CN108191755B - Herbicides compounds and its preparation method and application - Google Patents
Herbicides compounds and its preparation method and application Download PDFInfo
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- CN108191755B CN108191755B CN201810139901.7A CN201810139901A CN108191755B CN 108191755 B CN108191755 B CN 108191755B CN 201810139901 A CN201810139901 A CN 201810139901A CN 108191755 B CN108191755 B CN 108191755B
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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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- 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, a kind of herbicides compounds and its preparation method and application are particularly related to.
Background technique
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
The reasons such as continuously improve of development and 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 of rice is stablized 4.4
Hundred million mu or more, 30% or so of cereal crops sown area is accounted for, and rice yield accounts for 40% of total grain output or more, sown area
It is occupied first of cereal crops with total output, is the first big crop in China.There are about 2/3 populations using rice as staple food in the whole nation.And
Barnyard grass is to endanger most heavy one of malignant weed in the world, Severe Reduction can be caused even to have no harvest in paddy field generation.Paddy field
The prevention and control of barnyard grass rely on chemical herbicide, and wherein penoxsuam has special efficacy to barnyard grass, 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
Paddy field application area is up to 37,500,000 mu.But for many years due to application, barnyard grass has generated serious resistance at present.2017, south
The report such as capital agriculture university Dong Liyao, Chen Guoqi acquires 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, 4 populations be in resist, resistant multiple is 6-10 times, therefore being badly in need of one kind can
Prevent and kill off the herbicide of anti-penoxsuam barnyard grass.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of pair of barnyard grasses and herba digitariae good preventive effect, especially to five
The barnyard grass that penoxsulam generates resistance has the herbicides compounds and its preparation method and application of more superior activity of weeding.
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, the preparation method of above compound or its tautomer and pharmaceutically acceptable salt is provided, is closed
At route are as follows:
Compound (II) is dissolved in solvent, is added compound (III), reaction is under the conditions of certain temperature to get chemical combination
The crude product of object I distills and sloughs partial solvent, cools down, and crystallizes, filtering, can be prepared by target compound shown in logical formula (I) 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, methylene chloride or toluene；The compound (II) and the mass concentration ratio of solvent are
0.4-0.7g/ml；The reaction condition be 10-15 DEG C reaction 2-4 hours.
In another aspect, answering the present invention also provides above compound or its tautomer and pharmaceutically acceptable salt
With for preventing and treating gramineae weed and broadleaf weeds.
Further, the gramineae weed are as follows: wild avena sativa, herba bromi japonici, Triticum tauschii, amur foxtail, net grass, barnyard grass, dog tail
Grass, herba digitariae, herba setariae viridis；Broadleaf weeds is Siberian cocklebur, piemarker, knotweed, Chenopodiaceae, three-coloured amaranth, field bindweed.
Compound with chemical formula (I) may include asymmetric center and can be used as it is single reflect isomers, with appoint
The enantiomter of what ratio and exist, or in which there are more than one asymmetric center, include may ratio it is diastereomeric
Isomers.Compared with other possibilities, one of these typical enantiomters have the bioactivity of enhancing.
In addition, balance can be in the tautomeric form of substitution by having the compound of chemical formula (I).It should be understood that
It is that all tautomeric forms (or mixtures thereof single tautomer), racemic mixture and individual isomer should also belong to
In in the scope of the present invention.
The invention also includes pharmaceutically acceptable salts, have the compound of 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., are at least added a kind of liquid or solid carrier,
And it usually requires that surfactant appropriate is added.
Herbicides compounds of the invention generally comprise poidometer 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%, the preparation adjuvant is excellent
Choosing includes by weight from some surfactants of 0%-25%.
Other embodiments of the present invention are the method for controlling weeds, and this method includes that herbicide of the invention is imposed on institute
It states on the place of weeds or the weed growth or the surface of its somatomedin.Generally selecting more suitable effective dose is every public affairs
Hectare 0.1-1500 grams, preferably effective dose is 10-1000 grams of per hectare.
The invention has the following advantages:
In above scheme, leading to formula (I) compound or its isomers and pharmaceutically acceptable salt has excellent weeding living
Property, use can effectively control gramineae weed and part broadleaf weeds before seedling or after seedling.
Specific embodiment
To keep 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 the barnyard grass problem high to penoxsuam resistance in the prior art, provide a kind of special efficacy to five fluorine
The barnyard grass that sulphur grass amine generates resistance has the herbicides compounds and its preparation method and application of more superior activity of weeding.
Embodiment 1
The synthetic route of compound are as follows:
In 250 milliliters of three-necked flask, it is added 65.00 grams of 3,7- dichloroquinoline -8- acid chloride (0.250 mole), chlorine
It is 100 milliliters imitative, stir lower cooling；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 group) -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 chloride (0.200 mole), two
110 milliliters of chloromethanes, stir lower cooling；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 group) -3,7- is made
The dichloromethane crude solution of acid esters distills and sloughs 75 milliliters of methylene chloride, cools down, and crystallizes, filtering, and 75.5 grams are obtained after drying shallowly
Bis- bromoquinoline -8- formic acid esters of yellow solid compound (3- oxo -1- cyclohexenyl group) -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, it is added 58 grams of 3- nitro -7- chloroquinoline -8- acid chloride (0.215 mole), chlorine
It is 100 milliliters imitative, stir lower cooling；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 group) -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 group) -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 beneficial effect in order to further illustrate the present invention.
Bioactivity detection method:
The quantitative weed seed of sowing, every basin broadcast 15- in the disposable plastic flowerpot (hole is arranged at bottom) that diameter is 12cm
It 20, broadcasts rear earthing 0.5cm and flattens, be put in stainless steel square plate, suitable water is injected in square plate, inhale flowerpot from bottom natural
Water.
Test material is placed in a greenhouse culture, long to the 2-3 leaf phase to barnyard grass, herba digitariae, piemarker, Amaranthus retroflexus 2-4 leaf phase are 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 investigated after 20 days.
The preparation of medical fluid: the part of compounds 10g of the logical formula (I) of preparation is weighed with electronic balance, uses dimethylformamide
Raw medicine is dissolved, 10g Tween-80 surfactant is added, complements to 100ml. with acetone and 10% missible oil is made.It weighs a certain amount of
The medical fluid that the preparation prepared adds water to be configured to various concentration is sprayed, and 20Kg/ mus of spouting liquid.
The activity of weeding of compound
Note: * resistance barnyard grass seed picks up from Hunan Province, the town Yan Wanghu, Hanshou county, paddy field barnyard grass 3-5 leaf phase 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, Hunan academy of agricultural sciences, the present invention
The resistance index of the 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 to grass family and broadleaf weeds have 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 herba digitariae preventive effect.
The above is a 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, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (6)
1. the application of formula (I) compound represented and its pharmaceutically acceptable salt, which is characterized in that miscellaneous for preventing and treating grass family
Grass and broadleaf weeds:
Wherein, R1For halogen or nitro；R2For halogen or nitro.
2. application according to claim 1, which is characterized in that R1For chlorine, bromine or nitro, R2For chlorine, bromine or nitro.
3. application according to claim 1 or 2, which is characterized in that R1For chlorine, R2For chlorine.
4. application according to claim 1 or 2, which is characterized in that wherein R1For bromine, R2For bromine.
5. application according to claim 1 or 2, which is characterized in that wherein R1For nitro, R2For chlorine.
6. application according to claim 1, which is characterized in that the gramineae weed be wild avena sativa, herba bromi japonici, Triticum tauschii,
Amur foxtail, net grass, barnyard grass, herba setariae viridis grass, herba digitariae, herba setariae viridis；Broadleaf weeds is Siberian cocklebur, piemarker, knotweed, Chenopodiaceae, three-coloured amaranth, field bindweed.
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| Application Number | Priority Date | Filing Date | Title |
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| 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 CN108191755A (en) | 2018-06-22 |
| CN108191755B true CN108191755B (en) | 2019-08-16 |
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| 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 |
| 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 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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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