CN100344628C - Pyrazopyrimidinone compounds and use thereof - Google Patents
Pyrazopyrimidinone compounds and use thereof Download PDFInfo
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- CN100344628C CN100344628C CNB2005100461278A CN200510046127A CN100344628C CN 100344628 C CN100344628 C CN 100344628C CN B2005100461278 A CNB2005100461278 A CN B2005100461278A CN 200510046127 A CN200510046127 A CN 200510046127A CN 100344628 C CN100344628 C CN 100344628C
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Abstract
The present invention discloses a pyrazopyrimidinone compound which has herbicidal activity. The compound is shown in a general formula (I). In the formula, R1 is selected from C1 to C4 alkyl, R2 is selected from C1 to C4 alkyl, X is selected from halogen, C1 to C6 alkyl, halogenating C1 to C6 alkyl or CN, Y is selected from halogen, C1 to C6 alkyl, halogenating C1 to C6 alkyl, C1 to C6 cycloalkyl, C1 to C6 alkoxy, C3 to C6 ring alkoxy, C2 to C6 olefin oxy, C3 to C6 acetylene oxy, C1 to C4 alkoxycarbonyl, C2 to C6 olefin oxygen carbonyl, C3 to C6 acetylene oxygen carbonyl, or C1 to C4 alkoxycarbonyl C1 to C2 alkoxy, and X and Y can also form benzopyrene 6-element heterocycle shown as follows. The present invention also provides a herbicide composition which contains the compound in the general formula (I), and a method for controlling ruderal by the compound.
Description
Technical field
The invention belongs to the weedicide field.Specifically, relate to a kind of pyrazolopyrimidinones and as herbicide applications.
Background technology
Because weedicide or its composition are in use for some time, weeds can produce resistance to it, therefore, need constantly invention novel with improved herbicidal compound and composition.In addition, consider the factor of aspects such as energy economy ﹠ environment, the invention weedicide different with existing herbicide action mechanism also is very important.
Some pyrazolopyrimidinones is as the existing report of weedicide (JP57167902).But as (2-F-4,5-tri-substituted phenyl) pyrazolopyrimidinones shown in the present is not seen open.
Summary of the invention
The object of the present invention is to provide a kind of pyrazolopyrimidinones of novel structure, it can be applicable to agricultural and goes up to prevent and treat various weeds.
Technical scheme of the present invention is as follows:
The invention provides a kind of pyrazolopyrimidinones, shown in general formula (I):
In the formula:
R
1Be selected from C
1-C
4Alkyl;
R
2Be selected from C
1-C
4Alkyl;
X is selected from halogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl or CN;
Y is selected from halogen, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Cycloalkyl, C
1-C
6Alkoxyl group, C
3-C
6Cycloalkyloxy, C
2-C
6Alkene oxygen base, C
3-C
6Alkynyloxy group, C
1-C
4Carbalkoxy, C
2-C
6Alkenyloxycarbonyl, C
3-C
6Alkynes oxygen carbonyl or C
1-C
4Carbalkoxy C
1-C
2Alkoxyl group;
X and Y also can form benzo 6-unit heterocycle as follows:
Wherein:
L is selected from O or S;
R
3Be selected from H or C
1-C
4Alkyl;
R
4Be selected from H, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Cycloalkyl, C
3-C
6Thiazolinyl, halo C
3-C
6Thiazolinyl, C
3-C
6Alkynyl, halo C
3-C
6Alkynyl, C
1-C
6Alcoxyl C
1-C
2Alkyl, C
2-C
6Alkene oxygen C
1-C
2Alkyl, C
3-C
6Alkynes oxygen C
1-C
2Alkyl or cyanogen C
1-C
4Alkyl.
Comparatively preferred compound is among the present invention, in the general formula (I):
R
1Be selected from C
1-C
4Alkyl;
R
2Be selected from C
1-C
2Alkyl;
X is selected from halogen or CN;
Y is selected from C
1-C
6Alkoxyl group, C
3-C
6Cycloalkyloxy, C
2-C
6Alkene oxygen base, C
3-C
6Alkynyloxy group, C
1-C
4Carbalkoxy, C
2-C
6Alkenyloxycarbonyl, C
3-C
6Alkynes oxygen carbonyl or C
1-C
4Carbalkoxy C
1-C
2Alkoxyl group;
X and Y also can form benzo 6-unit heterocycle as follows:
Wherein:
R
4Be selected from C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Cycloalkyl, C
3-C
6Thiazolinyl or C
3-C
6Alkynyl.
The alkyl of indication comprises the straight or branched alkyl in the general formula.Thiazolinyl is meant the straight or branched form, the group of 1 to 2 carbon-carbon double bond is arranged, for example vinyl, propenyl, allyl group etc.Alkynyl is meant the straight or branched form, and 1 to 2 carbon carbon triple-linked group, for example ethynyl, proyl, propargyl etc. are arranged.Halogen is meant fluorine, chlorine, bromine, iodine.
General formula of the present invention (I) compound can be prepared by following method:
Raw material pyrazoles amine (II) (can obtain by buying on the market) is dissolved in The suitable solvent with oxalyl chloride, for example chloroform, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, THF or dioxane, temperature made isocyanic ester, i.e. compound (II-1) for-10 ℃ in 0.5-48 hour to the boiling point reaction.
Compound (II-1) and trisubstituted benzene amine are in The suitable solvent, and temperature made compound (II-2) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent can be selected from chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane etc.
Trisubstituted benzene amine can be by buying on the market or can being made (referring to the method for describing among the EP0083055A2) by currently known methods.
Compound (II-2) and sodium methylate are in The suitable solvent, and temperature made compound (II-3) for-10 ℃ in 0.5-48 hour to the boiling point reaction.Solvent can be selected from chloroform, methylene dichloride, methyl alcohol, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane etc.
Compound (II-3) and R
2X (R
2Definition is the same, X is halogen), in The suitable solvent, temperature is reacted down to boiling point and to be made compound (I) in 0.5-48 hour for-10 ℃.Solvent can be selected from chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane etc.Add alkaloids, as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or sodium bicarbonate etc. to reacting favourable.
Can the present invention be described with the compound of listing in the following table 1, but not limit the present invention.
Table 1
| Numbering | X，Y，R 1，R 2 | Fusing point (℃) |
| Compound 1 | X=Cl, Y=alkynes propoxy-, R 1＝Me，R 2＝Me | 214-216 |
| Compound 2 | X=Cl, Y=cyclopentyloxy, R 1＝R 2＝Me | 188-190 |
| Compound 3 | X=Cl, Y=allyloxy, R 1＝R 2＝Me | 196-198 |
| Compound 4 | X＝Cl，Y＝OCH 2COOCH 3，R 1＝R 2＝Me | 200-202 |
| Compound 5 | X=Cl, Y=cyclopentyloxy, R 1＝Me，R 2＝CH 2CH 3 | Half consolidates shape |
Compound 6:
Part of compounds
1H NMR (CDCl
3) data see Table 2:
Table 2
| Compound 5 | 8.002(s，1H，C-H)，7.277-7.246(t，1H，Ar-H)，6.797-6.775(d，1H，Ar- H)，4.712-4.775(m，1H，CH)，4.552-4.424(q，2H，CH2)，3.928(S，3H， CH3)，1.874-1.612(m，8H) |
| Compound 6 | 7.823(s，1H)，7.198-7.165(t，1H)，7.085-6.986(d，1H)，4.765-4.746( d，2H)，4.652(s，2H)，4.168(s，3H)，3.765(s，3H)，2.584(s，1H) |
General formula of the present invention (I) compound has weeding activity, uses behind Miao Qianmiao and can effectively control single broadleaf weed.Compare with compound of the prior art, have the weeding activity of wide spectrum more, especially broadleaf weeds is had beyond thought high reactivity.
The present invention comprises that also with general formula (I) compound be the herbicidal composition of active ingredient.The weight percentage of active ingredient is between 0.1-99% in this herbicidal composition.Comprise also in this herbicidal composition that agricultural goes up acceptable carrier.
The other technical scheme of the present invention is a method of controlling weeds, and this method comprises herbicidal composition of the present invention is imposed on the surface of growth medium of the places of described weeds or described weeds or described weeds.Usually the comparatively suitable significant quantity of selecting is that per hectare 50 restrains 5000 grams, and preferred significant quantity is that per hectare 100 restrains 3000 grams.
Compound of the present invention can preparation form be administered on soil or the blade face.This compound is dissolved in the carrier usually or is mixed with preparation so that be easier to disperse when using as weedicide.For example: but these chemicals can be made into wet-milling or missible oil.In these compositions, add a kind of liquid or solid carrier at least, and when needing, can mix suitable tensio-active agent.
Use for some, can in herbicidal composition of the present invention, add one or more other weedicide, can produce additional advantage and effect thus.
Compound of the present invention both can use separately also can be mixed together use with other known sterilant, sterilant, weedicide, plant-growth regulator or fertilizer etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
The following example and living test are tested the result and be can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic example
Synthesizing of compound 1:
Step 1
In 250 milliliters reaction flask, add pyrazoles amine (19.0 grams, 0.15 mole) and 100 milliliters of toluene, drop into oxalyl chloride (5 grams, 0.03 mole) stirring at room is not emitted to there being gas, slowly be warming up to backflow, the evaporated under reduced pressure solvent is not emitted in reaction to there being gas, in resistates, add 20 milliliters of orthodichlorobenzenes, slowly be warming up to no gas and emit, be cooled to room temperature, get pyrazolyl containing isocyanic ester (5.8 grams, 0.03 the mole, yield is by 100%) o-dichlorobenzene solution totally 32 the gram.
Step 2
In 50 milliliters reaction flask, add 2-fluoro-4-chloro-5-alkynes propoxy-aniline (1.0 grams, 0.005 mole) and 10 milliliters of toluene, stir and drip pyrazolyl isocyanic ester (containing about 10 grams of solution of orthodichlorobenzene, about 0.01 mole, excessive), room temperature reaction 5 hours down.Filter, get urea 1.1 grams, white solid, MP:176-178 ℃.
Step 3
Add urea (0.9 gram, 0.0023 mole) and 10 ml methanol at 50 milliliters reaction flasks, stir, add sodium methylate (0.14 gram, 0.0025 mole), reflux 6 hours, evaporated under reduced pressure solvent.Resistates is poured in 10 ml waters, with 20 milliliters of ethyl acetate extractions, the aqueous sodium hydroxide washes twice with 10% is collected inorganic phase, be acidified to pH with concentrated hydrochloric acid and equal 3, with 150 milliliters of ethyl acetate extractions, 150 milliliters of saturated sodium-chloride water solutions are washed anhydrous magnesium sulfate drying, concentrate, get PyrazolopyrimidinonecGMP 0.5 gram, white solid, MP:254-256 ℃.
Step 4
Compound 1
Drop into 10 milliliters of PyrazolopyrimidinonecGMPs (0.2 gram, 0.00057 mole), salt of wormwood (0.14 gram, 0.001 mole), DMF in 50 milliliters reaction flask, stir and slowly splash into methyl iodide (0.142 gram, 0.001 mole) down, stirring at room is to reacting completely.Add 50 milliliters of ethyl acetate in the mixed solution, 50 ml waters, layering, ethyl acetate layer are washed with twice, 50 milliliter of saturated sodium-chloride water solution of 50 milliliters of washings successively, anhydrous magnesium sulfate drying, concentrating, is ethyl acetate with developping agent: the silica gel column chromatography of sherwood oil=4: 1 separates, and must 0.1 digests compound 1, white solid, MP:214-216 ℃.
Other compounds in the general formula (I) can make by above similar method.For example, in step 2,2-fluoro-4-chloro-5-alkynes propoxy-aniline is replaced with by above-mentioned preparation method:
2-fluoro-4-chloro-5-cyclopentyloxy aniline can obtain compound 2;
2-fluoro-4-chloro-5-allyloxy aniline can obtain compound 3;
2-fluoro-4-chloro-5-methoxycarbonyl anisidine can obtain compound 4;
6-amino-7-fluoro-4-propargyl-1,4-benzoxazine-3 (2 hydrogen)-ketone can obtain compound 6;
Replace 2-fluoro-4-chloro-5-alkynes propoxy-aniline with 2-fluoro-4-chloro-5-cyclopentyloxy aniline in the step 2, replace methyl iodide with iodoethane in the step 4, can obtain compound 5.
Give birth to and survey example
Test before the seedling: after planting carry out, test compound sparges soil surface, handles and is placed on the greenhouse, waters then; Test behind the seedling, seed germination also grew 10-21 days, made the examination material that has a series of growing stages before the processing, selected size, the consistent examination material of growing stage then, handled, and handled to be placed on the greenhouse and to water.The examination material with compound treatment does not compare.The examination material is broadleaf weed youth-and-old-age, piemarker and Cassia tora; Monocotyledon weed barnyard grass grass, dog tail and lady's-grass.
With the former medicine of acetone solution, by design dosage, join in the certain water gaging that contains tensio-active agent, make certain density preparation.Spray with mobile belt atomizer.The examination material is put in spraying rolling in the cupboard and is with, and mobile shower nozzle is sprayed onto medicament on the examination material with the covering of the fan Sprayable through examination material top, identical on nozzle and the common field spray device.Roll band and will try material and shift out outside the cupboard, place loft drier dry.
Examination material after the spraying drying places the greenhouse.Test is from the top water spray before the seedling, and test is poured water from the bottom and kept 48 hours so that water does not touch the blade face behind the seedling.
Handling the back investigated in 4 weeks.Carry out active classification with 0% (invalid) to 100% (control fully).Inhibiting rate is total effect of various infringements such as chlorosis, withered spot, retarded growth or the calcination of leaf angle, obtains the result with blank after relatively.Partial test the results are shown in Table 3.
Table 3: the weeding activity of compound in the part general formula I
[before the seedling behind (2250 gram/hectare)/seedling (2250 gram/hectare)]
| Compound | The barnyard grass grass | Lady's-grass | Herba Setariae Viridis | Cassia tora | Piemarker | Youth-and-old-age |
| 1 | 98/95 | 100/100 | 100/100 | 98/100 | 100/100 | 100/98 |
| 6 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 | 100/100 |
Claims (4)
1, pyrazolopyrimidinones, shown in general formula (I):
In the formula:
R
1Be selected from C
1-C
4Alkyl;
R
2Be selected from C
1-C
2Alkyl;
X and Y form benzo 6-unit heterocycle as follows:
Wherein:
R
4Be selected from C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Cycloalkyl, C
3-C
6Thiazolinyl or C
3-C
6Alkynyl.
2, the described compound of claim 1 is used to control the purposes of single broadleaf weed.
3, a kind of herbicidal composition is characterized in that: active ingredient is the described pyrazolopyrimidinones of claim 1, and the weight content of active ingredient is 0.1-99% in the composition.
4, a kind of control method for weed is characterized in that: the herbicidal composition as claimed in claim 3 of using herbicidally effective amount on the growth mediums of weeds or weeds or place.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100461278A CN100344628C (en) | 2005-03-29 | 2005-03-29 | Pyrazopyrimidinone compounds and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100461278A CN100344628C (en) | 2005-03-29 | 2005-03-29 | Pyrazopyrimidinone compounds and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1670020A CN1670020A (en) | 2005-09-21 |
| CN100344628C true CN100344628C (en) | 2007-10-24 |
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ID=35041484
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100461278A Expired - Fee Related CN100344628C (en) | 2005-03-29 | 2005-03-29 | Pyrazopyrimidinone compounds and use thereof |
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|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0917934D0 (en) * | 2009-10-13 | 2009-11-25 | Syngenta Ltd | Herbicidal compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167902A (en) * | 1981-04-08 | 1982-10-16 | Otsuka Chem Co Ltd | Herbicidal composition |
| CN86101792A (en) * | 1985-03-20 | 1986-11-12 | 弗·哈夫曼-拉罗切有限公司 | The preparation method of heterogeneous ring compound |
| CN1355164A (en) * | 2000-11-30 | 2002-06-26 | 沈阳化工研究院 | 3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity |
-
2005
- 2005-03-29 CN CNB2005100461278A patent/CN100344628C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167902A (en) * | 1981-04-08 | 1982-10-16 | Otsuka Chem Co Ltd | Herbicidal composition |
| CN86101792A (en) * | 1985-03-20 | 1986-11-12 | 弗·哈夫曼-拉罗切有限公司 | The preparation method of heterogeneous ring compound |
| CN1355164A (en) * | 2000-11-30 | 2002-06-26 | 沈阳化工研究院 | 3-(2-fluo-4,5,6-substituted phenyl)-1,3-quinazoline-2,4-dione compound with herbiciding activity |
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| Publication number | Publication date |
|---|---|
| CN1670020A (en) | 2005-09-21 |
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Address after: F6-F12, middle seat of Kai Chen World Trade Centre, 28 Fuxing Man Street, Xicheng District, Beijing, zip code: 100031 Co-patentee after: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Patentee after: Sinochem Corp. Address before: F6-F12, middle seat of Kai Chen World Trade Centre, 28 Fuxing Man Street, Xicheng District, Beijing, zip code: 100031 Co-patentee before: Shenyang Research Institute of Chemical Industry Patentee before: Sinochem Corp. |
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Effective date of registration: 20091016 Address after: 28, Fuxing Man Street, Xicheng District, Beijing, zip code: 100031 Co-patentee after: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Patentee after: SINOCHEM Corp. Address before: F6-F12, middle seat of Kai Chen World Trade Centre, 28 Fuxing Man Street, Xicheng District, Beijing, zip code: 100031 Co-patentee before: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Patentee before: Sinochem Corp. |
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