CN103059010A - 1,4-benzoxazinone-1,2,3-triazole compound having antifungal activity, and its preparation method - Google Patents
1,4-benzoxazinone-1,2,3-triazole compound having antifungal activity, and its preparation method Download PDFInfo
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Abstract
The invention discloses a 1,4-benzoxazinone-1,2,3-triazole compound having an antifungal activity, and its preparation method. A technical scheme adopted by the invention is mainly characterized in that the structural general formula of the 1,4-benzoxazinone-1,2,3-triazole compound having an antifungal activity is shown in the specification; and in the structural general formula, X can be a halogen atom, an alkoxy group, an alkyl group, NO2, OH, H or CF3, Y is O or S, and R is H, Cl, Br, NO2 or OH. The invention also discloses the preparation method of the compound, and an application of the compound. Eight structures of the 1,4-benzoxazinone-1,2,3-triazole compound have been already synthesized in the invention; the 1,4-benzoxazinone-1,2,3-triazole compound has a certain antifungal activity, and can be well used for controlling the animal and plant diseases caused by fungi; and the preparation method has the advantages of simple and easily-controlled technology, and high yield of the target product.
Description
Technical field
The invention belongs to technical field of pesticide, be specifically related to the novel Isosorbide-5-Nitrae-benzoxazinone with anti-mycotic activity-1,2 of a class, 3-triazole compound and its preparation method and application.
Background technology
Heterogeneous ring compound is a class the hugest in the organic compound, and is widely distributed at occurring in nature, and its chemical structure is also ever-changing, and unique character and purposes are arranged separately.Nitrogen heterocyclic ring is one of focus of novel pesticide initiative research.Isosorbide-5-Nitrae-benzoxazine is that a class contains N and the heteroatomic heterogeneous ring compound of O.Since nineteen fifty-nine Virtanen etc. isolates compound 2 with Hamilton philosophy in 1962,4-dihydroxyl-2H-1,4-benzoxazine-3(4 from maize bud
H)-ketone (DIBOA) and 2,4-dihydroxyl-7-methoxyl group-2
H-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-ketone (DIMBOA), as parent, a large amount of Isosorbide-5-Nitraes-benzoxazine analog derivative is synthesized out, but research and comparison many be Isosorbide-5-Nitrae-benzoxazine ketone compounds, their main manifestations are weeding activity, and existing commercial pesticide species.Synthesize a series of tetrahydric phthalimide compounds that contain Isosorbide-5-Nitrae-benzoxazinone structure such as Nagano in 1987 etc., have good weeding activity.Sumitomo company has developed the weedicide flumioxazin that is used for soybean and peanut in 1989 on this basis.The Isosorbide-5-Nitrae that the inferior synthetic a series of oxazolidines of horizontal well constitution replace-benzoxazine ketone compounds, this compounds is used for the paddy field and shows very strong weeding activity for annual weeds.The synthetic once row such as Mitsuaki contain the Isosorbide-5-Nitrae of Carbamido substituted-benzoxazine ketone compounds, and research finds that they are typical inhibitor of photosynthesis in.The synthetic a series of Isosorbide-5-Nitrae that fragrant oxygen ether replaces-benzoxazine ketone compounds that contain such as Naoko, they to bud before or the weeds of bud aftertreatment good activity is arranged.China also has a lot of scholars that Isosorbide-5-Nitrae-benzoxazine ketone compounds is studied, and the compound main manifestations of reporting is weeding and anti-microbial activity.
Summary of the invention
The technical problem that the present invention solves has provided a kind of Isosorbide-5-Nitrae-benzoxazinone-1,2 with anti-mycotic activity, 3-triazole compound.
Another technical problem that the present invention solves provided a kind of simple to operate, be easy to control and the Isosorbide-5-Nitrae-benzoxazinone with anti-mycotic activity-1,2 that productive rate is higher the preparation method of 3-triazole compound.
The application problem that the present invention solves is this Isosorbide-5-Nitrae-benzoxazinone with anti-mycotic activity-1,2, and the 3-triazole compound is by the application in the fungus-caused animals and plants disease control.
Technical scheme of the present invention is: have the Isosorbide-5-Nitrae-benzoxazinone-1,2 of anti-mycotic activity, the 3-triazole compound is characterized in that: described Isosorbide-5-Nitrae-benzoxazinone-1,2, and the structural formula of 3-triazole compound is:
, wherein X is halogen atom, alkoxyl group, alkyl, NO
2, OH, H or CF
3, Y is O or S, R is H, Cl, Br, NO
2Or OH.
Of the present invention have 1 of an anti-mycotic activity, 4-benzoxazinone-1,2, the preparation method of 3-triazole compound, it is characterized in that comprising following synthesis step: step 1, Isosorbide-5-Nitrae-benzoxazinone and end-group alkyne compounds are formed Isosorbide-5-Nitrae-benzoxazinone end-group alkyne compounds through alkylation, wherein the ratio of the amount of substance of each raw material is n(1, the 4-benzoxazinone): n(end-group alkyne compounds)=1:1.4; Step 2, with step 1 obtain 1,4-benzoxazinone end-group alkyne compounds makes 1 with phenylazide or replacement phenylazide through the Click reaction at normal temperatures, 4-benzoxazinone-1,2,3-triazole compound, wherein the ratio of the amount of substance of each raw material is n(1,4-benzoxazinone end-group alkyne compounds): n(phenylazide or replacement phenylazide)=1:1.5, used catalyzer is cuprous chloride-anhydrous sodium acetate, and solvent is water, and the time of Click reaction is 24 hours.
Cuprous chloride is the n(cuprous chloride with the ratio of the amount of substance of anhydrous sodium acetate in the catalyzer of the present invention): the n(anhydrous sodium acetate)=1 ~ 1.5:1.Cuprous chloride is the n(cuprous chloride with the ratio of the amount of substance of anhydrous sodium acetate in the catalyzer of the present invention): the n(anhydrous sodium acetate)=1.2:1.
Of the present invention have 1 of an anti-mycotic activity, 4-benzoxazinone-1,2, the purposes of 3-triazole compound, it is characterized in that: described have 1 of an anti-mycotic activity, 4-benzoxazinone-1,2,3-triazole compound can be used for the control of the former bacterium of pepper anthracnose, the former bacterium of wheat hypochnus.
The present invention carries out chemically modified by " Click Chemistry " to Isosorbide-5-Nitrae-benzoxazinone, will have multiple bioactive
1,2,3-triazole ring is introduced in Isosorbide-5-Nitrae-benzoxazinone, synthesized 1 of various structures, 4-benzoxazinone-1,2, the 3-triazole compound, this compounds has excellent anti-fungal property, can be applied to preferably the control because of the animals and plants disease due to the fungi, and technique is simple in the preparation process, is easy to control and target product product yield high.
Embodiment
Below be the embodiment by the embodiment form, foregoing of the present invention is described in further details, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
2
H-Isosorbide-5-Nitrae-benzoxazine-3(4
HSynthesizing of)-ketone
In 250ml single port bottle, add 10g(0.095mol) ortho-aminophenol, 14g(0.122mol) methylene dichloride of chloroacetyl chloride and 150ml, in bathing, cryosel reacts 3h, react completely by TLC monitoring ortho-aminophenol, use dichloromethane extraction 3 times after the washing, underpressure distillation goes out methylene dichloride, gets gray solid, then adds together among the 100ml DMF with the 30g Anhydrous potassium carbonate, stirring at normal temperature is monitored to complete reaction (TLC).Decompression steams DMF, then uses dichloromethane extraction three times after the washing, and underpressure distillation goes out methylene dichloride, obtains the 11.5g white solid, and yield is 81%.
2
H-Isosorbide-5-Nitrae-benzoxazine-3(4
HSynthesizing of)-thioketones
In the 250ml reaction flask, add 10g(0.067mol) 2
H-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-ketone, 21g(0.054mol) lawesson reagent and 150ml toluene, be heated to backflow 24h, the reaction solution cooling is added in the frozen water (500ml), with dichloromethane extraction three times, each 30ml underpressure distillation goes out methylene dichloride, obtain the crude product compound, get target compound 6.4g through column chromatography, yield is 58.1%.
Embodiment 2
The 4-(2-proyl)-Isosorbide-5-Nitrae-benzoxazine-3(4
HSynthesizing of)-ketone
In 250ml single port bottle, add 10g(0.067mol) (2
H)-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-ketone, 13.6g(0.081mol) propargyl bromide, 13.9g(0.1mol) Anhydrous potassium carbonate and 150ml acetone, be heated to backflow 3h, then steam acetone by underpressure distillation, remaining compound washes with water three times, each 40 mL, dichloromethane extraction three times, then each 50 mL add anhydrous sodium sulfate drying, suction filtration, precipitation gets target compound 9.9g through column chromatography, yield 79%.
The 4-(2-proyl)-Isosorbide-5-Nitrae-benzoxazine-3(4
HSynthesizing of)-thioketones
In 250ml single port bottle, add 10g(0.06mol) (2
H)-Isosorbide-5-Nitrae-benzoxazine-3(4H)-thioketones, 8.8g(0.073mol) propargyl bromide, 12.4g(0.09mol) Anhydrous potassium carbonate and 150ml acetone, under the N2 protection, be heated to backflow 5h; then steam acetone by underpressure distillation; remaining compound washes with water three times with remaining compound, each 40 mL, dichloromethane extraction three times; each 50 mL; then add anhydrous sodium sulfate drying, suction filtration, precipitation; get target compound 9.1g through column chromatography, yield 74%.
Embodiment 3
The preparation of adjacent fluorine phenylazide
In 250 mL, two neck bottles, add the mixing solutions (14 mL, 1:1, v/v) of concentrated hydrochloric acid and water, add adjacent fluoroaniline (0.022 mol, 2.4 g), be stirred to dissolving.In the time of 0-5 ℃, slowly drip the frozen water solution that 8 mL are dissolved with Sodium Nitrite (0.022 mol, 1.5 g).After 20 minutes, slowly drip the aqueous solution that 18 mL are dissolved with sodiumazide (0.022 mol, 1.4 g).After dropwising, stirring at room, thin-layer chromatography (TLC) is followed the tracks of reaction, after reacting completely, with an amount of dichloromethane extraction three times, washes three times, anhydrous sodium sulfate drying, suction filtration, precipitation gets yellow liquid 2.6 g, yield 86%.
Embodiment 4
4-[1-(2-fluorophenyl)-4,5-dihydro-1
H-[1,2,3] triazole-4-yl methyl]-4
H-Isosorbide-5-Nitrae-benzoxazine-3(4
HThe preparation of)-ketone
In 250ml single port bottle, add 1.5g(8mmol) the 4-(2-proyl)-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-ketone, 1.5g(10mmol) adjacent fluorine phenylazide, add mixed solvent (100 mL, the 1:1 of the trimethyl carbinol and water, v/v), then add cuprous chloride (12 mol%), anhydrous sodium acetate (10 mol%), at room temperature reaction, TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains faint yellow solid 2.53g, productive rate 85%.
M.p.104.3-105.9,?
1H?NMR?(CDCl
3?400?MHz):?δ?=?8.13-8.12?(d,?
J?=?2.4?Hz,?1H,?CH-H),?7.95-7.89?(t,?
J?=?7.2?Hz,?IH,?Ar-H),?7.60-7.58?(d,?
J?=?7.2?Hz,?1H,?Ar-H),?7.45-7.40?(m,?1H,?Ar-H),?7.33-7.28?(t,?
J?=?8.0?Hz,?2H,?Ar-H),?7.09-6.98?(m,?3H,?Ar-H),?5.28?(s,?2H,?CH
2-H),?4.64?(s,?2H,?CH
2-H).?ESI?MS?m/z:?325?[M+H]+.
Embodiment 5
4-[1-(2-fluorophenyl)-4,5-dihydro-1
H-[1,2,3] triazole-4-yl methyl]-4
H-Isosorbide-5-Nitrae-benzoxazine-3(4
HThe preparation of)-thioketones
In 250ml single port bottle, add 2.0g(10mmol) the 4-(2-proyl)-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-thioketones, 1.64g(12mmol) adjacent fluorine phenylazide, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains white solid 2.65 g, productive rate 73%.
M.p.70.8-72.5,?
1H?NMR(CDCl
3?400?MHz):?δ?=8.16-8.15?(d,?
J=3.2Hz,?CH-H),?7.96-7.92?(t,
?J=7.6Hz,?1H,?Ar-H),?7.43-7.38?(m,?1H,?Ar-H),?7.33-7.30?(m,?2H,?Ar-H),?7.29-7.28?(d,?
J=2.8Hz,?1H,?Ar-H),?7.10-7.06?(t,?
J=7.6Hz,?1H,?Ar-H),?7.02-6.98?(d,?J=7.6Hz,?1H,?Ar-H),?6.89-6.86?(dd,?
J 1=1.6Hz,?
J 2=8.0Hz,?1H,?Ar-H),?4.60?(s,?2H,?CH
2-H),?4.50?(s,?2H,?CH
2-H).?ESI?MS?m/z:?341?[M+H]+.
Embodiment 6
4-[1-(2-aminomethyl phenyl)-4,5-dihydro-1
H-[1,2,3] triazole-4-yl methyl]-4
H-Isosorbide-5-Nitrae-benzoxazine-3(4
HThe preparation of)-ketone
In 250ml single port bottle, add 1.87g(10mmol) the 4-(2-proyl)-1,4-benzoxazine-3(4H)-ketone, 1.65g(12mmol) adjacent triazo-methane benzene, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains white solid 2.79 g, productive rate 75%.
M.p.161.1-162.4,?
1H?NMR?(400?MHz,?CDCl
3):?δ?=7.79(s,?1H,?CH-H),7.61-7.60?(d,?
J=7.6Hz,?1H,?Ar-H),?7.39-7.27(m,?4H,?Ar-H),?7.09-6.97?(m,?4H,?Ar-H),?5.28(s,?2H,?CH
2-H),?4.63(s,?2H,?CH
2-H),?2.18(s,?3H,?CH
3-H).?ESI?MS?m/z:?321?[M+H]
+.
Embodiment 7
4-[1-(2-aminomethyl phenyl)-4,5-dihydro-1
H-[1,2,3] triazole-4-yl methyl]-4H-1,4-benzoxazine-3(4
HThe preparation of)-thioketones
In 250ml single port bottle, add 2.0g(10mmol) the 4-(2-proyl)-1,4-benzoxazine-3(4H)-thioketones, 1.65g(12mmol) adjacent triazo-methane benzene, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains white solid 3.05 g, productive rate 90.7%.
M.p.96.1-98.7,?
1H?NMR?(400?MHz,?CDCl
3):δ?=?7.78?(s,?1H,?CH-H),?7.41-7.37?(m,?1H,?Ar-H),?7.35-7.30?(m,?3H,?Ar-H),?7.27?(dd,?
J?=?1.6,?7.7?Hz,?1H,?Ar-H),?7.10-7.06?(m,?1H,?Ar-H),?7.00-6.96?(m,?1H,?Ar-H),?6.88?(dd,?
J?=?1.3,?7.9?Hz,?1H,?Ar-H),?4.60?(s,?2H,?CH
2-H),?4.52?(s,?2H,?CH
2-H),?2.17(s,?3H,?CH
3-H).?ESI?MS?m/z:?337?[M+H]
+.
Embodiment 8
4-[1-(2-chloro-phenyl-)-4,5-dihydro-1H-[1,2,3] the triazole-4-yl methyl]-4H-1, the preparation of 4-benzoxazine-3(4H)-thioketones
In 250ml single port bottle, add 2.0g(10mmol) the 4-(2-proyl)-1,4-benzoxazine-3(4H)-thioketones, 1.83g(12mmol) adjacent chlorine phenylazide, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains micro white solid 2.55 g, productive rate 74%.
M.p.110.4-113.8,?
1H?NMR?(400?MHz,?CDCl
3):δ?=?8.061(s,?1H,?CH-H),?7.63-7.61(m,?1H,?Ar-H),?7.56-7.54(m,?1H,?Ar-H),?7.44-7.42(m,?2H,?Ar-H),?7.30-7.28?(dd,?
J 1 =2.0Hz,?
J 2 =8.0Hz,?1H,?Ar-H),?7.10-7.06?(t,?
J=7.6Hz,?1H,?Ar-H),?7.01-6.97(t,?
J=7.6Hz,?1H,?Ar-H),?6.89-6.87?(d,?
J=7.6Hz,?1H,?Ar-H),?4.60(s,?2H,?CH
2-H),?4.52(s,?2H,?CH
2-H).?ESI?MS?m/z:?357?[M+H]
+.
Embodiment 9
4-[1-(4-p-methoxy-phenyl)-4,5-dihydro-1H-[1,2,3] the triazole-4-yl methyl]-4H-1, the preparation of 4-benzoxazine-3(4H)-thioketones
In 250ml single port bottle, add 2.0g(10mmol) the 4-(2-proyl)-1,4-benzoxazine-3(4H)-thioketones, 1.79g(12mmol) to the methoxyl group phenylazide, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains micro white solid 2.83 g, productive rate 80%.
M.p.82.1-83.7,?
1H?NMR?(400?MHz,?CDCl
3):δ?=?7.98(s,?1H,?CH-H),?7.57-7.55(m,?2H,?Ar-H),?7.33-7.29(t,?
J=6.4Hz,?2H,?Ar-H),?7.27(s,?1H,?Ar-H),?7.12-7.08?(t,
?J=7.6Hz,?1H,?Ar-H),?7.03-6.98(dd,?
J 1 =7.6Hz,?
J 2 =14.8Hz,?1H,?Ar-H),?6.90-6.88(d,?
J=7.6Hz,?1H,?Ar-H),?4.59(s,?2H,?CH
2-H)?4.52(s,?2H,?CH
2-H),?2.40(s,?3H,?CH
3-H).?ESI?MS?m/z:?353?[M+H]
+.
Embodiment 10
4-[1-(4-p-methoxy-phenyl)-4,5-dihydro-1H-[1,2,3] the triazole-4-yl methyl]-4H-1, the preparation of 4-benzoxazine-3(4H)-ketone
In 250ml single port bottle, add 1.87g(10mmol) the 4-(2-proyl)-1,4-benzoxazine-3(4H)-thioketones, 1.44g(12mmol) to triazo-methane benzene, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains micro white solid 2.67 g, productive rate 83%.
M.p.147.3-148.1,?
1H?NMR?(400?MHz,?CDCl
3):δ?=?8.00?(s,?1H,?CH-H),?7.60-7.56?(t,?
J=10.8Hz,?3H,?Ar-H),?7.30-7.28?(d,?J=8.0Hz,?2H,?Ar-H),?7.08-6.97(m,?3H,?Ar-H),?5.26?(s,?2H,?CH
2-H),?4.64(s,?2H,?CH
2-H),?2.40(s,?3H,?CH
3-H).?ESI?MS?m/z:?321?[M+H]
+.
Embodiment 11
4-[1-(3-hydroxy phenyl)-4,5-dihydro-1H-[1,2,3] the triazole-4-yl methyl]-4H-1, the preparation of 4-benzoxazine-3(4H)-ketone
In 250ml single port bottle, add 1.87g(10mmol) the 4-(2-proyl)-Isosorbide-5-Nitrae-benzoxazine-3(4
H)-thioketones, 1.62g(12mmol) between the hydroxyl phenylazide, add entry 100ml, then add cuprous chloride (6 mol%), anhydrous sodium acetate (5 mol%), at room temperature stir the TLC monitoring.After reacting completely, use dichloromethane extraction, washing, anhydrous sodium sulfate drying, suction filtration, precipitation through column chromatography, obtains gray solid 2.43 g, productive rate 75%.
M.p.207.5-208.1,?
1H?NMR?(400?MHz,?DMSO):δ?=10.01(s,1H,?CH-H),?8.64(s,?1H,?Ar-H),?7.35-7.25(m,?3H,?Ar-H),?7.01-6.98(t,?
J=6.4Hz,?3H,?Ar-H),?6.85-6.83(d,?
J=8.0Hz,?1H,?Ar-H),?5.21(s,?2H,?CH
2-H),?4.72(s,?2H,?CH
2-H).?ESI?MS?m/z:?323?[M+H]
+.
Embodiment 12
The anti-mycotic activity test
Adopt the colony growth diameter method, testing compound is dissolved in is mixed with the finite concentration mother liquor among the DMSO, and add mother liquor in 60 ℃ of PDA substratum and make it Uniform Dispersion, being prepared into concentration is the pastille substratum of 20 mg/1000 mL.Inoculate respectively the former bacterium of wheat hypochnus and capsicum anthrax trichobacteria after the cooling, then in 25 ℃ of thermostat containers, cultivate, measure respectively the colony diameter (each bacterium colony is measured 2 times by the right-angled intersection method, represents the bacterium colony size with its mean number) of cultivating 24 h, 48 h, repeat 3 times, get its mean value.Length and control group according to bacterium colony expansion diameter compare, and obtain relative inhibition percentage, see Table 2.
Relative inhibition (%)=
* 100 %.
The chemical structure of table 1 part typical compound, productive rate, Click reaction times
Table 2 part typical compound is to the former bacterium of wheat hypochnus and the test of capsicum anthrax trichobacteria inhibiting rate bacteriostatic activity
The concentration of 8 kinds of effective ingredients is 0.5mg/ml in the table.
Above embodiment has described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; under the scope that does not break away from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (5)
1. have the Isosorbide-5-Nitrae-benzoxazinone-1,2 of anti-mycotic activity, the 3-triazole compound is characterized in that: described Isosorbide-5-Nitrae-benzoxazinone-1,2, and the structural formula of 3-triazole compound is:
, wherein X is halogen atom, alkoxyl group, alkyl, NO
2, OH, H or CF
3, Y is O or S, R is H, Cl, Br, NO
2Or OH.
2. one kind claimed in claim 1ly has 1 of an anti-mycotic activity, 4-benzoxazinone-1,2, the preparation method of 3-triazole compound, it is characterized in that comprising the following step that is collectively referred to as: step 1, Isosorbide-5-Nitrae-benzoxazinone and end-group alkyne compounds are formed Isosorbide-5-Nitrae-benzoxazinone end-group alkyne compounds through alkylation, wherein the ratio of the amount of substance of each raw material is n(1, the 4-benzoxazinone): n(end-group alkyne compounds)=1:1.4; Step 2, with step 1 obtain 1,4-benzoxazinone end-group alkyne compounds makes 1 with phenylazide or replacement phenylazide through the Click reaction at normal temperatures, 4-benzoxazinone-1,2,3-triazole compound, wherein the ratio of the amount of substance of each raw material is n(1,4-benzoxazinone end-group alkyne compounds): n(phenylazide or replacement phenylazide)=1:1.5, used catalyzer is cuprous chloride-anhydrous sodium acetate, and solvent is water, and the time of Click reaction is 24 hours.
3. has 1 of an anti-mycotic activity according to claim 2 is described, 4-benzoxazinone-1,2, the preparation method of 3-triazole compound is characterized in that: cuprous chloride is the n(cuprous chloride with the ratio of the amount of substance of anhydrous sodium acetate in the described catalyzer): the n(anhydrous sodium acetate)=1 ~ 1.5:1.
4. describedly has 1 of an anti-mycotic activity according to claim 2 or 3,4-benzoxazinone-1,2, the preparation method of 3-triazole compound is characterized in that: cuprous chloride is the n(cuprous chloride with the ratio of the amount of substance of anhydrous sodium acetate in the described catalyzer): the n(anhydrous sodium acetate)=1.2:1.
5. Isosorbide-5-Nitrae-benzoxazinone claimed in claim 1-1,2, the purposes of 3-triazole compound is characterized in that: described Isosorbide-5-Nitrae-benzoxazinone-1,2,3-triazole compound can be used for the control because of the animals and plants disease due to the fungi.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310005914.2A CN103059010B (en) | 2013-01-08 | 2013-01-08 | Isosorbide-5-Nitrae-benzoxazinone-1,2,3-triazole compound with anti-mycotic activity and preparation method thereof |
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| CN104892630A (en) * | 2015-05-22 | 2015-09-09 | 河南科技大学第一附属医院 | 1,4-benzoxazine-1,2,3-triazole compound as well as synthesis method and application thereof |
| CN107325112A (en) * | 2017-06-05 | 2017-11-07 | 毛琳琳 | 2H benzos [the b] [preparation method of 1,4] oxazines and pyrazole compound with antihepatitic activity |
| CN107417633A (en) * | 2017-05-31 | 2017-12-01 | 河南师范大学 | The method that copper acetate/hydroxylamine hydrochloride/sodium acetate catalyst system and catalyzing catalyzes and synthesizes 1,2,3 triazole compounds |
| CN109761968A (en) * | 2018-12-25 | 2019-05-17 | 河南师范大学 | Paeonol with anti-tumor activity and benzoxazine compounds and its preparation method and application |
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| CN107417633A (en) * | 2017-05-31 | 2017-12-01 | 河南师范大学 | The method that copper acetate/hydroxylamine hydrochloride/sodium acetate catalyst system and catalyzing catalyzes and synthesizes 1,2,3 triazole compounds |
| CN107325112A (en) * | 2017-06-05 | 2017-11-07 | 毛琳琳 | 2H benzos [the b] [preparation method of 1,4] oxazines and pyrazole compound with antihepatitic activity |
| CN109761968A (en) * | 2018-12-25 | 2019-05-17 | 河南师范大学 | Paeonol with anti-tumor activity and benzoxazine compounds and its preparation method and application |
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