CN103030607B - Thiadiazole-containing amide derivative, and preparation and application thereof as plant growth regulator - Google Patents
Thiadiazole-containing amide derivative, and preparation and application thereof as plant growth regulator Download PDFInfo
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Abstract
The invention provides a new thiadiazole derivative (I) and provides a preparation method and application thereof. The thiadiazole derivative (I) provided by the invention has excellent plant growth regulating activity.
Description
Technical field
The present invention relates to a kind of thiadiazoles derivative and its preparation method and application.
Background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in agricultural chemicals newly developed, more than 90% is all heterocyclic pesticide.In heterogeneous ring compound, again taking nitrogen heterocyclic ring as main.In recent years, plant induced resistance agent thiadinal, research and development success the listing of BTH, caused everybody research to thiadiazole compound.
1,3,4-thiadiazole compound is many classes of Recent study, and many commercial desinsections, sterilization, weedicide belong to such.As shown in the formula structure for exploitation some there is weeding, sterilization, 1,3 of insecticidal effect, 4-thiadiazole compound.
Summary of the invention
The object of the present invention is to provide a kind of new thiadiazoles derivative (I), and its preparation method and application are provided, thiadiazoles derivative provided by the invention (I) has excellent plant-growth activity.
The technical solution used in the present invention is as follows:
A kind of suc as formula the thiadiazoles derivative shown in I:
I
In formula I, R is the phenyl replacing, alkyl, furyl etc.
The present invention also provides the preparation method of the thiadiazoles derivative shown in formula I:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, adds solution C, and described solution C is that the 5-shown in formula IV replaces-1, and 3,4-thiadiazoles-2-aminated compounds is dissolved in organic solvent C and obtains, and then under 60 degree, refluxes 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, obtains thiadiazoles derivative (I) with ethyl alcohol recrystallization; Described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride; Described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, preferably tetrahydrofuran (THF); The ratio of the amount of substance of the aminated compounds shown in the chloride compounds shown in described formula II, formula IV is 1:1;
In formula IV, R is the phenyl replacing, furyl etc.
The reaction equation of described reaction is as follows:
In described method, described reaction solution method for separating and processing is: after reaction finishes, cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, obtains thiadiazoles derivative (I) with ethyl alcohol recrystallization.
The consumption of described organic solvent A is counted 1 ~ 3mL/mmol with the amount of substance of the acyl chlorides shown in formula II, preferably 1.1 mL/mmol.
The consumption of described organic solvent C replaces-1 with the 5-shown in formula IV, and the amount of substance of 3,4-thiadiazoles-2-aminated compounds is counted 0.5 ~ 1mL/mmol, preferably 1.0 mL/mmol.
Comparatively concrete, the preparation method of the thiadiazoles derivative shown in described formula I (I) carries out according to the following steps:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, adds the 5-shown in formula IV to replace-1, and 3,4-thiadiazoles-2-aminated compounds is dissolved in the solution C obtaining in organic solvent C, then under 60 degree, refluxes 5 hours.After reaction finishes, cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, obtains thiadiazoles derivative (I) with ethyl alcohol recrystallization; Described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride; Described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride; 5-shown in formula IV replaces-1, and the ratio of the amount of substance of 3,4-thiadiazoles-2-aminated compounds is 1:1.
In the inventive method, the chloride compounds shown in formula II can prepare by the following method: the compound shown in formula V and SOCl
2carry out chlorination reaction and obtain the chloride compounds shown in formula II, this is to well known to a person skilled in the art preparation method.
5-shown in described formula IV replaces-1, and 3,4-thiadiazoles-2-aminated compounds prepares by the following method, and these methods those skilled in the art all can obtain by existing document:
5-replaces-1,3,4-thiadiazoles-2-amine: the carboxylic acid of replacement and thiosemicarbazide join in phosphorus oxychloride, under reflux state, stir 5h, then reactant is poured in frozen water, suction filtration obtains above-claimed cpd, by above-claimed cpd recrystallization in the mixed solvent of DMF and water, obtains purer above-claimed cpd.
Thiadiazoles derivative shown in formula I of the present invention can be applied as plant-growth regulator, concrete, and described thiadiazoles derivative (I) can be used as the plant-growth regulator that cucumber cotyledons is taken root.
More specifically, described compound is as the application of sterilant, it is characterized in that the plant-growth regulator that described compound is taken root for cucumber cotyledons, wherein R is (2,4 dichloro benzene oxygen base) methyl, furyl, a tolyl, Chloro-O-Phenyl, o-methyl-phenyl-, adjacent fluorophenyl, rubigan, phenyl, p-nitrophenyl, p-methoxyphenyl.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Be prepared as follows raw material:
Described 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid makes by the following method:
Diethyl carbonate mixes than 1:0.95 by amount of substance with 85% hydrazine hydrate, at 50 DEG C, reflux 20 minutes, then stir 30 hours at 25 DEG C, remove methyl alcohol, water and a small amount of complete diethyl carbonate of unreacted under reduced pressure, obtain colourless transparent liquid, obtain the carbazic acid ethyl ester in formula 1;
Carbazic acid ethyl ester shown in formula 1 mixes with amount of substance 1:1 with methyl aceto acetate, and in alcohol solvent, stirring at normal temperature 6 hours, removes ethanol under reduced pressure, obtains white solid, is the 3-methoxycarbonyl hydrazone ethyl butyrate shown in formula 2;
3-methoxycarbonyl hydrazone ethyl butyrate shown in formula 2 and excessive thionyl chloride, taking methylene dichloride as solvent, stirring at room temperature 20 hours, under normal pressure, boil off excessive thionyl chloride, then underpressure distillation, collects 400Pa, the faint yellow cut of 76-78 DEG C, make the 4-methyl isophthalic acid shown in formula 3,2,3-thiadiazoles-5-ethyl formate.
4-methyl isophthalic acid shown in formula 3,2,3-thiadiazoles-5-ethyl formate and excessive sodium hydroxide, taking anhydrous methanol as solvent, stirring at room temperature 24 hours, under normal pressure, boil off anhydrous methanol, then by dissolution of solid in water, drip concentrated hydrochloric acid, there is faint yellow solid, make the 4-methyl isophthalic acid shown in formula 4,2,3-thiadiazoles-5-formic acid.
1.0 g4-methyl isophthalic acids, 2,3-thiadiazoles-5-formic acid and 10 mL SOCl
2under the condition of reflux, carry out chlorination reaction, after finishing, reaction under water pump reduced pressure, steams excessive thionyl chloride, obtain 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl chloride.
5-replaces-1,3,4-thiadiazoles-2-amine: the carboxylic acid of replacement and thiosemicarbazide join in phosphorus oxychloride, under reflux state, stir 5h, then reactant is poured in frozen water, suction filtration obtains above-claimed cpd, by above-claimed cpd recrystallization in the mixed solvent of DMF and water, obtains purer above-claimed cpd.
Above-mentioned preparation can be done several pots more, makes raw material for the following example.
Example 1: suc as formula I, R is the preparation of the thiadiazole compound of (2,4 dichloro benzene oxygen base) methyl
In 100mL round-bottomed bottle by 10mmol (2,4-dichlorophenoxy) methyl)-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 82.6 %, fusing point 150-153 DEG C;
1h NMR:9.96 (s, 1H, NH), 7.10-8.42 (m, 3H, ph), 5.19 (s, 2H, CH
2o), 2.90 (s, 3H, CH
3); IR (KBr) ν cm
-1: 1296 (C=S), 1680 (C=O), 3161,3334 (N-H); ESI-MS:460 (M-1); Anal. calcd. For C
14h
10cl
2n
6o
2s
3: C 36.45, H 2.18, N 18.22; Found:C 36.56, H 2.51, N 18.23.
Example 2: suc as formula I, the preparation of the thiadiazole compound that R is furyl
In 100mL round-bottomed bottle by 10mmol furyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 85.9 %, fusing point %:215-216 DEG C;
1h NMR:11.91 (s, 1H, NH), 7.66 (d,
j=5.31Hz, 1H, C
4h
3o-CH), 7.34 (d,
j=3.55Hz, 1H, C
4h
3o-CH), 7.19 (d,
j=3.52Hz, 1H, C
4h
3o-CH), 3.08 (s, 3H, CH
3); ESI-MS:292 (M-1); Anal. calcd. For C
10h
7n
5o
2s
2: C 40.95, H 2.41, N 23.88; Found:C 41.10, H 2.55, N 23.62.
Example 3: suc as formula I, R is the preparation of the thiadiazole compound of an aminomethyl phenyl
In 100mL round-bottomed bottle by 10mmol between aminomethyl phenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 83.8 %; Fusing point: 232-233 DEG C;
1h NMR:11.92 (s, 1H, NH), 7.69-7.73 (m, 1H, ArH), 7.34-7.44 (m, 3H, ArH), 3.06 (s, 3H, Het-CH
3), 2.46 (s, 3H, Ar-CH
3); ESI-MS:317 (M-1); Anal. calcd. For C
13h
11n
5oS
2: C 49.19, H 3.49, N 22.07; Found:C 49.43, H 3.81, N 21.89.
Example 4: suc as formula I, the preparation of the thiadiazole compound that R is Chloro-O-Phenyl
In 100mL round-bottomed bottle by 10mmol Chloro-O-Phenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 85.8 %; Fusing point: 210-211 DEG C;
1h NMR:11.96 (s, 1H, NH), 7.57-7.62 (m, 2H, ArH), 7.46-7.53 (m, 2H, ArH), 3.00 (s, 3H, CH
3); ESI-MS:337 (M-1); Anal. calcd. For C
12h
8clN
5oS
2: C 42.67, H 2.39, N 20.73; Found:C 42.65, H 2.48, N 20.66.
Example 5: suc as formula I, the preparation of the thiadiazole compound that R is adjacent fluorophenyl
In 100mL round-bottomed bottle by adjacent 10mmol fluorophenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 88.9 %; Fusing point: 200-201 DEG C;
1h NMR:11.94 (s, 1H, NH), 7.57-7.48 (m, 2H, ArH), 7.30-7.39 (m, 2H, ArH), 2.96 (s, 3H, CH
3); ESI-MS:320 (M-1); Anal. calcd. For C
12h
8fN
5oS
2: C 44.85, H 2.51, N 21.79; Found:C 44.91, H 2.56, N 21.44.
Example 6: suc as formula I, the preparation of the thiadiazole compound that R is o-methyl-phenyl-
In 100mL round-bottomed bottle by 10mmol o-tolyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 87.6 %; Fusing point: 189-190 DEG C;
1h NMR:11.98 (s, 1H, NH), 7.64-7.70 (m, 1H, ArH), 7.53-7.57 (m, 1H, ArH), 7.35-7.45 (m, 2H, ArH), 3.06 (s, 3H, CH
3), 2.64 (s, 3H, CH
3); ESI-MS:316 (M-1); Anal. calcd. For C
13h
11n
5oS
2: C 49.19, H 3.49, N 22.07; Found:C 48.96, H 3.56, N 22.44.
Example 7: suc as formula I, the preparation of the thiadiazole compound that R is rubigan
In 100mL round-bottomed bottle by 10mmol rubigan-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 88.2 %; Fusing point: 260-261 DEG C;
1h NMR:11.58 (s, 1H, NH), 7.92-8.07 (m, 2H, ArH), 7.47-7.56 (m, 2H, ArH), 3.02 (s, 3H, CH
3); ESI-MS:337 (M-1); Anal. calcd. For C
12h
8clN
5oS
2: C 42.67, H 2.39, N 20.73; Found:C 42.99, H 2.56, N 20.45.
Example 8: suc as formula I, the preparation of the thiadiazole compound that R is phenyl
In 100mL round-bottomed bottle by 10mmol 5-phenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 85.4 %; Fusing point: 206-207 DEG C;
1h NMR:11.83 (s, 1H, NH), 7.90-7.92 (m, 2H, ArH), 7.51-7.64 (m, 3H, ArH), 3.03 (s, 3H, CH
3); ESI-MS:302 (M-1); Anal. calcd. For C
12h
9n
5oS
2: C 47.51, H 2.99, N 23.09; Found:C 47.88, H 2.76, N 23.34.
Example 9: suc as formula I, the preparation of the thiadiazole compound that R is p-nitrophenyl
In 100mL round-bottomed bottle by 10mmol 5-p-nitrophenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 87.0 %; Fusing point: 250-251 DEG C;
1h NMR:11.80 (s, 1H, NH), 8.38 (d,
j=8.80Hz, 2H, ArH), 8.10 (d,
j=8.80Hz, 2H, ArH), 3.02 (s, 3H, CH
3); ESI-MS:347 (M-1); Anal. calcd. For C
12h
8n
6o
3s
2: C 41.37, H 2.31, N 24.12; Found:C 41.44, H 2.36, N 24.46.
Example 10: suc as formula I, the preparation of the thiadiazole compound that R is p-methoxyphenyl
In 100mL round-bottomed bottle by 10mmol 5-p-methoxyphenyl-1,3,4-thiadiazoles-2-amido is dissolved in the solution (10 mmol) of 5 mL anhydrous acetonitriles, and triethylamine (10mmol) is dissolved in the tetrahydrofuran (THF) of 30mL, under agitation drip acyl chlorides (11mmol), then under 60 degree, reflux 5 hours.Cooling, suction filtration, is then spin-dried for solvent, and remaining solid washes with water, uses ethyl alcohol recrystallization.
Yellow solid, productive rate 86.5 %; Fusing point: 165-166 DEG C;
1h NMR:11.91 (s, 1H, NH), 7.91 (d,
j=8.86Hz, 2H, ArH), 7.84 (d,
j=8.86Hz, 2H, ArH), 3.89 (s, 3H, CH
3), 3.05 (s, 3H, Het-CH
3); ESI-MS:332 (M-1); Anal. calcd. For C
13h
11n
5o
2s
2: C 46.83, H 3.33, N 21.01; Found:C 46.89, H 3.58, N 21.26.
The plant growth regulating activity of compound
Be made into the test sample solution of 10ppm with 95% ethanol, getting 0.3mL evenly drips on the filter paper dick of 6cm diameter, air-dry or dry up and make ethanol volatilization, in the culture dish that is 6cm at diameter, put into one of the filter paper dick of the above-mentioned test sample that contains various concentration, distilled water 3mL, be the test sample processing that is equivalent to 10ppm, taking the filter paper dick that drips 95% ethanol as contrast.In each culture dish, put into 10 of the in vitro yellow cucumber cotyledons chosen, in darkroom (26
oc) in, cultivate after 5 days, measure the number of taking root of every 10 cotyledon petiole bases, each processing repeats for 4 times.
Table 1. is implemented the plant growth regulating activity (10 ppm, % promotion rate) of compound
Claims (1)
1. the application of a plant-growth regulator of taking root as promotion cucumber cotyledons suc as formula the thiadiazole compound shown in I:
I
In formula I, R is (2,4 dichloro benzene oxygen base) methyl, a tolyl, Chloro-O-Phenyl, adjacent fluorophenyl, rubigan, phenyl, p-nitrophenyl or p-methoxyphenyl.
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Effective date of registration: 20191227 Address after: 225800, Jing Xi Road, Jinghe Town, Baoying County, Yangzhou, Jiangsu Patentee after: Yangzhou Junrui Enterprise Management Co.,Ltd. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20191227 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310014 City Zhaohui District Six Patentee before: Zhejiang University of Technology |