CN1120836C - 2-pirimioxybenzyl substituted pyridyl amine derivative - Google Patents
2-pirimioxybenzyl substituted pyridyl amine derivative Download PDFInfo
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Abstract
The present invention relates to 2-pyrimidine oxy benzyl substituted pyridinamine derivates shown in a structural formula (I). Substituted pyridinamine and salicylaldehyde react, and a product reacts with 2-methylsulfonyl-4, 6-dimethoxypyrimidine after reduced, and thereby, a (R1 =H) compound shown in the structural formula (I) is obtained. The compound reacts with acyl chloride, and thereby, a (R1, H) compound shown in the structural formula (I) is obtained, wherein R1 is unequal to H. The amine derivates shown in the structural formula (I) have high weed removal activity and can be used for compounding weed removal agents for rapes, etc. The present invention has the advantages of favourable effect, low dosage, wide weed removal range and no damage to crops and is friendly to the environment.
Description
Technical field
The present invention relates to pyridine derivatives, 2-pirimioxybenzyl substituted pyridyl amine derivative particularly, their preparation method and as the prescription and the application of agricultural chemicals weedicide.
Technical background
Now, the development of agricultural modernization need constantly provide effective, and consumption is low, to crop and environmentally friendly new herbicides, to reduce the agricultural workforce, promotes the raising of mechanization of agriculture, modernization development and crop yield.
The known various 2-phenoxy pyrimidine capable thing that spreads out is effective as weedicide, as United States Patent (USP) U.S.P4,906, the 285 Sulfadiazine Compound salicylic acid compounds of being set forth promptly belong to this compounds, they can with low dosage control such as common Siberian cocklebur, lead a cow and nutgrass flatsedge general unmanageable weeds, to rice safety.United States Patent (USP) U.S.P4 has disclosed the pyrimidine phosphorothioate salicyclic acid derivatives in 932,999 perennial and annual careless class has been demonstrated excellent herbicidal effect, has higher security for cotton simultaneously.But above-mentioned two parts of patent compound scope of applications have certain limitation, to other farm crop, the different injury of degree are arranged.
Summary of the invention
Need based on social development, and for enlarging use range, exploitation is applicable to the weedicide in rape field simultaneously, and the inventor is on existing invention basis, carry out guide's expansion, developed the novel 2-pirimioxybenzyl substituted pyridyl amine derivative of a class shown in structural formula (I).In the formula (1):
R
1Be hydrogen, C
1-C
4Alkyloyl or C
1-C
4Haloalkane acyl group, more preferably hydrogen;
R
2Be hydrogen, halogen or C
1-C
4Alkyl, more preferably hydrogen, chlorine or methyl.
R
1-N-group and R
2The position of group on pyridine ring can be in any one position in 2,3,4,5,6, wherein more
R preferably
1-N-group is in 2 on the pyridine ring, R
2Be on the pyridine ring any one position in 3,4,5,6.
The inventor changes R in the structural formula (I) by molecular designing
1, R
2Substituent position on substituted radical and the pyridine ring has synthesized a series of compounds, and student on commission surveys the expert it is carried out weeding activity and toxicity test evaluation, has wherein chosen the representative compounds that part has greater activity, sums up and lists in table 1.
Table 1
| Numbering | R 1 | R 2 | Ultimate analysis (%) | Mass spectrum M - | ||
| C | H | N | ||||
| 1 | H | 4-CH 3 | 64.70 | 5.55 | 15.99 | 352 |
| 2 | COCHCl 2 | 4-CH 3 | 54.55 | 4.29 | 12.21 | 462 |
| 3 | COCH 2CH 3 | 4-CH 3 | 64.56 | 5.77 | 13.78 | 408 |
| 4 | H | 4-H | 63.78 | 5.42 | 16.65 | 338 |
| 5 | H | 5-Cl | 57.89 | 5.39 | 15.19 | 372 |
| 6 | H | 3-CH 3 | 64.75 | 5.66 | 15.90 | 352 |
| 7 | H | 5-CH 3 | 64.60 | 5.72 | 15.85 | 352 |
| 8 | H | 6-CH 3 | 64.71 | 5.80 | 15.79 | 352 |
Give birth to survey and show that the compound shown in the structural formula (I) all has good weeding activity, and herbicidal spectrum is wide, low toxicity is environmentally friendly, does not injure crop, particularly to rape safety.Therefore, they all are effective active matters of preparation agricultural herbicide.
The compounds of this invention includes a plurality of derivatives, but structural formula is similar, belong to the homologous series compound, thereby its synthetic method is also basic identical, and existing details are as follows.(A) (R shown in the structural formula (I)
1=H) the synthetic method of compound, divided for three steps:
[the R in the above-mentioned reaction formula
2The substituting group of representative as previously mentioned, X is halogen or methylsulfonyl in the compound (3)]
That is to say (R shown in the structural formula of the present invention (I)
1=H) compound (2) synthetic, at first by substituted pyridines amine (4) and salicylic aldehyde (5) with 1: the 1.0-1.2 mol ratio is dissolved in methyl alcohol, ethanol or the propyl alcohol class alcoholic solvent, to the temperature range internal reaction of solvent boiling point 20 minutes to 12 hours, obtain intermediate (6) in room temperature.This reaction can be carried out under the situation of catalyst-free, but add catalyzer or azeotropic dehydration condition under, can accelerated reaction, improve reaction yield.Used catalyzer can be p-methyl benzenesulfonic acid, methylsulfonic acid, sulfuric acid or hydrochloric acid in the reaction.Solvent for use can also be aromatic solvents such as benzene, toluene or dimethylbenzene in the reaction, or tetrahydrofuran (THF), dioxane class ether solvents.
Then, the intermediate (6) of the first step gained in alcoholic solvents such as methyl alcohol, ethanol or propyl alcohol, is added sodium borohydride or potassium borohydride reduction agent and reacts, intermediate (7).
The 3rd step, make intermediate (7), 2-halogen (or methylsulfonyl)-4,6-dimethoxypyridin (3) and alkali are with 1: 1.0-1.1: the 1.2-3.0 mol ratio is in solvent, reaction is 2-8 hour under reflux temperature, again through suction filtration, remove and desolvate, and behind solvent wash, get one of the object of the invention product (R shown in structural formula (I)
1=H) compound (2).In this step reaction, used alkali can be sodium Metal 99.5 or potassium and so on basic metal, or sodium hydroxide, potassium hydroxide, basic metal, the oxyhydroxide of alkaline-earth metal, carbonate such as calcium hydroxide, yellow soda ash, salt of wormwood, or alcohol can be aromatic solvents such as benzene, toluene or dimethylbenzene with solvent, ether solvent such as tetrahydrofuran (THF), dioxane, alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol, ketone solvent or dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile or their mixtures such as acetone, mibk.(B) (R shown in the structural formula (I)
1≠ H) compound is synthetic:
As previously mentioned, through three step gained (R shown in structural formula (I)
1=H) compound (2), it is one of our needed actives with weeding function, and if itself and acyl chlorides are further reacted under alkaline condition in solvent, another purpose product of the present invention such as the structural formula (I) that also can be had weeding activity equally, reaction is shown in following reaction equation:
(R in the reaction formula
1, R
2Shown in group as previously mentioned)
To the solvent boiling point interval, the consumption of solvent for use and alkali is identical with the 3rd step that aforementioned secondary-amine compound synthesizes in the reaction in room temperature for the temperature of this reaction.
The synthetic method of formula provided by the invention (I) compound is uncomplicated, has very high weeding activity, be the effective active thing of preparation agricultural herbicide, before can be used for preparing farm crop cotton, rape, wheat paddock and preventing and kill off the bud of gramineous weeds, broadleaf weeds and nutgrass flatsedge, post-emergence herbicide.The concrete object of preventing and kill off comprises: (g ai/ha is gram actives/hectare to 15-75g ai/ha, as follows) the following effectively control gramineous weeds of low dosage, the high dosage of 90-300g ai/ha is is effectively prevented and treated broadleaf weeds and nutgrass flatsedge down, as barnyard grass grass (Echinochloa crusgalli), lady's-grass (Digitariasanguinalis), Herba Eleusines Indicae (Eleusine indica), Herba Setariae Viridis (Setaria viridis), annual bluegrass (Poa annua), wild avena sativa (Avena fatua), amur foxtail (Alopecurus aequalis), Japan amur foxtail (Alopecurusjaponicus), Amaranthus retroflexus (Amaranthus retroflexus), thorn amaranth (Amaranthus spinosus), lamb's-quarters (Chenopodium album), leaf mustard (Brassica juncea), purslane (Portulaca oleracea), Herba Acalyphae (Acalypha australis), Herba Cyperi Difformis (Cyperus difformis), Semen Euphorbiae (Leptochloachinensis), Rhizoma Cyperi (Cyperus rotundus), grass (Fimbristylis miliacea) floats sunshine, veronica (Veronica didyma), chickweed (Stallaria media), Herba Viviae Sativae (Vicia sativa), Stellaria alsine Grim. (Stellariaalsine), Herba Erigerontis Annui (Erigeron annuus), short arrowhead (Sagittaria sagittifolia), Herba seu Flos Convolvuli arvensis (Convolvulus arvensis) etc.As weedicide, they have the following advantage and characteristics:
1, has herbicidal effect after the shoot buds under the low dosage, also have herbicidal effect before the bud under the higher dosage;
2, broad weed-killing spectrum can not only effectively be prevented and treated gramineous weeds in the farmland, and can effectively prevent and kill off broadleaf weeds and nutgrass flatsedge;
3, safe, all safe and harmless to cotton, rape and wheat especially to crop;
4, the above the average age for marriage gramineous weeds of 3-7 leaf also had highly effective herbicidal effect;
5, residual period, is short in soil, and the crop rotation succession crop is had no adverse effects;
6, Mammals or fish are not had overt toxicity, the environmental safety height belongs to the environmentally friendly agricultural chemicals of low toxicity;
For reality is used, active compound of the present invention can be processed as various granulas, pulvis, finish, emulsion, aqueous suspension and capsule etc. by formula technique commonly used in the pesticide industry.
Embodiment
By the following examples, synthetic method of the present invention is done further to specifically describe, the present invention never only limits to this several examples.Synthesis example 1: (R shown in the structural formula (I)
1=H) the preparation of compound (2)
Example: 9.4 gram (0.1 mole) 2-amido pyridines are dissolved in 125 milliliters the anhydrous methanol, drip 12.2 gram (0.1 mole) salicylic aldehydes, at room temperature stirring reaction is after 10 minutes, filter, wash with anhydrous methanol, get 18.5 gram yellow solids, yield 93.4% is 2-N-(2-hydroxyl benzylidene) pyridine amine.
Get aforementioned made 2-N-(2-hydroxyl benzylidene) pyridine amine 9.9 grams (50 mmole), be dissolved in 150 milliliters of anhydrous methanols, at room temperature add 2.26 gram (60 mmole) sodium borohydrides in batches, stirring reaction is 20 minutes under the room temperature, concentrate and remove methyl alcohol, in residue, add 200 milliliters of chloroforms then, 150 milliliters in water stirs, and leaves standstill, tell organic layer, wash with water, anhydrous sodium sulfate drying, concentrate 9.5 gram white solids, yield 95.0% is 2-N-(2-hydroxybenzyl) pyridine amine.
Get the made 2-N-in front (2-hydroxybenzyl) pyridine amine 2.00 grams (10 mmole), 2-methylsulfonyl-4,6-dimethoxypyridin 2.18 grams (10 mmole), be dissolved in 100 milliliters of tetrahydrofuran (THF)s, add 3.71 gram (26.84 mmole) salt of wormwood under the room temperature, back flow reaction 11 hours, suction filtration, get solid, add 20 milliliters of tetrahydrofuran (THF) washings again, concentrate, remove tetrahydrofuran (THF), bottom product adds agitator treating in 10 milliliters of ethanol again, suction filtration gets 3.00 gram white solids, and yield 88.7% is N-(2-pyridyl)-2-(4,6-dimethoxypyridin-2-yl) oxygen base Phenoxybenzamine is mp93.3-94.0 ℃
MS：(M
+)338
Nucleus magnetic resonance: HNMR (CDCl
3) δ: 3.79 (6H, s), 4.50 (2H, d), 5.78 (1H, s), 6.35-8.05 (8H, m)
Ultimate analysis: theoretical value C63.78 H5.42 N16.65 experimental value C63.91 H5.33 N16.57
Synthesis example 2: (R shown in the structural formula (I)
1≠ H) the preparation of compound
Example: in 100 milliliters of single port bottles, add N-[2-(4-picolyl)]-2-(4,6-dimethoxypyridin-2-yl) oxygen base Phenoxybenzamine 3.52 grams (10 mmole), propionyl chloride 1.11 grams (12 mmole), salt of wormwood 1.66 gram (12 mmole) and 100 milliliters of THF, back flow reaction 10 hours, suction filtration, remove solid, organic layer concentrates to such an extent that wax shape white solid 3.99 restrains yield 97.8%.mp66.5-68.5℃
MS：(M
+)408
Nucleus magnetic resonance: HNMR (CDCl
3) δ: 1.11 (3H, t), 2.30 (5H, m), 5.71 (1H, s), 5.72 (1H, s),
6.80-8.30(7H，m)
Ultimate analysis: theoretical value C64.71 H5.88 N13.73 experimental value C64.56 H5.77 N13.78
Below provide The compounds of this invention and make active ingredient, the concrete instance of processing preparation several herbicides formulation, in these prescription examples, all " % " all refer to weight percent.But should indicate, the present invention's prescription only limits to this several routine examples by no means.
Formulation Example 1 (wettable powder):
No. 7 materials (Table I) with 15%, 5% sulfonated lignin (M
q), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% light calcium carbonate mix equably, pulverizes, and promptly gets wettable powder.
Formulation Example 2 (missible oil):
No. 602, No. 7 materials with 10%, 5% farming breast No. 500 (calcium salts), 5% farming breast, 5% N-N-methyl-2-2-pyrrolidone N-and 75% dimethylbenzene heated and stirred are even, promptly get missible oil.
Formulation Example 3 (granula):
No. 7 materials with 5%, 1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) and 90% clay mix equably, pulverize, and add 20 parts of water, kneading to these 100 parts of mixtures then; with the extruding granulator; make 14-32 purpose particle, drying promptly gets granule.
Below will give birth to the test of giving birth to of surveying that the expert provides tests weeding activity and the crop safety that example makes the weedicide of active ingredient preparation to part of compounds of the present invention and carries out test evaluation.Adopt 0-5 level evaluation assessment, judgement criteria is listed in table 2.
Table 2: weeding activity and phytotoxicity evaluating standard
| Grading index | Phytotoxicity (%) | Weeding activity comment (inhibition, deformity, albefaction etc.) | Crop safety comment (inhibition, deformity, albefaction etc.) |
| 0 | 0 | With contrast, anti-, eliminate | With contrast, anti-, normal |
| 1 | 10-20 | Gently, influential slightly, eliminate | Gently, influential slightly, can consider |
| 2 | 30-40 | Gently, influential, eliminate | Sensitivity, influential, eliminate |
| 3 | 50-60 | Sensitivity, influential, can consider further transformation | Responsive, poisoning is heavy, eliminates |
| 4 | 79-80 | Responsive, can consider | Extremely responsive, poisoning is heavy, eliminates |
| 5 | 90-100 | Extremely responsive, good | Extremely responsive, poisoning is heavy, eliminates |
Test examples 1: the weeding activity test that cauline leaf is handled behind the seedling
The seed that (diameter 9.5cm) even respectively sowing barnyard grass, lady's-grass, Cowhells, Amaranthus retroflexus and purslane in the native basin alms bowl are used in test is being housed, overburden soil 0.5cm is thick, place 20-25 ℃ greenhouse to cultivate ten days in the basin alms bowl, during the plant strain growth two leaf stage, the active missible oil dilute with water of each number that similar Formulation Example 2 is prepared, dosage with 750g ai/ha carries out cauline leaf spraying processing to cultivating the examination material, routine observation is respectively handled the plant strain growth state, the symptom of being injured, handled back 28 days, evaluate by table 2 standard, the results are shown in Table 3.
Table 3: the weeding activity (dry land condition) that the back cauline leaf of emerging is handled
| Compound number | The weeding activity index | |||||
| The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Purslane | |
| 2 | 4 | 4 | 4 | 0 | 5 | 5 |
| 3 | 0 | 0 | 3 | 0 | 4 | 0 |
| 4 | 5 | 5 | 5 | 4 | 5 | 5 |
| 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| 6 | 5 | 5 | 5 | 0 | 5 | 4 |
| 7 | 5 | 5 | 5 | 4 | 5 | 5 |
| 8 | 5 | 5 | 5 | 3 | 5 | 5 |
Test examples 2: the weeding activity of soil treatment test before the seedling
Be equipped with test with native basin alms bowl in (diameter 9.5cm) sow the seed of barnyard grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and purslane respectively equably, overburden soil 0.5cm is thick, 2-8 actives cream preparation dilute with water that similar Formulation Example 2 is prepared after 12 hours carries out soil surface and handles cultivating the examination material with the dosage of 750g ai/ha.Routine observation is respectively handled the plant strain growth state, the symptom of being injured, and handles back 28 days, evaluates according to the standard of determining in the table 2, the results are shown in Table 4.
Table 4: the weeding activity (dry land condition) of soil treatment before emerging
| Compound number | The weeding activity index | |||||
| The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Purslane | |
| 2 | 0 | 2 | 4 | 0 | 0 | 0 |
| 3 | 0 | 0 | 0 | 0 | 0 | 0 |
| 4 | 4 | 4 | 5 | 0 | 5 | 5 |
| 5 | 5 | 5 | 5 | 3 | 5 | 5 |
| 6 | 4 | 3 | 4 | 0 | 4 | 4 |
| 7 | 4 | 0 | 5 | 0 | 5 | 5 |
| 8 | 4 | 3 | 5 | 0 | 5 | 5 |
Test examples 3: the weeding activity dosage gradient test that cauline leaf is handled behind the seedling
With barnyard grass grass, lady's-grass, Cowhells, leaf mustard, Amaranthus retroflexus and purslane is the weeds target, carries out the test of various dose gradient.Test is provided with a grade dosage.When gramineous weeds growth two leaf stage, broadleaf weeds growth sheet leaf period, the 4-8 actives cream preparation dilute with water that similar Formulation Example 2 is prepared, with dosage shown in the table 5 the examination material of cultivating being carried out the cauline leaf spraying handles, handled back 28 days, evaluate according to the standard of determining in the table 2, the results are shown in Table 5.
Table 5: the weeding activity size that cauline leaf is handled behind the seedling is estimated
| Compound number | Dosage (g ai/ha) | The weeding activity index | |||||
| The barnyard grass grass | Lady's-grass | Herba Eleusines Indicae | Leaf mustard | Amaranthus retroflexus | Purslane | ||
| 4 | 375 | 5 | 5 | 5 | 4 | 5 | 4 |
| 150 | 4 | 3 | 4 | 2 | 4 | 4 | |
| 75 | 2 | 0 | 3 | 4 | 4 | 4 | |
| 5 | 375 | 5 | 5 | 4 | 5 | 5 | 4 |
| 240 | 5 | 4 | 4 | 3 | 5 | 4 | |
| 124 | 4 | 4 | 4 | 3 | 5 | 2 | |
| 6 | 375 | 0 | 0 | 0 | 0 | 0 | 0 |
| 7 | 375 | 4 | 3 | 3 | 4 | 5 | 5 |
| 240 | 4 | 3 | 2 | 4 | 5 | 4 | |
| 124 | 3 | 3 | 1 | 3 | 2 | 1 | |
| 8 | 375 | 5 | 5 | 4 | 3 | 4 | 2 |
| 240 | 4 | 4 | 3 | 3 | 4 | 2 | |
| 124 | 4 | 3 | 3 | 2 | 3 | 1 | |
Test examples 4: the crop safety test that cauline leaf is handled behind the seedling
Difference sowing cotton, Semen Brassicae campestris in the 12cm basin alms bowl that test soil is housed, place 20-25 ℃ of greenhouse to grow, after waiting to grow into the certain period, No. 4 actives cream preparation dilute with waters that similar Formulation Example 2 is prepared, with 375,150, the dosage of 75g ai/ha carries out the cauline leaf spraying to the examination material of cultivating and handles, the routine observation plant strain growth state and the symptom of being injured were handled back 28 days, evaluate by table 2 standard, the results are shown in Table 6.
Table 6: the crop safety evaluation (dry land condition) that the back cauline leaf of emerging is handled
| Compound number | Dosage (g ai/ha) | The phytotoxicity index | |
| Rape | Cotton | ||
| 4 | 375 | 1 | 0 |
| 150 | 0 | 0 | |
| 75 | 0 | 0 | |
Claims (4)
1. a class pyridine derivatives is characterized in that the 2-pirimioxybenzyl substituted pyridyl amine derivative, as structural formula
(I) shown in:
In the structural formula (I):
R
1Be hydrogen, C
1-C
4Alkyloyl or C
1-C
4The haloalkane acyl group;
R
2Be hydrogen, halogen or C
1-C
4Alkyl;
R
1-N-and R
2Position on pyridine ring can be in 2,3,4,5, and in 6 any one position.
2. according to the described pyridine derivatives of claim 1, it is characterized in that R in the structural formula (I)
1Be hydrogen; R
2Be hydrogen, chlorine or methyl; R
1-N-is in 2 on the pyridine ring, R
2Be in 3,4 on the pyridine ring, in 5,6 any one position.
3. according to the preparation method of claim 1 or 2 described pyridine derivatives, its feature is shown in following reaction equation:
R in the reaction formula
2Be hydrogen, halogen or C
1-C
4X is halogen or methylsulfonyl in the alkyl, compound (3)
Promptly at first by substituted pyridines amine (4) and salicylic aldehyde (5) with 1: the 1.0-1.2 mol ratio is dissolved in the alcoholic solvent, reacted 20 minutes to 12 hours in room temperature to solvent boiling point temperature range, get intermediate (6), make intermediate (6) again in alcoholic solvent, through sodium borohydride or potassium borohydride reduction, get intermediate (7), this intermediate (7) again with compound (3) with 1: the 1.0-1.1 mol ratio is reacted under alkaline condition in ether solvent, make compound (2), compound (2) reacts under alkaline condition in ether solvent with acyl chlorides again, make the compound shown in structural formula (I), wherein R
1≠ H,
R in the reaction formula
1Be C
1-C
4Alkyloyl or C
1-C
4The haloalkane acyl group; R
2Be hydrogen, halogen or C
1-C
4Alkyl.
4. according to claim 1 or 2 described pyridine derivatives, before it is characterized in that can be used for preparing farm crop cotton, rape, wheat paddock and preventing and kill off the bud of gramineous weeds, broadleaf weeds and nutgrass flatsedge, post-emergence herbicide.
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|---|---|---|---|
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Cited By (1)
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|---|---|---|---|---|
| CN100503578C (en) * | 2005-09-02 | 2009-06-24 | 浙江化工科技集团有限公司 | N-2-pyrimidinyl oxy-benzyl substituted cyclic amine compound, its preparation process and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381427C (en) * | 2005-09-02 | 2008-04-16 | 浙江化工科技集团有限公司 | Benzylamine compound, and its preparing method and use |
| CN100361978C (en) * | 2005-09-02 | 2008-01-16 | 中国科学院上海有机化学研究所 | 2-pyrimidine oxy-N-aryl 7-nitrile or organic phosphate benzylamine compound, its production and use thereof |
| CN112724074A (en) * | 2021-01-18 | 2021-04-30 | 浙江工业大学 | 4- (pyridine-2-yl) -4' -trifluoromethyl oxy phenyl benzyl ether derivative and preparation method and weeding application thereof |
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| CN100503578C (en) * | 2005-09-02 | 2009-06-24 | 浙江化工科技集团有限公司 | N-2-pyrimidinyl oxy-benzyl substituted cyclic amine compound, its preparation process and uses |
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