CN101874496B - Application of acyl hydrazone derivative as fungicide - Google Patents
Application of acyl hydrazone derivative as fungicideDownload PDFInfo
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- CN101874496B CN101874496BCN 201010213672CN201010213672ACN101874496BCN 101874496 BCN101874496 BCN 101874496BCN 201010213672CN201010213672CN 201010213672CN 201010213672 ACN201010213672 ACN 201010213672ACN 101874496 BCN101874496 BCN 101874496B
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- 0C*(C)(*)CC(C=C[C@]1C=NNC(c2c(C)nn[s]2)=O)=CC1BrChemical compoundC*(C)(*)CC(C=C[C@]1C=NNC(c2c(C)nn[s]2)=O)=CC1Br0.000description3
- CHLICZRVGGXEOD-UHFFFAOYSA-NCc(cc1)ccc1OCChemical compoundCc(cc1)ccc1OCCHLICZRVGGXEOD-UHFFFAOYSA-N0.000description2
- RZXMPPFPUUCRFN-UHFFFAOYSA-NCc(cc1)ccc1NChemical compoundCc(cc1)ccc1NRZXMPPFPUUCRFN-UHFFFAOYSA-N0.000description1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-NCc(cc1)ccc1[N+]([O-])=OChemical compoundCc(cc1)ccc1[N+]([O-])=OZPTVNYMJQHSSEA-UHFFFAOYSA-N0.000description1
- AONJFAMBTNZWOR-AWNIVKPZSA-NCc1c(C(N/N=C/c(cc2)ccc2Br)=O)[s]nn1Chemical compoundCc1c(C(N/N=C/c(cc2)ccc2Br)=O)[s]nn1AONJFAMBTNZWOR-AWNIVKPZSA-N0.000description1
- NHOVTPHXZHIEEU-AWNIVKPZSA-NCc1c(C(N/N=C/c(cc2)ccc2Cl)=O)[s]nn1Chemical compoundCc1c(C(N/N=C/c(cc2)ccc2Cl)=O)[s]nn1NHOVTPHXZHIEEU-AWNIVKPZSA-N0.000description1
- CEWYFQYMPLYQAL-WUXMJOGZSA-NCc1c(C(N/N=C/c(cc2)ccc2[N+]([O-])=O)=O)[s]nn1Chemical compoundCc1c(C(N/N=C/c(cc2)ccc2[N+]([O-])=O)=O)[s]nn1CEWYFQYMPLYQAL-WUXMJOGZSA-N0.000description1
- ZZTKLOUGZMGEFU-AWNIVKPZSA-NCc1c(C(N/N=C/c(cc2O)ccc2OC)=O)[s]nn1Chemical compoundCc1c(C(N/N=C/c(cc2O)ccc2OC)=O)[s]nn1ZZTKLOUGZMGEFU-AWNIVKPZSA-N0.000description1
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Abstract
Translated fromChineseDescription
(1) technical field
The invention provides a kind of acyl hydrazone derivative as the application of bactericide.
(2) background technology
Heterocyclic compound has been the main flow of novel pesticide development, and in heterocyclic compound, again take nitrogen heterocyclic ring as main.1,2,3 thiadiazole compounds are more rapidly classes of development in recent years, many commercial desinsections, sterilization, weed killer herbicide, and plant induced resistance agent belongs to such.For example, the bactericide tiadinil (thiadinal) with interior absorption of Japan agricultural chemicals company exploitation is mainly used in the control of rice blast, and other diseases such as brown spot, bacterial leaf-blight, banded sclerotial blight and gingili leaf rot etc. are also had preferably control efficiency; The N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole of Nankai University's exploitation has good sterilization and induction of resistance effect.And the induced resistance of plant activiator Bion (BTH) of Novartis Co.,Ltd's exploitation.
Hydrazone class compounds has diversified biologically active.A lot of bibliographical information thiourea derivatives have extensive biologically active, are applied to medicine, pesticide field.Some hydrazone class compounds have developed into commercial agricultural chemicals, pyrimidine hydrazone bactericide (Blasin) such as the exploitation of Japan military field pharmaceutical industries company, rice tail spore on the main control paddy rice, the microbial disease of cause of disease such as the rice blast such as rice Helminthosporium sp. and Magnaporthe grisea.
(3) summary of the invention
The object of the present invention is to provide a kind of 4-methyl isophthalic acid, 2,3-thiadiazoles acyl hydrazone derivative has excellent bactericidal activity.
The invention provides a kind of suc as formula the application of the acyl hydrazone derivative shown in I or the formula (9) as bactericide:
In the formula I, R is mono-substituted substituting group on the phenyl, and described substituting group is methyl, fluorine, chlorine, bromine, methoxyl group, dimethylamino, hydroxyl or nitro.
Comparatively preferred, described R is 4-methyl, 2-bromine, 4-chlorine, 4-fluorine, 3-methoxyl group, 4-dimethylamino, 4-methoxyl group, 4-bromine, 2-fluorine, 4-hydroxyl or 4-nitro.
Described have excellent bactericidal activity suc as formula the acyl hydrazone derivative shown in I or the formula (9), can be used as the application of the bactericide of wheat scab, early blight of tomato, the cercospora brown spot of peanut, ring rot of apple, cucumber Fusarium oxysporum.
Further, the described application that can be used as the bactericide of wheat scab suc as formula the acyl hydrazone derivative shown in I or the formula (9), described is one of shown in following formula (3), formula (4), formula (7), formula (8), formula (9), formula (10) or the formula (12) suc as formula the acyl hydrazone derivative shown in I or the formula (9):
Acyl hydrazone derivative one of shown in preferred described following formula (4), formula (8) or the formula (12) is as the application of the bactericide of wheat scab:
Further, the described application that can be used as the bactericide of early blight of tomato suc as formula the acyl hydrazone derivative shown in I or the formula (9), described is one of shown in following formula (1), formula (2), formula (4), formula (6), formula (7), formula (9), formula (10), formula (11) or the formula (12) suc as formula the acyl hydrazone derivative shown in I or the formula (9):
Acyl hydrazone derivative one of shown in preferred described following formula (1), formula (2) or the formula (11) is as the application of the bactericide of early blight of tomato:
Further, the described application that can be used as the bactericide of the cercospora brown spot of peanut suc as formula the acyl hydrazone derivative shown in I or the formula (9), described is one of shown in following formula (1)～formula (9), formula (11) or the formula (12) suc as formula the acyl hydrazone derivative shown in I or the formula (9):
Acyl hydrazone derivative one of shown in preferred described following formula (2), formula (4), formula (8) or the formula (12) is as the application of the bactericide of the cercospora brown spot of peanut:
Further, the described application that can be used as the bactericide of ring rot of apple suc as formula the acyl hydrazone derivative shown in I or the formula (9), described is one of shown in following formula (1)～formula (12) suc as formula the acyl hydrazone derivative shown in I or the formula (9):
Acyl hydrazone derivative one of shown in preferred described following formula (1)～formula (4), formula (6), formula (7) or the formula (12) is as the application of the bactericide of ring rot of apple:
Further, the described application that can be used as the bactericide of cucumber Fusarium oxysporum suc as formula the acyl hydrazone derivative shown in I or the formula (9), described is one of shown in following formula (3)～formula (12) suc as formula the acyl hydrazone derivative shown in I or the formula (9):
Acyl hydrazone derivative shown in the preferred described following formula (11) is the application as the bactericide of cucumber Fusarium oxysporum:
Of the present inventionly can prepare in accordance with the following methods suc as formula the acyl hydrazone derivative shown in I or the formula (9): the substituted benzaldehyde back flow reaction in ethanol shown in the hydrazide kind compound shown in the formula II and formula III or the formula a, the reaction of TLC tracking and monitoring, usually the reaction time is 1～5 hour, reaction finishes rear suction filtration of afterreaction liquid cooling, get filter cake and make respectively accordingly suc as formula the acyl hydrazone derivative shown in I or the formula (9) with ethyl alcohol recrystallization, the hydrazide kind compound shown in the described formula II is 1: 1～1.1 with the ratio of the amount of substance of the substituted benzaldehyde shown in formula III or the formula a;
In the formula III, R is mono-substituted substituting group on the phenyl, and described substituting group is methyl, fluorine, chlorine, bromine, methoxyl group, dimethylamino, hydroxyl or nitro.
Described preparation method is the known preparation method of acylhydrazone.
Hydrazide kind compound shown in the formula II is the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formylhydrazine can make by the following method: the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate mixes with molar ratio 1: 1～1.1 with hydrazine hydrate (80%), carries out back flow reaction 6～10 hours in ethanol, and reaction was left standstill 6～12 hours after finishing, suction filtration, get filtration cakes torrefaction and make the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formylhydrazine.
Described 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate makes by the following method:
Diethyl carbonate shown in the formula VIII mixes by molar ratio with 85% hydrazine hydrate at 1: 0.95,50 ℃ of lower backflows 20 minutes, then 25 ℃ were stirred 30 hours down, remove methyl alcohol, water and a small amount of complete diethyl carbonate of unreacted under reduced pressure, get colourless transparent liquid, be the carbazic acid ethyl ester shown in the formula VI;
Carbazic acid ethyl ester shown in the formula VI mixes with amount of substance with the ethyl acetoacetate shown in the formula VII at 1: 1, and stirring at normal temperature is 6 hours in alcohol solvent, removes ethanol under reduced pressure, gets white solid, is the 3-methoxycarbonyl hydrazone ethyl butyrate shown in the formula V;
3-methoxycarbonyl hydrazone ethyl butyrate shown in the formula V and excessive thionyl chloride, take carrene as solvent, stirring at room 20 hours, boil off excessive thionyl chloride under the normal pressure, 400Pa is collected in then decompression distillation, 76-78 ℃ faint yellow cut, make the 4-methyl isophthalic acid shown in the formula IV, 2,3-thiadiazoles-5-Ethyl formate.
This all is the known preparation methods of those skilled in the art.
Reaction equation is as follows:
The invention provides a kind ofly suc as formula the application of the acyl hydrazone derivative shown in I or the formula (9) as bactericide, wheat scab, early blight of tomato, the cercospora brown spot of peanut, ring rot of apple, cucumber Fusarium oxysporum are had preferably bactericidal action.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
The 4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formylhydrazine: the preparation of carbazic acid ethyl ester: with 85% hydrazine hydrate of 11.8g (0.1mol) diethyl carbonate and 0.095mol, join in the 100mL round-bottomed flask that the condensing reflux pipe is housed 50 ℃ of lower backflows 20 minutes, then 25 ℃ of lower stirrings 30 hours, water pump removes methyl alcohol, water and a small amount of complete diethyl carbonate of unreacted under reduced pressure, get colourless transparent liquid, be the carbazic acid ethyl ester, yield is 95%.Do several pots by this step, as the raw material of the next step more.
The preparation of 3-methoxycarbonyl hydrazone ethyl butyrate: the ethanolic solution of 7.8g (0.06mol) ethyl acetoacetate and 3.7mL is joined in the 100mL there-necked flask, slowly drip the solution of 5.029g (0.06mol) carbazic acid ethyl ester and 16.7mL ethanol under the normal temperature, reinforced complete, stirring at normal temperature 6 hours, remove ethanol under reduced pressure, get white solid 11.269g, be 3-methoxycarbonyl hydrazone ethyl butyrate, yield 98%. is done several pots by this step more, as the raw material of the next step.
The 4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-Ethyl formate: the 44mL thionyl chloride joined drying tube is housed, in the 250mL there-necked flask of device for absorbing tail gas, it is lower that cryosel is bathed cooling, slowly drip 40.579g (0.20mol) 3-methoxycarbonyl hydrazone ethyl butyrate and 45mL dichloromethane solution, the control temperature is below 20 ℃, and is reinforced complete, stirring at room 20 hours, boil off excessive thionyl chloride under the normal pressure, 400Pa is collected in decompression distillation, 76-78 ℃ faint yellow cut, obtain the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate 25.949g, yield 75.4%. does several pots by this step more, as the raw material of the next step.
The 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formylhydrazine: with 6.9g (40mmol) 4-methyl isophthalic acid, the hydrazine hydrate of 2,3-thiadiazoles-5-Ethyl formate and 44mmol 80%, 50mL ethanol join in the 250mL there-necked flask, add hot reflux 10h, then place and spend the night, separate out yellow solid, suction filtration, drying obtains the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formylhydrazine 4.9g, yield 77.5%.
Do several pots according to above step, as the reaction raw materials of the following example more.
Example 1:4-dimethylaminobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution of 3-thiadiazoles-5-formylhydrazine (30mL ethanol) adds 4-dimethylaminobenzaldehyde (1.49g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (1), be designated as 5a.
Red solid, productive rate 90.1%, fusing point 234-235 ℃;1H NMR (CDCl3, 300MHz), δ: 8.98 (s, CH, 1H), 7.81 (s, NH, 1H), 6.74-7.66 (m, ArH, 4H), 3.11 (s, N-CH3, 3H), 3.08 (s, N-CH3, 3H), 1.55 (s, Het-CH3, 3H) .MS (ESI), m/z:288[M-1]-.Elementalanal. (%), calculated:C, 53.96; H, 5.23; N, 24.20; Found:C, 53.80; H, 5.41; N, 24.51.
Example 2:3-methoxybenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution of 3-thiadiazoles-5-formylhydrazine (30mL ethanol) adds m-methoxybenzaldehyde (1.36g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (2), be designated as 5b.
Yellow solid, productive rate 93.5%, fusing point 209-210 ℃;1H NMR (CDCl3, 300MHz), δ: 8.88 (s, CH, 1H), 7.95 (s, NH, 1H), 6.89-7.34 (m, ArH, 4H), 3.88 (s, CH3, 3H), 1.45 (s, Het-CH3, 3H) .MS (ESI), m/z:275[M-1]-.Elemental anal. (%), calculated:C, 52.16; H, 4.38; N, 20.28; Found:C, 52.49; H, 4.25; N, 20.06.
Example 3:2-bromobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 2-bromobenzaldehyde (1.84g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (3), be designated as 5c.
Yellow solid, productive rate 92.5%, fusing point 141-142 ℃;1H NMR (CDCl3, 300MHz), δ: 9.74 (s, CH, 1H), 8.42 (s, NH, 1H), 7.35-8.13 (m, ArH, 4H), 1.58 (s, Het-CH3, 3H) .MS (ESI), m/z:324[M-1]-.Elemental anal. (%), calculated:C, 40.63; H, 2.79; N, 17.23; Found:C, 40.53; H, 2.77; N, 17.58.
Example 4:4-chlorobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-chlorobenzaldehyde (1.40g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (4), be designated as 5d.
Yellow solid, productive rate 94.6%, fusing point 200-201 ℃;1H NMR (CDCl3, 300MHz), δ: 9.14 (s, CH, 1H), 8.12 (s, NH, 1H), 6.88-7.68 (m, ArH, 4H), 1.51 (s, Het-CH3, 3H) .MS (ESI), m/z:279[M-1]-.Elemental anal. (%), calculated:C, 47.06; H, 3.23; N, 19.96; Found:C, 46.95; H, 3.05; N, 20.32.
Example 5:4-fluorobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-fluorobenzaldehyde (1.24g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (5), be designated as 5e.
Yellow solid, productive rate 90.0%, fusing point 179-180 ℃;1H NMR (CDCl3, 300MHz), δ: 9.26 (s, CH, 1H), 8.23 (s, NH, 1H), 7.14-8.08 (m, ArH, 4H), 1.57 (s, Het-CH3, 3H) .MS (ESI), m/z:263[M-1]-.Elemental anal. (%), calculated:C, 49.99; H, 3.43; N, 21.20; Found:C, 49.88; H, 3.77; N, 21.49.
Example 6:4-methoxybenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone is in the round-bottomed flask of 100mL, at the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), the ethanolic solution (30mL) of 2,3-thiadiazoles-5-formylhydrazine, add 4-methoxybenzaldehyde (1.36g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (6), be designated as 5f.
Yellow solid, productive rate 95.3%, fusing point 224-225 ℃;1H NMR (CDCl3, 300MHz), δ: 9.42 (s, CH, 1H), 8.34 (s, NH, 1H), 7.34-7.99 (m, ArH, 4H), 3.79 (s, OCH3, 3H), 1.52 (s, Het-CH3, 3H) .MS (ESI), m/z:334[M-1]-.Elemental anal. (%), calculated:C, 52.16; H, 4.38; N, 20.28; Found:C, 52.11; H, 4.55; N, 20.44.
Example 7:4-tolyl aldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-tolyl aldehyde (1.20g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (7), be designated as 5g.
Yellow solid, productive rate 93.3%, fusing point 235-236 ℃;1H NMR (CDCl3, 300MHz), δ: 9.33 (s, CH, 1H), 8.54 (s, NH, 1H), 7.04-8.08 (m, ArH, 4H), 2.45 (s, CH3, 3H), 1.57 (s, Het-CH3, 3H) .MS (ESI), m/z:259[M-1]-.Elemental anal. (%), calculated:C, 55.37; H, 4.65; N, 21.52; Found:C, 55.62; H, 4.35; N, 21.88.
Example 8:4-bromobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-bromobenzaldehyde (1.85g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (8), be designated as 5h.
White solid, productive rate 92.5%, fusing point: 272-273 ℃;1H NMR (CDCl3, 300MHz), δ: 9.55 (s, CH, 1H), 8.63 (s, NH, 1H), 6.98-7.89 (m, ArH, 4H), 1.50 (s, Het-CH3, 3H) .MS (ESI), m/z:324[M-1]-.Elemental anal. (%), calculated:C, 40.63; H, 2.79; N, 17.23; Found:C, 40.53; H, 2.77; N, 17.58.
Example 9:3-hydroxyl-4-methoxybenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 3-hydroxyl-4-methoxybenzaldehyde (1.52g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (9), be designated as 5i.
Yellow solid, productive rate 94.5%, fusing point 225-226 ℃;1H NMR (CDCl3, 300MHz), δ: 8.81 (s, CH, 1H), 7.83 (s, NH, 1H), 6.99-7.45 (m, ArH, 3H), 3.11 (s, CH3, 3H) 1.56 (s, Het-CH3, 3H) .MS (ESI), m/z:291[M-1]-.Elemental anal. (%), calculated:C, 49.31; H, 4.14; N, 19.17; Found:C, 49.62; H, 4.39; N, 19.54.
Example 10:2-fluorobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 2-fluorobenzaldehyde (1.24g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (10), be designated as 5j.
Yellow solid, productive rate 91.2%, fusing point 233-234 ℃;1H NMR (CDCl3, 300MHz), δ: 9.47 (s, CH, 1H), 8.26 (s, NH, 1H), 7.14-7.52 (m, ArH, 4H), 1.59 (s, Het-CH3, 3H) .MS (ESI), m/z:263[M-1]-.Elemental anal. (%), calculated:C, 49.99; H, 3.43; N, 21.20; Found:C, 50.12; H, 3.44; N, 21.30.
Example 11:4-hydroxy benzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-hydroxy benzaldehyde (1.22g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (11), be designated as 5k.
Yellow solid, productive rate 90.1%, fusing point＞300 ℃;1H NMR (CDCl3, 300MHz), δ: 9.27 (s, CH, 1H), 8.43 (s, NH, 1H), 7.28-7.98 (m, ArH, 4H), 1.54 (s, Het-CH3, 3H) .MS (ESI), m/z:261[M-1]-.Elemental anal. (%), calculated:C, 50.37; H, 3.84; N, 21.36; Found:C, 50.34; H, 3.53; N, 20.98.
Example 12:4-nitrobenzaldehyde-4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl hydrazone
In the round-bottomed flask of 100mL, in the 4-methyl isophthalic acid that is dissolved with 1.58g (10mmol), 2, the ethanolic solution (30mL) of 3-thiadiazoles-5-formylhydrazine adds 4-nitrobenzaldehyde (1.51g, 10mmol), stirring and refluxing, TLC follows the tracks of reaction, reacts completely cooling in 1 hour, suction filtration, get filter cake and get product with the 20mL ethyl alcohol recrystallization, shown in table 1 Chinese style (12), be designated as 51.
Yellow solid, productive rate 93.2%, fusing point 257-258 ℃;1H NMR (CDCl3, 300MHz), δ: 9.34 (s, CH, 1H), 8.56 (s, NH, 1H), 6.97-7.53 (m, ArH, 4H), 1.56 (s, Het-CH3, 3H) .MS (ESI), m/z:290[M-1]-.Elemental anal. (%), calculated:C, 45.36; H, 3.11; N, 24.04; Found:C, 45.09; H, 3.42; N, 24.33.
The structural formula of the compound that table 1 embodiment 1～12 makes
The bactericidal activity test of compound
Adopt biomass growth rate determination method (mycelium growth rate test), reagent agent is diluted to certain multiple under aseptic condition, then respectively drawing the 1mL liquid injects in the culture dish, add respectively again the 9mL agar medium, make the 50ug/mL pastille after shaking up dull and stereotyped, do blank with the flat board that adds the 1mL aqua sterilisa.Card punch with diameter 4mm cuts the bacterium dish along the mycelia outer rim, moves on the pastille flat board.Every processing triplicate.Culture dish is placed on cultivation in 24 ± 1 ℃ of constant incubators." Invest, Then Investigate " was respectively processed bacterium dish expansion diameter in 72 hours, averaged, and relatively calculated relative bacteriostasis rate with blank, saw the following form 2.
The bactericidal activity result of the compound that table 2 embodiment 1～12 makes (relative bacteriostasis rate, %)
Claims (1)
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| CN102002018B (en)* | 2010-11-09 | 2013-06-19 | 浙江工业大学 | (2-oxo-benzothiazole)-3-diacetyl hydrazone compound as well as preparation method and application thereof |
| CN109516952B (en)* | 2018-11-16 | 2020-07-28 | 西安科技大学 | A kind of pyridine acylhydrazone compound, synthetic method and application |
| CN111548320B (en)* | 2019-10-09 | 2023-03-24 | 贵州大学 | 1,3,4-oxadiazole hydrazide compounds and preparation method and application thereof |
| CN111635399B (en)* | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| CN111606903B (en)* | 2020-07-01 | 2022-11-01 | 南通大学 | Preparation method and application of pyrazole acylhydrazone containing trifluoromethylthiadiazole unit |
| CN111646988B (en)* | 2020-07-01 | 2022-11-01 | 南通大学 | Preparation and application of pyrazole compound containing 4-difluoromethyl-1, 2, 3-thiadiazole structure |
| CN116283822B (en)* | 2023-02-07 | 2024-11-15 | 西北农林科技大学 | Thiazole and imidazo[1,2-a]pyridylhydrazone compounds and their applications |
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| CN101223891A (en)* | 2008-01-25 | 2008-07-23 | 中国农业大学 | Star anise essential oil for inhibiting plant pathogenic fungi and preparation method thereof |
| CN101289422A (en)* | 2008-06-06 | 2008-10-22 | 华中师范大学 | 2,3,5,6-tetrasubstituted-4-aminopyridine with bactericidal and herbicidal activity and its preparation |
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| CN101223891A (en)* | 2008-01-25 | 2008-07-23 | 中国农业大学 | Star anise essential oil for inhibiting plant pathogenic fungi and preparation method thereof |
| CN101289422A (en)* | 2008-06-06 | 2008-10-22 | 华中师范大学 | 2,3,5,6-tetrasubstituted-4-aminopyridine with bactericidal and herbicidal activity and its preparation |
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