CN100500666C - Triazole pyrimidine sulphonates compound, preparing method and application thereof - Google Patents
Triazole pyrimidine sulphonates compound, preparing method and application thereof Download PDFInfo
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- CN100500666C CN100500666C CNB2007100673459A CN200710067345A CN100500666C CN 100500666 C CN100500666 C CN 100500666C CN B2007100673459 A CNB2007100673459 A CN B2007100673459A CN 200710067345 A CN200710067345 A CN 200710067345A CN 100500666 C CN100500666 C CN 100500666C
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- sulphonates
- pyrimidine
- triazole
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Abstract
The invention discloses a making method of triazolopyrimidosulfonate compound and application, whose chemical formula is as formula (I), wherein R1, R2 and R3 is individual H, C1-C4 alkyl or C1-C4 alkoxy; X1, X2, X3, X4 and X5 is individual H, halogen, nitro radical, C1-C4 alkyl or C1-C4 alkoxy; the compound possesses excellent weeding and plant growing and adjusting activity.
Description
(1) technical field
The present invention relates to a kind of triazole pyrimidine sulphonates compound and its production and application.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in heterogeneous ring compound, again based on nitrogen heterocyclic ring.The triazolo pyrimidine heterocyclic compounds is owing to contain triazole and the important active structure unit of pyrimidine two classes simultaneously in its molecular structure, thereby shown the biological activity of wide spectrum, that has now succeeded in developing has novel acetolactate synthestase (ALS) inhibitor class ultra-high efficiency weedicide DE498 (Flumetsulam), DE511 pesticide species such as (metosulams); Still very active to the composition optimizes and the bioactivity research of triazolopyrimidines in recent years.When the contriver studies, synthesized the new triazole pyrimidine sulphonates compound of a class in this area, found that it has weeding preferably and plant growth regulating activity, as yet not relevant for the report of this compounds.
(3) summary of the invention
The purpose of this invention is to provide a kind of new triazole pyrimidine sulphonates compound and preparation method thereof, with and as the application of weedicide or plant-growth regulator.
The technical solution used in the present invention is as follows:
A kind of triazole pyrimidine sulphonates compound is characterized in that described compound is suc as formula shown in (I):
Wherein, R
1, R
2, R
3Independent separately is alkyl or the alkoxyl group of hydrogen, C1～C4, X
1, X
2, X
3, X
4, X
5Independent separately is the alkyl of hydrogen, halogen, nitro, C1～C4 or the alkoxyl group of C1～C4.
Concrete, aforesaid triazole pyrimidine sulphonates compound is as follows:
Compound 1:
Compound 2:
Compound 3:
Compound 4:
Compound 5:
Compound 6:
Compound 7:
Compound 8:
Preferably, described compound is shown in compound 1 or compound 2.
The present invention also provides a kind of method for preparing aforesaid triazole pyrimidine sulphonates compound, 2-hydroxyl-1 suc as formula the replacement shown in (II), 2,4-triazole [1,5-a] pyrimidine with suc as formula the substituted benzene SULPHURYL CHLORIDE shown in (III) under the acid binding agent effect, 0～30 ℃ is carried out condensation reaction in solvent, aftertreatment promptly gets compound shown in the formula (I), and described acid binding agent is one of following: alkali metal hydroxide, alkaline carbonate or supercarbonate, triethylamine, DBU or pyridine; Described solvent is the mixture of following one or more arbitrary proportions: ether, methyl tertiary butyl ether, methylene dichloride, DMF, benzene, toluene, tetrahydrofuran (THF) or water, and in formula (II), the formula (III), R
1, R
2, R
3Independent separately is alkyl or the alkoxyl group of hydrogen, C1～C4, X
1, X
2, X
3, X
4, X
5Independent separately is alkyl or the alkoxyl group of hydrogen, halogen, nitro, C1～C4;
Reaction equation is:
Wherein, feed intake amount of substance than for formula (II) compound: formula (III) compound: acid binding agent is 1:1.0～1.3:0.5～2.0, and the consumption of described solvent is 10～50 times of formula (II) compound quality.
Further, described acid binding agent is sodium hydroxide or yellow soda ash.
Wherein, described formula (II) compound can prepare by the following method:
3-amino-5-hydroxyl-1,2,4-triazole and different beta-dicarbonyl compound under catalyst action in solvent back flow reaction 3～24 hours, the amount of substance that feeds intake is than being 3-amino-5-hydroxyl-1,2, the 4-triazole: beta-dicarbonyl compound is 1:1.0～2.0; Described solvent can be acetate, 20% aqueous hydrochloric acid or NaOH/ aqueous ethanolic solution (NaOH: ethanol: the quality ratio is 10～20:30～50:30～60), and consumption is 3-amino-5-hydroxyl-1,2,10～50 times of 4-triazole quality; Catalyzer can be selected piperidines, and consumption is 3-amino-5-hydroxyl-1,2,0.05～0.1 times of 4-triazole quality.
Comparatively concrete, the preparation method of described triazole pyrimidine sulphonates compound carries out according to following steps: the 2-hydroxyl-1 of the replacement shown in the formula (II), 2,4-triazole [1,5-a] the substituted benzene SULPHURYL CHLORIDE shown in pyrimidine and the formula (III) is at triethylamine, under sodium hydroxide or the yellow soda ash effect, in solvent, carry out condensation reaction 2～5 hours under the room temperature, column chromatography or recrystallization method separation and purification, promptly get described triazole pyrimidine sulphonates compound, the amount of substance that feeds intake ratio is formula (II) compound: formula (III) compound: acid binding agent is 1:1.0～1.1:0.5～1.1, and described solvent is an ether, methyl tertiary butyl ether, methylene dichloride or water.
Concrete, described post-treating method steams the salt of organic solvent, flush away generation for reducing pressure, and again with column chromatography or recrystallization method separation and purification reaction solution, solvent for use can be sherwood oil, ethyl acetate, normal hexane, acetone or their mixed solution.
Described triazole pyrimidine sulphonates compound has preferably as plant-growth regulator to be used.Wherein particularly compound 1 and 2 all has good biological activity, can be used as weedicide or plant-growth regulator, and compound 1 is used to promote that the plant-growth effect is preferable.Compound 2 is good especially as the weedicide effect.
Compound of the present invention when concrete the application, can with the carrier or the mixing diluents that allow in other plant protection, whereby with the normally used various formulations of its furnishing, wait as pulvis, granule, microemulsion or aqueous emulsion and to use; Also can mix use or while and usefulness with other weedicide or plant-growth regulator.Test result shows that under 3.75gai/ha～37.5gai/ha effective dose, part of compounds shows high inhibition activity, useful as herbicides to dicotyledons and monocotyledons; Part of compounds shows high promotion growth activity to monocotyledons, can be used as plant-growth regulator.
The present invention compared with prior art, its beneficial effect is embodied in:
Described triazole pyrimidine sulphonates compound is the new compound of a class, and plant-growth is had good regulating effect.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Synthesizing of embodiment 1 0-(1,2,4-triazolo [1,5-a] pyrimidine-2-base)-4-toluene sulfonic acide ester (compound 1)
In the 50mL there-necked flask, add 0.66g (0.004mol) 2-hydroxyl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.16g (0.004mol) sodium hydroxide, 20mL water, magnetic agitation dissolving, at room temperature splash into the 5mL diethyl ether solution of 0.77g (0.004mol) Tosyl chloride, approximately 0.5h drips off, and has solid to generate, continue to stir 5h, the pressure reducing and steaming ether, suction filtration gets gray solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, oven dry is used silica gel column chromatography, sherwood oil-acetone (50/50, v/v) make solvent, get colourless tabular crystal compound 1, yield 85.0%, 149 ℃～151 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.46(s，3H，Ph-CH
3)，2.64(s，3H，5-CH
3)，2.73(s，3H，7-CH
3)，6.84(s，1H，6-H)，7.38～8.07(m，4H，C
6H
4)
IR(/cm
-1)：(CH
3)2929，(v
(SO
2))1375，1180；(ph)1629
MS(m/e)：[M
+]319
Synthesizing of embodiment 2 O-(1,2,4-triazolo [1,5-a] pyrimidine-2-base)-benzene sulfonate (compound 2)
In the 50mL there-necked flask, add 0.66g (0.004mol) 2-hydroxyl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.16g (0.004mol) sodium hydroxide, 20mL water, magnetic agitation dissolving, at room temperature splash into the 5mL diethyl ether solution of 0.71g (0.004mol) benzene sulfonyl chloride, approximately 0.5h drips off, and has solid to generate, continue to stir 5h, the pressure reducing and steaming ether, suction filtration gets gray solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, oven dry is used silica gel column chromatography, sherwood oil-acetone (70/30, v/v) make solvent, get colorless prismatic crystal compound 2, yield 88.0%, 145 ℃～147 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.64(s，3H，5-CH
3)，2.74(s，3H，7-CH
3)，6.86(s，1H，6-H)，7.59～8.20(m，5H，C
6H
5)
IR(/cm
-1)：(v
(SO
2))1388，1187；(ph)1633
MS(m/e)：[M
+]305
Synthesizing of embodiment 3 O-(1,2,4-triazolo [1,5-a] pyrimidine-2-base)-4-nitrobenzene-sulfonic acid ester (compound 3)
In the 50mL there-necked flask, add 0.66g (0.004mol) 2-hydroxyl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.21g (0.004mol) yellow soda ash, 20mL water, magnetic agitation dissolving, at room temperature splash into the 10mL methyl tertbutyl ethereal solution of 0.89g (0.004mol) 4-nitrobenzene sulfonyl chloride, approximately 0.5h drips off, and has solid to generate, and continues to stir 5h, the pressure reducing and steaming methyl tertiary butyl ether, suction filtration gets gray solid, with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, washes with water more for several times respectively, oven dry, use silica gel column chromatography, and sherwood oil-acetone (70/30, v/v) make solvent, get white styloid compound 3, yield 92.0%.
Synthesizing of embodiment 4 compounds 1
In the 50mL there-necked flask, add 0.66g (0.004mol) 2-hydroxyl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, the 20mL methylene dichloride, 0.50g (0.005mol) triethylamine, magnetic agitation is dissolved, and at room temperature splashes into the 5mL dichloromethane solution of 0.77g (0.004mol) Tosyl chloride, and approximately 0.5h drips off, after continuing to stir 5h, add the 20mL washing, separatory is successively with 20mL3% aqueous hydrochloric acid and the washing of 20mL5% sodium bicarbonate aqueous solution, wash with water more for several times, separatory, oil phase anhydrous sodium sulfate drying, pressure reducing and steaming methylene dichloride, get gray solid, use silica gel column chromatography, and sherwood oil-acetone (50/50, v/v) make solvent, get colourless tabular crystal compound 1, yield 68.0%.
Synthesizing of embodiment 5 compounds 2
In the 50mL there-necked flask, add 0.66g (0.004mol) 2-hydroxyl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, the 20mL methylene dichloride, 0.81g (0.008mol) triethylamine, magnetic agitation is dissolved, and at room temperature splashes into the 5mL dichloromethane solution of 0.71g (0.004mol) benzene sulfonyl chloride, and approximately 0.5h drips off, after continuing to stir 5h, add the 20mL washing, separatory is successively with 20mL 3% aqueous hydrochloric acid and the washing of 20mL 5% sodium bicarbonate aqueous solution, wash with water more for several times, separatory, oil phase anhydrous sodium sulfate drying, pressure reducing and steaming methylene dichloride, get gray solid, use silica gel column chromatography, and sherwood oil-acetone (50/50, v/v) make solvent, get colorless prismatic crystal compound 1, yield 70.0%.
Adopt similar approach can prepare other compound equally.
The experiment of embodiment 6 weeding activity
In 3.75gai/ha～37.5gai/ha effective dose, formulation is synthetic part of compounds 100ppm of institute and 10ppm aseptic aqueous solution, solubility promoter DMF (DMF/ solution (volume ratio)=1/1000), emulsifying agent: tween-80, adopt greenhouse pot culture, under two kinds of dosage, two kinds of insecticide-applying way of rhizome rape and barnyard grass grass are handled, other establishes blank; The vegetable active test result is seen Table 1.
By test-results as can be seen, formula of the present invention (I) compound has very high activity to broadleaf weeds, can be used as weedicide and uses; Growth to grass has promoter action preferably, can be used as plant-growth regulator and uses.
Table 1 active testing result
Claims (11)
1. triazole pyrimidine sulphonates compound is characterized in that described compound is suc as formula shown in (I):
Wherein, R
1, R
2, R
3Independent separately is the alkyl of hydrogen, C1～C4, X
1, X
2, X
3, X
4, X
5Independent separately is the alkyl of hydrogen, halogen, nitro, C1～C4.
2. triazole pyrimidine sulphonates compound as claimed in claim 1 is characterized in that described compound is:
Compound 1:
Compound 2:
Compound 3:
Compound 4:
Compound 5:
Compound 6:
Compound 7:
Compound 8:
3. triazole pyrimidine sulphonates compound as claimed in claim 1 is characterized in that described compound is:
Compound 1:
4. triazole pyrimidine sulphonates compound as claimed in claim 1 is characterized in that described compound is:
Compound 2:
5. method for preparing triazole pyrimidine sulphonates compound as claimed in claim 1, it is characterized in that described method is the 2-hydroxyl-1 suc as formula the replacement shown in (II), 2,4-triazole [1,5-a] pyrimidine with suc as formula the substituted benzene SULPHURYL CHLORIDE shown in (III) under the acid binding agent effect, 0～30 ℃ is carried out condensation reaction in solvent, aftertreatment promptly gets compound shown in the formula (I), and described acid binding agent is one of following: alkali metal hydroxide, alkaline carbonate, triethylamine; Described solvent is the mixture of following one or more arbitrary proportions: ether, methyl tertiary butyl ether, methylene dichloride, DMF, benzene, toluene, tetrahydrofuran (THF) or water, and in formula (II), the formula (III), R
1, R
2, R
3Independent separately is the alkyl of hydrogen, C1～C4, X
1, X
2, X
3, X
4, X
5Independent separately is the alkyl of hydrogen, halogen, nitro, C1～C4;
6. the preparation method of triazole pyrimidine sulphonates compound as claimed in claim 5, it is characterized in that described formula (II) compound: formula (III) compound: the ratio of the amount of substance that feeds intake of acid binding agent is 1:1.0～1.3:0.5～2.0, and the consumption of described solvent is 10～50 times of formula (II) compound quality.
7. preparation method as claimed in claim 5 is characterized in that described acid binding agent is sodium hydroxide or yellow soda ash.
8. preparation method as claimed in claim 5, it is characterized in that described method carries out according to following steps: the 2-hydroxyl-1 of the replacement shown in the formula (II), 2,4-triazole [1,5-a] the substituted benzene SULPHURYL CHLORIDE shown in pyrimidine and the formula (III) is at triethylamine, under sodium hydroxide or the yellow soda ash effect, in solvent, carry out condensation reaction 2～5 hours under the room temperature, column chromatography or recrystallization method separation and purification, promptly get described triazole pyrimidine sulphonates compound, the amount of substance that feeds intake ratio is formula (II) compound: formula (III) compound: acid binding agent is 1:1.0～1.1:0.5～1.1, and described solvent is an ether, methyl tertiary butyl ether, methylene dichloride or water.
9. triazole pyrimidine sulphonates compound as claimed in claim 1 is as the application of plant-growth regulator.
10. application as claimed in claim 9 is characterized in that the application of described compound 1 as plant-growth regulator:
Compound 1:
11. compound as claimed in claim 42 is as herbicide applications.
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| CN106243110B (en) * | 2016-07-28 | 2018-05-29 | 浙江工业大学 | A kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group and its preparation method and application |
| CN106243109B (en) * | 2016-07-28 | 2018-07-06 | 浙江工业大学 | A kind of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methyl and its preparation method and application |
| CN106220633B (en) * | 2016-07-28 | 2018-08-31 | 浙江工业大学 | A kind of application of 1,2,4- triazole derivatives of the structure of benzopyrazines containing chlorine as fungicide |
| CN106432245B (en) * | 2016-07-28 | 2018-11-13 | 浙江工业大学 | A kind of 1,2,4- triazole derivatives of the structure containing benzopyrazines and its preparation method and application |
| CN106336415B (en) * | 2016-07-28 | 2018-05-29 | 浙江工业大学 | A kind of 1,2,4- triazole derivatives of chloride benzopyrazines structure and its preparation method and application |
| CN106234385B (en) * | 2016-07-28 | 2018-11-13 | 浙江工业大学 | A kind of application of 1,2,4- triazole derivatives of the structure containing benzopyrazines as fungicide |
| CN108395435B (en) * | 2018-05-10 | 2021-02-05 | 深圳大学 | Triazolopyrimidine sulfonamide compound and preparation method and application thereof |
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Assignee: Yancheng Ciyt Chunzhu Aroma Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2011330000048 Denomination of invention: Triazole pyrimidine sulphonates compound, preparing method and application thereof Granted publication date: 20090617 License type: Exclusive License Open date: 20070815 Record date: 20110221 |
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