CN110078721A - Dioctyl glutaricate and its preparation method and application of the one kind containing triazine - Google Patents
Dioctyl glutaricate and its preparation method and application of the one kind containing triazine Download PDFInfo
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- CN110078721A CN110078721A CN201910449787.2A CN201910449787A CN110078721A CN 110078721 A CN110078721 A CN 110078721A CN 201910449787 A CN201910449787 A CN 201910449787A CN 110078721 A CN110078721 A CN 110078721A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Organic Chemistry (AREA)
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
Dioctyl glutaricate and its preparation method and application the present invention relates to one kind containing triazine.The compound is as shown in formula A.Wherein X is selected from O, and R is phenyl, substituted-phenyl, substituted heterocyclic radical, R1For hydrogen atom or methoxyl group, R2For the alkyl etc. of phenyl, substituted-phenyl or C1-C6.The compounds of this invention has preferable control efficiency to tobacco ralstonia solanacearum, citrus stain ulcer germ and rice leaf spot bacteria.
Description
Technical field
The present invention relates to chemical technology fields, and it is derivative to relate in particular to a kind of Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone
Object, also relates to the Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketones derivant preparation method and this contains the Isosorbide-5-Nitrae-penta two of triazine
Application of the alkene -3- ketones derivant in terms of bacteriostatic activity.
Background technique
Natural activity molecule and its derivative have unique structure, the mode of action novel, less toxic to people and animals and friendly to environment
Good feature has very important meaning in the discovery procedure of pesticide poullant.Curcumin is derived from as one kind
Polyphenol compound in turmeric is widely used as fragrance, food preservative, monosodium glutamate and dyestuff.Isosorbide-5-Nitrae-pentadiene ketone
Close object, as a kind of important curcumin derivate, because its have such as desinsection, antibacterial, Antiphytoviral, anticancer, anti-inflammatory and
Anti-oxidant equal more wide spectrum biological activity, in occupation of important function in agricultural chemicals research and development work.
(Xue Wei, Gong Huayu, Chou Qiujuan, Zhao Hongju, Li Haichang, Han Feifei the curcumin of esters containing oxime are derivative by Xue in 2013 etc.
The synthesis of object and its bacteriostatic activity study [J] chemical reagent, 2013,35:201-205.) oxime ester structure is introduced into single carbonyl
In curcumin derivate Isosorbide-5-Nitrae-pentadiene -3- ketone compounds, a series of Isosorbide-5-Nitrae with inhibitory activity-pentadiene -3- have been synthesized
Ketoxime ester curcumin derivate, the tested results show: when concentration is 500mg/L, the series compound is to three kinds of diseases
Bacterium is presented with certain inhibiting effect.
(Gan Xiuhai, Hu Deyu, Li Pei, Wu Jian, Chen Xuewen, Xue Wei, Song Baoan contain 1,3,4- in 2016 seas Nian Ganxiu etc.
The design of the novel Isosorbide-5-Nitrae of oxadiazoles part-pentadiene -3- ketone derivatives, synthesis, antiviral activity and three-dimensional quantitative structure activity relationship
It is scientific to study [J] Pest Management, 2016,72:534-543.) have with Isosorbide-5-Nitrae-pentadiene -3- ketone for guide and 1,3,4- oxadiazoles
Machine synthesizes a series of containing Isosorbide-5-Nitrae-pentadiene -3- ketone structure compound, and Preliminary Determination activity shows most of target compound
Its comparison medicament virazole is above to the antiviral activity of TMV.
(Zhang Juping, Li Pu, Wang Yihui, Zhang Cheng, Chen Lijuan, Tang Xu, He Ming, Xue Wei contain benzo three to 2018 Nian Zhangju equalitys
The synthesis of the Isosorbide-5-Nitrae of piperazine ketone-pentadiene -3- ketone derivatives and bacteriostatic activity Chemical Journal of Chinese Universities, 2018,39:1455-
1461.) a series of Isosorbide-5-Nitrae-pentadiene -3- ketones derivant for having synthesized ketone containing phentriazine, it is found that such compound is expected into
For the inhibitor of citrus processing and tobacco ralstonia solanacearum.
1,2,4- triazine is a kind of important nitrogen-containing heterocycle, special structure and property make it have high chemical activity,
The advantages that reaction site is more.The advantages that cheap and easy to get, easy to maintain, stable structure is had both due to 1,2,4- triazine, 1,2,4- triazine
And its there are derivative antibacterial, anti-inflammatory and antalgic, anti-HIV-1, anticancer, anti-diabetic, many kinds of anti-malarial isoreactivity also to have
The advantages that low toxicity, low-residual.The MOLECULE DESIGN of such compound and synthesis and bioactivity research are pesticide and medicine wound at present
One of hot spot of system.
Tamboli in 2015 etc. (J.Enzym.Inhib.Med.Chem, 2015,5:1475-6366.) has synthesized a series of
5 of the ethamine containing morpholine, 6- diphenyl -1,2,4- triaizine compounds, and carried out that antiplatelet is external, body to the compound of synthesis
The measurement of outer and activity in vivo, the results showed that, such compound with good anti-thrombosis activity, the compound of synthesis have compared with
Good internal antithrombogenic properties.Its IC50Better than comparison medicine aspirin.
Fu in 2017 etc. (Eur.J.Med.Chem, 2017,138:1076-1088.) using active group splicing method by 1,
2,3- triazoles introduce 5,6- diphenyl -1,2, in 4- triazine, have synthesized a series of 5,6- diphenyl -1,2 containing 1,2,3-triazoles,
4- triazines noval chemical compound.Antitumor (MGC-803, EC-109 and PC-3) has been carried out to the compound of synthesis) active testing, knot
Fruit shows that such compound has good anti-tumor activity, wherein the minimum 503nhibiting concentration IC of compound50It is excellent for 7.59 μM
In control 5 FU 5 fluorouracil.
Wang in 2017 etc. (Bioorg.Med.Chem.Lett, 2017,27:1115-1118.) is spliced using active group
Method, has synthesized diphenyl -1,2 containing 5,6- of a series of new, 4- pyrrolotriazine derivatives and is pressed down to the compound of synthesis
The test of alpha-glucosidase activity processed, the results showed that, such compound has good inhibition alpha-Glucosidase, wherein compound
Minimum IC50=12.46 ± 0.13 μM is better than comparison medicine acarbose (IC50=817.38 ± 6.27 μM).
Yet there are no, which will contain triazine, is introduced into Isosorbide-5-Nitrae-pentadiene -3- ketone structure, and tests the relevant report of biocidal property.
Summary of the invention
The Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds for being there is provided it is an object of the invention to overcome disadvantages mentioned above and
Its derivative.
An object of the present invention provide the Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds or its stereoisomer,
Or its salt or its solvate.
Another object of the present invention is providing preparation above compound or its stereoisomer or its salt or its solvation
Midbody compound of object and preparation method thereof.
Further object of the present invention contains above compound or its stereoisomer or its salt there is provided one kind or its is molten
The composition of agent compound.
Further object of the present invention there is provided above compound or its stereoisomer or its salt or its solvate,
Or the purposes of the composition.
There is provided utilize above compound or its stereoisomer or its salt or its solvation for another object of the present invention
Object or the method for the composition for preventing and controlling agricultural pest.
To achieve the above object, present invention employs following technical proposals:
A kind of Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds or its stereoisomer or its salt or its solvate,
The compound, which has, such as leads to structure shown in formula A:
Wherein,
R independently selected from hydrogen, deuterium, any substituted or unsubstituted alkyl, any substituted or unsubstituted alkenyl, arbitrarily take
Generation or unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted naphthenic base, it is any replace or
One or more of unsubstituted aryl, any substituted or unsubstituted heteroaryl；
R1Independently selected from hydrogen, deuterium, halogen, any substituted or unsubstituted alkyl, any substituted or unsubstituted alkenyl,
It is any substituted or unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted naphthenic base, any
One or more of substituted or unsubstituted aryl；
R2Identical or differently independently selected from hydrogen, deuterium, halogen, any substituted or unsubstituted alkyl, it is any replace or
It is unsubstituted alkenyl, any substituted or unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted
Naphthenic base, any substituted or unsubstituted aryl, one or more of any substituted or unsubstituted heteroaryl；
X is independently selected from O, S or NH.
Preferably, R is independently selected from hydrogen, deuterium, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted aryl, substitution
Or one or more of unsubstituted heteroaryl；It is highly preferred that R is independently selected from hydrogen, deuterium, C1-C6Alkyl, C1-C6Alcoxyl
Base, C1-C6Alkenyl, C1-C6Alkynyl, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C10One in heteroaryl
It is a or multiple, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkenyl, C1-C6Alkynyl, amino,
Hydroxyl, halogen replace；Most preferably, R independently selected from hydrogen, deuterium, nitro, methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, cyclobutenyl, pentenyl, hexenyl,
Propinyl, butynyl, pentynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, phenyl, chlorphenyl, bromophenyl, fluorine
Phenyl, dichlorophenyl, dibromo phenyl, difluorophenyl, nitrobenzophenone, dinitrophenyl, methoxyphenyl, Dimethoxyphenyl,
Aminomethyl phenyl, 3,5-dimethylphenyl, amine phenyl, hydroxyphenyl, benzyl, adjacent luorobenzyl, luorobenzyl, to luorobenzyl, adjacent bromobenzyl,
Bromobenzyl, to bromobenzyl, o-chlorobenzyl, chlorobenzyl, p-chlorobenzyl, naphthalene, phenanthryl, pyridyl group, thienyl, adjacent fluorine pyridine
Base, fluorine pyridyl group, adjacent bromopyridine base, bromopyridine base, adjacent chloropyridine base, m-chloro pyridyl group, adjacent fluorine thienyl, fluorine thiophene
Base, adjacent fluorine furyl, fluorine furyl, adjacent fluorine tetrahydrofuran base, fluorine tetrahydrofuran base, adjacent bromothiophene base, bromothiophene base,
Adjacent bromine furyl, bromine furyl, adjacent bromine tetrahydrofuran base, bromine tetrahydrofuran base, adjacent chlorothiophene base, m-chloro thienyl, neighbour
Chlorine furyl, m-chloro furyl, adjacent chlorine tetrahydrofuran base, m-chloro tetrahydrofuran base, adjacent hydroxybenzyl, hydroxybenzyl, to hydroxyl
Base benzyl, adjacent aminobenzyl, aminobenzyl, aminobenzyl, adjacent methylbenzyl, methylbenzyl, to methylbenzyl, adjacent hydroxyl
Yl pyridines, hydroxy-pyridyl, to hydroxy-pyridyl, adjacent aminothiophene base, aminothiophene base, adjacent hydroxyfuryl, hydroxyl
Base furyl, adjacent hydroxyl tetrahydrofuran base, hydroxyl tetrahydrofuran base, sylvan base, methylfuran base, adjacent methyl four
Hydrogen furyl, methyltetrahydrofuran base, adjacent fural, fural, adjacent tetrahydrofuran methylene, tetrahydro furan
It mutters one or more of methylene；
Preferably, R1Independently selected from hydrogen, deuterium, halogen, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted virtue
One or more of base, substituted or unsubstituted heteroaryl or heterocycle；It is highly preferred that R1Independently selected from hydrogen, deuterium, C1-C6Alkane
Base, C1-C6Alkenyl, C1-C6Alkynyl, C1-C6Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C10
One or more of heteroaryl, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, amino, hydroxyl, halogen
Element replaces；Most preferably, R1Independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, tert-butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, cyclobutenyl, pentenyl, hexenyl, propinyl, butine
Base, pentynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, phenyl, chlorphenyl, bromophenyl, fluorophenyl, toluene
Base, amine phenyl, hydroxyphenyl, benzyl, adjacent luorobenzyl, luorobenzyl, to luorobenzyl, adjacent bromobenzyl, bromobenzyl, to bromobenzyl,
One or more of o-chlorobenzyl, chlorobenzyl, p-chlorobenzyl, naphthalene, phenanthryl, pyridyl group；
Preferably, R2Identical or differently independently selected from hydrogen, deuterium, halogen, alkyl, alkenyl, alkynyl, alkoxy, substitution
Or one or more of unsubstituted aryl, substituted or unsubstituted heteroaryl；It is highly preferred that R2Independently selected from hydrogen, deuterium,
C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkenyl, C1-C6Alkynyl, substituted or unsubstituted C6-C15It is aryl, substituted or unsubstituted
C6-C10One or more of heteroaryl, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkene
Base, C1-C6Alkynyl, amino, hydroxyl, halogen replace；Most preferably, R2Independently selected from hydrogen, deuterium, nitro, methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, butylene
Base, pentenyl, hexenyl, propinyl, butynyl, pentynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, benzene
Base, chlorphenyl, bromophenyl, fluorophenyl, nitrobenzophenone, methoxyphenyl, aminomethyl phenyl, amine phenyl, hydroxyphenyl, benzyl, adjacent fluorine
Benzyl, luorobenzyl, to luorobenzyl, adjacent bromobenzyl, bromobenzyl, to bromobenzyl, o-chlorobenzyl, chlorobenzyl, p-chlorobenzyl,
Naphthalene, phenanthryl, pyridyl group, thienyl, adjacent fluorine pyridyl group, fluorine pyridyl group, adjacent bromopyridine base, bromopyridine base, adjacent chloropyridine
Base, m-chloro pyridyl group, adjacent fluorine thienyl, fluorine thienyl, adjacent fluorine furyl, fluorine furyl, adjacent fluorine tetrahydrofuran base, fluorine
Tetrahydrofuran base, adjacent bromothiophene base, bromothiophene base, adjacent bromine furyl, bromine furyl, adjacent bromine tetrahydrofuran base, bromine four
Hydrogen furyl, adjacent chlorothiophene base, m-chloro thienyl, adjacent chlorine furyl, m-chloro furyl, adjacent chlorine tetrahydrofuran base, m-chloro tetrahydro
Furyl, adjacent hydroxybenzyl, hydroxybenzyl, to hydroxybenzyl, adjacent aminobenzyl, aminobenzyl, aminobenzyl, adjacent first
Base benzyl, methylbenzyl, to methylbenzyl, adjacent pyridone, hydroxy-pyridyl, to hydroxy-pyridyl, adjacent aminothiophene
Base, aminothiophene base, adjacent hydroxyfuryl, hydroxyfuryl, adjacent hydroxyl tetrahydrofuran base, hydroxyl tetrahydrofuran base,
Sylvan base, methylfuran base, adjacent methyltetrahydrofuran base, methyltetrahydrofuran base, adjacent fural, furan
It mutters one or more of methylene, adjacent tetrahydrofuran methylene, tetrahydrofuran methylene；
Further preferably it is selected from following compounds:
The Isosorbide-5-Nitrae containing the triazine-pentadiene -3- ketone compounds or its alloisomerism are prepared the present invention also provides a kind of
The midbody compound of body or its salt or its solvate, is shown below:
Wherein R, R1、R2It is as described above with X.
The present invention provides the described Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds or its stereoisomer or its salt
Or the preparation method of its solvate, it is characterised in that include the following steps:
Preferably, further comprise following step:
It is highly preferred that including the following steps:
Most preferably, include the following steps:
The present invention provides a kind of compositions, it is characterised in that containing the compound or its stereoisomer or its
Salt or its solvate, and agriculturally available auxiliary agent or fungicide, insecticide or herbicide；Preferably, the composition
Dosage form independently selected from missible oil (EC), pulvis (DP), wettable powder (WP), granule (GR), aqua (AS), suspending agent
(SC), ultra-low volume spray agent (ULV), soluble powder (SP), microcapsule formulations (MC), fumicants (FU), aqueous emulsion (EW), moisture
Dissipate property granula (WG).
The present invention provides the compound or its stereoisomer or its salt or its solvate or the groups
Close purposes of the object in terms of preventing and treating agricultural pest, it is preferable that the agricultural pest is vegetative bacteria or fungal disease；
It is highly preferred that the agricultural pest is plant leaf blight and plant canker；Most preferably, the agricultural pest is rice
Bacterial leaf-blight, tobacco bacterial wilt, tobacco mosaic disease, cucumber bacterial leaf-blight, konjaku bacterial leaf-blight, citrus bacterial canker disease, grape ulcer
Disease, canker of tomato, Prospect on Kiwifruit Bacterial Canker, apple canker, gray mold of cucumber, capsicum wilt, sclerotinia sclerotiorum, wheat are red
Mildew, the late blight of potato, capsicum wilt, blueberry root rot, wheat scab, the late blight of potato, sclerotinia sclerotiorum and
Dragon fruit anthracnose.
The present invention provides a kind of method for preventing and treating agricultural pest, make the compound or its stereoisomer or
Its salt or its solvate or the composition act on nuisance or its living environment；Preferably, the agricultural pest
For vegetative bacteria or fungal disease；It is highly preferred that the agricultural pest is bacterial blight of rice, tobacco bacterial wilt, cigarette
Showy flowers of herbaceous plants leaf disease, cucumber bacterial leaf-blight, konjaku bacterial leaf-blight, citrus bacterial canker disease, grape ulcer, canker of tomato, Kiwi berry are burst
Ulcer disease, apple canker, gray mold of cucumber, capsicum wilt, sclerotinia sclerotiorum, wheat scab, the late blight of potato, capsicum
Wilt disease, blueberry root rot, wheat scab, the late blight of potato, sclerotinia sclerotiorum and dragon fruit anthracnose.
The present invention provides the methods for protecting the plants from agricultural pest infringement comprising wherein makes plant and institute
The compound stated or the method and step of its stereoisomer or its salt or its solvate or the composition contact.
The term " alkyl " used herein be include the branch and linear saturation alkyl with given number carbon atom.Such as
“C1-10Alkyl " (or alkylidene) purpose is C1, C2, C3, C4, C5, C6, C7, C8, C9 and C10 alkyl.In addition, such as " C1-6Alkane
Base " indicates the alkyl with 1 to 6 carbon atoms.Alkyl can be to be non-substituted or substitution, so that its one or more hydrogen atom quilt
Other chemical groups replace.The embodiment of alkyl includes but is not limited to methyl (Me), ethyl (Et), propyl (such as n-propyl and different
Propyl), butyl (such as normal-butyl, isobutyl group, tert-butyl), amyl (such as n-pentyl, isopentyl, neopentyl) and the like.And
It further include its all isomerism in addition to including n-hexyl, n-heptyl, n-octyl and when mentioning hexyl, heptyl, octyl
Body.
" alkenyl " is hydrocarbon both including straight or branched structure, and there is one or more to appear in any stable point in chain
Carbon-to-carbon double bond.Such as " C2-6Alkenyl " (or alkenylene) purpose be include C2, C3, C4, C5 and C6 alkenyl.The example packet of alkenyl
Include but be not limited to vinyl, 1- acrylic, 2- acrylic, 2- cyclobutenyl, 3- cyclobutenyl, 2- pentenyl, 3- pentenyl, 4- amylene
Base, 2- hexenyl, 3- hexenyl, 4- hexenyl, 5- hexenyl, 2- methyl -2- acrylic, 4- methyl-3-pentenyl and its class
Like object.
" alkynyl " is hydrocarbon both including straight or branched structure, and there is one or more to appear in any stable point in chain
Three key of carbon-to-carbon.Such as " C2-6Alkynyl " (or alkynylene) purpose be include C2, C3, C4, C5 and C6 alkynyl；Such as acetenyl, third
Alkynyl, butynyl, pentynyl, hexin base and the like.
The term " substituted " used herein refers to any one or more hydrogen atoms on specified atom or group
Replaced with the specified group of selection, on condition that being no more than the general chemical valence of specified atom.If without other explanation, substituent group
It names to division center.For example, it is to be understood that when (naphthenic base) alkyl is possible substituent group, the substituent group to centre junction
The tie point of structure is in moieties.Ring double bond used herein is formed at two double bond (such as C closed between annular atom
=C, C=N or N=N).
When mentioning substitution, when especially polysubstituted, refer to multiple substituent groups on each position in specified group
Replace, as dichlorophenyl refers to 1,2- dichlorophenyl, 1,3- dichlorophenyl and Isosorbide-5-Nitrae-dichlorophenyl；In addition, dichlorophenyl can
Compound main structure is connected to any position.
The combination of substituent group and/or variable is allowed, and only generates stable compound or useful synthesis when these are combined
Intermediate.
Term " aryl " is referred in monocycle or Bicyclic alkyl that loop section has 6 to 12 carbon atoms, such as phenyl
And naphthalene, it each can be substituted.When mentioning monosubstituted or polysubstituted substituted aryl, as described above, refer to one or
Multiple substituent groups replace on each position in specified group, can any unsubstituted position be connected to compound main body knot
Structure；As dichlorophenyl refers to 1,2- dichlorophenyl, 1,3- dichlorophenyl and Isosorbide-5-Nitrae-dichlorophenyl, meanwhile, 1,2- dichlorophenyl,
1,3- dichlorophenyl and any unsubstituted position of Isosorbide-5-Nitrae-dichlorophenyl are connected to compound main structure.
Term " halogen " or " halogen atom " refer to chlorine, bromine, fluorine and iodine.
Term " halogenated alkyl " refers to the substitution alkyl with one or more halogenic substituents.Such as " halogenated alkyl "
Including single, double and trifluoromethyl；Even if in halogenated alkyl it is halogenated by clearly be fluorine, chlorine, bromine, iodine, again refer to have one
A or multiple fluorine, chlorine, bromine, iodine substituent group substitution alkyl.
Term " heteroaryl " refer to replace and non-substituted fragrant 5 or 6 unit monocycle group, 9- or 10- membered bicyclic group, and
11 to 14 membered tricyclic groups have at least one hetero atom (O, S or N) at least one ring, described excellent containing heteroatomic ring
Choosing has 1,2 or 3 hetero atom in O, S and N.Each ring containing heteroatomic heteroaryl can contain one or two oxygen or
Sulphur atom and/or by 1 to 4 nitrogen-atoms, on condition that heteroatomic sum is 4 or less in each ring, and each ring has extremely
A few carbon atom.Carbon atom can only be contained by completing bicyclic and three cyclic groups fused rings, and can be saturation, fractional saturation or
It is unsaturated.Nitrogen and sulphur atom can be optionally oxidized and nitrogen-atoms can be optionally quaternized.Bicyclic or tricyclic heteroaryl must wrap
At least one full aromatic rings is included, the other fused rings of nitrogen can be armaticity or nonaromatic.Heteroaryl can be in any of any ring
Using being connected on nitrogen or carbon atom.When chemical valence allows, if other rings are naphthenic base or heterocycle, in addition optionally with
=O (oxygen) replaces.When mentioning any heteroaryl, the heteroaryl can be connected on compound body position with any position,
Such as thienyl, refer to that 2,3,4,5 positions of thienyl are attached on compound body position.When heteroaryl is substituted
When, when especially polysubstituted, refer to that one or more substituent groups replace on each position in specified group, such as chloro thiophene
Pheno base base refers to 2- chlorothiophene base, 3- chlorothiophene base, 4- chlorothiophene base, 5- chlorothiophene base；Dichloro- thienyl refers to 2,
3- dichloro-thiophene base, 2,4- dichloro-thiophene base, 2,5- chlorothiophene base, 3,4- chlorothiophene base, 3,5- chlorothiophene base and 4,5- diuril
Pheno base, meanwhile, any unsubstituted position in described monosubstituted or polysubstituted thiophene base is connected to compound main structure.
Exemplary monocyclic heteroaryl includes pyrrole radicals, pyrazolyl, pyrazolinyl, imidazole radicals, oxazolyl, isoxazolyl, thiophene
Oxazolyl, thiadiazolyl group, furyl, thienyl, oxadiazoles base, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, triazine radical and its class
Like object.
Exemplary bicyclic heteroaryl include indyl, benzothiazolyl, benzodioxole base, benzoxazolyl,
Benzothienyl, quinolyl, tetrahydro isoquinolyl, isoquinolyl, benzimidazolyl, benzofuranyl, indolizine base, benzo furan
It mutters base, chromone base, cumarin base, benzofuranyl, cinnoline base, quinoxalinyl, indazolyl, pyrrolopyridinyl, fluorinated pyridine
Base, dihydro-iso indolyl, tetrahydric quinoline group and the like.
If the compound of the present invention is interpreted as including free state and its salt without other explanations.Term " salt " indicate with
Inorganic and/or organic bronsted lowry acids and bases bronsted lowry forms acid and/or basic salt.In addition, " salt may include amphoteric ion (inner salt) to term, such as work as
Compound of formula I contains basic moiety such as amine or pyridine or imidazole ring and acid segment such as carboxylic acid.It is pharmaceutically acceptable (i.e. non-
It is toxicity, physiologically acceptable) salt is preferred, such as acceptable metal and amine salt, wherein cation does not have notable contribution
The bioactivity of toxicity or salt.However, other salt can be useful, isolated or purified step is such as used during the preparation process, because
This is also contained in the scope of the invention.
Preferably, C1-C10Alkyl refers to methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, the last of the ten Heavenly stems
Base and its isomer；C1-C10Alkoxy refer to methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy,
Heptan oxygroup, octyloxy, nonyl epoxide, decyloxy and its isomer；C2-C5Alkenyl refer to vinyl, acrylic, allyl,
Cyclobutenyl, pentenyl and its isomer.Similar, C1-C5Alkyl refer to methyl, ethyl, propyl, butyl, amyl and its
Isomer；C1-C5Alkoxy refers to methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy and its isomer；
When mentioning substituent group, as alkenyl, alkynyl, alkyl, halogen, aryl, heteroaryl, alkoxy, naphthenic base, hydroxyl,
When amino, sulfydryl, phosphino- or these substituent groups are specifically some specific alkenyl, alkynyl, alkyl, halogen, aryl, heteroaryl
When base, alkoxy, naphthenic base, hydroxyl, amino, sulfydryl, phosphino-, one to three above-mentioned substituent group is referred to.Such as aminomethyl phenyl
Refer to one to three methyl substituted phenyl
It is highly preferred that the present invention also provides a kind of preparation methods of compound:
Its synthetic route is as follows:
(1) 2,3- butanedione or benzil synthesize 5,6- dimethyl -1,2 with thiosemicarbazides, 4- triazine -3- mercapto alcohol or 5,
6- diphenyl -1,2,4- triazine -3- mercapto alcohol (intermediate 1):
(2) acetone, 4- hydroxy benzaldehyde prepare 4- (hydroxy phenyl)-3- butene-2 -one (intermediate under alkaline condition
2)；
(3) substituted aroma aldehyde, 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 2) prepare 1- substitution under alkaline condition
Aryl -5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 3)；
(4) 1- substituted aryl -5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 3) and Bromofume, with carbon
Sour potassium is catalyst, with acetonitrile as solvents, prepares 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl)-Isosorbide-5-Nitrae-pentadiene -3-
Ketone (intermediate 4):
(5) 1- substituted aryl -5- (4- (2- bromine oxethyl) phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 4) and 5,6- bis-
Methyl-1,2,4- triazine -3- mercapto alcohol or 5,6- diphenyl -1,2,4- triazine -3- mercapto alcohol (intermediate 1), is catalysis with potassium carbonate
Agent, n,N-Dimethylformamide (DMF) are that solvent prepares the Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketones derivant (target compound
A), as follows:
Compared with prior art, the present invention have apparent beneficial effect, as can be known from the above technical solutions: the present invention with 2,
3- butanedione, benzil, thiosemicarbazides etc. are that raw material generates triazine, generate 4- (hydroxyl using acetone, 4- hydroxy benzaldehyde as raw material
Base phenyl)-3- butene-2 -one, substituted aroma aldehyde, 4- (hydroxy phenyl)-3- butene-2 -one are that raw material generates 1- substituted aryl-
5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone, 1- substituted aryl -5- (4- hydroxy phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone again with
Bromofume reaction, the product and triazine of generation act on obtaining the Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketones derivant.The present invention will
Triazine group with excellent activity is introduced into Isosorbide-5-Nitrae-pentadiene -3- ketone structure, i.e. Isosorbide-5-Nitrae-pentadiene -3- ketone position 4- hydroxyl
Upper connection triazine structure.A series of Isosorbide-5-Nitraes containing triazine-pentadiene -3- ketone compounds are synthesized, by containing triazine to synthesized
Isosorbide-5-Nitrae-pentadiene -3- ketones derivant suppression phytopathogen active testing, discovery the compound of the present invention has excellent suppression to plant
Object germ (tobacco ralstonia solanacearum, citrus processing and rice leaf spot bacteria) activity, can be used for preparing disinfectant use in agriculture.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that the method for the embodiment of the present invention
It is only used for illustrating the present invention, rather than limiting the invention, to preparation side of the invention under concept thereof of the invention
The simple modifications of method belong to the scope of protection of present invention.All raw materials and solvent used in embodiment are commercially available production
Product.
Embodiment 1
(1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- thiophene
Pheno) -5- substitution-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A1):
Preparation method, comprising the following steps:
(1) 5,6- diphenyl -1,2, the preparation of 4- triazine -3- mercapto alcohol (intermediate 1):
Benzil (1.5g) and 35mL glacial acetic acid are added in the three-necked flask of 100mL, then by thiosemicarbazides (0.65g)
Mixed system is added in three-necked flask after being dissolved in the hot water of 25mL, which stirs 4h under the conditions of 100 DEG C, wait react
After multiply heat filtering and obtain yellow solid, yield 78%.
(2) preparation of 4- (hydroxy phenyl)-3- butene-2 -one (intermediate 2):
4- hydroxy benzaldehyde (6.1g) is added in the acetone of 60mL, after stir about 15min, the ice bath reaction system is about
After 30min, 5% NaOH solution of about 100mL is added into system, after being added dropwise, removes ice bath room, stirring at normal temperature is about
24h.It is then molten with 5% dilute hydrochloric acid to after reaction, system is transferred in the beaker of 500mL and appropriate ice water is added
After liquid regulation system pH is about 5-6, there are a large amount of yellow solids to be precipitated, solid extracted out, is finally recrystallized with ethanol/water system,
Up to yellow solid, yield 65%.
(3) preparation of 1- (4- hydroxy phenyl) -5- (2- thiophene)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 3):
By 1- (4- hydroxy phenyl) -5- (2- thiophene)-Isosorbide-5-Nitrae-pentadiene -3- ketone (3.0g), 2 thiophene carboxaldehyde (2.24mL)
It is added in the three-necked flask of 250mL with 50mL ethyl alcohol, after stir about 30min, 5% NaOH solution of 60mL into system,
After being added dropwise, ice bath room is removed, stirring at normal temperature is about for 24 hours.To which after reaction, system is transferred in the beaker of 500mL
And appropriate ice water is added, and after being about then 5-6 with 5% dilute hydrochloric acid solution regulation system pH, there are a large amount of yellow solids to be precipitated, it will
Solid is extracted out to get yellow solid, yield 80%.
(4) preparation of 1- (4- (2- bromine oxethyl) phenyl) -5- (2- thiophene)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 4):
1- (4- (2- bromine oxethyl) phenyl) -5- (2- thiophene)-Isosorbide-5-Nitrae-penta two is sequentially added in 100mL round-bottomed flask
Alkene -3- ketone (1.6g), K2CO3After 1h that then mixed liquor flows back at 80 DEG C, 2.80mL bis- is added dropwise in (2.25g) and 60mL acetonitrile
Bromoethane continues the 7h that flows back at 80 DEG C, TLC tracking reaction (ethyl acetate: petroleum ether=1: 2, V/V).After reaction stops, instead
Answer the water dispersion of liquid 50mL, ethyl acetate extracts (3 × 25mL), merge organic layer, with saturated common salt water washing (3 ×
40mL), anhydrous Na2SO4Solvent, reduced pressure chromatography separating-purifying (petroleum ether: ethyl acetate=2: 1, V/V) is removed under reduced pressure in drying
Obtain yellow solid (intermediate 4), yield: 53%.
(5) (1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- thiophene
Pheno) -5- substitution-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A1) preparation:
5,6- diphenyl -1,2 of 0.5g, 4- triazine -3- mercapto alcohol (intermediate are added in the single necked round bottom flask of 100mL
1)、K2CO3(1.33g) and 60mL DMF, stirring at normal temperature 1h, after be slowly added to 1- (4- (2- bromine oxethyl) phenyl) -5- (2- thiophene
Pheno)-Isosorbide-5-Nitrae-pentadiene -3- ketone (intermediate 4) DMF solution, continues under room temperature to stir 6-8h.TLC tracking reaction, when reaction is tied
Beam stops reaction, the water dispersion of reaction solution 100mL, and ethyl acetate extracts (3 × 25mL), merges organic layer, uses saturated common salt
Water washing (3 × 40mL), anhydrous sodium sulfate are dry, solvent is removed under reduced pressure, and obtain crude product, through column chromatography (ethyl acetate: methanol=
1: 3, V/V) purification obtain target compound, yield: 44%.
Embodiment 2
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (4- chlorobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A2):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A2, yield: 56%.
Embodiment 3
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (4- nitro
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A3):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A3, yield: 35%.
Embodiment 4
(1E, 4E) -1- (4- chlorphenyl) -5- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) -3-
Methoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A4):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A4, yield: 46%.
Embodiment 5
(1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (3,4- bis-
Methoxyl group)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A5):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A5, yield: 44%.
Embodiment 6
(1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (4- nitro
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A6):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound target compound A6, yield:
34%.
Embodiment 7
(1E, 4E) -1- (4- methoxyphenyl) -5- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethoxy
Base) -3- methoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A7):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A7, yield: 56%.
Embodiment 8
(1E, 4E) -1- (2,4- Dimethoxyphenyl) -5- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl second
Oxygroup) -3- methoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A8):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A8, yield: 62%.
Embodiment 9
(1E, 4E) -1- (4- (2- ((5,6- dimethyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- thiophene
Pheno)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A9):
Be similar to embodiment 1 the step of, select corresponding raw material to prepare target compound A9) preparation, yield:
58%.
Embodiment 10
(1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (4- chlorobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A10):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A10, yield: 44%.
Embodiment 11
(1E, 4E) -1- (4- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- chlorobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A11):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A11, yield 54%.
Embodiment 12
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (3,4- bis-
Methoxyphenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A12):
Be similar to embodiment 1 the step of, select corresponding raw material to prepare target compound A12) preparation, yield:
36%.
Embodiment 13
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- pyrrole
Pyridine)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A13):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A13, yield: 46%.
Embodiment 14
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (3- methyl
Phenyl)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A14):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A14, yield: 38%.
Embodiment 15
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- fluorobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A15):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A15, yield: 41%.
Embodiment 16
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (2- furan
Mutter)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A16):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A16, yield: 61%.
Embodiment 17
(1E, 4E) -1- (2- (2- ((5,6- diphenyl -1,2,4- triazine -3- sulfydryl ethyoxyl) phenyl) -5- (4- bromobenzene
Base)-Isosorbide-5-Nitrae-pentadiene -3- ketone (target compound A17):
With the step of being similar to embodiment 1, corresponding raw material is selected to prepare target compound A17, yield: 60%.
The synthesized Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketones derivant physicochemical property is shown in Table 1, nuclear magnetic resonance spectroscopy (1H
NMR) and carbon spectrum (13C NMR) data are shown in Table 2.
Target compound physicochemical property made from 1 embodiment 1-17 of table
Target compound nuclear magnetic resonance spectroscopy and carbon modal data made from 2 embodiment 1-17 of table
Activity test example 1: anti-vegetative bacteria active testing:
(1) test method
Using nephelometry, under 100 and 50 μ g/mL concentration, test target compound is to tobacco ralstonia solanacearum, the white leaf of rice
The external inhibitory activity of blight bacterium and citrus processing, comparison medicament is Thiodiazole-copper in experiment.By tobacco ralstonia solanacearum, rice
Leaf spot bacteria and c itrus canker are cultivated on NA solid medium, be subsequently placed in 28 DEG C of constant-temperature bacterial culture box cultivate to
Grow single colonie.Suitable central yellow single colonie is chosen, is put it in NB fluid nutrient medium, in 28 DEG C, 180r/min perseverance
Shaken cultivation is spare to logarithmic growth phase in warm shaking table.100 and 50 μ g/mL concentration are configured by compound and comparison medicament, are taken
1mL is added in the test tube equipped with 4mL NB fluid nutrient medium, then is measured 40 μ L and contained tobacco ralstonia solanacearum, bacterial blight of rice
The NB fluid nutrient medium of bacterium and citrus processing is added in test tube, in 28 DEG C, 180r/min constant-temperature table shaken cultivation 48h.
On spectrophotometer, the OD of the sterile NB fluid nutrient medium of dosing at 595nm wavelength is measured595Value, while measuring each concentration
Bacterium solution OD595Value.
Correct OD595Value=OD containing bacterium culture medium595Aseptic culture medium OD595
Inhibiting rate (%)=(control medium bacterium solution OD after correction595Correct pastille culture medium OD595It is compareed after)/correction
Value × 100%. culture medium bacterium solution OD
(2) the biological activity test result of anti-plant pathogen
The bacteriostatic activity (inhibiting rate %) of 3 embodiment 1-17 of tablea
aIt is average to repeat three times；bThiodiazole-copper (20% wettable powder) is used as positive control.
Using nephelometry, using commodity medicament Thiodiazole-copper as positive control, when being 100,50 μ g/mL for examination concentration, test
Inhibitory activity (be shown in Table 3) of the target compound to tobacco ralstonia solanacearum, rice leaf spot bacteria and citrus processing.As a result
Display: all compounds have certain inhibitory activity to tobacco ralstonia solanacearum, rice leaf spot bacteria and citrus processing.
To tobacco ralstonia solanacearum, compound A1 (58.2%), A2 (53.9%), A9 (53.5%) and A10 in 100 μ g/mL
(61.9%) inhibiting rate is more than Thiodiazole-copper (50.1%)；To rice leaf spot bacteria, the compound A-45 in 100 μ g/mL
(54.6%), A8 (55.6%), A13 (60.5%) and A15 (56.5%) inhibiting rate are more than Thiodiazole-copper (49.7%)；To citrus
Ulcer bacteria, the compound A10 (91.8%) in 100 μ g/mL, A11 (95.4%) and A16 (74.6%) inhibiting rate are more than thiophene
Bacterium copper (70.5%).
Activity test example 2: activity of resisting tobacco mosaic virus test:
Test method
A. Virus purification
Quadratic method (Zhou, X.P. are avenged using week；Xu, Z.X.；Xu, J.；Li, D.B.J.South
Chin.Agric.Univ.1995,16,74-79.), inoculation 3 weeks or more are chosen, TMV systemic infection host Nicotiana
Tabacum.L plant upper blade, is homogenized in phosphate buffer, double gauze filtering, 8000r centrifugation, through 2 polyethylene glycol
Processing, then be centrifuged, precipitating phosphate buffer suspends to get the refining liquid body of TMV is arrived.Entire experiment carries out at 4 DEG C.With purple
The absorbance value of outer spectrophotometric determination 260nm wavelength calculates virus concentration according to formula.
Virus concentration (mg/mL)=(A260 × extension rate)/E0.1%1cm 260nm
Wherein E indicates extinction coefficient, i.e. when wavelength 260nm, concentration is the suspension of 0.1% (1mg/mL), is in light path
Absorbance value when 1cm.The E0.1%1cm260nm of TMV is 5.0.
B. the living body therapeutic effect that medicament infects TMV
Living body therapeutic effect of the medicament to infecting: the Nicotiana glutinosa of growing way consistent 5-6 leaf phase is selected to pinch, Xiang Quanye sprinkles evenly gold
Emery dips viral juice (6 × 10 with spread pen-3Mg/mL) full leaf virus inoculation is rinsed with clear water after natural drying.To blade
After dry, medicament is gently spread in Zuo Banye with writing brush, the solvent for the concentration that right half leaf spreads corresponding solvent compares, 6-7d postscript
Withered spot number is recorded, inhibiting rate is calculated according to the following formula.
C. the living body protective effect that medicament infects TMV
The living body protective effect that medicament infects TMV: it selects the Nicotiana glutinosa of growing way consistent 5-6 leaf phase to pinch, is existed with writing brush
Zuo Banye gently spreads medicament, and the solvent for the concentration that right half leaf spreads corresponding solvent compares.After for 24 hours, Xiang Quanye sprinkles evenly Buddha's warrior attendant
Sand dips viral juice (6 × 10 with spread pen-3Mg/mL) full leaf virus inoculation is rinsed with clear water, and withered spot number is recorded after 6-7d, is pressed
Following equation calculates inhibiting rate.
D. the living body passivation that medicament infects TMV
Medicament is mixed into passivation 30min with isometric viral juice, the mixed liquor of medicament and virus, people are dipped with spread pen
Work frictional inoculation is supported below blade with smooth plank on the left half of blade of the blade sprinkled with diamond dust.Aqua sterilisa and virus
Right half leaf of juice combined inoculation.Every chemicals treatment sets 3 plants, and plant is then placed on moisturizing in illumination box by every plant of 5-6 piece leaf
Culture controls 23 ± 1 DEG C of temperature, the number for generating withered spot is observed and recorded after illumination 10000Lux, 6-7d, based on following equation
Calculate inhibiting rate.
Inhibiting rate=(the average withered spot number-for being not coated with application half leaf of agent spreads half leaf withered spot number of medicament)/is not coated with application agent
Average withered spot number × 100% of half leaf
Wherein, the average withered spot number for being not coated with application half leaf of agent and the half leaf withered spot number for spreading medicament all use each group to weigh three times
Multiple average.
The biological activity test result of resisting tobacco mosaic virus
4 embodiment compound A1-17 of table is to the treatment of tobacco mosaic virus (TMV), protection and passivation activitya
aIt is average to repeat three times；bNingnanmycin is used as positive control.
It is control with commodity medicament Ningnanmycin using half leaf withered spot method, when for examination concentration being 500 μ g/mL, tests mesh
Compound A1-A17 is marked to the therapeutic activity of tobacco mosaic virus (TMV) (TMV), protection and is passivated active (being shown in Table 4).The test result
Show: most of target compound has certain therapeutic activity, protection and passivation activity to TMV.Wherein, target compound
A6, A10 and A11 possess preferable therapeutic effect to TMV, and inhibiting rate is respectively 53.8,66.3 and 59.9%, are more than that Ningnan is mould
Plain (45.7%)；Target compound A2, A4 and A7 possess preferable protective effect to TMV, and inhibiting rate is respectively 54.5,53.9
With 61.4%, it is better than Ningnanmycin (53.4%)；Target compound A1 and A4 possesses TMV certain passivation, inhibits
Rate is 66.2 and 63.6%, close to Ningnanmycin (77.3%).
The above assay activity statistics indicate that the Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketones derivant to plant virus (TMV) and
Phytopathogen (tobacco ralstonia solanacearum, rice blinds withered and citrus processing) has certain inhibiting effect, part of mesh
Mark Compounds Against plant virus and phytopathogen is inhibited to show excellent activity, can be used as potential Antiphytoviral and antibacterial
Drug, with good application prospect.
In conclusion being only presently preferred embodiments of the present invention, it is not intended to limit the present invention in any form, appoints
What is to the above embodiments according to the technical essence of the invention any simply to repair without departing from technical solution of the present invention content
Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (9)
1. a kind of Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds or its stereoisomer or its salt or its solvate,
It is characterized in that the compound has and such as leads to structure shown in formula A:
Wherein,
R independently selected from hydrogen, deuterium, any substituted or unsubstituted alkyl, any substituted or unsubstituted alkenyl, it is any replace or
Unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted naphthenic base, any substitution do not take
One or more of the aryl in generation, any substituted or unsubstituted heteroaryl；
R1Independently selected from hydrogen, deuterium, halogen, any substituted or unsubstituted alkyl, any substituted or unsubstituted alkenyl, any
Substituted or unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted naphthenic base, any substitution
Or one or more of unsubstituted aryl；
R2Identical or differently independently selected from hydrogen, deuterium, halogen, any substituted or unsubstituted alkyl, any substituted or unsubstituted
Alkenyl, any substituted or unsubstituted alkynyl, any substituted or unsubstituted alkoxy, any substituted or unsubstituted cycloalkanes
One or more of base, any substituted or unsubstituted aryl, any substituted or unsubstituted heteroaryl；
X is independently selected from O, S or NH.
2. a kind of Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds according to claim 1 or its stereoisomer or
Its salt or its solvate, it is characterised in that:
Preferably, R is independently selected from hydrogen, deuterium, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted aryl, substitution or not
One or more of substituted heteroaryl；It is highly preferred that R is independently selected from hydrogen, deuterium, C1-C6Alkyl, C1-C6Alkoxy, C1-
C6Alkenyl, C1-C6Alkynyl, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C10One or more in heteroaryl
It is a, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkenyl, C1-C6Alkynyl, amino, hydroxyl, halogen
Element replaces；Most preferably, R independently selected from hydrogen, deuterium, nitro, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, cyclobutenyl, pentenyl, hexenyl, propinyl,
Butynyl, pentynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, phenyl, chlorphenyl, bromophenyl, fluorophenyl, two
Chlorphenyl, dibromo phenyl, difluorophenyl, nitrobenzophenone, dinitrophenyl, methoxyphenyl, Dimethoxyphenyl, methylbenzene
Base, 3,5-dimethylphenyl, amine phenyl, hydroxyphenyl, benzyl, adjacent luorobenzyl, luorobenzyl, to luorobenzyl, adjacent bromobenzyl, bromobenzyl
Base, to bromobenzyl, o-chlorobenzyl, chlorobenzyl, p-chlorobenzyl, naphthalene, phenanthryl, pyridyl group, thienyl, adjacent fluorine pyridyl group,
Fluorine pyridyl group, adjacent bromopyridine base, bromopyridine base, adjacent chloropyridine base, m-chloro pyridyl group, adjacent fluorine thienyl, fluorine thienyl, neighbour
Fluorine furyl, fluorine furyl, adjacent fluorine tetrahydrofuran base, fluorine tetrahydrofuran base, adjacent bromothiophene base, bromothiophene base, adjacent bromine
Furyl, bromine furyl, adjacent bromine tetrahydrofuran base, bromine tetrahydrofuran base, adjacent chlorothiophene base, m-chloro thienyl, adjacent chlorine furan
Mutter base, m-chloro furyl, adjacent chlorine tetrahydrofuran base, m-chloro tetrahydrofuran base, adjacent hydroxybenzyl, hydroxybenzyl, to hydroxyl benzyl
Base, adjacent aminobenzyl, aminobenzyl, aminobenzyl, adjacent methylbenzyl, methylbenzyl, to methylbenzyl, adjacent hydroxyl pyrrole
Pyridine, hydroxy-pyridyl, to hydroxy-pyridyl, adjacent aminothiophene base, aminothiophene base, adjacent hydroxyfuryl, hydroxyl furan
It mutters base, adjacent hydroxyl tetrahydrofuran base, hydroxyl tetrahydrofuran base, sylvan base, methylfuran base, adjacent methyl tetrahydro furan
It mutters base, methyltetrahydrofuran base, adjacent fural, fural, adjacent tetrahydrofuran methylene, tetrahydrofuran Asia
One or more of methyl；
Preferably, R1Independently selected from hydrogen, deuterium, halogen, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted aryl, take
Generation or one or more of unsubstituted heteroaryl or heterocycle；It is highly preferred that R1Independently selected from hydrogen, deuterium, C1-C6Alkyl,
C1-C6Alkenyl, C1-C6Alkynyl, C1-C6Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C10Heteroaryl
One or more of base, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, amino, hydroxyl, halogen take
Generation；Most preferably, R1Independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, uncle
Butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, cyclobutenyl, pentenyl, hexenyl, propinyl, butynyl, penta
Alkynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, phenyl, chlorphenyl, bromophenyl, fluorophenyl, tolyl, amine benzene
Base, hydroxyphenyl, benzyl, adjacent luorobenzyl, luorobenzyl, to luorobenzyl, adjacent bromobenzyl, bromobenzyl, to bromobenzyl, adjacent benzyl chloride
One or more of base, chlorobenzyl, p-chlorobenzyl, naphthalene, phenanthryl, pyridyl group；
Preferably, R2It does not take identical or differently independently selected from hydrogen, deuterium, halogen, alkyl, alkenyl, alkynyl, alkoxy, substitution or
One or more of the aryl in generation, substituted or unsubstituted heteroaryl；It is highly preferred that R2Independently selected from hydrogen, deuterium, C1-C6Alkane
Base, C1-C6Alkoxy, C1-C6Alkenyl, C1-C6Alkynyl, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C10
One or more of heteroaryl, wherein described substituted refers to by C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkenyl, C1-
C6Alkynyl, amino, hydroxyl, halogen replace；Most preferably, R2Independently selected from hydrogen, deuterium, nitro, methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, acrylic, allyl, cyclobutenyl, penta
Alkenyl, hexenyl, propinyl, butynyl, pentynyl, hexin base, methoxyl group, ethyoxyl, propoxyl group, butoxy, phenyl, chlorobenzene
Base, bromophenyl, fluorophenyl, nitrobenzophenone, methoxyphenyl, aminomethyl phenyl, amine phenyl, hydroxyphenyl, benzyl, adjacent luorobenzyl,
Luorobenzyl, to luorobenzyl, adjacent bromobenzyl, bromobenzyl, to bromobenzyl, o-chlorobenzyl, chlorobenzyl, p-chlorobenzyl, naphthalene, phenanthrene
Base, pyridyl group, thienyl, adjacent fluorine pyridyl group, fluorine pyridyl group, adjacent bromopyridine base, bromopyridine base, adjacent chloropyridine base, m-chloro
Pyridyl group, adjacent fluorine thienyl, fluorine thienyl, adjacent fluorine furyl, fluorine furyl, adjacent fluorine tetrahydrofuran base, fluorine tetrahydro furan
It mutters base, adjacent bromothiophene base, bromothiophene base, adjacent bromine furyl, bromine furyl, adjacent bromine tetrahydrofuran base, bromine tetrahydrofuran
Base, adjacent chlorothiophene base, m-chloro thienyl, adjacent chlorine furyl, m-chloro furyl, adjacent chlorine tetrahydrofuran base, m-chloro tetrahydrofuran base,
Adjacent hydroxybenzyl, hydroxybenzyl, to hydroxybenzyl, adjacent aminobenzyl, aminobenzyl, aminobenzyl, adjacent methylbenzyl,
Between methylbenzyl, to methylbenzyl, adjacent pyridone, hydroxy-pyridyl, to hydroxy-pyridyl, adjacent aminothiophene base, ammonia
Base thienyl, adjacent hydroxyfuryl, hydroxyfuryl, adjacent hydroxyl tetrahydrofuran base, hydroxyl tetrahydrofuran base, adjacent methyl furan
It mutters base, methylfuran base, adjacent methyltetrahydrofuran base, methyltetrahydrofuran base, adjacent fural, furans methylene
One or more of base, adjacent tetrahydrofuran methylene, tetrahydrofuran methylene.
3. a kind of Isosorbide-5-Nitrae containing triazine-pentadiene -3- ketone compounds according to claim 1 or its stereoisomer or
Its salt or its solvate, it is characterised in that independently selected from following compounds:
4. a kind of Isosorbide-5-Nitrae prepared described in claim 1 containing triazine-pentadiene -3- ketone compounds or its stereoisomer or its
The midbody compound of salt or its solvate, it is characterised in that be shown below:
Wherein R, R1It is as described above with X.
5. Isosorbide-5-Nitrae-pentadiene -3- ketone compounds or its stereoisomer or its salt described in a kind of claim 1 containing triazine or
The preparation method of its solvate, it is characterised in that include the following steps:
Preferably, further comprise following step:
It is highly preferred that including the following steps:
Most preferably, include the following steps:
Wherein R, R1、R2It is as described above with X.
6. a kind of composition, it is characterised in that containing claim the 1-3 any compound or its stereoisomer or its
Salt or its solvate, and agriculturally available auxiliary agent or fungicide, insecticide or herbicide；Preferably, the composition
Dosage form independently selected from missible oil (EC), pulvis (DP), wettable powder (WP), granule (GR), aqua (AS), suspending agent
(SC), ultra-low volume spray agent (ULV), soluble powder (SP), microcapsule formulations (MC), fumicants (FU), aqueous emulsion (EW), moisture
Dissipate property granula (WG).
7. claim the 1-3 any compound or its stereoisomer or its salt or its solvate or claim
Purposes of the composition described in 6 in terms of preventing and treating agricultural pest, it is preferable that the agricultural pest is for vegetative bacteria or very
Fungal disease；It is highly preferred that the agricultural pest is plant leaf blight and plant canker；Most preferably, the agricultural disease
Insect pest is bacterial blight of rice, tobacco bacterial wilt, tobacco mosaic disease, cucumber bacterial leaf-blight, konjaku bacterial leaf-blight, c itrus canker
Disease, grape ulcer, canker of tomato, Prospect on Kiwifruit Bacterial Canker, apple canker, gray mold of cucumber, capsicum wilt, Sclerotina Sclerotiorum in Winter Rape
Core disease, wheat scab, the late blight of potato, capsicum wilt, blueberry root rot, wheat scab, the late blight of potato, oil
Dish sclerotiniose and dragon fruit anthracnose.
8. a kind of method for preventing and treating agricultural pest, it is characterised in that: make any compound of claim 1-3 or it is vertical
Body isomers or its salt or its solvate or composition as claimed in claim 6 act on nuisance or its living environment；
Preferably, the agricultural pest is vegetative bacteria or fungal disease；It is highly preferred that the agricultural pest is that rice is white
Leaf blight, tobacco bacterial wilt, tobacco mosaic disease, cucumber bacterial leaf-blight, konjaku bacterial leaf-blight, citrus bacterial canker disease, grape ulcer,
Canker of tomato, Prospect on Kiwifruit Bacterial Canker, apple canker, gray mold of cucumber, capsicum wilt, sclerotinia sclerotiorum, gibberella saubinetii
Disease, the late blight of potato, capsicum wilt, blueberry root rot, wheat scab, the late blight of potato, sclerotinia sclerotiorum and fire
Imperial fruit anthracnose.
9. the method for protecting the plants from agricultural pest infringement comprising wherein make plant and claim 1-3 any
The side of the compound or the contact of its stereoisomer or its salt or its solvate or composition as claimed in claim 6
Method step.
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