CN105481747A - Carbonic ester derivative of phenylpyrrole dipyrroline ketone, preparation method and application - Google Patents

Carbonic ester derivative of phenylpyrrole dipyrroline ketone, preparation method and application Download PDF

Info

Publication number
CN105481747A
CN105481747A CN201510937475.8A CN201510937475A CN105481747A CN 105481747 A CN105481747 A CN 105481747A CN 201510937475 A CN201510937475 A CN 201510937475A CN 105481747 A CN105481747 A CN 105481747A
Authority
CN
China
Prior art keywords
dihydro
dipyrrole
oxo
diylbis
dicarbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510937475.8A
Other languages
Chinese (zh)
Other versions
CN105481747B (en
Inventor
杨春龙
徐文琴
汪学伦
任正娇
王坤瑶
李凌霞
时松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Agricultural University
Original Assignee
Nanjing Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Agricultural University filed Critical Nanjing Agricultural University
Priority to CN201510937475.8A priority Critical patent/CN105481747B/en
Publication of CN105481747A publication Critical patent/CN105481747A/en
Application granted granted Critical
Publication of CN105481747B publication Critical patent/CN105481747B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C07D207/30—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 two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—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 two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/38—2-Pyrrolones
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof

Landscapes

  • 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)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention belongs to the field of bactericide and discloses a carbonic ester derivative of phenylpyrrole dipyrroline ketone, a preparation method and application. The structure of the compound is shown as formula (I) (please see the description). The compound is novel in structure and easy and convenient to prepare and has remarkable inhibitory activity on plant pathogenic fungi.

Description

Carbonate derivatives of phenylpyrrole dipyrrolinone, preparation method and application
Technical Field
The invention relates to a carbonic ester derivative of phenyl pyrrole pyrrolinone, a preparation method and application thereof in preventing and treating plant pathogenic fungi, and has application in preparing pesticide bactericides.
Background
The compounds containing pyrrole or pyrrolinone groups often have biological activity and are of interest in research and application in the field of pesticides. Nitropyrrolidin, fenpiclonil, fludioxonil, tetramycin C and the like are bactericides containing a pyrrole structure. Chlorfenapyr is an insecticide containing a pyrrole structure. Patent CN200910028039 discloses oxime ether compounds containing pyrrolinone groups, which have bactericidal and herbicidal activities. Patent CN201210586507 discloses a class of pyrrolinone compounds containing pyrazole groups, which has bactericidal and herbicidal activities.
According to the invention, 2-position of pyrrole and 3 '-position of pyrroline-2' -ketone are linked to form a bi-heterocyclic structure, substituted phenyl is introduced into 1-position of pyrrole, carbonate groups are respectively introduced into 5-position of pyrrole and 4 '-position of pyrroline-2' -ketone, a carbonate derivative of phenyl pyrrole-pyrroline-dipyrroline ketone with a novel structure is designed and synthesized, and biological assay finds that the carbonate derivative has obvious bactericidal activity on plant pathogenic fungi.
Disclosure of Invention
The invention aims to provide a carbonate derivative of phenylpyrrole dipyrrolinone.
The invention also aims to provide a preparation method of the carbonic ester derivatives of the phenylpyrrole dipyrrolinone.
The 3 rd object of the present invention is to provide the use of the above-mentioned compounds.
The invention provides a carbonic ester derivative of phenyl pyrrole pyrrolinone with a structure shown in a general formula (I).
Wherein,
r represents hydrogen, C1-20Alkyl, phenyl, substituted phenyl, benzyl, substituted phenylmethyl;
Y(n)wherein n is a 1-5 substitution, Y(n)Selected from the following 1-5 groups: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkyloxy, C1-6Alkylthio, halo C1-6Alkyl, halo C1-6Alkyloxy, halo C1-6Alkylthio, wherein the substituted phenyl represents 1-2C radicals containing 1-2 halogen atoms1-6The alkyl phenyl, halo represents 1-6 halogen substitutions, halo represents F, Cl, Br, I.
In formula (I), the respective groups have the preferred definitions as described below:
r represents hydrogen, C1-4Alkyl, phenyl, benzyl;
Y(n)wherein n is a 1-3 substitution, Y(n)Selected from the following 1-5 groups: hydrogen, halogen, methyl, methoxy, trifluoromethyl and trifluoromethoxy, wherein halogen represents F, Cl and Br.
In formula (I), the respective groups have further preferred definitions as described below:
r is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and benzyl;
Y(n)wherein n is a1 substitution, Y(n)Is selected from hydrogen, halogen, methyl, methoxy, trifluoromethyl and trifluoromethoxy, wherein halogen represents F, Cl and Br.
In formula (I), the individual radicals have the particularly preferred definitions indicated below:
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (A1),
Diethyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyldicarbonate (A2),
Di-n-propyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyl dicarbonate (A3),
Diisopropyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (A4),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-n-butyl (A5),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (A6),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyldiphenyldicarbonate (A7),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyl-dibenzyldicarbonate (A8),
2 '-oxo-1-phenyl-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B1),
1- (4-fluorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B2),
1- (2-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B3),
1- (4-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B4),
1- (4-bromophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B5),
2 '-oxo-1- (o-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B6),
2 '-oxo-1- (m-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B7),
2 '-oxo-1- (p-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B8),
1- (3-methoxyphenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B9),
2 '-oxo-1- (3- (trifluoromethyl) phenyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis (B10)
2 '-oxo-1- (3- (trifluoromethoxy) phenyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B11),
Diisopropyl 2 '-oxo-1- (m-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (B12).
In a second aspect, the invention provides a method for preparing the carbonate derivatives (I) of phenylpyrrolidine pyrrolinone. The method uses an intermediate (II)As starting material in Et3Reacting with chloroformate (III) in the presence of N to generate carbonate derivatives (I) of phenylpyrrole dipyrroline ketone. The reaction equation can be represented by the following general formula (A):
wherein in each of the above structural formulae:
r and Y(n)All have the meanings as described above.
The third aspect of the invention relates to an application of a carbonate derivative (I) of phenylpyrrole dipyrrolinone, which can be applied to the field of pesticides and used as a bactericide for preventing and treating plant diseases caused by plant pathogenic fungi.
Within the meaning of the present invention, phytopathogenic fungi are understood to mean phytopathogenic fungi. The compound of the invention can protect plants from infection and harm of the pathogenic bacteria after treatment.
The compound of the invention has obvious bacteriostatic activity on wheat scab, rice sheath blight and strawberry gray mold.
The compound is suitable for preventing and treating wheat scab, rice sheath blight and strawberry gray mold.
The compound is suitable for preventing and treating fungal diseases of wheat crops, such as wheat scab; preventing and treating fungal diseases of rice crops, such as rice sheath blight; preventing and treating fungal diseases of fruit and vegetable crops, such as gray mold of strawberry.
Has the advantages that:
1. according to the invention, the 2-position of pyrrole and the 3 '-position of pyrroline-2' -ketone are linked to form a bi-heterocyclic structure, substituted phenyl is introduced into the 1-position of pyrrole, carbonate groups are respectively introduced into the 5-position of pyrrole and the 4 '-position of pyrroline-2' -ketone, and a carbonate derivative of phenyl pyrrole-pyrroline is designed and synthesized, wherein the carbonate derivative is shown as the formula (I).
2. According to the preparation method of the carbonate derivatives of phenylpyrrole pyrrolinone, the adopted raw material (II) reacts with chloroformate under an alkaline condition to generate tautomerism, two pyrrolidones are respectively converted into pyrrolinone and pyrrole to simultaneously generate dicarbonate, and the preparation method has the advantages of ingenious design of a synthetic route, short reaction time and convenience in operation.
3. The carbonate derivative of the phenylpyrrole dipyrrolidone disclosed by the invention shows remarkable activity of inhibiting plant pathogenic fungi, has a wide bactericidal spectrum, and can provide effective service for preventing and treating plant fungal diseases in agricultural production.
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: synthesis of carbonate derivative (I) of phenylpyrrole dipyrrolinone
20mL of chloroform, 1.5mmol of the intermediate (II) and 3.6mmol of triethylamine were added to a 50mL single-neck flask, and 3.3mmol of chloroformate (III) was added dropwise in an ice bath at 0 to 5 ℃ and reacted for 0.5 to 2 hours in the ice bath. Washing the reaction solution with saturated sodium bicarbonate solution, drying with anhydrous magnesium sulfate, concentrating, and separating by column chromatography to obtain carbonate derivatives (I) of phenylpyrrole dipyrrolinone.
Using the procedure of example 1, the following A-B series of compounds were prepared:
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiocarbonate(A1)：
A white powder; the yield is 50.1%; mp decomposing at 164.6-166.2 deg.c;1HNMR(400MHz，CDCl3)(ppm)：7.35-7.28(m，3H，PhH)，7.13-7.07(m，1H，PhH)，6.57(d，J＝4.0Hz，1H，ArH)，6.39-6.22(brs，1H，NH)，6.10(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，CH2NH)，3.79(s，3H，CH3)，3.76(s，3H，CH3).
1- (3-chlorophenyl))-2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldicyclic acid diethyl ester(A2)：
A white powder; the yield is 82.4%; mp138.1-140.0 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.34(s，1H，PhH)，7.28(dd，J＝3.9，1.7Hz，2H，PhH)，7.14-7.08(m，1H，PhH)，6.75-6.35(br，1H，NH)，6.55(d，J＝4.0Hz，1H，ArH)，6.08(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，4.18(q，J＝7.1Hz，2H，OCH2)，4.14(q，J＝7.1Hz，2H，OCH2)，1.32(t，J＝7.1Hz，3H，CH3)，1.24(t，J＝7.1Hz，3H，CH3).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]Di-n-propyl-4', 5-diyl-dicarbonate(A3)：
A white powder; the yield is 69.3%; mp102.0-103.0 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.34-7.31(m，1H，PhH)，7.28(dd，J＝3.9，1.9Hz，2H，PhH)，7.14-7.10(m，1H，PhH)，6.54(d，J＝4.0Hz，1H，ArH)，6.42-6.19(brs，1H，NH)，6.07(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，4.09(t，J＝6.7Hz，2H，OCH2)，4.04(t，J＝6.8Hz，2H，OCH2)，1.75-1.66(m，2H，CH2CH3)，1.66-1.57(m，2H，CH2CH3)，0.96(t，J＝7.4Hz，3H，CH3)，0.89(t，J＝7.4Hz，3H，CH3).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]Diisopropyl (4', 5-diyl) dicarbonate(A4)：
A white powder; the yield is 40.2%; mp122.1-124.1 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.33(s，1H，PhH)，7.29-7.25(m，2H，PhH)，7.15-7.09(m，1H，PhH)，6.52(d，J＝3.9Hz，1H，ArH)，6.39-6.11(brs，1H，NH)，6.06(d，J＝4.0Hz，1H，ArH)，4.87-4.71(m，2H，2×OCH)，4.26(s，2H，CH2)，1.30(d，J＝6.3Hz，6H，2×CH3)，1.21(d，J＝6.3Hz，6H，2×CH3).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]Di-n-butyl-4', 5-diyl-dicarbonate(A5)：
A white powder; the yield is 51.3%; mp81.7-83.5 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.34-7.31(m，1H，PhH)，7.30-7.27(m，2H，PhH)，7.13-7.09(m，1H，PhH)，6.68-6.55(brs，1H，NH)，6.54(d，J＝4.0Hz，1H，ArH)，6.07(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，4.13(t，J＝6.6Hz，2H，OCH2)，4.08(t，J＝6.7Hz，2H，OCH2)，1.70-1.61(m，2H，OCH2CH2)，1.61-1.52(m，2H，OCH2CH2)，1.45-1.35(m，2H，CH2CH3)，1.34-1.25(m，2H，CH2CH3)，0.95(t，J＝7.4Hz，3H，CH2CH3)，0.90(t，J＝7.4Hz，3H，CH2CH3).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(A6)：
A white powder; the yield is 75.3%; mp104.8-106.0 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.33-7.31(m，1H，PhH)，7.28(dd，J＝3.9，1.9Hz，2H，PhH)，7.15-7.09(m，1H，PhH)，6.54(d，J＝4.0Hz，1H，ArH)，6.42-6.17(brs，1H，NH)，6.07(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，3.90(d，J＝6.7Hz，2H，OCH2)，3.86(d，J＝6.7Hz，2H，OCH2)，2.06-1.84(m，2H，2×CHCH3)，0.95(d，J＝6.7Hz，6H，2×CH3)，0.87(d，J＝6.7Hz，6H，2×CH3).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiphenylcarbonate(A7)：
A white powder; the yield is 30.6%; mp72.2-74.1 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.47-7.32(m，7H，PhH)，7.30(d，J＝7.4Hz，1H，PhH)，7.25-7.20(m，2H，PhH)，7.13(d，J＝7.8Hz，2H，PhH)，7.05(d，J＝7.7Hz，2H，PhH)，6.63(d，J＝4.0Hz，1H，ArH)，6.62-6.53(brs，1H，NH)，6.22(d，J＝4.0Hz，1H，ArH)，4.33(s，2H，CH2).
1- (3-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Diylbis-dicarbonate(A8)：
A white powder; the yield is 30.7%; mp132.2-135.0 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.42-7.31(m，9H，PhH)，7.25(d，J＝6.4Hz，2H，PhH)，7.18(d，J＝7.9Hz，1H，PhH)，7.11(t，J＝7.9Hz，1H，PhH)，7.05(d，J＝8.0Hz，1H，PhH)，6.52(d，J＝4.0Hz，1H，ArH)，6.25-6.10(brs，1H，NH)，6.07(d，J＝4.0Hz，1H，ArH)，5.12(s，2H，OCH2)，5.09(s，2H，OCH2)，4.22(s，2H，NHCH2).
2 ' -oxo-1-phenyl-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B1)：
A white powder; the yield is 32.6%; mp95.0-96.8 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.38-7.32(m，2H，PhH)，7.30(d，J＝7.0Hz，1H，PhH)，7.25(d，J＝8.7Hz，2H，PhH)，6.53(d，J＝4.0Hz，1H，ArH)，6.35-6.10(brs，1H，NH)，6.07(d，J＝4.0Hz，1H，ArH)，4.21(s，2H，NHCH2)，3.86(d，J＝6.7Hz，2H，OCH2)，3.81(d，J＝6.6Hz，2H，OCH2)，2.01-1.82(m，2H，2×CHCH3)，0.96(d，J＝6.7Hz，6H，2×CH3)，0.84(d，J＝6.7Hz，6H，2×CH3).
1- (4-fluorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B2)：
A white powder; the yield is 48.6%; mp93.9-95.1 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.25(dd，J＝8.5，4.9Hz，2H，PhH)，7.03(t，J＝8.4Hz，2H，PhH)，6.50(d，J＝3.7Hz，1H，ArH)，6.27-6.19(brs，1H，NH)，6.06(d，J＝3.8Hz，1H，ArH)，4.22(s，2H，NHCH2)，3.87(t，J＝6.9Hz，4H，2×OCH2)，2.02-1.82(m，2H，2×CHCH3)，0.96(d，J＝6.7Hz，6H，6H，2×CH3)，0.86(d，J＝6.7Hz，6H，6H，2×CH3).
1- (2-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B3)：
A white powder; the yield is 46.2%; mp107.2-109.1 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.44(d，J＝8.0Hz，1H，PhH)，7.34-7.21(m，3H，PhH)，6.57(d，J＝4.0Hz，1H，ArH)，6.23-6.14(brs，1H，NH)，6.12(d，J＝4.0Hz，1H，ArH)，4.21(s，2H，CH2NH)，3.90(dd，J＝6.8，1.2Hz，2H，OCH2)，3.86(dd，J＝6.6，2.7Hz，2H，OCH2)，2.03-1.84(m，2H，2×CHCH3)，0.98(d，J＝6.7Hz，6H，2×CH3)，0.85(d，J＝6.7Hz，6H，2×CH3).
1- (4-chlorophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -diAzole compounds]-4', 5-Dimethyldiiobutylborate(B4)：
A white powder; the yield is 59.2%; mp123.7-125.1 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.32(d，J＝8.7Hz，2H，PhH)，7.21(d，J＝8.7Hz，2H，PhH)，6.53(d，J＝4.0Hz，1H，ArH)，6.42-6.23(brs，1H，NH)，6.07(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，3.89(d，J＝6.7Hz，2H，OCH2)，3.86(d，J＝6.6Hz，2H，OCH2)，2.02-1.83(m，2H，2×CHCH3)，0.96(d，J＝6.7Hz，6H，2×CH3)，0.86(d，J＝6.7Hz，6H，2×CH3).
1- (4-bromophenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B5)：
A white powder; the yield is 60.0%; mp is 126.7-128.7 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.47(d，J＝8.7Hz，2H，PhH)，7.15(d，J＝8.7Hz，2H，PhH)，6.65-6.40(br，1H，NH)，6.54(d，J＝4.0Hz，1H，ArH)，6.07(d，J＝4.0Hz，1H，ArH)，4.24(s，2H，NHCH2)，3.89(d，J＝6.7Hz，2H，OCH2)，3.86(d，J＝6.6Hz，2H，OCH2)，2.01-1.92(m，1H，CHCH3)，1.91-1.83(m，1H，CHCH3)，0.97(d，J＝6.7Hz，6H，2×CH3)，0.87(d，J＝6.7Hz，6H，2×CH3).
2 ' -oxo-1- (o-tolyl) -2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B6)：
A white powder; the yield is 66.6%; mp91.3-92.9 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.25-7.10(m，4H，PhH)，6.70-6.54(brs，1H，NH)，6.52(d，J＝4.0Hz，1H，ArH)，6.08(d，J＝4.0Hz，1H，ArH)，4.18(s，2H，NHCH2)，3.87-3.80(m，4H，2xOCH2)，2.10(s，3H，PhCH3)，2.04-1.92(m，1H，CHCH3)，1.88-1.76(m，1H，CHCH3)，0.98(d，J＝6.7Hz，6H，2×CHCH3)，0.80(d，J＝6.7Hz，6H，2×CHCH3).
2 ' -oxo-1- (m-tolyl) -2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B7)：
A white powder; the yield is 59.7%; mp82.4-84.0 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.21(dd，J＝10.9，5.3Hz，1H，PhH)，7.07(dd，J＝15.2，6.8Hz，3H，PhH)，6.52(d，J＝4.0Hz，1H，ArH)，6.46-6.27(brs，1H，NH)，6.05(d，J＝4.0Hz，1H，ArH)，4.21(s，2H，NHCH2)，3.88(d，J＝6.7Hz，2H，OCH2)，3.81(d，J＝6.7Hz，2H，OCH2)，2.32(s，3H，PhCH3)，2.00-1.81(m，2H，2×CHCH3)，0.95(d，J＝6.7Hz，6H，2×CHCH3)，0.85(d，J＝6.7Hz，6H，2×CHCH3).
2 ' -oxo-1- (p-tolyl) -2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B8)：
A white powder; the yield is 40.2%; mp94.7-96.6 deg.C;1HNMR(400MHz，CDCl3)(ppm)：7.12(s，4H，PhH)，6.72-6.55(brs，1H，NH)，6.49(d，J＝4.0Hz，1H，ArH)，6.04(d，J＝4.0Hz，1H，ArH)，4.21(s，2H，NHCH2)，3.87(d，J＝6.7Hz，2H，OCH2)，3.81(d，J＝6.6Hz，2H，OCH2)，2.34(s，3H，PhCH3)，2.01-1.81(m，2H，2×CHCH3)，0.96(d，J＝6.7Hz，6H，2×CHCH3)，0.85(d，J＝6.7Hz，6H，2×CHCH3).
1- (3-methoxyphenyl) -2 ' -oxo-2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B9)：
A white powder; the yield is 61.2%; mp102.5-103.8 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.23(t，J＝8.0Hz，1H，PhH)，6.83(d，J＝8.0Hz，3H，PhH)，6.53(d，J＝4.0Hz，1H，ArH)，6.45-6.32(brs，1H，NH)，6.06(d，J＝4.0Hz，1H，ArH)，4.22(s，2H，NHCH2)，3.88(d，J＝6.7Hz，2H，OCH2)，3.81(d，J＝6.7Hz，2H，OCH2)，3.76(s，3H，PhOCH3)，1.99-1.82(m，2H，2×CHCH3)，0.94(d，J＝6.7Hz，6H，2×CHCH3)，0.86(d，J＝6.7Hz，6H，2×CHCH3).
2 ' -oxo-1- (3- (trifluoromethyl) phenyl) -2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B10)：
A white powder; the yield is 76.7%; mp81.4-83.5 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.61-7.54(m，2H，PhH)，7.47(d，J＝7.7Hz，1H，PhH)，7.44(s，1H，PhH)，6.54(d，J＝4.0Hz，1H，ArH)，6.47-6.32(brs，1H，NH)，6.10(d，J＝4.0Hz，1H，ArH)，4.23(s，2H，NHCH2)，3.89(d，J＝6.7Hz，2H，OCH2)，3.84(d，J＝6.8Hz，2H，OCH2)，2.00-1.81(m，2H，2×CHCH3)，0.93(d，J＝6.7Hz，6H，2×CHCH3)，0.85(d，J＝6.7Hz，6H，2×CHCH3).
2 '-oxy-1- (3- (trifluoromethoxy) phenyl) -2'，5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]-4', 5-Dimethyldiiobutylborate(B11)：
A white powder; the yield is 80.6%; mp87.5-89.3 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.38(t，J＝8.0Hz，1H，PhH)，7.23-7.14(m，3H，PhH)，6.52(d，J＝4.0Hz，1H，ArH)，6.49-6.38(brs，1H，NH)，6.09(d，J＝4.0Hz，1H，ArH)，4.23(s，2H，NHCH2)，3.89(d，J＝6.7Hz，2H，OCH2)，3.85(d，J＝6.7Hz，2H，OCH2)，2.01-1.84(m，2H，2×CHCH3)，0.94(d，J＝6.7Hz，6H，2×CHCH3)，0.87(d，J＝6.7Hz，6H，2×CHCH3).
2 ' -oxo-1- (m-tolyl) -2 ', 5 ' -dihydro-1H, 1 ' H- [2, 3 ' -dipyrrole]Diisopropyl (4', 5-diyl) dicarbonate(B12)：
A white powder; the yield is 45.0%; mp115.6-118.5 ℃;1HNMR(400MHz，CDCl3)(ppm)：7.36-7.28(brs，1H，NH)，7.22(t，J＝7.6Hz，1H，PhH)，7.06(dd，J＝14.1，8.1Hz，3H，PhH)，6.48(d，J＝3.9Hz，1H，ArH)，6.03(d，J＝3.9Hz，1H，ArH)，4.84-4.67(m，2H，2×OCH)，4.21(s，2H，NHCH2)，2.33(s，3H，PhCH3)，1.27(d，J＝6.3Hz，6H，2×CHCH3)，1.18(d，J＝6.3Hz，6H，2×CHCH3).
example 2: fungicidal Activity of Compound (I) of the present invention against plant pathogenic fungi
The fungicidal activity of the compound (I) of the present invention against 3 test phytopathogens, i.e., gibberellic disease (fusarium graminearum), rhizoctonia solani (rhizoctonia solani) and botrytis cinerea (botrytiscipinea), was measured by a hyphal growth rate method at a concentration of 100. mu.g/mL. Hydrazoctone was used as a control. The results are shown in Table 1.
As can be seen from table 1: the compound of the invention has better bactericidal activity to 3 test phytopathogens. Under the concentration of 100 mu g/mL, the inhibition rate of the compounds B1, B2, B5, B6, B7, B9 and B12 on wheat scab bacteria reaches over 50 percent. The inhibition rate of most compounds on rice sheath blight bacteria is over 50 percent. The inhibition rate of most compounds on the botrytis cinerea reaches more than 50%, wherein the inhibition rate of the compound B1 on the botrytis cinerea exceeds 80%.
TABLE 1 fungicidal Activity of Compound (I) against plant pathogenic fungi (%)

Claims (8)

1. A carbonic ester derivative of phenyl pyrrole pyrrolinone with the structure shown in formula (I),
wherein,
r represents hydrogen, C1-20Alkyl, phenyl, substituted phenyl, benzyl, substituted phenylmethyl;
Y(n)wherein n is a 1-5 substitution, Y(n)Selected from the following 1-5The following groups: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkyloxy, C1-6Kang based thio, halogeno C1-6Alkyl, halo C1-6Kang radical oxy, halogenated C1-6Alkylthio, wherein the substituted phenyl represents 1-2C radicals containing 1-2 halogen atoms1-6The alkyl phenyl, halo represents 1-6 halogen substitutions, halo represents F, Cl, Br, I.
2. The carbonate derivatives of phenylpyrrolopyridinone according to claim 1, wherein:
r represents hydrogen, C1-4Kang base, phenyl and benzyl;
Y(n)wherein n is a 1-3 substitution, Y(n)Selected from the following 1-5 groups: hydrogen, halogen, methyl, methoxy, trifluoromethyl and trifluoromethoxy, wherein halogen represents F, Cl and Br.
3. The carbonate derivatives of phenylpyrrolopyridinone according to claim 2, wherein:
r is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl and benzyl;
Y(n)wherein n is a1 substitution, Y(n)Is selected from hydrogen, halogen, methyl, methoxy, trifluoromethyl and trifluoromethoxy, wherein halogen represents F, Cl and Br.
4. The carbonate derivatives of phenylpyrrolopyridinone according to claim 3, wherein:
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (A1),
Diethyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyldicarbonate (A2),
Di-n-propyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyl dicarbonate (A3),
Diisopropyl 1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (A4),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-n-butyl (A5),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (A6),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyldiphenyldicarbonate (A7),
1- (3-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diyl-dibenzyldicarbonate (A8),
2 '-oxo-1-phenyl-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B1),
1- (4-fluorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B2),
1- (2-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B3),
1- (4-chlorophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B4),
1- (4-bromophenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B5),
2 '-oxo-1- (o-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B6),
2 '-oxo-1- (m-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B7),
2 '-oxo-1- (p-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B8),
1- (3-methoxyphenyl) -2 '-oxo-2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B9),
2 '-oxo-1- (3- (trifluoromethyl) phenyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis (B10)
2 '-oxo-1- (3- (trifluoromethoxy) phenyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-diylbis-dicarbonate (B11),
Diisopropyl 2 '-oxo-1- (m-tolyl) -2', 5 '-dihydro-1H, 1' H- [2, 3 '-dipyrrole ] -4', 5-dimethyldicarbonate (B12).
5. A process for producing a carbonic acid ester derivative of phenylpyrrolidinone according to claims 1 to 4, which comprises the steps of preparing a compound represented by the general formula (A),
wherein in each structural formula of the above formula (A):
r and Y(n)All have the meanings as described above.
6. Use of a carbonate derivative of phenylpyrrole-pyrrolinone (I) according to any one of claims 1 to 4 for the control of phytopathogenic fungi.
7. The application of the carbonic ester derivatives of phenylpyrrole dipyrrolinone (I) in the aspect of controlling plant pathogenic fungi, which is disclosed in claim 6, is characterized in that the carbonic ester derivatives are applied to the control of wheat scab, rice sheath blight and strawberry gray mold.
8. The use of the carbonic acid ester derivatives of phenylpyrrolopyrrolidinone (I) according to claim 6 for controlling phytopathogenic fungi, characterized by the use thereof for inhibiting Gibberella tritici, Rhizoctonia solani and Botrytis fragilis.
CN201510937475.8A 2015-12-15 2015-12-15 A kind of carbonates derivative of phenylpyrrole connection pyrrolinone, preparation method and application Expired - Fee Related CN105481747B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510937475.8A CN105481747B (en) 2015-12-15 2015-12-15 A kind of carbonates derivative of phenylpyrrole connection pyrrolinone, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510937475.8A CN105481747B (en) 2015-12-15 2015-12-15 A kind of carbonates derivative of phenylpyrrole connection pyrrolinone, preparation method and application

Publications (2)

Publication Number Publication Date
CN105481747A true CN105481747A (en) 2016-04-13
CN105481747B CN105481747B (en) 2018-03-27

Family

ID=55669069

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510937475.8A Expired - Fee Related CN105481747B (en) 2015-12-15 2015-12-15 A kind of carbonates derivative of phenylpyrrole connection pyrrolinone, preparation method and application

Country Status (1)

Country Link
CN (1) CN105481747B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347372A (en) * 1978-09-01 1982-08-31 Ciba-Geigy Corporation Benzoxazolyl-glyoxylonitrile-2-oxime ether derivatives
CN101475523A (en) * 2009-01-12 2009-07-08 南京农业大学 3-acyl pyrroline-2-ketoxime ether compound, and preparation and use thereof
CN103641803A (en) * 2013-12-30 2014-03-19 南京农业大学 Furandione compound containing substituted phenylhydrazine, preparation method and application
CN104910075A (en) * 2015-06-23 2015-09-16 安徽农业大学 Bis-pyrazole schiff base compound as well as preparation method and application thereof as bactericide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347372A (en) * 1978-09-01 1982-08-31 Ciba-Geigy Corporation Benzoxazolyl-glyoxylonitrile-2-oxime ether derivatives
CN101475523A (en) * 2009-01-12 2009-07-08 南京农业大学 3-acyl pyrroline-2-ketoxime ether compound, and preparation and use thereof
CN103641803A (en) * 2013-12-30 2014-03-19 南京农业大学 Furandione compound containing substituted phenylhydrazine, preparation method and application
CN104910075A (en) * 2015-06-23 2015-09-16 安徽农业大学 Bis-pyrazole schiff base compound as well as preparation method and application thereof as bactericide

Also Published As

Publication number Publication date
CN105481747B (en) 2018-03-27

Similar Documents

Publication Publication Date Title
EP1464642B1 (en) Novel substituted pyrazole derivative, process for producing the same, and herbicidal composition containing the same
US7557067B2 (en) Pyrazole sulfonylurea compound and herbicide
KR960011384B1 (en) Novel pyridinylpyrimidine derivatives
UA59380C2 (en) halogen pyrimidineILARYL (THIO) ETHERS AS PESTICIDES
JPH0641118A (en) Picolinic acid derivative and herbicide
JP2533331B2 (en) Carbmate derivatives and agricultural and horticultural fungicides containing them
CN105481747B (en) A kind of carbonates derivative of phenylpyrrole connection pyrrolinone, preparation method and application
EP0617014B1 (en) Oxime ether compound, processes for preparing the same and fungicide containing the same
EP0658547B1 (en) N-pyrazolyl carbamate derivative, agricultural/horticultural fungicide containing the same as active ingredient and production intermediate thereof
JP3511729B2 (en) 4- [2- (trifluoroalkoxy-substituted phenyl) ethylamino] pyrimidine derivative, its production method and pesticide for agricultural and horticultural use
JPH09268169A (en) Salicylic acid anilide derivative and controlling agent for plant disease injury containing the same derivative as active ingredient
US5444060A (en) N-sulfonyl carboxylic amide derivative including an N-containing 6-membered aromatic ring, or the salt of the same, method for producing the same, and biocide
KR100254649B1 (en) N-substituted phenylcarbamic acid derivatives, a process for roduction thereof, agricultural and horticultural fungicides
JPWO2007046440A1 (en) Herbicidal composition
US5131947A (en) 4-ethyl-3-(substituted phenyl)-1-(3-trifluoromethylphenyl)-2-pyrrolidinone derivatives, herbicidal compositions containing them and use thereof
JPH06220043A (en) Substituted thiophenecarboxyamide
KR100501146B1 (en) Triazole derivatives for antifungal composition of agriculture, method of preparing same and antifungal composition comprising same for agriculture
CN108707114B (en) Acetamide compound and preparation method and application thereof
JPH08113564A (en) 4-cyclohexylaminopyridine derivative, its production and agricultural and horticultural harmful organism controller
EP0477626A1 (en) 3,4-trans-4-ethyl-1-(substituted phenyl)-3-(substituted phenyl)pyrrolidin-2-ones, method for preparing the same, and herbicidal compositions containing the same as herbicidally active ingredients
JP2000095778A (en) Pyrazole derivative, production thereof and horticultural bactericide
JPH0183A (en) Pyridylpyrimidine derivatives and plant disease control agents containing them as active ingredients
JPH07112972A (en) Pyrazolcarboxamine derivative, its production and agricultural/horticultural pest-controlling agent
JP4824968B2 (en) Phosphonic acid derivatives and acid addition salts thereof, and agricultural and horticultural disease control agents using the same
JPS6342621B2 (en)

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180327

Termination date: 20191215

CF01 Termination of patent right due to non-payment of annual fee