New weedkillers, their preparation and use.
PATENT AS AFRICAN AND MALAGASY INDUSTRIAL PROPERTY (cameroon) classifying multinational® yaoundê!.: - 07 c. N° 02447 THE REQUEST 5 June 1967 to 16 hr 45 min to ro.A.M.p. 1. (Pp.v. № 52,963) by the company said: International Research on interface shell MAATSCHAPPIJ v. residing to the Netherlands. oo.vm ^ P.I.. V." DELIVERED THE 5 May 1970 PUBLISHED AT № OFFICIAL BALLOT 1 of 1970 Patent application deposited in the UK under the no. 25473 the 8 June 1966 and 2 May 1967 on behalf of the applicant. Novel herbicides, their preparation and use. The present invention relates to novel herbicidal anilinoalcoylcarboxamides, processes for their preparation, compositions containing herbicides in, and a method of combating bad 5 herbs. The anilinoalcoylcarboxamides novel according to the invention correspond to the general formula: wherein a represents a substituted or unsubstituted alkylene containing 1 to 6 carbon atoms; the R ^ ^ and R which may be the same or different each represents a hydrogen atom, an alkyl goupement, alkylene or substituted or unsubstituted aryl substituted, or a group NR R in which R and R 3, 4 3, 4 individually represent a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, with the proviso that R ^ ^ and R are not both hydrogen atoms or an NR ^ ^ the R groups, or R ^ ^ and R together with the nitrogen atom to which they are attached form a heterocyclic ring system containing another hetero atom; the X, Y or Z which may be the same or different, each represent a hydrogen or halogen atom, a cyano group or nitro, an alkyl group or substituted or unsubstituted aryl, a group or an amino group or alcoylsulfonylecarbomoyle or derivatives mono or di-n-octyl alkylated thereof, with the proviso that all of X, Y and Z are not both hydrogen atoms. The alkylene group is preferably an unsubstituted alkylene group such as a methylene or ethylene group, an alkylene substituted with alkyl group such as a methylene group substituted with alkyl (alkylidene), or alkylidene group substituted with alkylthio as=CH2 (ch-ch-^ ^ ^ SCHs). The alkyl group, aryl or alkylene which can be represented by or preferably comprise 1 to 20 carbon atoms, and more particularly to 1 10 carbon atoms, and may be substituted by one or more hydroxy groups or halogen atoms. Thus, suitable alkyls groups include acyclic groups methyl, ethyl, propyl, isopropyl, butyl, octyl, monyle, and octadecyl, cycloaliphatic cyclopentyl and cyclohexyl groups and the groups such as benzyl aralcoyles. Suitable aryl groups include phenyl group and the groups such as tolyl alcoylaryles, while groups include groups suitable alkylenes allyl, butenyl and héxényle. The NR group wherein R ^ ^ which can be represented by R ^ ^ or R is preferably a group substituted dimethyl amine, and preferably is only present when the other substituent on n is a hydrogen atom. When R ^ ^ and R, together with the nitrogen atom to which they are bound, represent a heterocyclic ring system, the latter is preferably a hexagonal system such as for example a morpholine or piperidine ring. Accordingly, preferred compounds of the present invention are those in which a represents an alkylene group which is unsubstituted or substituted by alkyl or alkylthio; X represents a halogen atom, a nitro group or an alkyl group and Z is X or a hydrogen atom. In particular, preferred are the compounds in which contains 1 to has 4 carbon atoms, which preferably comprise an alkylene group, alkylidene or substituted alkylidene methylthio; or represent a group NR where R ^ ^ than when the other represents a hydrogen atom, and R ^, preferably, hydrogen or aotme represents a methyl or ethyl and R represents an alkyl group of^1 to 10 carbon atoms, or a phenyl group, allyl or dimethylamino, or R ^ and together with the nitrogen atom to which they are attached form a six-membered heterocyclic ring; X represents a halogen atom, or a nitro group; Z represents a hydrogen or halogen atom or a nitro group and Y represents a hydrogen atom or an alkyl group or halogen-substituted or unsubstituted. X preferably represents a chlorine atom or a nitro group or methyl; Z represents a hydrogen or chlorine atom or a nitro group; and Y represents a hydrogen or chlorine atom or a cyano group, a nitro, methyl, trifluoromethyl, ethyl, propyl, butyl, octyl, méthylsufonyle, monoou di methylamino, carbamoyl or n-methylcarbamoyl or phenyl. Especially active herbicidal compounds are those wherein represents a hydrogen atom or an alkyl group or alkylene having up to 4 carbon atoms; R represents an alkyl group or alkylene having up to 4 carbon atoms; a represents a ethylidene; X and Z are nitro groups bonded to positions 2 and 6 of the benzene ring; and Y represents a hydrogen or chlorine atom or a methyl group or trifluoromethyl linked to position 4 of the benzene ring. Specific examples of compounds of this type are: 2 - (2, 6 a-dinitroanilino) - 2 - N-methylpropionamide (2.6 to-dinitrobenzoic 4-methylanilino) - N-methylpropionamide. 2 - (2, 6 a-dinitr0-a 4 a-trifluorornéthylanilino) - N-methylpropionamide. 2 - (2, 6 a-dinitrobenzoic 4 a-chloroanilino) - N-methylpropionamide. 2 - (2, 6 a-dinitroanilidinitroanili.no) - n-, -n-dimethylpropionamide. 2 - (2, 6 - dinitroanilino) - substituted n-ethylpropionamide. 2 - (2, 6 - dinitroanilino) - N allylpropionamide. It will recognize, when a is substituted unsymmetrical manner, that the compounds contain an asymmetric carbon atom. This asymmetric carbon atom leads to the existence of optical isomers of the compounds, and these individual isomers and mixtures thereof are within the scope of the present invention. It will be appreciated that the developed portion O 11 - NH-c-NR in the R ^ ^ of the general formula I above may be considered to be derived from an amino - 3< the NH ^ - acid-c-OH group. For example if a represents the group - telling a ^ " ^ ch ch-, the amino-acid relevant is the alphaalanine; if a represents - ch-ch-^ ^ -, the amino-acid is beta-alanine; if a represents CH CH-" SCHs the amino' 223 acid is methionine. Since, according to a method described later, can be prepared the compounds of the present invention of amino-acids from, the array has a substituted or unsubstituted alkylene is preferably a group as a developed portion of O the n - NH-c-a-NR NR in ^ ", of the formula I is derived from an amino acid commonly available such as alanine, aspartic acid, glutamic acid, leucine, lysin, valine or methionine. According to another aspect of the invention, the compounds may be prepared having the above general formula I, wherein at least one of between the groups X, Y and Z is a moiety that attracts strong centeredly electrons such as a methylsulfonyl group or nitro trifluoromethyl, by means of a method as conduct as reacting a compound having the general formula: THE II with an amino-acid - ^ the NH-COOH, which leads to an acid having the general formula: - - OH-III-A - C the conversion of the acid to the corresponding acid chloride and reacting the acid chloride with an amine of R ^ ^ MST, the X, the Y, Z-, has, the R ^ ^ and R having the above meanings provided that at least one of between X, Y and Z is a moiety that attracts the electrons, and hal represents a fluorine atom, chlorine or bromine. The reaction is carried out between the compound of formula II and the amino-acid-NH ^ _A COOH preferably in the presence of a suitable base to tie Hhal acid formed during the reaction. Suitable bases are, for example, bicarbonates, carbonates and alkali metal hydroxides, such as sodium and potassium and alkaline earth and nitrogenous bases such as for example, pyridine. The reaction is carried out, preferably, at a temperature between 50 and 150° C., and more preferably between 70 and 120° c in a suitable solvent or mixture of solvents, e.g. ethanol or aqueous ethanol. May be converted into acid III to the corresponding acid chloride using any conventional method. Good results were obtained with refluxing the acid with thionyl chloride in benzene. The reaction is carried out between the acid chloride and the amine NHR-the R ^ ^ preferably in a liquid reaction medium inert, methylene chloride being particularly suitable. Can however also be used other solvents, e.g. carbon tetrachloride, benzene, toluene, and diethyl ether. The reaction is carried out preferably at a temperature between - 20 and + 30° c but can also be used at higher temperatures e.g. up to 100° C. can work the reaction mixture in any manner that current, and the product may be purified by crystallization or chromatography if desired. According to another aspect of the invention, the compounds may be prepared according to formula I généraie above, but does not incorporate group in the benzene ring, which strongly attract electrons, by a process comprising reacting a compound having the general formula: with a compound hal-COOH " ', which results in an ester having the formula: V and the reaction of the ester with an amine MST ^ ^ the R, wherein X, the Y, Z and a, the R ^ ^ and R have the meanings specified above with the proviso that none of between X, Y and Z represents a group strongly attracting electrons, Hal is fluorine, chlorine or bromine, and R ^ _ represents an alkyl group containing 1 - 4 carbon atoms. The reaction can be performed between the compound IV with the compound hal-COCR ^ at room temperature, but is preferably performed at a temperature between 50 and 200° C., typically at between 80 and alder 120° C. isolating the ester V of the reaction mixture in any manner that current, for example, by distillation under reduced pressure. Can effect the conversion of the ester simple 1' amide corresponding to room temperature but is preferably performed by heating of the ester with the amine MST ^ ^ the R in a suitable solvent such as, for example ethanol. The reaction is carried out, preferably, at a temperature between 80 and 180° C., more preferably between 100 and 150° C. the amide can be isolated from the reaction mixture in any manner that current; it may be purified by crystallization from a suitable solvent or by chromatography if necessary. It is expected that the compounds of the invention as common for herbicidal, it is to say can be applied as a mixture with an inert diluent which may contain a surfactant. The invention therefore, also includes a herbicidal composition which comprises a compound of the invention and a vehicle or surfactant, or both a vehicle and a surfactant. The term "vehicle" as used herein against means a product, which may be inorganic or organic and of synthetic or natural origin which are mixed with the active compound or formulation so as to facilitate its application to the plant, seed, soil, or other object to be treated, or its storage, transportation or handling. The vehicle can be a solid or a fluid. Can be used as vehicle any product that is applied generally, to the formulation of pesticides. Examples of suitable solid carriers are silicates, clays, such as kaolinite clay, synthetic hydrated silicon oxides, synthetic calcium silicates, elements such as for example carbon and sulfur, natural and synthetic resins such as e.g. coumarone resins, rosin, the cleaned, shellac, dammar the, polymers and copolymers. polyvinyl chloride and styrene, the solid polychlorophenols, bitumen, the asphaltite, waxes such as for example beeswax, waxy wax, montanic wax and mineral waxes chlorinated, and the solid fertilizers, e.g. superphosphates. Examples of suitable liquid carriers are water, alcohols, such as isopropanol, ketones such as for example acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers, aromatic hydrocarbons such as for example, benzene and toluene, the petroleum fractions such as e.g. kerosene, chlorinated hydrocarbons, such as for example carbon tetrachloride, including liquefied gaseous compounds normally vaporous. Mixtures of different liquids are often suitable. The surfactant may be a wetting agent, an emulsifying agent or a dispersing agent; it may be non-ionic or ionic. One may use any of the surfactants applied generally in the formulation of herbicides or insecticides. Examples of suitable surfactants are the sodium or calcium salts of polyacrylic acids, condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; the partial esters of fatty acids above with glycerin, sorbitan, sucrose or pentaerythritol; condensation products of alkylphenols, e.g. the P-octylphenol or P-octylcrésol, with ethylene oxide and/or propylene oxide; the sulfates or sulfonates of these condensation products; and alkali metal salts, preferably sodium salts or esters of sulfuric acid or sulfonic acids containing at least 10 carbon atoms in the molecule, for example, lauryl sodium sulfate, the secondary sodium alkylsulfates, sodium salts of sulfonated castor oil, and the alcoylarylsulfonates sodium such as sodium dodecyl benzene sulfonate. May be formulated into the compositions of the invention in the form of wettable powders, powders, granules solution, emulsifiable concentrates, emulsions, and pastes. Combined typically wettable powders so that they contain 25, 50 or 75% of the toxicant and they typically contain, in addition to the solid carrier, 3 to 10% of a dispersing agent and when necessary 0 to 10% of a stabilizer or stabilizers and/or other additives such as penetration agents or bonding agents. Formula is, typically, powders in the form of a concentrated powder having a composition similar to that of a wettable powder but without a dispersant, and are diluted in-situ by using additional portions of solid carrier so as to obtain a composition composed of a Z - 10/o/ordinary ΐ toxicant. Prepared generally corresponding to sieve whose opening is between 0,152 and 1, 676 mm and they can be made using techniques of agglomeration or impregnation. In general contain toxicant 1/2 - 25% 25% to 0 and of additives such as stabilizers, retarders, binders, andc... The emulsifiable concentrates typically contain, in addition to the solvent and when needed, a cosolvent, 10 - 50% p/v of toxic agent, 2 - 20% p/v emulsifiers and 0 - 20% of appropriate additives such as stabilizers, penetrants and corrosion inhibitors. The pastes are combined so as to obtain a stable product and flowable and they generally contain 10 - 60% of toxic product, 2 - 20% of appropriate additives and as carrier, water or an organic liquid in which the toxic product is substantially insoluble. The compositions of the invention can contain other components, for example, of collordes protectors such as gelatin, thence glue, casein, gums and polyvinyl alcohol; sodium polyphosphates; cellulose ethers, of stabilizers such as ethylenediaminetetraacetic acid; other herbicides or pesticides; and bonding agents, for example non-volatile oils. The dispersions and emulsions, for example the compositions obtained by diluting a wettable powder or an emulsifiable cnncentréinven, except with water, are also included in the scope of the present invention. The emulsions may be of the water-in-oil or huiledans-to-water, and may be of a thick consistency "of the mayonnaise" type. The invention also includes a method of combating weeds which comprises applying a compound of the invention or a herbicidal composition containing it to said unwanted vegetation or soil to grow the weeds or on which is provided a thrust, and a method for improving crop yield comprising the application of a compound or a composition of the invention to a surface with crops. EXAMPLE 1 - Preparation of n-methyl 2 - (2, 6 a-dinitroanilino) - propionamide hydrochloride. O NHCH (HM) TO C-NHCH 3 u. Is mixed and heated to reflux a mixture of L-chloro 2, 6-dinitrobenzene (810 ρ), dl-alphaalanine (P-384), and sodium bicarbonate (840 w) in 95% ethanol (8000 volts) during 18 hours. The mixture is diluted with water (4000 volts), filtered, and separated from the ethanol by distillation under reduced pressure. Added more water (4000 volts) during the distillation so as to maintain the solids in solution. By cooling the aqueous solution by the addition of ice (2000 W) and is acidified with concentrated hydrochloric acid (congo red) during agitation. The precipitate tacky at the beginning crystallizes, when the stirring is continued, in a dark yellow solid is separated off by filtration, washed with water and dried in air. Acid yield 2 - (2, 6 a-dinitroanilino) propionic, 980 (95%) of P, P f 137 - 138 °C. Acid solution is stirred 2 - (2.6 dinitroanilino) propionic acid (P-490) in benzene (2500 volts) and is added thionyl chloride (570 volts) at a speed which is so high that a regular clearance of gas. When the addition is complete, the stirring is continued, and the mixture is heated at reflux for 12 hours. The reaction mixture is filtered, and then separating the benzene and excess thionyl chloride by distillation under reduced pressure. The acid chloride as an oil remains dark red. This oil is dissolved in methylene chloride (2500 volts) and the solution is cooled to 0° C. dissolves methylamine (P-l60) in methylene chloride (1000 volts), and the solution is added to the solution of the acid chloride with stirring at 0 - 5 °C. The precipitate is separated by filtration, and washed with methylene chloride (500 volts). The filtrate is evaporated to dryness, and the residue is stirred with denatured alcohol of business (1000 volts). The precipitate is separated by filtration, washed with alcohol denatured business (three times with 200 volts), and dried in air. The obtained n-methyl 2 - (2, 6 a-dinitroanilino) propionamide hydrochloride as a yellow powder, melting point 146 - 148 °C. total yield 310 w, 61%. Found: 44 C., 6; 4 hr, 5% Calculated for-leading: 44 C., 7; 4 hr, 5% 10, 12 4, 5^ SUCH AS II - Preparation of n-methyl 2 - (methyl-2, 6 a-dinitroanilino) propionamide hydrochloride The adduct is prepared by applying a similar method to that described in the example 1, but using the 4-chloro 3, 5 a-dinitrotoluene as starting material instead of the L-chloro 2, 6-dinitrobenzene. Overall yield of desired product is 67% relative to 4 a-chloro3, 5 a-dinitrotoluene. Melting point acid 2 - (4 methyl 2, 6 a-dinitroanilino) propionic acid intermediate is 158 - 161 °C; the melting point of n-methyl 2 - (4 methyl 2, 6 a-dinitroanilino) propionamide hydrochloride is approximately 32 149 - 151. Found: C. 47, 0; 4 hr, 7% Calculated for c11H 14NR 4 °5: 46 C., 8; 4 HR, 9% SUCH AS III Using the method described in the example The I, or suitable modifications thereof, are prepared derivatives-anilino-propionamide derivatives represented in tables 1 and 2 by preparing the acid anilinopropionic RNHCH (^ ch-COOH group, suitable, by reacting the acid with thionyl chloride, which results in the acid chloride and then reacting the acid chloride with methylamine or dimethylamine (Tableaul) (table 2) to give the desired propionamide. I (Result) TABLE 2 EXAMPLE VI Is a number of 2 - (2, 6 a-dinitroanilino) proprionamides by reacting chloride 2 - (2, 6 a-dinitroanilino) propionyl (prepared according to the Des 1 in the example) with more amines as described in the example 1 regarding the reaction with methylamine. The melting points and the analytical data of the compounds in question are represented in table 3. u-O-> Heated at reflux acid solution 2 - (2, 6 a-dinitroanilino) propionic acid (5 w) in a mixture of benzene (50 volts) and thionyl chloride (20 volts) during 4 hours. The reaction mixture is evaporated to dryness, and the residue is dissolved in methylene chloride (50 ml). The solution is cooled to 0° C., and adding a solution of 1, 1-dimethylhydrazine (6 w) in methylene chloride (20 volts). After concentrating the solution, washed with water and dried over magnesium sulfate. The residue is purified, obtained by distilling off the solvent, by chromatography on alumina using methylene chloride as eluent. Is requantized crystallizes the product into a mixture of benzene and petroleum ether (60 - 80 degrees C. E.G.). Yield 1, 5 w; melting point 102 - 103 °C. Found: 44 C., 6; 4 hr, 7% Calculated for c,, hr,C. NRC.O_: 44 C., 4; 5 HR, THE O % 11, 15 5, 5 EXAMPLE VI. - Preparation of 3 - (2, 6 a-dinitroanilino) - (I) Nméthylpropionamide and 3 - (2, 6 a-dinitroanilino) - n-, -n-dimethylpropionamide (ll) , NO." a ft - NHCH2 HM2 -C-R NO. 2 R=- NH-(HM3 ); THE R=- N-IL(HM3 )2 Compounds are prepared using the method described in the example I in reacting the 1-chloro 2, 6-dinitrobenzene with beta-alanine sodium bicarbonate, which leads to the acid 3 - (2, 6 a-dinitroanilino) propionic, by converting the acid to the acid chloride, and reacting the acid chloride with methylamine and dimethylamine, respectively. Compound I: melting point: 109 - 110 °C Analysis : Found: 44 C., 7; 4 hr, 2% Calculated for n-H 0:44 C., 7; 4 hr, 5% 10 Compound II: melting point: 95 - 96 °C Analysis : Found: 47 C., 1; 4 hr, 9% Calculated for c, hr. Ν, 0. : 46 C., 8; 5 HR, 0% the R 11, 14 4, 5 EXAMPLE VII. Prepared compounds represented in table 4 in a manner analogous to that described in Example VI below. TABLE VI EXAMPLE VIII. - Preparation of n-methyl-4-methylthio-a 2 - (2, 6 a-dinitroanilino) - butyramide derivatives The adduct is prepared using a method analogous to that described in the example 1 by reacting 1 - chloro 2, 6-dinitrobenzene with dl-methionine, by converting the acid obtained in acid chloride, and reacting the acid chloride with methylamine. Product is purified by chromatography on alumina using methylene chloride as eluent, melting point 88 - 89 °C. Found: 44 C., 0; 4 hr, 8; O 10, 4% Calculated for C, H-a. , N-, OSI : 43 C., 8; 4 HR, 9; E 9, 8% 12 lo 4 b. EXAMPLE IX. - Preparation of 2 - (2, 5 a-dichloroanilino) - Nméthylpropionamide IC / VBE1 - NHCH (HM3 ) CH-HCN3O IC ' Heating a mixture of 2, 5 a-dichloroaniline (32, 4 P-) and 2 tert-ethyl (18, 1 w) C. for 5 hours to 100°. Water is added to the melt hot, and the organic layer is taken up in ether. The ethereal solution is dried on the MgSO ^ and evaporation of the ether. The residue is distilled under reduced pressure. The fraction is collected (7 P-) boiling point 127 - 130 °C (0, 9 mm of Hg), in the form of 2 - (2, 5 a-dichloroanilino) ethyl propionate. Found 50 C., 4; 4 hr, 8; n is 5, 4; LC 27; 3 % Calculated forC11H1 3LC2N0 2 '■50 C. >4 ii4 HR >0 55 N. >4JLC Heating the 2 - 27.2% (2, 5 a-dichloroanilino) propionate (10 w) in a sealed tube with ethanolic methylamine (33% p/v, 50 volts) to C. for 15 hours 120°. The reaction mixture is concentrated, the mixture is filtered hot, and is allowed to cool. Removed by filtration the desired product which crystallizes from the solution. After recrystallization from ethanol melting point 168 - 169 °C. yield 6, 6 (70%) of P. Ation Found: C. 48, 8; 5 hr, 0; n is 11, 1; LC 28, 4% calculated forC10H12LC2NR2 DEGREES: C. 48, 6; 4 HR, 9; THE N 11, 3; LC 28, Using the same method as in example IX., the following compounds are prepared by reacting aniline with NH of R ^ ^ appropriate substituted by halogen or alkyl, (the meaning of R ^ being indicated in table 5 according) with 2 tert-ethyl, yields the 2 - ethyl propionate (halogénoanilino) (or the corresponding oylanilino or compound has. mixed halogeno, alcoylanilino) and then reacting this compound with methylamine or dimethylamine to obtain 1' amid. TABLE Y (result) O EXAMPLE XII - Preparation of 2 - (2, 6 a-dinitroanilino) - N-hydroxymethyl-N-methylpropionamide Passed dry hydrochloric acid gas for six hours in a stirring 2 - (2, 6 a-dinitroanilino) - N-methylpropionamide (P-27), prepared as in the example I-, paraformaldehyde (4, 5 w) and methylene chloride (200 volts). Maintaining the mixture at room temperature for that period of time and when the reaction is completed the solid precipitate is separated by filtration washed with a solution of sodium bicarbonate. By dissolving the free base obtained in this mania Re in methylene chloride and dried the solution of MgSO ^. Separating the pressurized solvent re uite and crystallizing the residue in ethanol, yields the 2 - (2, 6 a-dinitroanilino) - N-hydroxymethyl-N-methylpropionamide, e. f 135 - 136 °C. Found: 44 C., 7; 4 hr, 5% Calculated for n-O-H: 44 C., 3; 4 hr, 7% the R 11, 14 4, 6 EXAMPLE XII. - Preparation of n-methyl 2 - (2, 4, 6 a-trinitroanilino) propionamide hydrochloride (form PI) Stirred and heating a mixture of chloride picryl (6 the P, Q, m-024), of - amino-propion-methylamide (0, m-0215), sodium bicarbonate (4 w, 0, 047 meters) and alcohol denatures business to 40 - 50 degrees C. for 2 hours. The reaction mixture is éyapore to half its volume and water is added (100 volts). The collected yellow solid that precipitates, dried to air and is the recrystallized in ethanol, to give the desired product, f.w. 172 - 173 °C. Found: C. 38, 7; 3 hr, 8% Calculated for n-O-H: 38 C., 4; 3 hr, 5% UI it b. According to an analogous method to that described in the example XII as, preparing compound desires, e. F.. 229 - 230 °C. Found: C. 42, 2; 4 hr, 2% Calculated for c, 0 _N_. hr .,: C. 42, 4; h4, 2% 11, 13 5, 6 A wettable powder is prepared with good susceptibility to form a suspension in water by mixing together the constituents shown and subjecting the mixture to the hammer mill and at air mill. N-methyl 2 - (4 methyl 2, 6 a-dinitroanilino) propionamide hydrochloride Tamol 731, 3% 50% P-P-P-Empicol lz domain 2% to 100% P-clay YTG the Tamol 731 comprises sodium polyacrylate; the empicol lz domain comprises lauryl sodium sulfate; and clay YTG has a kaolinite clay. EXAMPLE XV FRAMES To evaluate the herbicidal activity, subjecting the compounds of the invention tested by using a representative range of plants, oats (has), ryegrass (I-), Peppers May (am), pea (w), sugar beet (BSs), linseed (I) and mustard (MB).. Out two categories of tests, the tests pre-emergence and post-emergence. Pre-emergence tests include spraying a liquid formulation of a compound of the invention on a floor newly seeded with seeds of the plant species. Post-emergence tests have two types of tests, i.e., tests of soaking the floor and spray of foliage. In the testing of soaking of the soil, the soil is sprayed with a liquid formulation comprising a compound of the invention after the seeds of the plant species above germinated and in the spray test of foliage, is sprayed plants with such a formulation. Formulations used in the above test are constituted by 40 parts by volume of acetone, 60 parts by volume of water, 0, 5 part by weight of a condensation product of alkylphenol/ethylene oxide available under the trade name as Triton-X 155, and by a compound of the invention in varying amounts. To sow and allowed to germinate the seeds of plant species mentioned above in a compost by John innate to steam sterilization. In the testing of soil spray and dip of the ground, the ground and the ground carrier-seeded plants are sprayed with the equivalent volume 4, 6 liters by ARE and quenched by a volume equivalent to 93 liters by ARE respectively. In the spray test of foliage, seedlings are sprayed by a volume equivalent to 4.6 liters by ARE. It is also used for control studies wherein treated to the ground seeded, ground bearing the planes not subcultured, and plants with the same compositions but which do not have any active compound. The phytotoxic effect is determined by determining the applied compounds reducing the fresh weight of the rods and sheets treated plants relative to control plants and to support a regression curve relating to growth inhibition (C. I.) and applied to the dose of the compound. The dose required to achieve 50% growth inhibition and 90% (it is to say the weight of the compound necessary to achieve a reduction of 50 to 90% of the fresh weight of a sheet and plant stem) is shown in table 6 next. Table 6 gives the dose as kilograms per hectare, the X, Y and Z representing doses higher than 11, the Z, 14 and 22, 4 kg per hectare. EXAMPLE XIV Determined the herbicidal activity of the compounds mentioned in the following tables 7, 8 and 9 by means of a method which differs from that described in the example Xv frames by the following points. Applied both compounds in two doses equivalent to 1 and 10 kg/per hectare in the test soil spray and spray of foliage and a dose equivalent to 20 kg/ha in the soak test soil. Determining the effects herbicidal compounds in question visually seven days after the spraying of the foliage and the soil soaking (post-emergence test) and eleven days after pulverizing the soil (pre-emergence test), and are recorded on a scale of 0 - 9 (0=none effect and potent herbicidal effect=9). A rate of 2 approximately corresponds to a reduction of 25% of the fresh weight of the stem and leaves treated plants, a rate of 5 corresponds approximately to a reduction of 55% of the weight, and a rate of 9 to a reduction of 95% of the weight, andc. The results are summarized in the following tables 7 - 9. TABLE 7 Performing an additional evaluation of the preemergence herbicidal activity of the compounds of the invention by spraying a composition of wettable powder, prepared according to example XIY above, on parcels of land. Sprayed the parcels of land, after 6 months of newly cultured fallow to 2 in a proportion of 4 kg of active ingredient per hectare and total counted amount of weeds on the plot of land after 54 days. The results obtained are shown in table 10 below and note that the control of the weed obtained using the anilino-to-alcoylcarboxamide is greater than that obtained using the herbicide diuron is commercially available, the only - (3, 6-dichlorophenyl) - n-, N-dimethylurea, and that untreated controls have a strong growth of weeds. TABLE 10 The invention relates to anilino alkyl-carboxamides of the general formula <FORM:1122043/C2/1> wherein A represents a substituted or unsubstituted alkylene group of 1 to 6 carbon atoms; R1 and R2, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, aryl or alkenyl group, or a group NR3R4, wherein R3 and R4 each individually represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, provided that both of R1 and R2 are not hydrogen atoms or NR3R4 groups, or R1 and R2 together wit the nitrogen atom to which they are attached form a heterocyclic ring system optionally containing a further hetero atom; X, Y and Z, which may be the same or different, each represents a hydrogen or halogen atom, a cyano or nitro group, a substituted or unsubstituted alkyl or aryl group, an alkylsulphonyl group, or an amino or carbamoyl group or mono- or di-N-alkyl derivatives thereof, provided that not all of X, Y and Z represent hydrogen atoms. Many compounds are claimed per se. The compounds in which at least one of the group X, Y and Z is a strongly electron-withdrawing group may be prepared by reacting a compound of the general formula <FORM:1122043/C2/2> with an amino acid NH2-A-COOH preferably in the presence of a base such as pyridine, sodium or potassium carbonate, bicaronate or hydroxide to give an acid having the general formula <FORM:1122043/C2/3> converting this acid into a corresponding acid chloride, e.g. by reaction with thionyl chloride in the presence of an inert solvent and reacting the acid chloride with an amine HNR1R2, wherein X, Y, Z, A, R1 and R2 are as above, with the proviso that at least one of the groups X, Y and Z is a strongly electron-withdrawing group and hal represents a fluorine, chlorine or bromine atom. The compounds in which none of X, Y or Z represents a strongly electron-withdrawing group are prepared by reacting a compound of a general formula <FORM:1122043/C2/4> with a compound hal-A-COOR5 to give an ester having the formula <FORM:1122043/C2/5> and reacting this ester with an amine HNR1R2, wherein X, Y, Z, A, R1 and R2 have the meanings set forth in claim 1, with the proviso that none of the groups X, Y, Z shall represent a strongly electron-withdrawing group, hal represents a fluorine, chlorine or bromine atom and R5 represents an alkyl group containing 1-4 carbon atoms. In an example, 1-chloro-2,6-dinitrobenzene is reacted with alpha-alanine to produce 2 - (2,6 - dinitroanilino) - propionic acid which is reacted with thionyl chloride to produce the acid chloride which is reacted with methylamine to yield N-methyl-2-(2,6-dinitroanilino) propionamide Many examples are given.ALSO:Herbicidal compositions comprise as active ingredient together with a carrier or surface active agent or both a carrier and surface active agent compounds of the general formula: <FORM:1122043/A5-A6/1> wherein A represents a substituted or unsubstituted alkylene group of 1 to 6 carbon atoms; R1 and R2, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, aryl or alkenyl group, or a group NR3R4 wherein R3 and R4 each individually represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, provided that both of R1 and R2 are not hydrogen atoms or NR3R4 groups, or R1 and R2 together with the nitrogen atom to which they are attached form a heterocyclic ring system optionally containing a further hetero atom; X, Y and Z, which may be the same or different, each represents a hydrogen or halogen atom, a cyano or nitro group, a substituted or unsubstituted alkyl or aryl group, an alkylsulphonyl group, or an amino or carbamoyl group or mono- or di-N-alkyl derivatives thereof, provided that not all of X, Y and Z represent hydrogen atoms. The compounds may be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions and pastes, Many Examples of active ingredients, carriers and surface active agents are specified. l) of anilinoalcoylcarboxamides responsive the formula: X wherein a represents a substituted or unsubstituted alkylene of 1 to 6 carbon atoms; The R ^ ^ and R, which may be the same or different each representing a hydrogen atom, an alkyl group, aryl or substituted or unsubstituted alkylene, or an NR group wherein R ^ ^ ^ wherein R and R ^ each individually represent a hydrogen atom or an alkyl group of 1 to 4 carbon atoms with the proviso that ^ and R are not both hydrogen atoms or groups where R ^ ^ an NR, or R ^ ^ and R together with the nitrogen atom to which they are attached form a heterocyclic ring system containing one additional hetero atom; the X, Y and Z which may be the same or different each represents a hydrogen or halogen atom, a cyano group or nitro group, an alkyl group or substituted or unsubstituted aryl, a group alcoylsulfonyle, or an amino group or carbamoyl or derivatives of di-n-alkylated thereof, provided that all of the The X, Y and Z is not hydrogen atoms. 2) Of anilinoalcoylcarboxamides according to paragraph I) having the following features considered singly or in combination: a) a represents a alkylene unsubstituted or substituted by alkyl or alkylthio; X represents a halogen atom, a nitro group or an alkyl group and Z is X or a hydrogen atom. b) 1 to 4 has contains carbon atoms; the R ^ ^ or R represents a group NR does the R ^ ^ than when the other represents a hydrogen atom; X represents a halogen atom or a nitro group; Z represents a hydrogen or halogen atom or a nitro group and Y represents a hydrogen atom or an alkyl group or halogen-substituted or unsubstituted. c) a represents a alkylidene substituted with alkylene, alkylidene or methylthio; the R ^ represents a hydrogen atom or a methyl or ethyl group, and R represents an alkyl group of^1 to 10 carbon atoms, or a phenyl group, allyl or dimethylamino - or R ^ ^ and R together with the nitrogen atom to which they are attached form a hexagonal ring heterocyclic. d) X represents a chlorine atom or a nitro group or methyl; Z represents a hydrogen or chlorine atom or a nitro group; and Y represents a hydrogen or chlorine atom or a cyano group, a nitro, methyl, trifluoromethyl, ethyl, propyl, butyl octyl, methylsulfonyl, or dimethylamino - single, carbamoyl or n-methylcarbamoyl or phenyl. e) X represents a chlorine atom or a nitro group; Z represents a hydrogen atom or a nitro group and Y represents a hydrogen or chlorine atom or a methyl group or trifluoromethyl. f) represents a hydrogen atom or an alkyl group or alkylene containing up to 4 carbon atoms; represents an alkyl group or alkylene having up to 4 carbon atoms; a represents a ethylidene; X and Z are nitro groups bonded in positions 2 and 6 of the benzene ring; and Y represents a hydrogen or chlorine atom or a methyl group or trifluoromethyl attached at position 4 of the benzene ring. 3) 2 - (2, 6 a-dinitroanilino) - N-methylpropionamide. 4) 2 - (4 methyl 2, 6 a-dinitroanilino) - N-methylpropionamide. 5) Compounds according to 1) specifically listed above except compounds according to 3) and 4). 6) A process for preparing compounds according to 1) or 2) wherein at least one of the d, Y and Z is strongly attracting electrons, which comprises reacting a compound having the general formula: X Z with an amino-acid - ^ the NH-COOH, which leads to an acid having the general formula: X WITH ? - N-C-OH GROUP m is the conversion of the acid to the corresponding acid chloride, and reacting the acid chloride with an amine MST ^ ^ R-I wherein X, the Y, Z-, has, the R ^ ^ and R have the meanings stated in paragraph I), with the proviso that at least one of the group X, a Y, Z is a moiety that attracts the electrons, and hal represents a fluorine atom, chlorine or bromine. 7) Modes of carrying out the method according to 6) have the following features considered singly or in combination: a) the reaction is carried out between the halide and the amino acid in the presence of a base; b) the base is a nitrogenous base or a carbonate, bicarbonate or alkali metal hydroxide or alkaline earth metal; c) the base is pyridine or carbonate, bicarbonate or sodium or potassium hydroxide; d) the reaction between the halide and the amino-acid is carried out in the presence of an inert solvent; e) the solvent is μη alcohol; f) the reaction is carried out between the halide and the amine at a temperature of between 50 - 150 °C; g) the reaction is carried out at a temperature between 70 - 120 °C; h) acid is converted obtained by the reaction of the halide and the amino-to-acideacide.en its acid chloride by reaction with thionyl chloride in the presence of an inert solvent; i) the inert solvent is benzene derivatives; j) the reaction is carried out between the acid chloride and the R ^ ^ MST the amine in the presence of an inert solvent; k) the solvent is methylene chloride; l) the reaction is carried out between the acid chloride and the amine MST ^ ^ R-at a temperature between - 20 and + 100° grams; m) the reaction is carried out at a temperature between - 20 and + 30° C.; n) none of the groups X, Y or Z represents a group which attracts the electrons, which comprises reacting a compound of general formula VI with a compound hal-COQR which results in an ester 5 corresponding to the formula: V and the reaction of the ester with an amine MST ^ ^ the R, wherein X, the Y, Z-, has, the R ^ ^ and R, have the meanings stated in paragraph I), with the proviso that none of the groups X, the Y, Z represents a group which attracts the electrons, Hal is fluorine, chlorine or bromine and R ^. represents an alkyl group containing 1 - 4 carbon atoms; o) the reaction is carried out between the amine aromatic ester and rearward Iy hal-COOH at a temperature 5 between 50 - 200 °C; p) reaction is effected between 80 and 120° C.; q) reacting the ester V in the corresponding amide by heating the ester with the amine MST ^ ^ R-at a temperature between 80 and 180° C.; r) method according to the paragraph q) wherein the reaction is carried out at a temperature between 100 and 150° C.; s) method according to the paragraphs of Q) - R-) according by heating the ester and the amine together R-MST V12 in an inert solvent; t) method according to paragraph e) wherein the solvent is an alcohol; u) a process for preparing compounds according to the paragraph I) substantially as described by previously thereagainst. 8) the compounds produced by the methods according to 6) or 7). 9) Herbicidal compositions comprising a compound according to L) to 5) or 8) comprising a vehicle or a surfactant or both with a vehicle and a surfactant. 10) Compositions according to 9) when the composition is in the form of a wettable powder, a powder, a concentrate, a solution, an emulsifiable concentrate, a conventional emulsion, an invert emulsion, an aerosol, granule, a paste or an encapsulated product. Il) a process to control the growth of weeds comprising applying to weeds, or floor on which is provided a thrust, of a compound according to paragraphs L) to 5) or 8) or a composition according to 9) or 10). 12) A method of increasing the yield of crops at a site which comprises applying to the locus a compound in an amount effective biocidally according to paragraphs L) to 5) or 8) or a composition according to paragraph 9) or 10). Mama.tip office.P. 887
PRIORITY:
Analysis
Analysis
RNHCH (HM3 ) CONHCH3 Melting point " C. Alanine derivatives RMAF T-analysis Calculation The R=2.4-dinitrophenyl 208 - 209 LID C. 44, 4; 4 HR, 3% C. 44, 7; 4 HR, 5% The R=2-nitrophenyl 140 - 141 LID C. 53, 5; 5 HR, 9% C. 53, 7; 5 HR, 8% The R=4 a-méthylsulphonyl-to-2-nitrophenyl 198 - 199 LID C. 43, 5; 5 HR, 0; THE N 13, 6; O 10, 6% C. 43, 8; 5 HR, THE O; N14, O;S10, 6% The R=2-nitrate 4 a-trifluoromtrifluorom.éthylphényle 225 - 226 LID C. 45, 5; 3 HR, 9% C. 45, 3; 4 HR, 1% The R=5-methylamino-2, 4-dinitrophenyl 271 - 273 LID C. 44, 4; 5 HR, 1% C. 44, 5; 5 HR, 0% R=2, 6 a-dinitrobenzoic 4-trifluoromethylphenyl 162 - 163 LID C. 39, 6; 3 HR, 6% C. 39, 3; 3 HR, 3% R=2, 6-dinitrophenyl 136 - 137 L C. 44, 8; 4 HR, 5% C. 44, 7; 4 HR, 5% R=2, 6-dinitrophenyl 136 - 137 D C. 44, 6; 4 HR, 5% C. 44, 7; 4 HR, 5% R=2, 6 a-dinitrobenzoic 4 a-trifluoromé thy a lphény the 190 - 191 L 39 C., 4; 3 HR, 5% C. 39, 3; 3 HR, 3% The R=4 a-methylcarbamoyl-2, 6 a-dinitrophenyle 238 - 239 LID C. 44, 3; 4 HR, 8% C. 44, 3; 4 HR, 6% R=4 - méthylsufphonyl-a 2, 6-dinitrophenyl 204 - 206 LID C. 37, 9; 3 HR, 8; S AT 9, 9% C. 38, 2; 4 HR, 0; E 9, 3% R=2, 6 a-dinitrobenzoic 4-trifluoromethylphenyl 189 - 190 : D. : 39 C., 6; 3 HR, 5% C. 39, 3; 3 HR, 3% The R=4 ethyl 2, 6-dinitrophenyl 130 - 131 ; LID : C. 48, 5; 5 HR, 4; N IS 18, 9% C. 48, 6; 5 HR, 4; N IS 18, 85% RNHCH (HM3 ) CONHCH3 : Point: melting °C To Ala at Nine Analysis Found Calculated The R=4 ethyl 2, 6-dinitrophenyl 143 - 144 D C. 48, 5. 5 HR, 4; N IS 18, 9% C. 48, 6; 5 HR, 4; N IS 18, 85 The R=4 ethyl 2, 6-dinitrophenyl 142 - 143 L C. 48, 5; 5 HR, 4; N IS 18, 9% C. 48, 6; 5 HR, 4; N-18;85% The R=4 chloro-2-nitrophenyl 187 - 188 LID C. 46, 6; 4 HR, 6 C. 46, 6; 4 HR, 7 The R=4-chloro 2, 6-dinitrophenyl 183 - 185 LID C. 39, 9; 3 hr, 8; LC 11, 9 C. 39, 7; 3 hr, 6; LC 11, 8% The R=4-chloro 2, 6-dinitrophenyl 149 - 150 The Li C. 39, 8; 3 hr, 6; LC 11, 9% C. 39.7; 3.6 hr; 11.8% of Cl The R=4-chloro 2, 6-dinitrophenyl 149 - 150 D C. 39, 7; h3, 9; LC 11, 9% C. 39, 7; 3 hr, 6; LC 11.8 The R=4-methyl 2, 6-dinitrophenyl 132 - 134 E C. 47, 0; 5 HR, 3% C. 46, 8; 5 HR, 0 The R=4-methyl 2, 6-dinitrophenyl 135 - 136 D C. 47, 0; 4 HR, 8 The R=4 n-propyl 2, 6-dinitrophenyl 121 - 122 LID 50 C., 3; 5 HR, 7; THE N 17, 9 50 C., 3; 5 HR, 8; N IS 18, 0% The R=4-dry. butyl 2, 6-dinitrophenyl 99 - 100 LID C. 51, 7; 6 HR, 2 C. 51, 8; 6 HR, 2 The R=4 ditertiary butyl 2, 6-dinitrophenyl 138 - 139 LID C. 51, 7; 6 HR, 2% C. 51, 8; 6 HR, 2% R=2, 6 a-dinitrobenzoic 4 T-octylphenyl 125 - 126 LID C. 56, 7; 7 HR, 5 C. 56, 8; 7 HR, 4 The R ≈ 4-cyano 2, 6 dinitrophenyl 155 - 156 LID C. 45, 3; 3 HR, 7% C. 45, 0; 3 HR, 8% The R=4 phenyl 2, 6-dinitrophenyl 135 - 136 LID C. 55, 8; 4 HR, 4 C. 55, 8; 4 HR, 6% RNHCH (HM3 ) ADAPTED (HM3 )2 Melting point °C Alanine derivatives Analysis Found Calculated R=2, 4-dinitrophenyl 1.83 - 184 LID C. 46, 7; 5 HR, 1 C. 46, 8; 5 HR, 0 R=2, 6-dinitrophenyl 81 - 83 LID C. 46, 7; 4 HR, 7 C. 46, 8; 5 HR, THE O % The R=5-dimethylamino-2 and 4-dinitrophenyl 185 - 186 LID C. 47, 9; 5 HR, 9% C. 48, 0; 5 HR, 9 The R=4-methylsulfonyl-2-nitrophenyl 231 - 232 LID C. 45, 7; 5 HR, 2; S AT 10, 1% C. 45, 7; 5 HR, 4; O 10, 2% The R=2-nitrate 4-trifluoromethylphenyl 156 - 158 LID C. 47, 3; 4 HR, 7% C. 47, 2; 4 HR, 6 R=2, 6 a-dinitrobenzoic 4-trifluoromethylphenyl 80 - 82 LID C. 41, 2; 3 HR, 6% C. 41.2; 3 HR, 7% The R=2-nitrophenyl 129 - 131 LID C. 55, 8; 6 HR, 4% C. 55, 7; 6 HR, 3% The R=4-methylsulfonyl-2, 6-dinitrophenyl 173 - 175 LID C. 40, 2; 4 HR, 5; E 9, 3% C. 40, 0; 4 HR, 5; S AT 8, 9% TABLE III
/NR °2 Point Amine used Analysis melting °C in the preparation T-RMAF Calculated THE R= - NHCH2 HM3 105 - 106 H 2NCH 2HM 3 C. 46, 9; 5 HR, 0% C. 46, 8; 5 HR, 0% THE R= the n - (a CB2 hM3 )2 93 - 94 AND HN (CH22 HM3 ) 2 C. 49, 9; 5 HR, 8% 50 C., 3; 5 HR, 8% THE R= HM 3 -C 6H 5 152 - 153 /HM 3 HN-VBE1C 6H 5 C. 55, 9; 4 HR, 6% C. 55, 8; 4 HR, 7% THE R= - NHCs, o 5 204 - 205 H 2THE NC 6H 5 C. 54, 4 ;Η 4, 3% C. 54, 5; 4 HR, 2% THE R= - nhch (HM3 ) hC2 hM3 113 - 114 HM3ÇHGH2HM 3 the NH2 50 C., 6; 5 HR, 8% 50 C., 3; 5 HR, 8% THE R= - NHCH2 HM=HM2 92 - 93 THE NH2 HM2 HM=HM2 C. 48, 9; 4 HR, 7% C. 48, 9; 4 HR, 8% /N0 2/vBE19 Melting point °C Amine used in the preparation Analysis T-RMAF Calculated - CH-CH- 116 - 117 Piperidine C. 52, 1; 5 HR, 6% C. 52, 2; 5 HR, 6 THE R=- NH-(HM2 )1? HM3 81 - 83 H 2THE N (HM 2>LfsH 3 C. 64, 2; 9 HR, 2% C. 64, 1:9 HR, 2% THE R=- NH-(HM2 )grams HM3 63 - 64 H 2NR <HM 2> 8HM 3 C. 56, 7; 7 HR, 4% C. 56, 9; 7 HR, 4% HM, HM -, 155 - 156 Morpholino C. 47, 8; 4 HR, 9% C. 48, 1; 4 HR, 9% R =- NHCS (HM3 )2 NC 173 - 178 hr2 the NC (HM3 )2 nC C. 48, 7; 4 HR, 8; THE N 22, 0% C. 48, 6; 4 HR, 7; N21, Analysis
NO." Melting point " C. Analysis Found Calculated hM=therein3 oS2 - HM=HAS2 HM2 - THE NH WHERE R=(HM3 ) 227 - 230 38 C., 4; 4 HR, 2; E 9, 3% C. 38, 2; 4 HR, 0; E 9, 3% YFS 3 - HM=HAS2 HM2 - THE NH WHERE R=(HM3 ) 122 - 124 C. 39, 7; 3 HR, 4; F. 16, 7% C. 39, 3; 3 HR, 3; F17, YFS 3 WITH -~HM 2HM 2 - R=N (HM3 )2 128 - 129 C. 41, 0; 3 HR, 9; F. 16, 2 the I 11 FIT - HM=HAS2 - THE NH WHERE R=(HM3 ) 171 - 172 C. 42, 5; 3 HR, 9% HM=therein3 oS2 - HM=HAS2 HM2 - R=N (HM3 )2 150 - 170 C. 40, 0; 4.4 HR; S AT 8, 9% Y=H WITH HM -=(C.4H9 ) - THE NH WHERE R=(HM3 ) DL) 86 - 87 50 C., 3; 5 HR, 6% 50 C., 3; 5 HR, 8% 1 tT WITH HM -=(C.3H7 ) - THE NH WHERE R=(HM3 ) DL) 144 - 146 C. 48, 9; 5 HR, 6% C. 48, 6; 5.4 HR Analysis
Analysis
R1NHCH (HM3 ) ORC2 fuspgn point Analysis With a molding ouvé Calculated The R ^=4-chlorophenyl the R2 The n=(HM3 )2 142 - 143 C. 58, 2; 6 hr, 8; n is 12, 6; of Cl 15, 8% C. 58, 3; 6 HR, 6; N IS 12, 4; C1 TO 15, 2 - Chlorophenyl - ^ the R THE R 2=THE NH (CH23 ) 120 - 121 C. 56, 4; 6 hr, 3; the n 13, 6; LC 17, 2% C. 56, 5; 6 hr, 1; the n 13, 2; LC 16, 7% The R ^=4-chlorophenyl the R2 The NH=(HM3 ) 168 - 169 C. 56, 4; 6 hr, 3; the n 13, 2; LC 17, the O % C. 56, 5; 6 hr, 1; the n 13, 2; LC 16, 7% THE R ^ the R2 the NH - (CH23 ) 186 - 187 The n 11.3; LC 29, 0% THE N 11, The R ^=3, 4 a-dichlorophenyl the R2 The NH=(HM3 ) 158 - 159 The n 11, 5; LC 28, 6% The n 11, 4; LC 28, 8% The R ^=2, 3 a-dichlorophenyl THE R 2=THE NH (CH23 ) 149 - 150 C48.5; Η 4, 9; the n 11.2; LC 29, 0% C. 48, 6; 4 HR, 9; THE N 11, The R ^=3-chlorophenyl R2 =NR <HM 3> 2 92 - 93 C. 58, 4; 6 hr, 4; for Cl 15, 9% C. 58, 3; 6 hr, 6; of Cl 15, 7% The R ^=3-chlorophenyl the R2 The NH=(HM3 ) 93 - 94 C. 56, 7; 6 hr, 3; the n 13, 3; CI 16, 5% C. 56, 5; 6 hr, 1; the n 13, 2; LC 16, 7% The R ^=2-chlorophenyl the R2 The n=(HM3 )2 oil C. 58, 1; 6 HR, 3% C. 58, 3; 6 HR, 6% The R ^=3, 5 a-dichlorophenyl the R2 The NH=(HM3 ) 115 - 116 C. 48, 5; 4 hr, 6; n is 11, 5; LC 28, 2% C. 48, 6; 4 hr, 9; the n 11, 4; LC 28, 8% The R ^=2.4, 5 a-trichlorophenyl the R2 the NH - (CH23 ) 182 - 183 C. 42, 5; 4 HR, THE O % C. 42, 6; 3 HR, 9% =2, 6 a-dichlorophenyl R2 The NH=(HM3 ) 55 - 56 C. 48, 6; 5 hr, 0; n is 11, 3; LC 28, 6% C. 48, 6; 4 hr, 9; the n 11, 4; LC 28, 8% R=2, 6 a-dichlorophenyl the R2 The NH=(HM3 )2 57 - 58 50 C., 6; 5 hr, 3; the n 10, 7; LC 26, 9% 50 C., 6; hr 5.4; the n 10, 7; LC 27, 2% The R ^=2, 6-dimethylphenyl the R2 The NH=(HM3 ) 68 - 69 C. 69, 8; 8 HR, 7; THE N 13, 8% C. 69, 9; 8 HR, 8; THE N 13, 6 R1NHCH (HM3 ) ORC2 Melting point °C Analysis Found Calculated The R ^=3.4-dimethylphenyl the R2 The NH=(HM3 ) 134 - 135 C. 69.7; 8.9 HR; ^ N-13.6 C. 69.9; 8 HR, 8; THE N 13, 6% The R ^=2, 6-dimethylphenyl the R2 The NH=(HM3 ) 68 - 69 C. 69, 8; 8 HR, 7; THE N 13, 8% C. 69, 9; 8.8 HR; THE N 13, 6% Rj=2, 4-dimethylphenyl the R2 The NH=(HM3 ) 137 - 138 C. 70, 1; 8 HR, 8; THE N 13, 3% C. 69, 9; 8 HR, 8; THE N 13, 6% The R ^=2, 3-dimethylphenyl the R2 The NH=(HM3 ) 134 - 135 C. 69, 7; 8 HR, 7; THE N 13, 5 C. 69.9; 8 HR, 8; THE N 13, 6 The R ^=2-methylphenyl the R2 The NH=(HM3 ) 116 - 117 68 C., 7; 8 HR, 2; THE N 14, 5 C. 68.7; 8 HR, 3; THE N 14, 6% The R ^=3, 4 a-dichlorophenyl the R2 The n=(HM3 )2 33 - 35 C. 50, 7; 5 hr, 2; n is 10, 7; LC 26, 9% 50 C., 6; 5 hr, 4; the n 10, 7; LC 27, 2% The R ^=2.4, 5 a-trichlorophenyl R2 THE N=(HM3 )2 115 - 116 C. 44, 4; 4 hr, 5; n is 9, 2; LC 35, 8 C. 44, 7; 4 hr, 4; n is 9, 5; LC 36, The R ^=4 a-methylphenyl the R2 The NH=(HM3 ) 175 - 176 C. 69, 2; 8 HR, 2 C. 68.7; 8 HR, 3% The R ^=3-methylphenyl the R2 THE NH=(HM3 ) 79 - 80 THE N 14.4% THE N 14.6 R=3, 4-dimethylphenyl the R2 . THE N (HM3 )2 104 - 105 C. 71, THE O; 9 HR, 1; N IS 12, 4 C. 70.9; 9 HR, 1; N IS 12, 7% The R ^=2, 5-dimethylphenyl the R2 THE N=(HM3 )2 79 - 80 70 C., 4; 8 HR, 9; N IS 12, 6% C. 70.9; 9 HR, 1; N IS 12, 7% The R ^=2, 5 a-dichlorophenyl the R2 The NH=(HM3 ) 168 - 169 The n 11, 1; LC 28, 4% The n 11.4; LC 28, 8 $ The R ^=2, 6-dimethylphenyl =■NR <HM 3> 2 oil C. 71, 6; 9 HR, 0; N IS 10, 0 C. 70.9; 9 HR, 1; N IS 12, 7% Rj=2, 4 a-dichlorophenyl =NR <HM 3> 2 47 - 48 C. 50, 5; 5 hr, 3; n is 10, 8; LC 27, 1 50, 6; 5 HR, 4; THE N 10, 7; 27 OF C1, 2% R1NHCH (HM3 ) ORC2 Melting °C ipo Int. Analysis Found [calculated The R ^=3, 5 a-dichlorophenyl R2 THE N=(HM3 )2 136 - 138 C. 50, 5; 5 hr, 3; 27 of Cl, 1% 50 C., 6; 5 hr, 4; LC 27, 2% The R ^=4 chloro-2-methylphenyl R2 The NH=(HM3 ) 158 - 160 C. 58, 3; 6 hr, 7; the n 12, 3; CI 15, 6% C. 58, 3; 6 hr, 6; n is 12, 4; 15.7% of Cl The R ^=3 - chlorophenyl 4-methylphenyl R2 THE NH=(HM3 ) 156 - 157 The n 12, 5; for Cl 15, 5% The n 12, 4; for Cl 15, 7% The R ^=3-chloro 2-methylphenyl the R2 The NH=(HM3 ) 136 - 137 C. 58, 4; 6 hr, 7; the n 12, 4; for Cl 15, 5% C. 58, 3; 6 hr, 6; n is 12, 4; for Cl 15, 7% The R ^=2-chloro 6 - methyl phenyl the R2 The NH=(HM3 ) 58 - 60 C. 58, 3; 6 HR, 6; N IS 12, 4% C. 58, 3; 6 HR, 6; N IS 12, 4% The R ^=5-chloro 2 - methyl phenyl the R2 The NH=(HM3 ) 200 - 202 N IS 12, 4% N IS 12, 4% The R ^=4 chloro-2-methylphenyl R 2 - " (C " HAS 50 - 52 C. 59, 9; 7 hr, 1; CI 15, 0% C. 59, 9; 7 hr, 1; CI 14, 8% The R ^=5-chloro 2-methyl phenyl THE R 2=N (HM3 ) 2 101 - 102 60 C., 1; 6 hr, 9; the n 11.4; 14.9% of Cl C. 59, 9; 7 HR, 1; THE N 11, The R ^=3-chloro 4-methyl phenyl the R2 The n=(HM3 )2 137 - 139 C. 60, 2; 7 hr, 2; n is 11.5; LC 14, 8% C. 59, 9; 7 hr, 1; n is 11, 6; LC 14, 8% The R ^=3-chloro 2-methyl phenyl the R2 THE N=(HM3 )2 130 - 131 C. 60.2; hr 6, 9; the n 11.3; LC 15, 0% C. 59, 9; 7 hr, 1; n is 11, 6; LC 14, 8% The R ^ - 3-methylphenyl - Ν (ΟΗ ^) ^ 70 - 72 C. 70, 8; 8 HR, 6; THE N 13, 3% C. 70, 0; 8 HR, 7; THE N 13, 6% Analysis
Analysis
Analysis
EXAMPLE-XIV- Preparing a composition of wettable powder
HM 3 R NHCHCONHCH3 THE R= Growth inhibition in kg per hectare I rate. C Pre-emergence (seeds)! j of post-emergence (plants) It ll soil spray it spray of foliage ITs soaking the floor!! hr Am WITH I P L The Mo The m am!! BSs WITH I P L The Mo Ll BSs Û AD-II WITH I P L life BSS 2 - chloroph enen.yle. 50, 90 8.45 THE X 2, 14, 5.2 1.9 3, 6 8, THE X 2 8, 45 THE X X iI-X-X-U-II-II-it|; X X X 9, 8 THE X X II-V-- - it Λ ., |ll ll ll ll NON-L. Rhythmic ' AEFI LLS VBE1 6 2, 5 a-dichlorophenyl 50, 90 X 0, 6, 0.9 0, 6, 0, 6 X X X x-Y-U-V-ϋ - 11 the II-II-II 2, 2 THEREIN 3 THEREIN Y Y Y The II therein Û 12 it 7 ll 8, 8 A Z 7 Z. the Z Z the Z Z 3, 4 a-dichlorophenyl 50, 90 X 7, 9, 4, 6 1, 12 THE X X 1, 12 THE X X V. II-X-U-U-U-U-U-therein Y Y Y Y Y j U-Z-II-II-II-II-| 5, 6 THE Z 9 Z. the Z the Z the Z Z hM3 R-NH-CH-COR(HM)=R.3 Z- a U II U-U-U-U-H-U-it it ll ll ll ll ll ll ll ll 2-chlorophenyl 50, 90 X 1.24 THE X 4.9 10 2.4 9 8, 5 THE X 1, 7 THE X 2, 8 V-Û THEREIN11 ^ u-U-hr Y Y 10, 1 Y 4 THEREIN the U 4, 6!! Y-U-Z-U II. 11 13, Z-5 11.2 Z. the Z the Z the Z 21, THE Z 2, 5 a-dichlorophenyl 50, 90 X 2, 25 THE X 1, 03, 8, 45 X 10 X. X x-U-|! there ll it U-hr Y Y Y 7 THEREIN 1, 7 THEREIN 4 iI-Z-Y-n-II in!! 14, A Z 6 6, 5 THE Z the Z the Z the Z Z 3, 4 a-dichlorophenyl 50 D 90 X X X 0, 6, 6.4 0, 6, 2, 8 0, 6, 2, 4 0, 68 2 u-U-II-R-Y. Y I THEREIN 7, 5 THEREIN 2, 14 THEREIN 2.25 j. 6, 4 the II 4, 9" U-Y-U-Z-ll11H Z Z the Z the Z the Z 17 Z- hM3 R NHCHCONHCH3 THE R= Amount in kg/ha. Growth inhibition Pre-emergence (seeds) S Post-emergence (seedlings) J.|soil spray spray of foliage Soaking the ground Am WITH I P L The Mo Π BSs üma ll WITH I P L The Mo 11 BSs|u Am WITH I P L The Mo BSS 2-nitrophenyl 10, 1 1, 0 9, 0 7, 0 3, 0 2, 0 4, 0 3 II-I-O-O!!! hr 1, 0 1, 0 3, 1 3, 1 7, 2 Ll 3 20 ∩ ddthe nthe U n-n - n 3 4 2 3 4 4 3 2, 4~Dinitrophenyl 10, 1 0 2 1 0 0 3 Π Z-O-H-ll ll!! it 0 0 3, 1 3, 1 7, 4 2, 1 20!? the II 0 1 1 0 0 0 0 2, 6-dinitrophenyl 10, 1 8, 4 9, 8 9, 5 6, 2 9, 5 9, 4 9 hr Û Û 5, 4 2 it ll 9, 5 7, 3 5, 3 8, 6 9, 9 9, 11 20 Q.11 8 u and IF 6 8 8 3 9 8 6 2, 6 A-dinitrobenzoic 4-trifluoromethylphenyl 10, 1 6, 3 7, 5 9, 6 1, 0 8, 0 9, 0 8 the II3 0 it 2 hr 1, 0 4, 1 3, 2 6, 4 6, 5 1 it 20" U-U-U-U-0 6 5 6 1 9 5 5 2, 6 A-dinitrophenyl (L aianinedériv.) 10, 1 2, 0 2, 0 0 1, 0 5, 0 8, 0 the n-II4 !!3 0 dd 2 ll 3, 1 2, 0 5, 2 7, 3 8, 8 8' 20! 3 n-it!! 3 6 7 3 7 8 8 2, 6 A-dinitrophenyl (dériv. D-alanine methyl) 10, 1 8, 5 9, 8 8, 6 5, 1 9, 5 9, 4 9 tFs II-j-|5, 6 dd 3 ll 8, 1 7, 2 6, 3 9, 7 8, 8 9!' 20, 1117 It!! 4 7 7 1 9 8 7 4-methyl 2, 6-dinitrophenyl 10, 1 9, 8 9, 8 9, 8 7, 4 9, 9 9, 9 the II-II 9 dd 7, 9 7 dd 8, 7 7, 3 6, 5 9, 9 9, 9 9 û 208 It!! 8 8 8 7 9 8 9 4 Chloro-2, 6-dinitrophenyl 10, 1 6, 0 8, 6 9, 7 1, 0 9, 4 4, 0 the II 7 hr 8 dd 7, 3 dd 5, 2 6, 3 4, 4 9, 8 7, 8 3 iI-n-U-u - ft - - 1 Û 20, 2 7 7 8 7 9 9 4 2, 6 A-dinitrobenzoic 4-trifluoromethylphenyl (derivative, n-alanine 10, 1 8, 1 8, 6 8, 6 0 8, 3 7, 3 The II 9 dd 3, 2 dd 2 ll 3, 1 2, 0 3, 1 9, 4 7, 6 0 j.|20 U. HM 3 R NHCHCON (HM3 )2 THE R= Dosage Growth inhibition in Pre-emergence (seeds) dd post emergence (plants) per kg/ha. Soil spray dd spray of foliage dd dosage Soaking the ground Am WITH I P L The Mo BSs||AD-II WITH I P L The Mo MBSS dd kg./ ha. Am WITH I P L The Mo BSS 2-methyl 4-chlorophenyl 10, 1 3, 0 3, 0 0 6, 0 9, 5 8, 2 The II!! 6 0 0 II-I-n- 1, 0 1, 0 6, 1 8, 2 8, 2 It ' 7" 20 of O11 3 THAT 9 0 0 0 0 0 0 0 2-nitrophenyl 10, 1 2, 0 7, 0 7, 0 4, 0 0 3, 0 0 0 iI-II-II-ii 3, 1 2, 1 6, 1 2, 1 8, 4 THE II 8 20, 1!!11 1 ((LL 5 5 4 2 6 4 2 2, 4-dinitrophenyl 10, 1 0 1, 0 0 0 0 5, 0 4 E 1 1, 0 M IN THE II 1, 0 1, 0 2, 1 5, 4 5, 4 2 20, 1!!11 1 it ll 0 0 0 0 3 1 0 2, 6-dinitrophenyl 10, 1 5, 0 6, 1 7, 0 1, 0 5, 0 8, 0 the I! 7 6 2 2 II-n-n-it 8, 1 7, 1 6, 2 9, 4 9, 8 The II 9 m to 20 C.11 5 Hr-II 5 7 9 5 9 9 9 2-nitrate 4-trifluoromethylphenyl 10, 1 0 0 0 0 0 4, 0 the II 2 0 U-0 THE I! 1, 0 2, 0 2, 0 5, 1 8, 7 the II 8 5 20 U-n-NM 0 2 5 2 2 5 5 2, 6 A-dinitrobenzoic 4-trifluoromethylphenyl 10, 1 0 0 0 0 3, 1 1, 3 the II 2 dd 2, 3 n-1 dd 0 1, 0 3, 0 3, 1 7, 1 5 dD 200 The H-II 2 1 3 1 6 5 3 /NR °2 II-II-II-II-II-II-II-II-II-II-II-m-IIL! it ll ll ll ll 1 H-I-II-II which it I the II - The II-II-II-II-II which is U it-making it it a multiple-n-n-n-it a U II U-multiple-plate -. J., L. /NR °2 / ( 'H3 Amount in kg/ha. Growth inhibition Pre-emergence (seeds) dd post emergence (plants) Soil spray dd spray of foliage dd Soaking the ground THE M: i I P L The Mo ll BSs!! 1 U-am) WITH I P L The MC It dosage) BSs ll it kilograms/Ka- Am WITH I P L The Mo BSS - NHCH2 HM3 10, 1 6, 1 8, 7 8, 1 0 9, 3 8, 1 the II 9" 7 4 1 m in the II-II 8, 6 8, 3 5, 2 7, 5 8, 7 9 II in 20, 6 II in the m 0 8 7 4 9 7 6 - NHCH2 HM=HM2 10, 1 7, 0 9, 5 8, 2 0 8, 0 7, 0 the II 8 m to 3 2 hr 1 II-it 6, 2 7, 1 5, 0 8, 5 8, 6 8 II in 20 hr 7 I-III; 2 6 7 1 8 7 7 - NHCH (HM) HC " HM 10, 1 1, 0 0 0 0 3, 0 1, 0 THE II3 THE II2°ii1 1, 1 1, 0 4, 1 6, 2 7, 5 the II 8 hr 20 1 it 1 the I 1 1 4 4 4 the n - (HC2 hM3 )2 10, 1 0 0 0 0 2, 0 2, 0 6|II-j-m is 5, 0 3 dd 6, 3 3, 1 4, 1 9, 5 7, 7 the II 9 20 dd 6 5 0 the I 4 0 7 2 6 5 - O-.h NHCs . 10, 1 0 4 4 0 0 0 0 THE II the O THE II 2 It 0 to n 0 0 0 5, 4 4, 2 7 hr 20, 5 dd 11 ^ ll hr 0 0 0 0 0 0 0 ^ _HM 3_N ^ ^C 6H 5 10, 1 0 0 0 0 2, 0 0 THE II-II ÎJ 2 011 1 it1 it is H-II 1, 0 0 0 6, 5 6, 3 ll it 8 dd 20, 611 H-II-it II in degrees 0 0 0 0 0 0 0 1. piperidine derivatives 10, 1 0 0 0 0 0 0 it o!! O-about H M. 0 0 2, 0 4, 1 9, 6 3 m to 20 ddthe U it ll 0 0 0 0 4 0 0 - nhn (HM3 )2 10 _J_i 0, 1. 0 0 0 4 °l 3, 0 4 hr 1, 0 1 II in the II-II 3, 1 1°| 3, 1 6 981 4 dd 20, 9 THE II 4 THE II 1 i therein 2 4 6 1 1 7, 1 9 2 /N0 2 ^ ^ NH-R- Amount in kg/ha. Growth inhibition ITs preemergence (seeds) dd post emergence (plants) U-it '=R2 iI-it-soil spray]] spray of foliage] j-dosage11, 11 the LL Uin Soaking the ground Am WITH I P L The Mo Bs and the II - II-I-U-am! WITH I P L The Mo the bs!! 11/kg./o û ha_ Am WITH I P L The Mo BSS CLCHC ^.the X the NH (CH23 ) 10, 1 0 0 1, 0 0 3, 0 4, 0 the II-II the II! 6, 1 4 0 4 II-II-II inhibitor 6, 4 6, 2 5, 3 6, 5 8, 8 11, 8 The II-II wears||20 7 0 6 7 0 7 5 5 HM - HMthe X the n (HM3 )2 10, 1 0 1, 0 0 0 2, 0 5, 0 The II!! 3 2 0 2! I-II-II-U-ll (1 2, 1 2, 1 3, 2 6, 2 9, 7 8||20 II-O-II in the II " 0 2 6 0 8 9 5 for CHCR -|" NHCH CH-CH-SCH LAYER 10, 1 0 0 0 0 2, 0 6, 0 The II 3 2 it!! I-O-U-U-U-U-U-it-II 4, 0 2, 0 3, 1 8, 7 9, 8 20, 11 9 7 u-II in the II11 2 wears it wears the U-U-lu 1 4 6 2 9 9 1 EXAMPLE XVII PROPERTIES - Evaluation of compounds on the premises.
Compound per kg/ha. The total grass N-methyl 2 - (4 methyl 2, 6 - 2 161 dinitroanilino) propionamide hydrochloride 4 62 Non - (3.4-dichlorophenyl) - n-, N. 2 320 dimethylurea 4 136 - 558 500 Without treatment - 590 - 652