GB2288394A - Herbicidally active amides of triclopyr and fluroxypyr - Google Patents
Herbicidally active amides of triclopyr and fluroxypyr Download PDFInfo
- Publication number
- GB2288394A GB2288394A GB9407344A GB9407344A GB2288394A GB 2288394 A GB2288394 A GB 2288394A GB 9407344 A GB9407344 A GB 9407344A GB 9407344 A GB9407344 A GB 9407344A GB 2288394 A GB2288394 A GB 2288394A
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- United Kingdom
- Prior art keywords
- compound
- fluroxypyr
- triclopyr
- percent
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Abstract
Compounds of the general formula: R<1>-O-CH2-CO-NH-CR<2> -CO2R3 (I) wherein R<1> is a group of the formula: <IMAGE> R<2> is H, CH3, CH(CH3)2 CH2CH(CH3)2, CH(CH3)CH2CH3, CH2CH2SCH3, CH2C6H5, CHCOR<3>, or CH2CH2COR<3> and each R<3> independently is H, C1-C6 alkyl or NH2, are useful are selective herbicides.
Description
HERBICIDALLY ACTIVE AMIDES OF TRICLOPYR AND FLUROXYPYR
The present invention relates to amino acid derivatives of 3,5,6-trichloro-2-pyridyloxyacetic acid (having the common name triclopyr) and 4-amino-3-,5dichloro-6-fluoro-2-pyridyloxyacetic acid (having the common name fluroxypyr) to processes for their preparation, herbicidal compositions containing them, and to methods for their use.
Triclopyr (3,5,6-trichloro-2-pyridyloxyacetic acid) is a known broad-leaved herbicide having the formula
Fluroxypyr (4-amino-3-,5-dichloro-6-fluoro-2pyridyloxyacetic acid) is also a known broad-leaved herbicide having the formula
Although safe to wheat, fluroxypyr and triclopyr are phytotoxic to various other commercially important crops (e.g., barley, cotton, rape, soya and sugar beet) at doses normally required to control broad-leaved weeds. The free forms of these herbicides are therefore unsuited to use with these crops.
EP-A-0247721 (The Dow Chemical Company) discloses various polyol esters of triclopyr which display reduced phytotoxicity to triclopyr-sensitive crops compared to triclopyr itself.
It has now surprisingly been found that certain amide derivatives of triclopyr and fluroxypyr show substantially reduced phytotoxicity, as compared with triclopyr and fluroxypyr themselves.
Accordingly, the present invention provides a compound of the general formula:
I R1-0-CH2-CO-NH-CR2-C02R3 wherein R1 is a group of the formula:
R2 is H, CH3 CH(CH3)2 CH2CH(CH3)2, CH(CH3)CH2CH31 CH2CH2SCH3, CH2C6H5, CHCOR3, or CH2CH2CoR3 and each R3 independently is H, C1-C6 alkyl or NH2.
The present invention also provides a process for the preparation of the foregoing compounds which process comprises reacting triclopyr or fluroxypyr, or a derivative thereof with an amino acid of the formula
NH2-CR2-02R3 or a derivative thereof wherein R2 and R3 are as defined above.
Also provided is a herbicidal composition comprising a compound of the present invention with an agricultural adjuvant or carrier or an additional active ingredient.
Advantageously, the active substances according to the invention or mixtures thereof are used in the form of preparations, for example, powders, sprayable agents, granulates, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers or diluents and, if desired, wetting agents, adhesion-promoting agents, emulsifiers and/or dispersing agents, but preferably in the form of emulsions and emulsifiable concentrates.
Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as, for example, benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide, and also mineral oil fractions.
Suitable solid carriers are, for example, mineral earths, for example, tonsil, silica gel, talcum, kaolin, attaclay, limestone, silica acid and vegetable products, for example, meals.
The preparation advantageously includes a surfaceactive substance(s). Suitable surface-active substances are, for example, calcium ligninsulphonate, polyoxyethylene alkylphenol ethers, naphthalenesulphonic acids and salts thereof, phenolsulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and substituted benzenesulphonic acids and salts thereof.
The proportion of the active substance(s) in the various preparations may vary within wide limits. For example, the preparations may contain from 5 to 95 percent by weight of active substances, from 95 to 5 percent by weight of liquid or solid carriers and, if desired, up to 20 percent by weight of surface-active substances.
The present invention further provides a method for controlling or preventing growth of weeds, which method comprises applying to the weeds or to a locus in which it is desired to prevent weed growth a compound or composition of the present invention.
Preferably in the latter method the weeds are broadleaved weeds such as Coffee weed, Cocklebur, Jimson weed,
Lambsquarters, Morning Glory, Pigweed, Velvet-leaf,
Cleavers, Chickweed, or Wild Buckwheat.
Suitably in said method the compound is applied in a total amount of from 0.2 to 2 kg/ha, preferably from 0.5 to 1.2 kg/ha.
In the method of the present invention the said compound may be applied to a crop area or an area adjacent to a crop area. The crop area may for example be a cotton, oilseed rape, sugar beet or soya bean area.
The compounds or preparations may be applied in customary manner, for example, using water as carrier in quantities of spraying liquor of from 100 to 1000 litres/ha. It is possible to use the agents in the socalled low volume and ultra low volume processes, and also to apply them in the form of so-called micro-granules.
The particular nature of the present invention will readily be understood from the following non-limiting
Examples, in which "m.p." denotes "melting point".
General method of Dreparation of amides of Triclopvr and Fluroxvpvr in accordance with the invention
A solution of 1,1-carbonyldiimidazole (3.24 g, 0.02 mol) in dry tetrahydrofuran (40 ml) was added dropwise to a stirred solution of triclopyr or fluroxypyr as appropriate (0.02 mol) in dry tetrahydrofuran (30 ml) under nitrogen.
The resulting mixture was stirred for a further 60 minutes.
An amino acid or amino acid ester (0.02 mol) in dry tetrahydrofuran (40 ml) was then added, and the mixture stirred for a further 45 minutes, and allowed to stand overnight.
The solvent was removed under reduced pressure, and the residue partitioned between methylene chloride (50 ml) and water (20 ml).
The organic layer was washed with water (2 x 50 ml) and dried over anhydrous magnesium sulphate. Removal of the solvent and crystallisation from a suitable medium furnished pure amides in good yields.
Example 1
In accordance with the above general method, an amide was prepared of fluroxypyr and glycine methyl ester.
Examples 3 to 10 and 16 to 21
By a generally analogous method, further amides of triclopyr and fluroxypyr were prepared, utilising the starting materials and purification conditions noted in
Table 1. The physical properties of the resulting compound are also given in Table 1.
Examples 11 to 15
The ester obtained in Example 1 (1.5g) was stirred with aqueous sodium hydroxide (25 ml, 1M) and then heated on a steam bath for two minutes, in order to hydrolyse the methyl ester. The resulting solution was cooled immediately in an ice bath, neutralised with dilute HCl, and extracted with diethyl ether. The solvent was removed, followed by recrystallisation from an appropriate solvent to give N-(((4-amino-3,5-dichloro-6-fluoro-2pyridinyl)oxy)acetyl)-glycine in good yield and purity.
The resulting compound was analysed by proton NMR spectroscopy in CDCl3 to verify its structure, and elemental analysis and melting point determinations were made. The results are shown in Table 1. The compounds of
Examples 12 to 15 were prepared by an analogous method form the compounds of Examples 2, 4, 8, and 10.
Ex. No. Acid Amino acid Purification Appearance M.Pt. Elemental Analysis %C %H %N 1 fluroxypyr glycine methyl ester recrystallisation Colourless solid 169 37.1 3.0 13.0 2 fluroxypyr 1-alanine methyl ester recrystallisation Colourless solid 162 38.7 3.5 12.7 3 fluroxypyr 1-valine methyl ester recrystallisation Colourless solid 156 42.6 4.4 11.5 4 fluroxypyr 1-leucine methyl ester recrystallisation Colourless solid 134 44.0 4.7 11.4 5 fluroxypyr 1-proline methyl ester recrystallisation Colourless solid 146 42.6 3.5 11.3 6 fluroxypyr 1-phenylalanine methyl recrystallisation Colourless solid 156 49.3 3.9 10.2 ester 7 fluroxypyr 1-methionine methyl recrystallisation Colourless solid 134 39.1 3.9 11.0 ester 8 fluroxypyr 1-aspartate dimethyl ester recrystallisation Colourless needles 137 39.1 3.5 10.6 9 fluroxypyr 1-glutamate dimethyl recrystallisation Colourless solid 126 41.1 4.0 10.2 ester 10 fluroxypyr 1-glutamate diethyl ester recrystallisation Colourless solid 109 43.4 4.4 9.7 11 fluroxypyr glycine recrystallisation Colourless solid 214-8 33.5 2.4 13.0 12 fluroxypyr 1-alanine recrystallisation Colourless solid 188-92 36.8 3.0 13.2 13 fluroxypyr 1-leucine recrystallisation Colourless solid 84 42.2 4.5 11.2 14 fluroxypyr 1-aspartate recrystallisation Colourless needles 174-8 34.9 2.8 11.2 15 fluroxypyr 1-glutamate recrystallisation Colourless solid 177-80 37.8 3.2 10.6 16 triclopyr glycine methyl ester recrystallisation Colourless needles 118 36.9 3.5 9.1 17 triclopyr 1-leucine methyl ester recrystallisation Colourless needles 100 43.7 4.4 7.0 18 triclopyr 1-aspartate dimethyl ester recrystallisation Colourless prisms 116-8 39.2 3.3 7.1 19 triclopyr 1-glutamate dimethyl recrystallisation Colourless needles 127 40.8 3.6 6.8 ester 20 triclopyr 1-glutamate diethyl ester recrystallisation Colourless needles 100 43.8 4.2 6.5 21 triclopyr 1-aspartate recrystallisation Colourless solid 150 35.7 2.5 7.5 Tests were carried out to compare the herbicidal efficiency of compounds of the invention against the herbicidal efficiency of triclopyr and fluroxypyr. Post emergent herbicide activity was assessed against a key weed species (Cleavers, Gallium aparine) and against an indicator broad leaf crop (field bean, Vicia faba).
Method
Bean and Cleaver seeds were sown in rows in trays and allowed to germinate and grow untreated to a height of about 10 cm. Plants were then sprayed with an aqueous solution or suspension of the respective amides or base compound at an initial concentration of 4000 mg litre~ followed by a sequence of 2-fold serial dilutions as necessary.- Phytotoxicity was evaluated at 14 days after treatment by visual assessment of treated plants compared to untreated plants grown under identical conditions. A scale of 0-100 was used with 0 representing no visible difference from the untreated plants and 100 indicating death of all plants. By using a series of concentrations a growth reduction factor GR50 was calculated for Cleavers, indicative of the concentration of chemical achieving 50% of growth regulation, and GR10 for beans. The results are shown in Table 2.
TABLE 1
Compound GR10 GR50 Ratio B/C Beans (B) Cleavers (C) 1 120 70 1.7 2 530 155 3.4 4 1220 400 3.1 8 1190 410 2.9 F-MHE 40 90 0.4 Improved selectivity of the compounds of this invention relative to the standard fluroxypyr 1methylheptyl ester (F-MHE) was demonstrated. The improved ratio of B/C in Table 2 indicates an improved selectivity to compounds of this invention, as compared with fluroxypyr.
Formulation Examples
The following Examples A to C are illustrations of typical formulations in which the compounds of the invention may be utilised.
A. Wettable Powder
a) 40 percent by weight of active substance
25 percent by weight of clay minerals
20 percent by weight of colloidal silica
10 percent by weight of cellulose pitch
5 percent by weight of surfactant based on a mixture of the calcium salt of lignin-sulphonic acid and alkylphenol polyglycol ethers.
b) 25 percent by weight of active substance
60 percent by weight of kaolin
10 percent by weight of colloidal silica
5 percent by weight of surfactant based on the sodium salt of N-methyl-N-oleyltaurine and the calcium salt of lignin-sulphonic acid.
c) 10 percent by weight of active substance
60 percent by weight of clay minerals
15 percent by weight of cellulose pitch
10 percent by weight of surfactants based on the sodium salt of N-methyl-N-oleyltaurine and the calcium salt of lignin-sulphonic acid.
B. Paste
45 percent by weight of active substance
5 percent by weight of sodium aluminium silicate
15 percent by weight of cetyl polyglycol ether with 8 moles of ethylene oxide
2 percent by weight of spindle oil
10 percent by weight of polyethylene glycol
23 percent by weight of water.
C. Emulsion Concentrate
a) 20 percent by weight of active substance
15 percent by weight of cyclohexanone
55 percent by weight of xylene
5 percent by weight of a mixture of nonylphenyl polyoxyethylenes and calcium dodecylbenzenesulphonate.
b) 10 percent by weight of active substance
6 percent by weight of cyclohexanone
36 percent by weight of xylene
12 percent by weight of a mixture of nonylphenyl polyoxyethylenes and calcium dodecylbenzenesulphonate
36 percent by weight of mineral oil having a high paraffin content.
Claims (8)
- CLAIMS 1. a compound of the general formula: R-O-CH2-CO-NH-CR-CO2R I wherein R1 is a group of the formula:R2 is H, CH31 CH(CH3)2, CHZCH(CH3)2, CH(CH)CH2CH31 CH2CH2SCH3, CH2C6H5, CHCOOR , or CH2CH2COOR and each R3 independently is H, C1-C6 alkyl or NH2.
- 2. A compound as claimed in Claim 1, substantially as hereinbefore described in any one of the foregoing specific Examples.
- 3. A compound as claimed in Claim 2, substantially as hereinbefore described in any one of Examples 1, 2, 4, or 8.
- 4. A process for the preparation of a compound as claimed in any one of the preceding Claims which process comprises reacting fluroxypyr, triclopyr, or a derivative thereof with an amino acid of the formula NH2-CR-CO2R or a derivative thereof, wherein R2 and R3 are as defined in Claim 1.
- 5. A herbicidal composition which comprises a compound as claimed in any one of Claims 1 to 3 or a compound prepared by a process as claimed in Claim 4, with an agricultural adjuvant or carrier or an additional active ingredient.
- 6. A method for controlling or preventing growth of weeds which method comprises applying to the weeds or to a locus in which it is desired to prevent weed growth a compound as claimed in any one of Claims 1 to 3 or a compound prepared by a process as claimed in Claim 4 or a composition as claimed in Claim 5.
- 7. A method as claimed in Claim 6, wherein the said compound is applied in a total amount of from 0.2 to 2 kg/ha.
- 8. A method as claimed in Claim 6 or Claim 7, wherein the said compound is applied to a crop area or an area adjacent to a crop area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9407344A GB2288394A (en) | 1994-04-14 | 1994-04-14 | Herbicidally active amides of triclopyr and fluroxypyr |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9407344A GB2288394A (en) | 1994-04-14 | 1994-04-14 | Herbicidally active amides of triclopyr and fluroxypyr |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9407344D0 GB9407344D0 (en) | 1994-06-08 |
| GB2288394A true GB2288394A (en) | 1995-10-18 |
Family
ID=10753487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9407344A Withdrawn GB2288394A (en) | 1994-04-14 | 1994-04-14 | Herbicidally active amides of triclopyr and fluroxypyr |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2288394A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1472485A (en) * | 1974-04-11 | 1977-05-04 | Dow Chemical Co | 3,5-dihalo-6-fluoro-2-pyridyloxy compounds and their use as herbicides |
-
1994
- 1994-04-14 GB GB9407344A patent/GB2288394A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1472485A (en) * | 1974-04-11 | 1977-05-04 | Dow Chemical Co | 3,5-dihalo-6-fluoro-2-pyridyloxy compounds and their use as herbicides |
Non-Patent Citations (3)
| Title |
|---|
| Pestic. Biochem. Physiol., 33(3), 249-56 * |
| Pestic. Biochem. Physiol., 36(2), 187-200 * |
| Pro. Br.Crop Prot. Conf.-Weeds,(1), 353-60 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9407344D0 (en) | 1994-06-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |