CN1028171C - Process for producing pyrimidine derivative or salt thereof - Google Patents
Process for producing pyrimidine derivative or salt thereof Download PDFInfo
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- CN1028171C CN1028171C CN 92102226 CN92102226A CN1028171C CN 1028171 C CN1028171 C CN 1028171C CN 92102226 CN92102226 CN 92102226 CN 92102226 A CN92102226 A CN 92102226A CN 1028171 C CN1028171 C CN 1028171C
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Abstract
A pyrimidine derivative having the formula <I> wherein X is a halogen atom, a lower alkyl group or a phenoxy group (wherein said phenoxy group may be substituted by halogen, lower alkyl or lower alkoxy), and R is a hydrogen atom, a lower alkyl group, an alkoxyalkyl group, a benzyloxyalkyl group, an alkoxycarbonyl alkyl group, a cyanoalkyl group or a * group (wherein R' is a hydrogen atom or a lower alkyl group, and R<2> is a lower alkyl group or a phenyl group which may be substituted by nitro).
Description
The present invention relates to the production method of Noval pyrimidine derivatives or its salt.
Recently, developed large quantities of weedicides and be used for practice, weedicide is to save the energy of agricultural operation and improve the efficient of producing to contribute.In addition, known various 2-phenoxy pyrimidine derivates are effective [(1) Japanese laid-open publications 174059/1987, (2) Japanese laid-open publication 55729/1979 and (3) agricultural biochemistry 30 are rolled up 896 pages (1966) No. 9] as weedicide.
Yet disclosed compound in above-mentioned reference (1) although they demonstrate efficient herbicidal effect, has individual safety issue to farm crop.In addition, the deficiency of disclosed compound is that its weeding activity to annual careless class is not enough in above-mentioned reference (2) and (3), and the perennial grass class is not demonstrated significant weeding activity yet.
The present inventor has carried out extensive studies to develop a kind of compound with more excellent weeding activity to pyrimidine derivatives, found that the compound of introducing substituent at the pyrimidine and the specific position on the phenyl ring of phenyl sulphur pyrimidine derivatives of the present invention demonstrates excellent herbicidal effect to perennial grass class and annual careless class, simultaneously, they are to farm crop, particularly, has tight security for cotton.Of the present invention finishing is based on these discoveries.
Pyrimidine derivatives provided by the invention has general expression:
Wherein X is the halogen atom such as chlorine, bromine, iodine or fluorine, low alkyl group, particularly C
1-C
4Alkyl, or phenoxy group (wherein said phenoxy group can be by the halogen atom such as chlorine, bromine, iodine or fluorine, low alkyl group, particularly C
1-C
4Alkyl replaces, or lower alkoxy, particularly C
1-C
4Alkoxyl group replaces), R is a halogen atom, low alkyl group, particularly C
1-C
6Alkyl, alkoxyalkyl, particularly C
1-C
4Alkoxy C
1-C
4Alkyl, benzyloxy alkyl, particularly benzyloxy C
1-C
4Alkyl, alkoxycarbonyl alkyl, particularly C
1-C
4Carbalkoxy C
1-C
4Alkyl, the cyano group alkyl or
SR
2(wherein R ' is hydrogen atom or low alkyl group, particularly C to group
1-C
4Alkyl, R
2Be low alkyl group, particularly C
1-C
4Alkyl or the phenyl that can be replaced by nitro), perhaps be its salt.
Now describe the present invention in detail with object lesson preferably.
In the molecular formula I, X replaces in the 6-position, and particularly X is chlorine atom, methyl or the fluorine atom in the 6-position.
R is preferably hydrogen atom, low alkyl group, alkoxyalkyl or benzyloxy alkyl.Best is hydrogen atom.
In the compound of molecular formula I, be preferably following general expression I-1 and I-2.
Wherein defined in R such as the claim 1, X is halogen atom or low alkyl group;
Wherein defined in R such as the claim 1, Y is hydrogen atom, halogen atom, low alkyl group or lower alkoxy.
Now the object lesson of The compounds of this invention is listed in table 1.The numbering of the compound of being given in the table is corresponding with the description order in the specification sheets.
Table 1
The volume fusing point (℃)
Number R X specific refractory power
1 H 6-Cl 148-151
2 H 6-CH
3131-132
3 CH
36-Cl n
20 D＝1.5770
4 CH
26-CH
3n
20 d＝1.5775
5 H 5-CH
3177-182
6 CH
3S
6-Cl n
20 D＝1.6166
7 CH
35-CH
371-72
8 H 5-Cl 203-206
9 H 3-Cl 128-131
10 H 6-F 133-135
Table 1(is continuous)
The volume fusing point (℃)
Number R X specific refractory power
11 CH
36-F 45-47
12 CH
2OCH
36-Cl 70-72
13 CH
2SCH
3
14 H 3-CH
3144-153
15
6-Cl n
20 D＝1.6273
16 C
2H
56-Cl 70-75
17 CH
2OC
2H
56-Cl n
20 D＝1.5590
18 CH
2OCH
2 6-Cl n
20 D＝1.5826
19
6-Cl fails to measure
20
6-Cl n
20 D＝1.5483
21
6-Cl n
20 D＝1.6041
22 CH
2CN 6-Cl 97-105
23 C
4H
9-i 6-Cl 68-70
24
6-Cl 149-151
Table 1(is continuous)
The volume fusing point (℃)
Number R X specific refractory power
25 ·HN（C
2H
4OH）
36-Cl 94-101
26 ·Na 6-Cl 246-250
27 H
2N(C
2H
4OH)
26-Cl fails to measure
28
140-145
29
172-175
30 H 6-0-
31 H 6-0-
124-127
32 ·NH
46-Cl 150-154
33 H 6-0-
34 H
In compound of the present invention, benzoic acid derivative (R wherein is a hydrogen atom) or its salt demonstrate excellent especially herbicidal effect.
Salt can be an alkali metal salt, alkaline earth salt, transition metal salt or organic ammonium salt.
Be numbered 1,2,11,12,17,18,21 compound and salt pair crop, particularly cotton are superior especially having aspect excellent weeding activity and the no obvious phytotoxicity.
Compound of the present invention can following method prepare,
In the formula, Y
1Be halogen atom, alkyl sulphonyl perhaps is that replace or unsubstituted benzyl alkylsulfonyl, and X and R are as defined above.
General expression of the present invention be I compound can by with the compound of the compound of molecular formula II and molecular formula III in the presence of alkali, be preferably in solvent, get to the temperature range internal reaction 1 to 24 hour of solvent boiling point in room temperature.Carry out when being reflected under the solvent-free situation, reaction can be carried out as alkali with alkaline carbonate in 120 to 160 ℃ temperature range, such as Anhydrous potassium carbonate.
Solvent used in this reaction comprises, have for instance, hydrocarbon solvent such as benzene, toluene or dimethylbenzene, halohydrocarbon such as methylene dichloride or chloroform, alcoholic solvent such as methyl alcohol, ethanol, Virahol, such as ether, isopropyl ether, tetrahydrofuran (THF), 1, the ether solvent of 4-diox, ketones solvent such as acetone or methylethylketone, such as the esters solvent of methyl acetate or ethyl acetate, such as N, dinethylformamide, the non-polar solvent of the non-proton transmission of N,N-dimethylacetamide or dimethyl sulfoxide (DMSO) and acetonitrile and water.
Alkali can be the basic metal such as sodium or potassium, alkalimetal hydride or alkaline earth metal hydride, such as, sodium hydride, potassium hydride KH or hydrolith; Carbonate such as yellow soda ash, salt of wormwood, sodium bicarbonate or saleratus; And such as the metal hydroxides of sodium hydroxide or potassium hydroxide.
In addition, compound of the present invention also can make as follows,
In the formula, R and X are as defined above.
The compound of molecular formula I can be by will transforming the diazonium salt of the molecular formula V of coming and molecular formula VI by the compound of molecular formula IV compound in alkaline solution in low temperature, particularly get at-20 ℃ to 10 ℃ temperature range internal reaction.
As diazonium salt, hydrogen borate salt, hydriodate, a tetrafluoro borate or vitriol can add in the hydrochloric acid.In addition, alkaline solution can be by will be such as sodium hydroxide, potassium hydroxide, and highly basic such as hydrated barta or calcium hydroxide add in the solvent formulated.
The 2-[(4 of molecular formula I, 6-dimethoxypyridin-2-yl) sulfo-] benzoic acid derivative can make as stated above, can with sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium hydride or analogue reaction change into its corresponding alkali metal salt.Then, can make the reaction of calcium chloride and an alkali metal salt, or lime carbonate or hydrolith and benzoic acid accordingly are to obtain alkaline earth salt.Also have, iron(ic) chloride or analogue are reacted with an alkali metal salt make it change into transition metal salt, such as molysite.
Further, can also with phenylformic acid by allow it with such as primary amine, secondary amine, tertiary amine, diethanolamine, trolamine, alkoxyalkyl amine, the aliphatic amine of hexahydroaniline or morpholine perhaps with such as the aromatic amine reaction of aniline or naphthylamines changes into organic ammonium salt.
Below in conjunction with embodiment the present invention is described in further detail, yet, should be understood that the present invention is not only limited to these special examples.
Embodiment 1
2-[(4,6-dimethoxypyridin-2-yl] sulfo-]-preparation of 6-tolyl acid (compound of numbering 2)
50 gram 2-amino-6-tolyl acid hydrochlorides are changed into diazonium salt with concentrated hydrochloric acid and 2.3 gram Sodium Nitrites.Then, in 0 to 5 ℃, this diazonium salt is dropwise splashed in the preprepared sodium disulfide solution (with 8.7 gram sodium sulphite, 1.1 gram sulphur, 1.5 gram sodium hydroxide and 15 ml waters are made into), after being added dropwise to complete, mixed solution in stirring at room 2 hours with complete reaction.Reaction soln is poured in the big water gaging, toward wherein adding concentrated hydrochloric acid.Then, with ethyl acetate extracting mixture, sodium bicarbonate aqueous solution is added in the ethyl acetate layer, the solvable composition of sodium bicarbonate is just extracted.5.8 gram sodium pyrosulfates are added in the aqueous solution, again mixture is refluxed 30 minutes with complete reaction.In reaction soln, add concentrated hydrochloric acid, use ethyl acetate extracting mixture then, dry extract, then decompression steams solvent, obtains the 2-sulfydryl-6-tolyl acid of 3.6 grams (productive rate 65%).
Subsequently, with 3.6 gram 2-sulfydryl-6-tolyl acids, 4.7 restrain 4,6-dimethoxy-2-sulfonyloxy methyl pyrimidine and 3.5 gram Anhydrous potassium carbonates are dissolved in 20 milliliters of dimethyl formamides, then, in 110 to 120 ℃ stirred the mixture 1 hour, in the big water gaging of reaction soln impouring, toward wherein adding concentrated hydrochloric acid.Then, dry again after chloroform layer washes with water with chloroform extracting mixture, pressure reducing and steaming solvent then.Coarse crystal is made on the post of developping agent the chromatogram chromatography and is purified with hexane/ethyl acetate, recrystallization obtains 0.8 gram 2-[(4,6-dimethoxypyridin-2-yl from ethyl acetate again] sulfo--6-tolyl acid, be white powdery, fusing point is 131-132 ℃.
Embodiment 2
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) sulfo-] preparation of phenylformic acid (being numbered 1 compound)
5.0 gram 2-amino-6-chloro-benzoate hydrochlorates are changed into diazonium salt with 2.3 gram Sodium Nitrites and concentrated hydrochloric acid.Then, this diazonium salt dropwise adds in 0 ℃ and contains 4.8 grams 4, and 6-dimethoxy-2-mercaptopyrimidine in the solution of 2.4 gram sodium hydroxide and 40 ml waters, after being added dropwise to complete, at room temperature stirs this mixture liquid 2 hours with complete reaction.Concentrated hydrochloric acid is added in the reaction solution, then, with ethyl acetate extracting mixed solution, dry extract, pressure reducing and steaming solvent again.The gained residue is purified through the chromatography method and is obtained 1.8 gram 2-chloro-6-[(4,6-dimethoxypyridin-2-yl) sulfo-] phenylformic acid, be the reddish brown powdery, fusing point is 148-151 ℃.
Embodiment 3
2-chloro-6-[(4,6-dimethoxypyridin-2-yl) sulfo-] preparation of phenylformic acid triethanol ammonium (being numbered 25 compound)
With 1.57 gram 2-chloro-6-[(4,6-dimethoxypyridin-2-yl) thiobenzoic acid and 0.72 gram trolamine be dissolved in 20 milliliters the tetrahydrofuran (THF), stirred this solution 30 minutes under room temperature.Solvent is steamed from solution, isopropyl ether is added to makes it curing in the residue.Filter to isolate solid, dry then, obtain 2.0 gram 2-chloro-6-[(4,6-dimethoxypyridin-2-yl) sulfo-] the phenylformic acid triethanol ammonium, and being white solid, fusing point is 94-101 ℃.
Herbicidal composition of the present invention comprises that it has herbicidally effective amount, such as, 0.5% to 95% weight part is the The compounds of this invention and the agricultural agent of 1 to 80% weight part preferably.Weedicide of the present invention can use separately, or is made into different preparations, such as, wettable powder, granule, and missible oil or be equipped with carrier, tensio-active agent, dispersion agent or be generally used for the pulvis of the auxiliary agent of agricultural chemicals preparation.
The carrier that is used for preparation can be such as Jeeklite, talcum, wilkinite, clay, kaolin, diatomite, white carbon black, vermiculite, white lime, silica sand, the solid carrier of ammonium sulfate or urea etc.; Such as Virahol, dimethylbenzene, the liquid vehicle of hexanaphthene or methylnaphthalene etc.Tensio-active agent described here and dispersion agent can be pure sulphonates, alkyl aryl sulfonate, sulfonated lignin, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether or polyoxyethylene sorbitol mono alkyl ester.Auxiliary agent can be carboxymethyl cellulose, polyoxyethylene glycol or Sudan Gum-arabic.In actual use, this weedicide can be diluted to suitable concentration before use, or can directly use.
Weedicide of the present invention can be used in combination with other weedicides.
Weedicide of the present invention carried out the surface irrigation dispenser or passed through foliage application the green bristlegrass grass in the rice terrace before or after germinateing at the green bristlegrass grass.In addition, when weedicide of the present invention puts on nonirrigated farmland or non-agricultural crop field, can before or after germinateing, the green bristlegrass grass carry out area spray or foliage application.
For area spray, the dosage that applies of weedicide of the present invention is that per 10 are of 1 gram is to 1 kilogram of activeconstituents.For foliage application, it is diluted to 1 to 10, the concentration of 000ppm applies with the dosage of per 10 are of 1 gram to 1 kilogram of activeconstituents.
Now provide the formulation examples of herbicidal composition of the present invention, but should be understood that the present invention is not only limited in these specific examples." % " expression weight percent in these examples.
Formulation examples 1(wettable powder)
Be numbered 1 compound with 10%, the 0.5%Emulgen810(trade mark, Kao company), 0.5%Demol N(trade mark, Kao company), 20% Kunilite201(trade mark, Kunimine Kogyo company) and 69% Jeeklite CA(trade mark, Jeeklite company limited) mixes also pulverize equably, obtain wettable powder.
Formulation examples 2(missible oil)
Be numbered 1 compound with 30%, 20% hexanaphthene, 11% polyoxyethylene alkylaryl ether, 4% alkyl benzene calcium sulfonate and 35% methylnaphthalene uniform dissolution obtain missible oil.
Formulation examples 3(granule)
Be numbered 1 compound with 5%; 2% lauryl alcohol-sulphonate sodium salt; 5% sodium lignosulfonate; 2% carboxymethyl cellulose and 86% clay uniform mixing and pulverize; get this mixture of 100 weight parts and add 20 weight parts waters; this mixture of kneading is extruded into 14 to 32 purpose particles with tablets press, and drying obtains pellet again.
Formulation examples 4(pulvis)
Be numbered 2 compound with 2%, 5% diatomite and 93% clay uniform mixing and pulverize obtain pulvis.
Compound of the present invention and herbicidal composition can control effectively long in rice terrace such as barnyard grass (Echinochloa crus-galli), nutgrass flatsedge (Cyperus difformis), Monochoria korsakowii annual grass such as (Monchoria vaginalis); And such as the Rush (Scirpus hotarui) of Waterplantain canaliculate (Alisma canaliculatum), the nutgrass flatsedge (Cyperus serotinus) that spend on evening, the perennial grass of short arrowhead (Sagittaria pygmaea) and water chestnut neat (Eleocharis Kurogwai) etc.In addition, also can control effectively long dry land such as barnyard grass (Echinochloa crus-galli), lady's-grass grass (Digitaria sanguinalis), yard grass (Eleusine indica), green foxtail (Setaria viridis), water foxtail (Alopecurus aequalis), annual precocious dogstail (Poa annua), wild avena sativa (Avena fatua), Italian ryegrass (Lolium multiform), arsesmart (polygonum Capathifolium), thin amaranth (Amaranthus viridis), lamb's-quarters (Chenopodium album), velvetleaf (Abutilon theophrasti), thorniness Radix sidae acutae (Sida spinosa), Cassia tora (Cassia tora), chickweed (Stellaria media), morning glory (lpomoea spp), common Siberian cocklebur (Xanthium strumarium) paddy nutgrass flatsedge (Cyperus iria), wide leaf arm shape grass (Brachiaria platphylla), Rottboellia exaltata (Rotloboellia exaltata), pubescence bromegrass (Bromus tectorum), Radix Et Rhizoma Fagopyri Tatarici (Polygonum convolvulus), the annual grass of wild cruciate flower (Brassica arvensis) and shirt rim Herba Bidentis Bipinnatae (Bidens frondosa) etc.; And such as Murex purpurea nutgrass flatsedge (Cyperus rotundus), Johnson grass (Sorghum halepense), the perennial grass of Bermuda grass (Cynodon dactylon) and Agropyron repens (Agropyron repens) etc.On the other hand, to farm crop, cotton particularly, its security is high.
When weedicide of the present invention is used as the cotton weedicide, have following characteristics; In addition, when it is used as the weedicide of the farm crop except that cotton, various advantages are arranged equally.
In every kind of application method of the foliage application after (1) area spray of weedicide of the present invention before grass germinates germinates with grass, be high safety for cotton.Correspondingly, weedicide of the present invention can be used as the cotton weedicide of the foliage application after the preceding area spray of grass germination germinates with grass.
(2) weedicide of the present invention has herbicide effect to the green bristlegrass grass that makes us feeling a delicacy about such as common Siberian cocklebur and morning glory, and before grass germinates to the germination over a long time in be effective.
(3) weedicide of the present invention has suitably decomposability in earth, and contiguous farm crop are not had obvious promoter action.
The weeding activity of weedicide of the present invention is now described with test examples.Area spray method before grass germinates in the test examples 1(nonirrigated farmland)
(surface area 600cm in one jar of earth
2), sow cotton (Go), barnyard grass (Ec), Johnson grass (So), arsesmart (Po), thin amaranth (Am), lamb's-quarters (Ch), the seed of morning glory (Ip) and common Siberian cocklebur (Xa); The stem tuber of Murex purpurea nutgrass flatsedge (Cr) under kind; Cover the thick earth of one deck 0.5 to 1cm again.Sowing one day after, the wettable powder dilute with water that the method in the formulation examples 1 of predetermined amount is made also is applied to earth surfaces with per 10 ares 100 liters ratio.Measured in the 20th day after dispenser, and being defined as standard evaluation gained result in the table 2, and index was listed in table 3 and table 4.
Table 2
Index is unequal to number herbicidal effect and value thing toxicity
0 no herbicidal effect (or plant-less toxicity)
1 herbicidal effect (or phytotoxicity) greater than 0% less than 30%
2 herbicidal effects (or phytotoxicity) are at least 30% and less than 50%
3 herbicidal effects (or phytotoxicity) are at least 50% and less than 70%
4 herbicidal effects (or phytotoxicity) are at least 70% and less than 90%
5 herbicidal effects (or phytotoxicity) are greater than 90%
Table 3
The plant herbicidal effect
Compound activity group toxicity
The numbering doses
（gai/10a） Go Ec So Po Am Ch Ip Xa Cr
1 100 0 5 5 5 5 5 5 5 5
25 0 4 5 5 5 5 5 5 5
2 100 0 5 5 5 5 5 3 4 5
25 0 3 5 5 5 5 0 3 4
Contrast closes 100 355555324
Thing I 25 245555003
Control compounds 1 as give a definition (being equally applicable in other tables):
Control compounds 1: 2-[(4,6-dimethoxypyridin-2-yl) oxo] phenylformic acid (disclosed in this pending trial publication 174059/1987)
Table 4
The plant herbicidal effect
Compound activity group toxicity
The numbering doses
（gai/10a） Go Ec So Po Am Ch Ip Xa Cr
10 25 1 5 5 5 5 5 4 3 5
11 100 1 5 5 5 5 5 4 4 5
25 0 5 5 5 5 5 3 2 5
12 100 0 5 5 5 5 5 5 5 5
25 0 5 5 5 5 5 5 4 5
13 100 1 4 5 5 5 5 5 5 5
14 100 1 5 5 5 5 5 3 3 4
17 100 1 5 5 5 5 5 5 5 5
25 0 5 5 5 5 5 5 5 5
18 100 1 5 5 5 5 5 5 5 5
25 0 5 5 5 5 5 5 5 4
21 100 0 5 5 5 5 5 5 4 5
25 0 5 5 5 5 5 3 2 5
24 25 1 5 5 5 5 5 5 5 5
25 25 1 5 5 5 5 5 5 4 5
27 100 1 5 5 5 5 5 5 5 5
25 0 1 5 5 5 5 5 5 4 5
28 100 0 5 5 5 5 5 5 5 5
25 0 5 5 5 5 5 4 4 5
Contrastization 100 355555224
Compound I 25 344555002
Foliage application method after grass germinates in the test examples 2(nonirrigated farmland)
(surface area is 600cm in one jar of mud
2) sow cotton (Go), barnyard grass (Ec), Johnson grass (So), arsesmart (Po), thin amaranth (Am), lamb's-quarters (Ch), the seed of morning glory (Ip) and common Siberian cocklebur (Xa) is planted the stem tuber of Murex purpurea nutgrass flatsedge (Cr) down; Cover the thick earth of one deck 0.5 to 1cm again.This jar cultivated for 2 weeks in 20 to 25 ℃ greenhouse, and then, the wettable powder dilute with water by the preparation of the method in the formulation examples 1 with predetermined amount puts on the blade with 100 liters every are ratios.Measured in the 14th day after the dispenser, and being defined as standard evaluation gained result in the table 2, and index was listed in table 5 and table 6.
Table 5
The plant herbicidal effect
Compound activity group toxicity
The numbering doses
（gai/10a） Go Ec So Po Am Ch Ip Xa Cr
1 100 1 5 5 5 5 5 5 5 5
25 0 4 5 5 5 5 5 5 5
2 100 1 5 5 5 5 5 4 5 5
25 0 3 5 5 5 5 3 4 5
Contrastization 100 555555334
Compound I 25 455555123
Table 6
The plant herbicidal effect
Compound activity group toxicity
The numbering doses
（gai/10a） Go Ec So Po Am Ch Ip Xa Cr
24 25 0 4 5 5 5 5 5 5 5
25 25 0 4 5 5 5 5 5 5 5
27 25 0 4 5 5 5 5 5 5 5
29 25 0 4 5 5 5 5 5 5 5
Control compounds I 25 454555112
Foliage application method in the test examples 3(nonirrigated farmland)
(surface area is 100cm in one jar of earth
2), sow barnyard grass (Ec), lady's-grass grass (Di), arsesmart (Po), the seed of thin amaranth (Am) lamb's-quarters (Ch) and paddy nutgrass flatsedge (Ci) covers with the thick earth of one deck 0.5 to 1cm again.Jar was cultivated for 2 weeks in 20 to 25 ℃ greenhouse, with the wettable powder dilute with water by the preparation of the method in the formulation examples 1 of predetermined amount, put on the blade then with per 10 ares 100 liters ratios.Measure with the 14th day after the herbicide treatment, being defined as standard evaluation gained result in the table 2, and index is listed in table 7 and table 8.
Table 7
Herbicidal effect
Compound number Ec Di Po Am Ch Ci
1 5 5 5 5 5 5
2 5 5 5 5 5 5
Contrast compound 1554555
Contrast compound 2012205
Contrast compound 3112115
Contrast compound 4111111
Table 8
Herbicidal effect
Bonded numbering Ec Di Po Am Ch Ci
3 5 5 5 5 5 5
10 5 5 5 5 5 5
11 5 5 5 5 5 5
12 5 5 5 5 5 5
13 5 5 5 5 5 5
14 5 5 5 5 5 5
16 5 5 5 5 5 5
17 5 5 5 5 5 5
18 5 5 5 5 5 5
21 5 5 5 5 5 5
24 5 5 5 5 5 5
25 5 5 5 5 5 5
26 5 5 5 5 5 5
27 5 5 5 5 5 5
28 5 5 5 5 5 5
29 5 5 5 5 5 5
31 5 5 5 5 5 5
32 5 5 5 5 5 5
Contrast compound 2012115
Contrast compound 3112115
Contrast compound 4101111
Control compounds 2,3 and 4 is as give a definition (being equally applicable in the table)
Control compounds 2: oxo ethyl-3-[(5-Chloropyrimide-2-yl)] benzoic ether (disclosed in the Japanese laid-open publication 55729/1979)
Control compounds 3: oxo ethyl-5[(5-Chloropyrimide-2-yl)]-2-nitrobenzoyl acid esters (disclosed in the Japanese laid-open publication 55729/1979)
Control compounds 4:2-(2-tolyloxy-4,6-dimethyl pyrimidine) agricultural and biological chemistry, 30 volumes, No. 9, disclosed in 896 pages)
Area spray method in the test examples 4(nonirrigated farmland)
(surface area is 100cm in one jar of earth
2), sow barnyard grass (Ec), lady's-grass grass (Di), arsesmart (Po), thin amaranth (Am), the seed of lamb's-quarters (Ch) and paddy nutgrass flatsedge (Ci), and cover the thick earth of one deck 0,5 to 1cm.Sow after one day,, and put on argillous surface (dosage of active constituent is 100g/10a) with per 10 ares 100 liters ratio with the wettable powder dilute with water by the preparation of the method in the formulation examples 1 of predetermined amount.Measured in the 20th day after the dispenser, and being defined as standard evaluation gained result in the table 2, and index was listed in table 9 and table 10.
Table 9
Herbicidal effect
Compound number Ec Di Po Am Ch Ci
1 5 5 5 5 5 5
2 5 5 5 5 5 5
Control compounds 1554555
Control compounds 2000005
Control compounds 3000025
Control compounds 4000000
Table 10
Herbicidal effect
Compound number Ec Di Po Am Ch Ci
3 5 5 5 5 5 5
4 5 5 5 5 5 5
5 5 5 5 5 5 5
6 5 5 5 5 5 5
7 5 5 5 5 5 5
9 5 5 5 5 5 5
10 5 5 5 5 5 5
11 5 5 5 5 5 5
12 5 5 5 5 5 5
13 5 5 5 5 5 5
14 5 5 5 5 5 5
16 5 5 5 5 5 5
17 5 5 5 5 5 5
18 5 5 5 5 5 5
21 5 5 5 5 5 5
22 5 5 5 5 5 5
23 5 5 5 5 5 5
24 5 5 5 5 5 5
25 5 5 5 5 5 5
26 5 5 5 5 5 5
27 5 5 5 5 5 5
28 5 5 5 5 5 5
29 5 5 5 5 5 5
31 5 5 5 5 5 5
Contrast compound 2000005
Contrast compound 3000024
Contrast compound 4000000
The test of control green bristlegrass grass in the test examples 5(rice terrace)
In one jar of rice terrace earth, sow barnyard grass (Ec), nutgrass flatsedge (Cd), Monochoria korsakowii (Mo) and Rush (Sc) seed, it is dark to add water to 3cm.Sow after 2 days,, and drop to water surface with the dosage of per 10 are of 100 gram active constituent with the wettable powder dilute with water by the preparation of the method in the formulation examples 1 of predetermined amount.Measured in the 21st day after the dispenser, and being defined as standard evaluation gained result in the table 2, and index was listed in table 11 and table 12.
Table 11
Herbicidal effect
Compound number Ec Cd Mo Sc
1 5 5 5 5
2 5 5 5 5
Table 12
Herbicidal effect
Compound number Ec Cd Mo Sc
3 5 5 5 5
5 5 5 5 5
6 5 5 5 5
7 5 5 5 5
8 5 5 5 5
9 5 5 5 5
10 5 5 5 5
11 5 5 5 5
12 5 5 5 5
13 5 5 5 5
14 5 5 5 5
15 5 5 5 5
16 5 5 5 5
17 5 5 5 5
18 5 5 5 5
19 5 5 5 5
20 5 5 5 5
21 5 5 5 5
22 5 5 5 5
23 5 5 5 5
24 5 5 5 5
25 5 5 5 5
26 5 5 5 5
27 5 5 5 5
28 5 5 5 5
29 5 5 5 5
30 5 5 5 5
31 5 5 5 5
32 5 5 5 5
33 5 5 5 5
34 5 5 5 5
Claims (8)
1, preparation has the method for pyrimidine derivatives or its salt of molecular formula I,
X is a halogen atom in the I formula, C
1-C
6(wherein said phenoxy group can be by halogen atom, C for alkyl or phenoxy group
1-C
4Alkyl or C
1-C
4Alkoxyl group replaces), R is a hydrogen atom, C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, benzyloxy C
1-C
4Alkyl, C
1-C
6Alkoxy carbonyl C
1-C
4Alkyl, cyano group C
1-C
6Alkyl or
Base (R wherein
1Be hydrogen atom or C
1-C
4Alkyl, R
2Be C
1-C
4Alkyl or the phenyl that can be replaced by nitro), it is characterized in that: this method comprises having the compound of molecular formula II
(X and R such as preceding definition in the II formula) and compound reaction with molecular formula III
(Y in the III formula
1Be halogen atom, C
1-C
4Alkyl sulphonyl, benzyl alkylsulfonyl replacement or unsubstituted) to obtain the having compound of molecular formula I or the compound that will have the molecular formula IV
(X and R such as preceding definition in the IV formula) changes into the diazonium salt with molecular formula V
(X and R such as preceding definition in the V formula) again with diazonium salt and the compound reaction with molecular formula VI, obtains the compound of molecular formula I;
Can also arbitrarily selectively be the formula I compound and the alkali reaction of hydrogen, obtain having the salt of the compound of molecular formula I R.
2, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, it is characterized in that R wherein is hydrogen atom, C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl or benzyloxy C
1-C
4Alkyl.
3, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, and its feature is that also described pyrimidine derivatives has molecular formula I-1:
Wherein the definition of R is described with claim 1, and X is halogen atom or C
1-C
6Alkyl.
4, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, and its feature is that also described salt is an alkali metal salt, alkaline earth salt, transition metal salt or organic ammonium salt.
5, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, and its feature is that also described pyrimidine derivatives has molecular formula I-2:
Wherein the definition of R is described with claim 1, and Y is a hydrogen atom, halogen atom, C
1-C
4Alkyl or C
1-C
4Alkoxyl group.
6, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, it is characterized in that it wherein being that R is a hydrogen atom.
7, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, and its feature is that also described pyrimidine derivatives is 6-chloro-2-((4,6 a ,-dimethoxypyridin-2-yl) sulfo-) phenylformic acid.
8, preparation as claimed in claim 1 has the method for pyrimidine derivatives or its salt of molecular formula I, and its feature is that also X wherein is 6 chlorine atom, methyl or a fluorine atom.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27889487 | 1987-11-04 | ||
| JP278894/87 | 1987-11-04 | ||
| JP278894 | 1987-11-04 | ||
| CN88107663A CN1025981C (en) | 1987-11-04 | 1988-11-04 | Pyrimidine derivatives, processes for their production and herbicidal method and compositions |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88107663A Division CN1025981C (en) | 1987-11-04 | 1988-11-04 | Pyrimidine derivatives, processes for their production and herbicidal method and compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065862A CN1065862A (en) | 1992-11-04 |
| CN1028171C true CN1028171C (en) | 1995-04-12 |
Family
ID=25742504
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92102225 Expired - Lifetime CN1033132C (en) | 1987-11-04 | 1992-03-26 | Method for killing weeds |
| CN 92102226 Expired - Lifetime CN1028171C (en) | 1987-11-04 | 1992-03-26 | Process for producing pyrimidine derivative or salt thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92102225 Expired - Lifetime CN1033132C (en) | 1987-11-04 | 1992-03-26 | Method for killing weeds |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1033132C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279950B (en) * | 2007-04-06 | 2010-08-11 | 中国中化股份有限公司 | 2-pyrimindinyloxy (pyrimindinylthio) benzoxy acetamide compound and application thereof |
| CN103039454B (en) * | 2013-01-22 | 2014-12-03 | 南京高正农用化工有限公司 | Pyrithiobac sodium-paraquat weeding composition and application thereof |
-
1992
- 1992-03-26 CN CN 92102225 patent/CN1033132C/en not_active Expired - Lifetime
- 1992-03-26 CN CN 92102226 patent/CN1028171C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1064586A (en) | 1992-09-23 |
| CN1065862A (en) | 1992-11-04 |
| CN1033132C (en) | 1996-10-30 |
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