CN108191755A - Herbicides compounds and its preparation method and application - Google Patents
Herbicides compounds and its preparation method and application Download PDFInfo
- Publication number
- CN108191755A CN108191755A CN201810139901.7A CN201810139901A CN108191755A CN 108191755 A CN108191755 A CN 108191755A CN 201810139901 A CN201810139901 A CN 201810139901A CN 108191755 A CN108191755 A CN 108191755A
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- Prior art keywords
- compound
- tautomer
- pharmaceutically acceptable
- acceptable salt
- grass
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- 0 *c(cnc1c2C(OC(CCC3)=CC3=O)=O)cc1ccc2Br Chemical compound *c(cnc1c2C(OC(CCC3)=CC3=O)=O)cc1ccc2Br 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N O=C(CCC1)CC1=O Chemical compound O=C(CCC1)CC1=O HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the compound of chemical formula (I) a kind of, the compound is
Description
Technical field
The present invention relates to field of pesticide preparation, particularly relate to a kind of herbicides compounds and its preparation method and application.
Background technology
Due to the succession of weed population, transition and generation and rapid development to chemical pesticide drug resistance；People are to life
The reinforcement of state environmental protection consciousness and on chemical pesticide pollution, pesticide on non-target organism influence and in pesticide ecological environment
The attention of home to return to problem；World's Cultivated Land Area Decrease and population, which increase, increases grain demand amount；Agriculture production technology it is rapid
Development and the reasons such as continuously improve of cropping system, need constantly to invent novel or improved herbicidal compounds.
Rice is the second-biggest-in-the-world cereal crops for being only second to wheat.In China, the annual sown area stabilization of rice is 4.4
Hundred million mu or more, 30% or so of cereal crops sown area is accounted for, and rice yield accounts for more than the 40% of total grain output, sown area
It is occupied first of cereal crops with total output, is the first big crop in China.The whole nation there are about 2/3 population using rice as staple food.And
Barnyard grass is to endanger one of most heavy malignant weed in the world, Severe Reduction can be caused even to have no harvest in rice terrace generation.Rice terrace
The prevention and control of barnyard grass rely on chemical herbicide, and wherein penoxsuam has barnyard grass special efficacy, and the medicament has broad weed-killing spectrum, height
Effect, the lasting period is long, risk of environmental pollution is low, it is long to be applicable in period, to people, animal, rice is highly safe the features such as.2015 in China
Rice terrace application area is up to 37,500,000 mu.But due to application for many years, barnyard grass has generated serious resistance at present.2017, south
Capital agriculture university Dong Li Yao, old state very wait report, are acquired on Jiangsu, Anhui, Shanghai, Heilungkiang, Ningxia, Hunan, Liaoning and other places
48 barnyard grass populations carry out resistant determination, the results showed that, 5 populations are high resistance, and resistant multiple reaches 101-218 times, 29
Population is highly resistance, and resistant multiple is 10-100 times, and 4 populations are moderate resistance, and resistant multiple is 6-10 times, therefore urgent need one kind can
Prevent and kill off the herbicide of anti-penoxsuam barnyard grass.
Invention content
There is good preventive effect to barnyard grass and lady's-grass the technical problem to be solved in the present invention is to provide a kind of, especially to five
The barnyard grass that penoxsulam generates resistance has herbicides compounds of more superior activity of weeding and its preparation method and application.
In order to solve the above technical problems, present invention offer technical solution is as follows：
On the one hand, a kind of formula (I) compound represented or its tautomer and pharmaceutically acceptable salt are provided：
Wherein, R1For methyl, halogen, nitro or methyl sulphonyl；R2For methyl, halogen, nitro or methyl sulphonyl.
Further, R1For chlorine, bromine or nitro, R2For chlorine, bromine or nitro.
Further, R1For chlorine, R2For chlorine.
Further, wherein R1For bromine, R2For bromine.
Further, wherein R1For nitro, R2For chlorine.
On the other hand, above compound or the preparation method of its tautomer and pharmaceutically acceptable salt are provided, closed
It is into route：
Compound (II) is dissolved in solvent, adds in compound (III), reaction is to get chemical combination under the conditions of certain temperature
Partial solvent is sloughed in the crude product of object I, distillation, and cooling crystallizes, filtering, you can target compound shown in logical formula (I) is made or it is mutual
Tautomeric.
Wherein, the molar ratio of the Compound Compound (II) and compound (III) is 1:1.
Wherein, the solvent is chloroform, dichloromethane or toluene；The compound (II) and the mass concentration ratio of solvent are
0.4-0.7g/ml；The reaction condition reacts 2-4 hours for 10-15 DEG C.
In another aspect, the present invention also provides above compound or its tautomer and pharmaceutically acceptable salt should
With for preventing grassy weed and broad leaved weed.
Further, the grassy weed is:Wild oat, bromegrass, Triticum tauschii, amur foxtail, net grass, barnyard grass, dog tail
Grass, lady's-grass, green bristlegrass；Broad leaved weed for Siberian cocklebur, piemarker, knotweed, lamb's-quarters, three-coloured amaranth, field bindweed.
Compound with chemical formula (I) can include asymmetric center and can be used as it is single reflect isomers, with appoint
The enantiomter of what ratio and exist or wherein there are more than one asymmetric center, include may ratio diastereomeric
Isomers.Compared with other possibilities, one of these typical enantiomters have the bioactivity of enhancing.
In addition, the compound with chemical formula (I) can be in balance with the tautomeric form of replacement.It should be understood that
It is that all tautomeric forms (single tautomer or its mixture), racemic mixture and individual isomer should also belong to
In in the scope of the present invention.
The invention also includes pharmaceutically acceptable salts, and the compound for having chemical formula (I) can be with amine, alkali metal
These pharmaceutically acceptable salts are formed with alkaline-earth metal bases or quaternary ammonium salt bases.With the alkali metal and alkaline earth for being made salt object
Among metal hydroxides, oxide, alkoxide and bicarbonate and carbonate.
The compound with chemical formula (I) according to the present invention can itself function as herbicide, usually also be helped using preparation
Agent (such as carrier, solvent and surfactant) is configured to herbicide formulations.Therefore, compound provided by the invention can be more
The form application of kind preparation.Such as：These compounds can be made into missible oil, aqua, emulsifiable concentrate, microemulsion, wettable powder, water
Suspending agent, oil-suspending agent, water dispersion granule or soluble powder (granula) etc., at least add in a kind of liquid or solid carrier,
And it usually requires to add in appropriate surfactant.
The herbicides compounds of the present invention generally comprise weight meter from 0.1%-99%, and especially grade by weight is from 0.1%-
95% has the compound of chemical formula (I) and by weight from a kind of preparation adjuvant of 1%-99.9%, and the preparation adjuvant is excellent
Choosing is included by weight from some surfactants of 0%-25%.
Other embodiments of the present invention are the method for controlling weeds, and this method includes the herbicide of the present invention imposing on institute
It states on the place of weeds or the weed growth or the surface of growth medium.It is per public to generally select more suitable effective dose
Hectare 0.1-1500 grams, preferably effective dose is 10-1000 grams of per hectare.
The invention has the advantages that：
In said program, leading to formula (I) compound or its isomers and pharmaceutically acceptable salt, there is excellent weeding to live
Property, after before seedling or seedling use can effectively control grassy weed and part broad leaved weed.
Specific embodiment
To make the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
The present invention for barnyard grass is high to penoxsuam resistance in the prior art the problem of, provide a kind of special efficacy to five fluorine
The barnyard grass that sulphur grass amine generates resistance has herbicides compounds of more superior activity of weeding and its preparation method and application.
Embodiment 1
The synthetic route of compound is：
In 250 milliliters of three-necked flask, 3,7- dichloroquinoline -8- acid chlorides 65.00 grams (0.250 moles), chlorine are added in
It is 100 milliliters imitative, stir lower cool down；After temperature drops to 10 DEG C, 28.03 grams of (0.250 mole) 1,3- rings are slowly added under stirring
Acetyl butyryl；It is kept for 10-15 DEG C react 2 hours, (3- oxo -1- cyclohexenyl groups) -3,7- dichloroquinoline -8- formic acid esters is made
Chloroformic solution；Chloroform is sloughed in distillation, is cooled down, and is crystallized, and filtering obtains 81.7 grams of off-white powder (3- oxo -1- cyclohexene after drying
Base) -3,7- dichloroquinoline -8- formic acid esters.
1H NMR (300MHz, CDCl3)：8.98 (d, 1H), 8.09 (d, 1H), 8.70 (d, 1H), 7.86 (d, 1H), 5.82
(m, 1H), 1.94 (m, 2H), 3.16 (m, 2H), 1.54 (m, 2H), yield 87.8%.
Embodiment 2：
The synthetic route of compound：
In 250 milliliters of three-necked flask, addition 3,7-, bis- 70.00 grams of bromoquinoline -8- acid chlorides (0.200 mole), two
110 milliliters of chloromethanes stirs lower cool down；After temperature drops to 10 DEG C, 22.42 grams of (0.200 moles) 1 are slowly added under stirring,
Hydroresorcinol；It is kept for 10-15 DEG C react 2.5 hours, bis- bromoquinoline -8- first of (3- oxo -1- cyclohexenyl groups) -3,7- is made
The dichloromethane crude solution of acid esters, distillation slough 75 milliliters of dichloromethane, cool down, crystallize, filtering, after drying 75.5 grams it is shallow
Bis- bromoquinoline -8- formic acid esters of yellow solid compound (3- oxo -1- cyclohexenyl groups) -3,7-.
1HNMR (300MHz, CDCl3)：8.99 (d, 1H), 8.85 (d, 1H), 8.31 (d, 1H), 8.02 (d, 1H), 5.82
(m, 1H), 1.94 (m, 2H), 3.16 (m, 2H), 1.54 (m, 2H), yield 81.7%.
Embodiment 3：
The synthetic route of compound：
In 250 milliliters of three-necked flask, 3- nitro -7- chloroquinoline -8- acid chlorides 58 grams (0.215 moles), chlorine are added in
It is 100 milliliters imitative, stir lower cool down；After temperature drops to 10 DEG C, 24.10 grams of (0.215 mole) 1,3- rings are slowly added under stirring
Acetyl butyryl；It is kept for 10-15 DEG C react 4 hours, crude product (3- oxo -1- cyclohexenyl groups) -3,7- dinitro quinoline -8- formic acid is made
70 milliliters of chloroforms are sloughed in the chloroformic solution of ester, distillation, are cooled down, and are crystallized, and filtering obtains 68.5 grams of brown solid compounds after drying
(3- oxo -1- cyclohexenyl groups) -3- nitro -7- chloroquinoline -8- formic acid esters.
1H NMR (300MHz, CDCl3)：8.98 (d, 1H), 9.62 (d, 1H), 8.86 (d, 1H), 8.08 (d, 1H), 5.82
(m, 1H), 1.94 (m, 2H), 3.16 (m, 2H), 1.54 (m, 2H) yields are 83.4%.
It should be noted that compound provided by the invention can be made by method like above.
Embodiment 1-3 is carried out bioactivity detection by advantageous effect in order to further illustrate the present invention.
Bioactivity detection method：
The quantitative weed seed of sowing in the disposable plastic flowerpot (hole is arranged at bottom) of a diameter of 12cm broadcasts 15- per basin
It 20, broadcasts rear earthing 0.5cm and flattens, be put in stainless steel square plate, suitable water is injected in square plate, flowerpot is made to be inhaled from bottom natural
Water.
Examination material is placed in greenhouse and is cultivated, barnyard grass, lady's-grass length to 2-3 leaf phases is treated, piemarker, Amaranthus retroflexus 2-4 leaf phases, is carrying out
Cauline leaf spraying treatment, 3 repetitions are carried out by experimental design dosage on belt crops sprayer, and sets blank control.It is small to handle 6
When be placed in greenhouse and routinely manage, and observed and recorded, the range estimation preventive effect of each processing is investigated after 20 days.
The preparation of liquid：The part of compounds 10g of the logical formula (I) of preparation is weighed with electronic balance, uses dimethylformamide
Active compound is dissolved, 10g Tween-80 surfactants is added in, complements to 100ml. with acetone and 10% missible oil is made.It weighs a certain amount of
The liquid that the preparation prepared adds water to be configured to various concentration is sprayed, 20Kg/ mus of spouting liquid.
The activity of weeding of compound
Note：* resistance barnyard grass seed picks up from Hunan Province Hanshou county Yan Wanghu towns, rice terrace barnyard grass 3-5 leaf phases five happinesses sulphur grass
Amine (45ga.i./hm2) processing, barnyard grass seed is collected after autumn, and Resistance Identification has been carried out by Institute of Plant Protection of Hunan academy of agricultural sciences, the present invention
The resistance index of resistance barnyard grass used is 43.68, ED50It is 192.8037, coefficient R=0.9334, during resistance level is
Grade.
Raw test the result shows that, the application compound have to grass family and broad leaved weed compared with high herbicidal activity, confrontation
The barnyard grass of penoxsuam also has excellent preventive effect.Even if comparison medicament penoxsuam dosage is increased to registration dosage
10 times, antagonism barnyard grass is also substantially invalid, while, only certain inhibiting effect poor to lady's-grass preventive effect.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. formula (I) compound represented or its tautomer and pharmaceutically acceptable salt：
Wherein, R1For methyl, halogen, nitro or methyl sulphonyl；R2For methyl, halogen, nitro or methyl sulphonyl.
2. compound according to claim 1 or its tautomer and pharmaceutically acceptable salt, which is characterized in that R1
For chlorine, bromine or nitro, R2For chlorine, bromine or nitro.
3. compound according to claim 1 or 2 or its tautomer and pharmaceutically acceptable salt, feature exist
In R1For chlorine, R2For chlorine.
4. compound according to claim 1 or 2 or its tautomer and pharmaceutically acceptable salt, feature exist
In wherein R1For bromine, R2For bromine.
5. compound according to claim 1 or 2 or its tautomer and pharmaceutically acceptable salt, feature exist
In wherein R1For nitro, R2For chlorine.
6. the preparation method of the arbitrary compounds of claim 1-5, which is characterized in that by compound (II)It is dissolved in solvent, adds in compound (III)Reaction is to get compound under the conditions of certain temperature
The crude product of I.
7. compound according to claim 6 or the preparation method of its tautomer and pharmaceutically acceptable salt,
It is characterized in that, the molar ratio of the Compound Compound (II) and compound (III) is 1:1.
8. compound according to claim 6 or the preparation method of its tautomer and pharmaceutically acceptable salt,
It is characterized in that, the solvent is chloroform, dichloromethane or toluene；The mass concentration ratio of the compound (II) and solvent is 0.4-
0.7g/ml；The reaction condition reacts 2-4 hours for 10-15 DEG C.
9. the application of claim 1-5 any compound or its tautomer and the pharmaceutically acceptable salt, special
Sign is, for preventing grassy weed and broad leaved weed.
10. the application of compound according to claim 9 or its tautomer and pharmaceutically acceptable salt, feature
It is, the grassy weed is wild oat, bromegrass, Triticum tauschii, amur foxtail, net grass, barnyard grass, herba setariae viridis grass, lady's-grass, dog tail
Grass；Broad leaved weed for Siberian cocklebur, piemarker, knotweed, lamb's-quarters, three-coloured amaranth, field bindweed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810139901.7A CN108191755B (en) | 2018-02-11 | 2018-02-11 | Herbicides compounds and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810139901.7A CN108191755B (en) | 2018-02-11 | 2018-02-11 | Herbicides compounds and its preparation method and application |
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| Publication Number | Publication Date |
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| CN108191755A true CN108191755A (en) | 2018-06-22 |
| CN108191755B CN108191755B (en) | 2019-08-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111771894A (en) * | 2020-07-30 | 2020-10-16 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing penoxsulam and application thereof |
| CN111802394A (en) * | 2020-07-30 | 2020-10-23 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing cyhalofop-butyl and application thereof |
| CN111838165A (en) * | 2020-07-30 | 2020-10-30 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing atrazine and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249996A (en) * | 2011-05-10 | 2011-11-23 | 北京法盖银科技有限公司 | 2-(quinoline-8-yl)carbonyl-cyclohexane-1,3-dione compounds |
-
2018
- 2018-02-11 CN CN201810139901.7A patent/CN108191755B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249996A (en) * | 2011-05-10 | 2011-11-23 | 北京法盖银科技有限公司 | 2-(quinoline-8-yl)carbonyl-cyclohexane-1,3-dione compounds |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111771894A (en) * | 2020-07-30 | 2020-10-16 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing penoxsulam and application thereof |
| CN111802394A (en) * | 2020-07-30 | 2020-10-23 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing cyhalofop-butyl and application thereof |
| CN111838165A (en) * | 2020-07-30 | 2020-10-30 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing atrazine and application thereof |
| CN111802394B (en) * | 2020-07-30 | 2021-11-09 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing cyhalofop-butyl and application thereof |
| CN111771894B (en) * | 2020-07-30 | 2021-11-09 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing penoxsulam and application thereof |
| CN111838165B (en) * | 2020-07-30 | 2021-11-09 | 定远县嘉禾植物保护剂有限责任公司 | Herbicide composition containing atrazine and application thereof |
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| Publication number | Publication date |
|---|---|
| CN108191755B (en) | 2019-08-16 |
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Denomination of invention: Herbicidal compounds and their preparation and Application Effective date of registration: 20200824 Granted publication date: 20190816 Pledgee: Dingyuan county development industry guidance fund management center (L.P.) Pledgor: DINGYUAN JIAHE CROP PROTECTION Co.,Ltd. Registration number: Y2020980005292 |
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Date of cancellation: 20221115 Granted publication date: 20190816 Pledgee: Dingyuan county development industry guidance fund management center (L.P.) Pledgor: DINGYUAN JIAHE CROP PROTECTION CO.,LTD. Registration number: Y2020980005292 |
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