CN1009087B - 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide - Google Patents
2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicideInfo
- Publication number
- CN1009087B CN1009087B CN 85107306 CN85107306A CN1009087B CN 1009087 B CN1009087 B CN 1009087B CN 85107306 CN85107306 CN 85107306 CN 85107306 A CN85107306 A CN 85107306A CN 1009087 B CN1009087 B CN 1009087B
- Authority
- CN
- China
- Prior art keywords
- compound
- chloroallyloxyamino
- trans
- alkene
- weeds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 230000002363 herbicidal effect Effects 0.000 title abstract description 7
- 239000004009 herbicide Substances 0.000 title abstract description 4
- 125000001118 alkylidene group Chemical group 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 abstract description 30
- 231100000674 Phytotoxicity Toxicity 0.000 abstract description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000009333 weeding Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 244000025670 Eleusine indica Species 0.000 description 4
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 244000075850 Avena orientalis Species 0.000 description 3
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 3
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 3
- 235000005476 Digitaria cruciata Nutrition 0.000 description 3
- 235000006830 Digitaria didactyla Nutrition 0.000 description 3
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 3
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 240000002439 Sorghum halepense Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
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- 238000009472 formulation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
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- 230000002269 spontaneous effect Effects 0.000 description 3
- 240000001592 Amaranthus caudatus Species 0.000 description 2
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 244000052363 Cynodon dactylon Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Methyl Chemical group 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000007189 Oryza longistaminata Nutrition 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001424495 Anigozanthos pulcherrimus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000007351 Eleusine Nutrition 0.000 description 1
- 241000209215 Eleusine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000320639 Leptochloa Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NNZYNGOLLPCTRF-UHFFFAOYSA-N OCCC=1C(=C(C=CC1)O)CCCCCCCC Chemical compound OCCC=1C(=C(C=CC1)O)CCCCCCCC NNZYNGOLLPCTRF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000015225 Panicum colonum Nutrition 0.000 description 1
- 235000008515 Setaria glauca Nutrition 0.000 description 1
- 235000001155 Setaria leucopila Nutrition 0.000 description 1
- 244000010062 Setaria pumila Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 description 1
- 241001141210 Urochloa platyphylla Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing 2-[1-(3-chloroallyloxyamino) propyl fork]-5-(2-ethylthio propyl) cyclohexane-1, 3-dione and salts thereof. The compound displays the phytotoxicity before and after seedling emergence and can be used as weed selective herbicide.
Description
The present invention relates to 2-(1-trans (3-chloroallyloxyamino amino) propylidene)-5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone and its esters and with of the use of this compounds as weedicide.
In my No. 4440566 United States Patent (USP) of announcing on April 3rd, 1984, I have disclosed the compound with following structural formula.
R for well, is best with ethyl and propyl group with alkyl or 1-3 carbon atom in the formula;
R
1Preferably 3-trans-chlorallyl or 4-benzyl chloride base;
R
2And R
3With alkyl or the 1-3 carbon atom of respectively doing for oneself for well, perhaps R
2With R
3In one for hydrogen another is the alkyl-thio-alkyl with 2-8 carbon atom, preferably R
2And R
3Methyl or R respectively do for oneself
2And R
3Among one for hydrogen another is a 2-ethylenebis dithiocarbamate propyl group.
Also describing out these compounds in my patent weeds are demonstrated removing activity, then is safe to broad-leaved cereal.
Have been found that a kind of compound (referring to following formula I, wherein R is an ethyl) of in No. the 4440566th, United States Patent (USP), being mentioned now, comprise that R is its homologue of propyl group, compare, have wonderful superior weeding activity with other compound.And why wonderful reason is, R is that the homologue of propyl group originally is a kind of very good weedicide.
These compounds are to Bermuda weeds (Bermudagrass), fox-brush shape plant (foxtail), lady's-grass is drafted a document (crabgrass), spontaneous corn (volunteer corn), spontaneous Chinese sorghum (volunteer sorghum), barnyard grass (barnyardgrass), wide leaf arm shape grass (broad-leaf signalgrass), Herba Eleusines Indicae (goosegrass), red rice (red rice), the weeds (sprangletop) of being unearthed spring, Johnson weeds (Johnsongrass) and Johnson's rhizome weeds weeds such as (Rhizone Johnsongrass) show the weeding activity that has before emerging, and have the weeding activity after very good the emerging again.
Even structural formula be the compound of I under low-down rate of application, also shown weeds had good phytotoxicity, under this rate of application, then be safe to broad-leaved cereal.Thereby these compounds are exactly very useful for the weeds in the control broad-leaved cereal, and are especially useful especially especially for the weeds in the control soybean crops.
Compound of the present invention can be represented with following structural formula:
R in the formula
1It is the trans chlorallyl of 3-.
The present invention comprises that also structural formula is the salt of the compound of I.
As confirmed, the compound that has structural formula and be I comes down to exist with the form of tautomer.These compounds also have two asymmetric carbon atoms, and also can show as optically active isomer.Above-mentioned structural formula also comprises various tautomeric forms, various optically active isomers and their mixture.Various tautomers, optically active isomer and their mixture all belong to category of the present invention.
And then the present invention also provides a kind of herbicidal composition, and it contains effective herbicidal compound or its mixture of the present invention's proposition of suitable carriers and doses.
The present invention also provide a kind of prevent or control the method for unwanted weeds vegetation growth, this method comprise effective herbicidal compound that the present invention with doses proposes or this vegetation of its mixture process growth medium and (or) leaf.
The present invention also provides a kind of method of coordinate plant growth, this method comprise the effective plant growth regulating compound that proposes with the present invention of doses or this vegetation of its mixture process growth medium and (or) leaf, change the normal growth situation of above-mentioned plant effectively.
The method that the present invention also provides chemical intermediate and prepared The compounds of this invention.
Below the present invention is given detailed description.
Structural formula is that the compound of I can prepare easily by the process of following reaction formula representative:
R in the formula
1Be 3-trans-chlorallyl.
This process can-chloroallyloxyamino amine (B) contact reacts trans by compound (A) and 3-be finished, to carry out in inert organic solvents to good.
Typical process condition is: temperature range is 0～80 ℃, with 20～40 ℃ for well; Last 1-48 hour, with 4-12 hour for well; The 3-that uses is trans-chloroallyloxyamino amine (B) is 1 to 2 to the amount of every mole compound (A), and with 1.05 to 1.2 moles for well.Spendable suitable inert organic solvents comprises, low-grade alkane alcohol, methyl alcohol for example, ethanol, ether, methylene dichloride.Biphase water and organic solvent (for example hexane) that can be miscible with water also can use their analogue or their compatible mixture.
Trans-chloroallyloxyamino amine is a kind of well-known compound, can use known method, and for example I am in the method described in No. the 4440566th, the United States Patent (USP) and prepare.The hydrochloride acceptable salts of trans-chloroallyloxyamino amine and alkali metal alcoholates neutralization reaction method are produced.Structural formula can prepare at the general method described in No. the 4440566th, the United States Patent (USP) by me for the initiator of (A).
Can pass through ordinary method with the corresponding to salt of structure formula I, for example with the compound and alkali with required cationic of structural formula for (I), such as sodium hydroxide, potassium hydroxide and analogue react to each other and prepare.Other remodeling positively charged ion can carry out ion-exchange with the ion exchange resin with required cationic by salt and prepare.
Reaction product can reclaim from mixture of reaction products by any suitable separation and method of purification, for example adopts chromatography.Suitable separation and method of purification can be referring to embodiment given below.
Generally speaking, above-mentioned reaction is a liquid phase reaction, and therefore, pressure is normally unessential.Carry out unless be reflected in the backflow, this moment, pressure can have influence on temperature (boiling point).Thereby these reactions generally are to carry out under the pressure of 300-3000 mmhg, and can carry out under normal atmosphere or environmental stress easily.
Although also praiseworthy in addition is to have provided processing condition (for example, temperature of reaction, time, the mol ratio of reaction raw materials, solvent or the like) typical and that recommend, still can select other processing condition for use.Optimum reaction condition (for example temperature, reaction times, mol ratio, solvent or the like) can change according to used special reagent or organic solvent, but, needs determine by optimization procedure.
After having obtained mixture of optical isomers, the dissolving method again of available routine obtains corresponding optically active isomer.Geometrical isomer can be by routine be based upon that the separation method on the physical properties difference separates between the geometrical isomer.Yet, generally in reaction, recommend to use the starting raw material that can generate required isomer.
Below used term, unless narration is arranged in addition, its connotation is as follows:
" corresponding to salt " refers to those also salts of the herbicidal properties of anti-phase indistinctively its parent compound of change.Suitable salt comprises the positively charged ion salt, lithium for example, sodium, alkaline-earth metal, copper, zinc, the cationic salts of ammonium, quaternary ammonium salt or the like.
" room temperature " or envrionment temperature are about 20-25 ℃.
Structural formula be the compound of I and its esters shown emerge preceding and emerge after weeding activity, especially weeds have been shown good especially weeding activity.These compounds are to fox-brush shape plant (foxtail), Bermuda weeds (Bermudagrass), lady's-grass is drafted a document (crabgrass), and the weeds that Johnson's rhizome weeds (rhizone Johnsongrass) and these kinds of spontaneous corn (volunteer corn) generally are difficult to control have shown good phytotoxicity.
Generally speaking, when using after emerging, be the other parts that the weeding compound directly imposed on leaf or plant.When using before emerging, be that the weeding compound is imposed in the growth medium, or in the plant expection growth medium.The optimum amount of weeding compound or composition will be according to concrete floristics, the degree of plant-growth, the privileged site of the plant that contact and the degree of contact and change.Optimal dose can also be according to the region, or the type of environment (for example shelterarea, as greenhouse and open-air district, as the contrast in field) and required control and degree and change.Generally speaking, for emerge preceding and emerge after control, the rate of application of this compound is about 0.02-60 kilogram/hectare, is advisable with 0.02-10 kilogram/hectare.
Although in theory, this compound can be without dilution be directly used, and actually, they all are to use with the composition of compound that contains effective dose and compatible carrier or the form of preparation usually.Compatible or corresponding to carrier (agricultural compatible carrier) is except playing diluting effect, and anti-phase indistinctively influence is by the carrier of the required biological effect that active compound obtained.It approximately is that 0.05～95% structural formula is compound or its mixture of I by weight that typical composition contains.Also can be made into the enriched material with height concentration of dilution before using.Carrier can be a solid phase, liquid phase or aerosol-type.Actual composition can be particle, powder, dust, solution, emulsion, slurries, aerosol or similar type.
The available solid phase carrier comprises, natural clay (as kaolin, attapulgite, montmorillonite or the like) for example, talcum, pyrophyllite, diatomite, synthetic silica particle, Calucium Silicate powder aluminium.Tricalcium phosphate or the like.Also have organic substance, for example, the nutshell powder, cotton seed hull, wheat-flour, wood powder, tree bark powder or the like all can be used as carrier and uses.The suitable liquid phase thinner of available comprises, water, organic solvent (for example, hydro carbons, as benzene, toluene, dimethyl sulfoxide (DMSO), kerosene, diesel oil, fuel oil, petroleum naphtha or the like) and analogue.The suitable aerosol carrier of available comprises conventional aerosol carrier, for example halogenated alkane or the like.
Can also contain in the composition and can improve promotor and the tensio-active agent of active compound to the plant tissue transport velocity, for example organic solvent, wetting agent and oils.Can also contain the reagent that reduces the compound seepage or improve soil stability in the composition that designs for using before emerging.Crop oil, soya-bean oil for example, alkane oils and alkene oils be because they can improve phytotoxicity, thereby becomes superior especially carrier or compound.
Can also contain various compatible adjuvants in the composition, stablizer, conditioning agent, sterilant, mycocide, and if desired, can also contain other weeding active compound.
A kind of suitable concentrate formulation contains and is the weedicide of the present invention of 23-27% by weight, is the emulsifying agent of 2-4% by weight, for example, alkyl benzene calcium sulfonate, hydroxyethyl octyl phenol or the like, or their mixture, the organic solvent of 70-75%, for example dimethylbenzene etc.Before using, enriched material is mixed with water, if can mix then better with vegetables oil.As containing the 0.5-2% crop oil, soya-bean oil for example, alkane oils, the emulsification aqua of alkene oils and using.Be about 0.02-0.6% by weight to contain, be preferably the weedicide of the present invention of 0.07-0.15%, the emulsifying agent that is about 0.001-0.01% by weight, it is then more convenient that the such water-emulsifiable weedicide of water that is about the organic solvent of 0.08-2.5% by weight and is approximately 95-99% is by weight used.Preferably contain the crop oil that is about 0.25-2% by weight in the composition again.Compositions for use can be mixed with the water of institute water requirement 1/4 to 1/2 and makes easily with concentrate formulation.Add crop oil and mixing then, add remainder water at last.If do not add crop oil, then get final product concentrate formulation is mixed with water.
In the preparation method of following indefiniteness and embodiment, can also further understand the present invention.Wherein, unless opposite narration is arranged in addition, all temperature and temperature range are Celsius, and term " environment " reaches " room temperature " and refers to about 20-25 ℃.Term " per-cent " or symbol " % " refer to significant percentage, and term " mole " refers to mol.The term equivalent refers to the reaction reagent of equimolar amount, promptly with this example in before or after it mole number of cited reagent identical, to limit mole number or weight or meausurement.As provide NMR (Nuclear Magnetic Resonance) spectrum (p.m.r. or NMR), then refer to and measure at the 60mHz place, appointment to symbol is, (s) is unimodal, (bs) is broad peak, (d) be bimodal, (dd) being double bimodal, (t) is three peaks, (dt) is double three peaks, (q) being four peaks, (m) is multimodal; Cps represents the revolution of per second.In addition, when needs, also can repeat embodiment, thereby provide additional starting raw material for follow-up embodiment.
Embodiment 1
2-(1-trans (3-chloroallyloxyamino amino) propylidene)-5-(2-ethylsuleenyl propyl)-3-hydroxyl hexamethylene-2-alkene-1-ketone.
In this embodiment; 2-propionyl-5-(2-ethylenebis dithiocarbamate propyl group with 17.2 grams (0.0636 mole)) hexanaphthene-1; the 3-diketone; 0.9 gram (0.0153 mole) acetate; 35 milliliters be dissolved with 10.9 gram (0.0757 mole) 3-trans-aqueous solution of chloroallyloxyamino amine, join in 20 milliliters of hexanes and stir.To be that 5% aqueous sodium hydroxide solution is added in the above-mentioned solution in during about 15 minutes lentamente by weight, when having added the sodium hydroxide of 3.0 grams (0.0757 mole+excessive a little) till, this moment, the pH value of reaction mixture was about 6.This mixture is heated to 40 ℃ and kept about 2-1/2 hour under this temperature, be cooled to room temperature then.Telling organic layer (being hexane), earlier is 5% salt pickling with 10 milliliters of weight percents, adds weight percent then and be 6.25% aqueous sodium hydroxide washes till the pH value reaches at 12 o'clock.Divide water-yielding stratum, adds 25 milliliters hexane and mix, the dropping weight percent is that 36% salt acid liquid transfers to 5.4 with the pH value under condition of ice bath.Tell organic layer, use dried over mgso,, obtain 18.0 gram crude products then through evaporation concentration.Crude product is purified with silica gel chromatography, uses hexane: the dichloromethane solution elution can obtain the purified title compound of buttery.Ultimate analysis, the theoretical value of carbon are 56.73%, and observed value is 56.63%; The theoretical value of hydrogen is 7.28%, and observed value is 7.55%; The theoretical value of nitrogen is 3.89%, and observed value is 3.55%.
Embodiment 2
2-(1-(3-trans-chloroallyloxyamino amino) propyl group fork)-3-oxo-5-(2-ethylenebis dithiocarbamate propyl group)-hexamethylene-1-alkene-1-sodium alkoxide
Present embodiment has been introduced a kind of method that can be used for making title compound.
Contain 0.01 mole of 2-(1-(3-trans-chloroallyloxyamino amino) propylidene with being dissolved with 2 milliliters of the aqueous solution of 0.01 molar sodium hydroxide, at room temperature joining)-the 5-(2-ethylsuleenyl propyl)-solution of 3-hydroxyl-hexamethylene-2-alkene-1-ketone in.Finish final vacuum evaporation when reaction and remove and desolvate, obtain 2-(1-(3-trans-chloroallyloxyamino amino) propyl group fork)-3-oxo-5-(2-ethylsuleenyl propyl)-the 1-hydroxyl sodium salt of hexamethylene-1-alkene-1-alcohol.
Embodiment 3
In the present embodiment, to title compound, be 2-(1-(3-trans-chloroallyloxyamino amino) propylidene)-the 5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone tests, the method of using is as described below, tested it to various weeds and broad-leaved value thing, comprise that emerging of a kind of cereal and a kind of broad leaf crop is preceding and emerge after phytotoxicity.
Weedicide test before emerging
Measured the preceding weeding activity of emerging by following mode.
The testing liquid of all cpds is prepared as follows:
355.5 the milligram test-compound is dissolved in 15 milliliters of acetone.In this solution, add 2 milliliters of acetone that contain 110 milligrams of nonionic surface active agent.Then 12 milliliters of such solution are added to and contain nonionic surface active agent of the same race and concentration is in the water of 625 mg/litre.
The seed implantation that is tried plant is equipped with in the little basin of soil, testing liquid is sprayed onto the surface of soil equably, unless have in addition in following table outside the narrator, the dosage of test-compound is 27.5 microgram/square centimeters.Water for little basin and be placed in the greenhouse.Water periodically for little basin, and situation of emerging and the healthy state of being emerged were observed for three weeks.When viewing duration finished, physiology phenomenon was according to the observation estimated the weeding validity of this compound.Used 0 to 100 yardstick, 0 representative does not have phytotoxicity, and 100 representatives are killed fully.This test the results are summarized in table 1.
Weeding test after emerging
The preparation of test-compound is identical with the above-mentioned mode described in the preceding test of emerging.This preparation is sprayed in 2 similar basins equably, every basin has 2 to 3 inches high plants (except wild avena sativa, outside soybean and the pasture and water (Watergrass), they are 3 to 4 inches high) (about 15 to 25 strains of every basin), unless in following table, have in addition special specified outside, the dosage of test-compound is 27.5 microgram/square centimeters.Behind the plant drying, they are put into the greenhouse, periodically water at its root on demand.Making plant toxic effect periodically, and to the biology and the morphology reaction of this processing.The Samsung after date is estimated the herbicidal effect of this compound according to these observations.Used 0 to 100 yardstick, 0 representative does not have phytotoxicity, and 100 representatives are all killed.These tests the results are summarized in table 2.
Embodiment 3
In the present embodiment, the title compound of the embodiment of the invention 1, (" 1 ") and its butyl fork homologue, promptly trans-2-(1-(3-chloroallyloxyamino amino) butyl fork)-the 5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone is together with the back weeding activity test of having carried out emerging of medium low dosage.
This experiment is by carrying out with the foregoing description 2 described identical modes, but rate of application table 3 described as follows decides, and each test uses 4 identical basins to replace 2 original basins.Provided the average result of four identical basins in following table 3, wherein 0 indication does not have phytotoxicity, and 100 indications are killed fully.Generally speaking, it is non-significance that the phytotoxicity that is lower than 20-30% is considered to, because plant can recover to get up from the damage of this degree.
The N.T.=not test (N.T.), but based on other test, control compounds also is safe to soybean when such rate of application.
1=2-(1-trans (3-chloroallyloxyamino amino) propylidene)-5-(2-ethylsuleenyl propyl)-3-hydroxyl hexamethylene-2-alkene-1-ketone.
C-1=is trans-2-(1-(3-chloroallyloxyamino amino) propyl group fork)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl hexamethylene-2-alkene-1-ketone.
*R/cm
2=every square centimeter micrograms
As can be seen from Table 3, concerning lady's-grass was drafted a document (crabgrass), chemical compounds I was superior to control compounds C-1 significantly, even also was like this when medium low dosage.To become more obvious in the low dosage test of the superiority of chemical compounds I in following embodiment 4.
Embodiment 4
In the present embodiment, title compound (" 1 ") is with trans-2-(1-(3-chloroallyloxyamino amino) butyl fork)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl hexamethylene-2-alkene-1-ketone (" C-1 ") and commercial herbicides Sethoxdm(" C-2 ") (being 2-(1-(oxyethyl group amino) butyl fork)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl hexamethylene-2-alkene-1-ketone, with very low dosage to the test of back weeding activity of having carried out emerging of a large amount of weeds.
Test is by carrying out with mode identical described in the foregoing description 3, and the dosage that only is to use is as shown in table 4.These result of experiment are summarized in table 4, and 0 indication does not wherein have phytotoxicity, and 100 indications are killed fully.Generally speaking, the phytotoxicity that is lower than 20-30% then is considered to insignificant, because plant can recover to get up from the damage of such degree.
As can seeing from table 4, except to wild avena sativa and the kangaroo-paw, for other was tried all kinds of weeds, chemical compounds I was better than control compounds C-1.Chemical compounds I and C-1 then are equivalent to the usefulness of wild avena sativa, and these two kinds of compounds are inactive to yellow kangaroo-paw under such dosage.Chemical compounds I and Compound C-1 all is better than Compound C-2.
By the dosage that can cause that equivalent reaction is required, the control lady's-grass is drafted a document and barnyard grass grass, 0.11q/cm
2Compound on rate of application approximate 0.28q/cm
2The rate of application of Compound C-1.For controlling yellow foxtail, 0.05q/cm
2The rate of application of chemical compounds I approximate 0.28q/cm
2Compound 0.28q/cm
2The rate of application of Compound C-1.
Obviously, do not departing from essence of the present invention and exceeding under the situation of its scope, can be to making many modifications and variation before this and than the described the present invention in back.
Claims (3)
1, a kind of method for preparing compound and corresponding to salt thereof is characterized in that, wherein said compound shown in following general formula (I),
R in the formula
1For 3-trans-chlorallyl: described method comprises 2-propionyl-5-(2-methyl sulfo-propyl group)-cyclohexane-1, and 3-diketone and 3-be trans-the contacted step of chloroallyloxyamino amine, can produce the compound of corresponding formula I under appropriate reaction conditions.
2, method according to claim 1, wherein said compound are 2-(1-trans-chlorallyl amino) propylidene)-5-(2-ethyl thiopropyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone.
3, according to claim 1 or 2 one of them described method, wherein said method is to carry out in inert organic solvents, about 0～80 ℃ of temperature range.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104073 CN1048785A (en) | 1985-10-07 | 1985-10-07 | 2-[1-is trans-(3-chloroallyloxyamino amino) propylidene]-5-(2-ethylsuleenyl propyl)-3-hydroxyl hexamethylene-2-alkene-1-ketone agent for eliminating |
| CN 90101367 CN1026283C (en) | 1985-10-07 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides |
| CN 85107306 CN1009087B (en) | 1984-06-11 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61897984A | 1984-06-11 | 1984-06-11 | |
| CN 85107306 CN1009087B (en) | 1984-06-11 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90101367 Division CN1026283C (en) | 1985-10-07 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85107306A CN85107306A (en) | 1987-04-15 |
| CN1009087B true CN1009087B (en) | 1990-08-08 |
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ID=25742082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107306 Expired CN1009087B (en) | 1984-06-11 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide |
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| Country | Link |
|---|---|
| CN (1) | CN1009087B (en) |
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| CN111423346B (en) * | 2020-05-21 | 2022-05-03 | 首建科技有限公司 | Preparation method of clethodim lithium salt standard sample |
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1985
- 1985-10-07 CN CN 85107306 patent/CN1009087B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85107306A (en) | 1987-04-15 |
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