CN104844507B - Application of the quinolinones compound in algal grown is suppressed and the algicide for suppressing algal grown - Google Patents
Application of the quinolinones compound in algal grown is suppressed and the algicide for suppressing algal grown Download PDFInfo
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- CN104844507B CN104844507B CN201510151216.2A CN201510151216A CN104844507B CN 104844507 B CN104844507 B CN 104844507B CN 201510151216 A CN201510151216 A CN 201510151216A CN 104844507 B CN104844507 B CN 104844507B
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- 0 *C(N*)=C(C(c(c(N1)c2*)c(*)c(*)*2S)=O)C1=O Chemical compound *C(N*)=C(C(c(c(N1)c2*)c(*)c(*)*2S)=O)C1=O 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen 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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Abstract
The present invention relates to agricultural chemicals and environmental area, disclose application of the dynamic isomer of the quinolinones compound shown in formula (1) and/or the quinolinones compound shown in formula (1) in algal grown is suppressed, and for suppressing the algicide of algal grown, the active component of the algicide is the dynamic isomer of the quinolinones compound shown at least one formula (1) and/or the quinolinones compound shown at least one formula (1), with the gross weight meter of the algicide, the content of the active component is 0.1 100 weight %, quinolinones compound of the present invention has inhibiting rate height when suppressing the growth of algae, the advantages of small toxicity.
Description
Technical field
The present invention relates to pesticide field, in particular it relates to application of the quinolinones compound in algal grown is suppressed with
And for suppressing the algicide of algal grown.
Background technology
In recent years, algal bloom event is constantly broken out in various regions on a large scale, algae evil directly affect surrounding area domestic water and
Industrial water, heavy damage ecological environment, huge economic loss is brought to fish production and tourism development, is also good for the public
Health brings very big hidden danger.
It is economical, efficient, convenient and rapid-action to be had the advantages that using chemical algicide, is always algae evil comprehensive regulation body
Indispensable important component in system, during especially breaking out on a large scale in algal bloom, be even more it is short-term it is quick administer and
Control the most important means of prevention of emergency such as algae evil.
Existing chemical algicide mainly has the heavy metal compound class algicide using copper sulphate and its complex compound as representative；
Using potassium permanganate, ferrate, peroxide as representative strong oxidizer class algicide；It is with triazolineone, triazines etc.
Classes of herbicides algicide of representative etc..But these algicides exist poor selectivity, dosage it is big, to zootoxins such as the fish in water
Property it is larger the problems such as, significantly limit the efficiency done harm to using chemical method preventing and treating algae and give full play to.
Therefore, poor selectivity, toxicity are big, algae resistance increasingly strengthens urgently is solved in modern chemistry algicide innovative research
The problem of one certainly is extremely important.
The content of the invention
The purpose of the present invention is the defects of overcoming prior art, there is provided it is a kind of be used for suppress algal grown algicide and
Application of the quinolinones compound in algal grown is suppressed.Quinolinones compound of the present invention is suppressing the life of algae
There is the advantages of inhibiting rate is high, small toxicity and selectivity are high when long.
To achieve these goals, on the one hand, quinolinones compound and/or formula (1) shown in offer formula (1) of the present invention
Application of the dynamic isomer of shown quinolinones compound in algal grown is suppressed,
Wherein, R1、R2Separately represent hydrogen, C1-C18 alkyl, C1-C18 alkenyl, C1-C18 alkynyl, C3-
C18 cycloalkyl, C3-C18 cycloalkenyl group, C3-C18 cycloalkynyl radical, benzyl, 2- picolyls, 3- picolyls, 4- pyridine first
Base, 2- furfuryls, 2- tetrahydrofuran methyls, 3- furfuryls, 3- tetrahydrofuran methyls, 2- thenyls, 3- thenyls,
3- thiazole methyls, 4- thiazole methyls, 5- thiazole methyls, 3- oxazoles methyl, 4- oxazoles methyl, 5- oxazoles methyl, 2- isoxazole first
Base, 4- isoxazoles methyl, 5- isoxazoles methyl, phenyl, thienyl, pyridine radicals, pyridazinyl, furyl, triazolyl, naphthyl, color
Man Ji, 2,3- dihydro -1,4- benzene and dioxazine base, 4H-1,3- benzene and dioxazine base, 2,3- dihydro-benzofuranyls, benzo furan
Mutter base, benzothiazolyl, 1,3- benzoxazolyls, 1,2- benzoisoxazoles base, benzimidazolyl, N- phenyl aminos or N, N- bis-
Phenyl amino, each group are unsubstituted, or are substituted by one or more following radicals：The alkane of halogen, C1-C4
Base, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkane
Sulfenyl, C1-C4 alkyl sulphinyl, C1-C4 alkyl sulphonyl, nitro, cyano group, hydroxyl, sulfydryl, carboxyl, C1-C4 alkane
Base carbonyl；
R3、R4、R5、R6Separately represent hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4
Haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkylthio group, nitro, cyano group, hydroxyl or carboxylic
Base.
On the other hand, the present invention provides a kind of algicide for being used to suppress algal grown, and the active component of the algicide is
The change of the quinolinones compound shown in quinolinones compound and/or at least one formula (1) shown at least one formula (1)
Isomers, with the gross weight meter of the algicide, the content of the active component is 0.1-100 weight %,
Wherein, R1、R2、R3、R4、R5And R6Quinolinones compound of the restriction as shown in previously described formula of the present invention (1) pressing down
Described in application in algal grown processed.
Using the quinolinones compound shown in formula of the present invention (1) and/or the quinolinones chemical combination shown in formula (1)
The dynamic isomer of thing suppresses have the advantages of inhibiting rate is high, small toxicity and selectivity are high during the growth of algae.
By the quinolinones compound shown in formula of the present invention (1) and/or the quinolinones compound shown in formula (1)
Dynamic isomer can show that when applying to as the effective ingredient of algicide in the comprehensive regulation of algal bloom efficiently and
Significant algae killing effect.
The quinolinones compound shown in quinolinones compound and/or formula (1) shown in formula (1) of the present invention
Dynamic isomer as algicide active component in use, above-claimed cpd is mixed with the carrier or diluent allowed in water body
Close it is adjustable usually used various formulations, such as hydrating agents, emulsion, aqueous solvent, flowable dose are made, as of the present invention
Algicide uses.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides the quinolinones compound shown in formula (1) and/or the quinolinones shown in formula (1)
Application of the dynamic isomer of compound in algal grown is suppressed,
Wherein, R1、R2Separately represent hydrogen, C1-C18 alkyl, C1-C18 alkenyl, C1-C18 alkynyl, C3-
C18 cycloalkyl, C3-C18 cycloalkenyl group, C3-C18 cycloalkynyl radical, benzyl, 2- picolyls, 3- picolyls, 4- pyridine first
Base, 2- furfuryls, 2- tetrahydrofuran methyls, 3- furfuryls, 3- tetrahydrofuran methyls, 2- thenyls, 3- thenyls,
3- thiazole methyls, 4- thiazole methyls, 5- thiazole methyls, 3- oxazoles methyl, 4- oxazoles methyl, 5- oxazoles methyl, 2- isoxazole first
Base, 4- isoxazoles methyl, 5- isoxazoles methyl, phenyl, thienyl, pyridine radicals, pyridazinyl, furyl, triazolyl, naphthyl, color
Man Ji, 2,3- dihydro -1,4- benzene and dioxazine base, 4H-1,3- benzene and dioxazine base, 2,3- dihydro-benzofuranyls, benzo furan
Mutter base, benzothiazolyl, 1,3- benzoxazolyls, 1,2- benzoisoxazoles base, benzimidazolyl, N- phenyl aminos or N, N- bis-
Phenyl amino, each group are unsubstituted, or are substituted by one or more following radicals：The alkane of halogen, C1-C4
Base, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkane
Sulfenyl, C1-C4 alkyl sulphinyl, C1-C4 alkyl sulphonyl, nitro, cyano group, hydroxyl, sulfydryl, carboxyl, C1-C4 alkane
Base carbonyl；
R3、R4、R5、R6Separately represent hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4
Haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkylthio group, nitro, cyano group, hydroxyl or carboxylic
Base.
In the present invention, the quinolinones compound shown in the formula (1) and/or the quinolinones chemical combination shown in formula (1)
The dynamic isomer of thing can be the change of the quinolinones compound shown in formula (1), the quinolinones compound shown in formula (1)
Isomers can be the mutual variation of the quinolinones compound shown in formula (1) and the quinolinones compound shown in formula (1)
Structure body.
In the present invention, the straight chained alkyl and carbon number that the alkyl of the C1-C18 is 1-18 including carbon number are 3-
18 branched alkyl.
In the present invention, the straight chained alkyl that carbon number is 1-18 includes methyl, ethyl, n-propyl, normal-butyl, positive penta
In base, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tetradecane base and n-hexadecyl extremely
Few one kind.Especially, the hydrogen on the carbon atom in C1-C18 of the present invention straight chained alkyl can be by including halogen
The substitution of non-carbon group, the halogen includes fluorine, chlorine, bromine and iodine.
In the present invention, carbon number is that the hydrogen on the carbon atom in 3-18 branched alkyl can be by including halogen
The substitution of non-carbon group, the halogen includes fluorine, chlorine, bromine and iodine.
In the present invention, the cycloalkyl of the C3-C18 refers to the cycloalkyl that carbon number is 3-18.Especially, it is of the invention
The hydrogen on carbon atom in described C3-C18 cycloalkyl can be by carbon containing substituent and the non-carbon including halogen
Base substitutes, and the halogen includes fluorine, chlorine, bromine and iodine.
In the present invention, the halogen includes fluorine, chlorine, bromine and iodine.
In the present invention, the Chromanyl, as chromanyl.
Under preferable case, in the present invention, R1、R2Separately represent hydrogen, C1-C18 alkyl, C3-C18 cycloalkanes
Base, benzyl, 2- picolyls, 3- picolyls, 4- picolyls, 2- furfuryls, 2- tetrahydrofuran methyls, 3- furans first
Base, 3- tetrahydrofuran methyls, 2- thenyls, 3- thenyls, 3- thiazole methyls, 4- thiazole methyls, 5- thiazole methyls, 3- Evil
Azoles methyl, 4- oxazoles methyl, 5- oxazoles methyl, 2- isoxazoles methyl, 4- isoxazoles methyl, 5- isoxazoles methyl, phenyl, thiophene
Base, pyridine radicals, pyridazinyl, furyl, Chromanyl, 2,3- dihydro -1,4- Ben Bing dioxazines base, 4H-1,3- Ben Bing dioxazines base,
2,3- dihydro-benzofuranyls, benzofuranyl, benzothiazolyl, 1,3- benzoxazolyls, 1,2- benzoisoxazoles base, benzene
And imidazole radicals, N- phenyl aminos or N, N- diphenyl amino, each group are unsubstituted, or by under one or more
State group substitution：Halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, hydroxyl, C1-C4 alkyl oxycarbonyl
Base；
R3、R4、R5、R6Separately represent hydrogen, halogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, methoxy or ethoxy.
In application of the present invention, particularly preferred R1Selected from hydrogen, methyl, ethyl, n-propyl, cyclopropyl, cyclobutyl,
Cyclopenta, cyclohexyl, phenyl and naphthyl.
In application of the present invention, particularly preferred R2Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Isobutyl group, the tert-butyl group, 1- methyI-oropvDs, n-pentyl, 3- methyl-butvls, 2- methyl-butvls, 1- methyl-butvls, n-hexyl,
Cyclohexyl, 2- methyl-cyclohexyls base, 3- methyl-cyclohexyls base, 4- methyl-cyclohexyls base, n-heptyl, n-octyl, n-nonyl, positive decyl,
Dodecyl, n-tetradecane base, n-hexadecyl, phenyl, naphthyl, N- phenyl aminos, N, N- diphenyl aminos, 4- (4- fluorine
Phenyl)-isoxazolyls and 5- (4- fluorophenyls)-isoxazolyls.
In the case of particularly preferably, in application of the present invention, the quinolinones compound shown in the formula (1) is selected from
At least one of compound in table 1.
Particularly illustrate, each compound in table 1 has general structure shown in formula (1) or for shown in formula (1)
The isomer of general structure：
In application of the present invention, the dynamic isomer tool of the quinolinones compound shown in preferably described formula (1)
There is the structure shown in formula (2),
Wherein, R1、R2、R3、R4、R5And R6Definition and formula (1) shown in quinolinones compound in R1、R2、R3、R4、
R5And R6Definition correspond to it is identical.
Table 1
In application of the present invention, relative to every 1 × 106Individual algae, the quinolinones shown in preferably described formula (1)
The dosage of the dynamic isomer of quinolinones compound shown in compound and/or formula (1) is 1 × 10-10- 5 micromoles；It is more excellent
Select the use of the dynamic isomer of the quinolinones compound shown in the formula (1) and/or the quinolinones compound shown in formula (1)
Measure as 5 × 10-8- 1 micromole, particularly preferably 1 × 10-4-5×10-2Micromole.In the present invention, will for above-mentioned used in amounts
Special instruction, when using the quinolinones compound shown in formula (1) or the quinoline shown in formula (1) in the application
During the dynamic isomer of ketone compounds, above-mentioned the dosage correspondingly quinolinones compound shown in expression (1) and formula (1)
The dosage of the dynamic isomer of shown quinolinones compound；When using the quinolinone shown in formula (1) in the application
During the dynamic isomer of the quinolinones compound shown in class compound and formula (1), the quinoline shown in above-mentioned dosage expression (1)
Total dosage of the dynamic isomer of quinolinones compound shown in ketone compounds and formula (1).
According to application of the present invention, application of the present invention can be directed to all types of algae, particularly preferably
In the case of, algae of the invention includes red algae and blue-green algae.
In the case of more preferably, in the present invention, the blue-green algae includes cytoalgae PCC 6803, anabena, section ball algae, nostoc
At least one of with microcystic aeruginosa 912.
On the other hand, be used to suppressing the algicide of algal grown present invention also offers a kind of, the activity of the algicide into
It is divided into the quinolinones compound shown at least one formula (1) and/or the quinolinones compound shown at least one formula (1)
Dynamic isomer, with the gross weight meter of the algicide, the content of the active component is 0.1-100 weight %,
Wherein, R1、R2Separately represent hydrogen, C1-C18 alkyl, C1-C18 alkenyl, C1-C18 alkynyl, C3-
C18 cycloalkyl, C3-C18 cycloalkenyl group, C3-C18 cycloalkynyl radical, benzyl, 2- picolyls, 3- picolyls, 4- pyridine first
Base, 2- furfuryls, 2- tetrahydrofuran methyls, 3- furfuryls, 3- tetrahydrofuran methyls, 2- thenyls, 3- thenyls,
3- thiazole methyls, 4- thiazole methyls, 5- thiazole methyls, 3- oxazoles methyl, 4- oxazoles methyl, 5- oxazoles methyl, 2- isoxazole first
Base, 4- isoxazoles methyl, 5- isoxazoles methyl, phenyl, thienyl, pyridine radicals, pyridazinyl, furyl, triazolyl, naphthyl, color
Man Ji, 2,3- dihydro -1,4- benzene and dioxazine base, 4H-1,3- benzene and dioxazine base, 2,3- dihydro-benzofuranyls, benzo furan
Mutter base, benzothiazolyl, 1,3- benzoxazolyls, 1,2- benzoisoxazoles base, benzimidazolyl, N- phenyl aminos or N, N- bis-
Phenyl amino, each group are unsubstituted, or are substituted by one or more following radicals：The alkane of halogen, C1-C4
Base, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkane
Sulfenyl, C1-C4 alkyl sulphinyl, C1-C4 alkyl sulphonyl, nitro, cyano group, hydroxyl, sulfydryl, carboxyl, C1-C4 alkane
Base carbonyl；
R3、R4、R5、R6Separately represent hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4
Haloalkyl, C1-C4 halogenated alkoxy, C1-C4 alkoxyalkyl, C1-C4 alkylthio group, nitro, cyano group, hydroxyl or carboxylic
Base.
In the present invention, it is necessary to special instruction, the quinolinones compound shown in the formula (1) of foregoing description of the present invention
And/or the dynamic isomer of the quinolinones compound shown in formula (1) it is involved in the application in suppressing algal grown in
Hold all to quote and be used to suppress the algicide of algal grown of the present invention, in order to avoid repeating, the present invention is herein not
Repeat one by one again.
Under preferable case, of the present invention in suppressing the algicide of algal grown, the active component to contain
Measure as 1-90 weight %.
According to the algicide of the present invention for being used to suppress algal grown, the formulation of preferably described algicide is hydration
Agent, pulvis, emulsion, suspending agent and granula.
In the present invention, to the mutual of the quinolinones compound shown in the application quinolinones compound and/or formula (1)
There is no particular limitation for the environmental condition of tautomeric, can in the art it is conventional it is various under the conditions of use.
In the present invention, to the mutual of the compound shown in the formula (1) and/or the quinolinones compound shown in formula (1)
There is no particular limitation for the preparation method of tautomeric, and those skilled in the art can be according to various methods known in the art
Prepare the dynamic isomer of the quinolinones compound shown in the compound and/or formula (1) shown in formula of the present invention (1).
Especially, the mutual variation of the compound shown in heretofore described formula (1) and/or the quinolinones compound shown in formula (1)
Structure body can use document (The discovery of 3- (1-aminoethylidene) quinolone-2,4 (1H, 3H)-
dione derivatives as novel PSII electron transport inhibitors,Mol Divers
(2013)17:701-710) method provided is prepared.
The present invention will be described in detail by way of examples below.In following examples, in the feelings being not particularly illustrated
Under condition, used various materials are all from commercially available.
Due to fructose 1,6-/sedoheptulose -1,7- diphosphatases (cy-FBP/SBPase) of generally existing in blue-green algae body
Critical role is in during blue-green algae Calvin cyclic carbon metabolic regulations, is a potential algicide target, this area skill
Known in art personnel, if blue-green algae fructose 1,6-/sedoheptulose 1,7-bisphosphatase is suppressed or undergone mutation, and will cause indigo plant
Algae can not grow even dead.Moreover, blue-green algae fructose 1, the 6-/sedoheptulose 1,7-bisphosphatase hydrolysis phosphorus of fructose -1,6- bis-
Acid is fructose-6-phosphate and inorganic phosphate.Therefore, by testing inorganic phosphate in the following examples and comparative example of the present invention
Incrementss determine the activity of blue-green algae fructose 1-6-/sedoheptulose 1,7-bisphosphatase, so as to for inquiring into the present invention's
Inhibiting rate of the compound to algae.
In the examples below, it is necessary to which special instruction, works as R1For methyl when, the quinolinones chemical combination shown in formula (1)
Thing can obtain by using following synthetic route：
Specifically preparation method is：Substituted Anthranilate (11) and ketene dimer are reacted to obtain compound
(12), compound (12) cyclization in the presence of alkali obtains compound (13), then can be made containing acetimide with amine addition condensation
4- hydroxyl -2- the quinolinones compounds of structure.Organic solvent is dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, first
Benzene, benzene, acetonitrile, acetone, tetrahydrofuran, ether, dioxane, DMF or DMSO；Alkali is MeONa, EtONa, NaOH, KOH, pyrrole
Pyridine, triethylamine or 4-N, TMSDMA N dimethylamine yl pyridines.
In the examples below, it is necessary to which special instruction, works as R1For phenyl when, the quinolinones chemical combination shown in formula (1)
Thing can obtain by using following synthetic route：
Specifically preparation method is：Substituted methyl anthranilate (11) and monoethyl malonate acid amide are condensed
To compound (14), cyclization obtains compound (15) to compound (14) in the basic conditions；Successively in alkalescence condition and acid bar
Compound (15) is handled under part, obtains compound (16)；Given birth in organic solvent by acid binding agent and chlorobenzoyl chloride reaction of alkali again
Into compound (17), compound (17) can be made sub- containing benzoyl by resetting (obtaining compound (18)) and addition condensation successively
4- hydroxyl -2- the quinolinones compounds of amine structure.Organic solvent is dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, first
Benzene, benzene, acetonitrile, acetone, tetrahydrofuran, ether, dioxane, DMF or DMSO；Alkali is MeONa, EtONa, NaOH, KOH, pyrrole
Pyridine, triethylamine or 4-N, TMSDMA N dimethylamine yl pyridines；Rearrangement catalyst be the Lewis such as alchlor, boron trifluoride acid and Cymag,
The cyanides such as potassium cyanide, acetone cyanohydrin, trimethyl cyanoalkysilane.
Preparation example
Compound I-1 synthesis：
In 100mL round-bottomed flasks add 2.0mmol 4- hydroxyl -3- acetyl group -2- quinolinones, sequentially add 50mL without
Water-ethanol, 2.0mmol n-butylamines are added under stirring condition, heat 8h, TLC monitoring reactions finish, and concentration of reaction solution obtains white
Color solid, ethyl alcohol recrystallization obtain the common 0.48g of target product I-1, yield 93.8%, 205-206 DEG C of fusing point.
Compound I-2~I-14 synthesis：
Reference compound I-1 preparation method, synthesis compound I-2~I-14.
Embodiment 1
Determine Tris- of the reaction buffer system containing 50mM of fructose 1,6-/sedoheptulose -1,7- diphosphatase enzymatic activitys
HCl (pH 8.3), 10mM dithiothreitol (DTT) (DTT), 15mM MgCl2.The compound in the table 1 of the present invention is taken respectively, is used
DMSO dissolving quinolinones compounds are configured to finite concentration, final concentration of 50 μM of quinolinones compound in reaction system (with
Inhibitor is also referred to as down).5mM substrate fructose 1 is added into the solution, 6- diphosphonic acid, reacts 5min at 30 DEG C.With more
Function ELIASA (Bioteck Synergy2, USA)) absorbance value of Detection wavelength when being 620nm.Absorbance value characterizes enzyme and existed
The amount of the product Phos of substrate generation is catalyzed under conditions of given.Absorbance value closes with the proportional example of enzymic catalytic reaction speed
System.Absorbance value is big, then enzymic catalytic reaction speed is with regard to big.The inhibiting rate of each compound is calculated by formula 1, is listed in Table 2 below.
Formula 1：Inhibiting rate %=(A0-Ai)/A0× 100%, wherein, A0For no inhibiting when fructose 1,6-/red-spotted stonecrop
The light absorption value of ketoheptose -1,7- diphosphatase, AiFructose 1,6-/sedoheptulose -1,7- diphosphatases during to add inhibitor
Light absorption value.
Embodiment 2
Cytoalgae PCC 6803 is most important a kind of pattern algae in blue-green algae.Cytoalgae PCC is selected in the present embodiment
6803 as effect of the experiment made on the living object for examining quinolinones compound suppression algal grown of the present invention.
Same amount of cytoalgae PCC 6803 is taken to be incubated at BG-11 (+N) Liquid Culture of the compound containing various concentrations respectively
In base, cultivated in artificial climate incubator.It is 28 DEG C ± 1 DEG C to control incubator temperature, humidity 60%, light intensity 6000lx,
12h (illumination)：12h (dark), vibration mode, separately manually shake 3 times daily.
Concrete operations are as follows：
The a collection of cytoalgae PCC 6803 of preculture, after 7 days to be grown to logarithmic phase, its OD680 is surveyed, inoculation is stand-by；
Above-mentioned logarithmic phase algae solution is diluted with fresh BG-11 (+N) culture medium, obtains inoculation algae solution, and control frustule dense
Degree about 1 × 106Individual/mL；
Compound is weighed in advance, is dissolved with DMSO, and preparing the quinolinones compounds of various concentrations, (concentration is respectively：
0mM, 0.01mM, 0.03mM, 0.1mM, 0.3mM, 1mM, 3mM, 10mM and 30mM.200 μ are added in each hole into 96 orifice plates
The inoculation algae solution that L has diluted, the quinolinones compound shown in the table 2 of the above-mentioned each concentration of 1 μ L is then separately added into again.It is each dense
The quinolinones compound of degree is parallel to do 5 groups, while sets the blank control (adding DMSO in algae solution system) without compound
With quinolinones compound ground control (the chemical combination objects system that preparation is dissolved with DMSO)；
OD680 is surveyed with ELIASA after being cultivated 7 days in artificial climate incubator, various concentrations quinoline is calculated according to formula 2
The inhibiting rate of ketone compounds；
Formula 2：Inhibiting rate %=[blank control group OD680- (experimental group OD680- quinolinones compound ground controls
Group OD680)]/blank control group OD680 × 100%；
Using the concentration of quinolinones compound as abscissa, the inhibiting rate that formula 2 is calculated is mapped for ordinate,
It is fitted in Origin with formula logistic, tries to achieve the EC of the quinolinones compound in table 250Value, the results are shown in Table 2.
Table 2
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that, with the prior art in this comparative example
Algicide copper sulphate replace embodiment 1 in quinolinones compound according to formula 3 test inhibiting rate, it is homogeneous in remaining condition
The use of inhibiting rate during copper sulphate is as a result 5% with the premise of.
Formula 3：Inhibiting rate %=(A0-Ai)/A0× 100%, wherein, A0Fructose 1,6-/red-spotted stonecrop during not add copper sulphate
The light absorption value of ketoheptose -1,7- diphosphatase, AiFructose 1,6-/sedoheptulose -1,7- diphosphatases during to add copper sulphate
Light absorption value.
Show that the inhibiting rate of quinolinones compound of the invention is obvious by the result for contrasting comparative example 1 and embodiment 1
The inhibiting rate of the copper sulphate used higher than prior art.
Comparative example 2
This comparative example is carried out using method similar to Example 2, except that, with the prior art in this comparative example
Algicide copper sulphate replace the quinolinones compound in embodiment 2 to suppress cytoalgae PCC 6803 growth, at remaining
On the premise of part all same, the EC of inhibiting rate, as a result copper sulphate is calculated using formula 450For 0.923 μM.
Formula 4：Inhibiting rate %=[blank control group OD680- (experimental group OD680- copper sulphate ground control groups
OD680)]/blank control group OD680 × 100%；
Shown by the result for contrasting comparative example 2 and embodiment 2, the suppression of quinolinones compound of the invention to blue-green algae
The copper sulphate that rate uses apparently higher than prior art when to the inhibiting rate of blue-green algae.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (7)
1. the dynamic isomer of the quinolinones compound shown in quinolinones compound and/or formula (1) shown in formula (1) is pressing down
Application in algal grown processed,
Wherein,
Quinolinones compound shown in the formula (1) is selected from least one of following compound：
Compound I-1, wherein, R1For methyl, R2For methyl, R3、R4、R5、R6It is hydrogen；
Compound I-2, wherein, R1For methyl, R2For ethyl, R3、R4、R5、R6It is hydrogen；
Compound I-3, wherein, R1For methyl, R2For n-propyl, R3、R4、R5、R6It is hydrogen；
Compound I-4, wherein, R1For methyl, R2For normal-butyl, R3、R4、R5、R6It is hydrogen；
Compound I-5, wherein, R1For methyl, R2For n-hexyl, R3、R4、R5、R6It is hydrogen；
Compound I-6, wherein, R1For methyl, R2For n-octyl, R3、R4、R5、R6It is hydrogen；
Compound I-7, wherein, R1For methyl, R2For positive decyl, R3、R4、R5、R6It is hydrogen；
Compound I-8, wherein, R1For methyl, R2For dodecyl, R3、R4、R5、R6It is hydrogen；
Compound I-9, wherein, R1For methyl, R2For 1- methyI-oropvDs, R3、R4、R5、R6It is hydrogen；
Compound I-10, wherein, R1For methyl, R2ForR3、R4、R5、R6It is hydrogen；
Compound I-11, wherein, R1For methyl, R2For cyclohexyl, R3、R4、R5、R6It is hydrogen；
Compound I-12, wherein, R1For methyl, R2ForR3、R4、R5、R6It is hydrogen；
Compound I-13, wherein, R1For phenyl, R2For phenyl, R3、R4、R5、R6It is hydrogen；
Compound I-14, wherein, R1For phenyl, R2For n-hexadecyl, R3、R4、R5、R6It is hydrogen.
2. application according to claim 1, wherein, the dynamic isomer of the quinolinones compound shown in the formula (1)
With the structure shown in formula (2),
Wherein, R1、R2、R3、R4、R5And R6Definition and formula (1) shown in quinolinones compound in R1、R2、R3、R4、R5With
R6Definition correspond to it is identical.
3. application according to claim 1, wherein, relative to every 1 × 106Individual algae, the quinolinone shown in the formula (1)
The dosage of the dynamic isomer of quinolinones compound shown in class compound and/or formula (1) is 1 × 10-10- 5 micromoles.
4. application according to claim 3, wherein, relative to every 1 × 106Individual algae, the quinolinone shown in the formula (1)
The dosage of the dynamic isomer of quinolinones compound shown in class compound and/or formula (1) is 5 × 10-8- 1 micromole.
5. application according to claim 3, wherein, relative to every 1 × 106Individual algae, the quinolinone shown in the formula (1)
The dosage of the dynamic isomer of quinolinones compound shown in class compound and/or formula (1) is 1 × 10-4-5×10-2It is micro- to rub
You.
6. application according to claim 1, wherein, the algae is red algae and blue-green algae.
7. application according to claim 6, wherein, the blue-green algae is cytoalgae PCC 6803, anabena, section ball algae, is read
At least one of pearl algae and microcystic aeruginosa 912.
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