CA1257608A - Certain n-phenyl amines and their use as herbicides - Google Patents
Certain n-phenyl amines and their use as herbicidesInfo
- Publication number
- CA1257608A CA1257608A CA000160332A CA160332A CA1257608A CA 1257608 A CA1257608 A CA 1257608A CA 000160332 A CA000160332 A CA 000160332A CA 160332 A CA160332 A CA 160332A CA 1257608 A CA1257608 A CA 1257608A
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- CA
- Canada
- Prior art keywords
- lower alkyl
- formula
- compound
- halogen
- composition
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF DISCLOSURES
Disclosed are compounds of the formula:
Disclosed are compounds of the formula:
Description
6~
This invention is in the chemical arts. More particularly, it relates to those arts pertainln~ to aromatic amines and herbicides.
In summary, this invention comprises a group of N-phenyl amines represented by the formula:
~c~ N--~4~
in which Rl and R2 are independently lower alkyl, R' is selected from the group consisting of mono-, di- and trihaloacetyls, R~ is lower alkylene and R5 is hydrogen lower alkyl or a salt-forming cation. Compounds of the ~eneral formula in ~ ich R' represents hydrogen are intermediates for the production of the novel compounds of the invention.
In the definitions, lower alkyl encompasses C1-C7 alkyl and includ0s both straight and branched chain alkyls, examples of which include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and the like. Halo comprises fluoro, chloro, bromo and iodo. Lower alkylene encompasses Cl-C7 alkylene and includes both straight and branched chain alkylenes having 1-7 carbon atoms, examples o~ which include ethylene, propylene, 1-methylethylene, 2-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 3-methylpropylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene and the like. Examples of salts include ammonium salt, alkali metal salts (sodium, potassium and the like, alkali sarth metal salts (calcium, magnesium and the like) and amine salts (methylamine, diethylamine, tripropylamine, diphen~lamine and -the like).
Examples of Cl-C7 alkanol esters include the methyl ester, ethyl ester, the propyl ester, the isopropyl ester and the like. Aryl includes phenyl, tolyl, naphthyl and the like.
fi~
Examples of compounds covered by the generic formula, including some intermediates in which R' = H, are:
1. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
This invention is in the chemical arts. More particularly, it relates to those arts pertainln~ to aromatic amines and herbicides.
In summary, this invention comprises a group of N-phenyl amines represented by the formula:
~c~ N--~4~
in which Rl and R2 are independently lower alkyl, R' is selected from the group consisting of mono-, di- and trihaloacetyls, R~ is lower alkylene and R5 is hydrogen lower alkyl or a salt-forming cation. Compounds of the ~eneral formula in ~ ich R' represents hydrogen are intermediates for the production of the novel compounds of the invention.
In the definitions, lower alkyl encompasses C1-C7 alkyl and includ0s both straight and branched chain alkyls, examples of which include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and the like. Halo comprises fluoro, chloro, bromo and iodo. Lower alkylene encompasses Cl-C7 alkylene and includes both straight and branched chain alkylenes having 1-7 carbon atoms, examples o~ which include ethylene, propylene, 1-methylethylene, 2-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 3-methylpropylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene and the like. Examples of salts include ammonium salt, alkali metal salts (sodium, potassium and the like, alkali sarth metal salts (calcium, magnesium and the like) and amine salts (methylamine, diethylamine, tripropylamine, diphen~lamine and -the like).
Examples of Cl-C7 alkanol esters include the methyl ester, ethyl ester, the propyl ester, the isopropyl ester and the like. Aryl includes phenyl, tolyl, naphthyl and the like.
fi~
Examples of compounds covered by the generic formula, including some intermediates in which R' = H, are:
1. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
2. N-dichloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
3. N-trichloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester
4. N-(2,6-dichlorophenyl)-glycine ethyl es-ter
5. N-chloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl es-ter
6. N-dichloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl ester
7. N-trichloroacetyl-N-(2,6-dichlorophenyl)-glycine ethyl ester
8. 4-(N-trichloroacetyl-2',6'-dichloroanilino)-butyric acid sodium salt
9. N-chloroacetyl-N-(2,6-diethylphenyl)-alanine ethyl ester
10. N-carbethoxyethyl-N-chloroacetyl-2,6-diethylaniline
11. N-chloroacetyl-N-(2-methyl-6-e-thylphenyl)-alanine ethyl ester
12. N-carbethoxyethyl-N-chloroacetyl-2-me-thyl-6-ethylaniline
13. N-chloroace-tyl-N-(2,6-dimethylphenyl)-glycine
14. N-chloroacetyl-N-(2,6-dimethylphenyl)-glycine sodium salt
15. N-chloroacetyl-N-(2,6-dimethylphenyl)-glycine ammonium salt
16. N-chloroace-tyl-N-(2,6-dimethylphenyl)-glycine ethyl es-ter
17. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ~8. N-chloroacetyl-N-(2,6-diethylphenyl)-glycine sodium salt 19. N-chloroacetyl-N-(2,6-die-thylphenyl)-ylycine ammonium salt 20. N-chloroacetyl-N-(2-methyl-6-ethylphenyl)-glycine 21. N-chloroacetyl-N-(2-methyl-6-ethylphenyl)-ylycine sodium salt 22. N-chloroace-tyl-N-(2-methyl-6-ethylphenyl)-glycine ammonium salt 23. N-chloroasetyl-N-(2-methyl-6-ethylphenyl)-glycine ethyl ester 24. N-bromoacetyl-N-(2,6-die-thylphenyl)-glyCine 25. N-bromoacetyl-N-(2,6-diethylphenyl)-glycine sodium salt 26. N-bromoacetyl-N-(2,6-diethylphenyl)-glycine ammonium sal-t 27. N-bromoace-tyl-N-(2,6-diethylphenyl)-glycine ethyl aster The compounds representad by the formula range in color from brown to yellow and in state at 20-25~C. from liquid to solid. In general, the esters of this invention are insoluble in water, but in solvents such as acetone and the like, and such as benzene and the like, they are soluble to the extent suitable for herbicidal uses. On the other hand, in general, the inventive acids, salts, amides and hydrazides are soluble in water at least to the extent suitable for herbicidal uses. The compounds of this invention are characterized by both pre- and post-emergence toxicity -to a number of weeds. On the other hand, at concentrations at which the toxiaities o~ the compounds of this invention are not tolerated by such weeds, a number of desirable plants are relatively unaffected by these compounds. Hence, the compounds of this invention are useful as selective herbicides.
The compounds of this invention are made by reacting in a liquid reactlon medium containing a base such as potassium hydroxide or the liko corresponding phenyl amine:
R~
R
with a haloalkanola acid or ester of the formula:
X - R4- C~
in which X is halo, to form the compounds of the class in whîch R' is hydrogen. The compounds are reacted with mono-, di- and tri-haloacetylhalide~ of the formula:
o X ~ C~ i n )~
~.
in which n is 0-~, to form the compounds of this invention, however, is not limitad to these ways of making the compounds of this invention.
For herbicidal uses the compounds o this invention preferably are incorporated into a dispersible composition. This composition comprises an effective ~uantity of phytotoxic material, and application aid material.
The phytotoxic material consists essentially of at least one compound of this invention. In some embodiments of this composition the phytotoxic material comprises only one compound of this invention. In other embodiments the phytotoxic material comprises -two or more compounds of this invention. In still other embodiments, it comprises other substances having phytotoxic activity.
Specific embodiments of the composition of this invention range from concentra-tes of the phytotoxic ~aterial to the ultimate use composition that is applied in the field.
Accordingly, an effective concentration of the phytotoxic material in the composition of this invention is in a broad range, generally being from about 0.1 to about 90~ by weight of the composition. Higher and lower concentrations, however, are within the broader concspts of this invention. In concentrate embodiments, the concentration of the phytotoxic material generally is in a range from about 10 to about 90~ by weight of the composition and preferably in a range from about 10 to about 50~ by weight of the composition. In -the ultimate use embodiments, the concentra-tion generally is in a range from about 0.1 to about 20-~ by weight of the composition and preferably in a range from about 0.5 to about 10-~ by weight of the composition.
Ap~ 2t.0r aid mat~r-~?l. .iS generalLv inert material that facilita-tes ~istribution or dispersion of the phytotoxic N
~5~3~3 material when it is applied to soil or to foliage of undesirable plants. It encompasses diluents, carriers, extenders, surfactan-ts, spreading agents, sticking agents, wind drift control agents, and -the like.
In those embodiments of the composition of this invention, which are normally solid, the application aid material generally comprises an inert solid in a divided condition.
Some embodiments of the solid composition are granular, while others are dispersible powders or dusts.
The granular compositions are of the coa-ted type, the impregnated type or the incorporated type.
The coated type of granular composition is made by dusting a wettable powder or ground powder comprising the phytotoxic material onto inert granular carrier material which either before or after the dusting has been admixed with an inert adhesive or a sticker. Water, oils, alcohols, glycols, aqueous gums, waxes and the like including mixtures thereof, are used as stickers. Examples of inert granular carrier ma-terial include attaclay, corn cobs, vermiculite, walnut hulls and almost any granular mineral or organic material screened to the desired particle size (generally 15-60 mesh, preferably about 30 mesh, U.S. screen size). Generally the phytotoxic material is abou-t 2-20% by weight of -the composition, and the granular carrier material is generally about 60-93~ by weight of -the composi-tion.
In the case of the impregnated type of granular composition, the phytotoxic ma-terial as such when liquid or after melting, or dissolved in a solvent, is sprayed on or poured into the inert granular carrier material. The solvent can be removed by evaporation, or permitted to remain. In either case, -the phytotoxic material impregnates the particles of -the granular carrier material. Examples of the iner-t granular carrier . ~
6- ~576~
material include those just mentioned wi-th respect to the coated type of granular composition. The phytotoxic material is generally about 2-20~ by weight of the composition, while the granular carrier material is generally about 80~98~ by weight of the composition.
The incorporated type of granular composition is made by admixing the phytotoxic material with an inert finely divided solid such as, ~or example, clay, carbon, plaster of paris and the like, and made into a mud with water or other inert evaporable liquid. The mud is then dried to a solid sheet or cake, broken up or comminuted, and screened to the desired particle size (generally 15-60 mesh, preferably 30 mesh, U.S.
screen size). In other embodiments, the mud is put into a granulating pan and granules are formed therein with subsequent removal of the water or solvent. In still another procedure, -the mud is extruded through a die into rods which are cut into small pieces. In the incorporated type of granular composition, the phytotoxic material generally is about 2-50~ by weight of the composition, and the solid carrier material is about 50-98% by weight of the composition.
In all granular embodiments of the composition of this invention, various additives in minor concentrations relative to the carrier material also can be present.
In other embodiments of -the solid composition of this invention, the carrier is usually a dispersible inert solid. A
typical dispersible solid of this type is clay. Other suitable solids ldispersible solid) include talc, attapulgite, pyropylite, diatomaceous earth, kaolin, aluminum magnesium silicate, montmorillonite, fullers earth, sawdust and -the lika. The solid dispersible composition can be air dispersible, in which case it is usually referred to as a dust. Generally, when it is in-tended '-~nat- the compc3ltion be wa'er d:~spersible, the compos1tion preferably contains emulsifying material ~one or more ~j 7~0~3 surfactants) at a concentration sufficient to enable a suspension of the desired degree of stability to be formed when the composition is admixed with a suitable quantity of water. The composition in such case is usually referred to as a wettable powder. A typical dispersible solid composition of this invention generally comprises about 10-80~ by weight of the phytotoxic material, about 20-90~ by weight of solid carrier material and, when emulsifying material is present, about 1-10%
by weight of emulsifying material.
Other specific embodiments of the herbicidal composition of this inven-tion comprise homogeneous liquid solutions of phytotoxic material in inert, preferably volatile solvents for the phytotoxic material. Examples of suitable solvents when the phytotoxic material is wa-ter-insoluble include isophorone, cyclohexanone, methyl isobutyl ketone, xylene and the like. When the phytotoxic ma-terial is water-soluble, water is a suitable solvent. Such a solution, which can be regarded as a concentrate, typically comprises about 10-50% by weight of phyto-toxic material and about 50-90% by weight of solvent. The solution can be applied as is, or diluted with more solvent and applied or, when water immiscible, dispersed in water, or water dispersed in it, and applied. Preferably, when i-t is intended that the solution be dispersed in water or wa-ter dispersed in it, the mixture of solution and water also comprises emulsifying material at a concentration sufficient to enable a dispersion of the desired degree of s-tability to be formed when the solution or concentrate is mixed with water. A typical emulsifying material concentration is about 1-10% by weight of the concentrate. The water concentration generally is such that -the phytotoxic material concentra-tion preferably is about 0.5-10% by weight of the total composi-tion.
Examples of the surfactants employed in bo-th the liquid and solid compositions of this inven-tion comprise the well known surface active agents of the anionic, cationic and non-ionic ~.f`~-~576~)~
types and include alkali mstal (sodium or potassium) oleates and similar soaps, amine salts of long chain fa-tty acids (oleates), sulfonates, animal and vegetable oils (fish oils and castor oil), sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glyceryl monosterate, poly(oxyethylene), ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amina and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridinium bromide, stearyl trime-thylammonium bromide, and cetyl dimethylbenzylammonium chloride. Still other examples are listed in "Detergents and Emulsifiers - 1968 Annual"
by John W. McCutcheon.
In addition to the phyto-toxic material and application aid material, some specific embodiments of the herbicidal composition of -this invention comprise one or more other components, examples of which include plant growth regulators, insecticides~ fungicides, plant nutrients and the like.
The herbicidal composition of this invention is used by applying it by conventional ways and means to soil and to foliage of weeds.
The rate of application of the composition of this invention is such as to provide an effective concentration of the phytoto~ic material in the soil, on the weed oliage, or both in the soil and on the foliage, depending on the me-thod of application and what is desired.
The bes-t mode now contemplated of carrying out -this invention is illustrated by the following working examples of various aspects of this invention, including specific emb(3~-3im~n-}c~ T~s ~vent;~ lS not llmited to these specific embodiments. In -these examples all percentages are by weight ~d 9 ~5~V~
unless otherwise indicated all parts by weight are indicated by "w", all parts of volume are indicated by "v", and each part by weight (w) bears the same relationship to each part by volume (v) as the kilogram does to the liter.
E~ample 28 This example illustrates a specific embodiment of a process for making N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester, the E~ample 1 compound.
Ethyl bromoacetat0 (4~0 w) is added dropwise to a stirred mixture of 2,6-diethylaniline (429 w), potassium hydroxide (161 w) and dimethylformamide (1500 v). During the addition of ethyl bromoac~tate, the temperature of the reaction mixture typically rises slightly. After addition is complete, the mixture is stirred at 90-llO~C. for one hour. During this period of time ths potassium hydroxide dissolves and a white precipitate slowly forms. The reaction mixture is cooled to 20-25C., poured into water (2000 v) and extracted with diethyl ether (700 v) three times. The ether extracts are combined, washed in water, an aqueous solution of hydrochloric acid (10~), an aqueous solution of sodium bicarbonate ~5%), and water, and then dried. The diethyl ether is r0moved by evapora-tion under reduced pressure. The residue (~26.8) is typically a red oil.
It consists essentially of N-(2,6-diethylphenyl)-glycine ethyl ester.
In similar fashion -the other intermediate compounds in which R' is H are made from the corresponding anilines and haloalkanoic acids or esters.
To a stirred solu-tion of the 2,6-di0thylphenylglycine ethyl ester (531.5 w) in benæene (2.5 v) is added dropwise chloroacetyl ch]o~ide (306 w) followed by pyridine (196 w).
During the additions the temp0rature of the reaction mixture N
~5~
typically rises from 20-25C. to about 40C. After the additions are complete, the resulting reaction mixture is stirred at 40-50C. for 3 hours, cooled to 20-25C., and filtered. The filtrate is washed with the water, an aqueous solu-tion of hydrochloric acid (10%), an aqueous solution of sodium bicarbonate (5~), and water, and then dried. The benzene is removed by evaporation under reduced pressure. The residue ~711.0 w), the desired product, is typically a red oil which crystallizes on standing. A typical analysis of the product is:
N = 4.4%, C1 = 11.9%; (calculated: N = 4.4%, Cl - 11.3%). The product consists essentially of N-chloroacetyl-(2,6-diethylphenyl)-glycine ethyl ester.
In similar fashion tha other compounds of this invention in which R ' iS mono-, di- and trihaloacetyl are made from the corresponding compounds in which R' is H, and -the I corresponding mono-, di- and -trihaloacetyl halides.
Example 29 This example illustrates a specific embodiment of the herbicidal composition of -this invention.
The general formulation o-f the composition is:
Components Concentration Phy-to-toxic material 1 w Poly(oxyethylene)sorbitan monolaurate in which the average oxyethylene content is 20 mole % 1 v Toluene 1 v The phytotoxic material in this example consists of the product of Example 28.
The composition of the foregoing formulation is made by admixing the components at 20-25 C. It ~s a water emulsi~iable concentrate.
This emulsifiable concentrate is used by admixing it with water to give an emulsion containing N-chloroacetyl-N-(2-6-diethylphenyl)-glycine e-thyl ester at the desired concentration.
This general formulation is applicable to the other compounds of this invention, whether alone or in mixture.
The herbicidal utilities of the compounds of this invention are illustrated by the test data set forth in the following Table. These test data were obtained in actual routir-e greenhouse testing of products consisting essentially of the compounds of this invention. In each case a water emulsi~iable t concentrate was made by dissolving a sample (15 w) of the product in acetone (400 v) and then admixing a commercially available emulsifier [a blend of polyoxyethylene (20) sorbitan monooleate in which -the average oxygethylene content is about 20 mole %, mono- and diglycerides of fat forming fatty acids, and an antioxidant mixture consisting essentially of butylated hydroxyanisole, butylated hydroxytoluene, citric acid and propylene glycol] (20 v). The liquid concentrate was then dispersed in water and the resulting emulsion applied by spraying at standard test ra-tes.
In the post emergence (foliage spray) -test, the emulsion was sprayed at rates of 1 and 10 pounds of test product per acre on growing plants a-t the first true leaf stage. The plants were millet, corn, mustard, cotton, tomato and marigold.
After a prescribed interval of time during which the sprayed plants as well as unsprayed plants of the same age were subjected to favourable growing conditions in a greenhouse, the sprayed plal~ts v,ere insL,3cted for injur-~ and li]l, compa:red with the unsprayed plants, and the extent of injury or kill rated on a N
)8 scale of 0-10 with 0 being no injury or kill and 10 being 100 injury or kill.
In the pre-emergence (soil germination) test the emulsion was sprayed a-t rates of 2 and 20 pounds of test product per acre on soil freshly seeded with the seeds of soybean, millat, corn, mustard and cotton. After subjecting the sprayed seeded soil as well as unsprayed soil freshly seeded with thess seeds to controlled favourable growing conditions in a greenhouse for a time sufficient for germination and plant growth, the containers of the soil were inspected for plant growth and injury, and compared to the containers of unsprayed seeded soil.
The extent of injur~ or kill was rated on a scale of 0-10 with 0 being no injury or kill and 1~ being 100~ injury or kill.
Although they do not form part of the invention, the intermediates of the general formula in which R' represents hydrogen possess herbicidal activity and the test results for the intermediates are included in the Table for reference purposes~
N
- 13 _ ~ r~
¦ O C~ O ~ O ~; O O O O O O O N O O O _l O ~ 'd 11~
'a~ O ~ O O O O O O O O O (~ ~ o o v~ O ~ O c~ o E-~ ~
C C:
C O t'1 ~ O ~ ~ N O O O O N ~ O ~ ~ O 0~ O O O O O CO O
_~ ~
O O O O O O ~ O O O O O `O Ir- O O O O O 0~ O O O o o O l O O t` ~ ) 0--I O O O ~ O ~') O ~ ~O O N t~ O O O ~ O cr~
N(`~NON N NO ~ CNN O N O N O
Il~
~ N 117 0 t`~O ~ O ~ N`O ~ N ~ O ~ O O O ~` N ~D
I
l N O O ~N OO Cl~ O ~! ~ ~O O ~ ~ (') `D O O ~ l 0) ¦ N a~ O U~ O ~' O ~') O ~D O N --I O ~1 O~ O ~ O t~) O ~ O ~
~ ~1 ~
~1 ~ o ~ ,~ V) o N O N O ~ O O 0~ N O O ~` .1 0 '1 O
a ::
2 ~¦ ~ N ~ N ~ N O ~ O ~1 0 (O O N O N ~ N O ~ O N O
ol ~ ~ O u~ O ~ O ~ O u~ O O ~ r) o u~ o O ~10 -~ O ~ O ~ O ~- O .-10 ~ O ~10 -~ O ~10 _1 ~0 o ol O' O X _I N ~ ~Ul 'D N a~ O ~-N
7~
Thus, it can be observed that the compounds of this invention are herbicidal. They also exhibit selective herbicidal activity. For example, in field testing of a 2 pound per gallon emulsifiable concentrate in which the phytotoxic material consisted essentially of N-chloroacetyl-N-~2,6-die-thylphenyl)-glycine eth~1 ester, the Example 1 compound, the activity of this compound was found to be primarily against grass weeds, but it also performed very well in controlling pig weed and smart weed.
Crops which were found to be tolerant to relatively high rates of this compound are sugar beets, corn, wheat, peas, cotton, peanuts and soybeans. Although greenhouse data showed low tolerance by sorghum and rice in this compound, these crops tolerated this compound under field conditions at rates that gave excellent grass control. Also, this compound was found to give effective wild oat control without injury to wheat or to barley.
Thus, this invention provides new and useful compounds and new and useful herbicidal compositions containing them.
Other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. Such specific embodiments are within the scope of the claimed subject matter unless expressly indicated to the contrary by claim language. Moreover, while specific embodiments of this invention have been described in considerable detail, variations and modifications of them can be eff~cted without depar-ting from the spirit and scope of the inven-tion as disclosed and claimed.
The term "consisking essentially of" as used in this specification excludes any unrecited substance at a concentration sufficient to substantially adversely affect the essen-tial properties and charac-teristics of the composition of matter being deL.ned, whi'P pa~:;mtting 'h~ p'L'e'S~.Ce of one or more l1nr~.ited ~ ~ ~3 substances at concentrations insufficient to substantially adversely affect said essential properties and characteristics.
N
The compounds of this invention are made by reacting in a liquid reactlon medium containing a base such as potassium hydroxide or the liko corresponding phenyl amine:
R~
R
with a haloalkanola acid or ester of the formula:
X - R4- C~
in which X is halo, to form the compounds of the class in whîch R' is hydrogen. The compounds are reacted with mono-, di- and tri-haloacetylhalide~ of the formula:
o X ~ C~ i n )~
~.
in which n is 0-~, to form the compounds of this invention, however, is not limitad to these ways of making the compounds of this invention.
For herbicidal uses the compounds o this invention preferably are incorporated into a dispersible composition. This composition comprises an effective ~uantity of phytotoxic material, and application aid material.
The phytotoxic material consists essentially of at least one compound of this invention. In some embodiments of this composition the phytotoxic material comprises only one compound of this invention. In other embodiments the phytotoxic material comprises -two or more compounds of this invention. In still other embodiments, it comprises other substances having phytotoxic activity.
Specific embodiments of the composition of this invention range from concentra-tes of the phytotoxic ~aterial to the ultimate use composition that is applied in the field.
Accordingly, an effective concentration of the phytotoxic material in the composition of this invention is in a broad range, generally being from about 0.1 to about 90~ by weight of the composition. Higher and lower concentrations, however, are within the broader concspts of this invention. In concentrate embodiments, the concentration of the phytotoxic material generally is in a range from about 10 to about 90~ by weight of the composition and preferably in a range from about 10 to about 50~ by weight of the composition. In -the ultimate use embodiments, the concentra-tion generally is in a range from about 0.1 to about 20-~ by weight of the composition and preferably in a range from about 0.5 to about 10-~ by weight of the composition.
Ap~ 2t.0r aid mat~r-~?l. .iS generalLv inert material that facilita-tes ~istribution or dispersion of the phytotoxic N
~5~3~3 material when it is applied to soil or to foliage of undesirable plants. It encompasses diluents, carriers, extenders, surfactan-ts, spreading agents, sticking agents, wind drift control agents, and -the like.
In those embodiments of the composition of this invention, which are normally solid, the application aid material generally comprises an inert solid in a divided condition.
Some embodiments of the solid composition are granular, while others are dispersible powders or dusts.
The granular compositions are of the coa-ted type, the impregnated type or the incorporated type.
The coated type of granular composition is made by dusting a wettable powder or ground powder comprising the phytotoxic material onto inert granular carrier material which either before or after the dusting has been admixed with an inert adhesive or a sticker. Water, oils, alcohols, glycols, aqueous gums, waxes and the like including mixtures thereof, are used as stickers. Examples of inert granular carrier ma-terial include attaclay, corn cobs, vermiculite, walnut hulls and almost any granular mineral or organic material screened to the desired particle size (generally 15-60 mesh, preferably about 30 mesh, U.S. screen size). Generally the phytotoxic material is abou-t 2-20% by weight of -the composition, and the granular carrier material is generally about 60-93~ by weight of -the composi-tion.
In the case of the impregnated type of granular composition, the phytotoxic ma-terial as such when liquid or after melting, or dissolved in a solvent, is sprayed on or poured into the inert granular carrier material. The solvent can be removed by evaporation, or permitted to remain. In either case, -the phytotoxic material impregnates the particles of -the granular carrier material. Examples of the iner-t granular carrier . ~
6- ~576~
material include those just mentioned wi-th respect to the coated type of granular composition. The phytotoxic material is generally about 2-20~ by weight of the composition, while the granular carrier material is generally about 80~98~ by weight of the composition.
The incorporated type of granular composition is made by admixing the phytotoxic material with an inert finely divided solid such as, ~or example, clay, carbon, plaster of paris and the like, and made into a mud with water or other inert evaporable liquid. The mud is then dried to a solid sheet or cake, broken up or comminuted, and screened to the desired particle size (generally 15-60 mesh, preferably 30 mesh, U.S.
screen size). In other embodiments, the mud is put into a granulating pan and granules are formed therein with subsequent removal of the water or solvent. In still another procedure, -the mud is extruded through a die into rods which are cut into small pieces. In the incorporated type of granular composition, the phytotoxic material generally is about 2-50~ by weight of the composition, and the solid carrier material is about 50-98% by weight of the composition.
In all granular embodiments of the composition of this invention, various additives in minor concentrations relative to the carrier material also can be present.
In other embodiments of -the solid composition of this invention, the carrier is usually a dispersible inert solid. A
typical dispersible solid of this type is clay. Other suitable solids ldispersible solid) include talc, attapulgite, pyropylite, diatomaceous earth, kaolin, aluminum magnesium silicate, montmorillonite, fullers earth, sawdust and -the lika. The solid dispersible composition can be air dispersible, in which case it is usually referred to as a dust. Generally, when it is in-tended '-~nat- the compc3ltion be wa'er d:~spersible, the compos1tion preferably contains emulsifying material ~one or more ~j 7~0~3 surfactants) at a concentration sufficient to enable a suspension of the desired degree of stability to be formed when the composition is admixed with a suitable quantity of water. The composition in such case is usually referred to as a wettable powder. A typical dispersible solid composition of this invention generally comprises about 10-80~ by weight of the phytotoxic material, about 20-90~ by weight of solid carrier material and, when emulsifying material is present, about 1-10%
by weight of emulsifying material.
Other specific embodiments of the herbicidal composition of this inven-tion comprise homogeneous liquid solutions of phytotoxic material in inert, preferably volatile solvents for the phytotoxic material. Examples of suitable solvents when the phytotoxic material is wa-ter-insoluble include isophorone, cyclohexanone, methyl isobutyl ketone, xylene and the like. When the phytotoxic ma-terial is water-soluble, water is a suitable solvent. Such a solution, which can be regarded as a concentrate, typically comprises about 10-50% by weight of phyto-toxic material and about 50-90% by weight of solvent. The solution can be applied as is, or diluted with more solvent and applied or, when water immiscible, dispersed in water, or water dispersed in it, and applied. Preferably, when i-t is intended that the solution be dispersed in water or wa-ter dispersed in it, the mixture of solution and water also comprises emulsifying material at a concentration sufficient to enable a dispersion of the desired degree of s-tability to be formed when the solution or concentrate is mixed with water. A typical emulsifying material concentration is about 1-10% by weight of the concentrate. The water concentration generally is such that -the phytotoxic material concentra-tion preferably is about 0.5-10% by weight of the total composi-tion.
Examples of the surfactants employed in bo-th the liquid and solid compositions of this inven-tion comprise the well known surface active agents of the anionic, cationic and non-ionic ~.f`~-~576~)~
types and include alkali mstal (sodium or potassium) oleates and similar soaps, amine salts of long chain fa-tty acids (oleates), sulfonates, animal and vegetable oils (fish oils and castor oil), sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glyceryl monosterate, poly(oxyethylene), ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amina and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridinium bromide, stearyl trime-thylammonium bromide, and cetyl dimethylbenzylammonium chloride. Still other examples are listed in "Detergents and Emulsifiers - 1968 Annual"
by John W. McCutcheon.
In addition to the phyto-toxic material and application aid material, some specific embodiments of the herbicidal composition of -this invention comprise one or more other components, examples of which include plant growth regulators, insecticides~ fungicides, plant nutrients and the like.
The herbicidal composition of this invention is used by applying it by conventional ways and means to soil and to foliage of weeds.
The rate of application of the composition of this invention is such as to provide an effective concentration of the phytoto~ic material in the soil, on the weed oliage, or both in the soil and on the foliage, depending on the me-thod of application and what is desired.
The bes-t mode now contemplated of carrying out -this invention is illustrated by the following working examples of various aspects of this invention, including specific emb(3~-3im~n-}c~ T~s ~vent;~ lS not llmited to these specific embodiments. In -these examples all percentages are by weight ~d 9 ~5~V~
unless otherwise indicated all parts by weight are indicated by "w", all parts of volume are indicated by "v", and each part by weight (w) bears the same relationship to each part by volume (v) as the kilogram does to the liter.
E~ample 28 This example illustrates a specific embodiment of a process for making N-chloroacetyl-N-(2,6-diethylphenyl)-glycine ethyl ester, the E~ample 1 compound.
Ethyl bromoacetat0 (4~0 w) is added dropwise to a stirred mixture of 2,6-diethylaniline (429 w), potassium hydroxide (161 w) and dimethylformamide (1500 v). During the addition of ethyl bromoac~tate, the temperature of the reaction mixture typically rises slightly. After addition is complete, the mixture is stirred at 90-llO~C. for one hour. During this period of time ths potassium hydroxide dissolves and a white precipitate slowly forms. The reaction mixture is cooled to 20-25C., poured into water (2000 v) and extracted with diethyl ether (700 v) three times. The ether extracts are combined, washed in water, an aqueous solution of hydrochloric acid (10~), an aqueous solution of sodium bicarbonate ~5%), and water, and then dried. The diethyl ether is r0moved by evapora-tion under reduced pressure. The residue (~26.8) is typically a red oil.
It consists essentially of N-(2,6-diethylphenyl)-glycine ethyl ester.
In similar fashion -the other intermediate compounds in which R' is H are made from the corresponding anilines and haloalkanoic acids or esters.
To a stirred solu-tion of the 2,6-di0thylphenylglycine ethyl ester (531.5 w) in benæene (2.5 v) is added dropwise chloroacetyl ch]o~ide (306 w) followed by pyridine (196 w).
During the additions the temp0rature of the reaction mixture N
~5~
typically rises from 20-25C. to about 40C. After the additions are complete, the resulting reaction mixture is stirred at 40-50C. for 3 hours, cooled to 20-25C., and filtered. The filtrate is washed with the water, an aqueous solu-tion of hydrochloric acid (10%), an aqueous solution of sodium bicarbonate (5~), and water, and then dried. The benzene is removed by evaporation under reduced pressure. The residue ~711.0 w), the desired product, is typically a red oil which crystallizes on standing. A typical analysis of the product is:
N = 4.4%, C1 = 11.9%; (calculated: N = 4.4%, Cl - 11.3%). The product consists essentially of N-chloroacetyl-(2,6-diethylphenyl)-glycine ethyl ester.
In similar fashion tha other compounds of this invention in which R ' iS mono-, di- and trihaloacetyl are made from the corresponding compounds in which R' is H, and -the I corresponding mono-, di- and -trihaloacetyl halides.
Example 29 This example illustrates a specific embodiment of the herbicidal composition of -this invention.
The general formulation o-f the composition is:
Components Concentration Phy-to-toxic material 1 w Poly(oxyethylene)sorbitan monolaurate in which the average oxyethylene content is 20 mole % 1 v Toluene 1 v The phytotoxic material in this example consists of the product of Example 28.
The composition of the foregoing formulation is made by admixing the components at 20-25 C. It ~s a water emulsi~iable concentrate.
This emulsifiable concentrate is used by admixing it with water to give an emulsion containing N-chloroacetyl-N-(2-6-diethylphenyl)-glycine e-thyl ester at the desired concentration.
This general formulation is applicable to the other compounds of this invention, whether alone or in mixture.
The herbicidal utilities of the compounds of this invention are illustrated by the test data set forth in the following Table. These test data were obtained in actual routir-e greenhouse testing of products consisting essentially of the compounds of this invention. In each case a water emulsi~iable t concentrate was made by dissolving a sample (15 w) of the product in acetone (400 v) and then admixing a commercially available emulsifier [a blend of polyoxyethylene (20) sorbitan monooleate in which -the average oxygethylene content is about 20 mole %, mono- and diglycerides of fat forming fatty acids, and an antioxidant mixture consisting essentially of butylated hydroxyanisole, butylated hydroxytoluene, citric acid and propylene glycol] (20 v). The liquid concentrate was then dispersed in water and the resulting emulsion applied by spraying at standard test ra-tes.
In the post emergence (foliage spray) -test, the emulsion was sprayed at rates of 1 and 10 pounds of test product per acre on growing plants a-t the first true leaf stage. The plants were millet, corn, mustard, cotton, tomato and marigold.
After a prescribed interval of time during which the sprayed plants as well as unsprayed plants of the same age were subjected to favourable growing conditions in a greenhouse, the sprayed plal~ts v,ere insL,3cted for injur-~ and li]l, compa:red with the unsprayed plants, and the extent of injury or kill rated on a N
)8 scale of 0-10 with 0 being no injury or kill and 10 being 100 injury or kill.
In the pre-emergence (soil germination) test the emulsion was sprayed a-t rates of 2 and 20 pounds of test product per acre on soil freshly seeded with the seeds of soybean, millat, corn, mustard and cotton. After subjecting the sprayed seeded soil as well as unsprayed soil freshly seeded with thess seeds to controlled favourable growing conditions in a greenhouse for a time sufficient for germination and plant growth, the containers of the soil were inspected for plant growth and injury, and compared to the containers of unsprayed seeded soil.
The extent of injur~ or kill was rated on a scale of 0-10 with 0 being no injury or kill and 1~ being 100~ injury or kill.
Although they do not form part of the invention, the intermediates of the general formula in which R' represents hydrogen possess herbicidal activity and the test results for the intermediates are included in the Table for reference purposes~
N
- 13 _ ~ r~
¦ O C~ O ~ O ~; O O O O O O O N O O O _l O ~ 'd 11~
'a~ O ~ O O O O O O O O O (~ ~ o o v~ O ~ O c~ o E-~ ~
C C:
C O t'1 ~ O ~ ~ N O O O O N ~ O ~ ~ O 0~ O O O O O CO O
_~ ~
O O O O O O ~ O O O O O `O Ir- O O O O O 0~ O O O o o O l O O t` ~ ) 0--I O O O ~ O ~') O ~ ~O O N t~ O O O ~ O cr~
N(`~NON N NO ~ CNN O N O N O
Il~
~ N 117 0 t`~O ~ O ~ N`O ~ N ~ O ~ O O O ~` N ~D
I
l N O O ~N OO Cl~ O ~! ~ ~O O ~ ~ (') `D O O ~ l 0) ¦ N a~ O U~ O ~' O ~') O ~D O N --I O ~1 O~ O ~ O t~) O ~ O ~
~ ~1 ~
~1 ~ o ~ ,~ V) o N O N O ~ O O 0~ N O O ~` .1 0 '1 O
a ::
2 ~¦ ~ N ~ N ~ N O ~ O ~1 0 (O O N O N ~ N O ~ O N O
ol ~ ~ O u~ O ~ O ~ O u~ O O ~ r) o u~ o O ~10 -~ O ~ O ~ O ~- O .-10 ~ O ~10 -~ O ~10 _1 ~0 o ol O' O X _I N ~ ~Ul 'D N a~ O ~-N
7~
Thus, it can be observed that the compounds of this invention are herbicidal. They also exhibit selective herbicidal activity. For example, in field testing of a 2 pound per gallon emulsifiable concentrate in which the phytotoxic material consisted essentially of N-chloroacetyl-N-~2,6-die-thylphenyl)-glycine eth~1 ester, the Example 1 compound, the activity of this compound was found to be primarily against grass weeds, but it also performed very well in controlling pig weed and smart weed.
Crops which were found to be tolerant to relatively high rates of this compound are sugar beets, corn, wheat, peas, cotton, peanuts and soybeans. Although greenhouse data showed low tolerance by sorghum and rice in this compound, these crops tolerated this compound under field conditions at rates that gave excellent grass control. Also, this compound was found to give effective wild oat control without injury to wheat or to barley.
Thus, this invention provides new and useful compounds and new and useful herbicidal compositions containing them.
Other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. Such specific embodiments are within the scope of the claimed subject matter unless expressly indicated to the contrary by claim language. Moreover, while specific embodiments of this invention have been described in considerable detail, variations and modifications of them can be eff~cted without depar-ting from the spirit and scope of the inven-tion as disclosed and claimed.
The term "consisking essentially of" as used in this specification excludes any unrecited substance at a concentration sufficient to substantially adversely affect the essen-tial properties and charac-teristics of the composition of matter being deL.ned, whi'P pa~:;mtting 'h~ p'L'e'S~.Ce of one or more l1nr~.ited ~ ~ ~3 substances at concentrations insufficient to substantially adversely affect said essential properties and characteristics.
N
Claims (10)
1. A compound of the formula (I) (I) R1 and R2 are independently lower alkyl R3 is lower alkyl substituted by 1 to 4 halogen atoms R4 is lower alkylene R5 is hydrogen, lower alkyl or a salt-forming cation.
2. A compound according to claim 1 wherein R1 and R2 are both C2H5, R3 is CH2Ha1, R4 is CH2 and R5 is C2H5.
3. A compound according to claim 1 of the formula (IV).
(IV) wherein:
R6 is methyl R7 and R8 are independently methyl or ethyl Hal is a halogen atom.
(IV) wherein:
R6 is methyl R7 and R8 are independently methyl or ethyl Hal is a halogen atom.
4. A compound according to claim 1 of the formula (VI) (VI) wherein:
R4 is lower alkylene R9 is hydrogen or lower alkyl R1 0 is lower alkyl or halogen R1 1 is halogen R1 2 is lower alkyl Hal is halogen.
R4 is lower alkylene R9 is hydrogen or lower alkyl R1 0 is lower alkyl or halogen R1 1 is halogen R1 2 is lower alkyl Hal is halogen.
5. A process for the preparation of a compound of the formula (I) (I) wherein:
R1 and R2 are independently lower alkyl R3 is lower alkyl substituted by 1 to 4 halogen atoms R4 is lower alkylene R5 is hydrogen, lower alkyl or a salt-forming cation which comprises reacting a compound of the formula (II) (II) wherein R1, R2 and R5 are as defined above with a compound of the formula (III) (III) wherein:
R3 is as defined above Hal is halogen in the presence of a dehydrohalogenating agent.
R1 and R2 are independently lower alkyl R3 is lower alkyl substituted by 1 to 4 halogen atoms R4 is lower alkylene R5 is hydrogen, lower alkyl or a salt-forming cation which comprises reacting a compound of the formula (II) (II) wherein R1, R2 and R5 are as defined above with a compound of the formula (III) (III) wherein:
R3 is as defined above Hal is halogen in the presence of a dehydrohalogenating agent.
6. A method according to claim 5 in which R1 and R2 are C2H5, R3 is CH2Cl, R4 is CH2 and R5 is C2H5.
7. A process for the preparation of a compound of the formula (IV) (IV) wherein:
R6 is methyl R7 and R8 are independently methyl or ethyl Hal is a halogen atom which comprises reacting a compound of the formula (V) (V) wherein R6, R7 and R8 are as defined above with a haloacetylating agent.
R6 is methyl R7 and R8 are independently methyl or ethyl Hal is a halogen atom which comprises reacting a compound of the formula (V) (V) wherein R6, R7 and R8 are as defined above with a haloacetylating agent.
8. A process for the preparation of a compound of the formula (VI) (VI) Wherein:
R4 is lower alkylene R9 is hydrogen or lower alkyl R1 0 is lower alkyl or halogen R1 1 is halogen R1 2 is lower alkyl Hal is halogen which comprises reaction of a compound of the formula (VII) (VII) wherein R4, R9, R1 0, R1 1 and R1 2 are as defined above, with a haloacetylating agent.
R4 is lower alkylene R9 is hydrogen or lower alkyl R1 0 is lower alkyl or halogen R1 1 is halogen R1 2 is lower alkyl Hal is halogen which comprises reaction of a compound of the formula (VII) (VII) wherein R4, R9, R1 0, R1 1 and R1 2 are as defined above, with a haloacetylating agent.
9. A method of inhibiting the growth of undesirable plants, which comprises applying to the habitat of said plants a phytotoxic quantity of a compound of the formula (I) (I) wherein:
R1 and R2 are independently lower alkyl R3 is lower alkyl substituted by 1 to 4 halogen atoms R4 is lower alkylene R5 is hydrogen, lower alkyl or a salt-forming cation.
R1 and R2 are independently lower alkyl R3 is lower alkyl substituted by 1 to 4 halogen atoms R4 is lower alkylene R5 is hydrogen, lower alkyl or a salt-forming cation.
10. A method according to claim 9 in which R1 and R2 are C2H5, R3 is CH2Cl, R4 is CH2 and R5 is C2H5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23381772A | 1972-03-10 | 1972-03-10 | |
| US233,817 | 1972-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257608A true CA1257608A (en) | 1989-07-18 |
Family
ID=22878810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000160332A Expired CA1257608A (en) | 1972-03-10 | 1973-01-02 | Certain n-phenyl amines and their use as herbicides |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS49232A (en) |
| KR (1) | KR800001698B1 (en) |
| AR (1) | AR203081A1 (en) |
| AT (1) | AT339284B (en) |
| AU (1) | AU476514B2 (en) |
| BE (1) | BE796263A (en) |
| BR (1) | BR7301703D0 (en) |
| CA (1) | CA1257608A (en) |
| DE (1) | DE2311897A1 (en) |
| IT (1) | IT981287B (en) |
| SE (2) | SE411206B (en) |
| TR (1) | TR18384A (en) |
| ZA (1) | ZA73316B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849578B1 (en) | 1999-11-17 | 2005-02-01 | Bayer Aktiengesellschaft | Selective herbicides based on 2,6-disubstituted pyridine derivatives |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4096167A (en) * | 1974-10-17 | 1978-06-20 | Chevron Research Company | Fungicidal and herbicidal alpha-haloacetanilides |
| JPS5240797U (en) * | 1975-09-16 | 1977-03-23 | ||
| US4165381A (en) * | 1975-09-30 | 1979-08-21 | Ciba-Geigy Corporation | Microbicidal compositions |
| US4098895A (en) * | 1975-09-30 | 1978-07-04 | Ciba-Geigy Corporation | Triazolylacetanilide compounds and microbicidal compositions |
| CH637368A5 (en) * | 1978-10-27 | 1983-07-29 | Ciba Geigy Ag | ANILINE DERIVATIVES AND Pesticides Manufactured From Them. |
| JPS62105574U (en) * | 1985-12-24 | 1987-07-06 | ||
| DE3723071A1 (en) * | 1987-07-11 | 1989-01-19 | Bayer Ag | METHOD FOR ISOLATING POLYARYL SULFIDES |
-
1973
- 1973-01-02 CA CA000160332A patent/CA1257608A/en not_active Expired
- 1973-01-16 ZA ZA730316A patent/ZA73316B/en unknown
- 1973-01-31 TR TR18384A patent/TR18384A/en unknown
- 1973-02-05 AU AU51831/73A patent/AU476514B2/en not_active Expired
- 1973-02-21 JP JP48020314A patent/JPS49232A/ja active Pending
- 1973-03-02 AR AR246904A patent/AR203081A1/en active
- 1973-03-05 BE BE128358A patent/BE796263A/en not_active IP Right Cessation
- 1973-03-09 AT AT208873A patent/AT339284B/en not_active IP Right Cessation
- 1973-03-09 BR BR731703A patent/BR7301703D0/en unknown
- 1973-03-09 DE DE2311897A patent/DE2311897A1/en not_active Ceased
- 1973-03-09 IT IT21429/73A patent/IT981287B/en active
-
1975
- 1975-02-12 SE SE7501572A patent/SE411206B/en unknown
- 1975-09-23 SE SE7510667A patent/SE7510667L/en not_active Application Discontinuation
-
1978
- 1978-01-04 KR KR7800001A patent/KR800001698B1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6849578B1 (en) | 1999-11-17 | 2005-02-01 | Bayer Aktiengesellschaft | Selective herbicides based on 2,6-disubstituted pyridine derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| BE796263A (en) | 1973-07-02 |
| SE411206B (en) | 1979-12-10 |
| TR18384A (en) | 1977-05-01 |
| SE7501572L (en) | 1975-02-12 |
| AT339284B (en) | 1977-10-10 |
| ZA73316B (en) | 1973-10-31 |
| JPS49232A (en) | 1974-01-05 |
| AU5183173A (en) | 1974-08-08 |
| KR800001698B1 (en) | 1980-12-31 |
| DE2311897A1 (en) | 1973-10-04 |
| IT981287B (en) | 1974-10-10 |
| ATA208873A (en) | 1977-02-15 |
| SE7510667L (en) | 1975-09-23 |
| BR7301703D0 (en) | 1974-07-11 |
| AR203081A1 (en) | 1975-08-14 |
| AU476514B2 (en) | 1976-09-23 |
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