CN102718700B - 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative preparations and applicatio is studied - Google Patents
3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative preparations and applicatio is studied Download PDFInfo
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- CN102718700B CN102718700B CN201210235682.5A CN201210235682A CN102718700B CN 102718700 B CN102718700 B CN 102718700B CN 201210235682 A CN201210235682 A CN 201210235682A CN 102718700 B CN102718700 B CN 102718700B
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- 0 CC(C*(C)COC(COc(c(Cl)c1)nc(Cl)c1Cl)=O)N(*)* Chemical compound CC(C*(C)COC(COc(c(Cl)c1)nc(Cl)c1Cl)=O)N(*)* 0.000 description 2
- RDPYUCUIBPKFCY-UHFFFAOYSA-N O=C(COc(nc(c(Cl)c1)Cl)c1Cl)OCCN1CCOCC1 Chemical compound O=C(COc(nc(c(Cl)c1)Cl)c1Cl)OCCN1CCOCC1 RDPYUCUIBPKFCY-UHFFFAOYSA-N 0.000 description 1
- RDPYUCUIBPKFCY-UHFFFAOYSA-O O=C(COc(nc(c(Cl)c1)Cl)c1Cl)OCCN1CC[OH+]CC1 Chemical compound O=C(COc(nc(c(Cl)c1)Cl)c1Cl)OCCN1CC[OH+]CC1 RDPYUCUIBPKFCY-UHFFFAOYSA-O 0.000 description 1
Abstract
A kind of oily 3,5,6-tri-molten Chloro-2-Pyridyle fluoroacetic acid derivatives of holding concurrently of water with weeding activity, as shown in general formula (I, II):
, wherein: X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... or (CH
2)
nrepresent the alkyl with side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; R
2represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; Or R
1, R
2be selected from following structure:
Description
Technical field:
The present invention relates to the preparation of 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid analog derivative and weeding activity.
Background technology:
Traditional Agricultural pharmaceutically dosage form is with missible oil, wettable powder, pulvis and granule are main, along with the manufacture and exploit of pesticides new formulation, following meeting is towards aqua, the future development such as aqueous emulsion and microemulsion, from this development trend, this just has higher requirement to the novel pesticide molecule being about to succeed in developing, not only want efficient, low toxicity, safety and and environmental friendliness, also wish that drug molecule has certain water-soluble simultaneously, directly use if drug molecule has the good water-soluble aqua that just can be made into, so not only can reduce production cost but also can reduce when drug molecule is made into certain preparation needs to add a large amount of solvent, tensio-active agent, the environmental pollution that auxiliary agent and permeate agent etc. bring.From this respect, good water-soluble of drug molecule has very important significance.Meanwhile, having necessarily water-soluble and fat-soluble drug molecule, is also that medicine is effectively necessary through microbial film.
No matter medicine is that epidermal absorption or other approach absorb, and all needs with the form of molecule through barrier membranes.First medicine need dissolve, and if medicine has desirable biopharmaceutical properties, its region from the regional diffusion of high density to lower concentration, strides across cytolemma and enters into the recycle system.All microbial films contain lipid as major ingredient.In biofilm structure, active molecule all has the end structure containing phosphatic high polarity, and, in most of the cases, the hydrocarbon chain of two very hydrophobic.Microbial film has bilayer structure, and hydrophilic chain end structure is towards the aqueous regions of both sides.Very hydrophilic medicine cannot stop wherein as a biomembranous part because of the similar reason mixed by very hydrophobic medicine through biomembranous lipid layer, thus effectively can not enter inner tenuigenin.
Patent documentation US2007/0117721A1, GB2288394A reports 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative has good herbicidal activity, wherein typical compound 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid is a kind of systemic herbicides, and be generally used for preventing and treating the weeds of broadleaf weeds in softwood tree young growth and rice field wheat paddock, its herbicidal spectrum is wide, drug effect is high, can degrade rapidly in soil.But the ammonium salt that this weedicide is formed or natrium brine dissolubility very good, and fat-soluble bad, generally to add a large amount of auxiliary agents when thus using, to improve its sticking power on crop, improve its bioavailability.
The object of the invention is by regulating the water-soluble and fat-soluble of 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative, making them can reach a well balance, reducing the loss of in vitro, thus improve the utilization ratio of medicine.3 of new design and synthesis, 5,6-tri-Chloro-2-Pyridyle fluoroacetic acid novel cpd has two identical constructional features: they have part (oil soluble part) and the one-level that protonated form exists under physiology PH condition of a close ester, secondary, or tertiary amine group (water-soluble portion).Water-soluble-oily molten balance is like this that medicine is effectively through microbial film institute necessary [SusanMilosovich, etal.J.Pharm.Sci., 82,227 (1993)].Amino with positive charge considerably increases the solubleness of medicine.This point can be able to be seen from experimental implementation: in product aftertreatment, does not become the compound of positive ion to be dissolved in sherwood oil and water insoluble, and after becoming quaternary amine, compound is present in water layer, and is insoluble to sherwood oil.As a rule, the solubleness of medicine is step that is the slowest in absorption process and maximum speed limit.When these novel cpds make medicament, in its molecule, amino understands the phosphate end group bonding with cytolemma.Therefore, the partial concn of medicine outside microbial film is very high thus contribute to these medicines by the region of area with high mercury to lower concentration.After these drug molecules enter into microbial film, hydrophilic parts can promote the tenuigenin that medicine enters into the concentrated aqueous solution of semi liquid state.
Summary of the invention:
The object of this invention is to provide compound and the synthetic method of class 3,5, a 6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative and salt thereof, this compounds has excellent weeding activity.
The invention provides a kind of 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivatives of novel structure and the compound of salt thereof, as shown in general formula (I, II):
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... or (CH
2)
nrepresent the alkyl with side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; R
2represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl of a 1-6 carbon atom or aryl; Or R
1, R
2be selected from following structure:
The comparatively preferred compound of the present invention is:
N=1 ~ 4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2be selected from H, C
1-C
4alkyl or R
1=R
2be selected from following structure:
In the present invention, more preferred structural formula of compound is as follows:
The following method preparation of general formula compound (I, II) of the present invention:
Reaction path is as follows:
Raw material propylene nitrile and trichoroacetic chloride are dissolved in suitable solvent, add catalyzer, temperature is react 1-24 hour under 0 DEG C to boiling point, obtained intermediate (T
1), suitable solvent is selected from DMF, toluene, dichlorobenzene, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride.Catalyzer is selected from cuprous chloride, cuprous iodide, tin protochloride etc.
Intermediate (T
1) in add in appropriate buck, under temperature is 0 DEG C to boiling point, stir 1-24 hour obtained intermediate sodium alkoxide (T
2), suitable alkali is selected from sodium hydroxide, sodium carbonate, sodium bicarbonate.
Sodium alkoxide (T
2) be dissolved in suitable solvent with ethyl chloroacetate, add catalyzer and phase-transfer catalyst, obtained intermediate (T
3), suitable solvent is selected from DMF, toluene, dichlorobenzene, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride, and suitable catalyzer is selected from potassiumiodide, cuprous iodide, and suitable phase-transfer catalyst is selected from Tetrabutyl amonium bromide, tri-tert benzylamine etc.
Intermediate (T
3) be dissolved in suitable solvent, with in alkaline aqueous solution, temperature reacts 1-24 hour under being 0 DEG C to boiling point, then through hydrochloric acid or sulfuric acid acidation, obtained intermediate acid (T
1), suitable solvent selected from methanol, toluene, dichlorobenzene, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride, suitable alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus.
Intermediate acid (T
4) and SOCl
2, PCl
3or oxalyl chloride is dissolved in suitable solvent, such as dioxane, benzene, toluene, ethyl acetate, THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride, with organic bases as pyridine, triethylamine take DMF as catalyzer, and temperature is react 1-24 hour obtained acyl chlorides (T under 0 DEG C to boiling point
5).
Acyl chlorides (T
5) and (n+1)-(dialkyl group) amino-1-(mercaptan, amine) alcohol (preparing), in suitable solvent, temperature is react 1-24 hour obtained product (I) under 0 DEG C to boiling point.Solvent can be dioxane, benzene, toluene, ethyl acetate, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.Add alkaline matter, as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood or saleratus etc. are favourable to reaction.
Product (I) and diluted acid YH, product (I) can be dissolved in suitable solvent, add diluted acid YH, temperature is react 1-24 hour obtained product (II) under 0 DEG C to boiling point.Solvent can be dioxane, benzene, toluene, ethyl acetate, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.
The present invention can also illustrate with the compound listed in table 1, table 2, but does not limit the present invention
Table 1: the compounds of this invention of part as shown in general formula I
Table 2: the compounds of this invention of part as shown in general formula I I
Part of compounds in table
1hNMR data are as follows:
Compound 1:(CDCl
3) δ: 2.25 (s, 6H, 2C
h 3), 2.57 (t, 2H, J
h=5.6Hz, C
h 2), 4.27 (t, 2H, J
h=5.6Hz, C
h 2), 4.96 (s, 2H, C
h 2), 7.75 (s, 1H, Ar
h);
Compound 2: δ: 2.47 (m, 4H, 2CH2), 2.64 (t, 2H, JH=5.7Hz, CH2), 3.69 (m, 4H, 2CH2), 4.32 (t, 2H, JH=5.7Hz, CH2), 4.97 (s, 2H, CH2), 7.78 (s, 1H, ArH);
Compound 3:(D2O) δ: 2.85 (s, 6H, 2CH3), 3.44 (br, 2H, CH2), 4.47 (br, 2H, CH2), 4.97 (s, 2H, CH2), 7.93 (s, 1H, ArH);
Compound 4:(D2O) δ: 3.19 (br, 2H, CH2), 3.40 (br, 2H, CH2), 3.49 (br, 2H, CH2), 3.78 (br, 2H, CH2), 3.98 (br, 2H, CH2), 4.49 (br, 2H, CH2), 4.96 (s, 2H, CH2), 7.87 (s, 1H, ArH);
General formula (I, II) compound of the present invention has weeding activity, uses the growth that can control broadleaf weeds well after seedling.Compare with existing similar compound, such compounds exhibit goes out better weeding activity and broad spectrum.
It is the herbicidal composition of active ingredient that the present invention also comprises with general formula (I, II) compound.In this herbicidal, the weight percentage of active ingredient is 1-99%.Agriculturally acceptable carrier is also comprised in this herbicidal composition.
General formula (I of the present invention, II) compound and the herbicidal composition as active ingredient thereof can make several formulations use, especially general formula (II), directly can be made into aqua to use, both decreased with an organic solvent to the pollution of environment, be more conducive to again absorption and the conduction of plant.In these compositions, also can add liquid or solid carrier, and add appropriate tensio-active agent and carry out compounding application.
Other embodiment of the present invention is the method for control broadleaf weeds, and the method comprises and compound of the present invention and composition thereof is applied on the surface of described weeds or its growth medium.Amount of application is generally per hectare 5 grams to 500 grams, and preferably having effective amount is per hectare 30 grams to 300 grams.In addition, also can add one or more other weedicide in compound of the present invention and in active composition, can produce more efficient thus, the effect of wide spectrum.
General formula (I, II) compound of the present invention both can be used alone as weedicide and other known sterilant, sterilant, plant-growth regulator or fertilizer also can be coordinated to mix together.
It is clear that within the scope of the claims in the present invention, should can carry out various change and conversion as required.
Embodiment
The following example and raw test-results of surveying can be used for weeding activity of the present invention is described further, but do not mean that restriction the present invention.
Synthesis example
The synthesis of compound 1:
(1).
Get in trichoroacetic chloride 18.2g to 250ml reaction flask, add dichlorobenzene 60ml, cuprous chloride 0.6g, stirring makes it to mix, heating, temperature is 50-120 DEG C, stirs the lower dichlorobenzene solution (30ml) dripped containing vinyl cyanide (6.9g), dropwise rear continuation stirring 6 ~ 7h, stop stirring, question response liquid temp is down to room temperature, transfers them in the single necked round bottom flask of 250ml, decompression precipitation, obtains chocolate liquid; ESI-MS:calcforC
5h
3cl
4nO, (M+H)
+232.90, found232.90.
(2).
Under ice-water bath, upwards walk in the chocolate liquid be obtained by reacting and add 30ml water, stir and make it to mix; Continue the sodium hydroxide solution dripping 30% in reaction solution, after dropwising, continue to stir 2h, obtain the mixed solution of brown color, the dichlorobenzene that air distillation removing is remaining, suction filtration, filtration cakes torrefaction obtains linen pressed powder 14.44g.ESI-MS：calcforC
5HCl
3NNaO，(M+H)
+219.91，found219.91。
(3).
Weigh 3,5,6 ,-three chloro-2-pyridol sodium (T of 22g
2) in 250ml round-bottomed flask, add 44mlDMF, 16g ethyl chloroacetate, 0.9g potassiumiodide and 0.8g Tetrabutyl amonium bromide is added, heated and stirred, stopped reaction after 2.5h in reaction solution, precipitation obtains viscous brown thing, add 50ml water and 80ml methylene dichloride, be uniformly mixed liquid 15min, be then transferred in separating funnel, leave standstill separatory, collect organic phase; With saturated common salt washing twice, get organic phase, anhydrous sodium sulphate, precipitation obtains light tan solid, fusing point 43 ~ 45 DEG C;
1hNMR (400MHz, CDCl
3) δ: 1.29 (t, 3H, J
h=7.1Hz, CH
2c
h 3), 4.25 (q, 2H, J
h=7.1Hz, C
h 2cH
3), 4.93 (s, 2H, C
h 2), 7.76 (s, 1H, Ar
h);
(4).
Get 3,5,6 ,-three Chloro-2-Pyridyle fluoroacetic acid ethyl ester (T
3) 9.18g is in 100ml reaction flask, add 10ml methyl alcohol, stirring makes molten; Add the solution 50ml of the sodium hydroxide of 30%, heated and stirred, stop heating after 2h, be cooled to room temperature, adjust PH to 3 ~ 4, have a large amount of white solid to separate out, suction filtration, obtain white solid 7.16g, fusing point 150 ~ 151 DEG C;
1hNMR (400MHz, DMSO) δ: 4.93 (s, 2H, C
h 2), 8.41 (s, 1H, Ar
h), 13.21 (br, H, COO
h);
(5).
Take 3,5,6 ,-three Chloro-2-Pyridyle fluoroacetic acid (T
4) in 2.2g to 50ml reaction flask, add methylene dichloride 15ml, stir and make molten, then in reaction solution, add 10ml thionyl chloride, heated and stirred, stop after 5 ~ 6h stirring, be cooled to room temperature; Precipitation obtains the solid 2.3g of brown color.
(6).
By 2.3g acyl chlorides (T
5)) be dissolved in 15ml methylene dichloride, under ice-water bath, drip the dichloromethane solution 18ml that 0.0086molN, N-bis-replaces hydramine, 0.0172mol triethylamine.After dropwising, stirring at room temperature reaction 16h, reaction solution is washed, and collects organic phase; Wash with saturated sodium bicarbonate solution and saturated nacl aqueous solution successively, organic phase anhydrous sodium sulfate drying, suction filtration precipitation obtains thick product again, and column chromatography is purified to obtain compound 1.
The synthesis of compound 3:
Get compound 10.6g in 50ml two mouthfuls of reaction flasks, add 20ml methylene dichloride, stirring makes molten, pass into dry HCl gas (to be added drop-wise in concentrated hydrochloric acid by the vitriol oil and obtained by vitriol oil drying), stir 0.5h, precipitation obtains white solid 0.65g, and this is compound 3.
In table 1, table 2, other compound all obtains by similar approach.
Raw survey example:
To the weeding activity of compound, have employed and Preliminary activation test and evaluation are carried out to the room temperature pot-culture method of different mechanism of action sensitivities.
Pot-culture method (soil treatment): put into a certain amount of soil in the plastic cassettes of diameter 7cm, add a certain amount of water, after planting cover certain thickness soil, cultivate in greenhouse, cover with plastic film before coming up.Every day, in addition quantitative clear water was to keep normal growth.Soil treatment is carried out before emerging.30 days " Invest, Then Investigate " results, measure overground part fresh weight, suppress percentage ratio to represent drug effect with fresh weight.
Pot-culture method (cauline leaf process): put into a certain amount of soil in the plastic cassettes of diameter 7cm, add a certain amount of water, after planting cover certain thickness soil, cultivate in greenhouse, cover with plastic film before coming up.After emerging, every day, in addition quantitative clear water was to keep normal growth.Cauline leaf spraying process is carried out when seedling grows to the certain period.Process 30 days " Invest, Then Investigate " results, measure overground part fresh weight, suppress percentage ratio to represent drug effect with fresh weight.Examination material is rape (Brassicacampestris), barnyard grass (Echinochloacrus-galli), three-coloured amaranth (AmaranthusretroflexusL.) and lady's-grass (Digitariasanguinalis (L.) Scop).
Compounds of formula II directly adds water, and does not add any tensio-active agent and auxiliary agent, is made into aqua and carries out weeding activity test.
Part is as follows in compound of Formula I test result:
Part is as follows in Compounds of formula II test result:
Claims (5)
1.3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative, as shown in general formula (I, II):
Wherein:
N=0,1,2,3,4; Y
-represent Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion; R
1represent the alkoxyl group of the alkyl of 1-6 carbon atom, a 1-6 carbon atom; R
2represent the alkoxyl group of the alkyl of 1-6 carbon atom, a 1-6 carbon atom; Or following particular compound structure:
2. compound as claimed in claim 1, is characterized in that, in general formula (I, II):
N=1 ~ 4; Y
-represent Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion; R
1, R
2be selected from C
1-C
4alkyl or following particular compound structure:
3. compound according to claim 1 is for controlling annual and perennial grass herbaceous weed and woody weeds purposes.
4. a herbicidal composition, containing, for example compound according to claim 1 and agriculturally acceptable carrier, in composition, the weight percentage of active ingredient is 1-99%.
5. control a method for weeds, it is characterized in that: the herbicidal composition as claimed in claim 4 using herbicidally effective amount on the growth medium or place of weeds or weeds.
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| CN104672127B (en) * | 2015-02-10 | 2016-08-10 | 湖南比德生化科技有限公司 | 3,5,6-trichlopyr and the preparation method of salt thereof |
| CN105566211A (en) * | 2016-02-18 | 2016-05-11 | 江苏丰山集团股份有限公司 | Triclopyr production method |
| CN107325044A (en) * | 2017-07-08 | 2017-11-07 | 杨子辉 | A kind of preparation method of herbicide triclopyr butoxyethyl ester |
| CN108586324A (en) * | 2018-06-01 | 2018-09-28 | 杨子辉 | A kind of preparation method of pyrrole fluoroacetic acid derivative and application |
| CN109180570A (en) * | 2018-06-29 | 2019-01-11 | 湖北犇星农化有限责任公司 | A kind of preparation method of trichlopyr fourth 2-ethoxyethyl acetate |
| CN109232401B (en) * | 2018-11-13 | 2020-04-03 | 湖南比德生化科技股份有限公司 | Resource treatment method for triclopyr rectification residual liquid |
| WO2020133090A1 (en) * | 2018-12-27 | 2020-07-02 | 青岛清原化合物有限公司 | Pyridyloxy thioester derivative and preparation method therefor, herbicidal composition, and application |
| CN109535070B (en) * | 2018-12-27 | 2022-03-29 | 青岛清原化合物有限公司 | Pyridyloxycarboxylate derivative, preparation method thereof, herbicidal composition and application |
| EP3904341A4 (en) * | 2018-12-27 | 2022-08-10 | Qingdao KingAgroot Chemical Compound Co., Ltd. | R-type pyridyloxycarboxylic acid, salt and ester derivative thereof, and preparation method therefor, and herbicidal composition and application thereof |
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