GB2025400A - Pyridyloxyphenoxy unsaturated derivatives and herbicidal compositions thereof - Google Patents
Pyridyloxyphenoxy unsaturated derivatives and herbicidal compositions thereof Download PDFInfo
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- 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
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- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
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- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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- 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
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Abstract
Novel pyridyloxyphenoxy unsaturated derivatives having the formula <IMAGE> wherein Z represents -CH2OH, COOR or -COSR', wherein R represents a hydrogen atom, an organic or inorganic salt or an alkyl, haloalkyl, alkenyl, alkynyl, phenyl, halophenyl, alkylphenyl, benzyl, alkoxyalkyleneoxyalkyl, pyridylmethyl or alkoxyalkyl group, and R' represents an alkyl group are disclosed, together with processes for their preparation, herbicidal compositions containing them and processes for treating weeds using such compositions.
Description
SPECIFICATION
Pyridyloxyphenoxy unsaturated derivatives and herbicidal compositions thereof
The present invention relates to pyridyloxyphenoxy unsaturated derivatives having the formula
wherein Z represents -CH2OH, COOR or -COSR', wherein R represents a hydrogen atom, an organic or inorganic salt or an alkyl, haloalkyl, alkenyl, alkynyl, phenyl, halophenyl, alkylphenyl, benzyl, alkoxyalkyleneoxyalkyl, pyridylmethyl or alkoxyalkyl group, and R' represents an alkyl group.
The present invention also relates to herbicidal compositions comprising said compound as an active ingredient in an agriculturally acceptable carrier, and a method of killing weeds which comprises applying a herbicidally effective amount of such a composition in a soil or foliage treatment.
Recently, many herbicides have been proposed and used to contribute to savings in agricultural labour.
Various problems of herbicidal effects and safety of the herbicides have been found in practical applications.
There is therefore a need for improved herbicides which have no adverse effect on crops while being effective against noxious weeds in smafl doses of the active ingredient and being significantly safe without risk of environmental pollution.
The inventors have synthesized various pyridyloxyphenoxy unsaturated derivatives so as to find satisfactory herbicides and have studied herbicidal effects thereof.
The novel compounds of pyridyloxyphenoxy unsaturated derivatives having the formula (I) of the present invention have superior herbicidal activity to gramineous weeds such as barnyard grass, crab grass and Johnson grass in comparison with the compounds described in Japanese Unexamined Patent
Publication No. 131540/1977 suchas -[4-(3,5-dichloropyrid-2-yloxy)phenoxy] valerianic acid derivatives such as methyl and isopropyl esters or sodium salt and in Japanese Unexamined Patent
Publication Nos. 48432/1976 and 87173/1977 such as a-[4-(3,5-dichloropyrid-2-yloxy)phenoxyj propionic acid derivatives such as methyl and ethyl esters or ammonium and sodium salts.
The novel compounds of the present invention have also superior herbicidal activities in comparison with butoxyethyl a-[4-(3 ,5,6-trichloropyrid-2-yloxy)phenoxyj propionate disclosed in Japanese
Unexamined Patent Publication No. 15382/1978.
The novel compounds of the present invention have superior residual activity in soil in a soil treatment and also have excellent effects such as a long suppression of weeds in later emergence; a tong suppression of recovery from an incomplete suppression of weeds in a foliage treatment; growth control of grown weeds and excellent stability to the factors for varying the activity caused by rain-fall, atmospheric pressure and high temperature to impart stable activity.
The novel compounds of the present invention have methyl group at a-position of the pyridyloxyphenoxy isobutenyl compounds, whereby the special herbicidal effect especially, significant herbicidal effect to gramineous weeds such as johnson grass, dent foxtail, barnyard grass and large crab grass can be imparted.
The novel compounds of the present invention have significant selectivity without phytotoxicity to broad leaf crop plants such as radish, soybean, adzuki bean, peanut, cotton, flax, sugar beet, potato, colza, sweet potato, cucumber, olive, Chinese cabbage, lettuce, tomato, eggplant, radish, onion, watermelon, strawberry, pimento, sunflower, tea, coffee, rubber, peppermint, hop and tobacco plants, but completely control gramineous weeds.
The novel compounds of the present invention can be applied as herbicides by desirable methods in every seaons such as the soil treatment and the foliage treatment in post-emergence and preemergence.
Typical gramineous weeds which are effectively controlled by the herbicides of the present
invention are as follows; johnson grass, quack grass, para-grass, southern sandbar, finger grass, bermuda grass, crowfoot grass, large crab grass, crab grass, barnyard grass, jungle rice, cattail grass,
goose grass, cogan grass, wrinkle grass, southern cut gras, bearded splangle top, red splangle top,
mexican splangle top, brown top panicum, sour paspalum, water paspalum, natal grass, raoul grass, green foxtail, bristly foxtail, yellow foxtail.
The novel compounds of the present invention have low vapor pressure and give no phytotoxic
effect to growing gramineous plants such as wheat, barley, oat, rye in the other fields.
The pyridyloxyphenoxy unsaturated derivatives having the formua (I) can be produced by the following processes.
1) The pyridyloxyphenoxy unsaturated derivatives having the formula (I)
(Z is defined above) can be produced by reacting an unsaturated halide having the formula
(Z' is Z defined above or a group convertible to Z and Hal is a halogen atom) with a pyridyloxyphenol having the formula
in the presence of a base at O to 1 500C for 1 to 20 hours and if necessary, converting Z' into Z. In the formula, the groups convertible to Z include cyano, halogen and other functional groups.
Suitable bases include alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate; alcoholates such as sodium ethylate and tertiary amines such as triethyl amine, dimethyl aniline or pyridine, etc.
Suitable reaction media include water, acetone, methylethyl ketone, methanol, isopropanol, butanol, dimethylformamida, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, etc.
The resulting compound can be converted into a desired pyridylphenoxy unsaturated derivative by the following process.
The object compounds of pyridyloxyphenoxy unsaturated derivatives (I) can be produced directly reacting a pyridyloxyphenol having the formula
with a halopentenoic compound of a halopentenol compound having the formula
in the presence of a base in suitable solvent at O to 1 500C for 1 to 20 hours.
The object compounds of pyridyloxyphenoxy unsaturated acid esters having the formula
can be produced by reacting the pyridyloxyphenol having the formula
with a halopentenoic acid to produce a pyridyloxyphenoxy unsaturated acid having the formula
and then, reacting the corresponding compund having the formula ROH with the pyridyloxyphenoxy unsaturated acid (IV) or its acid halide having the formula
in suitable solvent or without a solvent at O to 1 500C for 1 to 20 hours.
The pyridyloxyphenoxy unsaturated acid halide (IV') can be easily obtained by reacting a halogenating agent such as thionyl chloride and phosphorous trihalides with the pyridyloxyphenoxy unsaturated acid (IV).
The object compounds of pyridyloxyphenoxy unsaturated acid thiol esters having the formula
can be also produced by reacting the pyridyloxyphenoxy unsaturated acid (IV) or its acid halide (IV') with the corresponding mercaptane in the presence of a base as a dehydrogen halide agent in suitable inert solvent or without a solvent at -10 to 1 500C for 1 to 20 hours.
The object compounds of pyridyloxyphenoxy pentenols having the formula
can be produced by hydrogenating the pyridyloxyphenoxy unsaturated acid (IV) or its acid halide (IV') or its ester, with a reducing agent such as sodium borohydride and lithium aluminum hydride, in suitable inert solvent at -20 to 1000C for 1 to 20 hours.
These object compounds are produced by the main reaction of the pyridyloxyphenyl (Ill) with the unsaturated halide (II) and if necessary, converting the product into thee object compound.
The following shows certain processes for converting the product obtained by the main reaction.
a) The pyridyloxyphenoxy unsaturated derivatives having the formula (I) can be produced by reacting a pyridyloxyphenoxy unsaturated acid having the formula
with a compund having the formula
ROH (R is defined above) in the presence of a catalyst such as an aromatic sulfonic acid such as benzenesulfonic acid, toluenesulfonic acid or P-naphthalenesulfonic acid; an anhydrous sulfate such as anhydrous copper sulfate or anhydrous iron sulfate; phosphorus oxychloride, phosphoric acid anhydride, boron trifluoride or acidic ion-exchanger at 20 to 1 500C or under refluxing for 1 to 20 hours.
b) The pyridyloxyphenoxy unsaturated derivatives having the formula (I) can be produced by reacting a pyridyloxyphenoxy unsaturated acid having the formula
with a base such as alkali metal hydroxides, alkaline earth metal hydroxides and organic bases e.g.
amines and amino compounds, in a reaction medium at O to 1000C for 0.5 to 10 hours.
c) The pyridyloxyphenoxy unsaturated derivatives having the formula (I) can be produced by reacting pyridylphenoxy pentenoyl halide having the formula
with a compound having the formula
ROH, R'SH (R and R' are defined above) in the absence of dehydrogenhalide agent of a base in a reaction medium or excess of the compound having the formula
ROH or without a reaction medium, at -10 to 1 500C for 1 to 20 hours.
Suitable dehydrogenhalide agents of inorganic or organic bases include alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium bicarbonates; alcoholates such as sodium ethylate; and tertiary amines such as triethyl amine, dimethyl aniline or pyridine.
Suitable reaction media include acetone, methyl ethyl ketone, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride and dichloroethane.
The pyridyloxyphenoxy pentenoic halide (V) can be produced by reacting the pyridyloxyphenoxy unsaturated acid (IV) with thionyl chloride or phosphorus trihalide in a solvent.
d) The pyridyloxyphenoxy pentenoate having the formula
wherein M is an alkali metal, an alkaline earth metal, a heavy metal or an amino group including an alkylamino and an arylamino group, can be easily produced by neutralizing the corresponding acid or acid halide with the corresponding base.
The reaction is preferably carried out in a solvent at higher than room temperature.
e) The pyridyloxyphenoxy pentenol derivatives having the formula
wherein B represents hydrogen atom, an alkyl carbonyl, a haloalkyl carbonyl, an aryl carbonyl, an alkylamino carbonyl or an arylaminocarbonyl group can be easily produced by reacting 4-halogeno-2pentenol or its ester with a pyridyloxyphenol having the formula
The reaction is preferably carried out in a solvent in the presence of a base.
When the pyridyloxyphenoxy pentenol (B=H) is produced, the product can be esterified to obtain the corresponding ester.
f) The pyridyloxyphenoxy pentenols having the formula
can be produced by reducing a pyridyloxyphenoxy unsaturated derivative having the formula
(A' is OR, or a halogen atom) obtained in the proceses of a), b), c), d) or e) in the presence of a Seducing
agent such as lithium aluminium hydride and sodium borohydride in a reaction medium at -20 to 1000C for 1 to 20 hours.
If necessary, the resulting pyridyloxyphenoxy pentenol is esterifying with the corresponding acid to obtain its esters.
Certain examples for producing the compounds by this process will be described.
PREPARATION 1:
Methyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate: In a solution of 12.8 g (0.05 mole) of 4-(3,5-dichloropyrid-2-yloxy)phenol and 11.6 g (0.06 mole) of methyl 4-bromo-(2)-pentenoate in 70 ml of methanol, 7.6 g (0.055 mole) of potassium carbonate was added and the mixture was refluxed for 3 hours to react them. The reaction mixture was extracted with ether and ether phase was washed with water and then, with a dilute hydrochloric acid and then with water and dehydrated over anhydrous sodium sulfate and ether was distilled off and low boiling compounds were distilled off at 1 400C in vacuum under 0.01 mmHg to obtain 16.4 g (yield of 89.2%) of orange viscous liquid having nD 1.5548.
PREPARATION 2: 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2 )-pefltenoic acid:
A solution of sodium ethylate was prepared by adding 0.9 g (0.04 mole) of sodium metal in 70 ml of ethanol and 9.0 g (0.35 mole) of 4-(3,5-dichloropyrid-2-yioxy)phenol was added and then, 9.4 g
(0.045 mole) of ethyl 4-bromo-12)-pentenoate was added. The mixture was refluxed for 3 hours to react them and 24 ml of 10% aqueous solution of sodium hydroxide was added to the mixture and the mixture was further refluxed for 30 minutes. The reaction mixture was poured into 1 50 ml of water to obtain a solution of sodium 4-[4-3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate. A concentrated hydrochloric acid was added to the solution to give acidic condition whereby an oily product was formed and solidified.The solid product was filtered and dried and recrystallized from ethanol to obtain 9.7 g (yield of 78.3%) of white powdery crystals having a melting point of 1 57 to 1 590C.
PREPARATION 3:
Sodium 4-[4-(3,5-dichloropyrid-2-yloxy) phenoxy]-(2)-pentenoate: 1 7.7 Gram (0.05 mole) of 4-[4-3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid was dissolved in 24.1 g (0.05 mole) of 5% aqueous solution of sodium hydroxide to dissolve it and then water was distilled off to obtain 180 g (yield of 95.5%) of white powdery crystals having a melting point of 240 to 2450 C.
In the same method, potassium salt can be obtained by using potassium hydroxide. Calcium, iron, zinc, magnesium, manganese or aluminium salt celi be obtained by reacting the corresponding metal salt with an aqueous solution of the sodium salt or potassium salt.
PREPARATION 4: 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid dimethylamine salt:
In 30 ml of 5% dimethylamine aqueous solution, 14.2 g (0.04 mole) of 4-[4-(3,5-dichloropyrid-2yloxy)phenoxy]-(2)-pentenoic acid was dissolved and then excess of dimethylamine and water were
distilled off by a rotary evaporator to obtain 1 5.6 g (yieid of 97.4%) of orange viscous liquid.
In the same method, ammonium salt, methylamine salt, ethylamine salt, n-propylamine salt, isopropylamine salt, diethylamine salt, di-n-propylamine salt, di-isopropylamine, dibutylamine salt, triethylamine pyridine salts and picoline salt of 4-[4-3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid could be obtained.
PREPARATION 5:
Ethyl 4-[4-(3 ,5-dichloropyrid-2-yl oxy)phenoxy]-(2)-pentenoate: A mixture of 1 7.7 g (0.05 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid,
50 ml of ethanol, 50 ml of benzene and 3 g of concentrated sulfuric acid was refluxed for 4 hours under
removing water by a distillation trap. The reaction mixture was diluted with 100 ml of benzene and washed with water and benzene phase was dehydrated over anhydrous sodium sulfate and benzene was distilled off and low boiling compounds were distilled off a 1400C in vacuum under 0.01 mmHg to obtain 1 5.2 g (yield 82.8%) of orange viscous liquid having nD 1.5697.
PREPARATION 6: sec-Butyl 4-[4-(3,5-dichloropyrid-2-yloxy) phenoxy]-(2)-pentenoate: A mixture of 10.6 g (0.03 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-2-pentenoic acid and 30 ml of thionyl chloride was refluxed for 6 hours to react them. Excess thionyl chloride was distilled off from the reaction mixture and the residue of the acid chloride was admixed with 30 ml of sec-butanol. After the addition, the reaction mixture was gradually heated to react them at 600C for 5 hours. Excess of sec-butanol was distilled off to obtain 10.7 g (yield of 90.3%) of orange viscous liquid having n2Q 1.5565.
PREPARATION 7:
Allyl 4-[4-(3 ,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate: 11.2 Grams (0.03 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoyl chloride obtained by the process of Preparation 6 was added to a mixture of 2.3 g (0.04 mole) of allyl alcohol, 2.6 g (0.033 mol) of pyridine and 100 ml of anhydrous toluene with stirring and cooling and the mixture was stirred at room temperature for 3 hours. The product was washed with water and dehydrated over anhydrous sodium sulfate and toluene was distilled off and low boiling compounds were distilled off at 1 400C in vacuum under 0.01 mmHg to obtain 9.8 g (yield of 86.5%) of orange viscous liquid having n20 1.5706.
In accordance with the same process except using 2-butenyl alcohol or 1-butynyl alcohol instead of allyl alcohol, each esterification was carried out to obtain butenyl 4-[4-(3,5-dichloropyrid-2yloxy) phenoxy]-)2)-pentenoate and butynyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate.
PREPARATION 8:
Methoxyethoxyethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate: A mixture of 35.5 g (0.1 mole) of 4-[4-(3,5-dichiornpydd-2-yloxy)phenoxyj-(2)-pentenoic acid, 24 g (0.2 mole) of 2-(2-methoxyethoxy)ethanol; 100 ml of benzene and 5 g of concentrated sulfuric acid was refluxed for 7.5 hours until finishing distillation of water. After the reaction, benzene phase was sequentially washed with water, with 5% aqueous solution of sodium bicarbonate and with water and dehydrated over anhydrous sodium sulfate and benzene was distilled off and low boiling compounds were distilled off at 1 200C in vacuum under 0.06 mmHg to obtain 38.6 g (yield of 84.5%) of orangish yellow viscous liquid having n2Q 1.5685.
In accordance with the same process except using 2-(2-ethoxyethoxy ethanol or 2-(2-npropoxyethoxy) ethanol instead of 2-(2-methoxyethoxy) ethanol, each esterification was carried out to obtain ethoxyethoxy ethyl 4-[4-(3, 5-dichloropyrid-2 -yloxy)phenoxy]-(2 )-pentenoate or npropoxyethoxyethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate.
PREPARATION 9:
Pyridylmethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxyj-(2)-pentenoate: A mixture of 11.2 g (0.03 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoyl chloride and 7.1 g (0.065 mole) of 3-hydroxymethylpyridine in 50 ml of benzene was heated for 4 hours with stirring. After the reaction, the reaction mixture was cooled and sequentially washed with water,
with 5% aqueous solution of sodium bicarbonate, with water, with 5% hydrochloric acid and with water
and dehydrated over anhydrous magnesium sulfate and benzene was distilled off to obtain 12 g
(yield of 92.3%) of reddish brown viscous liquid having n2Q 1.5670.
In accordance with the same process except using benzyl alcohol instead of 3hydroxymethylpyridine, the esterification was carried out to obtain benzyl 4-[4-(3,5-dichloropyrid-2 yloxyXphenoxy]-(2)-pentenoate.
PREPARATION 10: 3-Methoxy-3 -methylbutyl 4-[4-(3 ,5-dich loropyrid-2-yloxy) phenoxy]-(2)-pentenoate:
In 50 ml of methylethyl ketone, 5.1 g (0.02 mole) of 4-(3,5-dichloropyrid-2-yloxy) phenol and 6.1 g. (0.022 mole) of 3-methoxy-3-methylbutyl 4-bromo-2-pentenoate were dissolved and 3.0 g (0.022 mole) of potassium carbonate was added to the solution at room temperature with stirring. The mixture was refluxed for 5 hours.After cooling it, it was filtered and 200 ml of benzene was added to the filtrate and washed with 50 ml of saturated aqueous solution of sodium bicarbonate for two times and then, with 50 ml of water for 3 times and dehydrated over anhydrous sodium sulfate and benzene was distilled off and low boiling compounds were distilled off at 1Q50C in vacuum under 0.12 mmHg to obtain 8.1 g (yield of 89.1%) of pale brown viscous liquid having n20 1.5547.
In accordance with the same process except using 3-ethoxy-3-methylbutyl-4-bromo-2pentenoate instead of 3-methoxy-3-methyl-butyl-4-bromo-(2)-pentenoate, the synthesis was carried out to obtain 3-ethoxy-3-methylbutyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate.
PREPARATION 11:
S-Methyl 4-[4-(3 ,5-dichlornpyrid-2-yloxy)phenoxyj-(2 )-pentenothiolate: In 100 ml of toluene, 2.9 g (0.06 mole) of methyl mercaptane and 7.6 g (0.055 mole) of
potassium carbonate were dissolved and 20.5 g (0.05 mole) of 4-[4-(3,5-dichloropyrid-2 ylbxy)phenoxyjA2)-pentenoyl bromide was added to the solution at 5 to 1 00C with stirring to react
them at room temperature for 4 hours. Water was added to the reaction mixture and toluene phase was
washed with water and dehydrated over anhydrous sodium sulfate and toluene was distilled off to
obtain 16.7 g (yield of 86.9%) of orange viscous liquid having nD 1.6072.
In accordance with the same process except using ethyl mercaptane, propyl mercaptane or butyl mercaptane instead of methyl mercaptane, each synthesis was carried out to obtain S-ethyl, Propyl or S-butyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenothiolate.
PREPARATION 12: 4-[4-(3 ,5-Dichloropyrid-2-yloxy)phenoxy]-(2)-penten-1 -ol:
In 50 ml of ether, 0.9 g (0.0226 mole) of lithium aluminium hydride was suspended and then, a solution of 8.4 g (0.0226 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoyl chloride in 50 ml of ether was added dropwise to the suspension at 10 to 1 Soc during 30 minutes. After the addition, the mixture was stirred at room temperature for 1 hour to react them and the reaction mixture was poured into 100 ml of ice water and the ether phase was washed with water and dehydrated over anhydrous sodium sulfate and ether was distilled off to obtain 6.0 g (yield of 77;9%) of orangish yellow viscous liguid having nD 1.5784.
PREPARATION 13: 2-Chloroethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxyj-(2)-pentenoate: In 50 ml of benzene, 5.6 (0.015 mole) of 444' (3,5-dichloropyrid-2-yloxy)phenoxy3-(2)-pentenoyl chloride and 1.3 g (0.017 mole) of ethylene chlorohydrin were mixed and the mixture was refluxed for 3 hours until finishing generation of hydrogenchloride. After cooling, the reaction mixture was washed with 5% aqueous solution of sodium hydroxide and then with water. The benzene layer was dehydrated over anhydrous sodium sulfate and benzene was distilled off and low boiling compounds were distilled off in vacuum under 11 00C/0.07 mmHg to obtain 5.2 g (yield of 83.2%) of orange viscous liquid having n2 1.5770.
In accordance with the same process except using ethylenebromohydrin, 2,2,2-trichloroethyl alcohol or 3-chloropropyl alcohol instead of ethylenechlorohydrin, each synthesis was carried out to obtain 2-bromoethyl, 2,2,2-trichloroethyl or 3-chloropropyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy] (2 )-pentenoate.
PREPARATION 14: p-Tolyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate: In 20 ml of acetone, 5.6 g (0.015 mole) of 4-t4-(3,5-dichloropyrid-2-yloxy)phenoxyj-(2)-pentenoyl chloride was dissolved. The solution was added dropwise to a solution of 1.6 g (0.01 5 mole) of 4methylphenol and 1.3 g (0.15 mole) of sodium bicarbonate in 20 ml of acetone at 10 to 15 C with cooling during 10 minutes. After the addition, the reaction was stirred at room temperature for 1 hour, and then, it was poured into water The resulting oily product was extracted with benzene.
The benzene layer was washed with 5% aqueous solution of sodium hydroxide and then, with water and dehydrated over an hydrous sodium sulfate and benzene was distilled off and low boiling compounds were distilled off in vacuum under 1000C/0.08 mmHg to obtain 5.8 g (yield of 86.5%) of brown viscous liquid having nD 1.5699.
In accordance with the same process except using phenol, 3-methylphenol or 4-chlorophenol instead of 4-methylphenol, each synthesis was carried out to obtain phenyl, 3-methylphenyl or 4chlorophenyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate.
The typical compounds obtained by said processes will be exemplified. The compound numerals are
referred in the following description.
COMPOUND NO. 1 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxyj-(2)-pentenoic acid:
white powdery crystal m.p. 157 to 1590C
COMPOUND NO.2
Sodium 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxyj-(2 )-pentenoate: white powdery crystal m.p. 241 to 2450C
COMPOUND NO. 3
4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid diethyl amine salt:
orange viscous liquid
COMPOUND NO.4
Methyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liqud n2 1.5548
b.p. > 130 C/0.01 mmHg
COMPOUND NO. 5
Ethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate::
orange viscous liquid n020 1.5697
b.p. > 1350C/0.07 mmHg
COMPOUND NO. 6
n-Propyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liquid n20 1.5614
b.p. > 1200C/0.1 mmHg
COMPOUND NO.7
iso-Propyl 4-[4-(3,5-dichlorpyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liquid n20 D 1.5593
b.p. > 1300C/0.01 mmHg
COMPOUND NO.8
sec-Butyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liquid n2 1.5565
b.p. > 1200C/0.2 mmHg
COMPOUND NO. 9
2-Chloroethyl 4-[4-3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-entenoate:
orange viscous liquid n20 D 1.5770
b.p. > 110 C/0.07 mmHg
COMPOUND NO. 10
2-Bromoethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate::
orange viscous liquid n020 1.5810
b.p. > 1250C/0.1 mmHg
COMPOUND NO. 11
Allyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liquid ng0 1.5706
b.p. > 1200C/0.1 mmHg
COMPOUND NO. 12
Propargyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
orange viscous liquid nD 1.5905
b.p. > 1300C/0.06 mmHg
COMPOUND NO.13
P henyl 4-[4-(3,5-dichloropyrid-2-yloxy) phenoxy]-(2)-pentenoate:
orange viscous liquid n20 1.5601
b.p. > 11 00C/0.07 mmHg
COMPOUND NO.14
Methoxyethoxyethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate::
brown viscous liquid n,20 1.5685
b.p. > 1250C/0.7 mmHg
COMPOUND NO.15
Pyridylmethyl 4-[4-(3,5-dichlorpyrid-2-yloxy)phenoxy]-(2)pentenoate:
brown viscous liquid n020 1.5670
b.p. > 110 C/0.07 mmHg
COMPOUND NO. 16
p-Tolyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate:
brown viscous liquid n,20 1.5699
b.p. > 100 C/0.08 mmHg
COMPOUND NO.17
3-Methoxy-3-methylbutyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoate
light brown viscous liquid nD 1.5547
b.p. > 110 C/0.1 mmHg COMPOUND NO.18
S-Methyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenothiolate:
brown viscous liquid n20 D 1.6072
COMPOUND NO. 19
S-Ethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenothiolate::
brown viscous liquid n20 1.5973
COMPOUND NO. 20
S-n-Propyl-4-[4-(3,5-dichloropyrid-2-yloxy)phenoxyl-(2)-pentenothiolate:
brown viscous liquid n20 D 1.6002
b.p. > 1250C/0.04 mmHg
COMPOUND NO.21 S-n-Butyl-4-[4-(3,5-dichloropyrid-2-yloxy) phenoxy]-(2)-pentenothiolate:
brown viscous liquid nD 1.6120
b.p. > 1200C/0.03 mmHg
COMPOUND NO.22 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-penten- 1 -ol::
orange yellow viscous liquid n020 1.5784
The novel compounds of the present invention produced by said syntheses have significant
herbicidal effect and non-phytotoxicity to many crop plants and can be applied to up-land, paddy fields, orchards, forests and non-cultured grounds by the soil treatment or the foliage treatment under selecting suitable method of application and suitable dose of the active ingredient.
The dose of the active ingredient of the compound of the present invention is depending upon a
weather condition, a soil condition, a form of the composition, a season of the application and a method
of the application and kinds of crop plants and kinds of weeds and growth stage of weeds and it is
usually in a range of 0.01 to 10 kg preferably 0.1 to 5 kg especially 0.5 to 3 kg per 1 hectare in the soil
treatment or the foliage treatment and it is usually applied in a concentration of 10 to 10,000 ppm
preferable 100 to 5,000 ppm especially 250 to 3,000 ppm of the active ingredient. In the case of
application of the herbicidal composition spraying from an airplane, a concentration of the active
ingredient is usually in a range of 10,000 to 75,000 ppm. For example, 0.5 to 1.5 kg of the active
ingredient is sprayed at a rate of 20 to 50 liter/ha.
When the compound of the present invention is used as the herbicide, the compound can be used
in the original form and also in the form of compositions such as granules, wettable powder, dusts, emulsifiable concentrates, fine powder, floables, suspensions, etc. to impart superior effect.
In the preparation of the herbicidal compositions, the compound of the present invention can be
uniformly mixed with or dissolved in suitable adjuvants such as solid carrier such as talc, bentonite, clay,
kaolin, diatomaceous earth, silica gel, vermiculite, lime, siliceous sand, ammonium sulfate or urea; liquid carriers such as alcohols, dioxane, acetone, cyclohexanone, methyl naphthalene or dimethylformamide; surfactants as emulsifiers dispersing agents or wetting agents such as alkyl sulfate, alkylsulfonate,
polyoxyethyleneglycol ethers, polyoxyethylenealkylaryl ethers such as polyoxyethylenenonylphenol
ether or polyoxyethylenesorbitane monoalkylate; and carboxymethyl cellulose, gum arabic and other
adjuvants.
The amounts of the active ingredients, adjuvants and additives in the herbicidal compositions of the present invention will be further illustrated.
WETTABLE POWDER:
Active ingredient: 5 to 95 wt.% preferably 20 to 50 wt.% Surfactant: 1 to 20 wt.% preferably 5 to 10 wt.% Solid carrier: 5 to 85 wt.% preferably 40 to 70 wt.% The active ingredient is admixed with the solid carrier and the surfactant and the mixture is pulverized.
EMULSIFIABLE CONCENTRATE:
Active ingredient: 5 to 95 wt.% preferably 20 to 70 wt.%
Surfactant: 1 to 40 wt.% preferably 5 to 20 wt.%
Liquid carrier: 5 to 90 wt.% preferably 30 to 60 wt.% The active ingredient is dissolved in the liquid carrier and the surfactant is admixed.
DUST:
Active ingredient: 0.5 to 10 wt.% preferably 1 to 5 wt.%
Solid carrier: 99.5 to 90 wt.% preferably 99 to 95 wt.% The active ingredient is mixed with fine solid carrier and the mixture is pulverized.
GRANULE:
Active ingredient: 0.5 to 40 wt.% preferably 2 to 10 wt.%
Solid carrier: 99.5 to 60 wt.% preferably 98 to 90 wt.%
The active ingredient is sprayed on the solid carrier or further coated with the solid carrier to form the granule.
The other herbicides can be incorporated in the herbicidal composition of the present invention.
Suitable additional herbicides include; carboxylic acid type compounds such as 2,3,6trichlorobenzoic acid and salts thereof, 2,3,5,6-tetrachlorobenzoic acid and salts thereof, 2-methoxy3,5,6-trichlorobenzoic acid and salts thereof, 2-methoxy-3,6-dichlorobenzoic acid and salts thereof, 2methyl-3,6-dichlorobenzoic acid and salts thereof, 2,3-dichloro-6-methy!benzoic acid and salts thereof, 2,4-dichlorophenoxyacetic acid and salts and esters thereof, 2,4,5-trichlorophenoxyacetic acid and salts and esters thereof, 2-methyl-4-chlorophenoxyacetic acid and salts and esters thereof, 2-(2,4,5- trichlorophenoxy) propionic acid and salts and esters thereof, 4-(2,4-dichlorophenoxy) butyric acid and salts and esters thereof, 4-(2-methyl-4-chlorophenoxy)butyric acid and salts and esters thereof. 2.3.6- trichlorophenylacetic acid and salts thereof, 3,6-endoxohexahydrophthalate and salts thereof, dimethyl 2,3,5,6-tetrachloroterephthalate, trichioroacetic acid and salts thereof,2,2-dichloropropionic acid and salts thereof and 2,3-dichloroisobutyric acid and salts thereof; and carbamic acid type compounds such as S-ethyl N,N-di(n-propyl) thiolcarbamate, S-n-propyl N,N-di(n-propyl) th iolcarbamate, S-ethyl N-ethyi
N-(n-butyl) thiolcarbamate, S-n-propyl N-ethyl-N-(n-butyl) thiolcarbamate, S-2-chloroallyl N,N-diethyl dithiocarbamate, N-methyl dithiocarbamate, S-ethyl hexahydro 1 H-azepine-1-carbothioate, S-(4chlorobenzyl) N,N-diethyl thiolcarbamate, S-benzyl N,N-di-sec-butyl thiolcarbamate, isopropyl N-phenyl carbamate, isopropyl N-(3-chlorophenyl) carbamate, 4-chloro-o-butyn-2-yI N-(3-chlorophenyl) carbamate, methyl N-(3,4-dichlorophenyl carbamate and methyl-N-(4-aminobenzene sulfonyl) carbamate: phenol type compounds such as 2-sec-butyl-4,6 dinitro,phenol and salts thereof and pentachlorophenol and salts thereof;
urea type compounds such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-phenyl-1 , 1 dimethyl urea, 3 (3 ,4-dichlorophenyl)-3-methoxy-1 1 dimethylurna, 3-(4-chlorophenyl)-3-methoxy-1 , 1 -dimethyl urea, 3-(3 ,4-dich lorophenyl)- 1 -n-butyl- 1 -methylurea, 3-(3,4-dichlorophenyl)- 1 -methoxy-1 -methylurea, 3-(4- chlorophenyl)-l -methoxy-l -methylurea, 3-(3,4-dichiorophenyI)-1 ,13-trimethylurea, 3-(3,4- dichlorophenyl)- 1 , 1 -diethyl urea, 1 -(2-methylcyclohexyl)-3-phenylu rea, 1 -(5-t-butyl- 1,3 ,4-triadiazol-2- yl)-1 ,3-dimethylurea, 3-(3-chloro-4-methylphenyl)-1 , 1 -dimethylurea, 3-(3-chloro-4-methoxyphenyl)
1,1 -dimethylurea and dichloralurea; triazine type compounds such as 2-chloro-4,6-bis(ethylamino)-s-triazine, 2-chloro-4-ethylamino-6- isopropyl-amino-s-triazine, 2-chloro-4,6-bis(methoxypropylamino)-s-tria bis(lsopropylamlno)-s-trlazine, 2-methylmercapto-4,6-bis(isopropylamino)-s-triazine, 2-methoxy-4,6methylmercapto-4,6-bis(ethylamino)-s-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-striazine, 2-chloro-4,6-bis(isopropylamlno)-s-triazine, 2-methoxy-4,6-bis(ethylamins)s-triazine,2 methoxy-4-ethylami no-6-isopropyla mino-s-triazi ne, 2-methyl mercapto-4-(2-methoxyethylamino)-6isopropylamino-s-triazine, 2-(2-chloro-4-ethylamino-s-triazine-ss-yl) amino-2-methyl propionitrile, 4amino-6-t-butyl-3-methylthio- 1 ,2,4-triazine-5-(4H)-one, and 3-cyclohexyl-6-dimethylamino- 1-methyl- s-triazine-2,4-(1H, 3H) dione; ether type compounds such as 2,4-dichloro-4'-nitrodiphenyl ether, 2,4,6-trichloro-4'-nitrodiphenyl ether, 2,4-dichloro-6-fluoro-4'-nitrodiphenyl ether, 3-methyl-4'-nitrodiphenyl ether, 3,5-dimethyl-4'
nitrodiphenyl ether, 2,4'-dinitro-4-trifluoromethyl diphenyl ether, 2,4-dichloro-3'-methoxy-4'nitrodiphenyl ether, 2-ch loro-4-trifluorom ethyl-4'-nitrodiphenyi ether, 2-chloro-4-trifluoromethyl-3'- ethoxy-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-ethoxy carbonyl-4'-nitrodiphenyl ether and 2-chloro-4-trifluoromethyl-3'-ethoxy carbonyl ethoxy-4'-nitrodiphenyl ether; aniline type compounds such as N-(3,4-dichlorophenyl)propionamide, N-(3,4-dichlorophenyl)-2methylacrylamide, N-(3-chloro-4-methylphenyl)-2-methylpenamide, N-(3,4-dichlorophenyl)-trimethyl acetamide, N-(3,4-dichlorophenyl)-2,2-dimethyl valeramide, N-isopropyl-N-phenylchloroacetamide, Nn-butoxymethyl-N-(2,6-diethylphenyl) chloroacetamide and N-n-methoxym ethyl-N-(2,6-diethylphenyl) chloroacetamide: uracil type compounds such as 5-bromo-3-sec-butyl-6-methyluracil, 5-bromo-3-cyclohexyl-1 ,6- dimethyluracii, 3-cyciohexyl-5,6-trimethyleneu racil, 5-bromo-3-isopropyl-6-methylu racil, and 3-tert.butyl-5-chloro-6-methyl uracil; nitrile type compounds such as 2,6-dichlorobenzonitrile, diphenylacetonitrile, 3,5-dibromo-4hydroxybenzonitrile, and 3,5-diiodo-4-hydroxybenzonitrile; others such as 2-chloro-N,N-diallylacetamide, NO(1 ,1 -dimethylpropynyl)-3,5-dichlorobenzamide, maleic hydrazide, 3-amino-1,2,4-triazole, mono-sodium methane arsonate, di-sodium methane arsonate, N,Ndimethyl-2,2-diphenyl acetamide, N,N-di(n-propyl)-2,6-dinitro-4-trifluoromethyl aniline, N,N-di(npropyl)-2,6-dinitro-4-methyl aniline, N, N-di(n-propyl)-2, 6-dinitro-4-methylsulfonyl aniline, 0-(2,4dichlorophenyl)-O-methyl-N-isopropyl phosphoramide thioate, 4-amino-3,5,6-trichloropicolinic acid, 2,3-dichloro-1 ,4-naphthoquinone, dimethoxythiocarbonyl disulfide, 3-isopropyl-1 H-2,1 3- benzothiadiazine-4(3H)-one-2,2-dioxide, 6,7-dihydrodipyrido[1,2-a:2': :1 '-c]pyrazinium salt, 1,1'- dimethyl-4,4'-bipyridinium salt, 3,4,5,6-tetrahydro-3,5-dimethyl-2H-1 ,3,5-thiadiazine-2-thione, 1,2- dimethyl-3,5-diphenylpyrazol ium methyl sulfate, N-sec-butyl-2,6-dinitro-3,4-xylidine, N-sec.-butyl-4-tbutyl-2,6-dinitroaniline, N ,N -diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine, 1,1,1 trifluoro(4'-,phenylsulfonyl)-methane sulfono-O-toluidine, 2-(1 -naphthoxy)-N,N-diethyl propionamide, 2- t-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazole-2(3H)one, 4-chloro-5-methylamino-2 (a,a,a-trifluorn-rn-tolyl)-3 (2H)-pyridazinone, N-cyclopropyl methyl-a,a,a-trifl uoro-2,6-dinitro-N-propyl
p-toluidine and N-phosphonomethyl glycine, etc.
When the other herbicide described is mixed with the compound of the present invention, the ratio of the compounds and the dose of the compounds are selected depending upon the selectivities and herbicidal effects of the compounds to the crop plants and the control of noxious weeds treated with them.
Certain examples of the preparations of the herbicidal compositions will be illustrated, however, the kinds and the ratio of the adjuvants are not limited and can be varied from the conventional consideration of the herbicidal compositions.
COMPOSITION NO. 1: WETTABLE POWDER:
Active ingredient 30 wt.%
Sodium higher alcohol sulfate 5 wt.%
Clay 65 wt.%
These components were uniformly mixed and pulverized to prepare a wettable powder.
COMPOSITION NO.2: EMULSIFIABLE CONCENTRATE:
Active ingredient 25 wt.%
Polyoxyethylenealkylaryl ether 10 wt.%
Calcium dinaphthylmethanesulfonate 5 wt.%
Xylene 60 wt.% These components were uniformly mixed to prepare an emulsifiable concentrate.
COMPOSITION NO.3: GRANULES:
Active ingredient 3 wt.%
Bentonite 40 wt.% Clay 50 wt.% Sodium lignin sulfonate 7 wt.%
These components were uniformly mixed and pulverized and then, kneaded with water and granulated and dried to prepare granulates.
COMPOSITION No.4: DUST:
Active ingredient 2 wt.%
Clay 98 wt.% The components were mixed and pulverized to prepare a dust.
COMPOSITION NO. 5: WETTABLE P.OWDER: Active ingredient 30 wt.%
Kaolin 43 wt.%
White carbon 20 wt.% Polyvinyl alcohol 5 wt.%
Poiyoxyethylenenonylphenol 2 wt.%
These components were uniformly mixed and pulverized to prepare a wettable powder.
COMPOSITION NO. 6: EMULSIFIABLE CONCENTRATE:
Active ingredient 50 wt.%
Polyoxyethylenenonylphenol 5 wt.%
Alkylarylsulfonate 5 wt.%
Xylene 40 wt.% These components were uniformly mixed to prepare an emulsifiable concentrate.
COMPOSITION NO. 7: GRANULES:
Active ingredient 5 wt.%
Siliceous sand 92 wt.%
White carbon 3 wt.%
These components were uniformly mixed and pulverized and then, kneaded with water and granulated and dried to prepare granulate.
COMPOSITION NO. 8: DUST:
Active ingredient 3 wt.%
White carbon 2 wt.% 'Kaolin 95 wt.% These components were mixed and pulverized to prepare a dust.
The herbicidal activity of the compounds of the present invention will be further illustrated by certain experimental tests.
In the experiments, the following reference compounds were used as comparative tests.
Reference Compound (A)
Reference Compound (B)
Reference Compound (C)
Reference Compound (D)
Reference Compound (E)
Reference Compound (F)
EXPERIMENT 1:
Test for crop plants and up-land weeds in pre-emergence (pre-germination) soil treatment.
Each pot of 600 cm2 was filled with up-land soil and seeds of wheat, barley, soybean, radish, barnyard grass and large crab grass were sown in a depth of 0.5 cm. Each emulsifiable concentrate
prepared in accordance with the method of Composition No.2 was diluted with water to give the
specific concentration of the compound for the application of 1 Klit/ha. and the diluted solution was
uniformly sprayed on the soil surface.
Twenty days after the treatment, the herbicidal effect and the phytotoxicity of the crop plants were observed and rated as follows:
The experiments were separately carried out as stated in Tables.
HERBICIDAL EFFECT OR PHYTOTOXICITY:
10: Complete growth suppression is found;
9: Growth suppression of from 90 to 100to; 8: Growth suppression of from 80 to 90%; 7: Growth suppression of from 70 to 80%;
6: Growth suppression of from 60 to 70%;
5: Growth suppression of from 50 to 60%;
4: Growth suppression of from 40 to 50%; 3: Growth suppression of from 30 to 40 /0; 2: Growth suppression of from 20 to 30%;
1: Growth suppression of from 0 to 20%;
0: No herbicidal effect.
Wh.: Wheat
So.: Soybean
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Ba.: Barley
Ra.: Radish
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
Results of Tests in pre-emergence soil treatments.
TABLE 1 (Test 1-1)
Dose active Compound ingredient No. (kg/ha) Wh, Ba. So. Ra. B.G. Cr. G.
Compound 0.5 5 s 0 '0 0 10 10 No. 1 0.25 1 0 0 0 10 10 Compound 0.5 5 3 0 0 10 10 No. 2 0.25 1 0 0 0 10 ~ 10 Compound 0.5 6 4 0 0 10 10 No. 3 0.25 1 0 0 0 10 10 Compound | 0.5 6 4 0 0 10 10 No. 4 0.25 1 0 0 0 10 10 Compound 0.5 6 4 0 0 10 10 No. 5 0.25 2 0 0 0 10 10 Compound 0.5 5 4 0 0 10 10 No. 6 | 0.25 1 0 0 0 10 10 Compound 0.5 5 3 0 0 10 10 No. 7 0.25 0 0 0 0 10 10 Compound 0.5 5 3 0 0 10 10 No. 8 0.25 0 0 0 0 10 10 Compound 0.5 5 3 0 0 10 10 No. 9 | 0.25 0 0 0 0 10 10 Compound 0.5 5 4 0 0 10 10 No. 10 0.25 0 0 0 0 10 10 Compound 0.5 5 3 0 0 10 10 No. 11 0.25 0 0 0 0 10 10 Compound 0.5 6 4 0 0 10 10 No. 12 0.25 2 1 0 0 8 8 Reference 0.5 3 4 0 0 5 6 Comp. (A) 0.25 1 2 0 0 6 2 Reference 0.5 6 7 0 0 4 5 Comp. (B) 0.25 3 4 0 0 1 3 Reference 0.5 4 3 0 0 4 5 Comp. (C) 0.25 2 1 0 0 2 2 Reference 0.5 5 4 0 0 6 7 Comp. (D) 0.25 3 2 0 0 3 4 Reference 0.5 7 7 0 0 5 6 Comp. (E) 0.25 3 4 0 0 2 3 TABLE 2 Tes 1-?)
Dose active Compound ingredient No. (kg/ha) Wh. Ba. So. Ra. B.G. Cr.G.
Compound 0.5 5 3 0 0 10 10 No. 13 0.25 2 1 0 0 10 10 Compound 0.5 2 2 0 0 10 10 No. 14 0.25 1 1 0 0 10 10 Compound 0.5 2 2 0 0 10 10 No. 15 0.25 1 1 0 0 10 10 Compound 0.5 2 2 0 0 10 10 No. 16 0.25 1 1 0 0 10 10 TABLE a (Test 1-3)
Dose active Compound ingredient No. (kg/ha) Wh. Ba. So; Ra. B.G. Cr.G.
Compound 0.5 0 0 0 0 10 10 No. 17 0.25 0 0 O O 10 10 TABLE 4 (Test 1-4)
Dose active Compound ingredient No (kg/ha) Wh. B@ So. Ra. B.G. Cr. G.
Compound 0.5 0 0 0 0 10 10 No. 18 0.25 0 0 0 0 10 10 Compound 0.5 0 0 0 0 10 10 No. 19 0.25 0 0 0 0 10 10 Reference 0.5 2 3 0 . ( 3 4 Comp. (F) 0.25 1 1 0 0 1 2 TABLE 5 (Test 1-5)
Dose active Compound ingredient No. (kg/ha) Wh. Ba. So. Ra. B.G. Cr.G, Compound 0.5 0 0 0 0 10 10 No. 22 0.25 0 0 0 0 10 10 EXPERIMENT 2:
Test for crop plants and up-land weeds in pre-emergence soil treatment.
Each polyethylene pot of 2,000 cm2 was filled with up-land soil and seeds of rice, maize, wheat, soybean, cotton, radish, barnyard grass, large crab grass, dent foxtail, johnson grass and goose foot (25 seeds for each plant) were sown in a depth of 0.5 cm.
Each emulsifiable concentrate prepared in accordance with the method of Composition No. 2 was diluted with water to give 0.25, 0.125 and 0.0625 KgIha. of the active ingredient, and the diluted solution was uniformly sprayed on the surface of the soil at a rate of 200 ml per one pot.
Twenty days after the treatment, the herbicidal effect and the phytotoxicity of the crop plants were observed and rated as described above.
Ric.: Rice
Mai.: Maize
Wh.: Wheat
So.: Soybean
Cot.: Cotton
Ra.: Radish
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
D.F.: Dent Foxtail (alopecurus aequalis sobolewski var amurensis ohwi)
J.G.: Johnson Grass (sorghum halepense)
G.F.: Goose Foot (chenopodium album linnaeus var centrorubrum makino)
The experiments were separately carried out as stated in Tables.
TABLE 6 (Test 2-1)
Compound active ingredient (kg/ha) Dose Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 0.25 3 2 0 0 0 0 10 10 10 10 0 No. 1 0.125 0 0 0 0 0 0 10 10 10 8 0 Compound 0.25 3 2 0 0 0 0 10 10 10 10 0 No. 2 0.125 0 0 0 0 0 0 10 10 10 8 0 Compound 0.25 3 2 0 0 0 0 10 10 10 10 0 NO. 3 0.125 0 0 0 0 0 0 10 10 10 7 0 Compound 0.25 2 2 0 0 0 0 10 10 10 10 0 No. 4 0.125 0 0 0 0 0 0 10 10 10 10 0 Compound 0.25 2 2 0 0 0 0 10 10 10 10 0 No. 5 0.125 0 0 0 0 0 0 10 10 10 10 0 Compound 0.25 1 2 0 0 0 0 10 10 10 10 0 No. 6 0.125 0 0 0 0 0 0 10 10 10 10 0 Compound 0.25 2 2 0 0 0 0 10 10 10 10 0 No. 7 0.125 0 0 0 0 0 0 10 10 10 9 0 Compound 0.25 1 2 0 0 0 0 10 10 10 10 0 No. 8 0.125 0 0 0 0 0 0 10 10 10 7 0 Compound 0.25 2 2 0 0 0 0 10 10 10 10 0 No. 9 0.125 0 0 0 0 0 0 10 10 10 6 0 TABLE 6 (Test 2-1) (Continued)
Compound active ingredient (kg/ha) Dose Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 0.25 2 2 0 0 0 0 10 10 10 10 0 No. 11 0.125 0 0 0 0 0 0 10 10 10 8 0 Refernece 0.25 2 3 2 0 0 0 4 5 5 2 0 Comp. 1 0.125 1 2 1 0 0 0 2 3 3 1 0 Reference 0.25 4 3 3 0 0 0 5 6 6 3 0 Comp. 2 0.125 2 1 2 0 0 0 3 3 4 0 0 Reference 0.25 3 2 2 0 0 0 5 6 6 3 0 Comp. 3 0.125 1 0 1 0 0 0 2 2 3 1 0 Reference 0.25 4 3 3 0 0 0 5 5 6 4 0 Comp. 4 0.125 1 1 2 0 0 0 3 2 2 2 0 Reference 0.25 6 5 4 0 0 0 7 7 7 6 0 Comp. 5 0.125 2 2 3 0 0 0 2 3 4 4 0 TABLE 7 (Test 2-2)
Dose active Compoundnt ingredient No. (kg/ha) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 0.25 2 1 1 0 0 0 10 10 10 10 0 No. 14 0.125 1 0 0 0 0 0 10 10 10 9 0 0.0625 0 0 0 0 0 0 6 7 7 6 0 Compound 0.25 2 1 1 0 0 0 10 10 10 10 0 No. 15 0.125 0 0 0 0 0 0 9 9 9 8 0 0.625 0 0 0 0 0 0 4 5 6 4 0 Compound 0.25 2 1 1 0 0 0 10 10 10 10 0 No. 16 0.125 1 0 0 0 0 0 9 9 10 8 0 0.0625 0 0 0 0 0 0 6 7 7 6 0 TABLE 8 (Test 2-3)
Dose active Compoundnt ingredient No. (kg/ha) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 0.25 2 1 0 0 0 0 10 10 10 10 0 No. 17 0.125 0 0 0 0 0 0 10 10 10 10 0 0.0625 0 0 0 0 0 0 10 10 10 10 0 TABLE 9 (Test 2-4)
Dose active Compoundnt ingredient No. (kg/ha) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 0.25 4 0 0 0 0 0 10 10 10 10 0 No. 18 0.125 0 0 0 0 0 0 10 10 10 10 0 Compound 0.25 4 0 0 0 0 0 10 10 10 10 0 No. 19 0.125 0 0 0 0 0 0 10 10 10 10 0 Reference 0.25 2 3 1 0 0 0 2 4 3 2 0 Comp. (F) 0.125 0 0 0 0 0 0 0 2 1 1 0 EXPERIMENT 3:
Test for crop plants and up-land weeds in (post-emergence or post germination) foliage treatment.
Each pot of 600 cm2 was filled with up-land soil and seeds of corn, barley, soybean, radish, barnyard grass and large crab grass were sown.
Each emulsifiable concentrate prepared in accordance with the method of Composition No. 2 was diluted with water to give the specific concentration of the compound and the diluted solution was uniformly sprayed at a rate of 1 kl/ha, when the gramineous weeds were grown to 3 leaf stage and the broad-leaf weeds were grown to the first divergence state.
Fifteen days after the treatment, the herbicide effect and the phytotoxicity of the crop plants were observed and rated a described above.
Wh.: Wheat
Ba.: Barley
So.: Soybean
Ra.: Radish
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
The experiments were separately carried out as stated in Tables.
TABLE 10 (Test 3-1)
Concen Compound tration No. (ppm) Wh. Ba. So. Ra. B.G. Cr.G.
Compound 500 0 0 0 0 10 10 No. 1 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 2 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 3 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 4 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 5 250 0 0 0 0 1D 10 Compound 500 0 0 0 0 10 10 No. 6 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 7 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 8 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10 No. 9 250 0 0 0 0 10 10 Compound 500 0 0 0 0 10 10' No. 11 25- 0 0 0 0 10 10 Reference 500 2 3 0 0 6 7 Comp. (A) 250 1 1 0 0 2 4 Reference 500 3 4 0 0 6 6 Comp. (B) 250 2 1 0 0 3 2 Referemce 500 2 3 0 0 4 4 Comp. (C) 250 0 1 0 0 1 2 Reference 500 3 4 0 0 5 6 Comp. (D) 250 2 2 0 0 6 4 Reference 500 4 4 0 0 6 6 Comp. (E) 250 3 3 0 0 3 4 TABLE 11 (Test 3-2)
Concen Compound tration No. (ppm) Wh. Ba. So. Ra. B.G. Cr.G.
Compound 500 10 10 0 . O 10 10 No. 14 250 10 10 0 0 10 10 Compound 600 10 10 0 0 10 10 No. 15 250 10 10 0 0 10 10 Compound 500 10 10 0 0 10 10 No. 16 250 10 10 0 0 10 10 TABLE 12 (Test 3-3)
Concen Compound tration No. (ppm) Wh. Ba. So. Ra. B.G. Cr.G.
Compound 500 3 2 0 0 10 10 No. 17 250 0 0 0 0 10 10 TABLE 13 (Test 3-4)
Concen Compound tration No. - (ppm) Wh. Ba. So. Ra. BG. Cr.G.
Compound 500 2 2 0 0 10 10 No. 18 250 0 1 0 0 10 10 Compound 500 10 9 9 0 0 10 10 No. 19 250 6 8 0 0 10 10 Reference 500 4 4 6 7 10 10 Comp. (F) 250 2 2 3 3 10 10 TABLE 14 (Test 3-5)
Concen Compound tration No. (ppm) Wh. Ba. So. Ra. B.G. Cr.G.
Compound 500 0 0 0 0 10 10 No.22. 250 0 0 0 0 10 10 EXPERIMENT 4:
Test for crop plants and up-land weeds in post-emergence foliage treatment.
Each polyethylene pot of 2,000 cm2 was filled with up-land soil and seeds of rice, maize, wheat, soybean, cotton, radish, barnyard grass, crab grass, dent foxtail, johnson grass and goose foot (25 seeds for each plant) were sown.
Each emulsifiable concentrate prepared in accordance with the method of Composition No. 2 was diluted with water to give the concentration of 125, 62.5 and 31.25 ppm and the diluted solution was uniformly sprayed at a rate of 20.0 ml per pot. when the plants were grown to 2 to 4 leaf stages.
Twenty days from the treatment, the herbicidal effect and the phytotoxicity of the crop plants were observed and rated as described above.
Ric.: Rice
Mai.: Maize
Wh.: Wheat
So.: Soybean
Cot.: Cotton
Ra.: Radish
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
D.F.: Dent Foxtail (alopecurus aequalis sobolewski var amurensis ohwi)
J.G.: Johnson Grass (sorghum halepense)
G.F.: Goose Foot (chenopodium album linnaeus var centrorubrum makino)
The experiments were separately carried out as stated in Tables.
TABLE 15 (Test 4-1)
Dose active Compoundnt ingredient No. (kg/ha) Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 125 0 0 0 0 10 10 10 10 0 No. 1 62.5 0 0 0 0 10 10 10 8 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 2 62.5 0 0 0 0 10 10 10 9 0 Compound 125 0 0 0 0 10 10 10 9 0 No. 3 62.5 0 0 0 0 10 10 10 8 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 4 62.5 0 0 0 0 10 10 10 10 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 5 62.5 0 0 0 0 10 10 10 10 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 6 62.5 0 0 0 0 10 10 10 10 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 7 62.5 0 0 0 0 10 10 10 9 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 8 62.5 0 0 0 0 10 10 10 10 0 Compound 125 0 0 0 0 10 10 10 10 0 No. 9 62.5 0 0 0 0 10 10 10 8 0 TABLE 15 (Test 4-1) (Continued)
Concen
Compoundnt trationent No. (ppm) Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 125 0 0 0 0 10 10 10 10 0 No. 11 62.5 0 0 0 0 10 10 10 7 0 Reference 125 2 0 0 0 3 4 4 4 0 Comp. (A) 62.5 1 0 0 0 1 2 2 1 0 Reference 125 3 0 0 0 5 6 6 5 0 Comp. (B) 62.5 2 0 0 0 3 4 3 2 0 Reference 125 2 0 0 0 4 5 6 4 0 Comp. (C) 62.5 0 0 0 0 2 2 3 2 0 Reference 125 2 0 0 0 5 5 5 4 0 Comp. (D) 62.5 1 0 0 0 3 2 3 1 0 Reference 125 3 0 0 0 6 7 7 6 0 Comp. (E) 62.5 2 0 0 0 4 4 3 4 0 TABLE 16 (Test 4-2)
Concen
Compoundnt tratlon No. (ppm) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 125 10 10 7 0 0 0 10 10 10 10 0 No. 14 62.5 7 6 3 0 0 0 10 10 10 10 0 31.25 4 3 0 0 0 0 10 10 10 10 0 Compound 125 10 10 6 0 0 0 10 10 10 10 0 No. 15 62.5 6 5 3 0 0 0 10 10 10 10 0 31.25 3 2 0 0 0 0 10 10 10 10 0 Compound 125 10 10 6 0 0 0 10 10 10 10 0 No. 16 62.5 6 5 3 0 0 0 10 10 10 10 0 31.25 3 2 0 0 0 0 10 10 10 10 0 TABLE 17 (Test 4-3)
Concen
Compoundnt tratlon No. (ppm) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G.
Compound 125 1 0 0 0 0 0 10 10 10 10 No. 17 62.5 0 0 0 0 0 0 10 10 10 10 31.25 0 0 0 0 0 0 10 10 10 10 TABLE 18 (Test 4-4)
Concen
Compoundnt tratlon No. (ppm) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 125 4 5 0 0 0 0 10 10 10 10 0 No. 18 62.5 0 0 0 0 0 0 10 10 10 10 0 Compound 125 3 5 0 0 0 0 10 10 10 10 0 No. 19 62.5 0 0 0 0 0 0 10 10 10 10 0 Comp. 20 125 3 5 0 0 0 0 10 10 10 10 0 Comp. 21 125 4 6 0 0 0 0 10 10 10 10 0 Reference 125 3 2 4 0 0 0 4 4 5 3 0 Comp. (F) 62.5 1 0 2 0 0 0 2 3 4 1 0 TABLE 19 (Test 4-5)
Concen
Compoundnt tratlon No. (ppm) Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.
Compound 125 1 0 0 0 0 0 10 10 10 10 0 No. 22 62.5 0 0 0 0 0 0 10 10 10 10 0 31.25 0 0 0 0 0 0 10 10 10 10 0
Claims (20)
1. A pyridyloxyphenoxy unsaturated derivative having the formula
wherein Z represents -CH2OH, COQR or -COSR1 wherein R represents a hydrogen atom, an organic or inorganic cation or an alkyl, haloalkyl, alkenyl, alkynyl, phenyl, halophenyl, alkylphenyl, benzyl, alkoxyalkyleneoxyalkyl, pyridylmethyl or alkoxyalkyl group, and R' represents an alkyl group.
2. A pyridyloxyphenoxy unsaturated derivative according to claim 1 having the formula
wherein R is as defined in claim 1.
3. A pyridyloxyphenoxy unsaturated derivative according to claim 1 having the formula
wherein R' is ás defined in claim 1.
4. A pyridyloxyphenoxy unsaturated derivative having the formula
5. A pyridyloxyphenoxy unsaturated derivative according to claim 1 substantially as herein described with reference to preparations 1 to 14.
6. Any one of the compounds numbered 1 to 24 herein.
7. A process for producing a pyridyloxyphenoxy unsaturated derivative according to any preceding claim which comprises reacting an unsaturated halide having the formula
wherein Z' is the group Z defined in claim 1 or a group convertible thereto and Hal is a halogen atom with a pyridyloxy-2-phenol having the formula
in the presence of a base as a dehydrogen halide agent at 0 to 1 50 C and if necessary, converting Z' into Z by an esterification, a hydrogenation, a neutralization or an amidation.
8. A process according to claim 7 wherein a pyridyloxyphenoxy unsaturated acid having the formula
or its acid halide having the formula
is produced by reacting an unsaturated halide having the formula Hal-CHCH=CHCOOH wherein Hal is as defined in claim 7 with the pyridyloxy-2-phenol (III) and if necessary, reacting a halogenating agent with the resulting pyridyloxyphenoxy unsaturated acid (IV), and then, the compound of formula (IV) or (IV') is converted into the desired compound.
9. A process according to claim 2 wherein the compound (IV) or (IV') is reacted with a compound having the formula
ROH or R'SH wherein R and R' are as defined above in claim 1 in the presence or absence of an inert solvent at O to 1500C.
1 O. A process according to claim 8 wherein the compound of formula (lV) or (IV') is hydrogenated to produce a pyridyloxyphenoxy unsaturated alcohol having the formula
and if necessary the unsaturated alcohol (VIII) is reacted with R"'H or R"Hal.
1 A process according to claim 7 substantially as herein described with reference to preparations 1 to 14.
12. A pyridyloxyphenoxy unsaturated derivative made by a process according to any one of claims 7to 11.
13. A herbicidal composition comprising as an active ingredient a pyridyloxyphenoxy unsaturated derivative according to any one of claims 1 to 6 or claim 1 2 in an agriculturally acceptable carrier.
1 4. A composition according to claim' 13 wherein the active ingredient is a compound according to claim 2.
1 5. A herbicidal composition according to claim 13 wherein the active ingredient is a pyridyloxyphenoxy unsaturated derivative having the formula
1 6. A herbicidal composition substantially as herein described with reference to any one of composition Nos. 1 to 8.
1 7. A method of combating weeds which comprises applying a herbicidally effective amount of a composition according to any one of claims 13 to 16 in a soil treatment or a foliage treatment.
1 8. A method according to claim 1 7 wherein the composition is applied in an amount to give an effective application rate of the active ingredient of 0.01 to 10 Kg per 1 ha.
1 9. A method according to claim 1 7 or claim 18 wherein the composition is applied at a diluted concentration of 1 0 to 1 0,000 ppm in the active ingredient in a foliage treatment.
20. A method according to claim 1 7 substantially as herein described with reference to
Experiments 1 to 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8572278A JPS5513220A (en) | 1978-07-14 | 1978-07-14 | Phenoxyphenoxypentenoic acid derivative, its preparation, and its herbicide |
| JP8642478A JPS5513247A (en) | 1978-07-15 | 1978-07-15 | Dichloropyridyloxyphenoxypentenoic acid derivative, its preparation and heribicide comprising it |
| JP12659278A JPS5553230A (en) | 1978-10-14 | 1978-10-14 | Phenoxy petenol derivative and herbicide comprising it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2025400A true GB2025400A (en) | 1980-01-23 |
| GB2025400B GB2025400B (en) | 1982-09-29 |
Family
ID=27304941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7918752A Expired GB2025400B (en) | 1978-07-14 | 1979-05-30 | Pyridyloxyphenoxy unsaturated derivatives and herbicidal compositions thereof |
Country Status (10)
| Country | Link |
|---|---|
| AR (1) | AR228239A1 (en) |
| CA (1) | CA1158244A (en) |
| CH (1) | CH642948A5 (en) |
| DE (1) | DE2921567A1 (en) |
| FR (1) | FR2430941A1 (en) |
| GB (1) | GB2025400B (en) |
| IL (1) | IL57253A (en) |
| IT (1) | IT1162529B (en) |
| NL (1) | NL7904242A (en) |
| OA (1) | OA06395A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4414391A (en) * | 1980-05-15 | 1983-11-08 | Imperial Chemical Industries Plc | A process for preparing 2-pyridinyloxyphenoxy-lower-alkanoates |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8005226A (en) * | 1979-08-23 | 1981-03-04 | Du Pont | HERBICIDE COMPOUND, COMPOSITION AND PROCESS FOR THE CONTROL OF UNDESIRABLE VEGETATION, COMPOSITION AND PROCESS FOR THE CONTROL OF GRASS Weeds IN LARGE LEAF PLANTS AND PROCESS FOR PREPARING A HERBICIDE COMPOUND |
| DE3263881D1 (en) * | 1981-07-08 | 1985-07-04 | Ciba Geigy Ag | Synergistic agent and process for the selective control of weeds, especially in crops |
-
1979
- 1979-05-09 FR FR7911741A patent/FR2430941A1/en active Granted
- 1979-05-11 IL IL57253A patent/IL57253A/en unknown
- 1979-05-16 CA CA000327737A patent/CA1158244A/en not_active Expired
- 1979-05-28 DE DE19792921567 patent/DE2921567A1/en not_active Withdrawn
- 1979-05-28 AR AR276680A patent/AR228239A1/en active
- 1979-05-28 CH CH493779A patent/CH642948A5/en not_active IP Right Cessation
- 1979-05-30 NL NL7904242A patent/NL7904242A/en not_active Application Discontinuation
- 1979-05-30 GB GB7918752A patent/GB2025400B/en not_active Expired
- 1979-05-31 IT IT23162/79A patent/IT1162529B/en active
- 1979-11-29 OA OA56958A patent/OA06395A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4414391A (en) * | 1980-05-15 | 1983-11-08 | Imperial Chemical Industries Plc | A process for preparing 2-pyridinyloxyphenoxy-lower-alkanoates |
Also Published As
| Publication number | Publication date |
|---|---|
| IT7923162A0 (en) | 1979-05-31 |
| FR2430941B1 (en) | 1983-12-30 |
| CH642948A5 (en) | 1984-05-15 |
| FR2430941A1 (en) | 1980-02-08 |
| IL57253A (en) | 1982-09-30 |
| NL7904242A (en) | 1980-01-16 |
| GB2025400B (en) | 1982-09-29 |
| AR228239A1 (en) | 1983-02-15 |
| IT1162529B (en) | 1987-04-01 |
| IL57253A0 (en) | 1979-09-30 |
| DE2921567A1 (en) | 1980-01-24 |
| OA06395A (en) | 1981-08-31 |
| CA1158244A (en) | 1983-12-06 |
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| PCNP | Patent ceased through non-payment of renewal fee |