CN1050029C - Thiophosphoryl amide ester herbicide for paddy fields and dry farmland - Google Patents
Thiophosphoryl amide ester herbicide for paddy fields and dry farmland Download PDFInfo
- Publication number
- CN1050029C CN1050029C CN96114746A CN96114746A CN1050029C CN 1050029 C CN1050029 C CN 1050029C CN 96114746 A CN96114746 A CN 96114746A CN 96114746 A CN96114746 A CN 96114746A CN 1050029 C CN1050029 C CN 1050029C
- Authority
- CN
- China
- Prior art keywords
- add
- gram
- grams
- milliliters
- acetone
- 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 - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to a double-function thio-phosphamide ester herbicide for both a paddy field and a dry field, which can be used for preventing and eliminating various grassy weeds and kargeleaf weeds in the fields of the crops of soybean, paddy rice, wheat, vegetables, etc., wherein 80 grams/mu of the herbicide is used in the field of the soybean, and 30 to 40 grams/mu of the herbicide is used in the field of the paddy rice. The herbicide belonging to a low toxic compound is safe and reliable to the crops.
Description
The present invention is the dual-purpose thio-phosphamide ester herbicide of a kind of floods and droughts.
Weed killer herbicide is significant in agricultural production, and at present the kind of weed killer herbicide is more with the paddy field kind, and dry land is of less types, floods and droughts field dual-purpose then still less, so can not satisfy the needs of agricultural production.SUMITOMO CHEMICAL chemical company finds that the thio-phosphamide ester type compound has activity of weeding, and has developed amiprophos-methyl, restrains kinds such as climing phosphorus.
The purpose of this invention is to provide a kind of noval chemical compound O-methyl-O-(2,4-dimethyl-6-nitro-phenoxy)-N-isopropylthio phosphoramidate-H9201, it has very high activity of weeding.
H-9201 is the dual-purpose weed killer herbicide of a kind of selectivity floods and droughts, and it can be used for crop Tanakas such as soybean, paddy rice, wheat and prevents and kill off multiple annual grassy weed and broad leaved weed.
The chemical name of H-9201 is O-methyl-O-(2,4-dimethyl-6-nitro-phenoxy)-N-isopropylthio phosphoramidate, and its structural formula is as follows
, its molecular weight is 318.It can take following two kinds of methods synthetic:
New herbicides H-9201 is the dual-purpose soil processing herbicide of a selectivity floods and droughts.It can be used for soybean.Paddy rice.Wheat.Crop Tanakas such as vegetables prevent and kill off multiple annual gramineous weed and broad leaved weed.Soybean field consumption 80 gram/mus; Paddy field consumption 30-60 gram/mu.It is reliable to crop safety.It belongs to lower toxicity compound, the oral LD of rat acute
50Male is 2413mg/kg, and female is 2157mg/kg.In addition, it is logical with existing weed killer herbicide kind weeding, careless jinx, Nongdeshi, nitrofen compare, and has the wider grass spectrum of killing, and the scope of application is wider, and agricultural cost is lower than logical, the careless jinx of weeding.Its synthesis technique is simple, yield is higher.
Example 1
Synthesizing of O-methyl-O-(2,4-dimethyl-6-nitro-phenoxy)-N-isopropylthio phosphoramidate
In 100 milliliters of four-hole bottles, add 3.34 gram (0.02mol) 2,4-dimethyl-6-nitrophenol, 30 milliliters of acetone, 3.7 gram (0.02mol) methoxyl group phosphorothioic dichlorides, be cooled to 8 ℃ with frozen water, add a small amount of triethylamine, stir down, be added dropwise to the aqueous solution of (0.023mol) 20% sodium hydroxide, the control reaction temperature drips and finishes below 10 ℃, continue to react half an hour, when pH is 5～6 left and right sides, finish to react the acetone soln of O-methoxyl group-O-(2,4-methyl-6-nitro-phenoxy) thiophosphoryl chloride.
Above-mentioned reactant liquor is cooled to about 10 ℃ again, slowly drip 1.4 gram (0.023mol) isopropylamines, the aqueous solution that splashes into 4.0 gram (0.02mol) 40% sodium hydroxide is again regulated pH to 8～9, continue reaction half an hour to pH be 5～6, finish reaction, filter, slough acetone, add 30 milliliters of extracted with diethyl ether, wash ether layer with water, anhydrous sodium sulfate drying, slough behind the solvent product, weigh 6.3 grams, through gas chromatographic analysis content 85%, yield 84% gets faint yellow crystallization with ethyl alcohol recrystallization, fusing point is 98～100 ℃, and its elementary analysis value is C:45.71% H:6.01% N:8.68%; Theoretical value C:45.28% H:5.97% N:8.81%
Example 2
Synthesizing of O-methyl-O-(2,4-dimethyl-6-nitro-phenoxy)-N-isopropylthio phosphoramidate
In four-hole bottle, add 6.78 gram phosphorus thiochloride and 10 milliliters of organic solvents, in about 0 ℃, be added dropwise to 3.34 grams 2,4-dimethyl-6-nitrophenol is dissolved in the solution of 5 milliliters of organic solvents, stirs after 20 minutes, drips the solution that 2.0 gram triethylamines are dissolved in 5 milliliters of organic solvents again, remain between 0～5 ℃ and reacted 2 hours, filter, filtrate water washing back drying is sloughed organic solvent and unreacted phosphorus thiochloride.
Above-mentioned products obtained therefrom is added in the four-hole bottle again, and add 20 milliliters of organic solvents, between 0～5 ℃, add the solution that 0.97 gram sodium methoxide is dissolved in methyl alcohol, between 0～5 ℃, react half an hour, and then add the solution that 2.13 gram isopropylamines are dissolved in 5 milliliters of organic solvents, after reaction finishes, filter, filtrate is used the frozen water washed twice, tells organic facies, after the drying, slough solvent, promptly get yellow oily liquid, solidify the cooling back, weighing 6.47 grams, is 85% through gas chromatographic analysis content, yield 86%.Get faint yellow crystallization with ethyl alcohol recrystallization.Fusing point is 98～100 ℃.
Example 3 pot-culture methods are broadcast preceding soil treatment dosage 25, the 50 gram/mus of back seedling.The examination material is barnyard grass grass, lady's-grass, oat, amaranth, clover, rape etc., broadcast the back seedling before the pesticide-clay mixture method handle.The result shows that H9201 is that 25,50 grams all show the inhibiting rate to rape, amaranth, oat, barnyard grass grass, lady's-grass etc. 100% at the mu consumption.The results are shown in Table 1.
Example 4 pot-culture methods., amiprophos-methyl activity of weeding logical with weeding compares
Mu restrains with effective dose 20,19,5,2.5.The pesticide-clay mixture method is handled before broadcasting the back seedling.The result shows (seeing Table 2)
A. three weed killer herbicides all have good activity of weeding, and the activity of preventing and kill off of gramineous plants is higher than broad leaved plant.The activity of amiprophos-methyl is lower than H-9201 and weeding is logical.
B. H-9201 is active logical a little less than weeding for preventing and kill off of grassy weed under low dosage, but it is logical that the preventive effect of broad leaved weed is higher than weeding.
Example 5 field trials
Place and time: 1993,1994 on the Hebei agricultural academy of sciences, academy of agricultural sciences, Shanghai (entrusting the Qingpu county institute of agricultural sciences to do) and other places in the soybean field, the transplanting rice field carried out the field plot trial of multiple spot.
(1) soybean field
Broadcast the preceding soil treatment of back seedling.Every mu of effective dose: H9201 25,50,100 grams, logical 68 grams of weeding.Measure herbicidal effect and to the influence of soybean yields.
The result shows that (table 3, table 4): H9201 can prevent and kill off the annual weed in soybean field effectively about every mu 80 gram, as: barnyard grass grass, eleusine indica, lady's-grass, amaranth, Amaranthus retroflexus, kitchen garden, lamb's-quarters, Radix seu Herba Astilbes rivularis, green foxtail, acalypha copperleaf etc., effect to grassy weed is logical less than weeding, effect to broad leaved weed is logical greater than weeding, and is invalid to the weeds after being unearthed.In the drug effect phase of field H9201 is 30-60 days.H9201 is to soybean safety.
(2) transplanting rice field
Dispenser in 5 days behind the rice transplanting, the water layer of protecting 5-7cm is about one week.Every mu of effective dose: H9201 15,30,60 grams, logical 34 grams of weeding, careless jinx (pyrarosulfuron-ethyl) 1 gram, Nongdeshi (bensulfuron) 2 grams, nitrofen (nitrofen) 125 grams.Measure herbicidal effect and to the influence of rice yield.
The result of table 5, table 6 shows: H9201 can prevent and kill off the barnyard grass grass, carp intestines, eel grass, Monochoria vaginalis, Sagittaria pygmaea, Procumbent Falsepimpernel, mexicana, wild arrowhead, wild water chestnut in transplanting rice field etc. effectively about every mu of 30-60 gram.Herbicidal effect is similar to careless jinx during mu consumption 60 grams, is higher than Nongdeshi.During mu consumption 30 grams, it is logical to be similar to weeding.H9201 is fool proof to transplanting rice.
The safety of 6 pairs of crops of example is measured
(1) with amiprophos relatively to the safety of crop
To paddy rice, soybean, wheat, the corn of rudiment broadcast the back seedling before soil treatment, seed level 12mm.Mu restrains with effective dose 150,50.Measure the overground part fresh weight after two weeks.Calculate the selectivity degree value, carry out the growth differences significance test with the contrast strain of not dispenser.
The result shows (table 7, table 8):
1. the growth differences significance test shows, two medicaments are to the growth and contrast strain indifference of soybean, wheat, paddy rice, and H9201 also has significant effect of gain to paddy rice when 50 grams.Two medicaments all have utmost point significant inhibitory effect to corn growth.Range estimation is found out corn seedling plant and leaf curling, the deformity of being injured, is not stretched, the leaf color depth.Every mu 50 gram of amiprophos has the sign of recovery, and the possibility of all the other recoveries is very little.
2. H9201 and amiprophos are soybean.Selectivity degree value between wheat, paddy rice and the weeds all 〉=100 two medicaments are described to these three kinds of crop safeties, and herbicidal effect is good.Selectivity to corn is relatively poor, and corn is injured heavily.
(2) safety of paddy rice is measured
1. cauline leaf is handled the safety to paddy rice
H9201 is with every mu 60,30, the effective doses of 15 grams, and logical 43 grams of weeding carry out the cauline leaf spraying in paddy rice and handle tri-leaf period.The result shows that (table 9) two medicaments are to the equal safety of paddy rice.
2. to safety and the different water layer management Influence on security of different seedling age paddy rice
The paddy rice seedling age: 2-3 leaf phase, young shoot just pushed up the soil phase, back seedling before (the dark 5mm of earthing), mu is with an effective dose 60 gram, the processing of spraying.The water layer situation code insurance water holding layer in rice field and two kinds of dampnesses,
The result shows (table 10):
1. having under the condition of water layer, the more little paddy rice of seedling age is injured heavy more.Illustrate that this medicine should not be used for rice direct seeding field.
2. under the condition of no water layer, medication has serious poisoning to paddy rice during the soil of before the paddy rice 2-3 leaf phase drug safety, bud and top.Before the seedling medication earthing too shallow be the reason that causes poisoning, under half non-irrigated state earthing greater than 10mm to rice safety.
3. dispenser in 3-5 days behind the rice transplanting is to rice safety.
Table 1 compares the medicament g/mu clover rape amaranth oat barnyard grass mare H9201 of Tang 50.0 76.7 with amiprophos activity of weeding (preventing and kill off %)
*100.0# 100.0 100.0 100.0 100.0
25.0 12.5
*100.0 100.0 100.0 100.0 100.0 amiprophos 50.0 63.6
*91.9
*100.0 100.0 100.0 100.0
25.0 25.1
*4.9
*100.0 96.6
*100.0 82.1
*#: " 100.0 " are and suppress growth and dead.Bud scale or cotyledon color depth, no lobus cardiacus, flavescence is thirst.
*: severe deformities.Dark green leaf color, thick, lobus cardiacus is little or not long.
*Deformity, lobus cardiacus grows.
Table 2 is logical with weeding, the amiprophos-methyl activity of weeding compares (preventing and kill off %) medicament g/mu amaranth rape barnyard grass grass green foxtail lady's-grass H9201 20.0 100.0 92.0 100.0 100.0 100.0
10.0 100.0 46.7 100.0 100.0 100.0
5.0 74.2 0.0 97.6 97.7 98.4
2.5 35.5 0.0 83.2 86.6 93.7 weedings logical 20.0 100.0 85.8 100.0 100.0 100.0
10.0 100.0 0.0 100.0 100.0 100.0
5.0 29.0 0.0 95.2 100.0 98.4
2.5 16.1 0.0 94.4 83.3 96.9 amiprophos-methyls 20.0 100.0 0.0 94.4 100.0 100.0
10.0 41.9 0.0 90.4 100.0 98.4
5.0 22.6 0.0 88.0 66.7 87.5
2.5 0.0 0.0 30.4 53.3 81.3
60 days herbicidal effects (Hebei) after the field dispenser of table 3 soybean
| Medicament | Dosage g/mu | Other are average for grass family (%) lady's-grass Cowhells dog tail | Other are average for broad leaved weed (%) acalypha copperleaf Amaranthus retroflexus kitchen garden | |
| The strain number | The H9201 weeding is logical | 25 50 100 68 | 75.5 82.1 46.9 100 74.1 84.5 83.3 46.9 100 74.1 95.5 97.6 56.2 100 88.9 95.5 97.6 97.8 100 97.5 | 35.6 0.0 75.3 0.0 50.0 37.0 33.0 92.2 0.0 60.8 58.0 100 100 57.1 77.7 24.7 100 96.1 85.8 60.8 |
| Fresh weight | The H9201 weeding is logical | 25 50 100 68 | 50.6 54.2 27.1 100 40.8 91.9 60.7 59.6 100 69.1 98.9 71.6 59.6 100 73.1 98.9 98.8 93.9 100 96.5 | 12.6 0.0 56.9 0.0 0.0 12.6 0.0 78.2 0.0 0.0 45.4 100 100 96.6 96.2 32.8 100 90.0 42.2 78.9 |
Analysis (Hebei) the drug dose g/mu pod of table 4 pair soybean yields is counted pod/strain grain number/pod grain number/strain grain and heavily restrains/strain 200 strain Kg plant height cmH9201 25 25.36 2.11 58.13 10.32 2.063 105 1 50 25.36 2.12 58.47 10.32 2.063 110
68 25.40 2.35 59.87 11.56 2.317 113 CK 23.98 2.27 57.30 10.15 2.030 110 are led in 100 24.08 2.34 62.00 10.13 2.027 110 weedings
Table 5 paddy field weeding effect (Shanghai) is handled the back wild water chestnut of fate drug dose gram/mu barnyard grass grass (%) Monochoria vaginalis (%) nutgrass flatsedge (%) (%) wild arrowhead (%)
H9201 15 27.8 45.0 0.0 60.0 100.0
30 50.0 76.8 85.7 50.0 20 60 100.0 95.7 100.0 40.0 100.0
Weeding logical 34 100.0 68.1 100.0 40.0 50.0
Grass jinx 1 95.7 100.0 100.0 100.0
Nitrofen 125 100.0 76.8 0.0 20.0 50.0
Nongdeshi 2 59.4 100.0 100.0 100.0
H9201 15 22.9 48.8 34.6 52.0 67.1
30 66.2 66.2 93.7 72.0 89.0 40 60 87.2 95.1 100.0 84.0 88.4
Weeding logical 34 78.8 87.0 98.4 70.0 76.0
Grass jinx 1 95.4 93.9 100.0 100.0 100.0
Nitrofen 125 31.6 67.1 21.0 52.0 0.0
Nongdeshi 2 66.1 88.2 68.2 100.0 65.8
Influence (Shanghai) drug dose gram/mu of table 6 pair rice yield is the empty flat grain of the total grain of fringe ten thousand/plant height spike length number thousand kernel weight theoretical yield effectively
Mu cm cm gram Kg/ mu H9201 15 17.75 91.6 14.6 102.0 10.4 24.5 385.43
30 17.75 90.0 13.8 98.8 9.5 24.6 394.10
34 16.75 92.2 14.2 103.30 12.3 24.5 372.21 careless jinx's 1 18.43 93.4 14.8 116.0 11.8 24.5 470.50 nitrofens 125 16.30 88.8 14.2 101.0 18.8 24.4 327.72 Nongdeshis 2 18.12 93.2 13.8 109.6 12.6 24.5 430.62 CK 11.32 88.6 13.8 84.60 13.7 24.3 195.11 are led in 60 17.65 89.8 14.2 104.8 11.6 24.6 404.67 weedings
It is heavy that table 7 couple plant growth significance of difference mensuration crop medicament g/mu respectively organizes the average individual plant of the heavy a of average individual plant
1 2 3
CK 1.37 1.28 1.10 1.25
Amiprophos 150 1.40 1.27 1.29 1.32 soybean 50 1.36 1.27 1.30 1.31
H9201 150 1.27 1.26 1.31 1.28
50 1.21 1.48 1.27 1.32
LSD0.05 0.19
LSD0.01 0.27
ck 42.5 40.0 39.0 40.5
Amiprophos 150 40.8 42.5 40.9 41.5 paddy rice 50 43.7 39.3 40.0 41.0
H9201 150 48.3 42.0 44.7 45.0
50 43.3 50.0 45.0 46.1
LSD0.05 4.97
LSD0.01 7.23
CK 278 286 255 273
Amiprophos 150 298 300 275 291 wheats 50 283 290 300 291
H9201 150 298 283 295 292
50 282 286 278 282
LSD0.05 21.1
LSD0.01 30.7
CK 1.49 1.43 1.52 1.48
Amiprophos 150 0.82 0.88 0.91 0.87
*
Corn 50 1.30 1.34 1.29 1.31
*
H9201 150 0.91 1.10 1.05 1.02
**
50 1.11 1.04 1.06 1.07
**
LSD0.05 0.11
LSD0.01 0.16a: individual plant is heavy: soybean, corn are " g ", and paddy rice, wheat are " mg "
Table 8 selectivity degree value
Medicament 150g/mu 50g/mu
H9201 amiprophos H9201 amiprophos
Crop: selectivity degree value a
Soybean 102 104 101 100
Wheat 106 105 101 102
Paddy rice 111 101 112 97
Corn 68 57 70 84a: selectivity degree value=(handle fresh weight (fresh weight * 100 of contrast crop)-(the handling fresh weight * 100 of the fresh weight ÷ contrast weeds of weeds) of crop
Dispenser is to the safety of paddy rice behind table 9 seedling
Medicament g/mu respectively organizes heavy (mg) mg/ strain of average individual plant
1 2 3
CK 95 101 96 97.3
H-9201 60 112 96 115 107.7
30 130 118 114 120.7
**
15 125 110 116 117.0
**
Weeding logical 43 94 115 105 104.7
LSD0.05 13.88
LSD0.01 19.48
Table 10 seedling age and water layer are to the safety effects of paddy rice
Seedling age has the moist attitude of water layer
Growth inhibition (%)
The 2-3 leaf phase 15.9-4.0
The top soil phase 44.7 33.0
Broadcast back seedling preceding 100.0 88.8
Claims (3)
1, the dual-purpose thio-phosphamide ester of a kind of floods and droughts weed killer herbicide, its feature is following (I) compound in it:
2, the synthetic method of the dual-purpose thio-phosphamide ester of the described floods and droughts of claim 1 weed killer herbicide (I) is characterized in that it is synthetic through following step:
In 100 milliliters of four-hole bottles, add 3.34 grams 2,4-dimethyl-6-nitrophenol, 30 milliliters of acetone, 3.7 gram methoxyl group phosphorothioic dichlorides are cooled to 8 ℃ with frozen water, add a small amount of triethylamine, under agitation drip 0.023 mole 20% sodium hydrate aqueous solution, the control reaction temperature drips off the back and continues to react half an hour below 10 ℃, PH finish during for 5-6 to react the acetone soln of O-methoxyl group-O-(2,4-dimethyl-6-nitro-phenoxy) thiophosphoryl chloride;
Above-mentioned reactant liquor is cooled to 10 ℃ again, slowly drips 1.4 gram isopropylamines, splash into 4.0 grams, 40% sodium hydrate aqueous solution again, regulate PH to 8～9, continue to react half an hour, treat that PH is end reaction in 5～6 o'clock, filter, slough acetone, add 30 milliliters of extracted with diethyl ether, wash ether layer with water, and use anhydrous sodium sulfate drying, slough behind the solvent product 6.4 grams, get faint yellow crystallization with ethyl alcohol recrystallization, fusing point is 98～100 ℃, its
1H NMR spectrum data element assay value is: C 45.71%, and H 6.01%, and N 8.68%; Theoretical value: C 45.28%, H 5.79%, and N 8.81%.
3, the synthetic method of the dual-purpose thio-phosphamide ester of the described floods and droughts of claim 1 weed killer herbicide (I) is characterized in that it can be synthetic through following step:
In four-hole bottle, add 6.78 gram phosphorus thiochloride and 10 milliliters of acetone, toluene or benzene, drip 3.34 grams 2 down in 0 ℃, 4-dimethyl-6-nitrophenol acetone soln, stir and block 20 minutes, add 2.0 gram triethylamines again, reaction is 2 hours between 0～5 ℃, filters, and sloughs organic solvent and unreacted phosphorus thiochloride; Above-mentioned products obtained therefrom is added in the four-hole bottle again, and add 20 ml methanol, between 0～5 ℃, add the solution that 0.97 gram sodium methoxide is dissolved in methyl alcohol, between 0～5 ℃, react half an hour, and then add 2.13 gram isopropylamines, filter after reaction finishes, filtrate is used the frozen water washed twice, tell organic facies, dry back desolventizing promptly gets yellow oily liquid, solidify the cooling back, get 6.74 grams, get faint yellow crystallization with ethyl alcohol recrystallization, fusing point is 98～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114746A CN1050029C (en) | 1996-11-26 | 1996-11-26 | Thiophosphoryl amide ester herbicide for paddy fields and dry farmland |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114746A CN1050029C (en) | 1996-11-26 | 1996-11-26 | Thiophosphoryl amide ester herbicide for paddy fields and dry farmland |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1159284A CN1159284A (en) | 1997-09-17 |
| CN1050029C true CN1050029C (en) | 2000-03-08 |
Family
ID=5122285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96114746A Expired - Fee Related CN1050029C (en) | 1996-11-26 | 1996-11-26 | Thiophosphoryl amide ester herbicide for paddy fields and dry farmland |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050029C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4818462B1 (en) * | 1969-02-08 | 1973-06-06 |
-
1996
- 1996-11-26 CN CN96114746A patent/CN1050029C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4818462B1 (en) * | 1969-02-08 | 1973-06-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1159284A (en) | 1997-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pernak et al. | Ammonium bio-ionic liquids based on camelina oil as potential novel agrochemicals | |
| CN1127293C (en) | 2-pyrimioxybenzyl substituted phenyl amine derivatives | |
| Cuhra et al. | Life cycle fitness differences in D aphnia magna fed R oundup‐R eady soybean or conventional soybean or organic soybean | |
| JPS5920285A (en) | 5-dibasic acid ester derivative of milbemycin d and its salt | |
| CN1094890A (en) | The fungi that soil has and due to the method and composition of prevention, control and improvement of disease | |
| RU2066313C1 (en) | 4-halogen-2-(substituted phenyl)-1-alkoxymethyl-5- (trifluoromethyl)pyrrole-3-carbonitriles, process for preparation thereof, intermediate compounds process for preparation thereof, and process for controlling insects and mites | |
| CN1079608A (en) | Prevent the method for sulfamoyl urea herbicide to the rice plants toxic effect | |
| CN1802912A (en) | Mixed herbicide for dry land | |
| CN1050029C (en) | Thiophosphoryl amide ester herbicide for paddy fields and dry farmland | |
| US2994638A (en) | Agent for combating rodents | |
| CN1031378C (en) | Combating insect infestation in rice | |
| SU586820A3 (en) | Method of fighting insects and ticks and pesticide composition for effecting same | |
| CN1098845C (en) | Thiadiazole carboxamide derivative, plant disease controlling agent and method of using same | |
| CN1067155A (en) | Agricultural compound bactericide octicin solution and uses thereof | |
| DE2412564A1 (en) | Biocidal 1,2,4-triazol-3-yl dimethylcarbamates - prepd. by reacting 3-hydroxy-5-thio-1,2,4-triazoles with dimethylcarbamoyl chloride | |
| CN87102978A (en) | 1, 5-diphenyl-1H-1, 2, 4-triazole-3-carboxamide derivatives and herbicidal formulations thereof | |
| CN1593142A (en) | Mixed herbicide | |
| Turek et al. | The need to change the approach to the safe use of herbicides by developing chiral and environmentally friendly formulations: a series of enantioselective (R)-and (S)-phenylethylammonium chloroacetates | |
| CN100486958C (en) | Synthesizing Z-2 eyan-3-(N(S)-alpha-methyl-p-fluorin benzyl amine group)-2-ethoxy carbethoxy pyroterebic acid, and weeding activity | |
| CN1557157A (en) | Broad spectrum weed removal composition | |
| CN1351991A (en) | Substituted phenoxy acetoxyl alkyl hypophosphorous ester with herbicide activity and preparation | |
| Okonkwo et al. | Insecticidal Potentials and Chemical Composition of Ethanol Extracts from the Leaves of Acanthus montanus on Selected Insect Pests | |
| CN1106393A (en) | Sulfonylurea compound herbicide | |
| SU671700A3 (en) | Antidote herbicide | |
| CN1233623C (en) | 2,6-dibromo-4-cyanophenyl ester compounds with herbicidal activity |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000308 Termination date: 20091228 |