CN113651760A - Pyrimidine selenium benzoic acid derivative, preparation method thereof and application of pyrimidine selenium benzoic acid derivative as herbicide - Google Patents
Pyrimidine selenium benzoic acid derivative, preparation method thereof and application of pyrimidine selenium benzoic acid derivative as herbicide Download PDFInfo
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Abstract
The invention belongs to the technical field of herbicides, and particularly relates to a pyrimidine selenium benzoic acid derivative, a preparation method thereof and application thereof as a herbicide. The compound is obtained by diazotizing aminobenzoic acid and nucleophilic substitution with sodium selenide to form a diselenide bisbenzoic acid intermediate, and then condensing the diselenide bisbenzoic acid intermediate with 4, 6-dimethoxy-2-methylsulfonyl pyrimidine. The compound is at 45g a.i./hm2Can effectively prevent and treat gramineous weeds and broadleaf weeds such as barnyard grass, purslane, eleusine indica, green bristlegrass and the like, is environment-friendly, has low toxicity and high safety to crop cotton, can be used as a candidate herbicide for a cotton field, and achieves the aim of improving the yield and the quality of crops.
Description
Technical Field
The invention belongs to the technical field of herbicides, and particularly relates to a pyrimidine selenium benzoic acid derivative, a preparation method thereof and application thereof as a herbicide.
Background
With the emergence of the pyrimidine salicylic acid herbicide, the herbicide has high efficiency, broad spectrum, short residual period in soil and less harm to crops and animals, and is widely used, but with the wide use of the pyrimidine salicylic acid herbicide, the field weeds also generate great drug resistance.
Disclosure of Invention
Aiming at the drug resistance of field weeds to the existing salicylic acid herbicides, selenium with bactericidal and anticancer functions is introduced into the main structure of the pyrithiobac-sodium, a class of 2- ((4, 6-dimethoxypyrimidine) seleno) -benzoic acid compounds are designed, systematic bioactivity evaluation and screening are performed, high-herbicidal-activity and low-toxicity compounds are provided, and compared with the herbicides of the previous class, the herbicide composition is safer for paddy fields and cotton field crops.
The selenium element is introduced for the first time, and the developed novel selenium herbicide has the characteristics of novel structure, high biological activity, low toxicity and strong selectivity, can be used for preventing and removing weeds, can enter the bodies of crops after being degraded, and achieves the purpose of improving the yield and quality of the crops.
An object of the present invention is to provide a novel pyrimidine selenobenzoic acid compound having high herbicidal activity, which has high herbicidal activity.
In order to realize the purpose, the invention adopts the following technical scheme: a novel pyrimidine selenium benzoic acid compound has a chemical structural formula shown as the following general formula (I):
R＝4-Cl、5-Cl、4-F、5-F、4,5-2F、4-OMe、4,5-2OMe、4-Br、5-Me、4,5-Me。
the novel pyrimidine selenium benzoic acid compound with high herbicidal activity has the following chemical name and chemical structural formula:
a: 2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
B: 4-chloro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
C5-chloro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4-fluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
E5-fluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-difluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
G is 4-methoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-dimethoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
I4-bromo-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
J5-methyl-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-dimethyl-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
Another object of the present invention is to provide a process for preparing a novel pyrimidine selenobenzoic acid compound, which has the reaction formula shown in the following formula:
the preparation method of the pyrimidine selenium benzoic acid compound comprises the following steps:
(1) preparation of substituent bisselenobenzoic acid:
substituted aminobenzoic acid is used as a raw material, water is used as a solvent, sodium nitrite is added under an acidic condition for diazotization, and the diazotization is carried out for later use at a low temperature. The selenium powder is reduced by sodium borohydride with water as solvent, and sodium selenite is prepared by adding sodium hydroxide or potassium hydroxide. Slowly dripping the diazo solution into sodium selenide, reacting for 3 hours at 70 ℃, and then reacting for 5-10 hours at normal temperature to obtain the substituent diselenide dibenzoic acid.
Wherein, the molar ratio of the substituent aminobenzoic acid, the sodium nitrite, the selenium powder, the sodium borohydride, the sodium hydroxide or the potassium hydroxide is as follows: 1: 1.1: 1.8: 4.0: 4.5.
(2) the compound of formula (I) is prepared:
and (2) gradually adding 1M sodium hydroxide solution into the substituent bisselenobenzoic acid compound prepared in the step (1) by taking water as a solvent until the compound is completely dissolved, adding 4, 6-dimethoxy-2-methylsulfonylpyrimidine into the solution by taking sodium borohydride as a reducing agent, condensing, and reacting at normal temperature for 24 hours. And after the reaction is finished, carrying out suction filtration, adjusting the acid of the filtrate, drying, and carrying out column chromatography purification to obtain the compound shown in the formula (I).
Wherein, the molar ratio of substituent bisselenobenzoic acid, 4, 6-dimethoxy-2-methylsulfonyl pyrimidine and sodium borohydride is 1: 2.4: 5.4.
the third purpose of the invention is to provide the application of the pyrimidine selenium benzoic acid compound as herbicide. The herbicide is applied to control weeds such as barnyard grass, goosegrass herb and chenopodium album.
The invention has the advantages that:
the invention provides a novel pyrimidine selenium benzoic acid herbicide, which introduces selenium for the first time, is very effective on weeds such as barnyard grass, goosegrass, chenopodium album and the like, is environment-friendly and low-toxic, and has higher safety to crops.
Detailed Description
The process of the present invention is further illustrated below with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1: preparation of diselenide dibenzoic acid
2-aminobenzoic acid (5.0g, 36.46mmol) and 6M hydrochloric acid (20 mL) are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.76g, 40.10mmol) is dissolved in 15mL water and slowly dropped into the reaction bottle for reaction for 30min, and 2-aminobenzoic acid diazonium salt is obtained. Meanwhile, adding selenium powder (5.18g, 65.63mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (5.52g, 145.84mmol) in 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (6.5g, 164.07mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 2-aminobenzoic acid diazonium salt into a 50mL reaction bottle at the controlled temperature of 5-10 ℃ in a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 6.56g of crude yellow diselenobenzoic acid is obtained with a yield of 90%.
Example 2: preparation of 2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenodibenzoic acid (1g, 2.49mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.51g, 13.44mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.32g, 5.97mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 1.40g of 2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 83% yield.
1H NMR(400MHz,DMSO-d6):δ8.23(dd,J＝8.1,1.1Hz,1H),7.92(dd,J＝7.7,1.6Hz,1H),7.57–7.51(m,1H),7.45–7.37(m,1H),6.03(s,1H),3.80(s,6H).
13C NMR(126MHz,DMSO-d6):δ170.77,168.53,168.20,134.77,132.56,132.42,132.15,130.78,127.60,87.49,54.76.
HRMS:m/z calculated for C13H12N2O4Se([M+H+]):341.0035,found:341.0038.
Example 3: preparation of diselenide bis (4-chlorobenzoic acid)
4-chloro-2-aminobenzoic acid (5.0g, 29.14mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, and sodium nitrite (2.21g, 32.05mmol) is dissolved in 15mL of water and slowly dripped into the reaction bottle to react for 30min, so as to obtain 4-chloro-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.14g, 52.45mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.41g,116.56mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.24g, 131.13mmol), stirring for 15min, and cooling to 5 ℃. 4-chloro-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle is slowly dripped into a 250mL three-necked bottle at the controlled temperature of 5-10 ℃, heated and stirred for reaction for 3 hours, and stirred for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 4.42g of crude yellow diselenide bis (4-chlorobenzoic acid) was obtained in 65% yield.
Example 4: preparation of 4-chloro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4-chlorobenzoic acid) (1g,2.13mmol) was added, 1M sodium hydroxide solution was slowly dropped until the solid just completely dissolved, sodium borohydride (0.44g, 11.50mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.13g, 5.11mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.89g of 4-chloro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 56% yield.
1H NMR(500MHz,DMSO-d6):δ8.69(d,J＝2.1Hz,1H),7.95(d,J＝8.4Hz,1H),7.48(dd,J＝8.4,2.1Hz,1H),6.11(s,1H),3.88(s,6H).
13C NMR(101MHz,DMSO-d6):δ170.21,167.97,167.64,134.22,131.98,131.85,131.60,130.23,127.06,86.93,54.20.
HRMS:m/z calculated for C13H11ClN2O4Se([M+H+]):374.9645,found:374.9646.
Example 5: preparation of diselenide bis (5-chlorobenzoic acid)
5-chloro-2-aminobenzoic acid (5.0g, 29.14mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.21g, 32.05mmol) is dissolved in 15mL of water and slowly dripped into the reaction bottle to react for 30min to obtain the 5-chloro-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.14g, 52.45mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.41g,116.56mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.24g, 131.13mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 5-chloro-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 4.72g of crude yellow diselenide bis (5-chlorobenzoic acid) was obtained in 69% yield.
Example 6: preparation of 5-chloro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (5-chlorobenzoic acid) (1g,2.13mmol) was added, 1M sodium hydroxide solution was slowly dropped until the solid just completely dissolved, sodium borohydride (0.44g, 11.50mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.13g, 5.11mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.92g of 5-chloro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 58% yield.
1H NMR(400MHz,DMSO-d6):δ8.28(d,J＝8.6Hz,1H),7.69(d,J＝8.1Hz,1H),7.64(dd,J＝8.6,2.5Hz,1H),7.54(t,J＝8.0Hz,1H),6.07(s,1H),3.81(s,6H).
13C NMR(126MHz,DMSO-d6):δ170.32,166.84,166.02,135.95,133.29,132.84,132.66,130.60,129.64,128.77,127.87,87.17,54.38.
HRMS:m/z calculated for C13H11ClN2O4Se([M+H+]):374.9645,found:374.9644.
Example 7: preparation of diselenide bis (4-fluorobenzoic acid)
4-fluoro-2-aminobenzoic acid (5.0g, 32.23mmol) and 6M hydrochloric acid (20 mL) are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.45g, 35.45mmol) is dissolved in 15mL water and slowly dripped into the reaction bottle to react for 30min to obtain 4-fluoro-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.58g, 58.01mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.88g,128.92mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.80g, 145.04mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 4-fluoro-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 5.34g of brown crude diselenide bis (4-fluorobenzoic acid) was obtained in a yield of 76%.
Example 8: preparation of 4-fluoro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4-fluorobenzoic acid) (1g,2.29mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.47g, 12.38mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.21g, 5.50mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.99g of 4-fluoro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 61% yield.
1H NMR(500MHz,DMSO-d6):δ8.48(dd,J＝10.6,2.6Hz,1H),8.02(dd,J＝8.7,6.2Hz,1H),7.28–7.14(m,1H),6.07(s,1H),3.86(s,6H).
13C NMR(126MHz,DMSO-d6):δ170.70,167.65,165.01,163.01,133.52(d,J＝9.2Hz),127.34,119.76(d,J＝26.0Hz),116.03(d,J＝21.7Hz),114.19(d,J＝21.8Hz),87.90,54.82.
19F NMR(471MHz,DMSO-d6):δ-107.33.
HRMS:m/z calculated for C13H11FN2O4Se:[M+H+]358.9941,found 358.9945.
Example 9: preparation of diselenide bis (5-fluorobenzoic acid)
5-fluoro-2-aminobenzoic acid (5.0g, 32.23mmol) and 6M hydrochloric acid (20 mL) are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.45g, 35.45mmol) is dissolved in 15mL water and slowly dripped into the reaction bottle to react for 30min to obtain 5-fluoro-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.58g, 58.01mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.88g,128.92mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.80g, 145.04mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 5-fluoro-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. The yellow-green crude product diselenide bis (5-fluorobenzoic acid) 5.20g is obtained, and the yield is 74 percent.
Example 10: preparation of 5-fluoro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (5-fluorobenzoic acid) (1g,2.29mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.47g, 12.38mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.21g, 5.50mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.90g of 5-fluoro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 55% yield.
1H NMR(500MHz,DMSO-d6):δ8.23(dd,J＝8.8,5.5Hz,1H),7.68(dd,J＝9.3,3.0Hz,1H),7.53–7.40(m,1H),6.03(s,1H),3.79(s,6H).
13C NMR(75MHz,DMSO-d6):δ170.79,168.07,167.47(d,J＝2.5Hz),163.06,159.80,137.66(d,J＝7.7Hz),135.29(d,J＝7.0Hz),126.79(d,J＝3.4Hz),119.37(d,J＝21.3Hz),117.21(d,J＝23.2Hz),87.43,54.79.
19F NMR(471MHz,DMSO-d6):δ-114.30.
HRMS:m/z calculated for C13H11FN2O4Se([M+H+]):358.9941,found:358.9941.
Example 11: preparation of diselenide bis (4, 5-difluorobenzoic acid)
4, 5-difluoro-2-aminobenzoic acid (5.0g, 28.88mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.19g, 31.77mmol) is dissolved in 15mL of water and slowly dropped into the reaction bottle to react for 30min to obtain 4, 5-difluoro-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.11g, 51.98mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.37g,115.52mmol) into 20mL water, slowly dropping into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution reacts to be colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.80g, 145.04mmol), stirring for 15min, and cooling to 5 ℃.4, 5-difluoro-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle is slowly dripped into a 250mL three-necked bottle at the controlled temperature of 5-10 ℃, heated and stirred for reaction for 3 hours, and stirred for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 4.90g of crude orange diselenide bis (4, 5-difluorobenzoic acid) was obtained in a yield of 72%.
Example 12: preparation of 4, 5-difluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4, 5-difluorobenzoic acid) (1g,2.12mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.43g, 11.44mmol) was added under nitrogen to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.12g, 5.09mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.80g of 4, 5-difluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 50% yield.
1H NMR(400MHz,DMSO-d6):δ8.66(dd,J＝12.1,7.9Hz,1H),7.94(dd,J＝11.0,8.2Hz,1H),6.07(s,1H),3.85(s,6H).
13C NMR(126MHz,DMSO-d6):δ170.72,167.66,166.78,152.52(d,J＝12.6Hz),150.51(d,J＝12.6Hz),149.09(d,J＝12.8Hz),147.12(d,J＝13.3Hz),130.63,128.72,122.40(d,J＝21.5Hz),119.85(d,J＝18.5Hz),92.53,87.85,54.85.
19F NMR(471MHz,DMSO-d6):δ-132.46(d,J＝22.7Hz),-139.25(d,J＝22.6Hz).
HRMS:m/z calculated for C13H10F2N2O4Se([M+H+]):376.9847,found:376.9844.
Example 13: preparation of diselenide di (4-methoxybenzoic acid)
4-methoxy-2-aminobenzoic acid (5.0g, 29.91mmol) and 6M hydrochloric acid (20 mL) are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.27g, 32.90mmol) is dissolved in 15mL water and slowly dripped into the reaction bottle to react for 30min to obtain 4-methoxy-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.25g, 53.84mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.53g,119.64mmol) in 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.38g, 134.60mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 4-methoxy-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 5.57g of crude yellow diselenide (4-methoxybenzoic acid) was obtained in a yield of 81%.
Example 14: preparation of 4-methoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4-methoxybenzoic acid) (1g,2.17mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.44g, 11.73mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.15g, 5.21mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 1.12g of 4-methoxy-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 70% yield.
1H NMR(400MHz,DMSO-d6):δ7.95(d,J＝2.5Hz,1H),7.86–7.75(m,1H),6.74(dd,J＝8.6,2.5Hz,1H),6.03(s,1H),3.87(s,6H),3.72(s,3H).
13C NMR(126MHz,DMSO-d6):δ170.85,170.06,159.58,135.09,131.47,115.91,113.04,110.17,86.50,55.19,54.18,21.84.
HRMS:m/z calculated for C14H14N2O5Se([M+H+]):371.0141,found:371.0147.
Example 15: preparation of diselenide di (4, 5-dimethoxybenzoic acid)
4, 5-dimethoxy-2-aminobenzoic acid (5.0g, 25.36mmol) and 6M hydrochloric acid (20 mL) are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (1.92g, 27.89mmol) is dissolved in 15mL water and slowly dropped into the reaction bottle to react for 30min to obtain 4, 5-dimethoxy-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (3.61g, 45.65mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (3.83g,101.04mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (4.56g, 114.12mmol), stirring for 15min, and cooling to 5 ℃.4, 5-dimethoxy-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle is slowly dripped into a 250mL three-necked bottle at the controlled temperature of 5-10 ℃, heated and stirred for reaction for 3 hours, and stirred for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 5.07g of yellow green crude diselenide bis (4, 5-dimethoxybenzoic acid) is obtained with a yield of 77%.
Example 16: preparation of 4, 5-dimethoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4, 5-dimethoxybenzoic acid) (1g,1.92mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.39g, 10.38mmol) was added under nitrogen to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.01g, 4.61mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.92g of 4, 5-dimethoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 60% yield.
1H NMR(500MHz,DMSO-d6):δ7.71(d,J＝1.7Hz,1H),7.47(d,J＝1.2Hz,1H),6.04(s,1H),3.82(s,3),3.81(s,6H),3.80(s,3H).
13C NMR(126MHz,DMSO-d6):δ170.87,168.87,168.01,151.60,147.94,124.70,124.56,117.51,113.45,87.17,56.28,55.99,54.73.
HRMS:m/z calculated for C15H16N2O6Se([M+H+]):401.0246,found:401.0244.
Example 17: preparation of diselenide di (4-bromobenzoic acid)
4-bromo-2-aminobenzoic acid (5.0g, 23.14mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (1.76g, 25.46mmol) is dissolved in 15mL of water and slowly dropped into the reaction bottle to react for 30min to obtain 4-bromo-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (3.29g, 41.65mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (3.50g,92.56mmol) into 20mL water, slowly dropping into the selenium powder water solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution reacts to be colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (4.17g, 101.13mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 4-bromo-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 5.10g of crude yellow diselenide bis (4-bromobenzoic acid) was obtained in 79% yield.
Example 18: preparation of 4-bromo-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4-bromobenzoic acid) (1g,1.79mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.36g, 9.68mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (0.95g, 4.30mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.78g of 4-bromo-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 52% yield.
1H NMR(500MHz,DMSO-d6):δ8.83(d,J＝2.0Hz,1H),7.87(d,J＝8.4Hz,1H),7.61(dd,J＝8.4,2.0Hz,1H),6.09(s,1H),3.88(s,6H).
13C NMR(126MHz,DMSO-d6):δ170.66,167.88,167.78,136.02,135.44,132.75,130.31,130.13,126.30,88.06,54.90.
HRMS:m/z calculated for C13H11BrN2O4Se([M+H+]):418.9140,found:418.9131.
Example 19: preparation of diselenide di (5-methylbenzoic acid)
5-methyl-2-aminobenzoic acid (5.0g, 33.08mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, and sodium nitrite (2.51g, 36.38mmol) is dissolved in 15mL of water and slowly dropped into the reaction bottle to react for 30min, so as to obtain the 5-methyl-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.11g, 59.54mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.99g,132.12mmol) in 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.95g, 148.86mmol), stirring for 15min, and cooling to 5 ℃. Slowly dropping 5-methyl-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle at the controlled temperature of 5-10 ℃ into a 250mL three-necked bottle, heating and stirring for reaction for 3 hours, and stirring for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 6.02g of crude yellow diselenide bis (5-methylbenzoic acid) was obtained in 85% yield.
Example 20: preparation of 5-methyl-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (5-methylbenzoic acid) (1g,2.34mmol) was added, 1M sodium hydroxide solution was slowly added dropwise until the solid just completely dissolved, sodium borohydride (0.48g, 12.61mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.24g, 5.62mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 1.06g of 5-methyl-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 64% yield.
1H NMR(300MHz,DMSO-d6):δ8.09(d,J＝8.2Hz,1H),7.76–7.71(m,1H),7.42–7.32(m,1H),6.04(s,1H),3.80(s,6H),2.34(s,3H).
13C NMR(75MHz,DMSO-d6):δ170.75,168.59,137.30,134.88,132.89,132.56,131.16,128.64,87.34,54.77,20.84.
HRMS:m/z calculated for C14H14N2O4Se([M+H+]):355.0192,found:355.0193.
Example 21: preparation of diselenide di (4, 5-dimethyl benzoic acid)
4, 5-dimethyl-2-aminobenzoic acid (5.0g, 30.27mmol) and 20mL of 6M hydrochloric acid are added into a 50mL reaction bottle, cooled to 0 ℃, sodium nitrite (2.30g, 33.29mmol) is dissolved in 15mL of water and slowly dripped into the reaction bottle to react for 30min to obtain 4, 5-dimethyl-2-aminobenzoic acid diazonium salt. Meanwhile, adding selenium powder (4.30g, 54.49mmol) into a 250mL three-neck flask, adding 40mL water, dissolving sodium borohydride (4.58g,121.08mmol) into 20mL water, slowly dropping the solution into the selenium powder aqueous solution under the protection of nitrogen through a constant-pressure dropping funnel until the solution is colorless and transparent, stirring at normal temperature for 30min, adding sodium hydroxide (5.45g, 136.22mmol), stirring for 15min, and cooling to 5 ℃.4, 5-dimethyl-2-aminobenzoic acid diazonium salt in a 50mL reaction bottle is slowly dripped into a 250mL three-necked bottle at the controlled temperature of 5-10 ℃, heated and stirred for reaction for 3 hours, and stirred for reaction for 5 hours at normal temperature. After the reaction is finished, adding HCl, and filtering and drying after the solid is completely separated out. 5.52g of crude yellow diselenide bis (4, 5-dimethylbenzoic acid) was obtained in 80% yield.
Example 22: preparation of 3, 4-dimethyl-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
In a 150mL three-necked flask, diselenide bis (4, 5-dimethylbenzoic acid) (1g,2.19mmol) was added, 1M sodium hydroxide solution was slowly dropped until the solid just completely dissolved, sodium borohydride (0.45g, 11.83mmol) was added under nitrogen protection to generate a large amount of gas, and after stirring for 10min, 4, 6-dimethoxy-2-methanesulfonylpyrimidine (1.16g, 5.26mmol) was added and stirred at room temperature for 24 h. And after the reaction is finished, adding HCl, filtering and drying when the solid is completely separated out. Purification by column chromatography (dichloromethane: methanol ═ 80:1) gave 0.72g of 3, 4-dimethyl-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid as a yellow solid powder in 45% yield.
1H NMR(500MHz,DMSO-d6):δ7.43(d,J＝7.7Hz,1H),7.31(d,J＝7.8Hz,1H),5.93(s,1H),3.64(s,6H),2.37(s,3H),2.33(s,3H).
13C NMR(126MHz,DMSO-d6):δ170.76,169.88,168.50,142.41,140.15,137.88,130.71,127.68,126.17,86.51,54.32,21.65,20.79.
HRMS:m/z calculated for C15H16N2O4Se([M+H+]):369.0348,found:369.0349.
Example 23: herbicidal Activity test
The pyrimidine selenium benzoic acid herbicide has good herbicidal activity, can be used as an effective active ingredient of the herbicide and is used for preparing various pesticides.
The results of the herbicidal activity test of the herbicide of the present invention are as follows:
1. preparation of pharmaceutical agents
10mg of pyrimidine selenium benzoic acid compound is weighed by a ten-thousandth analytical balance, dissolved by DMSO and diluted to 10mg/L by 0.1% Tween 80 aqueous solution.
2. Experiment design:
selecting a clean culture dish, attaching 2 pieces of filter paper, respectively adding 5mL of liquid medicines with series concentrations, soaking 10 test seeds with consistent germination in the liquid medicines, then placing the test seeds in an incubator, controlling the temperature at 25 ℃, the humidity at 80-90% and culturing for 3d in a dark environment. After 3d, the inhibition rate was calculated by directly measuring the root length of each treated weed, with no less than 3 replicates per treatment.
The seeds selected for use are as follows in sequence: barnyard grass, goosegrass herb, green bristlegrass herb, purslane, chenopodium album and amaranthus retroflexus.
And (3) calculating an inhibition rate: (control root length-treatment group root length)/control root length X100%
Pyrithiobac-sodium was used as a positive control. Water was used as a control.
From the table, it can be seen that the pyrimidine selenium benzoic acid compound has good activity inhibition effect on weeds such as barnyard grass, eleusine indica, purslane and the like at the concentration of 10 mg/L. The effect on eleusine indica is slightly worse than barnyard grass and purslane. The compound B, D, G, I has obviously better inhibition effect than other compounds, and has better effect than the pyrithiobac-sodium.
In the process of activity experiments, the compound containing fluorine, chlorine and bromine groups is found to have better effect than the compound containing methyl and methoxy, and meanwhile, the compound containing the groups at the para position of carboxyl has slightly better weeding effect than the compound containing the meta groups. The herbicide shows a superior herbicidal effect to the pyrithiobac-sodium herbicide.
Example 24: toxicity test of cotton field and paddy field
The safety experiment of the pyrimidine selenium benzoic acid as herbicide on cotton and rice crops is as follows:
1. preparation of pharmaceutical agents
Weighing pyrimidine selenium benzoic acid compound with ten-thousandth balance, dissolving with DMSO, and diluting with 0.1% Tween 80 water solution to obtain 100g a.i./hm2.
2. Experiment design:
the herbicide developed by the invention is used for carrying out crop safety research, and five cotton seeds are sown in the soil. The cotton seeds are treated with the drug at the 3-4 leaf stage. The distilled water group was used as a control group. The plant height of the crops is measured 21 days after the treatment, and the safety of the medicament to the crops is evaluated according to the damage inhibition degree and the plant height.
The rice experiment is carried out in water without soil, and the steps are the same. Water was used as a control.
From the above table results, it can be seen that the measured value is 100g a.i./hm2At concentrations of (a) and (b), the pyrimidine selenobenzoic acid compounds have a lower inhibitory effect on the activity of cotton and rice, compared with that of cotton, the compounds have a slightly higher inhibitory effect on rice than on cotton, and the compounds have a lower inhibitory effect on cotton and rice than pyrithiobac. The experimental results show that the compounds A-K can be used as safer herbicides to act on paddy fields and cotton fields.
Example 25: acetolactate synthase Activity assay
The main action target of the pyrimidine salicylic acid herbicide is acetolactate synthase. The acetolactate synthase can efficiently catalyze the conversion of pyruvic acid into acetolactate, and is an important synthetic element of branched chain amino acid. The acetolactate synthetase inhibitory effect of the compound is judged by detecting the activity of the acetolactate synthetase in escherichia coli.
1. Preparation of pharmaceutical preparations
0.5M phosphate buffer, 0.1M MgCl2Solution, 0.2M sodium pyruvate solution, 0.4N sulfuric acid solution, 0.25N sodium hydroxide solution, 0.5% creatine solution, 5% 1-naphthol solution, 1N sodium hydroxide solution, 10% ZnSO4And toluene.
Preparing a culture medium:
adjusting pH to 7.0 with beef extract 1%, sodium chloride 0.5% and peptone 1%, adding agar 2%, and sterilizing at 250 deg.C for 25 min.
2. Test protocol
An acetylmethylmethanol standard curve was prepared (acetyllactic acid did not react with the above reagents, and the resulting red color was the product of acetylmethylmethanol produced by decarboxylation of acetyllactic acid).
Coli suspensions were prepared by shake-culturing in a compound-free medium at 37 ℃ for 4 hours, and absorbance was measured.
10 of 10mL centrifuge tubes were taken and reagents were added as per the following table, with one repeat each.
(1) Tube 1 is a non-enzymatic control and bacteria are added after the reaction has ended
(2) Tube 2 is an enzymatic control
(3) Tube 3.4.5 is the assay tube.
The test tube is preheated for 15min, 0.2mL of sodium pyruvate is added, the temperature is kept for 30min, 0.2mL of 1M sodium hydroxide and 10% zinc sulfate are added, and the enzymatic reaction is stopped. Centrifuging at 10000rpm for 20 minutes, removing precipitate, sucking 0.5mL, adding 0.4N ammonium sulfate 0.5mL, shaking at constant temperature for 30min, adding 0.25N sodium hydroxide for neutralization, adding 2.5mL of distilled water, 0.5% creatine and 5% alpha-naphthol solution, and measuring absorbance at 520nm after 1 h. Comparing with standard curve of acetylmethylmethanol, calculating content to obtain enzyme activity (decarboxylation of 1 molecule of acetolactate to produce acetylmethylmethanol).
IC calculated from the inhibition of the acetolactate synthase Activity by the respective Compounds50It can be seen that compound B, D, F, I has higher acetolactate synthase inhibitory activity than pyrithiobac-sodium, wherein compound B, D, I also exhibits higher activity than pyrithiobac-sodium in the herbicidal activity test, and has lower inhibitory effect on cotton and rice growth than pyrithiobac-sodium in the safety test. Therefore, compound B, D, I can be further developed as a new candidate compound for herbicides.
Claims (8)
1. A pyrimidine selenium benzoic acid derivative is characterized in that the structural formula of the pyrimidine selenium benzoic acid derivative is shown as the following general formula (I):
wherein, R is 4-Cl, 5-Cl, 4-F, 5-F, 4,5-2F, 4-OMe, 4,5-2OMe, 4-Br, 5-Me and 4, 5-Me.
2. A pyrimidine selenium benzoic acid derivative according to claim 1, wherein the chemical name and chemical formula of the pyrimidine selenium benzoic acid derivative are as follows:
a: 2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
B: 4-chloro-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
C5-chloro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4-fluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
E5-fluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-difluoro-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
G is 4-methoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-dimethoxy-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
I4-bromo-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
J5-methyl-2- ((4,6 dimethoxypyrimidin-2-yl) seleno) benzoic acid
4, 5-dimethyl-2- ((4, 6-dimethoxypyrimidin-2-yl) seleno) benzoic acid
3. The preparation method of the pyrimidine selenium benzoic acid derivative is characterized by comprising the following steps:
(1): preparation of substituent bisselenobenzoic acid: using substituent aminobenzoic acid as a raw material, using water as a solvent, adding sodium nitrite under an acidic condition for diazotization, and keeping the mixture at a low temperature for later use; the selenium powder takes water as a solvent, sodium borohydride is reduced, and alkali is added to prepare sodium selenide; slowly dripping the diazo solution into sodium selenide, reacting for 3 hours at 70 ℃, reacting for 5-10 hours at normal temperature, and processing to obtain substituent bisselenobenzoic acid;
(2): preparation of a Compound of formula (I): and (2) gradually adding a sodium hydroxide solution into the substituent bisselenobenzoic acid compound prepared in the step (1) by taking water as a solvent until the substituent bisselenobenzoic acid compound is completely dissolved, adding 4, 6-dimethoxy-2-methylsulfonyl pyrimidine into sodium borohydride serving as a reducing agent, condensing, reacting at normal temperature for 24 hours, performing suction filtration after the reaction is finished, adjusting the acid of the filtrate, drying, and purifying by column chromatography to obtain the compound shown in the formula (I).
4. The process for producing a pyrimidine selenobenzoic acid derivative according to claim 3, wherein the base in the step (1) is sodium hydroxide or potassium hydroxide.
5. The method for preparing pyrimidine selenobenzoic acid derivatives as claimed in claim 3, wherein the molar ratio of the substituent aminobenzoic acid, the sodium nitrite, the selenium powder, the sodium borohydride and the alkali in the step (1) is as follows: 1: 1.1: 1.8: 4.0: 4.5.
6. the process for producing a pyrimidine selenobenzoic acid derivative as claimed in claim 3, wherein the concentration of sodium hydroxide in the step (2) is 1M.
7. The method for preparing pyrimidine selenobenzoic acid derivatives as claimed in claim 3, wherein the molar ratio of the substituent bisselenobenzoic acid, 4, 6-dimethoxy-2-methylsulfonylpyrimidine and sodium borohydride in step (2) is 1: 2.4: 5.4.
8. use of a pyrimidine selenobenzoic acid derivative according to claim 1, wherein the pyrimidine selenobenzoic acid compound is used as a herbicide.
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