CN106212482B - A kind of application of 1,3,4- thiadiazoles sulfide derivative in preparing herbicide - Google Patents
A kind of application of 1,3,4- thiadiazoles sulfide derivative in preparing herbicide Download PDFInfo
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- CN106212482B CN106212482B CN201610608978.5A CN201610608978A CN106212482B CN 106212482 B CN106212482 B CN 106212482B CN 201610608978 A CN201610608978 A CN 201610608978A CN 106212482 B CN106212482 B CN 106212482B
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- 0 CC(*(C)*1CC1)C(F)(F)F Chemical compound CC(*(C)*1CC1)C(F)(F)F 0.000 description 3
- CHEDSQDEDKGHMJ-XQQFMLRXSA-N C[C@@H](CCC1)[C@@H](CS/C(/S)=N/N)CC[C@H]1C(C)(C)C Chemical compound C[C@@H](CCC1)[C@@H](CS/C(/S)=N/N)CC[C@H]1C(C)(C)C CHEDSQDEDKGHMJ-XQQFMLRXSA-N 0.000 description 1
- SBPHOLBQPYATMW-UHFFFAOYSA-O Cc1[nH+][n](C)cc1-c1nnc(SCc(ccc(Cl)c2)c2Cl)[s]1 Chemical compound Cc1[nH+][n](C)cc1-c1nnc(SCc(ccc(Cl)c2)c2Cl)[s]1 SBPHOLBQPYATMW-UHFFFAOYSA-O 0.000 description 1
- GHGZGDGWFWIAQM-UHFFFAOYSA-N Cc1c[n](C)nc1C Chemical compound Cc1c[n](C)nc1C GHGZGDGWFWIAQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Abstract
The invention discloses one kind 1,3, application of the 4- thiadiazoles sulfide derivatives in preparing herbicide, compound of the present invention compound (I-1) and (I-14) under 100 μ g/mL concentration have preferable activity, compound I-1, compound I-9, compound I-13 and compound I-14 to have more than 80% inhibiting rate respectively to rape and radish wheat, sorghum, barnyard grass, cucumber, rape, radish；Compound of the present invention is the noval chemical compound with activity of weeding, is provided the foundation for the research and development of novel pesticide.
Description
Technical field
The present invention relates to a kind of 1,3,4- thiadiazoles sulfide derivative, that is, 5- (4- (1,3- dimethyl -1H- pyrazoles)) -1,3,
Application of the 4- thiadiazoles -2- thioether analog derivatives in preparing herbicide.
Background technology
In the past few decades, heterocyclic compound possesses extensive and various bioactivity, especially 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 sulphur.Many documents all report
1,3,4- thiadiazole compound shows extensive bioactivity, including anti-tubercular, antitumor activity, and bactericidal activity resists
Scorching activity, antioxidant activity inhibit cholinesterase activity, insecticidal activity etc..In addition, heterocycle thio-ketone derivative also show it is excellent
Elegant bioactivity, such as bactericidal activity, activity of weeding, antitumor activity etc..Particularly, 1,3,4- thiadiazoles thione structures exist
It is a kind of very important pharmacophore in terms of invention drug.On the other hand, pyrazole ring is present in many synthetic drugs or desinsection
In agent.
Invention content
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 to derive
Object, that is, 5- (4- (1,3- dimethyl -1H- pyrazoles)) -1,3,4- thiadiazoles -2- thioether analog derivatives answering in preparing herbicide
With.
Application of 1,3, the 4- thiadiazoles sulfide derivative of one kind 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, and the substituent group of the substituted-phenyl is halogen, methoxy
Base, cyano or C1~C9 alkyl.
The application, it is characterised in that the R is one of following：Phenyl, rubigan, p-bromophenyl, 2- chlorobenzenes
The chloro- 3- chloromethylpyridine of base, 2- fluorophenyls, 3- chlorphenyls, 2,4 dichloro benzene base, 6-, 2- chloro-5-chloromethyl thiazoles, 3,4- bis-
Chlorphenyl, chlorallylene, chloroacetonitrile, 2,4 dichloro benzene base, to cyano-phenyl or to tert-butyl-phenyl.
The application, it is characterised in that R is for phenyl or to tert-butyl-phenyl.
The application, it is characterised in that herbicide is in prevention wheat (Triticum aestivum), sorghum (Sorghum
Bicolor), barnyard grass (Echinochloa crusgalli), cucumber (Cucumis sativus), rape (Brassica
Campestris), the application of radish (Raphanus sativus).
The application, it is characterised in that herbicide is applied to prevention wheat, sorghum, barnyard grass, cucumber, rape, radish.
The application, it is characterised in that R is phenyl or to tert-butyl-phenyl, be applied to inhibit wheat, sorghum, barnyard grass,
The root growth of cucumber, rape, radish.
The application, it is characterised in that R is phenyl, p-bromophenyl, cyano or to tert-butyl-phenyl, is applied to inhibit rue
The growth of tongue and radish.
The application, it is characterised in that a concentration of 100ppm of 1,3, the 4- thiadiazoles sulfide derivative in herbicide.
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that include the following steps：
1) ethyl acetoacetate, triethyl orthoformate and acetic anhydride are added in there-necked flask, are heated to 115-125 DEG C instead
9-11h is answered, solvent is rotated after completion of the reaction and obtains brown liquid, brown liquid is added in organic solvent A, then in 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 spin off solvent after completion of the reaction
Obtain white solid -4 Ethyl formate of 1,3- dimethyl -1H- pyrazoles as shown in formula (II)；
2) -4 Ethyl formate of 1,3- dimethyl -1H- pyrazoles shown in formula (II) that step 1) obtains is dissolved in organic solvent B
In, 80% hydrazine hydrate is added, heating reflux reaction 7.5-8.5h rotates solvent after completion of the reaction, cooling that white is precipitated admittedly
Body -4 formylhydrazine of 1,3- dimethyl -1H- pyrazoles as shown in (III)；
3) -4 formylhydrazine of 1,3- dimethyl -1H- pyrazoles as shown in formula (III) and inorganic base A obtained step 2) is added
To 30min is stirred in organic solvent C, CS is then added dropwise2, then it is stirred to react 15-18h at room temperature, filter such as (IV) institute
The two thio potassium of 2- (1,3- dimethyl -1H- pyrazoles -4- carbonyls) hydrazides -1- shown；
4) two sulphur of 2- shown in the formula (IV) obtained step 3) (1,3- dimethyl -1H- pyrazoles -4- carbonyls) hydrazides -1-
It is added in 98% concentrated sulfuric acid for potassium, is stirred to react 4-6h at room temperature, then pours into mixed liquor in trash ice, precipitation is precipitated,
Filtering is washed, dry, and ethyl alcohol recrystallization obtains white solid 5- as shown in formula (V) (1,3- dimethyl -1H- pyrazoles -4- bases) -
1,3,4- thiadiazoles -2- mercaptan；
5) 5- shown in the formula (V) obtained organic solvent D, step 4) (1,3- dimethyl -1H- pyrazoles -4- bases) -1,
3,4- thiadiazoles -2- mercaptan, RCH2Cl and inorganic base B mixing, microwave-assisted reaction, be cooled to after reaction 50 DEG C hereinafter,
Then mixed liquor is poured into trash ice, solid is precipitated, filters to obtain 1,3,4- thiadiazoles sulfide derivative of target compound；
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that organic solvent described in step 1)
A is one or more, the preferred alcohol in methanol, ethyl alcohol, dichloromethane, tetrahydrofuran, DMF；The ethyl acetoacetate, original
The ratio between amount of substance of formic acid triethyl and acetic anhydride is 1:1~5:1~5；It is preferred that 1:2:2.5.
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that hydrazine hydrate water described in step 2)
Dosage with the gauge of the substance of hydrazine hydrate, the amount of the substance of -4 Ethyl formate of 1,3- dimethyl -1H- pyrazoles and hydrazine hydrate
The ratio between be 1:1~10, preferably 1:9；The organic solvent B is one in methanol, ethyl alcohol, dichloromethane, tetrahydrofuran, DMF
Kind or a variety of, preferred alcohol.
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that inorganic base A described in step 3)
To be one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferred potassium hydroxide；Organic solvent C is first
It is one or more in alcohol, ethyl alcohol, dichloromethane, tetrahydrofuran, DMF, preferred alcohol；1,3- dimethyl -1H- the pyrazoles -4
Formylhydrazine, inorganic base A and CS2The ratio between the amount of substance be 1:1~2:1~2；Preferably 1:1.2:1.
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that the volume of sulfuric acid is used in step 4)
Amount is denoted as with the amount of the substance of two thio potassium of the 2- as shown in formula (IV) (1,3- dimethyl -1H- pyrazoles -4- carbonyls) hydrazides -1-
0.1~1mmol/ml, preferably 0.2mmol/ml.
Described 1, the preparation method of 3,4- thiadiazoles sulfide derivatives, it is characterised in that organic solvent described in step 5)
D is one or more, the preferably DMF in methanol, ethyl alcohol, dichloromethane, tetrahydrofuran, DMF；The dosage of organic solvent D with
The amount of the substance of 5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles -2- mercaptan is calculated as 0.1~1mmol/ml, excellent
It is selected as 0.2mmol/ml；The inorganic base B is excellent to be one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate
It is selected as sodium hydroxide；5- (1,3- dimethyl -1H- pyrazoles -4- the bases) -1,3,4- thiadiazoles -2- mercaptan, RCH2Cl and inorganic
The ratio between amount of substance of alkali B is 1:1~2:1~2, preferably 1:1.1:1.2；Microwave radiation technology condition is：150W,90℃,
Microwave irradiation 15 minutes under 200psi.
Its reaction process is as follows：
Compared with prior art, the beneficial effects are mainly as follows：The present invention provides a kind of 5- (4- (1,3-
Dimethyl -1H- pyrazoles)) application of -1,3, the 4- thiadiazoles -2- sulfide derivatives in preparing herbicide, chemical combination of the present invention
Object under 100 μ g/mL concentration compound (I-1) and (I-14) to wheat (Triticum aestivum), sorghum (Sorghum
Bicolor), barnyard grass (Echinochloa crusgalli), cucumber (Cucumis sativus), rape (Brassica
Campestris), radish (Raphanus sativus) has preferable activity；Compound of the present invention is to live with weeding
Property noval chemical compound, provide the foundation for the research and development of novel pesticide.
Specific implementation mode
With reference to 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 -4 Ethyl formate formula (II) of 1,3- dimethyl -1H- pyrazoles
Ethyl acetoacetate (1mol), triethyl orthoformate (2mol) and acetic anhydride (2.5mol) are added to there-necked flask
In, 120 DEG C of reaction 10h are heated to, solvent is rotated after completion of the reaction and obtains brown liquid.Brown liquid is added to ethyl alcohol
In (550ml), then methyl hydrazine (1.5mol) is added drop-wise in above-mentioned solution under condition of ice bath, then reaction is stirred at room temperature
3h spins off solvent and obtains white solid (II) 1, -4 Ethyl formate 86.1g of 3- dimethyl -1H- pyrazoles, yield after completion of the reaction
51.2%.
(2) by above-mentioned (II) 1, -4 Ethyl formate (10mmol) of 3- dimethyl -1H- pyrazoles is dissolved in ethyl alcohol (10ml), is added
Enter 80% hydrazine hydrate (90mmol), heating reflux reaction 8h rotates solvent after completion of the reaction, cooling that white solid is precipitated
- 4 formylhydrazine 1.42g of (III) 1,3- dimethyl -1H- pyrazoles, yield 92.1%.
(3) above-mentioned -4 formylhydrazine (65mmol) of (III) 1,3- dimethyl -1H- pyrazoles and KOH (78mmol) are added to second
30min is stirred in alcohol (250ml), and CS is then added dropwise2(65mmol), then it is stirred to react 16h at room temperature, filter (IV) 2-
Two thio potassium 1.8g of (1,3- dimethyl -1H- pyrazoles -4- carbonyls) hydrazides -1-, yield 67.7%.
(4) by two thio potassium of (IV) 2- obtained above (1,3- dimethyl -1H- pyrazoles -4- carbonyls) hydrazides -1-
(11.8mmol) is added to 98%H2SO4In (60ml), it is stirred to react 5h at room temperature, then pours into mixed liquor in trash ice, is precipitated
Precipitation filters, and washes, dry, and ethyl alcohol recrystallization obtains white solid (V) 5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,
4- thiadiazoles -2- mercaptan, yield 43%.
(5) by DMF (5ML), 5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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), it is cooled to 50 DEG C after reaction hereinafter, then pouring into mixed liquor in trash ice, precipitation solid, mistake
2- (benzylthio) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1 shown in target compound (I-1) is filtered to obtain, 3,4- thiadiazoles are received
Rate 77.3%.
2- (benzylthio) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) m.p.106-108 DEG C of -1,3,4- thiadiazoles,
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
Benzyl chloride in 1 step of embodiment (5) is changed to the 2- chlorobenzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((2- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-2), yield 59.5%.
2- ((2- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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
Benzyl chloride in 1 step of embodiment (5) is changed to the 4- chlorobenzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((4- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-3), yield 75.4%.
2- ((4- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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 1 step of embodiment (5) is changed to the 4- itrile group benzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((4- itrile groups benzyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-4), yield 75.4%.
2- ((4- itrile groups benzyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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
Benzyl chloride in 1 step of embodiment (5) is changed to the 2- fluorobenzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((2- luorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-5), yield 87.5%.
2- ((2- luorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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 1 step of embodiment (5) is changed to 2, the 4- dichlorobenzyl chlorides of 1.1mol into, other operations are obtained with embodiment 1
2- ((2,4- dichloro benzyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-6), yield
73.9%.
2- ((2,4- dichloro benzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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
Benzyl chloride in 1 step of embodiment (5) is changed to the 3- chlorobenzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((3- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-7), yield 81.3%.
2- ((3- chlorobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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 1 step of embodiment (5) is changed to 3, the 4- dichlorobenzyl chlorides of 1.1mol into, other operations are obtained with embodiment 1
2- ((3,4- dichloro benzyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-8), yield
81.1%.
2- ((3,4- dichloro benzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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 1 step of embodiment (5) is changed to the 4- bromine benzyl chlorides of 1.1mol into, other operations obtain 2- with embodiment 1
((4- bromobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-9), yield 84.2%.
2- ((4- bromobenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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
Benzyl chloride in 1 step of embodiment (5) is changed to the 2- chloro-5-chloromethyl thiazoles of 1.1mol into, other operate same embodiment
1, obtain 2- (((2- diuril azoles -5- bases) methyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles
(I-10), yield 38.9%.
2- (((2- diuril azoles -5- bases) methyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiophenes two
M.p.155-156 DEG C of azoles, 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
Benzyl chloride in 1 step of embodiment (5) is changed to the chloroacetonitrile of 1.1mol into, other operations obtain 2- ((5- with embodiment 1
(1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles -2- bases) sulfydryl) acetonitrile (I-11), yield 18.6%.
2- ((5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles -2- bases) 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 1 step of embodiment (5) is changed to the chloro- 3- chloromethylpyridine of 6- of 1.1mol into, other operate same embodiment
1, obtain 2- (((6- chloropyridine -3- bases) methyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles
(I-12), yield 39.6%.
2- (((6- chloropyridine -3- bases) methyl) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiophenes two
M.p.110-112 DEG C of azoles, 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
Benzyl chloride in 1 step of embodiment (5) is changed to the chlorallylene of 1.1mol into, other operations obtain 2- with embodiment 1
(acrylic) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-13), yield 34.4%.
2- (acrylic) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- m.p.197-200 DEG C of thiadiazoles,
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 1 step of embodiment (5) is changed to the 4- tertiary butyl benzyl chlorides of 1.1mol into, other operations are obtained with embodiment 1
2- ((4- t-butylbenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -1,3,4- thiadiazoles (I-14), yield
41.0%.
2- ((4- t-butylbenzyls) sulfydryl) -5- (1,3- dimethyl -1H- pyrazoles -4- bases) -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)+.
15 activity of weeding of embodiment is tested
Subjects：Wheat (Triticum aestivum), sorghum (Sorghum bicolor), barnyard grass
(Echinochloa crusgalli), cucumber (Cucumis sativus), rape (Brassica campestris), radish
(Raphanus sativus)。
Medicament prepares：(I-1)-(I-14) each 5mg of compound prepared by Example 1-14, after adding 0.5ml acetone solutions
Again plus 10% POLYSORBATE 80s of 0.05ml, finally plus 50ml water fully dissolves, 100ppm Sample Reagents are obtained.Because 100ppm is
100mg/L so amount of water=5mg*1000/100mg=50ml, because of final content≤1% of organic solvent so plus acetone amount
=50ml*1%=0.5ml (dissolving), because the final content of tween is 0.1% so should have tween 0.05ml in 50ml water, i.e.,：It answers
Add 10% tween 0.05ml.
Experimental method：The active compound of certain mass is weighed with assay balance (0.0001g), is added and is contained 1% Tween-80 emulsifier
DMF dissolved, be configured to 1.0%-5.0% mother liquors, then with distilled water dilute it is spare.
Culture dish method (general sieve)：It is radish, cucumber, rape, wheat, sorghum and barnyard grass, wherein wheat, sorghum for examination target
Vernalization is carried out in advance with radish seed, the uniform seed that shows money or valuables one carries unintentionally is taken to be tested, and above-mentioned target is put into paving double-layer filter paper
Each noval chemical compound solution 9ml of concentration 100mg/L is added in internal diameter 9cm culture dishes；Number marks respectively after leaching medicine is uniform, is placed in
It is cultivated in growth cabinet, 28 DEG C of temperature is set；Illumination 3000Lux, light application time are 16h illumination, and 8h is dark, RH 75%, 7
Result is observed after it.
Activity of weeding test result is as shown in table 1.
The activity of weeding (% preventive effects) of each compound under 1 100ppm of table
All pyrazole derivatives have good activity, such as cucumber, rape to dicotyledon as can be seen from the table
And radish.On the contrary, in addition to (I-1) and (I-14), these compounds are to monocotyledon all without activity.In these compounds
In, (I-1), (I-9), (I-13) and (I-14) all has more than rape and radish 80% inhibiting rate respectively.Compound (I-1)
(I-14) is to wheat (Triticum aestivum), sorghum (Sorghum bicolor), barnyard grass (Echinochloa
Crusgalli), cucumber (Cucumis sativus), rape (Brassica campestris), radish (Raphanus
Sativus rhizome) has good activity.
Claims (8)
1. a kind of 1,3,4- thiadiazoles sulfide derivative is being prepared for inhibiting wheat, sorghum, barnyard grass, cucumber, rape, radish root
Application in the herbicide of Stem nematode, it is characterised in that the general structure such as formula of 1,3,4- thiadiazoles sulfide derivative（I）It is shown：
Formula（I）In：R is phenyl.
2. a kind of 1,3,4- thiadiazoles sulfide derivative is being prepared for inhibiting removing for wheat, cucumber, rape, radish root growth
Application in careless agent, it is characterised in that the general structure such as formula of 1,3,4- thiadiazoles sulfide derivative（I）It is shown：
Formula（I）In：R is to tert-butyl-phenyl.
3. a kind of 1,3,4- thiadiazoles sulfide derivative answering in preparing the herbicide for inhibiting rape, radish root growth
With, it is characterised in that the general structure such as formula of 1,3,4- thiadiazoles sulfide derivative（I）It is shown：
Formula（I）In：R is to cyano-phenyl, p-bromophenyl, acetonitrile-base, 6- chloro-3-pyridyls base, vinyl.
4. one kind 1,3, application of the 4- thiadiazoles sulfide derivative in preparing the herbicide for inhibiting cucumber root growth,
It is characterized in that the general structure such as formula of 1,3,4- thiadiazoles sulfide derivatives（I）It is shown：
Formula（I）In：R is rubigan.
5. one kind 1,3, application of the 4- thiadiazoles sulfide derivative in preparing the herbicide for inhibiting cucumber root growth is special
Sign is the general structure such as formula of 1,3,4- thiadiazoles sulfide derivatives（I）It is shown：
Formula（I）In：R is 2- chlorphenyls, to cyano-phenyl, p-bromophenyl, 6- chloro-3-pyridyls base, vinyl.
6. one kind 1,3, application of the 4- thiadiazoles sulfide derivative in preparing the herbicide for inhibiting jowar root growth is special
Sign is the general structure such as formula of 1,3,4- thiadiazoles sulfide derivatives（I）It is shown：
Formula（I）In：R be to cyano-phenyl, 3- chlorphenyls, 2,4 dichloro benzene base, 6- chloro-3-pyridyls base, to tert-butyl-phenyl.
7. one kind 1,3, application of the 4- thiadiazoles sulfide derivative in preparing the herbicide for inhibiting barnyard grass root growth is special
Sign is the general structure such as formula of 1,3,4- thiadiazoles sulfide derivatives（I）It is shown：
Formula（I）In：R is to tert-butyl-phenyl.
8. according to any application in claim 1-5, it is characterised in that 1,3,4- thiadiazoles sulfide derivative is in weeding
A concentration of 100ppm in agent.
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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 |
|---|
| 具有除草活性的吡唑类化合物的研究进展;谭成侠等;《现代农药》;20090430;第8卷(第2期);第6-12页 * |
| 新型含1，3，4-噻二唑的硫脲化合物的合成及除草活性;孙召慧等;《有机化学》;20130831(第33期);第2612-2617页 * |
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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 |