CN105399746B - Triazolopyrimidine sulfonamide compound, the composition containing the compound and its application - Google Patents
Triazolopyrimidine sulfonamide compound, the composition containing the compound and its application Download PDFInfo
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- CN105399746B CN105399746B CN201511009338.4A CN201511009338A CN105399746B CN 105399746 B CN105399746 B CN 105399746B CN 201511009338 A CN201511009338 A CN 201511009338A CN 105399746 B CN105399746 B CN 105399746B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract
The invention discloses a kind of triazolopyrimidine sulfonamide compound with structure as shown below formula, the composition containing the compound and its application：Wherein, X1、X2、B1、B2、R1、R2、R3、R4And R5It is defined as in the description.The triazolopyrimidine sulfonamide compound that the present invention is provided has higher growth inhibitory activity to a variety of broad leaved weeds and grassy weed, the various crops such as corn, paddy rice, cotton, wheat are acted on without obvious poisoning, with good crop safety, and synthesis step is few, method is easy, it is low to prepare cost, suitable for large-scale industrial production.
Description
Technical field
The invention belongs to chemical herbicide field, and in particular to triazolopyrimidine sulfonamide compound, contain the compound
Composition and its application.
Background technology
Studies have found that, triazolopyrimidine sulfonamide compound can suppress plant amino acid synthesis in key enzyme-second
The activity of acyl lactic acid synzyme, hinders the Amino acid synthesis of plant, causes plant metabolism disorderly so that plant growth it is serious by
Damage even dead, therefore, can be used as herbicide, such herbicide developed at present includes penoxsuam, double fluorine
Sulphur grass amine, Flumetsulam etc., its defect are that synthesis difficulty is big, and preparation method is complex and high cost, and carrying out structure to it repaiies
Activity of weeding and crop safety are more preferable, synthesis is simpler and prepare the lower triazolo pyrimidine sulphur of cost to obtain for decorations, transformation
Amide compound, development to chemical herbicide field and discloses the structure-activity relationship of such weeding active compound and has great meaning
Justice.
The content of the invention
In order to overcome above mentioned problem, the present inventor is carried out to triazolopyrimidine sulfonamides herbicide and preparation method thereof
Study with keen determination, obtained activity of weeding and crop safety more preferably, the easier triazolopyrimidine sulfonamide chemical combination of preparation method
Thing.
It is an object of the invention to provide following aspect：
(1) triazolopyrimidine sulfonamide compound, shown in its structural formula such as formula (I)：
Wherein, X1、X2Selected from N or C；And/or
A1、A2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；And/or
B1、B2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；And/or
R1、R2、R3And R4Selected from-H, alkyl, substitution alkyl, alkoxy, substituted alkoxy or halogen atom；And/or
R5Selected from-H, halogen atom, alkoxy, substituted alkoxy or group containing at least one heterocycle.
(2) preparation method containing (1) described compound as described above.
(3) composition containing (1) described compound as described above, wherein, the composition also includes emulsifying agent, cosolvent
And diluent.
(4) as described above (1) described compound as herbicide purposes, wherein, the compound is used for as herbicide
Weeds emerges or grows in suppression farm-forestry crop.
The present invention have the advantage that including：
(1) the triazolopyrimidine sulfonamide compound that the present invention is provided can effectively suppress many plantations under 100mg/L dosage
Root, Stem nematode and the seedling albefaction of thing, inhibiting rate are 80~100%；
(2) the triazolopyrimidine sulfonamide compound that the present invention is provided is under 150g a.i./ha dosage, the spray of after seedling cauline leaf
During mist processing, there is higher growth inhibitory activity to a variety of broad leaved weeds and grassy weed, inhibiting rate is more than 80%；
(3) the triazolopyrimidine sulfonamide compound that provides of the present invention under 37.5g a.i./ha dosage to some weeds
Plant has higher growth inhibitory activity, inhibiting rate >=90%；
(4) the triazolopyrimidine sulfonamide compound that provides of the present invention under 150g a.i./ha dosage to corn, paddy rice,
The various crops such as cotton, wheat are acted on without obvious poisoning, with good crop safety；
(5) the triazolopyrimidine sulfonamide compound synthesis step of the invention provided is few, method is easy, it is low to prepare cost,
Suitable for large-scale industrial production.
Brief description of the drawings
Fig. 1 shows that embodiment 1 prepares the hydrogen nuclear magnetic resonance spectrogram of product；
Fig. 2 shows that embodiment 2 prepares the hydrogen nuclear magnetic resonance spectrogram of product；
Fig. 3 shows that embodiment 3 prepares the hydrogen nuclear magnetic resonance spectrogram of product；
Fig. 4 shows that embodiment 4 prepares the hydrogen nuclear magnetic resonance spectrogram of product；
Fig. 5 shows that embodiment 5 prepares the hydrogen nuclear magnetic resonance spectrogram of product.
Embodiment
Below by experimental example and embodiment, the present invention is described in more detail.Illustrated by these, spy of the invention
Point and advantage will become more apparent from clearly.
According to the first aspect of the invention there is provided a kind of triazolopyrimidine sulfonamide compound, it has as shown in formula (I)
Structure：
Wherein, X1、X2Selected from N or C；And/or
A1、A2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；And/or
B1、B2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；And/or
R1、R2、R3And R4Selected from-H, alkyl, substitution alkyl, alkoxy, substituted alkoxy or halogen atom；And/or
R5Selected from-H, halogen atom, alkoxy, substituted alkoxy or group containing at least one heterocycle.
In a preferred embodiment in accordance with the present invention, X1And X2It is asynchronously N and is asynchronously C；
The alkyl is selected from C1~C10Alkyl, preferably C1~C6Alkyl, more preferably methyl, ethyl or propyl group, most
Preferably methyl；
The alkoxy is selected from C1~C10Alkoxy, preferably C1~C6Alkoxy, more preferably methoxyl group, ethoxy
Base or propoxyl group, most preferably methoxyl group.
The halogen atom is selected from F, Cl or Br, preferably F or Cl.
The alkyl that the substitution alkyl is replaced by H by halogen atom, is preferably the C containing 1~3 halogen atom1~C6Alkane
Base, the more preferably methyl containing 1~3 fluorine atom, ethyl or propyl group, are most preferably-CF3。
The alkoxy that the substituted alkoxy is replaced by H by halogen atom, is preferably the C containing 1~3 halogen atom1~C6
Alkoxy, the more preferably methoxyl group containing 1~3 fluorine atom, ethyoxyl or propoxyl group, most preferably F2HCH2CO-(2,2-
Two fluoro ethyls).
The group containing at least one heterocycle is the group containing at least one tetrahydrofuran ring, is preferably such as formula
(II) group shown in：
It is further preferred that in formula (I),
X1And X2In one be N, another is C；And/or
A1、A2Selected from-H or methoxyl group；And/or
B1、B2Selected from-H, methyl or methoxy；And/or
R1、R2、R3And R4Selected from-H, methyl ,-CF3Or-Cl；And/or
R5Selected from-H ,-F, F2HCH2CO- or the group as shown in formula (II).
Tied it is highly preferred that the triazolopyrimidine sulfonamide compound has as shown in one of following formula (III)~formula (VII)
Structure：
Most preferably, the triazolopyrimidine sulfonamide compound has the structure as shown in formula (III)：
According to the second aspect of the invention, the preparation of the triazolopyrimidine sulfonamide compound as shown in formula (I) is also provided
Method, comprises the following steps：
Step (1), the preparation of ethoxycarbonyl isothiocyanate：Using ethyl acetate as solvent, potassium rhodanide and chloro-carbonic acid second
Ester carries out substitution reaction, obtains the mixed liquor of ethoxycarbonyl isothiocyanate and ethyl acetate；
Step (2), the preparation of N- (substituted pyrimidyl)-N '-carbethoxyl group thiocarbamide：To carbethoxyl group made from step (1)
2- amino substituted pyrimidines or 4- amino substituted pyrimidines are added in the mixed liquor of isothiocyanates and ethyl acetate, progress replaces anti-
Should, obtain the product；
Step (3), the preparation of 2- amino-triazol substituted pyrimidines：Using ethanol as solvent, in the basic conditions, hydrochloric acid hydroxyl
Amine reacts with N- (substituted pyrimidyl)-N ' made from step (2)-carbethoxyl group thiocarbamide, obtains the product；
Step (4), the preparation of the fluoro- 6 substituted benzene dipropyl sulfides of 2-/2- substituted benzene dipropyl sulfides：Using tetrahydrofuran as solvent, in fourth
Under the catalysis of base lithium, dipropyl disulfide carries out substitution reaction with the fluoro- 1- substituted benzenes of 3-/1- substituted benzenes, obtains the product；
Step (5), the preparation of 2,6- substituted benzene dipropyl sulfides：Using Isosorbide-5-Nitrae-dioxane as solvent, under metallic sodium catalysis, contain
There is R5The fluoro- 6 substituted benzene dipropyl sulfide reactions of 2- made from the alcohol and step (4) of group, obtain the product；
Step (6), the synthesis of 2,6- substituted phenylsulfonyl chlorides/2- substituted phenylsulfonyl chlorides：Using glacial acetic acid and water as solvent, chlorine
Reacted with 2,6- substituted benzenes dipropyl sulfide made from step (5)/2- substituted benzenes dipropyl sulfide made from step (4), obtain the product；
Step (7), (triazol replaces 2- substitutions-N- (triazol substituted pyrimidines) -6- substituted benzene sulfonic acid amides/2- substitutions-N-
Pyrimidine) benzsulfamide preparation：Using acetonitrile and dimethyl sulfoxide (DMSO) as solvent, under the catalysis of 3,5- lutidines, step (3) system
2- amino-triazol the substituted pyrimidines obtained react with 2,6- substituted phenylsulfonyl chlorides made from step (6)/2- substituted phenylsulfonyl chlorides,
Obtain the product.
There is provided a kind of combination containing triazolopyrimidine sulfonamide compound as described above according to the third aspect of the invention we
Thing, wherein, the composition also includes emulsifying agent, cosolvent and diluent.
The emulsifying agent is tween emulsifier type, preferably Tween-60 or Tween-80, more preferably Tween-80.
The cosolvent is selected from DMF (DMF) or dimethyl sulfoxide (DMSO) (DMSO), preferably N, N- diformazans
Base formamide.
The diluent is water, preferably distilled water.
In the composition, the weight of triazolopyrimidine sulfonamide compound as described above, emulsifying agent and diluent
Than for (0.01~20)：(0.01~10)：(50~200), be preferably (0.1~15)：(0.1~5)：(70~150), more preferably
For (0.5~10)：(0.5~2)：(90~120).
It is preferred that the composition is prepared as follows：Emulsifying agent is mixed with cosolvent, the triazole is then added
And pyrimidinyl sulfonamide compounds dissolve it, add diluent and be configured to required concentration.
There is provided use of the triazolopyrimidine sulfonamide compound as described above as herbicide according to the fourth aspect of the invention
On the way, wherein, the compound is used to suppress emerging or growing for weeds in farm-forestry crop as herbicide.
The triazolopyrimidine sulfonamide compound can be used alone, can also composition forms containing it as described above
Use, it is directly contacted weeds plant or is applied in the soil of its growth or irrigation water to suppress emerging for weeds
Or growth.
Embodiment
Embodiment 1
The triazolopyrimidine sulfonamide compound as shown in formula (III) is prepared according to step (1)~(7) methods described.
Step (1), the preparation of ethoxycarbonyl isothiocyanate
It is furnished with 1000mL in agitator, thermometer, reflux condensing tube, the four-hole bottle of dropping funel, adds 600mL acetic acid
Ethyl ester, stirring is lower to add 97.2g (1mol) potassium rhodanide, is warming up to 40 DEG C, 106.3g (0.98mol) ethyl chloroformate is added dropwise,
Control temperature to be less than at 45 DEG C to be added dropwise, after completion of dropping, control 40 DEG C of temperature, be incubated 2h, treat that ethyl chloroformate reaction is complete, drop
To room temperature, sylvite is filtered to remove, the mixed liquor for obtaining ethoxycarbonyl isothiocyanate and ethyl acetate is standby.
Step (2), the preparation of N- (4,6- dimethoxypyridin -2- bases)-N '-carbethoxyl group thiocarbamide
2- amino -4,6- dimethoxypyridins 124.1g is added in the reaction solution of ethoxycarbonyl isothiocyanate
(0.8mol), controls 40 DEG C of temperature, is incubated 6h, treats that the reaction of raw material 2- amino-4,6-dimethoxy pyrimidines is complete, be down to room temperature,
Suction filtration, and washed with 50mL ethyl acetate and obtain product, weight in wet base 400g obtains product 192.9g after drying, purity 98.5% is received
Rate 84.3%.
Step (3), the preparation of 2- amino -5,7- dimethoxy [1,2,4] triazol [1,5-a] pyrimidine
It is furnished with 1000mL in agitator, thermometer, reflux condensing tube, the four-hole bottle of dropping funel, adds 600mL second
Alcohol, N- (4,6- dimethoxypyridin -2- bases)-N '-carbethoxyl group thiocarbamide 114.5g (0.4mol), hydroxylamine hydrochloride 40.3g
(0.58mol), is warming up to 60 DEG C, and 58.7g (0.58mol) triethylamine is added dropwise, and 0.5h completion of dropping, back flow reaction 5h treats raw material
N- (4,6- dimethoxypyridin -2- bases)-N '-carbethoxyl group thiocarbamide reaction is complete, is down to room temperature suction filtration, and with 200mL, 50 DEG C
Water agitator treating 20min, obtain product 71.4g after filtering drying, purity 98.6%, yield is about 91.5%.
Step (4), the preparation of the fluoro- 6- trifluoromethylbenzenes dipropyl sulfides of 2-
It is furnished with 1000mL in agitator, thermometer, the four-hole bottle of constant pressure funnel, by 3- fluoride trifluoro toluenes 82g
(0.5mol) is added in the dried tetrahydrofurans of 320mL, with nitrogen displacement air three times, and whole-process control reaction is closed, with
Dry ice acetone bath is cooled to -78 DEG C, and butyl lithium 200mL (0.5mol) is slowly added dropwise, and controlling reaction temperature is below -70 DEG C, drop
Add after finishing, dipropyl disulfide 75.1g (0.5mol) is slowly added dropwise in -70 DEG C of reaction 0.5h, and control temperature is anti-below -70 DEG C
1h is answered, 10%NaCl aqueous solution 100mL are slowly added dropwise, adjusts pH value to acidity with HCl, static layering washes organic layer, anhydrous sulphur
Sour sodium is dried, and is removed solvent under reduced pressure, is obtained product 79.1g, purity 96.2%, yield 66.5%.
Step (5), the preparation of 2- (tetrahydrofuran base -2- methoxyl groups) -6- trifluoromethylbenzene dipropyl sulfides
It is furnished with 1000mL in agitator, thermometer, air set pipe, the four-hole bottle of dropping funel and adds dried 1,
4- dioxane 600mL, metallic sodium 34.5g (1.5mol), are sufficiently stirred for, and tetrahydrofurfuryl alcohol 122.6g is slowly added dropwise at room temperature
(1.2mol), controlling reaction temperature is less than 30 DEG C, continues to react under 1h, reflux state after completion of dropping, the fluoro- 6- trifluoros of 2- are added dropwise
Methylbenzene dipropyl sulfide 238.2g (1mol), continues back flow reaction 2h, treats that the fluoro- 6- trifluoromethylbenzenes dipropyl sulfides of raw material 2- have reacted
Entirely, remove solvent under reduced pressure, add 15% aqueous hydrochloric acid solution, be extracted with ethyl acetate.Remove extract under reduced pressure solvent, obtain
Product 225.0g, purity 96.2%, yield 70.3%.
Step (6), the synthesis of 2- (tetrahydrofuran base -2- methoxyl groups) -6- trifluoromethyl benzene sulfonyl chlorides
It is furnished with 1000mL in agitator, thermometer, air set pipe, the four-hole bottle of airway tube and adds glacial acetic acid 400mL,
Water 100mL, 2- (tetrahydrofuran base -2- methoxyl groups) -6- trifluoromethylbenzene dipropyl sulfide 160.2g (0.5mol), control 30 DEG C of temperature
Chlorine is passed through below, until solution becomes clarification, raw material reaction is complete, and stopping is passed through chlorine, stirs 0.5h, adds 300mL dichloros
Ethane, and 3 times are washed to remove glacial acetic acid with saturated sodium bicarbonate aqueous solution 300mL, static layering removes solvent under reduced pressure, obtained
It is standby to product.
Step (7), (5,7- dimethoxys [1,2,4] triazol [1,5-a] is phonetic by 2- (tetrahydrofuran base -2- methoxyl groups)-N-
Pyridine -2- bases) -6- trifluoromethyl benzene sulfonamides preparation
It is furnished with 100mL in agitator, thermometer, air set pipe, the four-hole bottle of dropping funel and sequentially adds 3,5- bis-
Picoline 9.6g (0.09mol), acetonitrile 15mL, dimethyl sulfoxide (DMSO) 1mL, 2- amino -5,7- dimethoxy [1,2,4] triazol
[1,5-a] pyrimidine 6g (0.03mol), is sufficiently stirred for after 10min, and 2- (tetrahydrofuran base -2- methoxyl groups) -6- trifluoros are added portionwise
Toluene sulfonyl chloride 10.3g (0.03mol), control temperature is raised slowly to 33~35 DEG C of reaction 1h, then heats to 42 DEG C instead
1h is answered, treats that raw material 2- amino -5,7- dimethoxy [1,2,4] triazol [1,5-a] pyrimidine total overall reaction stops reaction after finishing,
Room temperature is cooled down to, reaction solution is slowly added in 10% sulfuric acid water, is stirred at 40 DEG C after 0.5h, cools down to room temperature,
Filtering, product 13.5g, purity 98.1%, yield 89.6%, its hydrogen nuclear magnetic resonance spectrogram such as Fig. 1 institutes are obtained with recrystallized from acetonitrile
Show.
Embodiment 2
Prepared, differed only according to method similar to Example 1：By the 2- amino -4,6- two in step (2)
Methoxy pyrimidine replaces with 2,5- dimethoxy-4 's-amine pyrimidine of equivalent, obtains the triazolo pyrimidine sulphur as shown in formula (IV)
Amide compound, purity 96.1%, its hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 2.
Embodiment 3
Prepared, differed only according to method similar to Example 1：By the 2- amino -4,6- two in step (2)
Methoxy pyrimidine replaces with 2- amino -4,6- dimethyl pyrimidine 100.1g (0.8mol), obtains the triazol as shown in formula (V)
Pyrimidinyl sulfonamide compounds, purity 97.9%, its hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 3.
Embodiment 4
Prepared, differed only according to method similar to Example 1：Step (5) is omitted, is obtained such as formula (VI) institute
The triazolopyrimidine sulfonamide compound shown, purity 98.5%, its hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 4.
Embodiment 5
Prepared, differed only according to method similar to Example 1：By the 2- amino -4,6- two in step (2)
Methoxy pyrimidine replaces with 2- amino -4,6- dimethyl pyrimidine 100.1g (0.8mol), and omits step (5), obtains such as formula
(VII) the triazolopyrimidine sulfonamide compound shown in, purity 97.5%, its hydrogen nuclear magnetic resonance spectrogram is as shown in Figure 5.
Experimental example
Triazolopyrimidine sulfonamide compound made from embodiment 1~5 is given birth to according to the methods described of experimental example 1~4
Thing determination of activity, it is specific as follows.
The activity of weeding test of experimental example 1-Plating
(1) sample is prepared
Triazolopyrimidine sulfonamide chemical combination made from the embodiment 1~5 of certain mass is weighed with assay balance (0.0001g)
Thing, is configured to 1.0~5.0% mother liquors with DMF (DMF) dissolving containing 1% Tween-80, then uses distilled water
Dilution is standby.
(2) test method
It is radish, cucumber, rape, wheat, sorghum and barnyard grass for examination target, wherein wheat, sorghum and radish seed is pre- advanced
Row vernalization, takes the seed that shows money or valuables one carries unintentionally of uniformity to be tested, and above-mentioned target is put into the internal diameter 9cm culture dishes of paving double-layer filter paper,
Concentration 100mg/L each triazolopyrimidine sulfonamide compound solution 9ml is added, as treatment group, with the nitre sulphur of same dose
Humulone is used as blank control as positive control using the sterile distilled water of equivalent；Numbering is marked respectively after leaching medicine is uniform, is placed in people
Cultivated in work climate box, 28 DEG C of temperature is set；Illumination 3000Lux, light application time is relatively wet according to 16h illumination, 8h dark cycles
(RH) 75% is spent, root, the growing state of stem are investigated after 7 days, and the compound of the invention provided is calculated as follows to target
Root, the Stem nematode inhibiting rate (%) of plant, the results are shown in Table 1.
Root growth inhibition rate (%)=(blank control group root growth amount-treatment group root growth amount)/blank control group root life
Long amount × 100%
Stem nematode inhibiting rate (%)=(blank control group Stem nematode amount-treatment group Stem nematode amount)/blank control group stem life
Long amount × 100%
The activity of weeding ware result of the test of the compound of table 1.
As shown in table 1, triazolopyrimidine sulfonamide compound made from the embodiment of the present invention 1~5 is in 100mg/L inorganic agents
Under amount, activity is respectively provided with to radish, cucumber, rape, wheat, sorghum and barnyard grass, wherein there is higher work to wheat, sorghum and radish
Property, root, Stem nematode inhibiting rate are 80~100%, show as suppressing root, Stem nematode and seedling albefaction, and performance symptom is with positive right
It is similar according to mesotrione.
The activity of weeding test of experimental example 2-pot-culture method
(1) sample is prepared
Triazolopyrimidine sulfonamide chemical combination made from the embodiment 1~5 of certain mass is weighed with assay balance (0.0001g)
Thing, is configured to 1.0~5.0% mother liquors with DMF (DMF) dissolving containing 1% Tween-80, then uses distilled water
Dilution is standby.
(2) test method
General sieve：It is winter weeds leaf mustard, annual bluegrass, chickweed, amur foxtail, small lamb's-quarters and caput grass for examination target, sample is this
Triazolopyrimidine sulfonamide compound made from inventive embodiments 1~5, dispenser dosage 150g a.i./ha.
Primary dcreening operation：It is summer weeds piemarker, lady's-grass, Amaranthus retroflexus, barnyard grass, Eclipta prostrata, green bristlegrass for examination target, sample is in general sieve
The compound of high activity is shown, i.e., triazolopyrimidine sulfonamide compound, dispenser dosage made from the embodiment of the present invention 1,4
37.5、75、150g a.i./ha。
Above-mentioned general sieve and primary dcreening operation are carried out by the following method：Internal diameter 7.5cm flowerpots are taken, composite earth (vegetable garden soil is filled：Nursery base
Matter (v:V)=1：2) at 3/4, above-mentioned weeds target (bud rate >=85%) is directly sowed, earthing 0.2cm treats weeds length to 3 leaves
Or so phase is standby.The sample of each compound is by auto spraying tower (model：3WPSH-700E) dispenser, applies the sterile distillation of equivalent
Water moves into hot-house culture as blank control after weeds blade face decoction dries, and suppression of the compound to weeds is investigated after 25 days
Activity, according to the activity of weeding of ten grades of ocular estimates (0 grade=without significant reaction, 10 grades=plant is completely dead) investigation compound,
Range estimation data are converted to biomass suppression percentage (such as 1.5 grade=15%) of the processing weeds plant relative to blank control, i.e.,
For growth inhibition ratio of the compound to weeds, 2 are the results are shown in Table.
The potted plant activity of weeding of the compound of table 2. tests general sieve result
As shown in table 2, triazolopyrimidine sulfonamide compound made from the embodiment of the present invention 1~5 is in 150g a.i./ha
Under dosage, after seedling cauline leaf spraying treatment when, to 3 kinds of broad leaved weed target leaf mustard, chickweed and small lamb's-quarters activity it is higher, 7 after dispenser~
Cause within 10 days weed growth to be stagnated and deformity, and then cause whole strain withered, weeds plant is all dead after 30 days, wherein, to mustard
The growth inhibition ratio of dish and chickweed is 100%, and the growth inhibition ratio to small lamb's-quarters is more than 80%；In addition, above-claimed cpd is to surveying
The part grassy weed of examination also has compared with Seedling height inhibitory activity, inhibiting rate >=80%.
The crop safety of experimental example 3 tests (one)
(1) sample is prepared
With triazolopyrimidine sulfonamide chemical combination made from assay balance (0.0001g) weighs the embodiment 1 and 4 of certain mass
Thing, is configured to 1.0~5.0% mother liquors with DMF (DMF) dissolving containing 1% Tween-80, then uses distilled water
Dilution is standby.
(2) test method
It is corn, paddy rice, soybean, cotton for examination target, takes internal diameter 12cm flowerpots, fills composite earth (vegetable garden soil：Seedling medium
(v:V)=1：2) at 3/4, above-mentioned crop seed (bud rate >=85%), earthing 0.2cm, plant to be planted length to 4~5 are directly sowed
Leaf or so is standby.Each compound, by auto spraying tower dispenser, applies the sterile distilled water of equivalent according to 150g a.i./ha dosage
As blank control, hot-house culture is moved into after blade face decoction dries, investigation test result after 15 days, and chemical combination is calculated as follows
Thing the results are shown in Table 4 to the fresh weight inhibition of target plant.
Fresh weight inhibition=(blank control group above-ground plant parts fresh weight-treatment group above-ground plant parts fresh weight)/blank
Control group above-ground plant parts fresh weight × 100%
The potted plant crop security test result (one) of the compound of table 4.
As shown in table 4, under 150g a.i./ha dosage, triazolopyrimidine sulfonamide made from the embodiment of the present invention 1
Compound is less than 10% to corn, paddy rice, cotton plants aerial part fresh weight inhibition, estimates without obvious symptom of chemical damage, relative peace
Entirely；Compound made from embodiment 4 is only to cotton range estimation without obvious poisoning, and above-ground plant parts fresh weight inhibition is less than 10%,
It is comparatively safe.
The present invention is described in detail above in association with preferred embodiment and exemplary example.But need what is stated
It is that these embodiments are only the illustrative explanations to the present invention, do not constitute any limit to protection scope of the present invention
System.In the case of without departing from spirit and scope of the present invention, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these are each fallen within protection scope of the present invention.Protection scope of the present invention is with appended power
Profit requires to be defined.
Claims (12)
1. triazolopyrimidine sulfonamide compound, it is characterised in that shown in its structural formula such as formula (I)：
Wherein, X1、X2Selected from N or C；
A1、A2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；
B1、B2Selected from-H, alkyl, substitution alkyl, alkoxy or substituted alkoxy；
R1、R2、R3And R4Selected from-H, alkyl, substitution alkyl, alkoxy, substituted alkoxy or halogen atom；
R5For the group as shown in formula (II)：
The alkyl is selected from C1~C10Alkyl,
The alkoxy is selected from C1~C10Alkoxy,
The halogen atom is selected from F, Cl or Br,
The alkyl that the substitution alkyl is replaced by H by halogen atom,
The alkoxy that the substituted alkoxy is replaced by H by halogen atom.
2. compound according to claim 1, it is characterised in that
The alkyl be methyl, ethyl or propyl group,
The alkoxy be methoxyl group, ethyoxyl or propoxyl group,
The halogen atom is F or Cl.
3. compound according to claim 1, it is characterised in that
The substitution alkyl is the C containing 1~3 halogen atom1~C6Alkyl,
The substituted alkoxy is the C containing 1~3 halogen atom1~C6Alkoxy.
4. compound according to claim 1, it is characterised in that
X1、X2Selected from N or C；
A1、A2Selected from-H or methoxyl group；
B1、B2Selected from-H, methyl or methoxy；
R1、R2、R3And R4Selected from-H, methyl ,-CF3Or-Cl.
5. compound according to claim 1, it is characterised in that the compound has following structure：
6. compound according to claim 1, it is characterised in that the compound has the structure as shown in formula (III)：
7. the preparation method of the triazolopyrimidine sulfonamide compound according to one of claim 1 to 6, it is characterised in that
Comprise the following steps：
Step (1), potassium rhodanide and ethyl chloroformate carry out substitution reaction, obtain ethoxycarbonyl isothiocyanate；
Step (2), ethoxycarbonyl isothiocyanate made from step (1) enters with 2- amino substituted pyrimidines or 4- amino substituted pyrimidines
Row substitution reaction, obtains N- (substituted pyrimidyl)-N '-carbethoxyl group thiocarbamide；
Step (3), hydroxylamine hydrochloride and N- (substituted pyrimidyl)-N ' made from step (2)-carbethoxyl group thiocarbamide reacts, and obtains 2-
Amino-triazol substituted pyrimidines；
Step (4), dipropyl disulfide and the fluoro- 1- substituted benzenes of 3- or 1- substituted benzenes carry out substitution reaction, obtain fluoro- 6 substituted benzenes of 2-
Dipropyl sulfide or 2- substituted benzene dipropyl sulfides；
Step (5), contain R5The alcohol of group reacts with the fluoro- 6 substituted benzene dipropyl sulfides of 2- made from step (4), obtains 2,6- substituted benzenes
Dipropyl sulfide；
Step (6), 2- substituted benzene dipropyl sulfides made from chlorine and 2,6- substituted benzenes dipropyl sulfide made from step (5) or step (4)
Reaction, obtains 2,6- substituted phenylsulfonyl chlorides or 2- substituted phenylsulfonyl chlorides；
Step (7), 2- amino-triazol substituted pyrimidines made from step (3) and 2,6- substituted phenylsulfonyl chlorides made from step (6)
Or the reaction of 2- substituted phenylsulfonyl chlorides, obtain 2- substitutions-N- (triazol substituted pyrimidines) -6- substituted benzene sulfonic acid amides or 2- substitutions-N-
(triazol substituted pyrimidines) benzsulfamide.
8. the composition containing the compound as described in one of claim 1 to 6, it is characterised in that the composition also includes breast
Agent, cosolvent and diluent.
9. composition according to claim 8, it is characterised in that
The emulsifying agent is tween emulsifier type,
The cosolvent is selected from DMF or dimethyl sulfoxide (DMSO),
The diluent is water,
The weight ratio of compound, emulsifying agent and diluent as described in one of claim 1 to 6 is (0.01~20)：(0.01~
10)：(50~200).
10. composition according to claim 9, it is characterised in that
The emulsifying agent be Tween-60 or Tween-80,
The weight ratio of compound, emulsifying agent and diluent as described in one of claim 1 to 6 is (0.5~10)：(0.5~
2)：(90~120).
11. as described in one of claim 1 to 6 compound as herbicide purposes, it is characterised in that the compound conduct
Herbicide is used to suppress emerging or growing for weeds in farm-forestry crop.
12. purposes as claimed in claim 11, it is characterised in that compound or such as right as described in one of claim 1 to 6
It is required that one of 8 to 10 compositions directly contact weeds plant or be applied to its growth soil or irrigation water in
Suppress emerging or growing for weeds.
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| US4822404A (en) * | 1984-01-26 | 1989-04-18 | The Dow Chemical Company | Sulfonamides derived from substituted 2-amino-1,2,4-triazolo (1,5-a) pyrimidines and compositions and methods of controlling undesired vegetation |
| US4685958A (en) * | 1986-05-06 | 1987-08-11 | The Dow Chemical Company | Sulfonamides derived from substituted 2-amino-1,2,4-triazolo[1,5-a]-1,3,5-triazines and compositions and methods of controlling undesired vegetation |
| DE4106100A1 (en) * | 1991-02-27 | 1992-09-03 | Bayer Ag | Substd. sulphonyl-amino-triazolo-triazine(s) - are herbicides prepd. by heating sulphonylated amino-guanidino-triazine derivs. with acids |
| CN1092195A (en) * | 1993-03-13 | 1994-09-14 | 北京联想计算机集团公司 | The method of PC synthetic speech music and sounding |
| AU723666B2 (en) * | 1996-09-24 | 2000-08-31 | Dow Agrosciences Llc | N-({1,2,4} triazoloazinyl)benzenesulfonamide and pyridinesulfonamide compounds and their use as herbicides |
| JP3809316B2 (en) * | 1999-01-28 | 2006-08-16 | キヤノン株式会社 | Solar power plant |
| DE60102215T2 (en) * | 2000-11-03 | 2004-07-22 | Dow Agrosciences Llc, Indianapolis | N- (5,7-DIMETHOXY [1,2,4] TRIAZOLO [1,5-A] PYRIMIDIN-2-YL) ARYLSULFONAMIDE COMPOUNDS AND THE USE THEREOF AS HERBICIDES |
| KR101111014B1 (en) * | 2004-03-26 | 2012-02-13 | 다우 아그로사이언시즈 엘엘씨 | An improved process for the preparation of n-[1,2,4]triazolopyrimidin-2-ylaryl sulfonamides |
| CN102167675B (en) * | 2011-03-21 | 2013-06-26 | 中南大学 | Methods for preparing N-alkoxycarbonyl isothiocyanate and derivative thereof |
| CN103319489B (en) * | 2013-07-12 | 2015-04-08 | 黑龙江大学 | Triazolopyrimidine sulfonamide compound, and synthetic method and application thereof |
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