CN101279951B - 2-pyrimindinyloxy (pyrimindinylthio) benzoxy enoates compound and application thereof - Google Patents

2-pyrimindinyloxy (pyrimindinylthio) benzoxy enoates compound and application thereof Download PDF

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CN101279951B
CN101279951B CN2007100108586A CN200710010858A CN101279951B CN 101279951 B CN101279951 B CN 101279951B CN 2007100108586 A CN2007100108586 A CN 2007100108586A CN 200710010858 A CN200710010858 A CN 200710010858A CN 101279951 B CN101279951 B CN 101279951B
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CN101279951A (en
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李斌
冀海英
崔东亮
白丽萍
张弘
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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Abstract

The invention discloses 2-pyridine-oxyl(sulfide) benzoyloxy enoates compound with general formula(I, II); wherein X is H or S; R1 is H, halogen, or 4,6- dimethoxy pyrimidine-2- radicel or one of the following groups; methyls on N-O bonds and double bonds are in maleinoid form or anti form; R2,R3,R4,R6,R7 are selected from H or alkyl from C1-C6; R5 is alkyl from C1-C6, alcoxyl-alkyl from C2-C6, alkenyl from C3-C6 or alkynyl from C3-C6; radicals of R6 and R7 are in maleinoid form or anti form; R8 is alkyl from C1-C6, alkenyl from C3-C6 or alkynyl from C3-C6. The compound (I, II)is of activity in weeding and is safe to crops like soybean, cotton, earthnut, cole, corn, etc.

Description

2-pyrimidine oxygen (sulphur) yl benzoic acid base olefin(e) acid ester compound and application thereof
Technical field
The invention belongs to the weedicide field, be specifically related to a kind of 2-pyrimidine oxygen (sulphur) yl benzoic acid base olefin(e) acid ester compound and application thereof.
Background technology
Because the succession of weeds population, transition and to the drug-fast generation of chemical pesticide with develop rapidly; people are to the continuous reinforcement of ecological environmental protection consciousness, to chemical pesticide pollute, agricultural chemicals to the understanding of non-target organism influence and in the agricultural chemicals ecotope attention of home to return to problem improve constantly.Along with the continuous growth of the reducing gradually of world's cultivated area, population and to the increase of grain demand amount, force people to develop agriculture production technology rapidly, improve and improve cropping system, and need constantly invention novel with improved herbicidal compound and composition.
EP223406 has reported that some 2-pyrimidine oxygen (sulphur) yl benzoic acid ester compound has weeding activity, and to peanut, Sunflower Receptacle safety.CN1749236A and CN1927811A disclose some 3-phenoxy benzoic acid base olefin(e) acid ester compound and have had weeding activity.Do not relate to preparation and application thereof in the prior art as 2-pyrimidine oxygen (sulphur) yl benzoic acid base olefin(e) acid ester compound shown in the present.
Summary of the invention
The purpose of this invention is to provide a kind of novel structure, have fine weeding activity and be the herbicidal composition of active ingredient, to satisfy the needs that agriculture production develops rapidly to 2-pyrimidine oxygen (sulphur) the yl benzoic acid base olefin(e) acid ester compound of crop safety and with this compounds.
Technical scheme of the present invention is as follows:
The invention provides a kind of 2-pyrimidine oxygen (sulphur) yl benzoic acid base olefin(e) acid ester compound of novel structure, as general formula (I, II) shown in:
Figure G07110858620070418D000011
In the formula:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen, halogen, 4,6-dimethoxypyridin-2-base or following radicals:
Figure G07110858620070418D000021
Wherein, the methyl on nitrogen-oxygen bond and the two keys is a cis or trans;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen or C respectively 1-C 6Alkyl;
R 5Be selected from C 1-C 6Alkyl, C 2-C 6Alkoxyalkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl;
R 6With R 7Group is a cis or trans;
R 8Be selected from C 1-C 6Alkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl.
Comparatively preferred compound is among the present invention, general formula (I, II) in:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen, halogen, 4,6-dimethoxypyridin-2-base or following radicals:
Wherein, the methyl on nitrogen-oxygen bond and the two keys is a cis;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen respectively; R 6With R 7Group is trans;
R 5Be selected from C 1-C 6Alkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl;
R 8Be selected from methyl.
Further preferred compound is among the present invention, general formula (I, II) in:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen or halogen;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen respectively; R 6With R 7Group is trans;
R 5Be selected from C 1-C 6Alkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl.
(I, II) alkyl of middle indication comprises the straight or branched alkyl to general formula.Alkoxyalkyl is meant the straight or branched form, contains the alkyl of alkoxy grp, for example methoxyl methyl, the different third oxygen ethyl etc.Thiazolinyl is meant the straight or branched form, and the group of 1 to 2 carbon-carbon double bond is arranged, for example, and propenyl, allyl group etc.Alkynyl is meant the straight or branched form, and 1 to 2 carbon carbon triple-linked group is arranged, for example, and proyl, propargyl etc.Halogen comprises fluorine, chlorine, bromine, iodine.
General formula of the present invention (I, II) compound can be prepared by following method:
Figure G07110858620070418D000031
(III) (has commercially available with compound, also can make by oneself, the preparation method is referring to Pestic.Sci.1996,47,115-124) be dissolved in the The suitable solvent, made compound (V) for-10 ℃ in 0.5-48 hour to reaction between the boiling point in temperature with compound (IV) (preparation method is referring to J.Org.Chem.32:3229 (1967)).The suitable solvent can be selected from for example toluene, acetone, DMF, THF or dioxane etc.Add alkaloids, as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood etc. to reacting favourable.
Compound (V) and suitable alkali are joined in the mixed solvent that suitable organic solvent and water forms, temperature be-10 ℃ to reacting 0.5-48 hour between the boiling point, reaction solution is through hydrochloric acid or sulfuric acid acidation, making intermediate acid is compound (VI).Suitable organic solvent is selected from chloroform, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, methyl alcohol, ethanol, THF or dioxane etc.; Suitable alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood etc.
(preparation method of VII is referring to synthetic chemistry with compound (VII) for compound (VI), 13 (3), 315-316, (2005)) be dissolved in The suitable solvent for example toluene, acetone, DMF, THF or dioxane etc., temperature be-10 ℃ between the boiling point reaction 0.5-48 hour, make compound (I).Add alkaloids such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood etc. to reacting favourable.In the compound (VII), Y can be chlorine, bromine or iodine.
Because the difference of starting raw material or reaction conditions can obtain R 6With R 7Group is cis or trans compound (VIII), or contains the cis of different ratios and the mixture (preparation of VIII is referring to CN1927811A) of trans-compound (VIII) simultaneously.In the compound (VIII), Y can be chlorine, bromine or iodine.
Compound (VI) and compound (VIII) are dissolved in The suitable solvent for example toluene, acetone, DMF, THF or dioxane etc., temperature be-10 ℃ to reacting 0.5-48 hour between the boiling point, make R 6With R 7Group is cis or trans compound (II), or contains the cis of different ratios and the mixture of trans-compound (II) simultaneously.Add alkaloids such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood etc. to reacting favourable.
Table 1: the The compounds of this invention of part shown in general formula (I)
Figure G07110858620070418D000041
Table 2: the The compounds of this invention of part shown in general formula (II)
Figure G07110858620070418D000043
Figure G07110858620070418D000051
Part of compounds 1H NMR (CDCl 3, 300MHz) δ (ppm) data are as follows:
Compound 1
3.807(s，9H，CH 3)，4.857(s，2H，CH 2)，5.736(s，1H)，5.857(s，1H，＝CH)，6.332(s，1H，＝CH)，7.328(m，2H，Ar-H)，7.569(m，1H，Ar-H)，8.040(q，1H，J＝1.8Hz，Ar-H).
Compound 2
0.947(t，3H，J＝7.3Hz，CH 3)，1.693(m，2H，CH 2)，3.804(s，6H，OCH 3)，4.110(t，2H，J＝6.6Hz，CH 2)，4.867(s，2H，CH 2)，5.736(s，1H)，5.834(d，1H，J＝1.2Hz，＝CH)，6.331(d，1H，J＝0.9Hz，＝CH)，7.352(m，2H，Ar-H)，7.594(m，1H，Ar-H)，8.040(q，1H，J＝1.8Hz，Ar-H).
Compound 3
2.492(t，1H，J＝2.4Hz，1H)，3.784(s，6H，OCH 3)，4.765(s，2H，CH 2)，4.878(s，2H，CH 2)，5.740(s，1H)，5.929(d，1H，J＝0.9Hz，＝CH)，6.402(d，1H，J＝0.9Hz，＝CH)，7.327(m，2H，Ar-H)，7.601(m，1H，Ar-H)，8.044(q，1H，J＝1.8Hz，Ar-H).
Compound 4
1.287(t，3H，J＝7.1Hz，CH 3)，3.780(s，6H，OCH 3)，4.219(q，2H，J＝7.2Hz，CH 2)，4.866(s，2H，CH 2)，5.732(s，1H)，5.831(s，1H，＝CH)，6.321(s，1H，＝CH)，7.324(m，2H，Ar-H)，7.590(m，1H，Ar-H)，8.039(q，1H，J＝1.2Hz，Ar-H).
Compound 5
1.305(t，3H，J＝7.1Hz，CH 3)，3.711(s，6H，OCH 3)，4.222(q，2H，J＝7.2Hz，CH 2)，5.045(s，2H，CH 2)，5.709(s，1H)，5，860(s，1H，＝CH)，6.339(s，1H，＝CH)，7.448(m，2H，Ar-H)，7.631(d，1H，Ar-H).
Compound 12
3.761(s，3H，CO 2CH 3)，3.788(s，6H，OCH 3)，4.786(q，2H，CH 2)，5.739(s，1H)，6.020(m，1H，＝CH)，6.840(m，1H，CH＝)，7.340(m，2H，Ar-H)，7.616(m，1H，Ar-H)，8.162(m，1H，Ar-H).
Compound 13
1.272(t，3H，CH 3)，3.789(s，6H，OCH 3)，4.189(q，2H，CH 2)，4.786(q，2H，CH 2)，5.740(s，1H)，6.006(m，1H，＝CH)，6.856(m，1H，CH＝)，7.282(m，2H，Ar-H)，7.616(m，1H，Ar-H)，8.031(m，1H，Ar-H).
Compound 14
0.970(m，3H，CH 3)，1.407(m，2H，CH 2)，1.659(m，2H，CH 2)，3.789(s，6H，CH 3)，4.191(m，2H，CH 2)，4.785(q，2H，CH 2)，5.739(s，1H)，6.014(m，1H，＝CH)，6.804(m，1H，CH＝)，7.342(m，2H，Ar-H)，7.618(m，1H，Ar-H)，8.052(m，1H，Ar-H).
Compound 15
0.960(m，3H，CH 3)，1.678(m，2H，CH 2)，3.790(s，6H，OCH 3)，4.112(m，2H，CH 2)，4.789(q，2H，CH 2)，5.746(s，1H)，6.014(m，1H，＝CH)，6.810(m，1H，CH＝)，7.260(m，1H，Ar-H)，7.369(m，1H，Ar-H)，7.613(m，1H，Ar-H)，8.053(m，1H，Ar-H).
Compound 16 is the mixture of two kinds of configurations, wherein contain cis 33% (among the general formula I I, R 6With R 7Group is at two key homonymies); Contain trans 67% (among the general formula I I, R 6With R 7Group is not at two key homonymies).
Cis: 1.271 (m, 3H, CH 3), 1.872 (s, 3H, CH 3), 3.800 (s, 6H, OCH 3), 4.172 (q, 2H, J=6.9Hz, CH 2), 5.266 (s, 2H, CH 2), 5.735 (s, 1H ,=CH), 5.788 (s, 1H), 7.325 (m, 2H, Ar-H), 7.617 (m, 1H, Ar-H), 8.059 (m, 1H, Ar-H). trans: 1.271 (m, 3H, CH 3), 2.105 (s, 3H, CH 3), 3.800 (s, 6H, OCH 3), 4.172 (q, 2H, J=6.9Hz, CH 2), 4.615 (s, 2H, CH 2), 5.735 (s, 1H ,=CH), 5.788 (s, 1H), 7.325 (m, 2H, Ar-H), 7.617 (m, 1H, Ar-H), 8.059 (m, 1H, Ar-H).
Compound 17
1.285(t，3H，CH 3)，3.720(s，6H，OCH 3)，4.199(q，2H，CH 2)，4.955(m，2H，CH 2)，5.717(s，1H)，6.012(m，1H，＝CH)，6.918(m，1H，CH＝)，7.469(m，2H，Ar-H)，7.635(d，1H，Ar-H).
(I, II) compound has weeding activity to general formula of the present invention.Compare with disclosed compound in the prior art, compound of the present invention uses before than seedling under the low dosage, behind the seedling can effectively control single broadleaf weed, especially gramineous weeds is had the higher activity of preventing and kill off.Therefore technical scheme of the present invention comprises that (I, II) compound is used to control the purposes of weeds to general formula.
General formula of the present invention (I, II) compound uses before seedling, to soybean, cotton, peanut and other crops safety; Behind seedling, use,, especially the security of gramineous crop corn is had and make us unexpected promising result, kept simultaneously the height of gramineous weeds barnyard grass grass is prevented and kill off activity crop safeties such as corn, peanut, rapes.
The present invention comprises that also (I, II) compound is as the herbicidal composition of active ingredient with general formula.The weight percentage of active ingredient is 5-90% in this herbicidal composition.Comprise also in this herbicidal composition that agricultural goes up acceptable carrier.
Herbicidal composition of the present invention can several formulations form use.Usually with compound dissolution of the present invention or be scattered in and be mixed with preparation in the carrier so that be easier to disperse when using as weedicide.For example: these chemicals can be made into wettable powder or missible oil.Therefore, in these compositions, add a kind of liquid or solid carrier at least, and need to add suitable tensio-active agent usually.
Other embodiments of the present invention are method of controlling weeds, and this method comprises herbicidal composition of the present invention is imposed on the surface of the place of described weeds or described weed growth or its growth medium.Usually the comparatively suitable significant quantity of selecting is that per hectare 10 restrains 5000 grams, and preferred significant quantity is that per hectare 20 restrains 2500 grams.Use for some, can in herbicidal composition of the present invention, add one or more other weedicide, can produce additional advantage and effect thus.
Compound of the present invention both can use separately also can be mixed together use with other known sterilant, sterilant, plant-growth regulator or fertilizer etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
The following example and living test are tested the result and be can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic example
Synthesizing of compound 4:
In 250 milliliters of round-bottomed flasks, add 4,6-dimethoxy-2-methanesulfonyl pyrimidine 7 grams (0.036 mole), 6 milliliters of wintergreen oils (0.047 mole), salt of wormwood 6 grams (0.043 mole), N, 100 milliliters of dinethylformamides.After 4 hours, be cooled to room temperature in 110-130 ℃ of stirring reaction.In reaction solution, add 180 milliliters in 200 milliliters of ethyl acetate and water, extraction.Organic phase is used 50 milliliters in 1% dilute hydrochloric acid, 50 milliliters of saturated sodium bicarbonates, 3 * 50 milliliters of saturated sodium-chloride water solution washings successively, anhydrous magnesium sulfate drying, the resistates that obtains behind the precipitation is through silica gel column chromatography (petrol ether/ethyl acetate=5/1) purifying, obtain 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy) methyl benzoate 8.35 grams.
Figure G07110858620070418D000072
In 150 milliliters of round-bottomed flasks, add 2-(4 successively, 6-dimethoxy-2-2-pyrimidinyl oxy) methyl benzoate 2.93 gram (0.01 mole), 50 milliliters of tetrahydrofuran (THF)s, sodium hydroxide 0.4 gram (0.01 mole) are dissolved in the solution of 50 ml waters, and the stirring at normal temperature reaction is spent the night.The back decompression that reacts completely steams tetrahydrofuran (THF).In resistates, add 2 milliliters of 200 milliliters of ethyl acetate, concentrated hydrochloric acids, 50 milliliters of washings, 3 * 50 milliliters of saturated sodium-chloride water solution washing organic phases, anhydrous magnesium sulfate drying gets 2-(4,6-dimethoxy-2-2-pyrimidinyl oxy) phenylformic acid 2.05 grams behind the precipitation.
Figure G07110858620070418D000081
In 100 milliliters of three mouthfuls of round-bottomed flasks, add 2-(4 successively, 6-dimethoxy-2-2-pyrimidinyl oxy) phenylformic acid 1.0 gram (3.6 mmole), N, 30 milliliters of dinethylformamides, salt of wormwood 0.50 gram (3.6 mmole), 2-brooethyl ethyl propenoate 0.69 gram (3.6 mmole).In 40-60 ℃ of stirring reaction after 8 hours, in reaction solution, add 180 milliliters in 200 milliliters of ethyl acetate and water, extraction, saturated sodium-chloride water solution washing organic phase with 180 milliliters, use anhydrous magnesium sulfate drying again, the resistates that obtains behind the precipitation obtains 2-(ethoxycarbonyl) allyl group-2-(4,6-dimethoxy-2-2-pyrimidinyl oxy) benzoic ether 1.05 grams through silica gel column chromatography (petrol ether/ethyl acetate=3/1) purifying.
Synthesizing of compound 17:
In 100 milliliters of three mouthfuls of round-bottomed flasks, add 6-chloro-2-(4 successively, 6-dimethoxy-2-pyrimidine sulfenyl) phenylformic acid 0.32 gram (0.9 mmole), N, 10 milliliters of dinethylformamides, salt of wormwood 0.17 gram (1.2 mmole), trans 4-bromobutene acetoacetic ester 0.34 gram (1.5 mmole).In 80 ℃ of stirring reactions after 4 hours, in reaction solution, add 180 milliliters in 200 milliliters of ethyl acetate and water, extraction, saturated sodium-chloride water solution washing organic phase with 200 milliliters, use anhydrous magnesium sulfate drying again, the resistates that obtains behind the precipitation obtains 4-(6-chloro-2-(4,6-dimethoxy-2-pyrimidine sulfenyl) benzoyloxy) trans-2-butene acetoacetic ester 0.28 gram through silica gel column chromatography (petrol ether/ethyl acetate=3/1) purifying.
Other compounds in table 1 and the table 2 can make by above similar method.
Give birth to and survey example
Behind the former medicinal acetone solution, leave standstill the liquid to be measured of tap water preparation desired concn with 1 ‰ tween 80 by test requirements document.Processing (spray pressure 1.95kg/cm sprays with track type crop spraying machine (Britain Engineer Research Ltd. designs production) 2, spouting liquid 50ml/m 2, crawler belt speed 30cm/s, nozzle are fan nozzle).
Test before the seedling: it is 100cm that quantitative weeds (piemarker, barnyard grass grass, Herba Setariae Viridis) and crop (paddy rice, wheat, corn, cotton, peanut, soybean) seed are sowed at sectional area respectively 2Culturing pot in, broadcast back earthing 1cm, test compound sparges soil surface, handles and is placed on the greenhouse, waters then, the tween 80 with 1 ‰ leaves standstill tap water to be handled in contrast.
Test behind the seedling: it is 100cm that quantitative weeds (piemarker, barnyard grass grass, Herba Setariae Viridis) and crop (corn, cotton, peanut, rape, soybean) seed are sowed at sectional area respectively 2Culturing pot in, broadcast back earthing 1cm, cultivate according to a conventional method in the greenhouse.Treat that weeds grew to for 1.5 leaf phases, paddy rice, wheat, corn, cotton, peanut, rape and soybean 2-3 leaf phase, the examination material of choosing the growth uniformity carries out behind the seedling cauline leaf spraying to be handled, and the tween 80 with 1 ‰ leaves standstill tap water to be handled in contrast.Be placed on dry ventilation after the examination material is handled, treat the soup natural air drying after, place management according to a conventional method in the greenhouse, handle the method that employing is poured water from the bottom in back 48 hours, avoid soup to be washed away.
Handle the back and 4 weeks estimated investigation, inhibiting rate is various degree of injury compared with the control, comprise kill, chlorosis, withered spot, distortion, deformity, growth-inhibiting or blade calcination etc.Partial test the results are shown in Table 3,4.
Table 3: the part general formula (I, II) weeding activity of compound (before the seedling/seedling after, inhibiting rate %)
Table 4: the part general formula (I, II) compound to the security of crop (before the seedling/seedling after, inhibiting rate %)
Figure G07110858620070418D000101
Annotate *: in table 3 and the table 4, "-" expression is not surveyed.

Claims (6)

1.2-pyrimidine oxy-benzoic acid base olefin(e) acid ester or 2-pyrimidine methylthio benzoic acid base olefin(e) acid ester compound, as general formula (I, II) shown in:
In the formula:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen or halogen;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen or C respectively 1-C 6Alkyl;
R 5Be selected from C 1-C 6Alkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl;
R 6With R 7Group is a cis or trans.
2. according to the described compound of claim 1, it is characterized in that, general formula (I, II) in:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen or halogen;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen respectively; R 6With R 7Group is trans;
R 5Be selected from C 1-C 6Alkyl, C 3-C 6Thiazolinyl or C 3-C 6Alkynyl.
3. according to the described compound of claim 2, it is characterized in that, general formula (I, II) in:
X is selected from oxygen or sulphur;
R 1Be selected from hydrogen or halogen;
R 2, R 3, R 4, R 6, R 7Be selected from hydrogen respectively; R 6With R 7Group is trans;
R 5Be selected from C 1-C 6Alkyl.
4. (I, II) compound is used to control the purposes of weeds to the described general formula of claim 1.
5. herbicidal composition, contain the general formula as active ingredient as claimed in claim 1 (I, II) compound and agricultural go up acceptable carrier, the weight percentage of active ingredient is 5-90% in the composition.
6. a control method for weed is characterized in that: the herbicidal composition as claimed in claim 5 of using the weeding effective dose on the growth mediums of weeds or weeds or place.
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