CN106212482A - The application in preparing herbicide of a kind of 1,3,4 thiadiazoles sulfide derivatives - Google Patents
The application in preparing herbicide of a kind of 1,3,4 thiadiazoles sulfide derivatives Download PDFInfo
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- CN106212482A CN106212482A CN201610608978.5A CN201610608978A CN106212482A CN 106212482 A CN106212482 A CN 106212482A CN 201610608978 A CN201610608978 A CN 201610608978A CN 106212482 A CN106212482 A CN 106212482A
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- XSULHYQANYPKGW-UHFFFAOYSA-N Cc1n[n](C)cc1/C(/S)=N/NC Chemical compound Cc1n[n](C)cc1/C(/S)=N/NC XSULHYQANYPKGW-UHFFFAOYSA-N 0.000 description 1
- MNBDXPVYZMJWRN-UHFFFAOYSA-N [U]C1CCCC1 Chemical compound [U]C1CCCC1 MNBDXPVYZMJWRN-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of 1,3, the application in preparing herbicide of the 4 thiadiazoles sulfide derivatives, Semen Tritici aestivi, Sorghum vulgare Pers., barnyard grass, Fructus Cucumidis sativi, Brassica campestris L, Radix Raphani are had preferable activity, compound I 1, compound I 9, compound I 13 and compound I 14 that Semen Brassicae Campestris and Radix Raphani are had more than the suppression ratio of 80% the most respectively by compound of the present invention compound (I 1) and (I 14) under 100 μ g/mL concentration；Compound of the present invention is the noval chemical compound with activity of weeding, and the research and development for novel pesticide provide the foundation.
Description
Technical field
The present invention relates to a kind of 1,3,4-i.e. 5-of thiadiazoles sulfide derivative (4-(1,3-dimethyl-1H-pyrazoles))-1,3,
The application in preparing herbicide of the 4-thiadiazoles-2-thioether analog derivative.
Background technology
In the past few decades, heterocyclic compound has extensive and various biological activity, particularly 1,3,4-thiadiazoles with
Pyrazole compound.1,3,4-thiadiazoles and pyrazoles are that two classes are nitrogenous or the five member ring heterocyclic compound of sulfur.Many documents all report
1,3,4-thiadiazole compound shows biological activity widely, including anti-tubercular, anti-tumor activity, bactericidal activity, resists
Scorching activity, antioxidant activity, suppresses cholinesterase activity, insecticidal activity etc..Additionally, heterocycle thio-ketone derivative also shows excellent
Elegant biological activity, such as bactericidal activity, activity of weeding, anti-tumor activity etc..Especially, 1,3,4-thiadiazoles thione structure exists
Invention medicine aspect is a kind of very important pharmacophore.On the other hand, pyrazole ring is present in many synthetic drugs or parasite killing
In agent.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the present invention to provide a kind of 1,3,4-thiadiazoles thioethers and derive
Thing i.e. 5-(4-(1,3-dimethyl-1H-pyrazoles))-1,3,4-thiadiazoles-2-thioether analog derivative answering in preparing herbicide
With.
Described one 1,3,4-thiadiazoles sulfide derivative application in preparing herbicide, it is characterised in that 1,3,4-
Shown in the general structure of thiadiazoles sulfide derivative such as formula (I):
In formula (I): R is C1～C14 alkyl, phenyl or substituted-phenyl, the substituent group of described substituted-phenyl is halogen, methoxy
Base, cyano group or C1～C9 alkyl.
Described application, it is characterised in that described R is one of following: phenyl, rubigan, p-bromophenyl, 2-chlorobenzene
Base, 2-fluorophenyl, 3-chlorphenyl, 2,4 dichloro benzene base, 6-chloro-3-chloromethylpyridine, 2-chloro-5-chloromethyl thiazole, 3,4-bis-
Chlorphenyl, chlorallylene, chloroacetonitrile, 2,4 dichloro benzene base, to cyano-phenyl or to tert-butyl-phenyl.
Described application, it is characterised in that R is phenyl or to tert-butyl-phenyl.
Described application, it is characterised in that herbicide is at preventing and treating Semen Tritici aestivi (Triticum aestivum), Sorghum vulgare Pers. (Sorghum
Bicolor), barnyard grass (Echinochloa crusgalli), Fructus Cucumidis sativi (Cucumis sativus), Semen Brassicae Campestris (Brassica
Campestris), the application of Radix Raphani (Raphanus sativus).
Described application, it is characterised in that herbicide is applied to prevent and treat Semen Tritici aestivi, Sorghum vulgare Pers., barnyard grass, Fructus Cucumidis sativi, Semen Brassicae Campestris, Radix Raphani.
Described application, it is characterised in that R is phenyl or to tert-butyl-phenyl, be applied to suppress Semen Tritici aestivi, Sorghum vulgare Pers., barnyard grass,
Fructus Cucumidis sativi, Semen Brassicae Campestris, the root growth of Radix Raphani.
Described application, it is characterised in that R is phenyl, p-bromophenyl, cyano group or to tert-butyl-phenyl, is applied to suppress rue
Tongue and the growth of Radix Raphani.
Described application, it is characterised in that 1,3,4-thiadiazoles sulfide derivative concentration in herbicide is 100ppm.
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that comprise the steps:
1) ethyl acetoacetate, triethyl orthoformate and acetic anhydride are joined in there-necked flask, be heated to 115-125 DEG C instead
Answering 9-11h, rotation evaporates solvent and obtains brown liquid after completion of the reaction, is joined by brown liquid in organic solvent A, then at ice bath
Under the conditions of methyl hydrazine is added drop-wise in above-mentioned solution, then be stirred at room temperature reaction 2.5-3.5h, after completion of the reaction, spin off solvent
Obtain white solid 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate as shown in formula II；
2) by step 1) 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate shown in formula II that obtains is dissolved in organic solvent B
In, adding the hydrazine hydrate of 80%, heating reflux reaction 7.5-8.5h, rotation evaporates solvent after completion of the reaction, and it is solid that cooling separates out white
Body 1,3-dimethyl-1H-pyrazoles-4 formylhydrazine as shown in (III)；
3) by step 2) 1,3-dimethyl-1H-pyrazoles-4 formylhydrazine as shown in formula III that obtains and inorganic base A add
In organic solvent C, stir 30min, be then added dropwise over CS2, then stirring reaction 15-18h under room temperature, filter such as (IV) institute
2-(1,3-dimethyl-1H-pyrazoles-4-carbonyl) hydrazides-1-dithio potassium shown；
4) by step 3) 2-(1,3-dimethyl-1H-pyrazoles-4-carbonyl) hydrazides-1-two sulfur shown in formula IV that obtains
Join in the concentrated sulphuric acid of 98% for potassium, under room temperature, stirring reaction 4-6h, then pours in trash ice by mixed liquor, separates out precipitation,
Filter, washing, be dried, ethyl alcohol recrystallization obtain white solid 5-(1,3-dimethyl-1H-pyrazoles-4-base) as shown in formula (V)-
1,3,4-thiadiazoles-2-mercaptan；
5) by organic solvent D, step 4) 5-(1,3-dimethyl-1H-pyrazoles-4-base)-1 shown in formula (V) that obtains,
3,4-thiadiazoles-2-mercaptan, RCH2Cl and inorganic base B mixing, microwave-assisted reacts, and reaction is cooled to less than 50 DEG C after terminating,
Then mixed liquor is poured in trash ice, separate out solid, filter to obtain target compound 1,3,4-thiadiazoles sulfide derivative；
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that step 1) described in organic solvent
A is one or more in methanol, ethanol, dichloromethane, oxolane, DMF, preferred alcohol；Described ethyl acetoacetate, former
The ratio of the amount of the material of formic acid triethyl and acetic anhydride is 1:1～5:1～5；Preferably 1:2:2.5.
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that step 2) described in hydrazine hydrate water
Consumption with the gauge of the material of hydrazine hydrate, the amount of the material of described 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate and hydrazine hydrate
Ratio be 1:1～10, preferably 1:9；Described organic solvent B is in methanol, ethanol, dichloromethane, oxolane, DMF
Plant or multiple, preferred alcohol.
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that step 3) described in inorganic base A
For one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably potassium hydroxide；Organic solvent C is first
One or more in alcohol, ethanol, dichloromethane, oxolane, DMF, preferred alcohol；Described 1,3-dimethyl-1H-pyrazoles-4
Formylhydrazine, inorganic base A and CS2The ratio of amount of material be 1:1～2:1～2；It is preferably 1:1.2:1.
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that step 4) in the volume of sulphuric acid use
Amount is designated as with the amount of the material of 2-(1,3-dimethyl-1H-pyrazoles-4-carbonyl) hydrazides-1-dithio potassium as shown in formula IV
0.1～1mmol/ml, preferably 0.2mmol/ml.
Described 1, the preparation method of 3,4-thiadiazoles sulfide derivatives, it is characterised in that step 5) described in organic solvent
D is one or more in methanol, ethanol, dichloromethane, oxolane, DMF, preferably DMF；The consumption of organic solvent D with
The amount of the material of 5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles-2-mercaptan is calculated as 0.1～1mmol/ml, excellent
Elect 0.2mmol/ml as；Described inorganic base B is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, excellent
Elect sodium hydroxide as；Described 5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles-2-mercaptan, RCH2Cl and inorganic
The ratio of the amount of the material of alkali B is 1:1～2:1～2, preferably 1:1.1:1.2；Microwave-assisted condition is: 150W, 90 DEG C,
Microwave irradiation 15 minutes under 200psi.
Its course of reaction is as follows:
Compared with prior art, the beneficial effects are mainly as follows: the invention provides a kind of 5-(4-(1,3-
Dimethyl-1H-pyrazoles)) application in preparing herbicide of-1,3, the 4-thiadiazoles-2-sulfide derivatives, chemical combination of the present invention
Thing under 100 μ g/mL concentration compound (I-1) and (I-14) to Semen Tritici aestivi (Triticum aestivum), Sorghum vulgare Pers. (Sorghum
Bicolor), barnyard grass (Echinochloa crusgalli), Fructus Cucumidis sativi (Cucumis sativus), Brassica campestris L (Brassica
Campestris), Radix Raphani (Raphanus sativus) has preferable activity；Compound of the present invention is lived for having weeding
The noval chemical compound of property, the research and development for novel pesticide provide the foundation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This:
Embodiment 1
(1) synthesis of 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate formula II
Ethyl acetoacetate (1mol), triethyl orthoformate (2mol) and acetic anhydride (2.5mol) are joined there-necked flask
In, it being heated to 120 DEG C of reaction 10h, rotation evaporates solvent and obtains brown liquid after completion of the reaction.Brown liquid is joined ethanol
(550ml), in, then under condition of ice bath, methyl hydrazine (1.5mol) is added drop-wise in above-mentioned solution, then is stirred at room temperature reaction
3h, after completion of the reaction, spins off solvent and obtains white solid (II) 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate 86.1g, yield
51.2%.
(2) by above-mentioned (II) 1,3-dimethyl-1H-pyrazoles-4 Ethyl formate (10mmol) is dissolved in ethanol (10ml), adds
Entering the hydrazine hydrate (90mmol) of 80%, heating reflux reaction 8h, rotation evaporates solvent after completion of the reaction, and cooling separates out white solid
(III) 1,3-dimethyl-1H-pyrazoles-4 formylhydrazine 1.42g, yield 92.1%.
(3) above-mentioned (III) 1,3-dimethyl-1H-pyrazoles-4 formylhydrazine (65mmol) and KOH (78mmol) is joined second
In alcohol (250ml), stirring 30min, is then added dropwise over CS2(65mmol), then stirring reaction 16h under room temperature, filter (IV) 2-
(1,3-dimethyl-1H-pyrazoles-4-carbonyl) hydrazides-1-dithio potassium 1.8g, yield 67.7%.
(4) by above-mentioned prepared (IV) 2-(1,3-dimethyl-1H-pyrazoles-4-carbonyl) hydrazides-1-dithio potassium
(11.8mmol) 98%H is joined2SO4(60ml), in, under room temperature, stirring reaction 5h, then pours in trash ice by mixed liquor, separates out
Precipitation, filters, and washing is dried, and ethyl alcohol recrystallization obtains white solid (V) 5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,
4-thiadiazoles-2-mercaptan, yield 43%.
(5) by DMF (5ML), 5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles-2-mercaptan (1mmol),
Benzyl chloride (1.1mmol) and NaOH (1.2mmol) are mixed to join in the rated pressure bottle of 10ml, and microwave-assisted reaction (150W, 90
DEG C, 200psi, 15min), reaction is cooled to less than 50 DEG C after terminating, and then pours in trash ice by mixed liquor, separates out solid, mistake
Filter to obtain 2-(benzylthio)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1 shown in target compound (I-1), 3,4-thiadiazoles, receive
Rate 77.3%.
2-(benzylthio)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.106-108 DEG C,
Yield 77.3%,1H NMR(500MHz,CDCl3) ppm 7.82 (s, 1H, pyrazole H), 7.46 (d, J=7.14Hz,
2H,Ar-H),7.38-7.30(m,3H,Ar-H),4.50(s,2H,-CH2-),3.91(s,3H,N-CH3),2.53(s,3H,
pyrazole CH3)；MS(ESI),m/z:303(M+1)+.
Embodiment 2
Changing benzyl chloride in embodiment 1 step (5) the 2-chlorobenzyl chloride of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-
((2-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-2), productivity 59.5%.
2-((2-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.105-
106 DEG C, yield 59.5%,1H NMR(400MHz,CDCl3) ppm 7.83 (s, 1H, pyrazole H), 7.60 (d, J=
6.50Hz, 1H, Ar-H), 7.41 (d, J=6.92Hz, 1H, Ar-H), 7.30-7.25 (m, 1H, Ar-H), 4.72 (s, 2H ,-
CH2-),3.90(s,3H,N-CH3),2.50(s,3H,pyrazole CH3)；MS(ESI),m/z:338(M+1)+.
Embodiment 3
Changing benzyl chloride in embodiment 1 step (5) the 4-chlorobenzyl chloride of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-
((4-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-3), productivity 75.4%.
2-((4-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.82-84
DEG C, yield 75.4%,1H NMR(400MHz,CDCl3) ppm 7.83 (s, 1H, pyrazole H), 7.40 (d, J=
7.42Hz,2H,Ar-H),7.31-7.29(m,2H,Ar-H),4.55(s,2H,-CH2-),3.91(s,3H,N-CH3),2.50(s,
3H,pyrazole CH3)；MS(ESI),m/z:338(M+1)+.
Embodiment 4
Benzyl chloride in embodiment 1 step (5) changes into the 4-itrile group benzyl chloride of 1.1mol, and other operations are with embodiment 1, it is thus achieved that 2-
((4-itrile group benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-4), productivity 75.4%.
2-((4-itrile group benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.46-
147 DEG C, yield 75.4%,1H NMR(400MHz,CDCl3)ppm 7.83(s,1H,pyrazole H),7.64-7.58(m,
4H,Ar-H),4.60(s,2H,-CH2-),3.90(s,3H,N-CH3),2.49(s,3H,pyrazole CH3)；MS(ESI),m/
z:328(M+1)+.
Embodiment 5
Changing benzyl chloride in embodiment 1 step (5) the 2-fluorobenzyl chloride of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-
((2-luorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-5), productivity 87.5%.
2-((2-luorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.107-
109 DEG C, yield 87.5%,1H NMR(400MHz,CDCl3) ppm 7.84 (s, 1H, pyrazole H), 7.53 (t, J=
7.50,7.50Hz, Ar-H), 7.34-7.25 (m, 1H, Ar-H), 7.10 (dd, J=16.96,8.61Hz, 2H, Ar-H), 4.63
(s,2H,-CH2-),3.91(s,3H,N-CH3),2.51(s,3H,pyrazole CH3)；MS(ESI),m/z:321(M+1)+.
Embodiment 6
Benzyl chloride in embodiment 1 step (5) changes into the 2 of 1.1mol, 4-dichlorobenzyl chloride, and other operations are with embodiment 1, it is thus achieved that
2-((2,4-dichloro benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-6), productivity
73.9%.
2-((2,4-dichloro benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles
M.p.100-101 DEG C, yield 73.9%,1H NMR(400MHz,CDCl3)ppm 7.82(s,1H,pyrazole H),7.56
(d, J=8.28Hz, 1H, Ar-H), 7.41 (s, 1H, Ar-H), 7.19 (d, J=8.14Hz, 1H, Ar-H), 4.65 (s, 2H ,-
CH2-),3.89(s,3H,N-CH3),2.48(s,3H,pyrazole CH3)；MS(ESI),m/z:372(M+1)+.
Embodiment 7
Changing benzyl chloride in embodiment 1 step (5) the 3-chlorobenzyl chloride of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-
((3-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-7), productivity 81.3%.
2-((3-chlorobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.94-96
DEG C, yield 81.3%,1H NMR(400MHz,CDCl3)ppm 7.83(s,1H,pyrazole H),7.46(s,1H,Ar-H),
7.38-7.31(m,1H,Ar-H),7.30-7.23(m,2H,Ar-H),4.56(s,2H,-CH2-),3.91(s,3H,N-CH3),
2.50(s,3H,pyrazole CH3)；MS(ESI),m/z:338(M+1)+.
Embodiment 8
Benzyl chloride in embodiment 1 step (5) changes into the 3 of 1.1mol, 4-dichlorobenzyl chloride, and other operations are with embodiment 1, it is thus achieved that
2-((3,4-dichloro benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-8), productivity
81.1%.
2-((3,4-dichloro benzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles
M.p.108-111 DEG C, yield 81.1%,1H NMR(400MHz,CDCl3)ppm 7.84(s,1H,pyrazole H),7.57
(s, 1H, Ar-H), 7.41 (d, J=8.26Hz, 1H, Ar-H), 7.33 (d, J=8.12Hz, 1H, Ar-H), 4.53 (s, 2H ,-
CH2-),3.92(s,3H,N-CH3),2.51(s,3H,pyrazole CH3)；MS(ESI),m/z:372(M+1)+.
Embodiment 9
Benzyl chloride in embodiment 1 step (5) changes into the 4-bromine benzyl chloride of 1.1mol, and other operations are with embodiment 1, it is thus achieved that 2-
((4-bromobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-9), productivity 84.2%.
2-((4-bromobenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.98-99
DEG C, yield 84.2%,1H NMR(400MHz,CDCl3) ppm 7.72 (s, 1H, pyrazole H), 7.36 (d, J=
7.05Hz, 2H, Ar-H), 7.23 (d, J=7.18Hz, 2H, Ar-H), 4.42 (s, 2H ,-CH2-),3.80(s,3H,N-CH3),
2.39(s,3H,pyrazole CH3)；MS(ESI),m/z:382(M+1)+.
Embodiment 10
Changing benzyl chloride in embodiment 1 step (5) the 2-chloro-5-chloromethyl thiazole of 1.1mol into, other operate same embodiment
1, it is thus achieved that 2-(((2-diuril azoles-5-base) methyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles
(I-10), productivity 38.9%.
2-(((2-diuril azoles-5-base) methyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiophene two
Azoles m.p.155-156 DEG C, yield 38.9%,1H NMR(400MHz,CDCl3)ppm 7.87(s,1H,pyrazole H),
7.53(s,1H,Thiazole-H),4.72(s,2H,-CH2-),3.93(s,3H,N-CH3),2.52(s,3H,pyrazole
CH3)；MS(ESI),m/z:345(M+1)+.
Embodiment 11
Changing benzyl chloride in embodiment 1 step (5) chloroacetonitrile of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-((5-
(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles-2-bases) sulfydryl) acetonitrile (I-11), productivity 18.6%.
2-((5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles-2-base) sulfydryl) acetonitrile m.p.162-
164 DEG C, yeild 18.6%,1H NMR(400MHz,CDCl3)ppm 7.83(s,1H,pyrazole H)4.14(s,2H,-
CH2-),3.88(s,3H,N-CH3),2.48(s,3H,pyrazole CH3)；MS(ESI),m/z:252(M+1)+.
Embodiment 12
Benzyl chloride in embodiment 1 step (5) changes into the 6-chloro-3-chloromethylpyridine of 1.1mol, and other operate same embodiment
1, it is thus achieved that 2-(((6-chloropyridine-3-base) methyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles
(I-12), productivity 39.6%.
2-(((6-chloropyridine-3-base) methyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiophene two
Azoles m.p.110-112 DEG C, yield 39.6%,1H NMR(400MHz,CDCl3)ppm 8.46(s,1H,Py-H),7.82(s,
2H, pyrazole H and Py-H), 7.29 (d, J=12.23Hz, 1H, Py-H), 4.54 (s, 2H ,-CH2-),3.90(s,
3H,N-CH3),2.48(s,3H,pyrazole CH3)；MS(ESI),m/z:339(M+1)+.
Embodiment 13
Changing benzyl chloride in embodiment 1 step (5) chlorallylene of 1.1mol into, other operations are with embodiment 1, it is thus achieved that 2-
(acrylic)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-13), productivity 34.4%.
2-(acrylic)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles m.p.197-200 DEG C,
Yield 34.4%,1H NMR(400MHz,CDCl3)ppm 7.85(s,1H,pyrazole H),6.10-5.99(m,1H,-CH
=), 5.38 (d, J=17.01Hz, 1H ,=CH2), 5.23 (d, J=9.90Hz, 1H ,=CH2), 3.99 (d, J=6.89Hz,
2H,-CH2-),3.92(s,3H,N-CH3),2.52(s,3H,pyrazole CH3)；MS(ESI),m/z:253(M+1)+.
Embodiment 14
Benzyl chloride in embodiment 1 step (5) changes into the 4-tert-butyl group benzyl chloride of 1.1mol, and other operations are with embodiment 1, it is thus achieved that
2-((4-t-butylbenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles (I-14), productivity
41.0%.
2-((4-t-butylbenzyl) sulfydryl)-5-(1,3-dimethyl-1H-pyrazoles-4-base)-1,3,4-thiadiazoles
M.p.104-108 DEG C, yield 41.0%,1H NMR(400MHz,CDCl3)ppm 7.84(s,1H,pyrazole H),7.38
(s,4H,Ar-H),4.58(s,2H,-CH2-),3.91(s,3H,N-CH3),2.50(s,3H,pyrazole CH3),1.33(s,
9H,-C(CH3)3)；MS(ESI),m/z:359(M+1)+.
Embodiment 15 activity of weeding is tested
Subjects: Semen Tritici aestivi (Triticum aestivum), Sorghum vulgare Pers. (Sorghum bicolor), barnyard grass
(Echinochloa crusgalli), Fructus Cucumidis sativi (Cucumis sativus), Brassica campestris L (Brassica campestris), Radix Raphani
(Raphanus sativus)。
Medicament prepares: (I-1) prepared by Example 1-14-each 5mg of (I-14) compound, after adding 0.5ml acetone solution
Add 0.05ml 10% POLYSORBATE 80 again, finally add 50ml water and fully dissolve, it is thus achieved that 100ppm Sample Reagents.Because 100ppm is
100mg/L is so amount of water=5mg*1000/100mg=50ml, because of final content≤1% of organic solvent so adding the amount of acetone
=50ml*1%=0.5ml (dissolves), because the final content of tween is 0.1% so should there be tween 0.05ml in 50ml water, it may be assumed that should
Add 10% tween 0.05ml.
Experimental technique: weigh the former medicine of certain mass with analytical balance (0.0001g), adds containing 1% tween 80 emulsifying agent
DMF dissolve, be configured to 1.0%-5.0% mother solution, then standby with distilled water diluting.
Culture dish method (general sieve): supplying examination target is Radix Raphani, Fructus Cucumidis sativi, Brassica campestris L, Semen Tritici aestivi, Sorghum vulgare Pers. and barnyard grass, wherein Semen Tritici aestivi, Sorghum vulgare Pers.
Carry out accelerating germination in advance with radish seed, the seed that shows money or valuables one carries unintentionally taking uniformity is tested, and above-mentioned target is put into paving double-layer filter paper
Internal diameter 9cm culture dish, adds each noval chemical compound solution 9ml of concentration 100mg/L；Leaching medicine uniformly after numbering labelling respectively, be placed in
Growth cabinet is cultivated, temperature 28 DEG C is set；Illumination 3000Lux, light application time is 16h illumination, and 8h is dark, RH 75%, 7
Observed result after it.
Activity of weeding test result is as shown in table 1.
The activity of weeding (% preventive effect) of each compound under table 1 100ppm
The most all pyrazole derivatives have good activity, such as Fructus Cucumidis sativi, Semen Brassicae Campestris to dicotyledon
And Radix Raphani.On the contrary, except (I-1) and (I-14), these compounds all do not have activity to monocotyledon.At these compounds
In, (I-1), (I-9), (I-13) and (I-14) has more than the suppression ratio of 80% the most respectively to Semen Brassicae Campestris and Radix Raphani.Compound (I-1)
(I-14) to Semen Tritici aestivi (Triticum aestivum), Sorghum vulgare Pers. (Sorghum bicolor), barnyard grass (Echinochloa
Crusgalli), Fructus Cucumidis sativi (Cucumis sativus), Semen Brassicae Campestris (Brassica campestris), Radix Raphani (Raphanus
Sativus) rhizome has good activity.
Claims (6)
1. one kind 1,3,4-thiadiazoles sulfide derivatives application in preparing herbicide, it is characterised in that 1,3,4-thiadiazoles sulfur
Shown in the general structure of ether derivant such as formula (I):
In formula (I): R is C1～C14 alkyl, phenyl or substituted-phenyl, the substituent group of described substituted-phenyl be halogen, methoxyl group,
Cyano group or C1～C9 alkyl.
Application the most according to claim 1, it is characterised in that described R is one of following: phenyl, rubigan, to bromine
Phenyl, 2-chlorphenyl, 2-fluorophenyl, 3-chlorphenyl, 2,4 dichloro benzene base, 6-chloro-3-chloromethylpyridine, 2-chloro-5-chloromethyl
Thiazole, 3,4-Dichlorobenzene base, chlorallylene, chloroacetonitrile, 2,4 dichloro benzene base, to cyano-phenyl or to tert-butyl-phenyl.
Application the most according to claim 1, it is characterised in that herbicide be applied to prevent and treat Semen Tritici aestivi, Sorghum vulgare Pers., barnyard grass, Fructus Cucumidis sativi,
Semen Brassicae Campestris, Radix Raphani.
Application the most according to claim 1, it is characterised in that R is phenyl or to tert-butyl-phenyl, be applied to suppress Semen Tritici aestivi,
Sorghum vulgare Pers., barnyard grass, Fructus Cucumidis sativi, Semen Brassicae Campestris, the root growth of Radix Raphani.
Application the most according to claim 1, it is characterised in that R is phenyl, p-bromophenyl, cyano group or to tert-butyl-phenyl,
It is applied to suppress Semen Brassicae Campestris and the growth of Radix Raphani.
6. according to described application arbitrary in claim 1-5, it is characterised in that 1,3,4-thiadiazoles sulfide derivative is in weeding
Concentration in agent is 100ppm.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787198A (en) * | 1969-07-01 | 1974-01-22 | Takeda Chemical Industries Ltd | Herbicidal compositions containing various benzylthiodiazoles and triazines |
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2016
- 2016-07-28 CN CN201610608978.5A patent/CN106212482B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787198A (en) * | 1969-07-01 | 1974-01-22 | Takeda Chemical Industries Ltd | Herbicidal compositions containing various benzylthiodiazoles and triazines |
Non-Patent Citations (2)
| Title |
|---|
| 孙召慧等: "新型含1，3，4-噻二唑的硫脲化合物的合成及除草活性", 《有机化学》 * |
| 谭成侠等: "具有除草活性的吡唑类化合物的研究进展", 《现代农药》 * |
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Application publication date: 20161214 Assignee: Wufeng Yangcheng Alloy Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980035865 Denomination of invention: Application of a 1,3,4-thiadiazole sulfide derivative in the preparation of herbicides Granted publication date: 20181113 License type: Common License Record date: 20230525 |