CN1026283C - 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides - Google Patents
2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides Download PDFInfo
- Publication number
- CN1026283C CN1026283C CN 90101367 CN90101367A CN1026283C CN 1026283 C CN1026283 C CN 1026283C CN 90101367 CN90101367 CN 90101367 CN 90101367 A CN90101367 A CN 90101367A CN 1026283 C CN1026283 C CN 1026283C
- Authority
- CN
- China
- Prior art keywords
- weight
- compound
- grass
- plant
- composition
- 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 - Lifetime
Links
- 239000004009 herbicide Substances 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 241000196324 Embryophyta Species 0.000 claims abstract description 37
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 244000025670 Eleusine indica Species 0.000 claims description 7
- 235000014716 Eleusine indica Nutrition 0.000 claims description 7
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- 240000002439 Sorghum halepense Species 0.000 claims description 5
- 230000002269 spontaneous effect Effects 0.000 claims description 5
- 244000052363 Cynodon dactylon Species 0.000 claims description 4
- 235000007189 Oryza longistaminata Nutrition 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 240000001592 Amaranthus caudatus Species 0.000 claims description 3
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000014820 Galium aparine Nutrition 0.000 claims description 2
- 241000320639 Leptochloa Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 claims description 2
- 241001141210 Urochloa platyphylla Species 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 241000209072 Sorghum Species 0.000 claims 1
- 231100000674 Phytotoxicity Toxicity 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000009333 weeding Methods 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 125000001841 imino group Chemical group [H]N=* 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 244000068988 Glycine max Species 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 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
- 244000058871 Echinochloa crus-galli Species 0.000 description 4
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 102000013275 Somatomedins Human genes 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000007320 Avena fatua Nutrition 0.000 description 3
- 241001647031 Avena sterilis Species 0.000 description 3
- 235000004535 Avena sterilis Nutrition 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- -1 Methyl Chemical group 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 241001424495 Anigozanthos pulcherrimus Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 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
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method 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
- 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
- VEEOFSUIWVGHHJ-UHFFFAOYSA-N 3-ethoxy-2-octylphenol Chemical compound CCCCCCCCC1=C(O)C=CC=C1OCC VEEOFSUIWVGHHJ-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
- 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
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum 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
- 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
- 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
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product 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
- 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
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000002917 insecticide 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
- 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
- 239000008263 liquid aerosol Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 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
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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 preparation method of 2-[1-trans-(3-chlorine allyloxy amino) propylidene]-5-(2-ethylthio propyl)-3-hydroxyl-cyclohexyl-2-alkene-1-ketone and salts thereof. The compound shows phytotoxicity before and after seedling emergence and can be used as selective herbicide for weeds.
Description
The application is dividing an application of No. 85107306 patent applications.
The present invention relates to 2-(1-trans-(3-chloroallyloxyamino imino group) propyl group)-5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone and its esters and with of the use of this compounds as weed killer herbicide.
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 activity of weeding with other compound.And why wonderful reason is, R is that the homologue of propyl group originally is a kind of very good weed killer herbicide.
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), eleusine indica (goosegrass), red rice (red rice), the weeds (sprangletop) of being unearthed spring, Johnson weeds (Johnsongrass), show the activity of weeding that has before emerging with Johnson's rhizome weeds weeds such as (Rhizone Johnsongrass), have the activity of weeding 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 dynamic isomer.These compounds also have two asymmetric carbon atoms, and also can show as optical isomer.Above-mentioned structural formula also comprises various tautomeric forms, various optical isomers and their mixture.Various dynamic isomers, optical 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 herbicides compounds 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 herbicides compounds that the present invention with doses proposes or this vegetation of its mixture process somatomedin 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 somatomedin 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 equation representative:
R in the formula
1Be 3-trans-chlorallyl.
This process can-chloroallyloxyamino amine (B) haptoreaction 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, carrene.The water of two-phase and organic solvent (for example hexane) that can be miscible with water also can use their analog 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 conventional method described in No. the 4440566th, the United States Patent (USP) by me for the starting material of (A).
Can pass through conventional method with the corresponding to salt of structural formula (I), for example with the compound and alkali with required cationic of structural formula for (I), such as sodium hydroxide, potassium hydroxide and analog react to each other and prepare.Other remodeling cation can carry out ion exchange with the ion exchange resin with required cationic by salt and prepare.
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 reactor, 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 millimetres of mercury, and can carry out under atmospheric pressure or environmental pressure easily.
Although also praiseworthy in addition is to have provided process conditions (for example, reaction temperature, time, the mol ratio of reaction raw materials, solvent or the like) typical and that recommend, still can select other process conditions for use.Optimum reaction condition (for example temperature, reaction time, 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 optical isomer.Geometric isomer can be by routine be based upon that the separating method on the physical property difference separates between the geometric isomer.Yet, generally in reaction, recommend to use the initiation material that can generate required isomeric compound.
Below used term, unless narration is arranged in addition, its connotation is as follows:
" corresponding to salt " refers to those and oppositely changes the salt of the herbicidal properties of its parent compound indistinctively.Suitable salt comprises the cation salt, lithium for example, sodium, alkaline earth metal, copper, zinc, the cationic salts of ammonium, quaternary ammonium salt or the like.
" room temperature " or environmental temperature are about 20-25 ℃.
Structural formula be the compound of I and its esters shown emerge preceding and emerge after activity of weeding, especially weeds have been shown good especially activity of weeding.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 somatomedin, or in the plant expection somatomedin.The optimum amount of weeding compound or composition will be according to concrete floristics, the degree of plant growing, 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 shielded area, 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 the carrier of the required biological effect that oppositely influences reactive compound indistinctively and 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 concentrate 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.
Available solid phase carrier comprises, natural clay (as kaolin, Attagel, montmorillonite or the like) for example, talcum, pyrophyllite, diatomite, synthetic silica particle, calcium silicates aluminium, tricalcium phosphate or the like.Also have organic substance, for example, the shuck powder, cotton seed hull, wheat flour, wood powder, bark powder or the like all can be used as carrier and uses.Available suitable liquid phase thinner comprises, water, organic solvent (for example, hydro carbons, as benzene, toluene, dimethyl sulfoxide (DMSO), kerosene, diesel oil, fuel oil, naphtha or the like) and analog.Available suitable aerosol carrier comprises conventional aerosol carrier, for example halogenated alkane or the like.
Can also contain in the composition and can improve promoter and the surfactant of reactive 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, stabilizing agent, conditioning agent, insecticide, fungicide, and if desired, can also contain other weeding active compound.
A kind of suitable concentrate formulation contains and is the weed killer herbicide of the present invention of 23-27% by weight, is the emulsifier of 2-4% by weight, for example, alkyl benzene calcium sulfonate, ethoxy octyl phenol or the like, or their mixture, the organic solvent of 70-75%, for example dimethylbenzene etc.Before using, concentrate is mixed with water, if can mix then better with vegetable 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 weed killer herbicide of the present invention of 0.07-0.15%, the emulsifier that is about 0.001-0.01% by weight, it is then more convenient that the such water-emulsifiable weed killer herbicide 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, the most really add remaining water.If do not add crop oil, then get final product concentrate formulation is mixed with water.
In following non-limiting preparation method 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 " environmental temperature " reaches " room temperature " and refers to about 20-25 ℃.Term " percentage " or symbol " % " refer to percentage by weight, and term " mole " refers to gram molecule.The term equivalent refers to the reaction reagent of equimolar amounts, promptly with this example in before or after it molal quantity of cited reagent identical, to limit molal quantity or weight or volume.As provide 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 initiation material for follow-up embodiment.
Embodiment 1
2-(1-trans-(3-chloroallyloxyamino imino group) propyl group)-5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone
In this embodiment; 2-propiono-5-(2-ethylenebis dithiocarbamate propyl group with 17.2 grams (0.0636 mole)) cyclohexane-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% sodium hydrate aqueous 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 reactant 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 percentage by weights, adds percentage by weight 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 percentage by weight 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 and concentration.Crude product is purified with silica gel chromatograph, uses hexane: the dichloromethane solution elution can obtain the pure title compound of oily.Elementary analysis, the theoretical value of carbon are 56.73%, and measured value is 56.63%; The theoretical value of hydrogen is 7.28%, and measured value is 7.55%; The theoretical value of nitrogen is 3.89%, and measured value is 3.55%.
Embodiment 2
2-(1-(3-trans-chloroallyloxyamino imino group) propyl group)-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 imino group) propyl group-5-(2-ethylsuleenyl propyl with being dissolved with 2 milliliters of the aqueous solution of 0.01 molar sodium hydroxide, at room temperature joining)-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 imino group) propyl group-3-oxo-5-(2-ethylenebis dithiocarbamate propyl group)-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 imino group) propyl group)-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 plant, comprise that emerging of a kind of cereal and a kind of broad leaf crop is preceding and emerge after phytotoxicity.
Weed killer herbicide test before emerging
Measured the preceding activity of weeding 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 health status 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 oat, 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 appointment 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.Observation of plant poisonous effect periodically, and to the physiology 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 imino group) butyl)-the 5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone is together with the back activity of weeding 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 imino group) propyl group)-5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone
C-1=is trans-2-(1-(3-chloroallyloxyamino imino group) propyl group)-the 5-(2-ethylsuleenyl propyl)-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 imino group) butyl)-the 5-(2-ethylsuleenyl propyl)-3-hydroxyl-hexamethylene-2-alkene-1-ketone (" C-1 ") and commercial herbicides Sethoxdm(" C-2 ") (being 2-(1-(ethoxy imino) butyl)-5-(2-ethylenebis dithiocarbamate propyl group)-3-hydroxyl-hexamethylene-2-alkene-1-ketone, with very low dosage to the test of back activity of weeding 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 oat and the yellow kangaroo-paw, for other was tried all kinds of weeds, compound 1 was better than control compounds C-1.Compound 1 and C-1 then are equivalent to the usefulness of wild oat, and these two kinds of compounds are inactive to yellow kangaroo-paw under such dosage.Compound 1 all is better than Compound C-2 with Compound C-1.
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 compound 1 approximate 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 to before this and after this described the present invention make many modifications and variation.
Claims (7)
1, a kind of combinations of herbicides agent, it contains the following formula: compound and the appropriate carriers of effective amount of herbicide
R in the formula
1For 3-trans-chlorallyl.
2, the described herbicidal composition of a kind of claim 1, it also contains oils.
3, the described herbicidal composition of a kind of claim 1, wherein said compound accounts for 0.02-0.6% by weight, described composition also contains and is the emulsifier of 0.001-0.15% by weight, is the organic solvent of 0.08-2.5% by weight and is the water of 95-99% by weight.
4, composition according to claim 3, it also contains and is the oils of about 0.25-2% by weight.
5, the described herbicidal composition of a kind of use claim 1 is controlled herbal method, and this method comprises the described composition of using effective amount of herbicide to the leaf of described plant or its cache.
6, the described method of a kind of claim 5, wherein said herbaceous plant comprises fox-brush shape plant (foxtail), Bermuda grass (Bermudagrass), spontaneous chinese sorghum (Volunteer Sorghum), wide leaf arm shape grass (broad-leaf Signal grass), yard grass (goosegrass), red rice (red rice), the weeds (sprangletop) of being unearthed spring, Johnson grass (Johnsongrass) and spontaneous corn class herbaceous plant such as (Volunteer corn).
7, a kind of concentrated property herbicidal composition, it contains and is the described compound of claim 1 of 23-27% by weight, by weight for the emulsifier of 2-4% be about the organic solvent of 70-75% by weight.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85107306 CN1009087B (en) | 1984-06-11 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107306 Division CN1009087B (en) | 1984-06-11 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046438A CN1046438A (en) | 1990-10-31 |
| CN1026283C true CN1026283C (en) | 1994-10-26 |
Family
ID=4795561
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90101367 Expired - Lifetime CN1026283C (en) | 1985-10-07 | 1985-10-07 | 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides |
| CN 90104073 Pending 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 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90104073 Pending 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1026283C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892520A (en) * | 2020-08-28 | 2020-11-06 | 山东潍坊润丰化工股份有限公司 | Environment-friendly synthesis method of clethodim |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884665B (en) * | 2016-04-21 | 2017-12-22 | 潍坊先达化工有限公司 | A kind of cyclohexenone compounds and preparation method and application |
-
1985
- 1985-10-07 CN CN 90101367 patent/CN1026283C/en not_active Expired - Lifetime
- 1985-10-07 CN CN 90104073 patent/CN1048785A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892520A (en) * | 2020-08-28 | 2020-11-06 | 山东潍坊润丰化工股份有限公司 | Environment-friendly synthesis method of clethodim |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046438A (en) | 1990-10-31 |
| CN1048785A (en) | 1991-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2016507511A (en) | Macrocyclic picolinamides as fungicides | |
| CN1051285A (en) | 2-[1-(3-chloroallyloxyamino) alkyl]-5-alkylthio alkyl-cyclohexane-1, the 3-dione herbicides | |
| CN1026283C (en) | 2-[1-(3-chloroallyloxyamino) alkyliaene]-5-alkylthioalkyl-cyclohexane-1,3-dione herbicides | |
| DE2046476A1 (en) | 2 alkyl glycene derivatives | |
| EP2146955B1 (en) | Pesticidal diazene oxide carboxylates | |
| US2814636A (en) | Organophosphoramide n-oxide pesticide product and process for making it | |
| CN1009087B (en) | 2-[1-(3-chloroallyloxyamino) alkylidene]-5-alkylthioalkyl-cyclohexane-1,3-diont herbicide | |
| JP7256332B2 (en) | Methanogenesis inhibitor composition and method for suppressing methanogenesis | |
| GB2145628A (en) | Herbicidal compositions | |
| DK168987B1 (en) | Plant microbicidal agent and methods for controlling or preventing microorganism infestation on plants | |
| US4388104A (en) | 3-Phenylmethoxytetrahydropyran herbicides | |
| US4704161A (en) | Photosynthesis enhancement by substituted α-hydroxybutynoic acids and derivatives | |
| IL41437A (en) | Phenyl and benzyl alkynyl ethers their production and pest-population control compositions containing them | |
| JPS6056948A (en) | Oxime derivative, preparation thereof and insecticide containing the same as active constituent | |
| US7399757B1 (en) | Pesticidal diazene oxide carboxylates | |
| SU1766236A3 (en) | Insecticide | |
| JPS632945A (en) | 2-phenylacetyl-1,3,5-cyclohexanetriones and salts | |
| US4978386A (en) | Herbicidal 2-(substituted-phenyl)-3-amino-2-cyclopentenone derivatives | |
| JP2745737B2 (en) | Benzylideneaminooxyalkanoic acid amide derivatives, their production and herbicides | |
| US4052411A (en) | Esters of derivatives of 2-imidazolidinylidenenitroacetic acid | |
| KR840001148B1 (en) | Process for preparing thiazolylidene-oxo-propionitriles | |
| JPS624A (en) | Plant growth regulator | |
| HU191521B (en) | Fungicid compositions containing alpha-hydroxy-ethyl-phosphinic acid esters as active substances and process for preparing the active substances | |
| Beck et al. | N 1-chloro-3, 5-dinitrosulfanilamides | |
| JPH0930904A (en) | Herbicide composition for paddy field |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Tokyo, Japan Applicant after: Thanks to the Co. Address before: U.S.A. Applicant before: Chevron Research Co. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: CHEVRON RESEARCH CO. TO: THOMEN COMPANY |
|
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |