CN101215270B - Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application - Google Patents
Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application Download PDFInfo
- Publication number
- CN101215270B CN101215270B CN2007101737068A CN200710173706A CN101215270B CN 101215270 B CN101215270 B CN 101215270B CN 2007101737068 A CN2007101737068 A CN 2007101737068A CN 200710173706 A CN200710173706 A CN 200710173706A CN 101215270 B CN101215270 B CN 101215270B
- Authority
- CN
- China
- Prior art keywords
- compound
- benzyl
- phenyl
- alkyl
- represent
- 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)
Abstract
The invention relates to a novel fluorine-containing benzothiazole sulfonyls compound, the synthesis process and the application of using as disinfection, parasiticide and herbicide and the like. The structure of the compound is showed as followed. The synthesis process of the compound comprises using o-thiophenol and sultone as starting material, firstly synthesizing , then reacting with a seriesof organic amine, and finally synthesizing fluorine-containing benzothiazole sulfonamide compound. The synthesis process of the invention is simple, which aims to find novel fluorine-containing benzo thiazole sulfonyls pesticides and synthesis process.
Description
Technical field
What the present invention relates to is class novel fluorine benzothiazole sulphonyl compounds and a synthetic method and an application.
Background technology
The fluoro-containing pesticide of global development and application is nearly about 150 kinds at present, especially contains CF
3, CHF
2, OCF
3, OCH
2F
2, OCF
2CHF
2, OCH
2CF
3,, SOCF
3Isostructural agricultural chemicals becomes novel pesticide exploitation focus.
Fluorine-containing benzothiazole sulfonamide compound can be used as a kind of disinfecting, desinsection, weeding agricultural chemicals, might substitute traditional agricultural chemicals of those poor efficiencys, high poison, high residue, development of new is efficient, the novel agrochemical of low toxicity, low residue has become the new direction of current pesticide manufacturing work.
Summary of the invention
The problem that will solve of the present invention provides a class novel fluorine benzothiazole sulphonyl compounds and a synthetic method thereof.The problem that the present invention also will solve is to seek above-claimed cpd as novel fluorine agricultural bactericidal, desinsection, herbicide applications.
The present invention is intended to seek a class novel fluorine agricultural bactericidal, desinsection, weedicide.In order to obtain under smaller dosage, just can to control various diseases, the active compound of insect pest, we have synthesized a kind of novel fluorine benzothiazole sulphonyl compounds, this compounds has preferably, and broad spectrum of activity one can be used for preventing and treating on various crops by the dogstail pythium spp, wheat septoria musiva bacterium, the beans rest fungus, Bermuda grass septoria musiva bacterium, multiple germ diseases such as wheat head blight Fusarium graminearum, and since these compounds to wheat powdery mildew, wheat glume blight, wheat scab, rice seedling blight, rice sheath blight disease, early blight of tomato, tomato late blight, the late blights of potato etc. have good prevention effect, the discovery that we are pleasantly surprised, compound of the present invention is to various pests such as cotten aphid, diamondback moth larvae, Heliothis virescens, fruit bats etc. are effective, and can remove annual bluegrass, weeds such as Arabidopis thaliana.
The structural formula of a class novel fluorine benzothiazole sulphonyl compounds provided by the invention is shown in (II):
Wherein: R
3Representative
X represents N, S or O, and when X represents S or O, R
2Do not exist;
When X represents N, R
1Represent H, C
1-C
8Alkyl, phenyl or benzyl; R
2Represent H, C
1-C
8Alkyl, phenyl or benzyl; Perhaps
Representative contains five of N and arrives seven membered heterocyclic base, for example hexahydroaniline, cyclopentamine, hexahydropyridine, tetramethyleneimine or imidazoles etc.;
When X represents S or O, R
1Represent H, C
1-C
8Alkyl, phenyl or benzyl; R
2Do not exist.
Typical compound involved in the present invention is listed in table 1, but is not limited to listed compound.
Table 1
What the present invention relates to is the second section or first and second parts that synthesis step that novel fluorine benzothiazole sulfonamide compound is recommended comprises the steps:
First part:
Second section:
R in the above-mentioned reaction formula
3As previously mentioned.
First part: contain the synthetic of fluoro benzothiazole sulfonic acid fluoride.
Near amino thiophenols and sultones heat 40～80 ℃ of reactions and can get intermediate product (I) in 2～10 hours in trichloromethane or tetrahydrofuran (THF).
Second section: fluorine-containing benzothiazole sulfonamide compound synthetic.
Intermediate product (I) and amine are under alkaline condition, and reaction obtains the fluorine-containing benzothiazole sulfonamide compound of target product (II).
In this reaction, used alkali can be hydride, alcoxyl metallic compound, the alkide of organic bases, monovalence or divalent metal.As triethylamine or pyridine; Sodium hydride, potassium hydride KH or hydrolith; Sodium methylate, potassium methylate, sodium ethylate or potassium ethylate; Butyllithium; Also can be with excessive response substrate self as acid binding agent.When adding solvent in the reaction, solvent can be the halogenated hydrocarbon solvent of methylene dichloride, trichloromethane, ethylene dichloride; Ether, tetrahydrofuran (THF), 1, the ether solvent of 4-dioxane; The varsol of benzene, toluene; Also can with and the mixture or the methyl-sulphoxide of above solvent, the mixture of acetonitrile and above solvent or solubilizing agent not.This reaction is that the optimum response solvent is an ether solvent.Temperature of reaction is recommended as room temperature to solvent boiling point, and the reaction times was advisable with 4 to 60 hours, especially was recommended as 4～56 hours.
In reaction, intermediate product (I), compound H R
3Be recommended as 1: 1 with the mol ratio of alkali～5: 0～10.
When using alkali, intermediate product (I), aminated compounds HNR
1R
2Be recommended as 1: 1 with the mol ratio of alkali～2: 3～10; When without alkali, intermediate product (I), aminated compounds HNR
1R
2With the mol ratio of alkali be 1: 3～5: 0.
Compound of the present invention can be used as agricultural chemicals.
Compound of the present invention has excellent bactericidal activity, they have systemic activity and can be used as the blade face and soil fungicides, can be applicable to the disease on the various crops of control, can prevent and treat the following plants disease: wheat powdery mildew, wheat glume blight, wheat scab, rice seedling blight, rice sheath blight disease, early blight of tomato, tomato late blight, the late blight of potato etc.
Compound of the present invention also has insecticidal activity, can be used for preventing and treating the insect on the various crops.For example can be used for preventing and treating insects such as cotten aphid, diamondback moth larvae, Heliothis virescens, fruit bat.
Compound of the present invention can also be removed weeds such as annual bluegrass, Arabidopis thaliana.
Embodiment:
Put up with the part example below and provide the required analytical data of detailed reaction conditions, purification process, physical constant and structural confirmation, it is to be noted that the present invention not merely is confined to the scope of following embodiment.
Embodiment 0
Synthesizing of intermediate product (I): 5g (40mmol) near amino thiophenols is dissolved in the exsiccant trichloromethane, splash into 3.6g (20mmol) sultones under the ice-water bath, drip off heating 60 degree reactions 4 hours, filter, recrystallization gets the 3.56g white solid, and productive rate is 66.8%.
1H-NMR (nucleus magnetic hydrogen spectrum) (CDCl
3) (ppm): 8.30 (1H, d), 8.04 (1H, d), 7.65 (2H, m).
19F-NMR (nuclear-magnetism fluorine spectrum) (CDCl
3) (ppm): 37.60 (1F, s) ,-92.72 (2F, s).
Embodiment 1
II-1's is synthetic: 0.534g (2mmol) (I) is dissolved in the 5ml methylene dichloride, splashes into the solution of 0.214g (2mmol) benzylamine, 0.404g (4mmol) triethylamine, 5ml methylene dichloride, reaction is spent the night under the room temperature, washes saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.361g white solid, and productive rate is 46%.
1H-NMR(CDCl
3)(ppm)：8.20(1H，d)，8.02(1H，d)，7.59(2H，m)，5.22(1H，s)，4.55(2H，d)。
19F-NMR(CDCl
3)(ppm)：-97.03(2F，s)。
Embodiment 2
II-2's is synthetic: 0.534g (2mmol) (I) is dissolved in the 5ml methylene dichloride, splashes into the solution of 0.198g (2mmol) hexahydroaniline, 0.404g (4mmol) triethylamine, 5ml methylene dichloride, reaction is spent the night under the room temperature, washes saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.323g white solid, and productive rate is 51%.
1H-NMR(CDCl
3)(ppm)：8.18(1H，d)，7.97(1H，d)，7.55(2H，m)，4.78(1H，d)，3.55(1H，s)，2.09(2H，d)，1.73(2H，d)，1.36(4H，q)，1.17(2H，d)。
19F-NMR(CDCl
3)(ppm)：-98.09(2F，s)。
Embodiment 3
II-3's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml ether, adds 0.684g (6mmol) allylamine, reaction is spent the night under the room temperature, washes saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.294g white solid, and productive rate is 39.6%.
1H-NMR(CDCl
3)(ppm)：8.21(1H，d)，7.99(1H，d)，7.59(2H，m)，5.91(1H，m)，5.29(2H，q)，5.01(1H，s)，4.01(2H，t)。
19F-NMR(CDCl
3)(ppm)：-97.37(2F，s)。
Embodiment 4
II-4's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml ether, adds 0.488g (6mmol) n-Butyl Amine 99, the lucifuge reaction is spent the night under the room temperature, washes saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.341g white solid, and productive rate is 51.4%.
1H-NMR(CDCl
3)(ppm)：8.21(1H，d)，8.01(1H，d)，7.59(2H，m)，4.91(1H，s)，3.40(2H，t)，1.63(2H，t)，1.43(2H，t)，0.96(3H，t)。
19F-NMR(CDCl
3)(ppm)：-97.38(2F，s)。
Embodiment 5
II-5's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), splashes into 0.510g (6mmol) piperidines, heat 60 ℃ of reactions and spend the night, wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.352g white solid, and productive rate is 34.4%.
1H-NMR(CDCl
3)(ppm)：8.19(1H，d)，7.92(1H，d)，7.52(2H，m)，3.48(4H，s)，1.62(6H，s)。
19F-NMR(CDC
3)(ppm)：-97.68(2F，s)。
Embodiment 6
II-6's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.174g (2mmol) imidazole natrium, 60 ℃ of reactions are spent the night, and wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.431g white solid, productive rate is 76.6%.
1H-NMR(CDCl
3)(ppm)：8.21(1H，d)，8.01(1H，d)，7.90(1H，s)，7.61(2H，m)，7.34(1H，s)，7.20(1H，s)。
19F-NMR(CDCl
3)(ppm)：-96.09(2F，s)。
Embodiment 7
II-7's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), splashes into 0.426g (6mmol) tetramethyleneimine, heat 60 ℃ of reactions and spend the night, wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, and recrystallization gets the 0.363g white solid, and productive rate is 38.6%.
1H-NMR(CDCl
3)(ppm)：8.16(1H，d)，7.94(1H，d)，7.50(2H，m)，3.51(4H，t)，1.95(4H，m)。
19F-NMR(CDCl
3)(ppm)：-97.10(2F，s)。
Embodiment 8
II-8's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds the sodium salt of 0.180g (2mmol) morphine woods, 60 ℃ of reactions are spent the night, and wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.364g white solid, productive rate is 54.3%.
1H-NMR(CDCl
3)(ppm)：8.21(1H，d)，8.11(1H，d)，7.52(2H，m)，3.67(4H，t)，3.51(4H，t)。
19F-NMR(CDCl
3)(ppm)：-96.95(2F，s)。
Embodiment 9
II-9's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), splashes into 0.488g (6mmol) diethylamine, 60 ℃ of reactions are spent the night, and wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.213g white solid, productive rate is 33.2%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，2.59(4H，m)，1.08(6H，t)。
19F-NMR(CDCl
3)(ppm)：-95.08(2F，s)。
Embodiment 10
II-10's is synthetic: the methylphenylamine of 0.534g (2mmol) is dissolved in the 20ml exsiccant tetrahydrofuran (THF), be chilled to-78 ℃ and slowly splash into 1.1 normal butyllithiums, be back to room temperature reaction 2 hours, and slowly splashed into intermediate product (I), after dripping off, 60 ℃ were reacted 56 hours, after adding ammonium chloride saturated aqueous solution cancellation reaction, ethyl acetate extraction separatory, organic phase water successively, dilute hydrochloric acid, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale white solid, productive rate is 22.1%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，6.94(3H，m)，6.43(2H，m)，2.78(3H，s)。
19F-NMR(CDCl
3)(ppm)：-97.01(2F，s)。
Embodiment 11
II-11's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), splashes into 0.355g (6mmol) Isopropylamine under the ice-water bath, room temperature reaction spends the night, and washes with water successively, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.349g white solid, productive rate is 49.02%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，4.56(1H，s)，3.53(1H，m)，1.08(6H，d)。
19F-NMR(CDCl
3)(ppm)：-96.08(2F，s)。
Embodiment 12
II-12's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.607g (6mmol) Diisopropylamine, room temperature reaction spends the night, and washes with water successively, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.512g white solid, productive rate is 73.83%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，3.17(2H，m)，1.13(12H，d)。
19F-NMR(CDCl
3)(ppm)：-96.96(2F，s)。
Embodiment 13
II-13's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.607g (6mmol) di-n-propylamine, room temperature reaction spends the night, and washes with water successively, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.546g white solid, productive rate is 78.93%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，2.74(4H，t)，1.53(4H，m)，1.53(6H，t)。
19F-NMR(CDCl
3)(ppm)：-96.01(2F，s)。
Embodiment 14
II-14's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.776g (6mmol) Di-n-Butyl Amine, room temperature reaction spends the night, and washes with water successively, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 1.012g white solid, productive rate is 79.63%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，8.12(1H，d)，7.52(2H，m)，2.78(4H，t)，1.50(4H，m)，1.23(4H，m)，0.86(6H，t)。
19F-NMR(CDCl
3)(ppm)：-95.01(2F，s)。
Embodiment 15
II-15's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.232g (2mmol) sodium phenylate, room temperature reaction spends the night, and washes with water successively, saturated NaHCO
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.521g white solid, productive rate is 71.81%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，7.92(1H，d)，7.52(2H，m)，7.35(5H，m)。
19F-NMR(CDCl
3)(ppm)：-94.51(2F，s)。
Embodiment 16
II-16's is synthetic: 0.534g (2mmol) (I) is dissolved in the 20ml tetrahydrofuran (THF), adds 0.264g (2mmol) thiophenol sodium, heat 60 ℃ of reactions and spend the night, wash saturated NaHCO successively with water
3Solution washing, separatory, anhydrous sodium sulfate drying filters, the post layer inhale the 0.425g white solid, productive rate is 56.29%.
1H-NMR(CDCl
3)(ppm)：8.23(1H，d)，7.92(1H，d)，7.52(2H，m)，7.29(5H，m)。
19F-NMR(CDCl
3)(ppm)：-95.51(2F，s)。
Bioactive mensuration
The mensuration of embodiment 17 fungicidal activities
With compound of the present invention a series of plant epiphyte pathogen kind has been carried out the mycelial growth experiment, the program of experiment is as follows:
Carry out potted plant with plant examination material.The former medicinal small amount of N of testing compound, the dinethylformamide dissolving is diluted with water to desired concn.Spray pesticide carries out mycelium inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the fixed temperature and humidity incubator, makes to infect and continue, after 4-7 days, detect.
The effect of partial test is as follows:
During 20ppm, to the early blight of tomato preventive effect be 100% compound be II-1, II-3, II-4, II-9, II-13, etc.; Preventive effect is that 75% compound is II-5, II-7, II-8 etc.
During 20ppm, be that 100% compound is II-1, II-3, II-5, II-7 etc. to the rotten mildew preventive effect of dogstail.
During 20ppm, be that 75% compound is II-1, II-3 etc. to the rice sheath blight disease preventive effect.
During 20ppm, be that 100% compound is II-1, II-3, II-4 etc. to wheat glume blight preventive effect;
During 20ppm, be that 100% compound is II-8, II-15, II-16 etc. to the wheat scab preventive effect;
During 50ppm, be that 75% compound is II-9, II-13, II-14 etc. to the wheat powdery mildew preventive effect;
During 200ppm, be that 100% compound is II-1, II-3, II-4 etc. to late blight of potato preventive effect; Preventive effect is that 75% compound is II-7, II-8 etc.
The mensuration of embodiment 18 insecticidal activities
With the compound configuration solution-treated leaf of Semen Maydis of our invention, to go a certain amount of larva to put into and raise ware, the leaf of Semen Maydis that treated with medicaments is crossed is raised.
The effect of partial test is as follows:
When liquor strength was 10ppm, Compound I I-4, II-5 etc. were 100% to the mortality ratio for test-object target cotten aphid
When liquor strength was 50ppm, Compound I I-7 was 100% to the mortality ratio for test-object target cotten aphid; Compound I I-4, II-8 etc. are to showing suitable activity for test-object target diamondback moth larvae, greater than 50%.
When liquor strength was 50ppm, Compound I I-8, II-15 etc. were to showing suitable activity for test-object target Heliothis virescens, greater than 50%.
The mensuration of embodiment 19 weeding activity
Compound with our invention disposes weeds such as solution-treated annual bluegrass, Arabidopis thaliana, also shows certain weeding activity.
Claims (9)
1. fluorine benzothiazole sulphonyl compounds is characterized in that having following structural formula:
Wherein: R
3Representative
X represents N, S or O, and when X represents S or O, R
2Do not exist;
When X represents N, R
1Represent H, C
1-C
8Alkyl, phenyl or benzyl; R
2Represent H, C
1-C
8Alkyl, phenyl or benzyl; Perhaps
Representative contains five of N and arrives the seven membered heterocyclic base; Five of the described N of containing is hexahydroaniline, cyclopentamine, hexahydropyridine, tetramethyleneimine or imidazolyl to the seven membered heterocyclic base;
When X represents S or O, R
1Represent H, C
1-C
8Alkyl, phenyl or benzyl; R
2Do not exist; And when X represents O, R
1≠ H.
2. compound according to claim 1 is characterized in that having following structural formula:
Wherein: R
1Represent H, C
1-C
8Alkyl, phenyl or benzyl; R
2Represent H, C
1-C
8Alkyl, phenyl or benzyl; Perhaps
Representative contains five of N and arrives the seven membered heterocyclic base; Described five of the N that contains arrives the seven membered heterocyclic base according to claim 1.
3. the synthetic method of a compound as claimed in claim 1 is characterized in that comprising the steps (2), or step (1) and (2):
(1): near amino thiophenols and sultones
In organic solvent, heating 40～80 degree reactions got intermediate product (I) in 2～10 hours and contain the fluoro benzothiazole sulfonic acid fluoride,
(2): be in or be not in the organic solvent, in room temperature to the solvent boiling point temperature of reaction, intermediate product (I), compound H R
3Or MR
3With the mol ratio of alkali be 1: 1～5: 0～10; Wherein M is Alkali-Metal Na or K, reacts to such an extent that contain fluoro benzothiazole sulphonyl compounds (III),
R wherein
3According to claim 1.
4. synthetic method as claimed in claim 3 is characterized in that described compound H R
3Be aminated compounds HNR
1R
2, wherein intermediate product (I), compound H NR
1R
2With the mol ratio of alkali be 1: 1～2: 3～10, described intermediate product (I) is as described in the claim 3; Described alkali is hydride, alcoxyl metallic compound or the alkide of organic bases, monovalence or divalent metal.
5. synthetic method as claimed in claim 4 is characterized in that described organic bases is triethylamine or pyridine; The hydride of described monovalence or divalent metal is sodium hydride, potassium hydride KH or hydrolith; Described alcoxyl metallic compound is sodium methylate, potassium methylate, sodium ethylate or potassium ethylate; Described alkide is a butyllithium.
6. synthetic method as claimed in claim 4 is characterized in that described organic solvent is halohydrocarbon, ether, varsol, methyl-sulphoxide or acetonitrile.
7. synthetic method as claimed in claim 4 is characterized in that described product is through reacting direct acquisition or obtaining through silica gel column chromatography, recrystallization, distillation.
8. the application of each described compound of claim 1 to 2 in the preparation agricultural chemicals.
9. the application of each described compound of claim 1 to 2 on preparation sterilant, sterilant or weedicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101737068A CN101215270B (en) | 2007-12-28 | 2007-12-28 | Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101737068A CN101215270B (en) | 2007-12-28 | 2007-12-28 | Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215270A CN101215270A (en) | 2008-07-09 |
| CN101215270B true CN101215270B (en) | 2011-06-15 |
Family
ID=39621788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101737068A Expired - Fee Related CN101215270B (en) | 2007-12-28 | 2007-12-28 | Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101215270B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068822A (en) * | 1991-05-24 | 1993-02-10 | 先灵公司 | The benzothiazole derivant that replaces, its preparation and as herbicide applications |
-
2007
- 2007-12-28 CN CN2007101737068A patent/CN101215270B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068822A (en) * | 1991-05-24 | 1993-02-10 | 先灵公司 | The benzothiazole derivant that replaces, its preparation and as herbicide applications |
Non-Patent Citations (2)
| Title |
|---|
| V.P.Nazaretyan et al..Benzothiazol-2-yl(difluoro)methanesulfonic Acid: Synthesisand Reactions.Russian Journal of Organic Chemistry42 8.2006,1188-1191. |
| V.P.Nazaretyan et al..Benzothiazol-2-yl(difluoro)methanesulfonic Acid: Synthesisand Reactions.Russian Journal of Organic Chemistry42 8.2006,1188-1191. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101215270A (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2733511C2 (en) | Halogen-substituted phenoxyphenylamidines and use thereof as fungicides | |
| RU2735177C2 (en) | Phenoxyhalogenphenylamidines and use thereof as fungicides | |
| CA2862939C (en) | Synergistic fungicidal active combinations comprising a carboxamide and a dithiocarbamate | |
| KR101015511B1 (en) | Fungicidal active ingredient combinations | |
| CN104684909B (en) | Terazololine-one compound and the purposes as insecticide thereof | |
| CN104684908B (en) | Terazololine-one compound and the purposes as insecticide thereof | |
| ES2424335T3 (en) | Synergistic combinations of fungicidal active ingredients | |
| CN105636957B (en) | Terazololine-one compound and application thereof | |
| JP2017522290A (en) | Difluoromethyl-nicotinic acid-indanyl carboxamides | |
| EP3130584B1 (en) | Aromatic compound and uses thereof | |
| CN104892591A (en) | Preparation method of pyrazole oxime compound containing 3-aryl-1,2,4-oxdiazole heterocycle structure and application thereof | |
| EP3124474A1 (en) | Aromatic compound and uses thereof | |
| KR20100021484A (en) | Fungicidal substance combinations | |
| CN108069984A (en) | Substituted five-membered heterocycle compound of the ring containing pyrimido and its preparation method and application | |
| CN108347948B (en) | Active compound combinations comprising (thio) carboxamide derivatives and fungicidal compounds | |
| KR100269420B1 (en) | Substituted thiophene derivative and plant disease control agent comprising the same as active ingredient | |
| CN101215270B (en) | Fluorine-containing benzothiazole sulphuryl compounds and its preparation and application | |
| JP6763380B2 (en) | Harmful arthropod control agent | |
| BRPI0719312A2 (en) | FUNGICID MIXTURES OF AMIDINYLPHENYL COMPOUNDS | |
| CN103772356B (en) | Replace fragrant oxy picolinate compounds and uses thereof | |
| CN105541794A (en) | Heptafluoroisopropyl-containing pyridyl pyrazole amide derivative and application thereof | |
| BRPI0612030A2 (en) | combinations of fungicidal active substances | |
| EP3124484B1 (en) | Tetrazolinone compound and application thereof | |
| KR20190052007A (en) | Active compound combinations comprising 5-substituted imidazole derivatives | |
| CN109988150B (en) | N-alkyl-N-cyanoalkyl benzamide compounds and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110615 Termination date: 20171228 |