CN110143946A - A kind of quinolines and its synthetic method and application - Google Patents
A kind of quinolines and its synthetic method and application Download PDFInfo
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- CN110143946A CN110143946A CN201910554548.3A CN201910554548A CN110143946A CN 110143946 A CN110143946 A CN 110143946A CN 201910554548 A CN201910554548 A CN 201910554548A CN 110143946 A CN110143946 A CN 110143946A
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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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
- C07D401/06—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 carbon chain containing only aliphatic carbon atoms
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Abstract
The invention discloses a kind of quinolines and its synthetic method and application, structure is as follows:The present invention introduces pyrrazole structure on the basis of traditional quinolinic acid structure, forms the derivative of a kind of new quinolinic acid.Quinolines synthetic method in the present invention is simple and easy, it is easy to accomplish mass production.Quinolines herbicidal effect of the invention is preferable, and has good effect to resistant weeds.
Description
Technical field
The invention belongs to organic syntheses and technical field of pesticide, and in particular to a kind of quinolines and its synthetic method
With application.
Background technique
Dichloro quinolinic acid chemical name: 3,7- bis- chloro- 8- quinolinic acids, it is the characteristic selective herbicidal for preventing and kill off barnyard grass in paddy field
Agent belongs to hormone-type quinoline acids herbicide.Seed, root, stem and the leaf portion that medicament can be sprouted absorb rapidly, and rapidly to stem and
Top conduction makes it be poisoned to death, and symptom is similar to auxin in the world, continues to apply dichloro quinolinic acid, barnyard grass extensively
Grass produces drug resistance to it.From dichloro quinolinic acid in 1993 China obtain registration come, prevention and treatment barnyard grass, black herba bromi japonici, herba setariae viridis,
Herba digitariae etc., it can also effectively prevent and kill off Monochoria vaginalis, Chinese celery, ambatch and class weeds etc. of leading a cow.Continuous administration more than 20 years.
The nearest main rice producing region in China has barnyard grass and develops drug resistance to it, and the degree of drug resistance is in get worse.
Currently, being the drug resistance for slowing down weeds to it, other herbicides of general compatibility, which are used in conjunction with, has slowed down its drug resistance,
In patent 201811297362.6 " a kind of Herbicidal combinations and its application containing dichloro quinolinic acid ", dichloroquinoline is used
Acid, aromatic oxygen-phenoxy group propionates class and sulfonylurea can improve herbicidal effect as Herbicidal combinations to a certain extent, can also
Slow down resistance weed, but it is not significant to the weeds effect to have developed drug resistance.Thoroughly to solve herbicide resistance
Problem, researching and developing new quinolines herbicide is best approach, but quinolines herbicide type new at present is less, pair having
Weeds with drug resistance are ineffective, and some synthesis technologies are complicated.
Summary of the invention
It is good that the object of the present invention is to provide a kind of herbicidal effects, the simple quinolines of synthesis technology and its synthesis side
Method and application.
This quinolines of the present invention, structural formula are any one in I or II:
Wherein: R1For any one in methyl, halogen, cyano, nitro, hydroxyl and hydrogen；R2For C1-C8Alkyl, C2-C6Alkene
Base, C3-C6Naphthenic base, C1-C8Alkoxy, the phenyl of different substituents, the benzyl of different substituents, C2-C6It is any in alkynyl
It is a kind of.
Moieties can be linear chain or branched chain, such as C individually or as group a part4Alkyl can be positive fourth
Base, tert-butyl, isobutyl group etc. are such；The part of alkenyl and alkynyl can be the form of linear chain or branched chain, and part alkene
Base has the configuration of (E) or (Z)；There are a naphthenic base such as three, four, five, six in the part of naphthenic base, the different location of ring it is also substituted
Base, substituent group include electrophilic, supplied for electronic and neutral atom etc.；C1-C8The part of alkoxy can as group a part
To be linear chain or branched chain.Such as have methoxyl group, ethyoxyl, propoxyl group or tert-butoxy etc., in alkoxy, there is 1~2 oxygen original
Son；The phenyl moiety of different substituents include it is o-, m-, to monosubstituted, group includes containing electrophilic, supplied for electronic and neutral former
Son/group such as nitro, methoxyl group, chlorine atom etc..There are also the disubstituted group of phenyl ring, disubstituted group i.e. electrophilics simultaneously, power supply
Son and neutral atom/group can also be the different atom/groups for replacing electrical property；The benzyl moiety of different substituents include it is adjacent,
Between, to monosubstituted, group includes containing electrophilic, supplied for electronic and neutral atom/group such as nitro, methoxyl group, chlorine atom etc.；Also
There is a disubstituted group of the phenyl ring of benzyl, disubstituted group i.e. electrophilic, supplied for electronic and neutral atom/group simultaneously can also be not
With the atom/group for replacing electrical property.
The preparation method of the quinolines, comprising the following steps:
1) compound N and chloride reagent are dissolved in solvent, are reacted, obtains intermediate M；
2) compound L or compound K and chemical bases are put into reaction dissolvent, heating reflux reaction setting time
Afterwards, the intermediate M that dropwise reaction solvent dissolves thereto, continues to be stirred at reflux reaction, after completion of the reaction, reaction solution is poured into ice
In water, and its pH is adjusted, after being filtered, obtains Primary product (white solid)；
3) after being purified the Primary product in step 2), obtaining structural formula is I or II quinolines；
Its synthetic route is as follows:
In the step 1), the molar ratio of the compound N and chloride reagent is 1:(5~10)；Chloride reagent
For SOCl2, POCl3(COCl)2One of or it is a variety of；The molal volume of compound N and solvent ratio is 1:(10~30)；It is molten
Agent is toluene, acetonitrile, one or more in chloroform；Reaction time is 8~14h.
In the step 2), the molar ratio (1~3) of compound L or K and chemical bases: (1~5), chemical bases are hydroxide
One of calcium, magnesium hydroxide, calcium oxide and magnesia are a variety of；The molal volume of compound L or K and reaction dissolvent ratio is
(10~15): 80mmol/mL；Reaction dissolvent is one of toluene, 1,4- dioxane, acetonitrile and tetrahydrofuran；Compound M
Molal volume ratio with reaction dissolvent is 10:(70~150) mmol/mL；The molar ratio of compound L or K and intermediate M be (1~
3):1；The reaction time is set as 0.5~1h；The reaction was continued time is 12~for 24 hours, adjust pH to 4~5.
In the step 3), the method for purification is one of recrystallization method or column chromatography.
Middle application of the quinolines in herbicide field.
Beneficial effects of the present invention: the present invention introduces pyrrazole structure on the basis of traditional quinolinic acid structure, is formed
The derivative of a kind of new quinolinic acid.Quinolines synthetic method in the present invention is simple and easy, it is easy to accomplish batch metaplasia
It produces.Quinolines herbicidal effect of the invention is preferable, and has good effect to resistant weeds.
Detailed description of the invention
The hydrogen spectrogram of I formula quinolines prepared by Fig. 1 embodiment 1；
The carbon spectrogram of I formula quinolines prepared by Fig. 2 embodiment 1；
The hydrogen spectrogram of I formula quinolines prepared by Fig. 3 embodiment 2；
The carbon spectrogram of I formula quinolines prepared by Fig. 4 embodiment 2；
The hydrogen spectrogram of I formula quinolines prepared by Fig. 5 embodiment 3；
The carbon spectrogram of I formula quinolines prepared by Fig. 6 embodiment 3；
The hydrogen spectrogram of II formula quinolines prepared by Fig. 7 embodiment 4；
The carbon spectrogram of II formula quinolines prepared by Fig. 8 embodiment 4.
Specific embodiment
Embodiment 1
By 10mmol substituent R1For the chloride SOCl of compound N (its structural formula is as follows) and 80mmol of Cl atom2Examination
Agent is dissolved in the toluene solvant of 150mL, cooling after carrying out reaction 12h, vacuum rotary steam solvent and extra SOCl2, obtain
Substituent R1For the intermediate M (its structural formula is as follows) of Cl, for use.
The substituent R of 10mmol2For the compound L (its structural formula is as follows) of ethyl, the calcium hydroxide of 17mmol, 3mmol
Calcium oxide be added in bis- mouthfuls of flasks of 250mL, be added 80mL acetonitrile heating stirring reflux 0.5h after, be dissolved in 20mL's
10mmol intermediate M in acetonitrile solvent is added drop-wise in reaction system, continues back flow reaction 12h, and after completion of the reaction, cooling is poured into
In the ice water of 200mL, pH=4~5 are adjusted with hydrochloric acid, white solid is obtained by filtration.
After white solid is dissolved with chloroform, water is added thereto and is extracted, takes organic phase, is removed with anhydrous magnesium sulfate
Water then filters away water, and organic phase is spin-dried for, and is recrystallized with chloroform/n-hexane, and the quinoline that structural formula is I formula is obtained
Quinoline class compound (wherein R1Base is Cl, R2Base is ethyl), yield 60.2%.
Nuclear-magnetism identification, result such as Fig. 1 (hydrogen spectrum) and Fig. 2 are carried out to the quinolines of I formula manufactured in the present embodiment
Shown in (carbon spectrum):
1HNMR (400MHz, CDCl3) δ: 8.87 (d, 1H), 8.14 (d, 1H), 7.78 (d, 1H), 7.59 (1H, d), 6.25
(1H,s),4.01-4.07(2H,q),2.31(3H,s),1.38-1.42(3H,t)；
13CNMR (100MHz, CDCl3)δ:163.07,153.62,151.33,143.76,138.94,133.69,
132.32,132.19,129.55,129.26,128.82,126.54,95.75,48.83,15.24,11.40.
MS:(M+H): 351.08
It can be complied fully with structural formula of the invention according to hydrogen spectral peak and the result of carbon spectral peak.
Embodiment 2
By 10mmol substituent R1For the chloride POCl of compound N (its structural formula is as follows) and 80mmol of nitro3Examination
Agent is dissolved in the toluene solvant of 150mL, cooling after carrying out reaction 12h, vacuum rotary steam solvent and extra SOCl2, obtain
Substituent R1For the intermediate M (its structural formula is as follows) of Cl, for use.
The substituent R of 12mmol2For the compound L (its structural formula is as follows) of phenyl, the magnesium hydroxide of 17mmol, 3mmol
Magnesia be added in bis- mouthfuls of flasks of 250mL, will be molten after Isosorbide-5-Nitrae-dioxane heating stirring back flow reaction 1h of 80mL is added
10mmol intermediate M of the solution in Isosorbide-5-Nitrae-dioxane solvent of 20mL is added drop-wise in reaction system, back flow reaction (same mistake for 24 hours
Thin-layer chromatography monitors raw material point and disappears) after, cooling is poured into the ice water of 200mL, adjusts pH=4~5 with sulfuric acid, is obtained by filtration solid
Body.
Solid is dissolved with chloroform, water is added to be extracted, organic phase extracted is removed water with anhydrous magnesium sulfate, is then filtered
Magnesium sulfate is removed, after organic phase is spin-dried for, is recrystallized with chloroform/n-hexane, the quinolines that structural formula is I formula are obtained
(wherein R1Base is NO2, R2Base is phenyl), yield 46.1%.
Nuclear-magnetism characterization is carried out to the quinolines of I formula manufactured in the present embodiment, hydrogen spectrum is as shown in figure 3, carbon is composed such as
Shown in Fig. 4, result is as follows:
1HNMR (400MHz, CDCl3) δ: 8.80 (d, 1H), 8.15 (s, 1H), 7.81 (d, 1H), 7.64 (d, 1H), 7.52
(d, 1H), 7.62 (d, 1H), 7.60 (d, 1H), 7.58 (s, 1H), 7.31-7.35 (t, 1H), 7.25-7.27 (s, 1H), 6.46
(s, 1H), 2.39 (s, 3H)
13CNMR (100MHz, CDCl3) δ: 161.275,151.243,149.035,144.076 143.601,137.908,
133.837,132.483,131.094,129.830,128.823,127.064,126.572,123.565,96.114,14.578
MS:(M+H): 409.08
According to hydrogen spectrum with carbon compose as a result, it is complied fully with structural formula of the invention.
Embodiment 3
By 10mmol substituent R1For the chloride SOCl of compound N (its structural formula is as follows) and 80mmol of Cl atom2Examination
Agent is dissolved in the tetrahydrofuran solvent of 150mL, cooling after carrying out reaction 12h, vacuum rotary steam solvent and extra SOCl2,
Obtain substituent R1For the intermediate M (its structural formula is as follows) of Cl, for use.
15mmol substituent group is R2For the compound L (its structural formula is as follows) of benzyl, the calcium hydroxide of 17mmol, 3mmol
Magnesia be added in bis- mouthfuls of flasks of 250mL, after the acetonitrile heating stirring back flow reaction 0.5h of 100mL is added, be dissolved in
10mmol intermediate M in the acetonitrile solvent of 20mL is added drop-wise in reaction system, and reflux is for 24 hours.The cooling ice water for pouring into 200mL
In, pH=4-5 is adjusted with sulfuric acid, solid is obtained by filtration.
Solid is dissolved with chloroform, water is added to be extracted, organic phase extracted is removed water with anhydrous magnesium sulfate, is then filtered
Magnesium sulfate is removed, after organic phase is spin-dried for, is recrystallized with chloroform/n-hexane, the quinolines that structural formula is I formula are obtained
(wherein R1Base is Cl, R2Base is benzyl), yield 57.2%.
Nuclear-magnetism characterization is carried out to the quinolines of I formula manufactured in the present embodiment, hydrogen spectrum is as shown in figure 5, carbon is composed such as
Shown in Fig. 6, result is as follows:
1HNMR (400MHz, CDCl3) δ: 8.88 (d, 1H), 8.15 (d, 1H), 7.79 (d, 1H), 7.60 (d, 1H), 7.24-
7.31(m,3H),7.14(d,2H),6.32(s,1H),5.23(s,2H),2.24(s,3H)
13CNMR (100MHz, CDCl3) δ: 158.325,149.181,146.621,139.026,135,348,131.821,
128.967,127.617,127.390,124.833,124.566,124.090,124.005,122.950,122.115,
121.805,91.882,48.297,6.924
MS:(M+H): 413.10
According to hydrogen spectrum with carbon compose as a result, it is complied fully with structural formula of the invention.
Embodiment 4
By 10mmol substituent R1For the chloride SOCl of compound N (its structural formula is as follows) and 100mmol of Cl atom2
Reagent is dissolved in the acetonitrile solvent of 240mL, cooling after carrying out reaction 12h, vacuum rotary steam solvent and extra SOCl2, obtain
To substituent R1For the intermediate M (its structural formula is as follows) of Cl, for use.
The substituent R of 30mmol2For the compound K (its structural formula is as follows) of 3- chlorobenzyl, the calcium hydroxide of 17mmol,
The calcium oxide of 3mmol is added in bis- mouthfuls of flasks of 250mL, after Isosorbide-5-Nitrae-dioxane heating stirring reflux 0.5h of 80mL is added,
The 10mmol intermediate M being dissolved in Isosorbide-5-Nitrae-dioxane solvent of 20mL is added drop-wise in reaction system, and it is anti-to continue reflux
Answer 12h.Cooling is poured into the ice water of 200mL, adjusts pH=4-5 with hydrochloric acid, solid is obtained by filtration.
Solid is dissolved with chloroform, water is added to be extracted, organic phase extracted is removed water with anhydrous magnesium sulfate, is then filtered
Magnesium sulfate is removed, after organic phase is spin-dried for, is recrystallized with chloroform/n-hexane, the quinolines chemical combination that structural formula is II formula is obtained
Object (wherein R1Base is Cl, R2Base is 3- chlorobenzyl), yield 61.4%.
Nuclear-magnetism characterization is carried out to the quinolines of II formula manufactured in the present embodiment, hydrogen spectrum is as shown in fig. 7, carbon is composed such as
Shown in Fig. 8, result is as follows:
1HNMR (400MHz, CDCl3) δ: 8.74 (d, 1H), 8.16 (d, 1H), 7.82 (d, 1H), 7.61 (d, 1H), 7.18-
7.19 (m, 3H), 7.08-7.10 (m, 1H), 6.26 (s, 1H), 5.23 (s, 2H), 2.31 (s, 3H)
13CNMR (100MHz, CDCl3) δ: 161.213,151.403,148.332,144.472,143.634,138.685,
134.370,133.911,132.520,131.016,129.939,129.867,128.867,127.809,127,600,
126.606,125.626,94.587,50.595,14.597
MS:(M+H): 468.30
According to hydrogen spectrum with carbon compose as a result, it is complied fully with structural formula of the invention.
Embodiment 5
Indoor poison is carried out to the quinolines in embodiment 1-3 using cauline leaf spray-on process (NY/T 1155.4-2006)
Power measurement test.
Reagent agent: embodiment 1 (a)；(b) embodiment 2；(c) embodiment 3；(d) dichloro quinolinic acid；Dilution 1 times, 10 times,
20 times, 30 times, 40 times of five concentration gradients it is stand-by, clear water control；
Material to be tested: barnyard grass [Echinochloa crusgalli]；Semen euphorbiae [Euphorbia lathyris]；Field
Collect Seed storage.
Point is sowed at the sectional area 0.25m equipped with soil after barnyard grass, semen euphorbiae seed presoaking and germinating2Plastic tub in, every basin
100 are broadcast, is cultivated in greenhouse to the target weeds careless 3 leaf phases and handle.By the dose concentration designed above, sprayed with spray tower
It is administered liquid, spouting liquid is every processing 50mL, keeps ground moistening after medicine.Every processing is repeated 4 times, and weighs each processing barnyard grass within 20 days after medicine
Careless aerial part fresh weight calculates the fresh weight preventive effect (%) of each processing as follows:
E=100 × (C-T)/C
In formula: E is fresh weight preventive effect；C is control weeds aerial part fresh weight；T is processing weeds aerial part fresh weight.
As shown in Tables 1 and 2, The Toxicity Determination result shows this quinolines to the virulence of barnyard grass and semen euphorbiae
Higher, opposite dichloro quinolinic acid has higher preventive effect.
Toxicity test result of the 1 quinolines noval chemical compound of table to barnyard grass
2 quinolines noval chemical compound of table is to semen euphorbiae toxicity test result
6 field trial of experimental example
Embodiment 1, embodiment 2, embodiment 3, comparison medicament dichloro quinolinic acid are applied to farmland and prevent and treat annual and many years
Raw weeds: embodiment 1,2,3 is diluted with water by spraying by 200g.a.i/ha, is to the strain preventive effect of total careless strain number within 30 days after medicine
90.76%, 86.22% and 92.79%；Fresh weight preventive effect, respectively 83.39%, 87.85% and 89.64%, comparison medicament two
Chloro-quinolinic acid is diluted with water by spraying by 200g.a.i/ha, and strain number preventive effect and fresh weight preventive effect are 78.53% and 76.63%.Illustrate quinoline
Quinoline class noval chemical compound is annual to paddy field and perennial weeds control efficiency is obvious, high to dichloro quinolinic acid preventive effect is compared, no
But has exploitation into the potentiality of herbicide, and have the advantages that low cost and environmental protection.
Prevent and kill off the test of resistance barnyard grass in 7 field of experimental example
Embodiment 1, embodiment 2, embodiment 3, comparison medicament dichloro quinolinic acid are prevented and treated applied to paddy field resistance barnyard grass: real
Apply example 1,2,3 be diluted with water by 200g.a.i/ha it is spraying, after medicine 30 days be 86.47% to the strain preventive effect of total careless strain number,
89.46% and 90.41%；Fresh weight preventive effect, respectively 84.57%, 86.40% and 84.90%, comparison medicament dichloro quinolinic acid
It is diluted with water by spraying by 200g.a.i/ha, strain number preventive effect and fresh weight preventive effect are 35.11% and 36.00%.Illustrate that quinolines are newly changed
Conjunction object is annual to paddy field and perennial weeds control efficiency is obvious, to compared to dichloro quinolinic acid preventive effect height, not only has out
The potentiality of herbicide are sent out into, and have the advantages that low cost and environmental protection.Illustrate to be obvious to paddy field resistance barnyard grass preventive effect, than
It is good to compare dichloro quinolinic acid preventive effect.
Finally, method of the invention is only preferable embodiment, it is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of quinolines, structural formula is any one in I or II:
Wherein: R1For any one in methyl, halogen, cyano, nitro, hydroxyl and hydrogen；R2For C1-C8Alkyl, C2-C6Alkenyl,
C3-C6Naphthenic base, C1-C8Alkoxy, the phenyl of different substituents, the benzyl of different substituents, C2-C6It is any one in alkynyl
Kind.
2. a kind of preparation method of quinolines according to claim 1, comprising the following steps:
1) compound N and chloride reagent are dissolved in solvent, are reacted, obtains intermediate M；
2) compound L or compound K and chemical bases are put into reaction dissolvent, after heating reflux reaction setting time, to
The wherein intermediate M of dropwise reaction solvent dissolution, continues to be stirred at reflux reaction, after completion of the reaction, reaction solution is poured into ice water,
And its pH is adjusted, after being filtered, obtain Primary product (white solid)；
3) after being purified the Primary product in step 2), obtaining structural formula is I or II quinolines；
Its synthetic route is as follows:
3. the preparation method of quinolines according to claim 2, which is characterized in that described in the step 1)
Compound N and chloride reagent molar ratio be 1:(5~10)；Chloride reagent is SOCl2, POCl3(COCl)2In
It is one or more.
4. the preparation method of quinolines according to claim 2 or 3, which is characterized in that in the step 1), change
The molal volume ratio for closing object N and solvent is 1:(10~30)；Solvent is toluene, acetonitrile, one or more in chloroform；Reaction time
For 8~14h.
5. the preparation method of quinolines according to claim 2, which is characterized in that in the step 2), chemical combination
The molar ratio (1~3) of object L or K and chemical bases: (1~5), chemical bases are calcium hydroxide, magnesium hydroxide, calcium oxide and magnesia
One of or it is a variety of.
6. the preparation method of quinolines according to claim 2 or 5, which is characterized in that in the step 2), change
The molal volume ratio for closing object L or K and reaction dissolvent is (10~15): 80mmol/mL；Reaction dissolvent is toluene, 1,4- dioxy six
One of ring, acetonitrile and tetrahydrofuran.
7. the preparation method of quinolines according to claim 2, which is characterized in that in the step 2), chemical combination
The molal volume of object M and reaction dissolvent ratio is 10:(70~150) mmol/mL；The molar ratio of compound L or K and intermediate M is
(1~3): 1.
8. the preparation method of the quinolines according to claim 2 or 7, which is characterized in that in the step 2), if
Determining the reaction time is 0.5~1h；The reaction was continued time is 12~for 24 hours, adjust pH to 4~5.
9. the preparation method of quinolines according to claim 2, which is characterized in that in the step 3), purification
Method be one of recrystallization method or column chromatography.
10. quinolines according to claim 1 or 2 are in the middle application in herbicide field.
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| CN115160238A (en) * | 2022-08-04 | 2022-10-11 | 湖南省农业生物技术研究所 | Quinoxaline phenoxyacetic acid ester compound and preparation method and application thereof |
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| US4497651A (en) * | 1982-02-17 | 1985-02-05 | Basf Aktiengesellschaft | Dichloroquinoline derivatives for use as herbicides |
| CN1240440A (en) * | 1996-12-20 | 2000-01-05 | 纳幕尔杜邦公司 | Substituted benzothiopyranes salts and their use as herbicides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160238A (en) * | 2022-08-04 | 2022-10-11 | 湖南省农业生物技术研究所 | Quinoxaline phenoxyacetic acid ester compound and preparation method and application thereof |
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