GB1573014A - 2,6 dinitroaniline herbicides - Google Patents
2,6 dinitroaniline herbicides Download PDFInfo
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- GB1573014A GB1573014A GB52441/76A GB5244176A GB1573014A GB 1573014 A GB1573014 A GB 1573014A GB 52441/76 A GB52441/76 A GB 52441/76A GB 5244176 A GB5244176 A GB 5244176A GB 1573014 A GB1573014 A GB 1573014A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/19—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
- C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
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Description
(54) 2,6-DINITROANILINE HERBICIDES
(71) We, AMERICAN CYANAMID COMPANY, a Corporation organized
and existing under the laws of the State of Maine, United States of America, of
Berdan Avenue, Township of Wayne, State of New Jersey, United States of
America, do hereby declare the invention for which we pray that a patent may be
granted to us, and the method by which it is to be performed, to be particularly
described in and by the following statement:- This invention relates to certain 2,6-dinitroanilines 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:
wherein (a) R2 is sec-alkyl C3-C7; monochloro-sec-alkyl C3 or C4 or methoxy-sec-alkyl C3 or C4; Z is -CHR3OCH3, R3 being hydrogen or -CH2; and Y is chloro or alkyl selected from -C2H5, n-Pr, i-Pr, sec-Bu and i-Bu; (b) Z is -CH3; and R2 and Y respectively are -CH(C2H5)2 and i-Pr or -CH(C2H5)2 and -C2 H5 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 sec-Bu and
i-Pr or -CH(C2H5)CH2Cl and -Cl or -CH(CH3)-n-Pr
and -C2H5 or -CH(C2H5)CH2Cl and -C2H5 or CH(CH3)CH2Cl and -C2H5 or -CH(CH3)CH2CH2Cl
and -C2H5 or -CH(C2H5)-n-Pr and -C2H5
or sec-Bu and n-Pr or -CH(CH3)-n-Pr and n-Pr or -CH(CH2)-n-Pr and i-Pr or -CH(C2H5)CH2Cl
and n-Pr or -CH(C2H5)CH2Cl and i-Pr or
-CH(CH3)CH2Cl and n-Pr or -CH(CH3)CH2Cl and
i-Pr or -CH(CH3)CH2CH2Cl and n-Pr or
-CH(CH3)CH2CH2Cl and i-Pr or -CH(C2H5)-n-Pr and n-Pr or -CH(C2H5)-n-Pr and i-Pr or -CH(CH3)Ch2OHC3 and - 2H5 or -CH(CH3)CH2OCH3 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-Pr or -CH(CH3)CH2CH2OCH3
and i-Pr; (c) R2 is i-C4H9 or n-Pr, Z is -CH2OCH3 and Y is i-Pr or -CH3 or -C2H5; (d) R2 is -CH(C2H5), Y is n-Bu and Z is -CH2OCH3; (e) R2 is n-Bu, Z is -CH2OCH3 and Y is i-Pr; (f) R2 is i-Pr, Z is -CH2OCH3 and Y is n-C4Hg; (g) R2 is CH(C2H5)2, Z is -CM2OC2H5, and Y is H3.
Within this class of compounds, those having a methoxymethylene substituent
meta to the amino group are especially preferred. This is based upon the un
expected 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 - (I - ethyl
propyl) - 2,6 - dinitro - 3 - methoxymethyl - p - toluidine.
The preemergence 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 generally
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 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 1/16 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 1% to 15% by weight of the active material with from 990/, to 85% by weight of a solid diluent, such as an attaclay, kaolin, diatomaceous earth, fullers earth, talc or pumice.
Dust concentrates are prepared in similar fashion to the dusts excepting that generally 156o to 95 Ó by weight of active material is 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 of the invention 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 used in the dust formulations. Usually, 25% to 75% by weight of the active material and from 73 Ó to 23% by weight of solid carrier is used. In addition, there is generally added 1 ó to 5% by weight of a dispersing agent, such as alkali metal salts of naphthalene sulfonic acid and anionic-nonionic blends, and from 1% to 50o 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% , ,ó 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 herbicides, 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 2methyl-5-nitrobenzyl compound to produce methyl 2-methyl-5-nitrobenzyl ether and the obvious equivalents thereof. The ether is a useful intermediate in the preparation of metamethoxymethylene compounds of formula (I).
This reaction is illustrated below:
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 (II) compound. It is preferred to employ methanol or a non-protic organic solvent such as dimethoxvethane 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 80"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 potasium methoxide are preferred. The reaction is preferably 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 compounds which can be employed in the practice of the present invention involves a nucleophilic substitution of a l-substituent, such as a chloro group, with the appropriately substituted amine. While chloro is a preferred substituent, and the discussion is in terms 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 usually carried out by heating the reactants, preferably at between 50"C. and 150"C.
The chlorobenzene intermediates can be prepared by reacting an appropriate 3,4-disubstituted aniline with ethyl chloroformate in benzene at about 10 C. to 50"C. to yield the correspondingly substituted N-(ethoxycarbonyl)-3,4-disub- stituted aniline. This product is then treated with a cold solution of sulfuric and nitric acid, i.e. at about 0 C. to 200 C. to obtain the N-(ethoxycarbonyl)-3,4-disubstituted2,6-dinitroaniline. 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 thus-formed mixture to about 400C. to 80"C. to obtain the chlorinated compound.
A preferred route for the preparation of compounds of formula (I) wherein R2 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
SOCI2.
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
wherein Z is chloro, bromo or tosyl, R3 is H or CH3 and Y has the identity required to provide the final compound; with an at least equimilar 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 a compound of formula:
wherein Z' is -CH2OCH3,
or -CH2OC2H; and either
a) subjecting compound (A) to reductlve allcylatlon using an appropriaie ketone, to yield a compound of the formula;
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:
wherein Q is a C3-C7 alkylidene group derived from the ketone and then reducing the compound (C) to yield a compound having the formula:
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 raemic composition.
Unless there is indication to the contrary by reference to such a compound, the unresolved composition is intended herein. Separaton 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 preparaton 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 '-methyl-5-nitrobenzyl ether (11.5 g.) was dissolved in 125 ml. of absolute ethanol. To this solution was added a solution of sodium sulfide monohydrate (48.3 g.) and sodium bicarbonate (16.7 g.) in 75 ml. of water. The resulting mixture was refluxed until tlc 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.
Illustartion B.
Preparation of N-(1-Ethylpropyl)-3-(Methoxymethyl)-p-toluidine
A slurry of 3-methoxymethyl)-p-toluidine (9.3 g.) in 40 ml. of diethylketone and SA 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 (10-15ml.) 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 magnesium 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 4250C. under a vacuum of 0.4.5 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; N, 6.24.
Illustration C.
Preparation of N-( 1 - Ethylpropyl) - 3 - (methoxymethyl) - 2,6 - dinitro - p
toluidine; also named (1 - ethylpropyl - 3 - methoxymethyl - 4 - methyl
2,6 - dinitroanaline
A solution of N - (1 - ethylpropyl) - 3 - (methoxymethyl) - p - toluidine (2.13g.) in 10 ml. of dichlorethane was prepared and treated with a nitrating mixture consisting of 3.78 g. of nitric acid, 3.0 g. of concentrated sulfuric acid, and 1.4 g. of water. The addition was carried out at 30 C. # 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 colum chromatography on silica gel with benzene as the eluting agent. All fractions consisting of the same compound by tlc were combined to give 1.3 g. of orange solid with m.p. 55--570C. A sample recrystallized 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; H6.69;
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-2,4-dinitrobenzyl methyl ether and the appropriate amine the following compounds of formula (I) wherein Z is -CH2OCH3 may be obtained:
R2 Y MP "C C3H7-n CH3 67.5-69 C3Hri ,, orange oil C4Hg-sec ,, orange oil C4Hg-i ,, 41.5--43.5" R2 Y MP C
CH(CH3)C3H7-n CH3 31.5-32.5
CH(CH3)C3H7-i ,, orange oil
CH(CH3)C4H8-n ,, orange oil
CH(C2H5)C3H7-n ,, orange oil
CH(CH3)C4H9-i " 61-62
CH(C3H7-n)2 ,, orange oil
CH(CH3)CH2Cl " 55-56.5
CH(C2H5)CH2Cl ,, red oil
CH(CH3)CHClCH3 " 93-97
C3H7-n C2H5 45-46
C3H7-i ,, orange oil C4Hg-sec ,, yellow-orange oil C4Hg-i ,, orange oil
CH(CH3)C3H,-n ,, orange oil
CH(C2H5)2 " 29.5-29
CH(C2H5)C3H,-n ,, orange oil
CH(CH3)C4H9-i ,, orange oil
CH(CH3H,-n)2 ,, orange oil
CH(CH3)CH2Cl " 38-40
CH(C2H5)CH2Cl ,, yellow oil
CH(CH3)CH2CH2Cl " 62-63
C3H7-n C3H7-i 45.5-48.5
C3H,-i ,, red-orange oil C4Hg-n ,, red oil C4Hg-sec ,, red oil C4Hg-i ,, red oil
CH(CH3)C3H,-n ,, red oil
CH(C2H5)2 ,, red-orange oil
CH(CH3)C4H9-n ,, red oil
CH(C2H5)C3H7-n ,, red oil
CH(C2H5)CH2C1 ,, red oil
R2 Y MP C
CH(CH3)CHC1CH3 C3H,-i red oil
C3H,-i C3H,-n orange oil C4H,-sec ,, orange oil
CH(C2H5)2 " 42-43
C3H7-i C4Hg-n orange oil
CH(C2H5)2 ,, orange oil
C3H7-i C4Hg-sec orange oil CH(C2Hs)2 ,, red-orange oil
CH(C2H5)2 C4Hg-i orange oil
C4H9-sec Cl 44-47 CH(CH3)C3H7-n ,, orange oil
CH(C2H5)2 " 70-72
Illustration E.
Preparation of 2'-Methyl-5'-nitroacetophenone
To 120 ml. of concentrated sulfuric acid were 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 stirred for 2 hours at 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 Na2CO3 solution, H20 and finally brine. The ether solution was dried over MgSO4 and evaporated to dryness to give 56.2 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.
Illustartion F.
Preparation of 1-(2'-methyl-5'-nitrophenyl)-ethanol
To a stirred mixture of 23.5 g. of 2'-methyl-5'-nitroacetophenone and 350 ml. of ethanol was added NaB H4 in one portion and the solution was stirred at room temperature for 1 3/4 hours. Water and 2N HCI were 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
MgSO4 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--850. Recrystallization from chloroform and hexane gave pure product, m.p. 85--880.
Illustration G.
Preparation of α,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 indicated starting material remaining. Therefore, 0.52ml. of 50% NaOH solution and 2.0ml. 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".
Illustration H.
Preparation of N-(l -Ethylpropyl)-3-(l -methoxyethyl)-I-toluidine A mixture of 14.6 g. of a-2-dimethyl-5-nitrobenzene methyl ether, 100 ml. of diethyl ketone, 1.0 g. of -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 MgSO4 and evaporation to dryness afforded 17.8 g. of an orange oil. Purification by column chromatography gave pure product as orange liquid.
Illustration 1.
Preparation of N - (I - Ethylpropyl) - 3 - (1 - methoxyethyl) - 2,6 - dinitro - p toluidine
To a stirred solution of 28 g. of 700o H2SO4 and 10.1 ml. of 70% HNO3 was added a solution of 9.41 g. of N - (1 - ethylpropyl) - 3 - (1 - methoxyethyl) -p toluidine in 30 ml. of ethylene chloride. The addition was accomplished at 250 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 I 1/4 hours. After stirring overnight at room temperature, the organic layer was separated and washed with water and brine. The ethylene dichloride solution was mixed with 6 g. of NH2SO3H and 25 ml. of concentrated HCI 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 Na2CO3 solution, water and brine. The ethylene dichloride solution after drying over MgSO4 and evaporation to dryness gave 9.35 g. of crude product as a red oil. Column chromatography afforded 6.27 g. of pure product.
Illustration J.
Preparation of o-Cymen-5-aminehydrochloride
Hydrogenation in 95 iio of 2-isopropyl-5-nitrobenzyl chloride in 95% ethanol (100 ml.) with 10% palladium on carbon catalyst (0.5 g.) at 18--360 and 33-15 psi of hydrogen afforded 12.9g. (935 o) 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-(l -Ethylpropyl)-o-cymen-5-amine o-Cymene-5-amine (8.8 g., 0.064 mole, prepared by neutalization of cymene-5amine hydrochloride with aqueous NaOH) was dissolved in 3-pentanone (43 g., 0.5 mole) and 5A molecular seive (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 6N HCI (30 ml.) to give pH 1, and then with 50% aqueous NaOH to give pH 10. The resulting mixture was filtered to remove inoranic 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 Mg SO4, and concentrated to leave 11.6g. (82.2%) of N-(l-ethylpropyl)-cymen-5-amine, a red liquid. Analysis by glc showed 99.6 area % purity.
Illustration L.
Preparation of N-(l -ethylpropyl)-o-cymen-5-amine A solution of o-cymen-5-amine (33.6 g., 0.24 mole) in 3-pentanone (300 ml.) 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 440 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-(l-ethylpropyl)o-cymen-5-amine of 99.3 area % purity by glc analysis.
Illustration M.
Preparation of N-(1-Ethylpropyl)-4,6-dinitro-o-cymen-5-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 acid (14.0 g. of conc. nitric acid, 0.156 mole). The ice bath was then removed and the reaction mixture was stirred at 3W32 C. for 16 hours. The mixture was then poured on ice and the organic layer (diluted with chloroform) was separated, washed with aqueous sodium bicarbonate solution, dried over MgSO4, 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 hexane, to afford 4.3 g. (41%) of pure product.
Illustration N.
Preparation of 4,6-Dinitro-o-cymen-5-amine
A mixture of 4,6-dinitro-N-(1-ethylpropyl)-o-cymen-5-amine (55 g., 0.18 mole) and aqueous sulfuric acid (1360 ml.) (from concentrated sulfuric acid (680 ml.) and water 680 ml.) was stirred and heated at 7750C. 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., 0.012 mole) 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 slowly to a solution of cuprous chloride (1.5 g.) in concentrated hydrochloric acid (40 ml.). The resulting mixture was stirred at 220 C. for 2 hours, and the precipitated solid product was then filtered off from the cooled reaction mixture, washed with water, and dried in vacua. The product was recrystallized from hexane to afford 2.1 g. of pure 5-chloro-4,6-dinitroo-cymene, m.p. 76 C.
Illustration P.
Preparation of N-Isopropyl-4,6-dinitro-o-cymen-5-amine 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 1000C. 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 colume chromatography to yield 3.2 g. of product with m.p.
5550C.
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 apropriate amine with the desired 3-chloro-2,4-dinitro-6-alkyltoluene the following compounds of formula (I) wherein Z is -CH3 were prepared.
R2 Y R2 y MP C C3H,-i C3H7-n 55" CH(C2Hs)2 ,, orange oil
C3H7-i C3H7-i 54--55" C4Hg-sec " orange oil CH(C2Hs)2 C4Hg-n 47.550 CH(C2Hs)2 C4H9-sec orange oil
Illustration R.
Preparation of 4' - Isopropyl - 2',6' - dinitro - N - propyl - m - propiono
toluidide
A solution of 4,6-dinitro-N-propyl-o-cymen-5-amine (2.7 g., 0.0096 mole), propionic anhydride (4.9 g., 0.038 mole) and concentrated sulfuric acid (2 drops) was heated at 900 C. for 4 hours. The cooled reaction solution was then diluted with aqueous sodium bicarbonate solution and stirred at 250 C. for 0.5 hour. The resulting 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".
Illustration S.
Preparation of a a-Chloro-2-ethyl-5-nitrotoluene
Paraformaldehyde (105.1 g.) was added portionwise to a stirred solution of 620 ml. of concentrated sulfuric acid and 720 ml. of fuming sulfuric acid at 30C. 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 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 1140C. to 1180C. 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. achloro-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 30C. 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 23.50C.
Illustration U.
Preparation of 4-Ethyl-N-( 1 -ethylpropyl)-n-methoxy-m-toluidine A mixture of 10.0 g. of 2-ethyl-5-nitrobenzyl methyl ether, 10.38g. of 3pentanone, 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 480C. to 600C. The mixture was diluted with 200 ml. of ether, filtered and the filtrate shaken with 2.5 4 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 tlc analyses.
Illustration V.
Preparation of 4 - Ethyl - N - (1 - 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-(l-ethylpropyl)-a-methoxy-rn-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 yelloworange 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 1. of 50% sulfuric acid with stirring and then warmed to 700 C. 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 CCI4 (100 ml.) and poured with stirring into 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 750 ml. acetic acid) was added slowly with stirring to a solution of NaNO2 (17 g.) in 136 ml. sulfuric acid at 10--15"C After 30 minutes this reaction mixture was added to a solution of
CuCI (37.8 g.) in 480 ml. hydrochloric acid with stirring. The product (25.0g.) precipitated from the cooled reaction mixture in 58% yield with m.p. 81--82". The filtrate upon dilution yielded another lOg. of product.
Illustration Y.
Preparation of 4 - Ethyl - ez - methoxy - N - [1 - (methoxymethyl) - propyl]
2,6 - dinitro - m - toluidine The benzyl ether obtained in illustration X (5g.) and l-(methoxymethyl)propylamine (4.1 g.) were dissolved in toluene (100 ml.) and heated to reflux. After 20 hours the reaction mixture 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 -CM2OCM3 were prepared.
R2 Y MP C.
CH(CH3)CH2OCH3 C2H5 62-64
CH(C2H5)CH2OCH3 CH3 34.5-36.5 CH(C2H5)CH2OCH2 C3H7-i red oil
Illustration AB.
Preparation of α -methoxy-N-(2-methoxy-1-methylethyl)-3,4-xylidine A mixture of methyl 2-methyl-5-nitrobenzyl ether (12 g., 0.066 M), 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 (0.26 M) 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%; H9.48%; N-6.26%; Found: C-69.88%; H-9.19%; N-6.36%.
Illustration AC.
Preparation of a2 - Methoxy - N - (2 - methoxy I - methylethyl) - 2,6
dinitro - 3,4 - xylidine
A nitration mixture consisting of concentrated sulfuric acid (1.4g.), water (0.7 g.) and 70% nitric acid (1.8 g.) is added at 250 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 250 for 1 hour, then at 40 for I 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. (64%) 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 the appropriate a3-methoxy-3,4- xylidine or 4-chloro-α-methoxy-m-toluidine was dinitrated to give the following compounds of formula (I) wherein Z is -CH2OCH3.
R2 Y MP C CH(CH3)CH2OCH3 C3H,-i orange oil CH(CH3)CH2CH20CH3 ,, orange oil
CH(CH3)CH2CH2OCH3 Cl orange oil
CH(CH3)CH2OCH3 " 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 planting, 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 four weeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system set forth below.
Rating System
%Difference in Growth
Rating System 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, 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-(l-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 preemergence herbicidal activity of the test compound is provided in the table below.
Plant Abbreviations:
SE - Sesbania (Sesbania exaltata) MU - Mustard (Brassica kaber)
PI - Pigweed (Amaranthus retroflexus) RW - Ragweed (Ambrosia artemisiifolia)
MG - Morningglory (Ipomoea purpurea)
BA - Barnyardgrass (Echinochloa crusgalli)
CR - Crabgrass (Digitaria sanguinalis) FO - Green foxtail (Setaria viridis)
TW - Teaweed (Sida spinosa)
VL - Velvetleaf (Abutilon theophrasti)
CN - Corn (Zea mays) CO - Cotton (Gossypium hirsutum)
SY - Soybean (Glycine max)
RI - Rice (Oryza sativa) TABLE 1
Selective Preemergence Herbicidal Evaluation
ooooo ooooo 0 coooo U Z Inoooo U Ir, .O Rate a X ; > co 9 9 9 7 9 8 9 9 9 9 5 2 3 0 3 Oo x oo 00 > 0.28 7 9 9 0 1 8 9 9 9 9 0 0 0 0 0.16 3 9 9 0 0 8 7 9 9 9 0 0 0 0 U 0 7 # 9 -coo 3 > o o o o S 2 cz ~ X cs o U N aD 00 V: F 8 g Examples 2-66.
Following the procedure of Example 1, the compounds indicated in Table 2 below were tested with the reported results.
TABLE 2
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(C2H5)2 -CH3 -C3H7-n 1.0 0 9 8 0 1 8 3 9 9 9 0 0 0 0 0.5 0 9 7 0 0 6 0 9 9 9 0 0 0 0 0.25 0 0 5 0 0 0 0 5 9 7 0 0 0 0 0.13 0 3 0 0 0 0 0 9 5 0 0 Example 2 0.06 0 0 0 0 0 0 0 0 2 0 0 0 0 0.03 0 0 0 0 0 0 0 3 0 0 0 0 -CH(CH3)C2H5 -CH3 -C2H5 1.0 8 8 7 2 2 8 6 9 9 9 2 0 5 0.5 2 0 6 0 0 8 3 9 9 9 0 0 0 0.25 0 5 0 0 7 0 9 9 9 0 0 0 0 Example 3 0.13 0 0 0 0 3 0 8 9 8 0 0 0.06 0 0 0 0 0 0 6 9 0 0 0 0 0.03 0 0 0 0 0 0 0 3 3 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(C2H5)CH2Cl -CH3 -Cl 2.0 9 9 9 1.0 8 9 9 0.5 9 9 9 Example 4 0.25 7 9 6 0.13 6 7 5 **-CH(C2H5)2 -CH3 -CH(CH3)2 1.0 8.5 9 9 1.5 7 8.5 8 9 9 9 2 0 0 0 0.5 5.5 8.5 9 0 4 7.5 5.5 9 9 9 1 0 0 0 0.25 1 8 8 0 1 7.5 7 8.5 9 9 0 0 0 0 Example 5 0.13 0 5 5 0 1 3.5 1.5 6.5 9 7 0 0 0 0 0.06 0 1 1.5 0 0 3.5 0.5 1 8 4 0 0 0 0 0.03 0 0 0 0 0 0 0 0 6.5 2.5 0 0 0 0 **Average two tests.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI ***-CH(C2H5)2 -CH3 -C2H5 1.0 6.7 8.3 8 4.3 7.3 8 8.6 9 9 9 3.3 0.3 0 1 0.5 4.6 7.3 8 1 5 7.6 7 9 9 9 1.3 0.3 0 0 0.25 2.3 4.6 5.6 0 1.6 7.6 3.6 8.3 9 9 0.6 0 0 0 0.13 1 4 4.3 0 0.6 5 1.3 6.6 9 7.6 0.3 0 0 0 Example 6 0.06 1 0 2.6 0 0.3 2.3 1 3 8 5.3 0 0 0 0 0.03 0.6 0 1 0 0 1.6 0 1.6 7 3 0 0 0 0 -CH(CH3)2 -CH3 -C2H5 1.0 6 9 7 7 0 8 2 9 9 9 3 0 0 0.5 0 9 2 0 0 3 0 9 9 9 0 0 0 0.25 0 0 0 0 2 0 9 9 7 0 0 0 0.13 0 0 0 0 0 0 9 9 7 0 0 0 0 Example 7 0.06 0 0 0 0 0 0 0 3 7 3 0 0 0 0 0.03 0 0 0 0 0 0 0 0 3 0 0 0 0 ***Average three tests.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI C3H7-i -CH3 -C3H7-i 1.0 7 9 7 0 0 7 5 9 9 9 1 0 0 0 0.50 0 0 5 0 0 2 0 9 9 9 0 0 0 0 0.25 0 5 0 0 0 0 8 9 9 0 0 0 0 0.13 0 0 0 0 0 0 0 8 9 8 0 0 0 0 Example 8 0.06 0 0 0 0 0 0 0 2 5 5 0 0 0 0 0.03 0 0 0 0 0 0 0 0 2 2 0 0 0 0 -C4H9-sec -CH3 -C3H7-i 1.0 8 8 8 3 5 8 7 9 9 9 5 0 0 2 0.50 7 8 7 0 3 8 2 9 9 9 0 0 0 0 0.25 0 0 6 0 0 3 1 9 9 9 0 0 0 0.13 0 0 3 0 0 0 0 9 9 9 0 0 0 0 Example 9 0.06 0 0 0 0 0 9 9 6 0 0 0 0 0.03 0 0 0 0 0 0 0 5 7 5 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(C2H5)2 -CH3 -C4H9-sec 1.0 0 0 8 0 0 7 2 9 9 9 0 0 0 0 0.50 0 6 0 0 0 8 9 8 0 0 0 0 0.25 0 0 0 0 0 0 8 9 7 0 0 0 0 Example 10 0.13 0 0 0 0 0 0 0 7 2 0 0 0 0 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(CH3)C2H5 -CH2OCH3 -C3H7-n 1.0 2 8 8 0 0 8 5 9 9 9 7 0 0 0 0.5 0 8 3 0 0 2 1 9 9 9 0 0 0 0 0.25 0 9 7 0 0 0 0 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0 9 9 9 0 0 0 0 Example 11 0.06 0 0 0 0 0 0 7 7 9 0 0 0 0 0.03 0 0 0 0 0 0 0 8 6 6 0 0 0 0 -CH(CH3)2 -CH2OCH3 -C3H7-n 1.0 0 0 7 0 0 8 2 9 9 9 2 0 0 0.5 0 0 6 0 0 7 0 9 9 9 0 0 0 0 0.25 0 0 0 0 0 2 0 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0 8 8 8 0 0 Example 12 0.06 0 0 0 0 0 0 8 8 7 0 0 0 0 0.03 0 0 0 0 0 0 0 5 3 3 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(C2H5)2 -CH2OCH3 -C4H9-i 1.0 2 9 6 0 0 7 6 9 9 9 0 0 3 0 0.5 0 9 2 0 0 2 3 8 9 9 0 0 0 0.25 0 0 0 0 0 2 8 9 8 0 0 0 0 0.13 0 0 0 0 0 0 0 7 7 6 0 0 0 Example 13 0.06 0 0 0 0 0 0 0 2 2 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 -CH(C2H5)2 -CHOCH3 -CH3 1.0 6 5 8 0 2 8 6 9 9 9 0 0 2 0.5 0 6 0 0 7 5 9 9 9 0 0 0 2 CH3 0.25 0 5 0 0 2 9 9 9 0 0 0 1 0.13 2 0 0 1 0 8 9 8 0 0 0 Example 14 0.06 0 0 0 0 0 0 5 8 3 0 0 0 0.03 0 0 0 0 0 0 3 3 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI * -C4H9-i -CH2OCH3 -C3H7-i 1.0 8 8 0 0 2 0 9 9 9 0 0 0 3 0.50 0 8 7 0 0 0 0 9 9 9 0 0 0 0 0.25 0 0 2 0 0 0 0 8 9 8 0 0 0 0 0.13 0 0 0 0 0 0 0 3 8 5 0 0 0 0 Example 15 0.06 0 0 0 0 0 0 0 7 2 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 -C3H7-i -CH2OCH3 -C4H9-sec 1.0 2 9 8 0 0 7 9 9 9 9 2 0 0 0 0.50 2 9 7 0 0 7 0 9 9 9 2 0 0 0 0.25 0 7 3 0 0 0 0 9 9 8 0 0 0 0 0.13 0 0 2 0 0 0 0 9 8 7 0 0 0 0 Example 16 0.06 0 0 2 0 0 0 0 6 8 6 0 0 0 0 0.03 0 0 0 0 0 0 0 3 7 2 0 0 0 0 -CH(CH3)CH2Cl -CH2OCH -CH3 1.0 2 6 8 0 0 6 5 9 9 9 3 0 0 0 0.50 0 9 0 0 2 0 9 9 9 0 0 0 0.25 0 0 3 0 0 0 0 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0 7 8 7 0 0 0 0 Example 17 0.06 0 0 0 0 0 0 0 6 6 6 0 0 0 0 0.03 0 0 0 0 0 0 6 3 0 0 0 0 0 *Novel but not covered in proposed generic formula.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -CH(C2H5) C3H7-n -CH2OCH3 -C3H7-i 1.0 8 9 7 2 8 9 9 9 9 2 0 0 0 0.50 7 9 0 2 8 5 9 9 9 0 0 0 0 0.25 2 9 0 0 8 4 9 9 9 0 0 0 0 0.13 0 7 0 0 6 4 7 9 9 0 0 0 0 Example 18 0.06 0 5 0 0 2 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 0 9 9 0 0 8 2 9 9 9 0 0 0 3 -CH(CH3)CH2CH2Cl -CH2OCH3 -C2H5 0.50 9 7 0 0 6 0 9 9 9 0 0 0 3 0.25 0 9 0 0 0 0 0 9 9 9 0 0 0 0 0.13 0 9 0 0 0 0 0 9 9 9 0 0 0 0 Example 21 0.06 0 8 0 0 0 0 0 9 9 6 0 0 0 0 0.03 0 8 0 0 0 0 0 8 8 8 0 0 0 0 1.0 2 9 8 8 2 8 8 9 9 9 2 0 0 0 -CH(C2H5)2 -CH2OCH3 -C3H7-n 0.50 0 9 8 0 0 7 1 8 9 9 0 0 0 0 0.25 0 9 8 0 2 0 8 9 9 0 0 0 0 0.13 0 0 0 0 0 0 8 9 9 0 0 0 0 Example 22 0.06 0 0 0 0 0 0 5 8 7 0 0 0 0 0.03 0 0 0 0 0 0 0 5 5 0 0 0 0 1.0 8 9 9 3 9 8 9 9 9 4 0 0 0 -C4H9-sec -CH2OCH3 -C3H7-i 0.50 7 9 3 2 9 8 9 9 9 1 0 0 0 0.25 3 9 0 1 7 7 9 9 9 0 0 0 0 0.13 0 8 0 0 6 3 7 9 9 0 0 0 0 Example 23 0.06 0 7 0 0 2 1 2 9 9 0 0 0 0 0.03 0 0 0 0 2 9 5 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO CY SB RI 1.0 0 8 9 0 0 8 0 9 9 9 0 0 0 0 -CH(CH3)CHClCH3 -CH2OCH3 -C3H7-i 0.50 0 8 8 0 0 2 0 8 9 9 0 0 0 0.25 0 0 6 0 0 0 0 3 9 9 0 0 0 0 0.13 0 0 0 0 0 0 0 9 7 0 0 0 0 Example 24 0.06 0 0 0 0 0 0 0 0 9 3 0 0 0 0 0.03 0 0 0 0 0 0 0 7 0 0 0 0 0 1.0 0 9 8 0 0 2 0 8 9 9 0 0 0 0 -CH(CH3)C4H9-n -CH2OCH3 -C3H7-i 0.50 0 5 2 0 0 0 0 8 9 9 0 0 0 0 0.25 0 0 0 0 0 0 0 2 9 9 0 0 0 0.13 0 0 0 0 0 0 2 9 6 0 0 0 0 Example 25 0.06 0 0 0 0 0 0 0 2 2 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 1.0 0 8 8 0 0 7 0 9 9 9 0 0 0 0 -CH(CH3)CH2C3H7-i -CH2OCH3 -CH3 0.50 0 0 5 0 0 2 0 8 9 9 0 0 0 0 0.25 0 0 0 0 0 0 0 8 9 9 0 0 0 0 0.13 0 0 0 0 0 0 8 7 3 0 0 0 0 Example 26 0.06 0 0 0 0 0 0 3 6 2 0 0 0 0 0.03 0 0 0 0 0 0 0 0 3 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI -C4H9-i -CH2OCH3 -CH3 1.0 3 3 3 0 0 2 0 8 9 6 0 0 0 0 0.50 0 0 0 0 0 0 0 2 2 0 0 0 0 0 Example 27 0.25 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.0 6 8 9 2 7 8 7 9 9 9 0 0 0 5 -CH(C2H5)CH2Cl -CH2OCH3 -C3H7-i 0.50 0 9 9 0 7 2 9 9 9 0 0 0 0 0.25 0 7 8 0 0 6 2 9 9 9 0 0 0 0 0.13 0 0 7 0 0 0 0 9 9 9 0 0 0 0 Example 28 0.06 0 6 0 0 0 0 0 8 9 8 0 0 0 0 0.03 0 0 0 0 0 0 0 9 0 0 0 0 0 1.0 0 3 0 0 7 2 9 9 9 0 0 0 0 -CH(CH3)CHClCH3 -CH2OCH3 -CH3 0.50 0 0 0 0 3 0 9 9 9 0 0 0 0 0.25 0 0 0 0 0 5 7 6 0 0 0 0 0.13 0 0 0 0 0 0 2 6 2 0 0 0 0 Example 29 0.06 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 7 9 0 2 8 7 9 9 9 2 0 0 2 -CH(CH3)C3H7-n -CH2OCH3 -C3H7-i 0.50 2 9 0 0 8 6 9 9 9 0 0 0 0 0.25 0 9 0 0 2 2 9 9 9 0 0 0 0 0.13 0 8 0 0 0 1 9 9 9 0 0 0 0 Example 30 0.06 5 0 0 0 1 7 9 9 0 0 0 0 0.03 0 0 0 0 0 0 2 9 7 0 0 0 0 1.0 2 8 9 0 1 8 5 9 9 9 0 0 0 0 -CH(C2H5)CH2Cl -CH2OCH3 -C2H5 0.50 0 0 8 0 0 7 2 9 9 9 0 0 0 0.25 0 0 6 0 0 7 0 9 9 9 0 0 0 0.13 0 2 0 0 0 0 9 9 7 0 0 0 0 Example 31 0.06 0 0 0 0 0 0 0 8 9 6 0 0 0 0 0.03 0 0 0 0 0 0 2 9 3 0 0 0 0 1.0 2 9 9 3 0 7 3 9 9 9 0 0 0 7 -CH(C2H5)2 -CH2OCH3 -C4H9-sec 0.50 0 9 7 0 0 3 0 8 9 9 0 0 0 3 0.25 0 5 7 0 0 0 0 8 9 9 0 0 0 0 0.13 0 0 3 0 0 0 0 7 9 9 0 0 0 0 Example 32 0.06 0 0 0 0 0 0 0 8 8 0 0 0 0 0.03 0 0 0 0 0 0 0 8 5 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 0 9 7 0 0 7 2 9 9 9 1 0 0 0 -CH(C2H5)CH2Cl -CH2OCH3 -CH3 0.50 0 9 8 0 0 2 0 9 9 9 0 0 0 0 0.25 0 2 2 0 0 0 0 8 9 9 0 0 0 0 0.13 0 0 0 0 0 0 5 9 8 0 0 0 Example 33 0.06 0 0 0 0 0 0 2 7 2 0 0 0 0 0.03 0 0 0 0 0 0 0 3 0 0 0 0 0 1.0 0 8 8 0 0 2 2 2 9 9 2 0 0 2 -C3H7-n -CH2OCH3 -CH3 0.50 0 0 0 0 0 0 0 2 9 9 0 0 0 0.25 0 0 0 0 0 0 0 8 2 0 0 0 0 Example 34 0.13 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.0 0 9 7 0 0 3 0 8 9 9 0 0 0 0 -C4H9-n -CH2OCH3 -C3H7-i 0.50 0 7 2 0 0 0 0 7 9 9 0 0 0 0.25 0 0 0 0 0 0 3 6 9 0 0 0 0 0.13 0 0 0 0 0 0 0 1 6 0 0 0 0 Example 35 0.06 0 0 0 0 0 0 0 0 2 2 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 0 8 7 0 0 2 2 9 9 9 0 1 0 0 -CH(CH3)C3H7-i -CH2OCH3 -CH3 0.50 0 9 6 0 0 0 0 9 9 9 0 0 0 0 0.25 0 0 2 0 0 0 0 8 9 9 0 0 0 0 0.13 0 0 0 0 0 0 6 8 5 0 0 0 0 Example 36 0.06 0 0 0 0 0 0 2 5 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.0 2 9 8 6 0 8 0 9 9 9 0 0 0 0 **-C4H9-sec --CH2OCH3 -Cl 0.50 0 9 6 0 0 2 0 9 9 9 0 0 0 0 0.25 0 0 3 0 0 0 0 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0 5 9 9 0 0 0 0 Example 37 0.06 0 0 0 0 0 0 0 2 7 2 0 0 0 0 0.03 0 0 0 0 0 0 0 0 2 0 0 0 0 0 1.0 0 8 9 0 0 8 2 9 9 9 3 0 0 0 -CH(CH3)CH2Cl -CH2OCH3 -C2H5 0.05 0 9 8 0 0 7 1 9 9 9 1 0 0 0 0.25 7 0 0 2 0 9 9 9 0 0 0 0.13 0 0 0 0 0 0 9 9 9 0 0 0 Example 38 0.06 0 0 0 0 0 0 0 2 8 9 0 0 0 0 0.03 0 0 0 0 0 0 0 0 5 1 0 0 0 0 *Average of two tests.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 7 7 9 5 7 7 7 9 9 9 3 6 0 0 -C4H9-sec -CH2OCH3 -C2H5 0.5 7 7 7 3 5 7 6 9 9 9 2 1 0 0 0.25 5 7 0 1 7 3 9 9 9 1 0 0 0 0.13 3 0 6 0 0 7 3 9 9 9 1 0 0 Example 39 0.06 0 0 3 0 0 5 0 7 8 8 0 0 0 0 0.03 0 2 0 0 3 0 6 8 8 0 0 0 0 1.0 0 9 9 0 0 8 8 9 9 9 1 0 0 0 -CH(CH3)C3H7-n -CH3OCH3 -CH3 0.50 0 6 6 0 0 7 6 9 9 9 0 0 0 0 0.25 0 6 6 0 0 6 1 7 9 9 0 0 0 0 0.13 0 0 2 0 0 3 0 2 9 5 0 0 0 0 Example 40 0.06 0 0 0 0 0 0 2 9 3 0 0 0 0 0.03 0 0 0 0 0 0 0 6 0 0 0 0 0 1.0 0 8 9 0 3 8 5 9 9 9 1 0 0 0 -CH(C2H5)C3H7-n -CH2OCH3 -CH3 0.50 0 8 8 0 0 6 3 9 9 9 0 0 0 0 0.25 0 9 7 0 0 2 2 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0 0 8 9 9 0 0 0 0 Example 41 0.06 0 0 0 0 0 0 0 0 7 5 0 0 0 0 0.03 0 0 0 0 0 0 0 0 3 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 0 9 6 0 0 3 3 9 9 9 0 2 0 0 -C4H9-i -CH2OCH3 -C2H5 0.50 0 0 6 0 0 0 0 8 9 8 0 2 0 0 0.25 0 3 0 0 0 0 3 9 6 0 0 0 0 0.13 0 0 0 0 0 0 0 0 7 0 0 0 0 0 Example 42 0.06 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1.0 5 9 9 2 0 8 7 9 9 9 2 5 2 3 -CH(CH3)CH2C3H7-i -CH2OCH3 -C2H5 0.50 0 7 9 0 0 8 3 9 9 9 0 3 0 0 0.25 0 7 8 0 0 3 1 9 9 9 0 0 0 0 0.13 0 0 7 0 0 0 0 9 9 9 0 0 0 0 Example 43 0.06 0 0 5 0 0 0 0 5 9 9 0 0 0 0 0.03 0 0 0 0 0 0 0 0 9 3 0 0 0 0 1.0 8 9 9 0 8 8 8 9 9 9 2 2 2 2 -C3H7-i -CH2OCH3 -C3H7-i 0.50 7 9 8 0 8 8 7 9 9 9 0 2 0 0 0.25 2 9 8 0 2 7 3 9 9 9 0 0 0 0 0.13 2 2 2 0 0 2 1 9 9 9 0 0 0 0 Example 44 0.06 0 0 0 0 1 0 9 9 9 0 0 0 0.03 0 0 0 0 0 0 0 2 9 9 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 8 9 9 7 3 8 9 9 9 9 1 0 0 0 -CH(C2H5)C3H7-n -CH2OCH3 -C2H5 0.50 0 9 9 0 0 8 6 9 9 9 0 0 0 0 0.25 0 7 9 0 0 7 5 7 9 9 0 0 0 0 0.13 0 0 7 0 0 3 2 5 9 9 0 0 0 0 Example 45 0.06 0 5 0 0 0 0 1 9 6 0 0 0 0 0.03 0 0 5 0 0 0 0 0 7 3 0 0 0 0 1.0 2 8 9 0 0 7 7 9 9 9 1 5 0 0 -CH(C3H7-n)2 -CH2OCH3 -C2H5 0.50 0 9 9 0 0 3 2 9 9 9 0 2 0 0 0.25 0 3 9 0 0 2 0 9 9 9 0 2 0 0 0.13 0 0 5 0 0 0 0 2 9 8 0 0 0 0 Example 46 0.06 0 0 3 0 0 0 0 0 7 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 5 0 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 8 8.3 8.3 5 6 8.3 8 9 9 9 5 4 4.7 0 5 -CH(C2H5)2 -CH2OCH3 -C2H5 0.50 4.7 8.3 8 2.3 4 8 8 9 9 9 1.3 1.7 0 0 5 0.25 2 8 8 1 1.7 8 5.3 9 9 9 1.5 1 0 0 2 0.13 2 4.3 5.3 0 0.3 8 2.7 8.7 9 9 1 0 0 0 0 Example 47 0.06 2.5 3 2 0 0 7 1 8 9 9 0.5 0 0 0 0 0.03 0 0 1.7 0 0 3.3 0 5 8.3 7 0.5 0 0 0 0 1.0 2 9 9 0 0 8 7 9 9 9 0 0 0 0 -C3H7-i -CH2OCH3 -C2H5 0.50 0 0 7 0 0 8 6 9 9 9 0 0 0 0 0.25 0 0 3 0 0 7 3 9 9 9 0 0 0 0 0.13 0 0 0 0 2 0 3 9 9 0 0 0 0 Example 48 0.06 0 0 0 0 0 0 0 3 9 9 0 0 0 0 0.03 0 0 0 0 0 0 0 9 7 0 0 0 0 1.0 6 9 9 3 0 8 7 9 9 9 2 0 0 0 -CH(CH3)C3H7-n -CH2OCH3 -C2H5 0.25 0 9 7 0 0 6 2 9 9 9 0 0 0 0.13 0 9 6 0 0 3 2 3 9 9 0 0 0 0 Example 49 0.06 0 0 2 0 0 2 0 1 9 9 0 0 0 0 0.03 0 0 1 0 0 0 0 0 8 6 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 2.5 9 8.5 1.5 3 8 8 9 9 9 2 0 0 0 ***-CH(C2H5)2 -CH2OCH3 -Cl 0.50 0 7.5 6.5 0 1 7.5 5 9 9 9 1.5 0 0 0 0.25 0 #9 6.5 0 0.5 4.5 2 8.5 9 8 0.5 0 0 0 0.13 0 #5 4 0 0 1.5 0.5 2 9 7.5 0 0 0 0 Example 50 0.06 0 0 0 0 0 1 0 2 8.5 3 0 0 0 0 0.03 0 0 0 0 0 0 0 1 6.5 2 0 0 0 1.0 0 9 8 0 0 5 0 7 9 9 0 0 0 -CH(CH3)C3H7-n -CH2OCH3 -Cl 0.50 0 7 5 0 0 0 0 7 9 9 0 0 0 0.25 0 8 0 0 0 0 0 7 8 9 0 0 0 0 0.13 0 0 0 0 0 0 0 0 7 7 0 0 0 0 Example 51 0.06 0 0 0 0 0 0 0 0 6 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ***Average of two tests. # Single test.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 7 6 7 0 0 7 1 9 9 9 2 0 0 0 -C3H7-n -CH2OCH3 -C3H7-i 0.50 6 1 6 0 0 5 1 9 9 9 1 0 0 0 0.25 1 0 2 0 0 1 0 7 9 7 0 0 0 0.13 0 0 0 0 0 0 0 3 7 6 0 0 0 Example 52 0.60 0 0 0 0 0 0 0 1 6 5 0 0 0 0 0.03 0 0 0 0 0 0 0 0 3 3 0 0 0 0 1.0 3.5 1.5 6.5 1.5 0 7 2.5 9 9 9 0 0 0 0 -C3H7-i -CH2OCH3 -CH3 0.50 1 1 4 0 0 3.5 1.5 9 9 9 0 0 0 0 0.25 0 0 2.5 0 0 1.5 0 9 9 9 0 0 0 0 0.13 0 0 0 0 0 0.5 0 4.5 7.5 7.5 0 0 0 0 Example 53 0.06 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 7.6 7.5 8.7 3.6 4.3 8.5 8.3 9 9 9 2.4 3.0 0.6 .9 *-CH(C2H5)2 -CH2OCH3 -CH3 0.50 5.3 8.5 8.5 0 2.5 8.3 7.5 9 9 9 0.9 1.3 0 0 0.25 2.4 7.6 8.1 0 0.7 7.6 5.9 8.8 9 9 0.7 0 0 0 0.13 1.0 5.4 5.8 0 0 6.8 3.2 8.7 8.9 9 0 0 0 0 Example 55 0.06 0 2.1 3.8 0 0 3.9 1.1 6.5 8.9 8.5 0 0 0 0 0.03 0 0 1.1 0 0 0.8 0 4.6 8.2 6.1 0 0 0 0 1.0 6.0 7.3 8.3 2 1 8 7.7 9 9 9 1 1 0 0.7 **-C4H9-sec -CH2OCH3 -CH3 0.50 3.5 5.3 7 0 0.7 7.7 5.7 9 9 9 0 1.7 0 0 0.25 0 3 4.5 0 0 6 2 8.3 9 9 0 0 0 0 0.13 0 0 1 0 0 2.3 0.7 8 9 9 0 0 0 0 Example 56 0.06 0 0 0 0 0 1 0 7 9 7.7 0 0 0 0 0.03 0 0 0 0 0 0 0 6.7 8.3 6.7 0 0 0 0 1.0 7.7 8 8.3 6 7.7 8.3 8 9 9 9 5 2.7 0 0 6 -CH(C2H5)2 -CH2OCH3 -C3H7-i 0.50 7.7 8 8 4.7 4.3 8.3 8 9 9 9 3 2.3 0 0 3 0.25 6.7 8 8 2.7 6 8 6.3 9 9 9 1 1.7 0 0 0 0.13 5.3 8 7.6 0.7 2 7.3 3 8.7 9 9 0.3 1.7 0 0 0 Example 57 0.06 0 3.5 7 0 0.3 6 1.7 7.6 9 9 0.3 0 0 0 0 0.03 1 1 1.7 0 0.3 1.3 0 3.8 8.7 8.3 0.3 0 0 0 0 *Average of 10 to 15 tests. **Average of 2 to 3 tests.
TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 10.0 9 9 9 9 8 9 8 9 9 9 9 1.0 0 9 9 0 0 7 3 9 9 9 0 6 0 0 -CH(CH3)CH2CH2OCH3 -CH2OCH3 -C3H7-i 0.50 0 9 9 0 0 2 2 9 9 9 0 3 0 0 0.25 0 8 7 0 0 0 0 9 9 9 0 0 0 0 0.13 0 8 2 0 0 0 0 9 9 9 0 0 0 0 Example 58 0.06 0 0 0 0 0 0 8 9 6 0 0 0 0 0.03 0 0 0 0 0 0 3 8 3 0 0 0 0 10.0 8 9 9 8 8 8 8 9 9 9 9 1.0 0 7 0 0 8 0 9 9 9 0 0 0 0 -CH(CH3)CH2OCH3 -CH2OCH3 -Cl 0.50 0 0 0 0 0 0 9 9 9 0 0 0.25 0 0 0 0 0 0 3 9 8 0 0 0 0 0.13 0 0 0 0 0 0 2 6 0 0 0 0 0 Example 59 0.06 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 0 10.0 8 9 9 9 8 8 8 9 9 9 1.0 8 9 9 3 1 8 6 9 9 9 5 0 0 0 -CH(C2H5)CH2OCH3 -CH2OCH3 -C3H7-i 0.50 5 9 9 3 1 8 5 9 9 9 8 0 0 0.25 5 0 8 0 1 7 3 9 9 9 3 0 0 0 0.13 0 8 0 0 5 2 9 9 9 1 0 0 0 Example 60 0.06 0 0 7 0 0 2 0 9 9 9 0 0 0 0.03 0 0 2 0 0 0 0 9 9 9 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 10.0 9 9 9 9 9 9 9 9 9 9 8 1.0 7 8 9 0 2 9 9 9 9 9 5 5 7 0 -CH(C2H5)CH2OCH3 -CH2OCH3 -C2H5 0.50 6 9 9 0 0 8 8 9 9 9 2 8 0 0 0.25 2 9 9 0 0 7 6 9 9 9 0 0 0 0 0.13 0 3 7 0 0 3 3 9 9 9 0 0 0 0 Example 61 0.06 0 0 6 0 0 0 2 9 9 9 0 0 0 0 0.03 0 5 0 0 0 0 9 9 9 0 0 0 0 10.0 9 9 9 9 8 9 9 9 9 9 9 1.0 0 9 9 0 2 9 8 9 9 9 2 7 0 2 -CH(C2H5)CH2OCH3 -CH2OCH3 -CH3 0.50 0 8 9 0 0 8 8 9 9 9 0 3 0 0 0.25 0 0 7 0 0 2 2 9 9 9 0 2 0 0.13 0 0 5 0 0 0 0 9 9 8 0 2 0 0 Example 62 0.06 0 0 0 0 0 0 0 8 9 7 0 0 0 0 0.03 0 0 0 0 0 0 0 2 2 0 0 0 0 0 10.0 9 9 9 9 8 9 8 9 9 9 9 1.0 6 9 9 7 7 7 8 9 9 9 2 6 0 2 -CH(CH3)CH2OCH3 -CH2OCH3 -C3H7-i 0.50 6 9 9 0 0 8 6 9 9 9 2 0 0 2 0.25 9 8 0 0 6 5 9 9 9 0 0 0 0 0.13 0 5 6 0 0 0 2 9 9 9 0 0 0 0 Example 63 0.06 0 2 0 0 0 9 9 9 0 0 0 0 0.03 0 0 0 0 0 0 0 9 9 0 0 0 0 TABLE 2 (Continued)
Preemergence Herbicidal Evaluation of
Structure Plant Species Rate R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 10.0 8 9 9 9 8 8 8 9 9 9 8 1.0 6 3 7 0 1 7 6 9 9 9 2 1 0 -CH(CH3)CH2OCH3 -CH2OCH3 -CH3 0.50 2 0 7 0 0 6 3 9 9 9 1 0 0 0 0.25 2 0 6 0 0 5 1 7 7 6 0 0 0 0 0.13 0 0 1 0 0 3 1 6 7 7 0 0 0 0 Example 64 0.06 0 0 0 0 0 1 0 1 6 6 0 0 0.03 0 0 0 0 0 1 0 0 2 2 0 0 0 10.0 8 9 9 9 9 9 9 9 9 9 9 1.0 2 9 9 0 8 9 8 9 9 9 0 0 0 0 -CH(CH3)CH2OCH3 -CH2OCH3 -C2H5 0.50 0 2 9 0 0 8 7 9 9 9 0 0 0 0 0.25 0 9 0 0 3 3 9 9 9 0 0 0 0 0.13 0 0 2 0 0 2 0 8 9 9 0 0 0 0 Example 65 0.06 0 0 2 0 0 0 0 6 9 9 0 0 0 0 0.03 0 0 0 0 0 0 0 2 6 6 0 0 0 0 10.0 0 8 9 0 8 8 7 9 9 9 3 -CH(CH3)CH2CH2OCH3 -CH2OCH3 -Cl 1.0 9 0 0 0 0 0 2 5 9 7 0 0 0 0 0.50 0 0 0 0 0 0 0 2 6 6 0 0 0 0 Example 66 0.25 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Example 67.
Postemergence Herbicidal Evaluation
Postemergence herbicidal activity is demonstrated by the following tests, wherein a variety of 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 0.59d 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. From 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.
~ Difference in Growth Rating System: from the Check* # - 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 - Abmormal growth, that is, 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.
Plant Abbreviations:
SE ~ Sesbania (Sesbania exaltata) MU - Mustard (Brassica kaber)
PI ~ Pigweed (Amaranthus retroflexus) RW - Ragweed (Ambrosia artemisEifolia) MG - Morningglory (Ipomoea purpurea)
BA - Barnyardgrass (Echinochloa crusgalli)
CR - Crabgrass (Digitaria sanguinalis) FO - Green foxtail (Setaria viridis) WO - Wild Oats (Avena fatua) TW - Teaweed (Sida spinosa)
VL ~ Velvetleaf (Abutilon theophrastil TABLE 3
Postemergence Herbicidal Evaluation
0 O m 4 d U Plant t .X No. > kg./hectare SE MU PI RW MG VL TW BA CR FO WO c a 2 t u CH3 2 crx m t m O Ms i bI cs EA =Xz cs E 5 ts Y vD m l Examples 68-95.
Postemergence Herbicidal Evaluation
Following the procedure of Example 80 above, the compounds set forth in the table below were evaluated for postemergence herbicidal activity with the following results.
TABLE 4
Postemergence Herbicidal Evaluation of
Structure Plant Species Ex. Rate No. R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 68 -CH(CH3)C3H7-n -CH2OCH3 -C3H7-i 10.0 4 4 4 4 4 7 4 7 7 7 7 69 -CH(C2H5)CH2Cl -CH2OCH3 -C2H5 10.0 4 4 4 4 4 4 4 7 7 7 7 70 -CH(C2H5)2 -CH2OCH3 -C4H9-sec 10.0 4 7 4 4 4 4 4 7 7 7 6 71 -C4H9-i -CH2'OCH3 -CH3 10.0 4 4 0 0 4 0 4 7 9 8 4 72 -CH(C2H5)CH2Cl -CH2OCH3 -C3H7-i 10.0 3 4 4 4 4 4 4 4 4 4 4 73 -CH(CH3)CH2C3H7-i -CH2OCH3 -C2H5 10.0 4 7 4 4 4 4 4 4 4 4 2 74 *-C3H7-i -CH2OCH3 -C3H7-i 10.0 5 6 3.5 0 5.5 5 5 6 6.5 5 5.5 75 *-CH(C3H7-n)2 -CH2OCH3 -CH3 10.0 5.5 5.5 5.5 5 5 5.5 6 5.5 6.5 5.5 76 *-CH(CH3)C4H9-n -CH2OCH3 -CH3 10.0 5.5 6 5.5 3 6 6 6 5.5 6 4.5 77 *-C4H9-sec -CH2OCH3 -C2H5 10.0 6 6 5 5 6 5.5 6 6 6.5 6 78 *-CH(CH3)C3H7-n -CH2OCH3 -CH3 10.0 6 6 5.5 5 5.5 5.5 6 5.5 6 5.5 TABLE 4 (Continued)
Postemergence Herbicidal Evaluation of
Structure Plant Species Ex. Rate No. R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 79 *-CH(C2H5)C3H7-n -CH2OCH3 -CH3 10.0 6 6 5 4.5 5.5 5 6 6 6 6 5.5 80 *-CH(CH3)C3H7-i -CH2OCH3 -CH3 10.0 6 4.5 5 6 6 6 6 6 5.5 81 -C4H9-sec -CH2OCH3 -Cl 10.0 2 4 2 0 3 7 7 7 4 4 4 82 *-CH(CH3)CH2Cl -CH2OCH3 -C2H5 10.0 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 83 -CH(C2H5)CH2Cl -CH2OCH3 -CH3 10.0 5 7 6 3 0 4 4 7 7 7 4 1.0 8 5 7 7 8 7 3 7 0 6 7 0 84 -CH(C2H5)2 -CH2OCH3 -C2H5 0.50 8 5 6 7 7 7 3 1 0 5 7 0 0.25 8 5 6 7 6 7 2 0 0 5 5 0 1.0 8 6 6 7 8 7 0 0 0 3 3 0 85 -C3H7-i -CH2OCH3 -C2H5 0.50 6 5 5 7 0 0 0 0 0 1 3 0 0.25 2 5 7 0 0 0 0 0 1 0 0 1.0 8 5 6 7 7 7 2 0 0 5 3 0 86 -CH(CH3)C3H7-n -CH2OCH3 -C2H5 0.50 5 5 6 7 5 0 1 0 0 5 3 0 0.25 3 5 5 6 3 0 0 0 0 5 0 0 *Average of Two Tests.
TABLE 4 (Continued)
Postemergence Herbicidal Evaluation of
Structure Plant Species Ex. Rate No. R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 3 5 6 7 5 0 2 5 0 5 3 0 87 -CH(C2H3)C3H7-n -CH2OCH3 -C2H5 0.50 3 5 6 7 0 0 1 0 0 5 3 0 0.25 3 3 6 7 0 0 0 0 0 5 0 0 88 -CH(C3H7-n)2 -CH2OCH3 -C2H5 10.0 8 8 4 4 8 8 7 7 7 7 89 -C4H9-i -CH2OCH3 -C2H5 10.0 4 4 4 0 4 2 4 4 4 4 2 1.0 0 0 3 5 0 5 3 0 0 2 0 0 0.50 0 0 1 3 0 1 1 0 0 2 0 0 90 -C3H7-i -CH2OCH3 -CH3 0.25 0 0 0 2 0 0 1 0 0 1 0 0 0.13 0 0 0 1 0 0 0 0 0 0 0 0 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1.0 8 0 5 8 2 3 3 0 0 2 0 0 91 -CH(C2H5)2 -CH2OCH3 -Cl 0.50 0 0 3 6 3 1 0 0 0 2 0 0 0.25 0 0 1 6 0 0 0 0 0 2 0 0 1.0 9 0 5 6 7 0 0 0 0 2 1 0 92 -CH(CH3)C3H7-n -CH2OCH3 -Cl 0.50 6 0 5 5 7 0 0 0 0 1 1 0 0.25 0 5 6 1 0 0 0 0 1 1 0 0.13 0 0 5 5 0 0 0 0 0 0 1 0 TABLE 4 (Continued)
Postemergence Herbicidal Evaluation of
Structure Plant Species Ex. Rate No. R2 Z Y lb/Acre SE MU PI RG MG TW VL BA CR GF WO CN CO SY SB RI 1.0 8.5 6.3 7.3 7.8 7.7 8 5.1 1.4 0 5.6 3.6 0 0.50 8.3 4.8 6.5 7.2 6.5 7.2 3.5 0 0 5.5 2.8 0 93 *-CH(CH2H5)2 -CH2OCH3 -CH3 0.25 7.3 2.6 4.3 6.7 4.3 6.2 2 0 0 5.5 3.6 0 0.13 6 1 5.3 5.6 4.8 5 3 0 0 4.8 1.8 0 0.06 2.5 0 5 6 1 3.5 1.5 0 0 3.5 2 0 1.0 2 3 6 8 7 7 2 0 0 3 0 0 0.50 0 0 3 6 6 5 1 0 0 1 0 0 94 -C4H9-sec -CH2OCH3 -CH3 0.25 0 0 0 5 2 3 0 0 0 1 0 0 0.13 0 0 0 2 0 1 0 0 0 1 0 0 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0.03 0 0 0 0 0 0 0 0 0 0 0 0 95 -CH(C2H5)2 -CH2OCH3 -C3H7-i 10.0 4 4 4 4 4 4 4 4 4 4 6 *Average of Two to 6 Tests.
* Example 96.
Preparation of Methyl 2-methyl-5-nitrobenzyl ether
2-Methyl-5-nitrobenzyl chloride (16.2 g.) was dissolved in methanol (180 ml.) and then sodium methoxide (5.4 g.) was added and the mixture refluxed. The reaction was followed by thin layer chromatography (tlc) eluting with a 75/25 v/v hexane/benzene mixture. Additional quantities of sodium methoxide added and heating continued until the reaction was complete. Finally, the mixture was cooled and filtered. The filtrate was concentrated in vacuo and the residue taken up in methylene chloride and washed with water. The organic layer was then separated and dried over magnesium sulfate. Removal of the drying agent by filtration and concentration of the filtrate in vacuo left 15.8 g. of solid material which was recrystallized from 150 ml. of hexane to give 11.5 g. of white solid with m.p.
45-49 C. Another run gave a solid which after recrystallization from hexane gave a solid with m.p. 50-52 C. Elemental analysis of the product gave the following results:
Calculated for CgH11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.65; H, 6.17;
N, 7.64.
Claims (26)
1. A compound having the structure:
wherein (a) R2 is sec-alkyl C3-C7; monochloro-sec-alkyl C3 or C4 or methoxy-sec-alkyl C3 or
C4; Z is -CHR3OCH3, R3 being hydrogen or -CH3; and Y is chloro or alkyl
selected from -CH3, -C2H3, n-Pr, i-Pr, sec-Bu and i-Bu; (b) Z is -CH3; and R2 and R2 and Y respectively are
i-Pr and n-Pr or, -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 sec-Bu and i-Pr or CH(C2H5)CH2Cl and -Cl or -CH(CH3)-n-Pr and -C2H5 or CH(C2H5)CH2Cl and -C2H5 or -CH(CH3)CH2Cl and -C2H5 or
-CH(CH3)CH2CH2Cl and -C2H5 or -CH(C2H5)-n-Pr and -C2H5 or sec-Bu and n-Pr or -CH(CH3)-n-Pr and n-Pr or -CH(CH3)-n-Pr and i-Pr or -CH(C2H5)CH2Cl and n-Pr
or -CH(C2H5)CH2Cl and i-Pr or -CH(CH3)CH2Cl and n-Pr
or -CH(CH3)CH2Cl and i-Pr or -CH(CH3)CH2CH2Cl and
n-Pr or -CH(CH3)CH2CH2Cl and i-Pr or -CH(C2H5)-n-Pr and n-Pr or -CH(C2H5)-n-Pr and i-Pr or -CH(CH3)CH2OCH3 and -C2H5 or -CH(CH3)CH2OCH3 and n-Pr or -CH(CH3)CH2OCH3 and i-Pr or -CH(C2H5)CH2OCH3 and
i-Pr or -ClI(CH3)CH2CH2OCH3 and -CH3 or
-CH(CH3)CH2CH2OCH3 and -C2H5 or -CH(CH3)CH2CH2OCH3
and n-Pr or -CH(CH3)CH2CH2OCH3 and i-Pr; (c) R2 is i-C4H, or n-Pr, Z is -CH2OCH3 and Y is i-Pr or -CH3 or -C2115; (d) R; is -CH(C2H5)2, Y is n-Bu and Z f-CH2OCH3; (e) R2 is n-Bu, Z is -CH2OCH3 and Y is i-Pr; (f) R2 is i-Pr, Z is -CH2OCH, and Y is n-C4H5; and (g) R2 is -CH(C2H5)2, Z is CH2OC2Hç and Y is CH.
2. A compound of Claim 1 wherem Z is -CH2OCH3.
3. The compound N - (I - ethylpropyl - 3 - methoxymethyl) - 2,6 - dinitro p - toluidine.
4. N-isopropyl-2,6-dinitro-4-propyl-m-toluidine.
5. 4-Ethyl-N-isopropyl-α-methoxy-2,6-dinitro-m-toluidine.
6. n-isopropyl-7-methoxy-4,6-dinitro-o-cymen-5-amine.
7. N-sec-butyl-7-methoxy-4,6-dinitro-o-cymen-5-amine.
8. 4-Ethyl-N-(1-ethylpropyl)-α-methoxy-2,6-dinitro-m-toluidine.
9. N-(l-ethylpropyl)-7-methoxy-4,6-dinitro-o-cymen-5-amine.
10. 4-Sec-butyl-N-(1-ethylpropyl-α-methoxy-2,6-dinitro-m-toluidine.
11. 4-Ethyl-a-methoxy-N-( 1 -methylbutyl)-2,6-dinitro-m-toluidine.
12. N-(l-ethylbutyl)-7-methoxy-4,6-dinitro-o-cymen-5-amine.
13. 7-Methoxy-N-(2-methoxy-1-methylethyl)-4,6-dinitro-o-cymen-amine.
14. 4-Ethyl-N-(ethylpropyl)-2,6-dinitro-m-toluidine.
15. N-(1-ethylpropyl)-4,6-dinitro-o-cymen-5-amine.
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.
17. A herbicidal composition which is an admixture of a herbicidal adjuvant and a herbicidally 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.
19. A composition according to Claim 17, including the 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 1, which comprises the step of reacting an alkali metal methoxide with a 2-methyl-5-nitrobenzyl 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.
23. A method for making a compound of the structure.
wherein R2, 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: R2NH2
24. A method for making a compound in accordance with Claim 1 in which Z is -CH2OCH .
or -CM2OC2H 5. which comprises reacting a compound having the formula
wherein X is chloro, bromo or tosyl, R3 is H or CH3 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 a compound of formula:
wherein Z is -CH2OCH3; @
or -CH2OC2H5 a) subjecting compound (A) to reductive alkylation using an appropriate ketone, to yield a compound of the formula:
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:
wherein Q is a C3-C7 alkylidene group derived from the ketone and then reducing the compound (C) to yield a compound having the formula:
and then nitrating the thus formed amine from a) or b).
25. A process for the preparation of a compound in accordance with Claim 1, and substantially as described with reference to any one of illustrations A to C, or
DorEtolorJto M,orNto PorQorRorStoWorXtoY,orAAorAB and AC or AD or Example 96.
26. A compound in accordance with Claim 1, prepared by the process of any one of Claims 20 to 25.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64322675A | 1975-12-22 | 1975-12-22 | |
US69608576A | 1976-06-14 | 1976-06-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1573014A true GB1573014A (en) | 1980-08-13 |
Family
ID=27094213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB52441/76A Expired GB1573014A (en) | 1975-12-22 | 1976-12-15 | 2,6 dinitroaniline herbicides |
Country Status (21)
Country | Link |
---|---|
JP (1) | JPS5278841A (en) |
AT (1) | AT362612B (en) |
AU (2) | AU514612B2 (en) |
BE (1) | BE849681R (en) |
BG (2) | BG28256A4 (en) |
CA (1) | CA1100998A (en) |
CH (1) | CH618076A5 (en) |
DD (3) | DD130033A6 (en) |
DE (1) | DE2657327A1 (en) |
DK (1) | DK574676A (en) |
FI (1) | FI67209C (en) |
GB (1) | GB1573014A (en) |
IE (1) | IE44488B1 (en) |
IL (1) | IL51079A (en) |
IN (1) | IN145613B (en) |
IT (1) | IT1066705B (en) |
KE (1) | KE3135A (en) |
MY (1) | MY8200076A (en) |
OA (1) | OA05519A (en) |
PT (1) | PT66000B (en) |
SE (1) | SE442109B (en) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE787939A (en) * | 1971-08-25 | 1973-02-26 | American Cyanamid Co | 2,6-DINITRANILINES HAVING HERBICIDAL PROPERTIES |
-
1976
- 1976-12-08 IN IN2170/CAL/76A patent/IN145613B/en unknown
- 1976-12-10 IL IL51079A patent/IL51079A/en unknown
- 1976-12-13 CA CA267,749A patent/CA1100998A/en not_active Expired
- 1976-12-15 GB GB52441/76A patent/GB1573014A/en not_active Expired
- 1976-12-17 DE DE19762657327 patent/DE2657327A1/en not_active Withdrawn
- 1976-12-21 IT IT52719/76A patent/IT1066705B/en active
- 1976-12-21 AT AT949076A patent/AT362612B/en not_active IP Right Cessation
- 1976-12-21 DK DK574676A patent/DK574676A/en not_active Application Discontinuation
- 1976-12-21 OA OA56021A patent/OA05519A/en unknown
- 1976-12-21 PT PT66000A patent/PT66000B/en unknown
- 1976-12-21 CH CH1610676A patent/CH618076A5/de not_active IP Right Cessation
- 1976-12-21 IE IE2801/76A patent/IE44488B1/en unknown
- 1976-12-21 BE BE173489A patent/BE849681R/en active
- 1976-12-21 SE SE7614384A patent/SE442109B/en unknown
- 1976-12-22 BG BG7637521A patent/BG28256A4/en unknown
- 1976-12-22 FI FI763684A patent/FI67209C/en not_active IP Right Cessation
- 1976-12-22 AU AU20840/76A patent/AU514612B2/en not_active Ceased
- 1976-12-22 DD DD7600196549A patent/DD130033A6/en unknown
- 1976-12-22 DD DD76203902A patent/DD134836A5/en unknown
- 1976-12-22 BG BG7634978A patent/BG27524A3/en unknown
- 1976-12-22 JP JP51154802A patent/JPS5278841A/en active Granted
- 1976-12-22 DD DD76203903A patent/DD134516A5/en unknown
-
1980
- 1980-12-24 AU AU65872/80A patent/AU531431B2/en not_active Ceased
-
1981
- 1981-06-05 KE KE3135A patent/KE3135A/en unknown
-
1982
- 1982-12-30 MY MY76/82A patent/MY8200076A/en unknown
Also Published As
Publication number | Publication date |
---|---|
MY8200076A (en) | 1982-12-31 |
FI67209C (en) | 1985-02-11 |
ATA949076A (en) | 1980-10-15 |
IL51079A0 (en) | 1977-02-28 |
CA1100998A (en) | 1981-05-12 |
AU531431B2 (en) | 1983-08-25 |
JPS615469B2 (en) | 1986-02-18 |
DK574676A (en) | 1977-06-23 |
FI67209B (en) | 1984-10-31 |
FI763684A (en) | 1977-06-23 |
OA05519A (en) | 1981-04-30 |
IE44488L (en) | 1977-06-22 |
SE7614384L (en) | 1977-06-23 |
SE442109B (en) | 1985-12-02 |
AU514612B2 (en) | 1981-02-19 |
PT66000B (en) | 1978-06-16 |
CH618076A5 (en) | 1980-07-15 |
PT66000A (en) | 1977-01-01 |
IE44488B1 (en) | 1981-12-16 |
DD130033A6 (en) | 1978-03-01 |
IN145613B (en) | 1978-11-18 |
AT362612B (en) | 1981-06-10 |
BG28256A4 (en) | 1980-03-25 |
BE849681R (en) | 1977-06-21 |
BG27524A3 (en) | 1979-11-12 |
AU2084076A (en) | 1978-06-29 |
DD134516A5 (en) | 1979-03-07 |
IL51079A (en) | 1981-11-30 |
IT1066705B (en) | 1985-03-12 |
KE3135A (en) | 1981-07-03 |
DD134836A5 (en) | 1979-03-28 |
DE2657327A1 (en) | 1977-07-07 |
JPS5278841A (en) | 1977-07-02 |
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Legal Events
Date | Code | Title | Description |
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PS | Patent sealed [section 19, patents act 1949] |