CN101723923A - N-2, 4-dichlorophenoxy acetyl (sulfur) carbamide weedicide and preparation method thereof - Google Patents
N-2, 4-dichlorophenoxy acetyl (sulfur) carbamide weedicide and preparation method thereof Download PDFInfo
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- CN101723923A CN101723923A CN200910201117A CN200910201117A CN101723923A CN 101723923 A CN101723923 A CN 101723923A CN 200910201117 A CN200910201117 A CN 200910201117A CN 200910201117 A CN200910201117 A CN 200910201117A CN 101723923 A CN101723923 A CN 101723923A
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Abstract
The invention discloses an N-(substituted heterocycle methyl)-2, 4-dichlorophenoxy acetyl (sulfur) carbamide weedicide which not only has high wedding activity, but also can boost the growth of crops and a preparation method thereof. The structural formulas of the weedicide comprise (I) and (II), wherein R is 2-tetrahydrofurfuryl, 2-furfuryl, 2-picolyl, 6-chlorine-3-picolyl, 5-2-chlorine-thiazolmethyl and other five-membered or six-membered heterocycle methyls. The invention has the advantages of high-efficiency weeding activity, favorable weeding effect, low toxicity, no harm to people and livestock, promotion of crops growth, simple and convenient use method and simple preparation method.
Description
Technical field
The invention belongs to the agriculture production weedicide, specifically a kind of N-2,4-Dichlorophenoxy acetyl (sulphur) carbamide weedicide and preparation method.
Background technology
Weeds are formidable enemies of agriculture production, and weeds and farm crop contention fertilizer, moisture, sunlight make farm crop healthy and strong not grow, and have influenced the output of agricultural-food greatly.People are in order to promote the development of agriculture production, the weedicide of invention and use number of different types.Phenoxy carboxylic acid herbicides is mainly made the cauline leaf treatment agent in the prior art, be used in cereal crop, softwood tree, bare place, herbage, lawn, prevent and kill off annual and perennial broadleaf weeds, effective as weeds such as amaranth, lamb's-quarters, Siberian cocklebur, Herba seu Flos Convolvuli arvensis, purslane, Herba Viviae Sativae, Persian veronica, descurainia sophia (l.) webb ex prantl.Easily produce medicament drift phenomenon when but the main drawback of this class weedicide is dispenser, thereby influence herbicidal effect.
The 2,4 dichlorophenoxyacetic acid of prior art can be used as processing soil treatment agent, uses before emerging after soybean is broadcast.2,4 dichlorophenoxyacetic acid can promote plant-growth under lower concentration, the effect that prevents that fallen flowers, shedding and promotion from blooming is arranged.The phenoxy acetic acid compounds have selectivity height, interior absorption strong, be easy to biological degradation,, characteristics such as volatility less few to environmental hazard, be current widely used weedicide.This class weedicide has the effect of similar plants growth hormone.After ruderal plant absorbed, the concentration of growth hormone was higher than normal value in the body, thereby has broken the intravital hormonal equilibrium of plant, has influence on the eubolism of plant, causes a series of Physiology and biochemistry variations, tissue abnormalities and the damage of weeds.
Acyl group (sulphur) carbamide compounds is not only important organic synthesis intermediate; and have good weeding, desinsection, a biological activity such as antibiotic, antiviral; because the plurality of advantages of this compounds; the usage quantity of acetamide-group herbicides is only second to organophosphorus herbicide, is the farmland chemical herbicide in modern age that occupies the second place of the world.Because the toxicity of organophosphorus herbicide is big, acyl group (sulphur) carbamide compounds becomes the weedicide that has advantage most.
The present invention is excellent according to prior art 2,4 dichlorophenoxyacetic acid weedicide and acyl group (sulphur) carbamide compounds
Point is a raw material with 2,4 dichlorophenoxyacetic acid and heterocycle methylamine in the world first, has synthesized N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) carbamide compounds of general formula for (I), (II) two series.The weedicide that contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas that makes it not only have efficient weeding activity but also can promote crop growth.Measure to show through weeding activity: series (I) and (II) weedicide dicotyledonss such as leaf mustard, Amaranthus retroflexus and Eclipta prostrata are had very high weeding activity.
Summary of the invention
The present invention seeks to for a kind of weedicide that contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas that had not only had efficient weeding activity but also can promote crop growth is provided.
Purpose of the present invention is achieved through the following technical solutions:
N--2,4-Dichlorophenoxy acetyl (sulphur) carbamide weedicide, represent with general formula (I) with (II):
General formula (I) is for containing N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides:
General formula (II) is for containing N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide:
Wherein: R is five yuan or hexa-atomic substituted heterocycle methyl such as 2-tetrahydrofuran methyl, furfuryl, 2-picolyl, 6-chloro-3-picolyl, 5-chloro-2-thiazole methyl.
General formula (I) expression contain N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides, the preparation method is as follows:
(1) preparation 2,4 dichloro benzene acetamide oxide:
A. 2,4 dichlorophenoxyacetic acid is dissolved in the toluene of new steaming, dripping thionyl chloride, reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil;
B. reaction solution is splashed in the excessive strong aqua, be stirred well to and separate out white crystal, wash with water, get the 2,4 dichloro benzene acetamide oxide after the drying;
(2) preparation general formula (I) contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides:
A. the 2,4 dichloro benzene acetamide oxide with above-mentioned (1) preparation is dissolved in the toluene, slowly drips oxalyl chloride, refluxes 2 hours;
B. decompression is removed toluene and excessive oxalyl chloride down, drips the chloroform soln that is dissolved with the substituted heterocycle methylamine, refluxes 3 hours, makes general formula (I) and contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides.
The preparation method is as follows for N-(substituted heterocycle the methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide that contains of general formula (II) expression:
(1) preparation 2,4 dichloro benzene oxygen acetyl lsothiocyanates:
A. 2,4 dichlorophenoxyacetic acid is dissolved in the toluene of new steaming, dripping thionyl chloride, reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil;
B. reaction solution is added dropwise to the anhydrous acetonitrile and the PEG-400 of potassium sulfocyanate, stirring and refluxing, filter orange-yellow 2,4 dichloro benzene oxygen acetyl lsothiocyanates;
(2) preparation contains the weedicide of N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class:
A. the acetonitrile solution of the 2,4 dichloro benzene oxygen acetyl lsothiocyanates that above-mentioned (1) is prepared slowly is added drop-wise in the acetonitrile solution that contains the substituted heterocycle methylamine;
B. under 60 ℃ of conditions, refluxed 2～4 hours, make general formula (II) and contain N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide.
With general formula (I) or the weedicide that (II) contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas be raw material, make emulsion, aqueous suspension and water and milk formulation weedicide agricultural chemicals.
The reaction formula of above-mentioned preparation process is:
A. the preparation process reaction formula that contains the weedicide (I) of N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl ureas:
The preparation process reaction formula that contains the weedicide (II) of N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class:
Main points of the present invention are:
With 2,4 dichlorophenoxyacetic acid and heterocycle methylamine is raw material, has synthesized both to have efficient weeding activity, has the weedicide that contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas that promotes the crop growth function again.
Contain N-(substituted heterocycle methyl)-2 with general formula (I), (II) expression, the weedicide of 4-Dichlorophenoxy acetyl (sulphur) ureas has good weeding activity, the effective active composition of useful as herbicides is made the various pesticide formulation, example emulsion, aqueous suspension and aqueous emulsion etc.
Use the various formulation weedicides of the present invention's preparation to carry out the weeding activity test, the result is as follows:
1. test medicament and preparation:
Take by weighing the former medicine of certain mass with analytical balance (0.0001g), be mixed with 1.0～5.0% the little preparation of missible oil, become finite concentration standby with the distilled water diluting that contains 0.1% tween-80 then with solvent (acetone, DMF or DMSO Chinese mark etc.) dissolving.
2. test design:
3. test method
To divide single, double cotyledon evenly to broadcast respectively in the internal diameter 9cm basin alms bowl for the examination weed seed, in the greenhouse, cultivate.Treat monocotyledon weed length to 1～1.5 leaf phases, during the broadleaf weed leaf period, cauline leaf is handled after carrying out bud on the automatic sprayer.Every processing 3 times repeats, and establishes blank, leaves standstill after the processing 4～5 hours, treat that soup is done on the blade after, move into cultivation in the greenhouse.Observe the plant strain growth situation every day, the periodic logging symptom of being injured, the comprehensive weeding activity of range estimation investigation when symptom of chemical damage is obvious.
4. result's investigation
The result investigates the employing appearance method, the visual assessment medicament to plant strain growth inhibition, deformity, yellow, rot, influence degree such as necrosis, press 0～100% staging visual assessment weeding activity and security according to comprehensive extent of injury then, 0 for having no effect, 100 for the plant that is injured suppresses fully, and judgement criteria sees Table 1.
Table 1: greenhouse pot culture weeding activity judgement criteria
Target compound weeding activity measurement result sees Table 2.
Table 2: the weeding activity of target compound (I)～(II)
Benzene oxygen acetylurea compounds (I) and benzene oxygen acetyl thiourea compounds (II) have kept roughly equal inhibition activity as can be seen from the above table, illustrate that to build benzene oxygen acetylurea compounds with the urea bridge the same with the effect of building benzene oxygen acetyl thiourea compounds with the thiocarbamide bridge.In addition, target compound (I)～(II) to the inhibiting rate of dicotyledons apparently higher than monocotyledons, Compound I
cInhibiting rate to barnyard grass grass, lady's-grass, annual bluegrass is respectively 70%, 70%, 50% obviously high and other compounds.
Advantage of the present invention is:
1, have efficient weeding activity, herbicidal effect is good.
2, toxicity is low, the person poultry safety.
3, promote crop growth.
4, using method is easy.
5, the preparation method is simple.
The present invention is that raw material has synthesized the weedicide that series contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas with 2,4 dichlorophenoxyacetic acid and heterocycle methylamine in the world first, has tangible novelty and creativeness; The present invention has measured the efficient weeding activity of this weedicide, has significant practicality in modern agriculture production.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
(1) have the weedicide that contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl ureas of efficient weeding activity, with general formula (I) expression:
Wherein: R is five yuan or hexa-atomic substituted heterocycle methyl such as 2-tetrahydrofuran methyl, furfuryl, 2-picolyl, 6-chloro-3-picolyl, 5-chloro-2-thiazole methyl.
The example of the weedicide of N-(substituted heterocycle the methyl)-2,4 dichloro benzene oxygen acetyl ureas of the present invention's preparation is:
(I
a), N-(2-tetrahydrofuran methyl)-2,4 dichloro benzene oxygen acetylurea;
(I
b), N-(furfuryl)-2,4 dichloro benzene oxygen acetylurea;
(I
c), N-(2-picolyl)-2,4 dichloro benzene oxygen acetylurea;
(I
d), N-(6-chloro-3-picolyl)-2,4 dichloro benzene oxygen acetylurea;
(I
e), N-(5-chloro-2-thiazole methyl)-2,4 dichloro benzene oxygen acetylurea.
Embodiment 1:
Preparation N-(2-tetrahydrofuran methyl)-2,4 dichloro benzene oxygen acetylurea (I
a):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil.Reaction solution is splashed in the excessive strong aqua, separate out white crystal after fully stirring.Water washing gets the 2,4 dichloro benzene acetamide oxide after the drying.
In the 50mL round-bottomed flask, take by weighing 1.10g (0.005mol) 2, the 4-dichlor phenoxyacetic amide is dissolved in the 15mL toluene, taking by weighing 2.62mL (0.03mol) oxalyl chloride in the normal pressure dropping funnel slowly drips, reflux and remove toluene and excessive oxalyl chloride after 2 hours under the decompression, obtain the thick product of isocyanic ester, do not need purifying, promptly can be used for the next step.2-tetrahydrofuran (THF) methylamine with 0.404g (0.004mol) is dissolved in the 10mL chloroform soln again, adds in the titration funnel, slowly drips in the supreme step isocyanate solution, stirring at room 30min, rise to 60 ℃ and refluxed 3 hours, TLC tracks to reaction and finishes standing over night.Suction filtration, with suction filtration after 95% washing with alcohol, oven dry uses the mixed solvent recrystallization of alcohol-water-DMF promptly to get faint yellow solid powder I
aProductive rate: 63%.
Ultimate analysis: measured value C%48.43 H%4.64 N%8.07
Calculated value C%48.40 H%4.65 N%8.04
IR (KBr compressing tablet cm
-1) 3227 (N-H), 3134 (N-H), 1713 (C=O), 1686 (C=O);
1H?NMR(CDCl3/400MHz)：10.53(s，1H，N-H)，8.73(s，1H，N-H)，7.08～7.59(m，3H，Ph-H)，5.14(s，2H，CH
2)，4.38(d，J＝8.0Hz，2H，THF-CH
2)，4.02-4.08(m，1H，THF)，3.89-3.95(m，1H，THF)，3.77-3.83(m，1H，THF)，3.47-3.53(m，1H，THF)，2.54-2.59(m，2H)，2.01-2.08(m，1H，THF)。
Embodiment 2:
Preparation N-(furfuryl)-2,4 dichloro benzene oxygen acetylurea (I
b):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil.Reaction solution is splashed in the excessive strong aqua, separate out white crystal after fully stirring.Water washing gets the 2,4 dichloro benzene acetamide oxide after the drying.
In the 50mL round-bottomed flask, take by weighing 1.10g (0.005mol) 2, the 4-dichlor phenoxyacetic amide is dissolved in the 15mL toluene, taking by weighing 2.62mL (0.03mol) oxalyl chloride in the normal pressure dropping funnel slowly drips, reflux and remove toluene and excessive oxalyl chloride after 2 hours under the decompression, obtain the thick product of isocyanic ester, do not need purifying, promptly can be used for the next step.2-furylamine with 0.388g (0.004mol) is dissolved in the 10mL chloroform soln again, adds in the titration funnel, slowly drips in the supreme step isocyanate solution, stirring at room 30min, rise to 60 ℃ and refluxed 2.5 hours, TLC tracks to reaction and finishes standing over night.Suction filtration, with suction filtration after 95% washing with alcohol, oven dry uses the mixed solvent recrystallization of alcohol-water-DMF promptly to get yellow solid powder I
bProductive rate: 65%.
Ultimate analysis: measured value C%49.00 H%3.52 N%8.16
Calculated value C%48.94 H%3.55 N%8.21
IR (KBr compressing tablet cm
-1) 3228 (N-H), 3134 (N-H), 1710 (C=O), 1694 (C=O);
1H?NMR(CDCl
3/400MHz)：10.52(s，1H，N-H)，8.73(s，1H，N-H)，7.05～7.59(m，3H，Ph-H)，7.54(d，J＝8.0Hz，1H，Fr-H)，7.14(d，J＝3.2Hz，1H，Fr-H)，6.65(dd，J
1＝2.0Hz，J
2＝2.0Hz，1H，Fr-H)，5.12(s，2H，CH
2)，4.41(d，J＝8.0Hz，2H，Fr-CH
2)。
Embodiment 3:
Preparation N-(2-picolyl)-2,4 dichloro benzene oxygen acetylurea (I
c):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil.Reaction solution is splashed in the excessive strong aqua, separate out white crystal after fully stirring.Water washing gets the 2,4 dichloro benzene acetamide oxide after the drying.
In the 50mL round-bottomed flask, take by weighing 1.10g (0.005mol) 2, the 4-dichlor phenoxyacetic amide is dissolved in the 15mL toluene, taking by weighing 2.62mL (0.03mol) oxalyl chloride in the normal pressure dropping funnel slowly drips, reflux and remove toluene and excessive oxalyl chloride after 2 hours under the decompression, obtain the thick product of isocyanic ester, do not need purifying, promptly can be used for the next step.2-pyridyl-methanamine with 0.432g (0.004mol) is dissolved in the 10mL chloroform soln again, adds in the titration funnel, slowly drips in the supreme step isocyanate solution, stirring at room 30min, rise to 60 ℃ and refluxed 2.5 hours, TLC tracks to reaction and finishes standing over night.Suction filtration, with suction filtration after 95% washing with alcohol, oven dry uses the mixed solvent recrystallization of alcohol-water-DMF promptly to get white solid powder I
CProductive rate: 73%.
Ultimate analysis: measured value C%50.87 H%5.70 N%11.86
Calculated value C%50.83 H%5.74 N%11.83
IR (KBr compressing tablet cm
-1) 3226 (N-H), 3137 (N-H), 1714 (C=O), 1696 (C=O);
1H?NMR(CDCl
3/400MHz)：10.53(s，1H，N-H)，8.75(s，1H，N-H)，7.25～8.51(m，4H，Py-H)，7.05～7.59(m，3H，Ph-H)，5.12(s，2H，CH
2)，4.47(d，J＝5.6Hz，2H，Py-CH
2)。
Embodiment 4:
Preparation N-(6-chloro-3-picolyl)-2,4 dichloro benzene oxygen acetylurea (I
d):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil.Reaction solution is splashed in the excessive strong aqua, separate out white crystal after fully stirring.Water washing gets the 2,4 dichloro benzene acetamide oxide after the drying.
In the 50mL round-bottomed flask, take by weighing 1.10g (0.005mol) 2, the 4-dichlor phenoxyacetic amide is dissolved in the 15mL toluene, taking by weighing 2.62mL (0.03mol) oxalyl chloride in the normal pressure dropping funnel slowly drips, reflux and remove toluene and excessive oxalyl chloride after 2 hours under the decompression, obtain the thick product of isocyanic ester, do not need purifying, promptly can be used for the next step.6-chloro-3-pyridyl-methanamine with 0.562g (0.004mol) is dissolved in the 10mL chloroform soln again, adds in the titration funnel, slowly drips in the supreme step isocyanate solution, stirring at room 30min, rise to 60 ℃ and refluxed 3 hours, TLC tracks to reaction and finishes standing over night.Suction filtration, with suction filtration after 95% washing with alcohol, oven dry uses the mixed solvent recrystallization of alcohol-water-DMF promptly to get white solid powder I
d, productive rate: 70%.
Ultimate analysis: measured value C%46.36 H%3.11 N%10.81
Calculated value C%46.32 H%3.08 N%10.78
IR (KBr compressing tablet cm
-1) 3225 (N-H), 3132 (N-H), 1711 (C=O), 1688 (C=O);
1H?NMR(CDCl
3/400MHz)：10.50(s，1H，N-H)，8.56(s，1H，N-H)，7.46～8.33(m，3H，Py-H)，7.05～7.77(m，3H，Ph-H)，4.89(s，2H，CH
2)，4.34(d，J＝7.6Hz，2H，Py-CH
2)。
Embodiment 5:
Preparation N-5-chloro-2-thiazole methyl)-2,4 dichloro benzene oxygen acetylurea (I
e):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil.Reaction solution is splashed in the excessive strong aqua, separate out white crystal after fully stirring.Water washing gets the 2,4 dichloro benzene acetamide oxide after the drying.
In the 50mL round-bottomed flask, take by weighing 1.10g (0.005mol) 2, the 4-dichlor phenoxyacetic amide is dissolved in the 15mL toluene, taking by weighing 2.62mL (0.03mol) oxalyl chloride in the normal pressure dropping funnel slowly drips, reflux and remove toluene and excessive oxalyl chloride after 2 hours under the decompression, obtain the thick product of isocyanic ester, do not need purifying, promptly can be used for the next step.5-chloro-2-pyridyl-methanamine with 0.562g (0.004mol) is dissolved in the 10mL chloroform soln again, adds in the titration funnel, slowly drips in the supreme step isocyanate solution, stirring at room 30min, rise to 60 ℃ and refluxed 3 hours, TLC tracks to reaction and finishes standing over night.Suction filtration, with suction filtration after 95% washing with alcohol, oven dry uses the mixed solvent recrystallization of alcohol-water-DMF promptly to get white solid powder I
eProductive rate: 76%.
Ultimate analysis: measured value C%39.56 H%2.55 N%10.65
Calculated value C%39.54 H%2.49 N%10.68
IR (KBr compressing tablet cm
-1) 3221 (N-H), 3134 (N-H), 1706 (C=O), 1691 (C=O);
1HNMR(CDCl
3/400MHz)：10.57(s，1H，N-H)，8.58(s，1H，N-H)，7.52s，1H，Thi-H)，7.04～7.54(m，3H，Ph-H)，4.87(s，2H，CH
2)，4.46(d，J＝6.0Hz，2H，CH
2).
(2) have the weedicide that contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class of efficient weeding activity, with general formula (II) expression:
Wherein: R is five yuan or hexa-atomic substituted heterocycle methyl such as 2-tetrahydrofuran methyl, furfuryl, 2-picolyl, 6-chloro-3-picolyl, 5-chloro-2-thiazole methyl.
The example of the weedicide of N-(substituted heterocycle the methyl)-2,4 dichloro benzene oxygen acetyl thiourea class of the present invention's preparation is:
(II
a), N-(2-tetrahydrofuran methyl)-2,4 dichloro benzene oxygen acetyl thiourea;
(II
b), N-(furfuryl)-2,4 dichloro benzene oxygen acetyl thiourea;
(II
c), N-(2-picolyl)-2,4 dichloro benzene oxygen acetyl thiourea;
(II
d), N-(6-chloro-3-picolyl)-2,4 dichloro benzene oxygen acetyl thiourea;
(II
e), N-(5-chloro-2-thiazole methyl)-2,4 dichloro benzene oxygen acetyl thiourea.
Embodiment 6:
Preparation N-(2-tetrahydrofuran methyl)-2,4 dichloro benzene oxygen acetyl thiourea (II
a):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and toluene and excessive sulfur oxychloride are removed in decompression down.The anhydrous acetonitrile 20mL and the 0.5mL PEG-400 that in debris, add the potassium sulfocyanate of 1.46g (0.015mol), stirring and refluxing reaction 0.5h removes by filter the KCl precipitation, gets orange-yellow 2, the acetonitrile solution of 4-Dichlorophenoxy acetyl lsothiocyanates, it is synthetic to be directly used in down the step.This mixed solution is dropped in the 10mL acetonitrile solution of the 2-tetrahydrofuran (THF) methylamine that contains 0.808g (0.008mol), 60 ℃ of backflow 3h, TLC track to reaction and finish standing over night.Suction filtration, oven dry, crude product carries out recrystallization with DMF and alcoholic acid mixing solutions, gets yellow solid powder (II
a); Productive rate: 63%.
Ultimate analysis: measured value C%46.29 H%4.44 N%7.71
Calculated value C%46.25 H%4.47 N%7.68
IR (KBr compressing tablet cm
-1) 3220 (N-H), 2991 (N-H), 1714 (C=O), 1190 (C=S);
1H?NMR(CDCl3/400MHz)：10.39(s，1H，N-H)，8.73(s，1H，N-H)，7.09～7.60(m，3H，Ph-H)，5.14(s，2H，CH
2)，4.38(d，J＝8.0Hz，2H，THF-CH
2)，4.02-4.08(m，1H，THF)，3.89-3.95(m，1H，THF)，3.77-3.83(m，1H，THF)，3.47-3.53(m，1H，THF)，2.54-2.59(m，2H)，2.01-2.08(m，1H，THF)。
Embodiment 7:
Preparation N-(furfuryl)-2,4 dichloro benzene oxygen acetyl thiourea (II
b):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and toluene and excessive sulfur oxychloride are removed in decompression down.The anhydrous acetonitrile 20mL and the 0.5mL PEG-400 that in debris, add the potassium sulfocyanate of 1.46g (0.015mol), stirring and refluxing reaction 0.5h removes by filter the KCl precipitation, gets orange-yellow 2, the acetonitrile solution of 4-Dichlorophenoxy acetyl lsothiocyanates, it is synthetic to be directly used in down the step.This mixed solution is dropped in the 10mL acetonitrile solution of the 2-tetrahydrofuran (THF) methylamine that contains 0.776g (0.008mol), 60 ℃ of backflow 3.5h, TLC track to reaction and finish standing over night.Suction filtration, oven dry, crude product carries out recrystallization with DMF and alcoholic acid mixing solutions, gets yellow solid powder (II
b).Productive rate: 66%.
Ultimate analysis: measured value C%46.81 H%3.37 N%7.80
Calculated value C%46.77 H%3.35 N%7.84
IR (KBr compressing tablet cm
-1) 3226 (N-H), 2993 (N-H), 1715 (C=O), 1196 (C=S);
1H?NMR(CDCl
3/400MHz)：10.31(s，1H，N-H)，8.70(s，1H，N-H)，7.06～7.60(m，3H，Ph-H)，7.53(d，J＝8.0Hz，1H，Fr-H)，7.17(d，J＝3.2Hz，1H，Fr-H)，6.68(dd，J
1＝2.0Hz，J
2＝2.0Hz，1H，Fr-H)，5.13(s，2H，CH
2)，4.40(d，J＝8.0Hz，2H，Fr-CH
2)。
Embodiment 8:
Preparation N-(2-picolyl)-2,4 dichloro benzene oxygen acetyl thiourea (II
c):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and toluene and excessive sulfur oxychloride are removed in decompression down.The anhydrous acetonitrile 20mL and the 0.5mL PEG-400 that in debris, add the potassium sulfocyanate of 1.46g (0.015mol), stirring and refluxing reaction 0.5h removes by filter the KCl precipitation, gets orange-yellow 2, the acetonitrile solution of 4-Dichlorophenoxy acetyl lsothiocyanates, it is synthetic to be directly used in down the step.This mixed solution is dropped in the 10mL acetonitrile solution of the 2-tetrahydrofuran (THF) methylamine that contains 0.864g (0.008mol), 60 ℃ of backflow 4h, TLC track to reaction and finish standing over night.Suction filtration, oven dry, crude product carries out recrystallization with DMF and alcoholic acid mixing solutions, gets white solid powder (II
c); Productive rate: 69%.
Ultimate analysis: measured value C%48.66 H%3.54 N%11.35
Calculated value C%48.69 H%3.50 N%11.39
IR (KBr compressing tablet cm
-1) 3213 (N-H), 2986 (N-H), 1721 (C=O), 1189 (C=S);
1H?NMR(CDCl
3/400MHz)：10.37(s，1H，N-H)，8.72(s，1H，N-H)，7.38～8.52(m，4H，Py-H)，7.08～7.61(m，3H，Ph-H)，4.96(s，2H，CH
2)，4.86(d，J＝4.8Hz，2H，Py-CH
2)。
Embodiment 9:
Preparation N-(6-chloro-3-picolyl)-2,4 dichloro benzene oxygen acetyl thiourea (II
d):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and toluene and excessive sulfur oxychloride are removed in decompression down.The anhydrous acetonitrile 20mL and the 0.5mL PEG-400 that in debris, add the potassium sulfocyanate of 1.46g (0.015mol), stirring and refluxing reaction 0.5h removes by filter the KCl precipitation, gets orange-yellow 2, the acetonitrile solution of 4-Dichlorophenoxy acetyl lsothiocyanates, it is synthetic to be directly used in down the step.This mixed solution is dropped in the 10mL acetonitrile solution of the 6-chloro-3-pyridyl-methanamine that contains 1.144g (0.008mol), 60 ℃ of backflow 3h, TLC track to reaction and finish standing over night.Suction filtration, oven dry, crude product carries out recrystallization with DMF and alcoholic acid mixing solutions, gets white solid powder (II
d); Productive rate: 72%.
Ultimate analysis: measured value C%44.52 H%2.99 N%10.38
Calculated value C%44.49 H%2.96 N%10.34
IR (KBr compressing tablet cm
-1) 3221 (N-H), 2987 (N-H), 1711 (C=O), 1190 (C=S);
1HNMR(CDCl
3/400MHz)：10.35(s，1H，N-H)，8.68(s，1H，N-H)，7.46～8.39(m，3H，Py-H)，7.03～7.74(m，3H，Ph-H)，4.69(s，2H，CH
2)，4.34(d，J＝6.0Hz，2H，Py-CH
2).
Embodiment 10:
Preparation N-(5-chloro-2-thiazole methyl)-2,4 dichloro benzene oxygen acetyl thiourea (II
e):
In the 50mL round-bottomed flask, newly steam the 2,4 dichlorophenoxyacetic acid that toluene dissolves 2.21g (0.01mol) with 15mL, drip the sulfur oxychloride of 2.9mL (0.025mol), reflux stirred 2 hours, and toluene and excessive sulfur oxychloride are removed in decompression down.The anhydrous acetonitrile 20mL and the 0.5mL PEG-400 that in debris, add the potassium sulfocyanate of 1.46g (0.015mol), stirring and refluxing reaction 0.5h removes by filter the KCl precipitation, gets orange-yellow 2, the acetonitrile solution of 4-Dichlorophenoxy acetyl lsothiocyanates, it is synthetic to be directly used in down the step.This mixed solution is dropped in the 10mL acetonitrile solution of the 5-chloro-2-thiazole methylamine that contains 1.184g (0.008mol), 60 ℃ of backflow 3.5h, TLC track to reaction and finish standing over night.Suction filtration, oven dry, crude product carries out recrystallization with DMF and alcoholic acid mixing solutions, gets white solid powder (II
e); Productive rate: 72%.
Ultimate analysis: measured value C%38.02 H%2.45 N%10.23
Calculated value C%38.06 H%2.41 N%10.20
IR (KBr compressing tablet cm
-1) 3219 (N-H), 3012 (N-H), 1708 (C=O), 1196 (C=S);
1H?NMR(CDCl
3/400MHz)：10.32(s，1H，N-H)，8.73(s，1H，N-H)，7.55(s，1H，Thi-H)，7.02～7.65(m，3H，Ph-H)，4.68(s，2H，CH
2)，4.46(d，J＝5.6Hz，2H，CH
2)。
The above embodiment of the present invention is not limited to the present invention.For a person skilled in the art, the preparation method of product of the present invention can change.Within the spirit and principles in the present invention all, that is done is equal to replacement, improves etc., all should be included within protection scope of the present invention.
Claims (4)
1.N-2,4-Dichlorophenoxy acetyl (sulphur) carbamide weedicide, represent with general formula (I) with (II): general formula (I) is for containing N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides:
General formula (II) is for containing N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide:
Wherein: R is five yuan or hexa-atomic substituted heterocycle methyl such as 2-tetrahydrofuran methyl, furfuryl, 2-picolyl, 6-chloro-3-picolyl, 5-chloro-2-thiazole methyl.
General formula (I) expression contain N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides, the preparation method is as follows:
(1) preparation 2,4 dichloro benzene acetamide oxide:
A. 2,4 dichlorophenoxyacetic acid is dissolved in the toluene of new steaming, dripping thionyl chloride, reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil;
B. reaction solution is splashed in the excessive strong aqua, be stirred well to and separate out white crystal, wash with water, get the 2,4 dichloro benzene acetamide oxide after the drying;
(2) preparation general formula (I) contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides:
A. the 2,4 dichloro benzene acetamide oxide with above-mentioned (1) preparation is dissolved in the toluene, slowly drips oxalyl chloride, refluxes 2 hours;
B. decompression is removed toluene and excessive oxalyl chloride down, drips the chloroform soln that is dissolved with the substituted heterocycle methylamine, refluxes 3 hours, makes general formula (I) and contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl carbamide herbicides.
General formula (II) expression contain N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide, the preparation method is as follows:
(1) preparation 2,4 dichloro benzene oxygen acetyl lsothiocyanates:
A. 2,4 dichlorophenoxyacetic acid is dissolved in the toluene of new steaming, dripping thionyl chloride, reflux stirred 2 hours, and decompression removes toluene down and excessive sulfur oxychloride gets yellow oil;
B. reaction solution is added dropwise to the anhydrous acetonitrile and the PEG-400 of potassium sulfocyanate, stirring and refluxing, filter orange-yellow 2,4 dichloro benzene oxygen acetyl lsothiocyanates;
(2) preparation contains the weedicide of N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class:
A. the acetonitrile solution of the 2,4 dichloro benzene oxygen acetyl lsothiocyanates that above-mentioned (1) is prepared slowly is added drop-wise in the acetonitrile solution that contains the substituted heterocycle methylamine;
B. under 60 ℃ of conditions, refluxed 2～4 hours, make general formula (II) and contain N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl thiourea class weedicide.
4. according to claim 1N-2,4-Dichlorophenoxy acetyl (sulphur) carbamide weedicide, it is characterized in that: with general formula (I) or the weedicide that (II) contains N-(substituted heterocycle methyl)-2,4 dichloro benzene oxygen acetyl (sulphur) ureas be raw material, make emulsion, aqueous suspension and water and milk formulation weedicide agricultural chemicals.
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| CN103044336A (en) * | 2012-12-28 | 2013-04-17 | 中国农业大学 | Acylthiourea compound, preparation method and application thereof |
| CN104713981A (en) * | 2014-05-21 | 2015-06-17 | 江苏德峰药业有限公司 | Content calculation method of 2,4-dichloro-3-nitro-5-fluorobenzoyl chloride generated by acylation reaction |
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| CN100339071C (en) * | 2005-11-03 | 2007-09-26 | 上海师范大学 | Application of diacyl thiourea derivative in preparing antiviral medicine |
| CN101220022B (en) * | 2007-11-23 | 2010-12-08 | 上海师范大学 | 2-(5-chlorophenyl-2-tetrol formamido)ethanamide pyrimidine derivant, preparation and application thereof |
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| CN103044336A (en) * | 2012-12-28 | 2013-04-17 | 中国农业大学 | Acylthiourea compound, preparation method and application thereof |
| CN103044336B (en) * | 2012-12-28 | 2014-11-19 | 中国农业大学 | Acylthiourea compound, preparation method and application thereof |
| CN104713981A (en) * | 2014-05-21 | 2015-06-17 | 江苏德峰药业有限公司 | Content calculation method of 2,4-dichloro-3-nitro-5-fluorobenzoyl chloride generated by acylation reaction |
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