IL32178A - N-cycloalkane-substituted nitroanilines and their helical barbed tape unit use as herbicides - Google Patents

Description

and use herbicides ESSO HBSEARCH AND ENGINEERING COMPANY 30491 2 This Invention relates to novel cycloalkane tives of nitrated aniline compounds and their use as particularly as When so used the compounds are preferably formulated vith a diluent derivatives of nitrated compounds use as herbicides are well known in the For a commercial herbicide known in the art as is closed in Patent herbicidally active sulfanilamides of the structure in which and are the same or different and are among others alkenyl or may also be and are the same or different are each with the proviso that when one of them is hydrogen then the other contains less than 7 carbon atoms and when neither of them is they a total of not more than 4 carbon are disclosed in Patent 2a aromatic amines of the formula in which R is lower methyl or lower alkyl is alk preferably cyclohexylmethyl or and n 1 or known from Patents and have a selective herbicidal activity against The cycloalkane derivatives of nitrated aryl compounds of this invention characterized by the formula 3 2 to 6 carbon atoms or is hydrogen or and or where R is with the proviso that when and are all cannot be are biologically active especially useful as herbicides of broad spectrum of activity and are well tolerated by desirable An especially preferred nitrated aniline cyclopropane derivative according to the invention is the compound of formula The compounds of formula I can be readily prepared by the following synthetic For the preferred method for preparation of these products comprises reaction of the highly reactive compound trifluoride with an amine of the general structure where and have the same meanings as TYPICAL REACTION CONDITIONS FOR PREPAR WOULD S Molar Ratio of Reactants 1 trifluoride propyl amine 1 triethyl amine TYPICAL REACTION CONDITIONS FOR PREPARATION OF AM T Molar Ratio of Reactants Preferred Solve Step Cyclopropanecarboxylic acid to 1 toluen chloride 1 c chlorinated hyd amine 2 Step to 1 t carboxamide ben lithium aluminum hydride laniline and aniline Preferred solid carriers can be natural occurring minerals for example diatomaceous mineral silicates such as and clays of the or attapulgite calcium or magnesium or calcite and Carriers produced as for synthetic hydrated silica oxides and synthetic calcium silicates or an elemental substance such as sulfur or preferably an activated can also be For some a resinous or waxy carrier can be preferably one which is or including fusible Examples of such carriers are natural or synthetic resins such as a coumarone polyvinyl styrene polymers and a solid grade of polychlorophenol such as is available under the registered trademark a an a wax for example beeswax or a mineral wax such as paraffin wax or montan or a chlorinated mineral a microcrystalline wax such as those available under the registered trademark Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted Fluid carriers can be as for or an organic including a liquified normally vaporous or gaseous or a vaporous or gaseous and can be solvents or for the active For about to about and having an unsul onatable residue of at least about preferably of at least about or mixtures of these two types of are particularly suitable liquid The carrier can be mixed or formulated with the active material during its manufacture or at any stage The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the One or more can be used in The compositions of this invention can be suitable for storage or transport and for from about 5 to about weight of the active preferably from about 20 to about 80 These concentrates can be diluted with the same of different carrier to a tion suitable for The compositions of this tion may also be dilute compositions suitable for in concentrations of about to about by of active material based on the total weight of the composition are although lower and higher concentrations can e applied if the compositions can suitably contain from about 0 to about by weight of the active ingredient The compositions of this invention can also be lated as they can be formulated as table powders comprising a proportion of the active ingredient mixed with a deflocculating or if a finely divided solid carrier a wetting The active ingredient can be particulate form or adsorbed on the carrier and preferably constitutes at least about more preferably at least about about by weight of the total although larger or smaller amounts can be used if The dispersing agents used can be protective colloids such as or a synthetic polymeric material such as polyvinyl alcohol and methyl the dispersants used are sodium or calcium salts of high molecular weight sulfonic acids for the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors The calcium or sodium salts of condensed sulfonic for the products known as are also The wetting agents used can be type as for the condensation products of fatty acids containing at least preferably l6 to carbon atoms the or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or propylene or with for the condensation product of oleic acid and ethylene oxide containing about to ethylene oxide units in the Other wetting agents like polyalkylene oxide commercially known as can be Partial esters of the above acids with polyhydric alcohols as or mannitol can also be Suitable anionic wetting agents include the alkali metal preferably sodium of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a for the sodium secondary dialkyl sodium sulfosuccinate available under the registered trademark sodium salts of sulfonated castor therein are also included in this The carrier used can consist of or contain a fertilizer or fertilizer as for a The compositions of this invention can also be lated as solutions of the active ingredient in an organic vent or mixture of such as for example alcohols especially acetone ethers Where the toxicant itself is a liquid these materials can be sprayed on crops or insects without further Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above an example of this being a refined aromatic extract of Auxiliary solvents such as and polyalkylene glycol ethers and esters can be used in conjunction with these leum Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic preferably a organic containing an added emulsifying These concentrates can also contain a proportion of for up to about by based on the total to facilitate subsequent dilution with Suitable organic liquids the above petroleum hydrocarbon fractions previously The present invention is further illustrated in greater detail by the following EXAMPLE 1 Preparation of luoride and a maximum of The resultant deep reaction mixture was heated at to for two hours with casional After cooling the ether was added and the insoluble the amine was removed by The filtrate was washed with 60 portions of hydrochloric acid and and then dried with The ether was removed under leaving the oily residue of The was then crystallized by dissolving in hexane and chilling the solution with stirring in a The resulting bright yellow solids which were obtained upon filtering melted at Elemental The nuclear magnetic resonance spectrum of this compound was consistent with its proposed EXAMPLE 2 Preparation of trifluorometh In a reaction flask was placed 3 benzotrifluoride and triethylamine dissolved in 800 ml of The solution was cooled to approximately with stirring and 35 7 dissolved in 100 ml of was added dropwise over The mixture was refluxed for hours and then allowed to Filtration of the solids gave a filtrate which was washed with HC1 and After drying the solution with the solvent was removed at reduced pressure to yield a yellow solid which was lized from cold The product obtained was Elemental The nuclear magnetic resonance spectrum substantiated its posed EXAMPLE 3 Preparation of Addition of an ether solution of to propylmeth and dissolved in yielded a precipitate of amine The mixture was heated at reflux for one and The after workup in usual yielded orange in a yield of The product was crystallized from petroleum ether and had a melting point range of Elemental EXAMPLE 4 Preparation of trifluoromethy Following the general procedure of Example was reacted with 3 to yield grams of after recrystalliza from hexane The material melted at Elemental EXAMPLE 5 Preparation of According to the general procedure of Example to yield the which was recrystallized from hexane and had a melting point range of Elemental 4 EXAMPLE 6 Preparation of trifluorometh Following the general procedure of Example amine was reacted with to yield grams of crude Recrystallization of this material from hexane gave a product having a melting point range of Elemental EXAMPLE 7 Preparation of cloprop lanlline To a suspension of sulfone in 60 ml of methanol was added solved in twice its volume of methanol over a period of 10 A slight exothermic reaction was noted as yellow colored solids formed during the The mixture was heated at reflux for approximately one chilled to and then This process effected the separation of the product from the amine hydrochloride The golden crystalline product was recrystallized from hot The melting point range of this final product was Elemental EXAMPLE 8 Preparation of Following the general procedure of Example was reacted with methylsulfone to give a crystalline product melting at after recrystallization from Elemental EXAMPLE Preparation of Following the procedure of Example was reacted with methylsulfone to yield a product melting at Elemental EXAMPLE 10 Preparation of According to the general procedure of Example was reacted with methylsul one to give a product melting at Elemental EXAMPLE 11 Preparation of a suitable reaction flask was placed dinitrobenzene and benzene To this dropwise at room The resulting solution was refluxed for 15 After cooling the solution and filtering off the amine the filtrate was washed with then with and finally dried with Removal of the solvent under reduced pressure yielded a viscous red oil which soon crystallized to a yellow solid weighing Recrystallization from a ether mixture gave a product melting at Elemental EXAMPLE 12 Preparation of Following the general procedurerof Example was reacted with to yield a product melting at after the usual workup and recrystallization from Elemental EXAMPLE Preparation of was dissolved in 100 ml of To this stirred solution was added a solution of dropwise over a period of The resulting solution was refluxed for 40 Workup of the product in the usual manner gave a bright yellow solid melting at Elemental EXAMPLE l4 Preparation of trifluorometh Cyclopropylmethylamine hydrochloride prepared according to the procedure of Roberts and Mazur was dissolved in 20 ml of A solution of grams of sodium hydroxide was followed by a addition of solid The resulting mixture was refluxed for one After the oily product was separated from the aqueous phase and dissolved in boiling Chilling of the alcoholic solution precipitated solids which were filtered and air and had a melting point range of Elemental EXAMPLE 15 Preparation of According to the general procedure of Example was reacted with using benzene as a The reflux time was extended to 21 Workup of the reaction mixture in the usual way yielded a red which when subjected to vacuum gave a main cut of red oil having a boiling point range of at of Elemental EXAMPLE l6 According to the general procedures outlined in the preceding the following additional compounds were Elemental Elemental thlo meth Elemental 4 Elemental Elemental clobuty lmethy luorometh Elemental lmethy luoromethy Elemental Elemental ί room and filtered to remove the insoluble white hydrochloride The filtrate was washed successively with 150 ml portions of 10 and The solution after being dried with drous was stripped of solvent to yield a crude oil 108 which crystallized to a solid upon A sample was recrystallized from petroleum ether at temperatures to give material melting at Elemental 10 EXAMPLE 18 Preparation of a reaction flask was placed a suspension of lithium aluminum hydride 30 in anhydrous ether 1 A nitrogen was held over the mixture out the To the stirred mixture was added dropwise a solution of 50 0 in 300 ml of dry ether over a period of two Gentle refluxlng of the solvent was evident during the After the addition was the mixture was heated at reflux for approximately 10 The solution was cooled with an ice while aqueous sodium hydroxide was cautiously added dropwise to destroy the unreacted lithium aluminum The resulting white aluminate salts were removed by filtration and the clear ethereal filtrate was dried with potassium hydroxide After the ether was removed by the was distilled at atmospheric pressure and found to have a boiling point range of The yield was 27 Elemental 10 97 times with The acidic aqueous solution was basified with excess aqueous sodium and the amine which formed an insoluble upper layer was extracted with After ing the ether solution with KOH the distillation cedure as described above was carried Exemplary of products prepared in accordance with the procedures set forth in Examples are those listed in Table II TABLE II CONHR2 Nitrogen Analysis Pound Calculated b CH3 48 51 91 9 CH2CH3 110 34 35 136 91 92 12 36 37 158 56 58 168 NMR spectroscopy was used to verify the structures indicated in this EXAMPLE 19 which are used in the i preparation of compounds illustrated by Example and may be synthesized by reduction of the corresponding amides under mild The method of Brown and JACS 3566 utilizing diborane as the reducing can be used to prepare these The following synthesis shows the general In a flask was placed ml of a 1 borane in hydrofuran solution The solution was cooled to approximately and a solution of acetamide in tetrahydrofuran was added dropwise with stirring over a period of 60 maintaining a temperature of The solution was heated at reflux for three hours and then cooled to room About of N HCl solution was added dropwise and the reaction ture was heated to reflux for The drofuran was removed by distillation at atmospheric pressure and the residue was made basic with excess NaOH This basic solution was extracted with ether and the extracts were dried over KOH Distillation afforded grams of lamine boiling at The structure was confirmed by its nuclear magnetic resonance EXAMPLE 20 Representative nitrated aryl cycloalkane derivatives from those prepared in the previous examples were evaluated for herbicidal activity in this The test procedure employed was as velvet Johnson and were sprayed with a formulation containing the test chemical at a rate equivalent to 10 The test chemicals were sprayed as acetone solutions or very small particle acetone suspensions onto the test Sprayers were calibrated to deliver a certain volume of liquid and the calculated amount of active ingredient which would give a rate corresponding to the indicated The flats were then held in the greenhouse and a response rated after 12 days to 16 Response was rated by a scale of The scale is fined slight moderate plants may severe plants will probably and 10 all plants dead Treflan was used as the standard the amount of Results of this test are shown below in Table III and it is indicative that many of these compounds show a high degree of herblcidal activity against certain weed yet remain highly tolerant of desirable crop O O o o O O O o o O ro o o Soybean Ω 3 H H o o 0C o o Cotton a ro ro OJ rovo o o Rice a Morning a ui ro HVJ1 ro H roui o o o ro Rice a Morning EXAMPLE 21 In this example representative cycloalkane tives of the nitrated aryl compounds of this invention were evaluated for The test procedure was as Flats were as described in the previous and held the first true leaves had appeared on all which were then sprayed in the same fashion as in the preceding example at a rate of 10 The plant responses were rated days after treatment on the same scale as described The test results are shown in Table EXAMPLE 22 this example a herbicide study was carried out to compare the activity of the commercial material Tre with that of a specific example disclosed in this namely dinitroaniline Tests were carried out on a number of crop and weed species and the chemicals were applied to the surface the soil as well as incorporated into the Observations were made four weeks after the planting date to determine the relative effects on the crops as well as the overall effect on broadleaf weed species and grassy weed The data is summarized in Table The results show that in general the scope of activity of both compounds against weed species is quite in the cyclopropyl tive appears to show some unexpected crop tolerance which exceeds the tolerance of Treflan to these same H Rate O O O o O o lbs H Ω o o c o o ro ro Corn Ω ro UJ l Soybean H o o o UJ ro Cotton o O ro ro ro o UJ l ro Rice Mornin Ω TABLE V Rate Treatment Cotton Soybeans Corn Suga 6 9 5 4 9 CPTD broadleaved weeds S surface app grassy weeds I soil incorp EXAMPLE 23 The effect of against a series of weeds in a soil incorporated herbicide test was carried out at a rate of The data is marized Quack Johnson Annual Yellow Barnyard grass grass Rye foxtail grass grass 7 8 9 8 9 acre Examples 24 and illustrate typical pesticidal compositions or formulations of this Parts are by weight EXAMPLE 24 A typical wettable powder concentrate that is diluted to the desired concentration by dispersing it in water has the following Parts Active Ingredient 50 Solid Carrier 42 of polymeric alkylaryl sulfonic 4 Wetting Agent Alkyl Naphthalene Sulfate 4 EXAMPLE A liquid concentrate that is diluted in the field ί with water has the following 1 Parts Active Ingredient X lene of calcium dodecyl benzenesulfonate and alkyl aryl poly 33 insufficientOCRQuality

Claims (1)

1. CLAIMS nitroanlllnee of the formula wherein is is 4 and n ie 0 or is vith 2 to carbon atoms or is hydrogen or and cyano or where R is with the proviso that when and are all cannot be Compounds according to Claim o the ormula and can be or a group where R is 34 insufficientOCRQuality