℃; IR (KBr): v =3442, 3336, 3293, 1678, 1632, 1583, 1512, 1468, 1404, 1384, 1359, 1224, 1171, 997, 815cm -1 ； 1 H NMR(400MHz，DMSO-d 6 )：cis-isomer：δ＝11.47(s，1H，CH 3 CNHNH)，9.75(s，1H，NHNHC＝O)，8.23(s，1H，CH 3 CNHNH)，7.86(s，1H，NHNHC＝O)，7.73(s，1H，CHNH)，7.27-7.24(m，2H，ArH)，7.07-7.05(m，2H，ArH)，6.73-6.63(m，4H，ArH)，3.97-3.94(m，1H，CH)，2.63-2.57(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.39-2.32(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm；trans-isomer：δ＝11.63(s，1H，CH 3 CNHNH)，9.75(s，1H，NHNHC＝O)，8.31(s，1H，CH 3 CNHNH)，7.86(s，1H，NHNHC＝O)，7.39(s，1H，CHNH)，7.27-7.24(m，2H，ArH)，7.07-7.05(m，2H，ArH)，6.73-6.63(m，4H，ArH)，4.04-4.01(m，1H，CH)，2.63-2.57(m，1H，CH 2 )，2.47(s，3H，CH 3 )，2.39-2.32(m，1H，CH 2 )，2.21(s，3H，ArCH 3 )ppm； 13 C NMR(100MHz，DMSO-d 6 )：cis-isomer：δ＝195.39(s，pyrrolidine-5-C)，174.83(s，pyrrolidine-3-C)，169.87(s，CONH)，169.81(s，＝CNH)，149.04(s，ArC)，145.38(s，ArC)，131.67(s，ArC)，130.17(s，ArC)，129.70(s，ArC)，114.82(s，ArC)，113.32(s，ArC)，109.65(s，ArC)，93.79(s，pyrrolidine-4-C)，58.16(s，CH)，36.83(s，CH 2 )，20.65(s，ArCH 3 )，13.10(s，CH 3 )ppm；trans-isomer：δ＝198.31(s，pyrrolidine-5-C)，171.58(s，pyrrolidine-3-C)，170.12(s，CONH)，169.71(s，＝CNH)，149.04(s，ArC)，145.24(s，ArC)，131.67(s，ArC)，130.17(s，ArC)，129.70(s，ArC)，114.82(s，ArC)，113.32(s，ArC)，109.65(s，ArC)，95.59(s，pyrrolidine-4-C)，55.94(s，CH)，36.83(s，CH 2 )，20.65(s，ArCH 3 )，12.40(s，CH 3 )ppm；HR-MS(ESI + )：m/z calcd for C 21 H 22 BrN 5 NaO 3 ([M+Na] + )494.0798，found 494.0798.
Examples of the use
Example 3: the derivative (I) of the dioxopyrrolidine acetic acid has bactericidal activity on plant pathogenic fungi
Measurement of
The bactericidal activity of compounds I-a-I-l in a derivative (I) of dioxopyrrolidine acetic acid on 3 test plant pathogenic bacteria of Rhizoctonia solani (Rhizoctonia solani), fusarium graminearum (Fusarium graminearum) and Botrytis cinerea (Botrytis cinerea) at a concentration of 10 mu g/mL is measured by a hyphal growth rate method.
The determination method comprises the following steps: dissolving 9mg of a compound to be tested (comprising control medicaments of hymexazol, carbendazim and boscalid) in 0.4mL of DMSO, sucking 0.1mL of solution from the DMSO, adding 0.4mL of DMSO, mixing uniformly, sucking 0.1mL of solution from the DMSO, adding the solution into 44.9mL of sterilized potato glucose agar culture medium (PDA culture medium), fully shaking uniformly to prepare a drug-containing culture medium with the concentration of 10 mu g/mL, and pouring the drug-containing culture medium into 3 sterile culture dishes with the diameter of 9cm on average. The culture medium prepared by adding equal amount of solvent is used as blank control. Meanwhile, a culture medium which is prepared by adding the bactericides hymexazol, carbendazim and boscalid and has the concentration of 10 mu g/mL is used as a medicament control. Punching the normal colony with a puncher (inner diameter of 0.5 cm) to obtain bacterial cake, inoculating the bacterial cake into the center of the culture medium plate with an inoculating needle, and culturing in a biochemical incubator at 25 deg.C. The diameter of the colonies on the blank control medium was measured when the diameter was as long as 2/3 of the plate, and the diameter of each colony was measured 2 times by the cross method, and the average value (unit: cm) thereof was calculated. Three replicates were set for each concentration treatment and each control. And (3) calculating the growth inhibition rate after medicament treatment, wherein the calculation formula is as follows:
the calculation method comprises the following steps: inhibition (%) = (solvent control colony diameter-treated colony diameter) ÷ (solvent control colony diameter-0.5) × 100%.
And (3) measuring results: the results of the growth inhibition rate measurement of 3 test phytopathogens by a derivative (I) of dioxopyrrolidine acetic acid are shown in Table 1.
Table 1 shows that a derivative (I) of dioxopyrrolidine acetic acid has significant bactericidal activity against 3 test phytopathogens. Wherein, the growth inhibition rates of the compounds I-a to I-l to Rhizoctonia solani are 54.75 to 92.58 percent which are all higher than 7.80 percent of that of a contrast medicament hymexazol, and the inhibition rates of the compounds I-e, I-f, I-g, I-I and I-k reach 87.33 to 92.58 percent which are higher than 82.51 percent of that of the contrast medicament boscalid. The growth inhibition rates of the compounds I-a to I-l on the wheat scab germ are 19.85 to 89.70 percent and are all higher than 12.18 percent of the control medicament hymexazol, the inhibition rates of the compounds except the compounds I-g and I-k are all higher than 38.02 percent of the control medicament boscalid, and the inhibition rates of the compounds I-f and I-h are more than 80 percent. The growth inhibition rates of the compounds I-a to I-l on the botrytis cinerea are 41.58-66.00 percent, which are higher than 39.53 percent of the contrast medicament hymexazol and 28.91 percent of the carbendazim, and the inhibition rates of the compounds I-e, I-f, I-g and I-h reach more than 60 percent.
TABLE 1 inhibition rate (%, 10. Mu.g/mL) of dioxopyrrolidine acetic acid derivative (I) against 3 plant pathogenic bacteria
Claims (9)
1. A derivative of dioxy pyrrolidine acetic acid with a structure shown in formula (I),
wherein,
Y (m) wherein m =1-5 substitution, Y (m) Selected from the following 1-5 groups: x, R, wherein X represents halogen; r represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens 1-6 An alkyl group;
Z (n) wherein n =1-5 substitution, Z (n) Selected from the following 1-5 groups: x, R, wherein X represents halogen; r represents hydrogen, C unsubstituted or substituted by 1 to 6 halogens 1-6 An alkyl group;
k is selected from 0 and 1.
2. A dioxolane acetic acid derivative according to claim 1, wherein said dioxolane acetic acid derivative is selected from the group consisting of:
Y (m) wherein m =1-2 substitution, Y (m) 1-2 groups selected from: x, R, wherein X represents halogen; r represents C 1-3 An alkyl group;
Z (n) wherein n =1-2 substitution, Z (n) Selected from 1-2 halogens;
k is selected from 0 and 1.
3. A derivative of dioxopyrrolidine acetic acid according to claim 2, wherein:
Y (m) wherein m =1 substitution, Y (m) Selected from the following 1 group: 4-X, 4-CH 3 Wherein X represents F, cl, br;
Z (n) wherein n =1-2 substitution, Z (n) Selected from 1-2F, cl, br;
k is selected from 0 and 1.
4. A dioxolane acetic acid derivative according to claim 3, wherein said dioxolane acetic acid derivative is selected from the group consisting of:
Y (m) selected from 4-Cl, 4-CH 3 ；
Z (n) Selected from 2-Cl, 4-Cl, 2,4- (Cl) 2 、4-Br；
k is selected from 0 and 1.
5. A derivative of dioxopyrrolidine acetic acid according to claim 4, which is one of the following compounds:
n- (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide,
N- (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide,
N- (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide,
N- (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetamide,
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide,
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide,
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide,
N' - (4-bromophenyl) -2- (4- (1- (2- (4-chlorophenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide,
N' - (2-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide,
N' - (4-chlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide,
N' - (2, 4-dichlorophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acethydrazide,
N' - (4-bromophenyl) -2- (4- (1- (2- (4-methylphenyl) hydrazino) ethylidene) -3, 5-dioxopyrrolidin-2-yl) acetohydrazide.
6. A process for producing a derivative of dioxopyrrolidine acetic acid according to any one of claims 1 to 5, which comprises the step of preparing a compound represented by the general formula (A):
wherein in each of the above structural formulae:
Y (m) 、Z (n) k have the meaning stated in any one of claims 1 to 5.
7. Use of a derivative of dioxopyrrolidine acetic acid according to any one of claims 1 to 5 for controlling fungal diseases of plants.
8. Use according to claim 7, characterized in that a derivative of dioxopyrrolidine acetic acid according to any one of claims 1 to 5 is used for inhibiting Rhizoctonia solani, fusarium graminearum, botrytis fragilis.
9. The use of the derivatives of dioxopyrrolidine acetic acid according to claim 7 for preventing and treating rice sheath blight disease, wheat head blight, and strawberry gray mold.
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