IE44488B1 - 2,6 dinitroaniline herbicides - Google Patents

Abstract

This invention relates to certain novel substituted 2,6-dinitroaniline compounds of formula (I) wherein R2 is sec-alkyl C3-C7; monochloro-sec-alkyl C3-C4 or methoxy-sec-alkyl C3-C4; Z is -CHR3OCH3, R3 being hydrogen or-CH3 and Y is chloro or alkyl selected from the group consisting of -CH3, -C2H5, n-Pr, i-Pr, sec-Bu and i-Bu, and compounds of formula (I) selected from the group wherein: z is -CH3; and R2 and Y respectively are -CH(C2H5)2 and i-Pr or -CH(C2H5)2 and -C2H5 or -CH(C2H5)2 and sec-Bu or -CH(C2H5)2 and n-Pr or-CH(C2H5)2 and n-Bu or i-Pr and -C2H5 or sec-Bu and -C2H5 or i-Pr and i-Pr or i-Pr and n-Pr or sec-Bu and i-Pr or -CH(C2H5)-CH2Cl and -Cl or sec-Bu and n-Pr and compounds of formula (I) selected from the group wherein: R2 is i-C4H9 or n-Pr, Z is-CH2OCH3 and Y is i-Pr or -CH3 or -C2H5; R2 is -CH(C2H5)2, Y is n-Bu and Z is CH2OCH3; or R2 is n-Bu, Z is -CH2OCH3 and Y is i-Pr; R2 is i-Pr, Z is -CH2OCH3 and Y is n-C4H9; R2 is CH(C2H5)2, Z is CH2OC2H5 and Y is CH3. It further relates to certain novel preemergence herbicidal methods and compositions employing substituted 2,6-dinitroaniline compounds.

Description

This invention relates to certain 2,6-dinitroaniIines and to their use in herbicidal compositions.

The herbicide art is replete with substituted 2,6-dinitroaniline herbicides having various levels of efficacy.

The novel compounds of the present invention may be represented by the following structural formula H. '2' (I) wherein ’ (a) K2 is soc-alkyl c^~cy’ monochloro-sec-alkyl C3-C4 or methoxy-sec-alkyl (1$ or C^; Z is-CHR3OCH3, R3 being hydrogen or -CH^: and Y is chloro or alkyl selected from -C2Hg > n-Pr, i-Pr, sec-Bu and i-Bu; (b) Z is "CH3; and R2and Y respectively are -CH(C2Hg)2 and i-Pr or -CH(C2Hg)2 and -C^g or -CH and sec-Bu or -CH(C2H5)2 and n-Pr or -CH (C2H5) 2 and 2-Bu °r i"Pr and -c2n5 or sec~Bu an<3 -C2H5 or i-Pr and i-Pr or sec-Bu and i-Pr or -CH(C2H5)CH2C1 and -Cl or -CH(CHg)-n-Pr and -C2Hg or CH(C2H5)CH2C1 and -C2H5 or CH(CH3)CH2C1 and -C2Hg or -CH(CH3)CH2CH2C1 and -C2Hg or -CH(C2Hg)-n-Pr and -C2Hg or sec-Bu and n-Pr or -CH(CH^)-n-Pr and n-Pr or CH(CH3)-n-Pr and i-Pr or -CH(C2Hg)CH2Cl and n-Pr or -CH(C2H5)CH2C1 and i-Pr or -CH(CH^)CH2C1 and n-Pr or -CH(CH3)CH2C1 and i-Pr or -CHiCH^C^CH^l and n-Pr or -CH(CH3)CH2CH2C1 and i-Pr or -CH(C2Hg)-n-Pr and n-Pr or -CH(C2H5)-n-Pr and i-Pr or -CH(CII3)CH2OCH3 and -C2Hg or -CH(CH3)CiI2OCH3 and n-Pr or -CH(CH3)CH2OCH3 and i-Pr or -CH(C2H5)CH2OCH3 and i-Pr or -CH(CH3)CH2CH2OCH3 and -CH3 or -CH(CH3)CH2CH2OCH3 and -C2H5 or -CH(CH3)CH2CH2OCH3 and n-'t’r or -CH(CH3)CH2OCH3 and i~Pr; (c) P2 is i-iJu or ji-Pr, z is -CH2OCH3 and Y is i-Pr R2 is -CH(C2Hg)2 and or -CH3 or -C2H5? (d) Y is rr -Bu and Z is -CH2OCH3; (e)RZ is Π-BU, Z is -CH20CH3 and Y is i-Pr; (f) r2 is i_-Pr, Z is -CHgOCHg and Y is _n-Bu; or (g) r2 is CHfCgHg^, Z is -CH20C2H5, and Y is -ch3 Β © Within this class of compounds, those having a methoxymethylene substituent meta to the amino group are especially preferred. This is based upon the unexpected enhancement in the preemergence herbicidal activity attributable to a methoxy substituent on a meta methyl group. Coupled with the usefulness of these compounds as a preferred compound within this category is N-(l-ethylpropyl)-2,6-dinitro-3-methojcymethyl-g-toluidine.

The preemergenqe herbicidal method of the present invention comprises application of a herbicidally effective amount of one or more of the above novel compounds to the soil containing the seeds of undesirable plant species to be controlled.

The postemergence herbicidal method of the present invention comprises application of a herbicidally effective amount of one or more of the above novel compounds wherein Z is -CH2OCH3 to the foliage of the undesirable plants to be controlled.

Preferably, application of the active .ingredients is made using the herbicidal compositions described below with conventional application methods.

The herbicidal compositions of the present invention are solid or liquid formulations comprising an effective amount of one or more of the novel 2,6-dinitroaniline compounds with a herbicidal adjuvant, i.e., an inert carrier or other conventional formulation aid. > Preparation of said compositions broadly involves admixing an effective amount of the herbicidal agent and adjuvant.

The usual use of the compounds of the present - 4 44488 invention broadly involves application of an effective amount thereof, preferably formulated as a herbicidal composition as described above to the soil containing seeds of the plants to be controlled.

Typical formulations include, for example, dusts, dust concentrates, wettable powders and granules. Application by conventional methods and equipment is usually made at rates of from 1/6 pound per acre to 20 pounds per acre and preferably 1/4 to 8 pounds per acre of active material.

Dusts are generally prepared by grinding together from about 1% to 15% by weight of the active material with from 99% to 85% by weight of a solid diluent, such as an attaclay, kaolin, diatomaceous earth, fullers earth, talc, pumice, or the like.

Dust concentrates are prepared in similar fashion to the dusts excepting that generally 15% to 95% by weight of active material us used.

Granular formulations may be prepared by applying a liquid solution of the active material to sorptive granular carriers, such as attaclay, kaolin, or diatomite granules. Alternatively, the active compounds may be mixed with inert carriers and applied to non-sorptive granules, such as sand or limestone.

Wettable powders are prepared by grinding the active ingredient with a solid carrier, such as usedin the dust formulations. Usually, 25% to 75% by weight of the active material and from 73% to 23% by weight of solid carrier is used. In addition, there is generally added 1% to 5% by weight of a dispersing agent, such as alkali metal salts of naphthalene sulfuric acid and anionic-nonionic blends, and from 1¾ to 5¾ by weight of a surfactant, such as polyoxyethylene alcohols, acids, adducts, sorbitan fatty acid esters and sorbitol esters.

Thus, in general, herbicidal compositions in accordance with the present invention are admixtures of from 1% to 95% of active ingredient with the remainder being one or more herbicidal adjuvant or formulation aid. Particular preferred ranges for various types of compositions are specified above. As mentioned, they are used in a conventional manner as such or with further dilution depending upon the particular circumstances facing the farmer.

The wettable powder formulations are usually dispersed in water and applied as a liquid spray to the area or locus where control of undesirable plant species is desired.

For use as preemergence herbicides, the dusts or liquid sprays containing the active compound can be applied to the soil shortly after planting or they may be incorporated Into the soil by the technique referred to as preplant incorporation.

For use as postemergence herbicies, application is made to the foliage of the undesired plant species.

The preferred chemical process of the present invention involves the one step nucleophilic substitution reaction between an alkali metal methoxide and a 2-methyl-5-nitrobenzyl compound to produce methyl 2-methyl-5-nitrobenzyl - 6 44488 I ether and the obvious equivalents thereof. The ether is a useful intermediate in the preparation of meta-methoxymethylene compounds of formula (I) .

This reaction is graphically depicted below: CH, CH, " -J (II) (III) (IV) wherein M is an alkali metal and X is a leaving benzyl substituent, preferably Chloro, bromo or tosyl. 2-Methyl-5-nitrobenzyl chloride is preferred as the formula (IX) compound. It is preferred to employ meth15 anol or a non-protic organic solvent such as dimethoxyothane or benzene as a solvent for this reaction. The conversion can conveniently be conducted by admixing the reactants and heating at temperatures varying from room temperature to about 30°C. When using methanol, heating to reflux is preferred to avoid the need to resort to sealed containers.

Other reactions useful in conjunction with the present invention are set forth in the illustrations below.

As the base, sodium or potassium methoxide are preferred. The reaction is pref rably conducted by heating the reactants in an organic solvent. An alcohol, such as methanol may be used as the reaction medium.

Another approach to the synthesis of various dinitroaniline conipoundE which can be employed in the practice of the present invention involves a nucleophilic· substitution of a 1-substituent, such as a chloro group, with the appropriately substituted amine. While chloro is a preferred substituent,. and the discussion is in terms .5 thereof other conventional equivalent substituents, such as bromo or iodo are included therein. The displacement may be conducted with or without an organic solvent, such as toluene, benzene or preferably xylene.

The reaction, which is illustrated / below, is carried out by heating the reactants, preferably at between 50°C. and 15O°C.

(V) Ra xylane (15 (VI) The chlorobenzene intermediates can be prepared by reacting an appropriate 3,4-substitUted aniline with ethyl chloroformate in benzene at about 10°C. to 50°C, to yield the correspondingly substituted N-(ethoxycarbonyl)-3,4-substiiuted aniline. This product is then treated with a cold solution of sulfuric and nitric acid, i.e. at about 0°C. to 20°C. to obtain the N-(eth25 oxycarbonyl)-3,4-disubstitUted-2,6-dinitronailine. Reaction of the thus-formed product with sulfuric acid at an elevated-temperature, preferably between 100°C. and 150°C., converts the N-(ethoxycarbonyl) product to the 3,4-disubstituted-2,6-dinitroaniline. The amino group is replaced by a chlorine atom by first heating the compound with glacial acetic acid and diazotizing the amine with a mixture of sodium nitrite in sulfuric acid. This is followed by treating the diazotized mixture with a mixture of cuprous chloride in hydrochloric acid, and then heating the thus5 formed mixture to about 40°C. to 80°C. to obtain the chlorinated compound.

A preferred route for the preparation of compounds of formula (I) wherein Rc is a monochloro-sec-alkyl group involves the reaction of the appropriate hydroxyalkyl amine with the formula (V) compound. The resulting N-hydroxyalkyl aniline is converted into the desired N-chloroalkylaniline or formula (I) by reacting it with SOCl^.

According to another aspect of the invention we provide a method of preparing compounds in accordance with the invention comprising a method for making a compound of the structure in which R2, Z and Y are as defined above, which comprises reacting a compound having the formula Y CHR3X wherein 1 is chloro, bromo or tosyl, Rg is H or CHg and Y has the identity required to provide the final compound; with an at least equimolar amount of an alkali metal methoxide or alkali metal ethoxide in the presence of a lower alkyl alcohol or nonprotic organic solvent, at a temperature between ambient and 80°C to yield the compound of formula: •Z (A) wherein Z1 is -CHgOCH^j-CHOCHg, or -CHgOCgHgj and either C&3 a) subjecting compound (A) to reductive alkylation using an appropriate ketone, to yield a compound of the formula: IHR2 y., Y or b) reducing compound (A) with an alkali metal sulfide to the corresponding 3-(alkoxyalkyl)-4-substituted aniline; reacting the thus formed aniline, in the presence of a molecular sieve, with a ketone to yield a compound of the formula: N =Q (C) wherein Q is a C3-Cy alkylidene group derived from the ketone and then reducing the compound (C) to yield a compound having the formula: nhr2 Y (D) and then nitrating the thus formed amine from a) or b).

When an asymmetric carbon atom exists in the dinitroaniline compounds above, optical isomerism may exist. Accordingly such compounds may be employed as separate enantiomers or in admixture, as in a racemic composition. Unless there is indication to the contrary by reference to such a compound, the unresolved composition is intended herein. Separation of enantiomers, where desired may be effected by conventional resolution techniques.

A convenient method relates to the introduction of an optically active substituent, such as a (-)-sec-butylamino group into the ring system, as by nucleophilic substitution.

The present invention and preparation of the active ingredients is further· illustrated by the following Examples and Illustrations. Parts and percentages herein are by weight unless otherwise indicated.

Illustration A Preparation of 3-(Methoxymethyl)-p-toluidine Methyl 2-methyl-5-nitrobenzyl ether (11.5 g.) was dissolved in 125 ml. cf absolute ethanol. To this was added a solution of sodium sulfide monohydrate (48.3 g.) and sodium bicarbonate (15.7 g.) in 75 ml. of water. The resulting mixture was refluxed until tic indicated all the starting material was gone. The mixture was then concentrated in vacuo to an oily solid. Methylene chloride was added and the mixture filtered. The methylene chloride layer was separated and dried. After removal of the drying agent, the solvent was concentrated in vacuo to give 9.3 g. of a mobile orange liquid which was used to prepare the compound of Illustration B.

Illustration B Preparation of M-(1-Ethylpropyl)-3-(Methoxymethyl)-p-toluidine A slurry of 3-(methoxymethyl)-p-toluidine (9.3 g.) in 40 ml. of diethyl ketone and 5A molecular sieves (19 g.) was stirred at room temperature for 15 hours.

The mixture was then filtered and the filtrate treated with more diethyl ketone (10-15 ml.) and fresh molecular sieves (10 g.). After 40 minutes at 40-50°C., the mixture was filtered and concentrated in vacuo. The crude product (9.0 g.) was dissolved in 50 ml. of methanol and cooled to 10°C. Then sodium borohydride (3.7 g.) was added in small portions. During the addition more methanol (25 ml.) was added. Thirty minutes after the addition was complete, the mixture was made acidic with 10% hydrochloric acid and ice. The mixture was extracted with ether and the ether extract discarded. The aqueous extract was then made basic and extracted with ether.

After drying the ether extract over maqnesium sulfate, the drying agent was removed and the ether concentrated to an orange oil ¢8.1 g.) which by gas liquid chromatography was more than 97% one component. Fractional distillation gave a sample having a boiling point of 125°C. under a vacuum of 0.4-0.5 mm. The elemental analysis of the product was as follows: Calculated for C14H23NO: C, 75.97; H, 10.47; N, 6.33. Found: C, 75.87; H, 10.62; W, 6.24. Illustration C Preparation of K-(1-Ethylpropyl)-3-(methoxymethyl)-2,6-dinitro-p-toluidine; also named (l-ethylpropyl)-3-methis oxymethyl)-4-methyl-2,6-dinitroaniline A solution of N-(l-ethylpropyl)-3-(methoxymethyl) -p-toluidine (2.13 g.) in 10 ml. of dichloroethane was prepared and treated with a nitrating mixture consisting of 3.78 g. of nitric acid, 3.0 g. oi concen20 trated sulfuric acid, and 1.4 g. of water. The addition was carried out at 30°C. ί 3°C. and then held there for 3 hours. The crude product was poured into water and extracted with methylene chloride. The methylene chloride layer was separated and dried over magnesium sulfate Removal of the drying agent by filtration and concentration of the filtrate in vacuo left a residue of 3.2 g. ( ^> 100%). The crude product was purified by column chromatography on silica gel with benzene as the eluting agent. All fractions consisting of the same compound by tic were combined to give 1.3 g. of orange solid with m.p. 55-57°C. A sample recrystalliaed for analysis from hexane had m.p. 56-57°C. Its elemental analysis was: Calculated: C14H21N3O5: C, 54.01; H, 6.80; N, 13.50. Found: C, 54.00; H, 6.69; N, 13.44.

Illustration D Following the general procedure of Illustrations A-C and Example 111, the appropriate 4-alkyl nitrobenzene can be converted to a methyl 2-alkyl-5-nitrobenzyl ether followed by reductive alkylation with the appropriate ketone and then dinitration or alternatively following the procedure described in illustrations U-Z and using the appropriate 3-chloro-6-alkyl~2,4dinitrobenzyl methyl ether and the appropriate amine the following compounds of formula (I) wherein Z is -CHgOCH-j may be obtained. —2— Y MP °C C3H7-n CH3 67.5-69°C3H7-i (1 orange oil C^Hg-sec II orange oilc4H9~i II 41.5-43.5° CH(CH3)C3H7-n II 31.5-32.5 CH(CH3)C3H7-£ II orange oil CH(CHj)C^Hg-n It orange oil ch (c2h5 )C3H7-n II orange oil CH(CH3i C4Hg-i_ II 61-62° CH(C3H7-n)2 II orange oil CH(CH3)CH2C1 II 55-56.5° CH(C2H5)CH2C1 II red oil CH(CH3)CHC1CH3 II 93-97° C3H7-I1 θ2Ηε 45-46° MP °C 6367-½ c2h5 orange oil C4Hq-s«c H yellow-oranqe 11 orange oil CH(CH3)C3H7-n II orange oil ch(c2h5)2 II 27.5-29° CH(C2H5)C3H7-n 11 orange oil CHCCHgJC^-i 11 orange oil CH(C3H7-n)2 II orange oil CH(CH3)CH2C1 II 38-40° CH(C2Hs)CH2C1 11 yellow oil ch(ch3)ch2ch2ci II 62-63° CgH-y-n C3H7-i 45.5-48.5° C3H7-i 11 red-orange oilc4H9H II red oil C„Hg-sec II red oil 11 red oil CH(CH3)C3H7-n It red oil CH(C2H5)2 11 red-orange oil CH(CH3)C4Hg-n It red oil CH(C2H5)C3H7-n II red oil ch(c2h5)ch2ci It red oil ch(cii3)chcich3 red oil C3H7-i CgHy-n orange oil C4Hg~-SSC It orange oil ch(c2h5)2 It 42-43° CgHy-iC4H9-il orange oil ch(c2h5)2 II orange oil ch(c.,h5)2 CH(C2H5) C^Hg-sec CH(CH3)C3H7-n CH(C^H5)2 Illustration E Y MP °C C^Hg-sec orange oil It red-orangec4^9*i orange oil Cl 44-47° It orange oil II 70-72 Preparation of 2'-Methyl-5'-nitro-acetophenone 1q To 120 ml. of concentrated sulfuric acid was added 53.6 g. of o-methyl acetophenone, while cooling at -10°C. To this cold, stirred solution was added a mixture of 32 ml. of 70% nitric acid and 48 ml. of concentrated sulfuric acid. The reaction solution was stir15 red for 2 1/2 hours between -9° and 0°C. and then poured over 800 g. of ice. The mixture was extracted with ether and the organic phase washed with H2O, saturated Na^O^ solution, H2O and finally brine. The ether solution was dried over MgSO^ and evaporated to dryness to give 56.2 2Q g. of a pale yellow oil. The oil was crystallized from cold 95% ethanol to give 25.4 g. of product, m.p. about 50°C. Recrystallization from hexane afforded product, m.p. 53-55°C.

Illustration F Preparation of 1-(2'-Methyl-5'-nitrophenyl)-ethanol To a stirred mixture of 23.5 g. of 2'-methyl-5'-nitro acetophenone and 350 ml. of ethanol was added NaBH4 in one portion and the solution was stirred at room temperature for 1 3/4 hours. Water and 2N HC1 was added to give pH 5 and the solution concentrated to remove ethanol. The mixture was extracted with ether and the organic phase washed with water and brine. The solution was dried over MgSOd and evaporated to give 23.12 g. of a yellow oil. Hexane (150 ml.) was added and the resulting solid collected and washed with hexane affording 22.7 g. of crude product, m.p. 79-85°. Recrystallization from chloroform and hexane gave pure product, m.p. 85-88°.

Illustration G Preparation of a,2-Dimethyl-5-nitrobenzyl methyl ether 1-(2'-Methyl-5'-nitrophenyl)ethanol (0.9 g.) was dissolved in 5 ml. of benzene and 0.8 g. of 50% aqueous sodium hydroxide, 10 mg. of tetrabutyl ammonium chloride, 5 ml. of ether and 1.25 ml. of methyl iodide were added. The reaction mixture was stirred at room temperature for 2 hours and heated at 30-35° for 4 hours. An additional 1.0 ml. of methyl iodide was added and the mixture was stirred at room temperature for 22 hours. Thin layer chromatography indicates starting material remaining. Therefore, 0.52 ml. of 50% NaOH solution and 2.0 ml. of methyl iodide were added and the mixture stirred at room temperature for 5 days. Water was added and the mixture extracted with ether. The organic layer was washed with water and brine. The solution was evaporated to dryness giving 0.97 g. of oil which was purified by column chromatography to give pure material, m.p. 35-37°. 4 4θ® Illustration Η Preparation of N-(1-Ethylpropyl)-3-(1-methoxyethyl)-p-toluidine A mixture of 14.6 g. of a,2-dimethyl-5-nitrohenzene methyl ether, 100 ml. of diethyl ketone, 1.0 g. of S-naphthalene sulfonic acid and 1.5 g. of 5% Pt/C was hydrogenated using a Parr Hydrogenation apparatus.

After 22 hours the reaction mixture was filtered, the filtrate evaporated to dryness and water and ether added. This mixture was basified to pH 11 with IN NaOH and the organic phase separated and washed with water and brine. The ether solution after drying over MsSO4 and evaporation to dryness afforded 17.8 g. of an orange oil. Purification by column chromatography gave pure product as orange liquid.

Illustration I Preparation of N-(1-Ethylpropyl)-3-(1-methoxyethyl)-2,6-dinitro-£-toluidine To a stirred solution of 28 g. of 70% H2SO4 and 10.1 ml. of 70% HNO3 was added a solution of 9.41 g. of N-(l-ethylpropyl)-3-(1-methoxyethyl)-£-toluidine in 30 ml. of ethylene dichloride. The addition was accomplished at 25° to 32° over a period of 45 minutes. The reaction mixture was stirred at room temperature for 2 1/4 hours and warmed at 35-40° for 1 1/4 hours. After stirring overnight at room temperature, the organic layer was separated and washed with water and brine. The ethylene di chloride solution was mixed with 6 g. of NH2SO3H and 25 ml, of concentrated HC1 and the mixture stirred and heated at reflux for 5 1/2 hours. The reaction mixture was diluted with water and the organic layer separated and washed with water, saturated Na2CO2 solution, water and brine.

The ethylene dichloride solution after drying over MgSO^ and evaporation to dryness gave 9.35 g. of crude product as a red oil. Column chromatography afforded 5.27 g. of pure product.

Illustration. J Preparation of O-Cymen-5-aminehydrochloride Hydrogenation in 9555 of 2-isopropyl-5-nitrobenzyl chloride in 95% ethanol (100 ml.) and 10% palladium on carbon catalyst (0.5 g.) at 18 - 36° and -15 psi of hydrogen afforded 12.9 g. (93.5%) of o-cymen-5-amine hydrochloride after concentration of the filtered reaction solution. Recrystallization of the crude product from a mixture of 2-propanol and ethyl acetate gave the pure compound, m.p. 212-222°C.

Illustration K Preparation of N-(1-Ethylpropyl)-o-cymen-5-amine o-Cymene-5-amine (8.8 g., 0.064 mole, prepared by neutralization of cymene-5-amine hydrochloride with aqueous NaOH) was dissolved in 3-pentanone (43 g., 0.5 mole) and 5A molecular sieve (40 g.) was added. The mixture was shaken for 16 hours. Then the used 5A molecular sieve was removed by filtration and 40 g. more 5A molecular sieve was added. After 24 hours of agitation the mixture was filtered and the filtrate was concentrated to leave an oil (11.4 g.). A solution of the oil in absolute ethanol (60 ml.) was added rapidly to a cooled (12° C), stirred, mixture of sodium borohydride (partially dissolved) in absolute ethanol (100 ml.). Following the addition, the mixture was stirred for 1.5 hour at 25-27°. The resulting solution was treated with 4 4 θ ® 6Ν HC1 (30 ml.) to give pH 1, and then with 50% aqueous NaOH to give pH 10. The resulting mixture was filtered to remove inorganic solids, which were washed with ether. The ether washes were combined with the filtrate and the solution was concentrated to leave an oil which was dissolved in ether. The ether solution was washed with saturated aqueous sodium chloride, dried over MgSO^, and concentrated to leave 11.6 g. (87.2%) of N-(1-ethylpropyl) -cymen-5 -amine, a red liquid. Analysis by glc showed 99.6 area % purity.

Illustration L Preparation of N-(1-ethylpropyl)-o-cymen-5-amine A solution of o-cymen-5-amine (33.6 g., 0.24 mole) in 3-pentanone (300 nil.) was mixed with a catalyst consisting of 50% water-wet 5% platinum on carbon (5.9 g.) and 2-naphthalenesulfonic acid (1.1 g.) and subjected to 42.5-18.3 psi of hydrogen at 44° for ca 16 hours.

The mixture was cooled and filtered, and the filtrate was concentrated to leave a red liquid which was dissolved in ether. The ether solution was washed with 10% sodium hydroxide solution, dried over magnesium sulfate and concentrated to leave 45.1 g. (88.6%) of N-(1-ethylpropyl ) -o-cymen-5-amine of 99.3 area % purity by glc analysis.

Illustration M Preparation of N-(l-Ethylpropyl)-4,6-dinitro-o-cymen-S-amine A solution of N-(1-ethylpropyl)-o-cymen-5-amine (7.0 g., 0.034 mole) in ethylene dichloride (70 ml.) was cooled in ice during the successive addition of 70% sulfuric acid (16.8 g. of 70%, 0.12 mole) and 70% nitric 4 4 8 8 acid (14.0 g. of cone, nitric acid, 0.156 mole). The ice bath was then removed and the reaction mixture was stirred at 30-32°C. for 16 hours. The mixture was then poured on ice and the organic layer (diluted with chloro5 form) was separated, washed with aqueous sodium bicarbonate solution, dried over MgSO^, and concentrated in a rotary evaporator to leave 8.3 g. of a red liquid which was twice chromatographed on silica gel dry columns once with a 2:1 mixture of hexane and benzene and once with 1° hexane, to afford 4.3 g (41%) of the pure product.

Illustration N Preparation of 4,6-Dinitro-o-cymen-5-amine A mixture of 4,6-dinitro-N-(1-ethylpropyi)-o-cymen-5-amine (55 g., 0.18 mole) and aqueous sulfuric 15 acid (from concentrated sulfuric acid (680 ml.) and water (680 ml.) was stirred and heated at 70-75°C. for several hours. The mixture was then diluted with ice and water and extracted with chloroform to give 37.7 g. of crude 4,6-dinitro-o-cymen-5-amine, a liquid which crystallized, and which was determined to be 83 area % pure by glc analysis. Recrystallization from hexane gave the pure product, m.p. 67-68°C.

Illustration 0 Preparation of 5-Chloro-4,6-dinitro-o-cymene A solution of the amine prepared in illustration N (3.0 g., O-OJ,§iej in acetic acid (60 ml.) was added to a cooled (10-15°C.), stirred solution of sodium nitrite (1.35 g.), in concentrated sulfuric acid (10.5 ml.). The resulting mixture was stirred for 10 minutes at 10-15°C. and was then added 4448 slowly to a solution of cuprous chloride (1.5 g.) in concentrated hydrochloric acid (40 ml.). The resulting mixture was stirred at 22°C. for 2 hours, and the precipitated solid product was then filtered off from the cooled reaction mixture, washed with water, and dried in vacuo. The product was recrystallized from hexane to afford 2.1 g. of pure 5-chloro-4,6-dinitro-o-cymene, m.p. 76°C.

Illustration P Preparation of N-lsopropyl -4,6-dinitro-£-cymen-5-ann'ne A mixture of 5-chloro-4,6-dinitro-o-cymene (4.0 g., 0.0155 mole) and isopropylamine (3.2 g., 0.054 mole) in toluene was heated in a bomb at 100°C. for 4 hours. The cooled mixture was washed with aqueous bicarbonate solution, dried over magnesium sulfate, and concentrated to leave the crude product which was purified by dry column chromatography to yield 3.2 g. of product with m.p. 54-55°C.

Illustration Q By using one of the aforementioned procedures for the dinitration of the appropriate N-alkyl-4-alkyl-m-toluidines or by reacting the appropriate amine with the desired 3-chloro-2,4-dinitro-5-alkyltoluene the following compounds of formula (I) wherein Z is -CH3 were prepared.

MP °C C3H7-i C^Hg-sec CH(C2H5)2c2h5 II II η C3H7»i 46-46.5° 37.5-38° 51-53° 55° orange oil 54-55° 5 ^3^7-1. CH(C2H5)2c3H7-i CAHg-sec It orange oil ch(c2h5)2 C4H9-n 47.5-50° 10 ch(c2h5)2 C4Hg-sec orange oil Illustration R Preparation of 4'-Isopropyl-2',6'-dinitro-N-propyl-m-propionotoluidine A solution of 4,6-dinitro-N-propyl-0"cymenr515 -amine (2.7 g., 0.0096 mole), propionic anhydride (4.9 g., 0.038 mole) and concentrated sulfuric acid (2 drops) was heated at 90°C. for 4 hours. The cooled reaction solution was then diluted with aqueous sodium bicarbonate solution and stirred at 25°C. for 0.5 hour. The result20 ing mixture was extracted with chloroform. The dried (MgSO4) chloroform solution was concentrated to leave the crude product which was purified by dry column chromatography (silica gel, 1:1 benzene-hexane) to give 2.0 g. (62%) 4'-isopropyl-2',6'-dinitro-N-propyL-m-propionotoluidide, m.p. 78-80°. . 24 •2 4 4 8 8 Illustration S Preparation of a-Chloro-2-ethyl-5-m'trotoluene Paraformaldehyde (105.1 g.) was added portionwise to a stirred solution of 620 ml. of concentrated sulfuric acid and 720 ml. of fuming sulfiric acid at 3°C. to 10°C. Anhydrous calcium chloride (252.5 g) was then added portionwise maintaining the temperature of the mixture between 4°C. and 11 °C. The mixture was stirred in an ice bath for 1.5 hours and then treated dropwise with 264.0 g of 4-ethylnitrobenzene to maintain the reaction temperature between 6°C. and 9°C. The mixture was stirred between 9°C. and 18°C. for 13 hours and then between 18°C. and 20°C. for 123 hours. The mixture was poured into a slurry of ice and water and the crude product was extracted with chloroform. The chloroform layer was partially concentrated, shaken with 100 ml. of potassium bicarbonate, water, and stirred over magnesium sulfate.

The filtered solution was concentrated under vacuum to yield 317.6 g. of an amber liquid. The crude product was fractionated by vacuum distillation to yield a light yellow liquid with boiling point 114°C. to 118°C. at 0.2 mm. Hg, Illustration T Preparation of 2-Ethyl-5-nitrobenzyl methyl ether Sodium methoxide (44.7 g.) was added portionwise to a solution of 150.0 g. of a-chloro-2-ethyl-5-nitrotoluene in 1.15 1. of methanol maintained between 18°C. and 30°C. The mixture was refluxed for 2 hours, cooled to 3°C. and filtered. The filtrate was concentrated under vacuum and the resulting slurry shaken with saturated aqueous sodium chloride and methylene chloride. The methylene chloride layer was washed, filtered through sodium sulfate, and stirred over magnesium sulfate. The filtered solution was concentrated under vacuum to yield 133.89 g. of a dark brown liquid. The crude product was fractionated by vacuum distillation to yield a yellow liquid with boiling point 113°C. at 0.35 mm. Hg. which solidified to light yellow prisms with m.p. 21.5°C. to 23.5°C.

Illustration U Preparation of 4-Ethyl-N-(l-ethylpropyl)-g-methoxy-m-toluidine A mixture of 10.0 g. of 2-ethyl-5-nitrobenzyl methyl ether, 10.38 g. of 3-pentanone, 0.23 g. of 2-napthalene sulfonic acid, and 0.60 g. of 5% platinum on carbon catalyst was shaken under hydrogen for 2 hours at room temperature and for 4 hours at 48°C. to 60°C. The mixture was diluted with 200 ml. of ether, filtered and the filtrate shaken with 2.5% aqueous sodium hydroxide, washed with water, filtered through sodium sulfate and stirred over magnesium sulfate. The filtered solution was concentrated under vacuum to yield 10,76 grams of an amber liquid, pure by glc and tic analyses.

Illustration V Preparation of 4-Ethyl-N-(l-ethylpropyl)-a-methoxy-2,6-dinitro-m-toluidine A solution of 13.0 g. of concentrated nitric acid, 10.75 g. of concentrated sulfuric acid, and 4.88 grams of water was added dropwise over a 2.3 hour period to a stirred solution of 7.75 g. of 4-ethyl-N-(1-ethylpropyl)-α-methoxy-m-toluidine in 35 ml. of 1,2-dichloroethane. The temperature of the mixture was maintained between 18°C. and 21°C. during the addition and for an additional 44 hours. The mixture was poured onto 30 g. of ice and then extracted with methylene chloride. The extracts were combined with the dichloroethane layer, the combined organic layers washed with 2.5% aqueous sodium hydroxide and water and stirred over magnesium sulfate. The filtered solution was concentrated under vacuum to yield 10.86 g. of a dark brown solid. Purification by chromatography yielded yellow-orange crystals with m.p. 28°C. to 29°C.

Illustration W Preparation of 4-Ethyl-a-methoxy-2,6-dinitro-m-toluidine The amine prepared in illustration V (100 g.) was slowly added to 2 litres of 50% sulfuric acid with stirring and then warmed to 70eC. for 22 hours. The reaction mixture was diluted with ice water, extracted with benzene and the benzene layer concentrated to an oily residue. The residue was taken up in CC14 (100 ml.) and poured with stirring into 4448S hexane (1.2 1.). The resulting solid after drying weighed 74 g. (94% yield) and had m.p. 71-73°.

Illustration X Preparation of 3-Chloro-6-ethyl-2,4-dinitrobenzyl methyl ether A solution of the aniline prepared in illustration W (40 g. in 750ml. acetic acid) was added slowly with stirring to a solution of NaNC>2 (17 g.) in 136 ml. sulfuric acid at 10-15°C.

After 30 minutes this reaction mixture was added to a solution of CuCl (37.8 g.) in 480 ml. hydrochloric acid with stirring. The product (25.0 g.) precipitated from the cooled reaction mixture in 58% yield with m.p. 81-82°. The filtrate upon dilution yielded another 10 g. of product.

Illustration Y Preparation of 4-Ethyl-a-methoxy-N-[1-(methoxymethyl)propyl]-2,6-dinitro-m-toluidine The benzyl ether obtained in illustration X (5 g.) and 1-methoxymethyl)-propylamine (4.1 g.) were dissolved in toluene (100 ml.) and heated to reflux. After 20 hours the reaction mix20 ture was cooled, washed with dilute hydrochloric acid, water and then dried. After passing the solution through a column of neutral alumina, the toluene was removed in vacuo leaving 3.7 g. of an orange oil which upon standing crystallized. Recrystallization from methanol gave the pure product, m.p. 54-55°C.

Illustration AA Following the general procedure of Illustration Y using the appropriate benzyl ether and methoxyamine the following compounds of formula (I) wherein Z is -CH2OCH3 were prepared. MP °C. —2— Y CH(CH3)CH2OCK3C2H5 62-64° CH(C2H5)CH2OCII3 ch3 34.5-36.5 CH(C2H5)CH2OCH3C3Ii:7~i red oil Illustration AB Preparation of a3-methoxy-Kt-(2-methoxy-l-methylethyl)-3,4-xylidine A mixture of methyl 2-methyl-5-nitrcbenzyi ether (12 g., 0.066M), methoxyacetone [20 g. (used as solvent)], 2-naphthalenesulfonic acid (0.3 g.) and 5% Pt/C (0.7 g.) is shaken on a Parr hydrogenator maintaining the temperature below 40° with external cooling. The theoretical amount of hydrogen (0.26M) is consumed and further uptake ceases after 2 hours.

The reaction mixture is filtered and the excess methoxyacetone removed in vacuo to yield a red oil. This oil is purified on a silica gel column, eluting with benzene, yielding 7.6 g. (52%) of a colorless oil. Analysis calculated: C-69.91%; H-9.48%; N-6.26%; Found: C-69.88%; H-9.19%; N-6.36%.

Illustration AC Preparation of a3-Methoxy-N-(2-methoxy-l-methylethyl)-2,6-dinitro-3,4-xylidine A nitration mixture consisting of concentrated sulfuric acid (1.4 g.), water (0.7 g.) and 70% nitric acid (1.8 g.) is added at 25° to a solution of a3-methoxy-N-(2-methoxy-l- methylethyl)-3,4-xylidine (1.0 g., 0.004 M) in 10 ml. of dichloroethane. After Stirring at 25° for 1 hour, then at 40° for 1 hour, the reaction mixture is cooled and poured onto ice. The desired product is obtained by extraction with chloroform and isolated as an orange oil, which is purified using a silica gel column, eluting with hexane/benzene (90/10). The resulting solid is crystallized from a small amount of methanol yielding 0.8 g. (64¾) of light yellow crystals melting at 54.5-56°. Analysis calculated: C-49.83%; H-6.11%; N-13.'41%; Found: C-49.77%; H-5.90; N-13.24%.

Illustration AD Following the procedure of Illustration AC 3 the appropriate a -methoxy-3,4-xylidine or 4-chloro-a- -methoxy-m-toluidine was dinitrated to give the fol ing compounds of formula (I) wherein Z is -CH2OCH3. r2 Y MP °C. ch(ch3)ch2och3C3H7-£ orange oil CH(CH3)CH2CH2OCH3 II orange oil CH(CH3)CH2CH2OCH3 Cl orange oil CH(CH3)CH2OCH3 II 31-34° Example 1 Selective preemergence herbicidal activity was established by the following tests in which the seeds of a variety of monocotyledonous and dicotyledonous plants were separately mixed with potting soil and planted on top of approximately one inch of soil in separate pint cups. After plantinq, the cups were sprayed with the selected aqueous-acetone solution containing the test compound. The treated cups were then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. Three or fourweeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system set forth below.

Rating System Rating System - no effect - possible effect - slight effect - moderate effect - definite injury - herbicidal effect - good herbicidal effect - approaching complete kill - complete kill % Difference in Growth from the Check* 1-10 - 25 - 40 - 60 - 75 - 90 - 99 100 - abnormal growth, i.e. a definite physiological malformation but with an over-all effect less than a 5 on the rating scale, * Based on visual determination of stand, size, vigor, chlorosis, growth malformation and over-all plant appearance.

Using this rating system and the following species of plants: Sesbania, Mustard, Pigweed, Ragweed, Morningglory, Barnyardgrass, Crabgrass, Green foxtail, Teaweed, Corn, Cotton, Soybeans, Rice and Velvetleaf N-( 1-ethylpropyl)-3-methoxymethyl-4-methyl-2,6-dinitroaniline was tested as a spray to cups planted with seeds of the above-named plant species. Applications were sufficient to provide from 1.12 kg./hectare to 0.07 kg./hectare of test compound. The selective preemer10 gence herbicidal activity of the test compound is provided in the table below.

Plant Abbreviations: SE - Sesbania (Sesbania exaltata) MU - Mustard (Brassica kaber) PX - Pigweed (Amaranthus retroflexus) RW - Ragweed (Ambrosia artemisiifolia) MG - Morningglory (Ipomoea purpurea) BA - Barnyardgrass (Echinochloa crusgalli) CR - Crabgrass (Digitaria sanguinalis) PO - Green foxtail (Setaria viridis) TW - Teaweed (Sida spinosa) VL - Velvetleaf (Abutilon theophrasti) CN - Corn (Zea mays) CO - Cottonhirsutum) SY - Soybean (Glycine max) RI - Rice (Oryza sativa) 488 Examples 2-66 Following the procedure of Example 1, the compounds indicated in Table 2 below were tested with the reported results. «Ν| CM o c / CM O X i —J— ~ ' © ο ο © o c moo © © X >· ITj © © © o ο ο © o | O υ © o o o o o © Plant Species 2 o © o © © © © CM © © © © © o £ ϋ © © r* m o © σι © © oo o © & u ο cn σι σ> cm m σι σι © © σι η c X ©©moo© © σι ο co © ci J > ~s t- nooooo © ω © ο ο © CO © Ο Ο O © co αο r* m © ο o £ f-4 © © © © © cm © © ο ο oj z o o o © o © CM Ο Ο Ο Ο Ο H CM co Γ in <*» © © r· © m ο © © X X © © ο o ω ο ο © X © o © © o © CO CM Ο Ο Ο Rate lb/Acre in Mi£>n ΟιΛΝΗΟΟ Η © Ο Ο Ο O m co © co © m cm Η © © Η Ο Ο Ο Ο Ο ! Structure X dl 1 X m U 1 ΙΛ X CM υ 1 N co X o CO X υ 1 CM Oi CM m ffi CM υ ο *· r-4 x a □ e i rc κ w m » CM 2 « η X φ υ η — Οι χ g υ to I Μ X Preemergence Herbicidal Evaluation of oj O S tq S OJ O j Plant Species | H (Si X W Ο Ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο S w 8 --------------- 55 a o & ο» η ο ο ο σ Cm a σι σι σι id in σ» σι σι r* jQ oi υ σισισι σι σι σι σι co Lg eC m σι co σι η» ιο σιοιηιηπο «5 ID J > CO Ώ Ο- Ώ LQ Ο E* ιη ιη ιη ιη ιη ο a5SSMrf X o & qooooo H & σι σι co ιη ο X S σι ιη οο in w ο co M W in tn Η ο ο ο cd ιη in rn ο o in nJ η Β » β β · OJ Η Ο Ο Ο in m id η ο in OJ Η ο ο Η ο ο ο ο ο , Structure Ρ-3 υ 1 03 m X υ X υ 1 N ΓΠ χ υ 1 η X ο ! 03 |"ί U OJ X υ *s* 3° a Η £ X 2 ϊ « ** -CH(C2H5)2 Example 5 ♦Average two tests § •Η G :* ; W Pi © © © © © © [ Plant Species I CQ ω ίΜ CO rd O © © © © o © © o o o V Ο Ο Ο Ο O © o o © 25 U ggoooo fO © © o o o g 3333°° fc, o © σν σ» vo co co H in σν σν n« n· co ο Pi o σι σ» σ» © co r- σν σν σν σν r- co CQ ο cn rn vo co ιο CO Vd ι-ί σν σν σν σν co ο > Sr'33^° C4 © © © © ο s Pl 03 vO VO in CQ M3 S S nJ h oo co nj © © ο ϋ £ co in vo vo cq © r< Η o © © © ο © © ο o ca ηΗΟΟΟΟ η» ο ο ο ο ο H & o s oo co vo m vo rd id CN r- cm © © ο ο rQ CO VO XT o o oo S Ch Cft ο © w to Γ*; VO CO rd rd Ό vc •'a5 nJ © V0 Ο Ο Ο Ο Ο c 4 r 0 o u I) 0 J < fS X] rH in co vo co © in ni rd © o rd © © © © © in co to co ο in ηι rd © © Η ο ο ο ο ο ( Structure | in X nj υ 1 m W ηι Ο N Π U 1 co 5G U 1 CM K "* -CH2 Example 6 ηι co 22 Ο η* 33 J2 7 £ • ε <β X Η W W Φ +J Φ Φ Μ XJ «Ρ Φ re Li φ £ * ♦ * ,44488 j Ό Φ β •Η μ β Ο U Φ Ο C Φ, fal ω ε 0) φ b CM CM Ο i Plant Species I M os ο ο ο ο ο o CM Ο Ο Ο Ο O ra co co O o o o o o σ σ ο ο ο ο o o o o o o o o o o o o o s o Η Ο Ο Ο Ο O ιτ\σ ο ο ο o o is fe o σ\σ\σ\οο in cm σ\σ\σ\σ\\χ> in PS o σ\ cr\ cp> o\ia cm σ\ σ\ c\ σ\ o\ b- < P3 cn σ\οο oo cm o o\cno\o\chin £ ιηο ο ο ο o SMHOOO is EH E^-CM o o o o 30 00 mo ο o o s ο ο b ο ο o mono ο ο o o PS o o o o o o mo ο ο ο o H P4 ^-ifiino ο o 20 n-\o moo s 0\0 ο ο o 30 CO o o o ω CO o o o o o 30 t>-o o o Rate lb/Acre o Lf\m o inmuj co o in cm κ ο o Η Ο Ο Ο Ο O | Structure 1 >« •Hl 1 c- ;β cn o 1 •Hi c— as m o ES3 m id o m W o CM 05C3H7"t Example 8 ol Φ ω| 1 σι σ\ OS Φ =r h o & i ε <0 X w TABLE 2 (Continued) rt Ό ι-t o •H £1 L.

O X Φ ϋ c Φ bt f? Φ E Φ Φ Jw X o r\j _/ K\ // S3 r\j o ( 1 Plant Species 1 l·—· cc ο ο ο o © co co co o o © o o o © ο ο © o 2: o o o o o o o o O\C0 0- 04 © © 0\CftO\C*-0 CT\COCO o o til > OJOOCO 5 fr- o o o o © E o o o o © K ο © ο ο o w cu 00 VO © o o © E o o co co Φ Φ o i-3 < « X r—( o o o o o o in mvo © inoj rH © pH Ο Ο Ο O ! Structure oj 0) wi 1 Ch X o ES3 1 00 X © 1 04 X 1 -CH(C2H5)2 Example 10 Φ fi •rl C ο υ <μ| Φ Ό Ή υ •Η Λ Μ Φ X Φ ϋ c φ cr Μ Φ Φ Φ Μ Μ α ο ο ο ο α ο Ο Ο Ο Ο Ο Ο Λ ιη X ω ο ο ο ο ο ο ο ο ο ο ο υ ο ο ο ο ο ο ο ο ο ο ο 2 U γ* ο ο ο ο ο 03 ο Ο Ο Ο Ο Ο Ϊ2 φ •Η 04 ϋ σι σ*» οχ οχ οχ ίο οχ οχ σχ co > ro U Φ α α ο σχ σχ σι σι χ co σχ σχ ο ω co η -μ 4 m σχ σι σχ σχ ο» co σχ σχ σι co co in φ ι-Η A g ιη Η ο ο ο ο OJ ο ο ο ο ο S 6η CO 03 ο ο ο ο co Ο· 03 ο ο ο ϋ £ ο ο ο ο ο ο ο ο ο σ ο ο ϋ & ο ο ο ο ο ο ο ο ο ο ο ο Η 04 co mr- ο ο ο οιοο οοο Ο a co co σι ο ο ο ο ο W co 03 Ο Ο Ο Ο Ο ο ο ο ο ο ο 0) Μ «) 0 •Ρ < .Is· « 43 r-i in m νσ m ο ιη οι Η ο ο Η ο ο ο ο ο 1.0 0.5 0.25 0.13 0.06 0.03 β| CI X Γ* 2 η U I Γ- 2 η U I Structure Ν m « U Ο ΟΙ 2 V (Ό 2 U Ο 03 κ υ 1 ΟΙ pi ιη ® οΐ υ η 2 U S υ Example 11 ΟΙ η κ υ κ υ ί ί Example |2 1_— TABLE 2 (Continued) o c H +J id P r-f id > ω rH fd •ϋ 1 Plant Species j h-ί Cm © o © © © CM CM Η Ο © O ffi CO w co ο ο © © O © © Ο © © O o u o o o o O O Z o © o © © o O O O O O O o X Em ϋ © co © ο © © © © 00 CO O K o os © o r* cm © qs os os os co co ¢0 © oo oo r* cm o © © © co in co -q > © rs cm ο ο o © in cm © © © £-i > CM Ο Ο © o oo r* κ ο o o a © O © © o © CM © © © © O o & ο ο ο ο © o O O O O © O H tfNOOOO co vo m cm ο o □ £ σ» os ο o in ω tn CM Ο Ο © © © © o © © o Rate lb/Acre in m φ hi OiTiMmOO «-» © Ο © O © m m © rs © in CM ri Q O HOOOOO 1 Structure ] >< •i-l 1 1 OS w XT u I rs S3 Q 1 n S3 Li O CM K □ 1 cq S3 O O cn X X u-u 1 CM -CH(C2H5)2 Example 13 CM in £ e' CM — U £ r-i U 04 X ω φ ΰ β •Η -μ C Ο U C-4 Ο C ο >τ4 rt Η rt ω γΗ rt τ3 ♦Η ο •Η £> Φ X ω ο ί: φ bi Ρ< Φ ε φ φ $4 X CM Ο (Μ Ο aecies 1 ►H X eno ο ο ο © © © o o o o © © o © © © co >< co o o o o o o ο ο ο ο ο o o © © o o o o © © ο ο ο o © ο ο ο σ ο o o © o o o © ο ο ο ο ο o CM CM Ο Ο Ο O eno ο ο ο o o ►>· © ChO^CO in CM o ChChCO 0-© CM ChChOsb-© O X o chchchoo o-o Ch Ch o\oo 00 b- ch chChco© cn I Plant Si X Ch σ\οο cn © © chChChowo cn ChthOAb-©© J > o o o o o o ®) o o o o o mo o o © o posed generic formula. Er* CM Ο Ο Ο © © 0-0-0 o © © © CM © Ο Ο O O g ο ο ο ο ο o ο ο ο ο © o o © o o o o e X o o o o o o © ο ο ο ο o o o O o o o H X 00 0—CM Ο Ο O oo t— m ruW o 30 chm ο ο o X g <33 00 Ο O oscho-o © o © ο o Ed CO © oo ο ο o CM CM Ο Ο © O CM Ο Ο Ο Ο O Rate lb/Acre o men© m © in CM ho© Η Ο 0 © Ο O o men© on o in CM h © o Η Ο ο ο © o o in cn© cn o in CM H o o Η Ο Ο Ο Ο O I Structure 1 >4 •Hl Ο- Χ cn o 1 oj Φ w| 1 Ch X •=r o 1 m X o 1 03 cn X o o CM X o I cn X © o CM X o 1 cn X o o CM X o I •Novel but not covered in pro CM X s -c4K9-i Example 15 V c- S3 n ID O p-l i a ¢4 M r4 o CM 5 S z—\ cn X Φ Ο H Q< x e © to 1 X w 'Ο ο β •Η +J Γί ο υ « g| OJ. σ χ OJ ο Les j ί—1 χ ! ο οο ο I m W . . i .. ιο ο ο ο ο ο ο J e ο ο o u\ O O 0 o o Ή 0 C ’ 0 < I O o C Ο ο ο ο Ο ο ο 'oooo ο ο ο ο ο ο ο o o o o o e o a o o ο ΟΙ ο ο ο ο ο me ο ο ο o o X ο σι σι σι σ\ c\ cn Q\OJO O ζ?\ ςη m m m o t^\ri Ο φ α X ο co ο\ σ\ σ\ ο\σ\ cos-mo o\o\co b-xr o < CO σι CO >-OQO σιο ο o oj m ο o C*5 Plant -J o.m^r^r-=r η oooo m m ο ο ο o OJ ci co CO CO KO OJ o OOOC5 IO L^HOO C t—i Ο ε Ο X OJ OJ o o o o t- ο ο ο σ o oooo o o o o o o oooo r-5 O O O O O Μ co Ch σι σι t*- m m oooo -=T 1-J K o o o X ε co coo o Lf\mo ο o o o W ω C0f-(\|O oc oooo r4 m ο ο ο o o Φ C Φ ο CC Χ5 γΗ o mco\o co o ir.cj hOo μ ο ο α ο o o men OLflM H Η Ο Ο O σ mmko m o m oj «π ο o h o o o o o J Structure I Μ *h| 1 t*~ X CQ o 1 Cl ! σι X ^T ο co X 0 ! Ό m X 0 o Oj X 0 1 co X O o OJ X 0 1 m X OJ o o OJ X 0 1 04 X Cl 1 c- X co 8 co m ** Xoi a> 8 & X g o r κ 0 -CH(C3H5) Example 19 OJ v—> m X O I OJ OJ 0 x Ό Φ C ♦Η •Ρ « Ο Ο CM Ο •Η Χ3 h Φ to φ ο C1 φ fa£ Μ φ S' φ φ -.

S CM Ο :i Plant Species I v-i CC (nmoooo © © ο σ ο o 03 CO X to ο ο ο ο σ σ o o o o © o o o o © © © σ ο ο © ο o 1.» ooooo o o a ο ο ο ο o to o o o o o o o CM ο Ο Ο ο O o o o o o o o ►7» Η © © Ο O fc o σχ σχ σχ σνο co σχ σχ σχ σχ ο- in σχ σχσχ σχσχ in K o σχ σχσχ σχσχ co σχσχσχΟχοο in σχ σχ σχ σχ σχσχ 03 σχ σχ σχ σχ σχοο σχ co co co ino ©X OX ΟΧ IS-CM CM a > CM ο ο ο ο ο co κ ο ο ο o coοο ε— mn ο ΪΞ2 F« XiWOOOO X) >-CM ο Ο O σχσχέ—χο cm o 2 ο ο σ σ σ ο CM Ο Ο Ο O cncxj Η ο ο ο 0 K ο ο ο ο ο ο 30 o o o o o oxen ο ο ο ο n 04 σχε—ο ο ο ο Όωωοοο σχ σχσχ co ο- 0 s σχ σχ σχ σχοο co σχ σχ σχ w co ο ο ο ο ο CM Ο Ο Ο Ο Ο so s-mo ο ο « ·' Rate ! lb/Acre ο trxmko m Ο IfXCM HOO Η Ο Ο Ο Ο Ο ο uxmxo m ο incM Η ο ο Η © © Ο Ο Ο ο inmvo m ο tnexj η σ ο Η οο ο ο ο 1 Structure X ιη to CM 0 Cl 1 t- w co ο I ήΙ f to m 0 I N m to a o CM to o 1 cn to o O CM to 0 1 cn to 0 o CM to 0 1 CM oi r-H o CM to 0 CM _ g ς\1 m ® a t! S ε a 10 »4-1 M ? M -CH(C2H5), Example 22 Si Wl | CO σχ oj J - 1 X 0 φ c ‘Η •μ δ Preemergence Herblcldal Evaluation of (M Ο N Si CM © 1 Plant Species 1 M x © o o iao ο © σ σ CQ to X co o o o © o o o o o ο ο ο ο ο ο o o o o o o o o o o © ο ο ο ο ο ο X o O O o o o o o © © © Ο Ο Ο Ο ο o ο ο ο ο ο ο fe o vo © o O\ 0Ί ΟΊ O\CO © σ> cr»vo cm ο ο X o O\CM O σ\ σ\ os σ\ σ\ o O\O\b-VO CM Ο < CQ CO CM O σ\ o\ σ\ o\co ο σ\σ\ΐη<υ ο ο t-q > © Ο © c*~ cm cm ο ο ο cm ο ο ο α ο 13 E-< CM Ο O «ο E—VO ο ο ο s«m © ο ο O X Ο © O ο ο © ο © ο ο ο ο ο o X ο ο o CM Ο Ο Ο Ο Ο ο ο ο ο ο ο H Pm moo σ\θΛοο c·—ο mo ο ο Ο ο § mo o χι cns- ο ο ο ο w CO moo Ο © Ο © © © ο ο ο ο ο ο Rate lb/Acre o la Ο LA CM Η Ο O © la mvo m Ο LA CM r-iOO Η Ο Ο Ο Ο Ο ο in mvo m © LA CM Η Ο Ο Η Ο Ο Ο Ο Ο I Structure j X m X o 1 ή| 1 ρ- X m 7 m X ο I CSJ m X o O CM x O m X Ο ο CM X ο m X ο ο CM X ? CM Example 27' rH Ο CM g κ tv ω ο "J g ° Π3 1 X W m X ο Η Ο g © ο <Μ 3 & w § ο X 1 Η Ό Φ C •d μ Ο υ «ί-.! 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Plant Species 1 H PS CQ CO ΪΗ CO o o o o © © o o o o o o o o o o o o o o o o o o o ο ο ο ο σ o o © o o o o £ o o o o o o o o © o o o o o £ ρίγμηηοο Η Ο Ο Ο Ο O r-i Ο Ο Ο Ο O pH o Os Os OS Os00 00 osososlacoo OS Os OS OS LAO PS o os os os os co 00 os os os os os VO os os os os b- co OS OS OS OS b—VO OS OS b- CM CM O osososco ο o iACnoj Ο ο o £ b-vo romo o COkOHOOO £ b-f—b-b-LACO CO b-vo coo o :o vo CM Ο Ο O o s b-iAr-ι ο ο o o o o o o o coo o o o O o OS ia mo ο ο o ο ο ο ο ο o o o o o o o H cu OSb-b-VO co CM OS VO VO CM Ο O OS CO b- o o o g b-b- ο O OS VO vo o OCOOSOOO w CO bbiArno o ώ ο ο ο ο o Ο o o o o o Rate I lb/Acre lacovo co o iacm η ο o r-i Ο Ο Ο Ο O O LACOVO 00 O LA CM η ο o Η Ο Ο Ο Ο O o lacovo co O IACM K Ο O Η Ο Ο Ο Ο o 1 Structure ΪΗ 1 sh2o- CO £ o 1 co £ o N CO a o o CM a V co W O o CM as ? m £ o o CM £ o CM DS si c Ml CO I OS Φ as h •=r 0< Ο β i nJ X w Cl 1 b- £ co o o co Q) as ή ο Λ s £ id O X i w cl I b— £ CO r- o Ία o as h CM fX ο β '-s rd £ X Ο H 1 Π3 Φ C •Η 4-> C Ο U oil 1 Plant Species ! i-i cc ai to (MOO© © S co o o o o o o o o m © © ο ο © Ο Ο Ο O © © CM Ο Ο Ο Ο O CM Ο Ο Ο O © z ο CM CM ο Ο Ο O nmoο ο o CM CM© © Ο O o Ο O © © © © mo©©©© CM © © © © © to 0 Choo M3 O C: O σχ σχσχ ©σχσχ σχσχϋ\σχσχσ> K 0 σχ σχ σχ s- m © σχ σχ σχ σχ σχ σχ σχ σχσχ σχ σχσχ < to σχ® co ο ο o ©σχσχσχιηο σχ σχσχ σχσχ cm > mo ο ο o oS- m moo© X) t—m hoc & Eh m ο ο ο o ojo oo m ο ο o I 33 €ϋ S CM Η Ο O 2 Ο O © © © ©I© o o o o o f 23 CO CM Ο © Ο 0 to ο ο © © © o (Μ Ο Ο © Ο Ο Ο Ο © Ο Ο Ο w to soxo mo ο o σ. cxco s- ιη ο σχοο® cm ο ο g oxo o o o σχ s s ο © ο οχ σχσχ cm ο to co ο ο ο ο ο o η© ο ο ο © X) S CM cm ο ο Rate lb/Acre o inmvo m © in CM H o o rH Ο Ο Ο O © ο inmxo m © in cm η ο ο Η ο © ο ο ο ο inmxo σχ ο η CM Η © ο Η Ο Ο Ο Ο Ο ! Structure 1 in to CM 0 1 ιη to CM 0 1 •Hl 1 C-— to σχ © I S3 m to o O m to 0 1 m to ο Ο CM to ? m to ο Ο CM to 0 1 CM to •Hl y a Ή ? ε ‘ φ X ω - CH(CR3)CH2C3H7-i Example 43 -CgH?-! Example 44 I § c •rf *P C Ο U V) φ Ή Ο Φ h-f X X CO ΪΗ CO Ο Ο Ο Ο Ο Ο ο σ ο ο ο ο ο ο Ο Ο Ο Ο ο ο σ ο ο ο ο ο ο Ο Ο © © © <Ρ ΙΑ CM <Μ © Ο Ο ο ί2 Η Ο Ο Ο Ο Ο Η Ο Ο Ο Ο Ο X ο σ\ σ\ σ\ os© m σ\ o> o\co ο ο X ο σ\ σ\ σ> σν ο\ c*· σ\ σ\ σ\ σ\ t—in CO •Ρ C Φ σ\σ\ρ— la η ο σ\σ\σ\χ ο ο £ ζΛΜ3 LAX Ο Ο P-OJ ο ο ο ο χ EM Ο 2 coco p-mo ο mooooo ρ-mcM ο ο ο ο ο ο ο ο ο ΰ X Η X t—o ο ο σ ο ο σ σ ο ο ο σ\ σ\ σ> ρ-ια ια ΟΛΟΛΟλ [ΑΓΑ Ο S σ\σ\ρ*ο ο X) σ, m ο ο ο W εο CO ο ο ο ο ο CM Ο Ο © Ο Ο φ C Φ ο 4.3 < Π}\ X 40 Η ο lAmvo m Ο LA CM Η Ο Ο η ο ο ο ο α Ο ΙΑΓΠΜΟ 0Π © ΙΑ CM Η © Ο Η ο α ο ο σ 1 Structure 1 Η ΙΑ X <Μ ο 1 ΙΑ X CM Ο 1 CQ m X ο ο CM X ο 1 m X Ο Ο CM X V CM X Cl C— X m lo Ο «53- ο S :c § 8 * V w CM ζ—«. cl • © t— X θ 0} w & V « 1 X H Ό φ α •Η •μ C d γΗ <ϋ > ω <Ν{ <υ φ X CM CM Ο | Plant Species 1 W X in u~\ cm © ο ο ffi W b< co ο Ο ο ο ο© ο ο ο ο ο ο o oo o o ο ο c-.© ο ο ο© ο ο ο ο ο ο o © © o 2 Ο iK(\HO ΟΟ r>4 ο ο α ο ο ο ο ο ο ο o Ο unon inr-i ιηις !·ή r~i ci© Ο Ο Ο Ο Ο ο CM Ο Ο Ο O X ϋ ChChChChO'b· ch Ch ch ch Ch i- ChChChCh© X ο Ch Ch σ\ σ\ σ\Γ<· ctf Ch Ch Ch Ch Ch ChChChChoo < X Ch ChChe- co it co chchchmm© σ\θΜηκ o X > 00 CO ΓΟ '.'v i-i © in cm >-© moo© E*—CM CM © O 3 on co oooo b-(\ co OC0 c—cm © o CO © m CM O ο S © -=r ε— on oo r-} O © © ο ο © o © o o o o Ο X in co η o © c cm o o o o o o mo © © © Η X on co co on c\j b·. CO LiS Γ-4 σ\ b- m ο © o Chi'-© CM H © Ε on mco r-n roc coco -4· OX© © © chchcho o ω W CO b- CM CM un© zt OJ CM 6 Ο Ο Ο O © © © © © Φ Ρ Φ ο Ρ < Μ V X © γΗ omm© m o tncM ι-ί ο o r4 oo o o o © m m© on © in CM r-i O © i—1 Ο Ο Ο Ο O inm© on © CM r-i © o r-ί Ο Ο Ο O 1 Structure 1 >Η in X CM O 1 in X CM O 1 in X CM 7 03 co X o o CM X O 1 m X o o CM X o 1 m X o O CM X P CM X CM Uh «-j. X o™ 0 X E 1 κ ω •nil § rT 9§ £ c 1 b- J’S O & H Ό Φ □ β •ri +> β Ο ο CM Ο <\J X I \\ // CM ο 03 Φ Η ϋ Φ η X co co X co ο ο ο ο ο o oooo o o o o o o o ο ο ο ο ο ο X o ο ο ο ο ο o ο ο ο σ ο ο o J3 cm in in ο ο o r-f o ο ο ο ο ο ο X o ChOsco men cm t-i O\O\0\t—Ο Ο X 0 chcncnosinm co’m3 O\ChC0 t-MD ο 1 Plant Si « os σ\ in cm cm <-! oo 33 inSj mo o o SM-O ο ο σ ο ο ο ο ο & Eh co in in ιηκ o t-·^ l"4 ιη ο ο ο ο ο O S on h m ο ο o d ο ο ο ο ο ο o X ιηο ο ο ο o 1—1 ο ο ο ο ο ο H X in m in ο o »M5VO □ο ιη ο ο © ο g Ch men in ο o ¢-145-4¼ chb-co ο ο ο td CO inooooo nJ ο ο ο ο ο ο Rate lb/Acr.e o monvo on O in CM r4 o o Η Ο Ο Ο Ο O ο in onio on Ο ΐη<Μ ΗΟΟ η σ ο ο ο ο Structure I X r4 0 1 Η ο N on X 0 o CM X 0 1 m X C » C· CM a: 0 1 CM X CM in o X in CM 8 φ S3 ·-< o a i ε * κ * Μ cl 3 c— X on O in on X OJ 0 X £ O g w μ Φ μ φ r*4 to β •Η CO μ Φ μ Ο μ Cm Ο Φ to φ β φ > * Preemergence Herbicldal Evaluation o: HN-R„ w CD H Φ a co w c β rH X H X * X CO co Ο o OOOlOOQGQQ . I. Ο © Ο Ο O © o © o o o o © oo o o oo o o o o o o X o ooooxo OO O o OO ο ο ο ο ο o o SS t\l ΓΗ o o o o oo o o oo rH Ο Ο Ο Ο O X o cr,o\b-vo men cr>cno\mmLQ 1 σ\σ\ί—c—mo X o cho\er\r-O on σ\σ\ σ\ m mm S-V0C5 cnChoovo mo < σ\ ch t>- m η o oo o\ m mo .=r o co vo c~-mo o > H fH Ο Ο Ο O mmo o oo fMH CM © Ο © © O Ε-» S if< Η Ο Ο O ^-m X» ms ο o Mho SfJOOOO O s ο ο ο ο ο o oo o o oo ο ο ο ο ο o e X —J— ο © ο ο o o, mo ο o oo ? o o o o o o H X t-vo cv ο o o’ (/vs- ino oo ! d ru o\o ο ο ο o © % O r-i o o o o mrH O o oo H chmo ο ο o w CO l>-\£> η © ο o LQr-1 Ο © OO O © O O o o Rate lb/Acre o mm o on O m C\J i-f Ό o Η Ο Ο Ο Ο O o m mvo on O m o m mvo m © mcM HOO Η Q © © © O i Structure iw •h] i t*~ X m o 1 on X o 1 m X CM O 1 t»3 on X o o CM X ο m X o o CM X o 1 m X O o CM X o 1 (V X tM X m φ o H i a a β M W •Hi 1 (Π O- in ·% Gt V- S ? S' m X M $ 4 S § Preemergence Herbleidal Evaluation of (M O w ft ft on ο ο ο o CQ CO >4 CO o\o o o o o b-σ ο ο ο o d o o o o o o o o ΙΟ Ο Ο Ο O © id ooooo© © © © ο o © X o Ο 03 0 o o o Tf id id b- Ο ο Ο O (-3 br 0 » b- b- Ο O cvJ cv] <—l c4 o & XT OVb-O o o CM © O rd Ο Ο Ο Ο O in on η corner c5 o d w Φ o mmm σν σν σν σν b-b? frivd σν σν σν σν σν o’ οο o Φ X o σνσνσνσνσν cm oo co cd σν σν a\ σν σν on CD σ\ σ\ σν σν σν Γόο co m ovovco.b-tnft CO 03 vo sr σνσνοηοο b-bcd vd OVOvOVbrft 00 cd S· ο* Plant £ tninwoJHO C'SLOmn bbOJ o SiA c3 co oo on on b-σ ft rl in cnftco.ovco co ayt^ft ono co b-ft on η o S' o3 ononco on ft o; coco S· rd o s πνιηΝΟΟ o σ* CM O' id b~O Q Ο O cd o-ojft cm ono; b--=r ο σ o X ftooooo cd CM Ο Ο Ο Ο O ft b-b-b-O o σ- cm o H ft t-inrdCOCO id OO'CO CO'lAOird on b-in η ο o ad -=f on co co ft t— !>30 S rd g in in ft σ-ho b-co t—in cvf on co on ο © o Sirt 30 03 co 00 ITVid w (0 ft on-=r ο ο o in of r—f oinoooo vd on b-b-b-OQO id SSft in 1 i Rate 1 lb/Acre O inonvp on o in CM rd © o rd Ο O OO O o inonft on o in CM rd o o id o o o o o o in on ft cn o in cm rd ο o i-JOOOOO ! Structure 1 td on X on X o 1 idj 1 Ο- Χ on o 1 cq on X o o CM X V on X o o CM X ? on X o o CM X CM X CM »— in X ™ in O m g ® ? £ iti * w °) Φ wl ft 1 in σν - 3 ? I * X -chcc2h5)2 Example 57 Average of 10 to 15 tests *’*’ Average of 2 to 3* Tests Φ Ρ Ρ •Η Ρ C ο υ (Μ ν CM1 κο ££ £ CM Ο J Plant Species 1 n OS ·'- Ο o o o o o CQ W >4 CO ο ο ο ο ο o o o o o o ο σ ο ο ο o o o ο ο ο ο ο o o o o o o O o o o o £ o vo o s ο ο ο o o o o o o LA CO 00 rd Ο O Q £ os ο ο ο ο o © oso ο ο ο ο σ £ O OS os os os os vo co OS OS osco o o o OS OS OS OS Os OS OS £ o σ\σ\σ\σ\σΛσιοο OS OS OS pS VO co o OS Os OS OS Os OS OS CQ OS OS OS CIS osco co OS OS OS CO CM o o OS OS OS OS OS OS OS !> » co cm ο © ο o x> o o © o © CO VO LA CO CM © O g OS b*· CM Ο Ο Ο O »00 Ο Ο Ο Ο o »coco b-in cm o o s »OOOOOO »000000 » rd r-Ί rd Ο Ο O o £ oso ο ο ο ο o »000000 OS co coo o o o H £ OS OS OS b- CM Ο O OS b~ Ο Ο Ο Ο O OS OS OS CO CO b-CM o s OS OS OS 00 co OS o o OS OS OS O o o £ co OSO O o o o o »000000 » 00 in LA o o o Rate lb/Aere O LA CO VO co Ο O LA CM HOO Ο Η ο Ο Ο Ο O H O LACOVO CO O O in CM H o o Ο Η Ο Ο Ο Ο O H O LACOVO CO Ο O IACM HOO Ο Η Ο Ο Ο Ο O H ί Structure 1 •Hl 1 r— £ co o I rd o T1 b- £ co O 1 1X1 co £ o o CM £ co £ o o CM £ o 1 co £ o o CM £ O 1 CM £ CO £ O O CM £ O CM CO £ LO O Ί» Φ 3 e hH 0 ~ X V H co £ o o OJ os o 10 4 a a ε 9 x 1 w co £ o o CM r\ O S-7 ςβ IA WCM * O Q, hr* β 9 x 1 w Ό Φ β »rl -μ β ο □ ί Plant Species 1 Η to CQ CO X w ο ο ο ο ο o CM Ο Ο Ο O CM CM Ο Ο O © o o s ο ο ο ο o O O © © O O O O © O O O 2 O in® ο ο ο o StnCM CM o o kO © O O o o O ►—» » in cm ο ο ο o ©CM Ο Ο Ο Ο O ©CM CM Ο Ο Ο O to Ο ©©©©©©© ©©©©® so ©©©©©©© to o © σχσχ © © © © © © © © © © CM © © © © © © © < CQ ©©©©©©© ©©©©©® CM ©©©©©©© £ © ©® ko cn cm o ©mm cm ο ο o 30 CO kO LA CM Ο O IS © ©® s cn ο o © ©® CM Ο Ο O ©S®kOO O 0 2 ©CM ο ο ο ο o X5 CM Ο Ο Ο Ο O 20 SO Ο Ο Ο O 0 to ©o ο ο © ο o ©ο © ο ο ο o ©so ο ο ο o H to ©©©©sko in ©©©sino o © © ©co ko cm o g ©® ©©cn© ©©® o o o o ©©©©in to w © SkO CM o o o ©o o o o o o ©kOkO oo© Rate lb/Acre o incnko cn o oincM woo Ο Η © © O © © H o men® m ο o in cm ι-l ο o O <—j Ο Ο Ο Ο O H o men® cn O O ©CM Η o o O H o o o o o H Structure X in to CM O 1 cn to o 1 •hI s to co o 1 ESI m to o o CM to o I cn to o o CM to o I m to o o CM to o 1 CM to . cn to o o CM to rO io ? ® CM rH o & to g ? 0 cn to o o CM to OJ O k0 ? ® CM Γ7 o & a S ? 0 m to o o CM co to ® o cn (¾ •τ· Ή s £ a S CX 1 « Ό Φ β Ή -μ β Ο Ο χ| X: Ο β Ο »Η Ρ d d > ω d Ό •Η ϋ •Η £5 β Φ X φ Ο β Φ bC μ φ Example 67 Postemergence Herbicidal Evaluation Postemergence herbicidal activity is demonstrated by the following tests, wherein a variety of 5 monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. In the tests, seedling plants are grown in jiffy flats for about 2 weeks. The test compounds are dispersed in 50/50 acetone/water mixtures containing 0.5% of a polyoxyethylene sorbitan monolaurate surfactant in sufficient quantity to provide the equivalent of about 11.2 kg. per hectare of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. Prom 4 to 13 weeks after treatment, the seedling plants are examined and rated according to the rating system provided below.

The data obtained are reported in the table below.

Rat ng System: 1 Difference in Growth | from the Check* 0 - No effect 0 1 - Possible effect 1-10 2 - Slight effect 11-25 3 - Moderate effect 26-40 5 - Definite injury 41-60 6 - Herbicidal effect 61-75 7 - Good herbicidal effect 76-90 8 - Approaching complete kill 91-99 9 - Complete kill 100 4 - Abnormal growth, that is, malformation, but with an a 5 on the rating scale. a definite physiological over-all effect less than *Based on visual determination of stand, size, vigor, chlorosis, growth malformation and over-all plant appearance.

Plant Abbreviations: SV. - Sesbania (Scsbania exaltata) MU - Mustard (Brassica kaber) Pl - Pigweed (Amarantlius rctroflexus) RW - Ragweed (Ambrosia artemisiifolia) MG - Morningglory (Ipomoea purpurea) BA - Barnyardgrass (Bchinochloa crusgalli) CR - Crabgrass (Digitaria sanguinalis) FO - Green foxtail (Setaria viridis) WO - Wild oats (Avena fatua) TW - Teaweed (Sida spir.osa) VL - Velvetleaf (Abutilon theophrasti) 4 4 8 8 tO -P c »— •r- O 0.3 P Φ S_ 3 © -P 43 > Ο -rCX-P H © © <0 i. ο ω .© 3 s © to c © © cn r- G.

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Elemental analysis of the product gave the following results: Calculated for Cg^NC^: C, 59.66; H, 6.12; N, 7.73 Found: C, 59.65; H, 6.17; N, 7.64.

Claims (6)

CLAIMS 1. /. A neroicldal composition which is an admixture of a 15 nerbicidal adjuvant and a herbici dally effective compound according to any one of Claims 1 to 16. 18. A composition according to claim 17, including a compound according to Claim 2. ]y. A composition according to Claim 17, including the 2o compound of Claim 3. 20. A composition according to Claim 17, substantially as herein described with reference to any one of the Examples herein. 21. A process for the preparation of a compound as defined in Claim I, which comprises the step of reacting an alkali metal 25 methoxide with a 2-methyl-5-mtrobenzyI compound to form a methyl 2-methyl-5-nitrobenzyl ether and the obvious chemical equivalents thereof. 22. A process according to Claim 21» wherein the methoxide is a sodium methoxide. A method for making a compound of the structure. wherein R 2 , Z and Y are as defined in Claim 1, comprising reacting a compound of the structure wherein Hal represents a halide or functionally equivalent group, with an amine of the formula: r 2 nh 2 7Z ¢4488 A method for making a compound in accordance with Claim I in which Z is -CF^UCH^ CH. '3 CHOCH.

1. A compound having the structure: wherein 5 (a) R 2 is -sec-alkyl C,-C,: rconochloro-sec-alkyl C, or C or methoxy-sec-alkyl 37 4 C 3 or C4 Z is -CHR 3 OCH 3 , R 3 being hydrogen or -CH 3 ; and Y is chloro or alkyl selected from -CH 3 ,-C 2 H g , n-Pr, i-Pr, sec-Bu and i-Bu; 1U (b) Z is -CH,; and R 2 and Y respectively are £-Pr and n-Pr or, -CH(C 2 H 5 ) 2 and i-Pr or -CH(C 2 H g ) 2 and -C 2 «g or -CHiC 2 H 5 ) 2 and sec-Bu or -CH(C 2 H 5 ) 2 and n-Pr or -CH(C 2 H g ) 2 and n-Bu or i-Pr and -C 2 Hg or sec-Bu and 15 -( '2 h 5 or i _Pr an 4 i-Pr or sec-Bu and i-Pr or -CH(C 2 H 5 )CH 2 C1 and -Cl or -CH(CH 3 )-n-Pr and -CjHg or CH(C 2 H 5 )CH 2 C1 and -C 2 H 5 or -CH(CH 3 )CHjCl and -C 2 H 5 or ~CH(CH 3 )CH 2 CH 2 C1 and “C 2 H 5 or -CH(C 2 Hg)-n-Pr and -C 2 H 5 or sec-Bu and n-Pr or -CH(CH 3 )-n-Pr and n-Pr or ZO -CH(CH g )-n-Pr and i_-Pr or -CH(C 2 H g )CH 2 C1 and n-Pr or -CH(C 2 H 5 )CH 2 C1 and i-Pr or -CH(CH 3 )CH-jCl and n-Pr or -CH(CH 3 )CH 2 C1 and i-Pr or -CH(CH 3 )CH 2 CH 2 C1 and n-Pr or -CH(CH 3 )CH 2 CH 2 C1 and i-Pr or -CH(C 2 H 5 )-n-Pr and n-Pr or -CH(C 2 H 5 )-n-Pr and i-Pr or -CH(CH 3 )CH 2 OCH 3 and 25 C 2 H 5 or CH(CH 3 )CH 2 OCH 3 and n-Pr or -CH(CH 3 )CH 2 OCH 3 and i-Pr or -CH(C 2 H 5 )CH 2 OCH 3 and i-Pr or -CH(CHj)CH 2 CH 2 OCH 3 and -CH 3 or -CH(CH 3 )CH 2 CH 2 OCH 3 and -C-jHg or 2. ' («) 4448® CH, 1 I wherein Z is -CHgOCH^; CHOCH^ or -CHgOCgHga) subjecting compound (A) to reductive alkylation using an appropriate ketone, to yield a compound of the formula: Y 5 b) reducing compound (A) with an alkali metal sulfide to the corresponding 3-(alkoxyalkyl)-4-substituted aniline, reacting the thus formed aniline, in the presence of a molecular sieve, with a ketone to yield a compound of the formula: N =Q Z' (C) lO wherein Q is a C^-C^ alkylidene group derived from the ketone and then reducing the compound (C) to yield a compound having the formula: 14 4 8 8 NHR, ί ά ι and tnen nitrating the thus formed amine from a) or bj. 25. A process fo” the preparation of a compound in accordance with Claim 1, and substantially as described witn reference to any

2. A compound of Claim 1 wherein Z is -CHgOCHj. 2 is CH 2 0C 2 Hg and Y is CH 3 . 2 is -CH 2 0CH 3 and Y is n-Bu; or (9) B 2 is -CH(C 2 H b ) 25 3. ‘3 or -CHgOCgHg, which comprises reacting a compound having the formula NO. wherein X is chloro, bromo or tosyl, is H or CHg and Y has the identity required to provide the final compound, with an at least equimolar amount of an alkali metal methoxide or alkali metal ethoxide in the presence of a lower 10 alkyl alcohol or non-protic organic solvent, at a temperature between ambient and 80°C to yield a compound of formula: NO. 'o

3. The compound N - (1 - ethylpropyl - 3 - methoxymethyl) - 2,b dinitro - £ - toluidine. 4. 4 4 8 8 ίθ 4-Sec-butyl-N- (I -etiiy IpropyI-a-methoxy-2,6-di nitro -m-toluidine. 11. 4-tthyl-a-metnoxy-N-(1-methyl butylj-2,5-dinitro-mtoluidine. b 12. M-(I-ethyl butyl)-7-methoxy-4,6-dinitro-£-cymen-5-amine. 13. 7-Methoxy-N-(2-methoxy-l-methylethyl)-4,6~dinitro-ocymen-amlne. 14. 4-£thyl-N-(i-ethylpropyI)-2,6-dinitro-m-toluidine. 15. N-(1-ethyl propyl )-4,6-dini tro-o-cymen-5-ami ne. 10 16. A compound according to Claim 1 and substantially as described with reference to any one of the illustrations C, D, i, P, Q, R, V, X, AA, AC or AD or any one of the Examples herein.

4. N - isopropyl - 2,6 - dinitro - 4 - propyl - m - toluidine. 5. 4 - Ethyl - N - isopropyl - a - methoxy - 2, 6 - dinitro - m toluidine. b. n - isopropyl - 7 - methoxy - 4,5 - dinitro - 0 - cymen - 5 - amine. 7. N - sec - butyl - Z - methoxy - 4,6 - dinitro - £ - cymen - 5 amine. 8. 4 - Ethyl - N - (1 - ethylpropyl) - a - methoxy - 2,6 dinitro - m - toluidine. 9. N - (1 - ethylpropyl) - 7 - methoxy - 4,6 - dinitro - 0 - cymen - 5 - amine. 4 4 4 8 8 °r CH(CH 3 )CH 2 CH 2 0CH 3 and ji-Pr or -CH(CH 3 )CH 2 CH 2 0CH 3 and £-Pr; (c) R 2 Is j-Bu or £-Pr, Z Is -CHgOCHg and Y is i_-Pr or -CH 3 or (dj R 2 is -CH(C 2 H 5 ) 2 , Y is jt-Bu and Z is -CH 2 0CH 3 ; (e) R 2 is £-Bu, Z is -CHgOCHg and Y is i_-Pr; (f) R^ is bPr,

5. One of illustrations A to C, or D or E to I or J to M, or N to P or Q to R or b to w or x to Y, or AA to AB ana AC or AD or Example 96. z

6. a compound in accordance witn claim 1, prepared by the process of any one of Claims 20 to 25.