Herbicidal compositions containing m-aminobenzaldoxime compounds
United States Patent [191 Kornis et al.  
 [ Apr. 29, 1975 1 IIERBICIDAL COMPOSITIONS CONTAINING M-AMINOBENZALDOXIME COMPOUNDS [75] Inventors: Gabriel Kornis; Eldon G. Nidy, both of Kalamazoo, Mich.  
 [73] Assignee: The l l pjohn Company, Kalamazoo,  
 Mich.  
 [22] Filed: May 29, 1973 [21] Appl. No.: 364,821  
 Related U.S. Application Data [62] Division of Scr. No. 145,016, May 19, 1971, Pat. No.  
 [52] U.S. Cl. 7I/98; 7l/76; 71/100; 7l/111; 71/120 [51] Int. Cl AOIn 9/12 [58] Field of Search 71/98, 100, 111,120,121  
 [56] References Cited UNITED STATES PATENTS 3.771.995 11/1973 Gutman et al. 71/121 3,772,385 11/1973 Hubclc 71/111 OTHER PUBLICATIONS Chemical Abstracts, Vol. 21, Cols. 1118 &amp; 1119 (1927).  
 Primary Examiner-James 0. Thomas, Jr. Attorney, Agent, or Firm-John Kekich 57 ABSTRACT 4 Claims, No Drawings I-IERBICIDAL COMPOSITIONS CONTAINING M-AMINOBENZALDOXIME COMPOUNDS This is a division. of application Ser. No. 145.016, filed May 19, 1971 now U.S. Pat. No. 3.778.473.  
 SUMMARY OF THE INVENTION This invention pertains to new organic compounds. to a process for preparing the same. to a new method for controlling weeds, and to new herbicidal compositions. The invention is more particularly directed to new benzaldoximem-urea and henzaldoxime-mcarbamate derivatives; to a new process for preparing the same. particularly lower alkyl and aryl derivatives; to a new method of controlling weeds with the benzaldoxime urea and benzaldoxime carbamates of this invention; and to new herbicidal compositions containing the same.  
 The new m-aminobenzaldoxime compounds of this invention have the general structural formula:  
 c-u-o-a,  
 P J-C-V H I where:  
 R H or nitrophenyl. X O or S.  
 . R: v a  
 orOR R2 H OI R3 R alkyl of from I to 8 carbon atoms. inclusive, alkenyl of from 3 to 8 carbon atoms. inclusive. aralkyl of from 7 to 13 carbon atoms, inclusive, aryl of from 6 to carbon atoms, inclusive (provided both R and R are not aryl at the same time).  
  the m-aminobenzaldehyde oxime, used as a starting material can be made by known methods. For practical reasons, we have prepared it be reacting hydroxylamine, as the hydrohalide salt. with polymeric maminobenzaldehyde as is illustrated in the Preparation below.  
  Treatment of m-aminobenzaldehyde oxime of Formula II with an isocyanate or isothiocyanate yields disubstituted ureas or thioureas of Formula I where X is oxygen or sulphur and Y is NHR R, and R having the meaning described previously.  
  The reaction is carried out in an organic solvent. preferably in the presence of a catalytic amount of a tertiary organic base such as a trialkylamine. The reaction product can be recovered from the reaction mixture usually by filtration, and it can be purified by re crystallization. Other methods such as extraction or chromatographic separation can also be used to recover and to purify the products.  
  Trisubstituted ureas and thioureas of formula I where X is -M V and R- is not hydrogen, but otherwise R R and R are as previously described, are prepared by reacting compound with a disubstituted carbamoyl or thiocarbamoyl halide in the presence of an organic base. such as a pyridine.  
  The reaction is preferably carried out in a basic organic solvent, such as pyridine and the carbamoyl halide added to the cooled reaction medium. The product can be recovered from the reaction mixture by extraction, evaporation or any other suitable method as will occur to those skilled in the art.  
  The compounds of formula I where Y is OR as defined above. can be prepared by reacting compound II with a haloformic acid ester as follows:  
 H H t=noa Luca,  
 NH; mwcooa The reaction is carired out in a mildly basic reaction medium. At the end of the reaction. the mixture is treated with aqueous acid, and the product can be recovered by extraction from the mixture. evaporation of solvent, and purified by recrystallization.  
  O-Alkylation of the oxime amine (II; R,=H) is ef fected by treating the sodium salt of II with an aliphatic or aromatic halide.  
  The reaction is preferably carried out in an aqueous basic reaction medium from which the substituted oxime usually precipitates and can be recovered by filtration. Other methods of working up the mixture will be apparent to those skilled in the art, for example extraction and evaporation followed by recrystallization.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation 1 m-Aminobenzaldehyde oxime To a vigorously stirred suspension of hydroxylamine hydrochloride (22.5 g; 0.325M) and sodium acetate trihydrate (45 g.; 0.33M) in percent ethanol ml.) a suspension of polymeric m-aminobenzaldehyde (36.3 g.; 0.3M) in 95 percent ethanol (300 ml.) was added. The reaction mixture was stirred overnight, filtered, and the filtrate poured onto ice (800 ml.). After two hours, the clear solution was concentrated under reduced pressure at 45 C., and the resultant oil was extracted with hot benzene (3 X 250 ml.). The combined benzene extract was decolorized with charcoal. and on cooling, long silky needles were deposited. M.P. 889  
  C. Publ. 88 C. Beilstein XIV. 28.  
 Anal. Calcd. for C;H.,N- ,O (136.15): C. 61.75: H. 5.92:  
  N. 20.58. Found: C. 61.70: H. 5.60; N. 20.59.  
 m-Aminobenzaldehyde-O-( p- Anal. Calc&#39;d. for CmHnNaOfl (257.24): C. 60.69; H. 4.31;  
 Found: C. 60.66; H. 4.66; N. 15.83.  
 Preparation 3 oxime To a chilled solution of m-amino-benzaldehyde oxime (13.6 g.; 0.1 M) in ether (280 m1.), triethylamine 12 drops) was added, followed by the dropwise addition of methyl isocyanate (6.3 g.; 0.1 1 M) with vigorous stirring. Precipitation commenced within minutes. The reaction mixture was stirred overnight at 1-Methyl-3-( m-formylphenyl )urea room temperature. filtered, washed with ether, and recrystallized from acetone/hexane. M.P. l79l81 C.  
 Anal. Calcd. for C,,H N;,O- (193.20): C. 559.2; H. 5.74:  
  N. ..l.7 Found: C. 55.93; H. 5.54: N. 21.60.  
 Preparation 4 Preparation of l-ethyl-3-(mformylphenyl) urea oxime Following the procedure of Preparation 3 but substituting ethyl isocyanate for methyl isocyanate. there was prepared l-ethyl-3-(m-formylphenyl) urea oxime having a melting point of l72172.5 C.  
 Anal. Calcd. for C,.,H..,N..O C. 57.96; H. 6.32; N. 20.28. Found: C. 58.20; H. 6.64; N. 20.28.  
 Preparation 5 Preparation of 1-al1yl-3-(mformylphenyl) urea oxime Following the procedure of -methylurea-O-(2,4-  
 dinitrophenyl) oxime. 3, but substituting allyl isocyahate for methyl isocyanate. there was prepared l-a11yl-3-(m-formylphenyl) urea oxime having a melting point of l61.5-162 C.  
 Anal. Calcd. for c..H, ..N.,o.. c. 60.26; Found: C. 60.06;  
 Preparation 6 -(m-formylphenyl) thiourea l-n-Butyl-3-(m-formylphenyl) urea oxime Following the procedure of Preparation 3. but substituting n-butyl isocyanate for methyl isocyanate there Preparation 7 In the manner given in the preceding examples (3-6), other substituted urea oximes can be prepared by treating m-amino benzaldehyde oxime with other isocyanates: Representative compounds thus prepared include:  
 1-( Z-butyl)-3-(m-formylphenyl) urea oxime,  
 1 -isobutyl-3-(m-formylpheny1)urea oxime.  
 1-n-penty1-3-( m-formylphenyl)urea oxime.  
 l-isopentyl-3-(m-formylphenyl)urea oxime. 1-(2-butenyl)-3-(m-formylphenyl)urea oxime. l-(3-butenyl)-3-(m-formylphenyl)urea oxime, l-(2-hexeny1)-3-(m-formylphenyl)urea oxime. 1-(4-hexeny1)-3-(m-formylphenyl)urea oxime. 1-(3-heptenyl)-3-(m-formy1phenyl)urea oxime. l-(S-heptenyl)-3-(m-formylphenyl)urea oxime. l-(4-octenyl)-3-(m-formylphenyl)urea oxime. 1-phenyl-3-(m-formylpheny1)urea oxime. 1-(p-bromophenyl)-3-(m-formylphenyl)urea oxime. l-(m-chlorophenyl)-3-(m-formylphenyUurea oxime. 1-(m-nitrophenyl)-3-(m-formylphenyl)urea oxime. 1-(p-tolyl)-3-(m-formylphenyl)urea oxime. l-benzyl-3-(m-formylphenyl) urea oxime. 1-(p-nitrobenzyl)-3-(m-formylphenyl)urea oxime. 1-(2,4-dimethylbenzy1)-3-(m-formy1phenyl)urea oxime.  
 1-(a-naphthyl)-3-(m-formylphenyl)urea oxime. and  
  1-(B-naphthyl)-3-(m formylphenyl)urea oxime. Preparation 8 Preparation of 1-ethyl-3-(m-formylphenyl)-2-thio urea oxime Following the procedure of Preparation 3, but substituting ethyl isot&#39;hiocyanate for methyl isocyanate. there was prepared 1-ethy1-3-(m-formylpheny1)-2-thio urea oxime having a melting point at 147.5149 C.  
 Anal. Calcfd. for c..,H,.,N..os&#39; (223.23): C. 53.80; H. 5.87;  
 Found: C. 54.03; H. 5.88; N. 18.64.  
 Preparation 9 y 1n the manner given in Preparation 3, other substituted thiourea oximes can be prepared by treating murea l-(4-bromophenyl)-3-(m-formy1phenyl)-2-thio urea oxime, 1-( 3-nitrophenyl)-3-( m-formylphenyl )-2-thio urea oxime, l-(4-propy1pheny1)-3-(m-formylphenyU-Z-thio urea oxime,  
 l-methyl-3-(m-formylphenyl)-2-thio urea oxime,  
 1-allyl-3-(m-formylphenyl)-2-thio urea oxime.  
 l-(2-butenyl)-3-(m-formylphenyl)-2-thio urea oxime.  
 l-( 3-penteny1)-3(m-formlphenyl)-2-thio urea oxime,  
 l-(4-hexenyl)-3-(m-formylphenyl)-2-thio urea oxime.  
 1-benzyl-3-(m-formylphenyl)-2-thio urea oxime,  
 1-(1-naphthyl)-3-(m-formylphenyl)-2-thio urea oxime. and  
 l-(2-naphthyl)-3-(m-formylphenyl)-2-thio urea oxime. Preparation dimethylurea oxime A solution of m-amino-benzaldehyde oxime 1.36 g.; 0.01 M) in pyridine (8 ml.) was cooled to 10 C. and treated drop by drop with dimethyl carbamoyl chloride (1.07 g.; 0.01 M) during ten minutes. The reaction mixture was kept at room temperature for 5 hours. poured into water (40 ml.). the aqueous layer was extracted with ethyl acetate (3 X ml.). the combined ethyl acetate layer was washed with N hydrochloric acid (3 X 15 ml.). water (3 X 15 ml.) and dried (sodium sulphate). The solvent was removed under reduced pressure and the solid obtained was recrystallized from acetone/hexane. M.P. l65166 C.  
 Anal. Calc&#39;d. for C...H.:.N=.o. (207.23): C, 57.96; H.632;  
 Found: C. 57.92; H. 6.46; N. 20.03.  
 &#39; Preparation 12 Following the procedure of Preparation 10. N.N- disubstituted thiourea oximes can be prepared by treating m-aminobenzaldehyde oxime with N,N- disubstituted thiocarbamoyl chlorides. Representative compounds thus obtained, include:  
 3-(formylphenyl)- l ,1 -dimethyl-2-thiourea oxime.  
 3-(formylphenyl)-l,l-diethy1-2-thiourea oxime,  
 3-(formylphenyl)-l l -dihexy1-2-thiourea oxime,  
 3-(formylphenyl 1 -methyl- 1 -ethyl-2-thiourea ime.  
 3-(formylphenyl )-1-propyl- 1 -ethy1-2-thiourea oxime.  
  6 3-( formylphenyl 1 -butyll -hexyl-2-thiourea oxime. 3-(formylphenyl)-l,1-dicyclohexyl-2-thiourea oxime. 3-(formylphenyl l 1 -dipheny1-2-thiourea oxime, 3-(formylpheny1)-1-methyl-l-phenyl-2-thiourea oxime.  
 and  
  3-(formylphenyl)- l l -dibenzyl-2-thiourea oxime. Preparation 13 Methyl m-formylcarbanilate oxime To a solution of m-aminobenzaldehyde oxime (6.8 g.; 0.05 M) in ethyl acetate (35 ml.). magnesium oxide (1.7 g.; 0.0425 M) and water (25 ml.) was added. The vigorously stirred solution was kept between 101 5 C. and treated with methyl chloroformate (4.7 g.; 0.05 M) at such a rate as to keep the internal temperature between lO-l5 C. The reaction mixture was stirred for 30 minutes at room temperature, acidified with N hydrochloric acid. the ethyl acetate layer decanted, and the aqueous layer extracted with ethyl acetate (1 X 15 ml.). The combined ethyl acetate layers were washed with water (2 X 10 ml.). dried (sodium sulphate) and evaporated under reduced pressure. The resultant oil was crystallized from ether/hexane or chloroform/hexane M.P. l05106 C.  
 Anal. Calcd for C,H..,N.o.. (194.19): C. 55.6621-1, 5.19.  
 Found: C. 55.56; H. 5.10; N. 14.62.  
 Preparation 14 n-Butyl-m-formylcarbanilate oxime Following the procedure of Preparation 13. but substituting n-butyl chloroformate for methyl chloroformate, there was obtained n-butylm-formylcarbanilate oxime which after recrystallization from ether/hexane or chloroform/hexane had a melting point at 99100 C.  
 Anal. Calc&#39;d. for C H N Q (236.26): C, 61.00; H. 6.83;  
  N. 11.86. Found: C. 60.87; H. 6.88: N. 11.83.  
 Preparation 15 Benzyl-m-formylcarbanilate oxime Following the procedure the Preparation 13. but substituting benzyl chloroformate for methyl chloroformate, there was obtained benzyl-m-formyl carbanilate oxime which after recrystallization from ether hexane or chloroform/hexane had a melting point at 107-l08 C.  
 Anal. Calc&#39;d. for C, -,H N O,, (270.28): C. 66.65; H. 5.22;  
  N. 10.37. Found: C. 66.51; H. 5.41; N. 10.26.  
 &#34;Preparation 26 Benzyl nitrophenyl) oxime 0.02 M) in ethyl acetate (80 ml.), a suspension of magnesium oxide (1.0 g.: 0.025 M) in water (22 ml.) was added. The reaction mixture was cooled to C. and  
 methyl chloroformate (2.1 g.: 0.022 M) was added at such a rate as to keep the internal temperature between 10 and C. and then further stirred at room temperature for 2 hours. The mixture was acidified with Nhy= &#39;tained&#39; was combined with thesolid filtered off after acidification and&#39;recrystallized from methylene chloride/hexane. M.P. 173-l74 C.  
 Anal. Calcd. for C -H N O (315.28): C. 57.14; H. 4.16:  
 Found: C. 57.25; H. 4.24: N. 13.19.  
 Preparation 25 2,2,2-Trichloroethyl m-formyl carbanilate O-(p-nitrophenyl oxime v y Following the procedure of Preparation 24, butsubstituting 2,2,2-trichloroethyl chloroformate for methyl oxime having a melting point of 140-141c.  
 Anal. Calcd. for c.H..c|..N.o. (432.65): C. r H. 2.79:,N. 9.711Cl. Found: C. 44.76.11 g.04 N.9.4U: Cl.  
 Following the procedure&#39; ofPreparation24, but sub..-  
  stituting benzyl&#34;chloroforrlnate for methyl&#34; chlorofor mate. there was&#39; prepared lq eniyl m-formyl barbariilate: O-(p-nitrophenyl) oxime having a rif1elti r&#39;1g point of UGO-151 C.  
 Anal. Calc&#39;d. for C l&#39;l N o (391.37): C. 64.44;; H. 4.38;  
 Found: C. 64.73; H. 4.61; N. l 1.00.  
 Preparation 27 chloroformate there was prepared 2,2,2- trichloromethyl m-formyl carbaniliate O-(p-&#39; nitrophenyl) mate. p-bromophenyl chloroformate for methyl chloro-&#39; isobutyl m-formylcarbanilate O-(p-nitrophenyl) o x- 65 hexyl m-formylcarbanilate O-(p-nltrophenyl) ox1me ime,  
 pentyl m-formylcarbanilateO-(p-nitrophenyl) ox.-  
 ime,  
  12 neopentyl m-formylcarbanilate O-(p-nitrophenyl) oxime, heptyl m-formylcarbanilate O-(p-nitrophenyl) oxime,  
 .octyl m-formylcarbanilate O-(p-nitrophenyl) oxime. cyclohexyl m-formylcarbanilate O-(p-nitrophenyl) oxime.  
 (p-bromophenyl)-m-formylcarbanilate nitrophenyl) oxime.  
  For purposes according to the method of this invention, benzaldoxime compounds (compound according to Formula 1) are formulated in herbicidal compositions. Such compositions in accordance with the invention include solutions, emulsions. suspensions, dispersible powders. emulsifiable concentrates, granular formulations, and dusts. All of these compositions comprise the compound in dispersed or readily dispersible form and adispersible carrier, withor without adjuvants. In general, selective inhibition of undesired weed species in the presence of desired plants. e.g., field agronornic or horticultural crops, or in turf is obtained by employing a phytonomic carrier, that is to say, a carrier which can be applied to plants without phyotoxicity or other adverse effects. On the other hand, when general herbicidal activity is desired a phytotoxic carrier. for example, high-boiling petroleum fractions such as kerosene can be used.  
  The efficacy of the n-aminobenzaldoxime&#39;derivatives of this invention as herbicides is of high order. and the compounds can be applied at relatively low rates per acre for controlling growth of weed plants. elgl. germinati n&#39;g weed seeds and weed seedlings. lllustratively.  
 , the compounds;  
 m formylcarbanilate O-(p;  
 nitrophenyl) oxime.  
 3-(m-forr&#39;nylphenyl)-l-methylurea oxime.  
 , I 3-(m-formylphenyl)-1.l-dimethylurea oxime,  
 3-(m-fo rmylphenyU-l-ethylurea oxime. 3-(m-formylphenyl)-1-allylurea oxime.  
 S-(m-fOrrnylphenyU-I -butylureaox-ime.  
 3-(m-formylphenyl-)-l-ethylurea-2-thio oxime. 3 m-formylphnyl)-l -methylurea-O-( -dinitrophenyl)oxime, I r  
 3-(m-for&#39;m ylphenyl)-1.1-d&#39;imethy lurea-O-(p.-&#39;  
 .&#39; methyl (m formyDcarbanilate oxime.  
 2.2.2-trichloroethyl-(m-formyl)carbanilate oxime, butyl (n&#39;i-formyl)carbanilate oxime, benzyl (m-formyl)carbanilate oxime, methyl (m-formyl)carbanilate-O-(p-nitrophenyl) ox- 2.2,2-trichloroethyl(m-formyl); nitro-phenyl) oxime. 1 benzyl (m-formyl)carbanilate-O-(prnitrophenyl) oxime, Gave complete or substantially complete suppression of buckhorn plantain (plantago [unpeolate L.), commonn purslane (Portulace oleracea -L.). yellow foxtail (Se&#39;tariaflaupqL. ).,-bindweed Convqlvolus arvensis).  
  carbani1ate-0-( P- lambsquarters (Chorropodium album). and red sorrell -&#39;-(&#39;-sheep,.s qrrell) (Rumex acerosella L.). when applied at rates of-about 6 lbs. per acre. Rates of application of about 0.1 toabout 15 lbs. per acre are efficacious under usual conditions, depending upon the particular circumstances such as type .of soil. amount of rainfall or-irrigation. and the most prevalent kindsof weeds. At higher rates of application. tag. at 20 to 50 lbs. per acre the compound acts, as a soil sterilant.  
  lllustratively, excellent control of weeds in rice fields has been obtained. without significant damage to the rice plants, using concentrations of maminobenzaldoxime derivatives ranging from about 1000 ppm (parts per million) to about 5000 ppm applied at the rates of about 1 lb. to about 3.0 lbs. per acre. In general, a desired rate of application can be achieved by distributing, over the area to be treated, an aqueous composition in accordance with the invention. containing from about 700 ppm to about 30,000 ppm of active ingredient. it will be understood, of course, that a choice of concentration of active ingredient depends upon the method of application as well as the type of composition and the degree of herbicidal control desired. In general, concentration is not critical within the range indicated since as effective quantity of active ingredient can be applied to a given area by applying greater quantities of a low concentration than of a higher concentration. THe concentration of active ingredient in the dispersible powder and emulsifiable concentrations from which the aqueous compositions are prepared can be as high as 99.5 percent by weight. The concentration of active ingredient in the dust and granular formulations of the invention can vary from about 0.25 percent to about 80 percent or more, but advantageously is of the order of 0.50 to 20 percent.  
  The granular formulations of this invention are prepared with about 0.25 percent to about 80 percent, preferably 0.50 to 20 .percent by weight. of active ingredient and a granular carrier, for example, vermiculite, pyrophyllite, or attapulgite. The active ingredient can be dissolved in a volatile solvent such as methylene chloride, acetone, and the like, and sprayed on the granular carrier as it is mixed and tumbled. The granules are then dried. The granular carrier can range in particle size from about to about 60 mesh, preferably about 30 to 60 mesh.  
  The herbicidal dust compositions of the invention are prepared by intimate admixture of from about 0.25 percent to about 80 percent by weight, preferably 0.50 to 20 percent of the active ingredient with a solid pulverulent carrier which maintains the composition in a dry, free-flowing condition. the herbicidal dusts of the invention can be prepared by admixing the compound with a solid diluent and then milling. Preferably, however, the active indredient is dissolved in a volatile organic solvent, of the kinds indicated above, and then sprayed on the solid carrier so as to assure thorough distribution. The mixture is then dried and milled to the desired size, e.g., less than about 60 microns.  
  Solid carriers that can be used in the dust compositions of the invention include the natural clays such as China clay and bentonite, minerals in the natural state such as talc, pyrophyllite, quartz, diatromaceous earth, fullers earth, chalk, and rock phosphate, and the chemically modified minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, precipitated calcium silicate, and colloidal silica. The solid diluents which can be employed in the composition also include solid, compounded fertilizers. Such solid compositions can be applied to vegetation in the form of dusts by the use of conventional equipment.  
  A preferred composition, in accordance with the invention, is a dispersible powder which is prepared by incorporating a surfactant in a dust composition prepared as described above. Such a dispersible powder can be dispersed in water to any desired concentration and applied to vegetation by conventional spray equipment. Conveniently, the dispersible powders are formulated with higher concentrations of active ingredient than the dust compositions, for example, up to about percent, preferably about 10 to 80 percent. Surfactants useful in preparing such dispersible powder compositions include alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene-sorbitan monolaurate, alkyl aryl polyethyl sulfates, alkyl aryl polyether alcohols, alkyl naphthalene sulfonates, alkyl quaternary. ammonium salts, sulfated fatty acids and esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, lignin sulfonates, and the like. A preferred class of surfactants includes blends of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77), blends of polyoxyethylene ethers and oil-soluble sulfonates (Emcol H-400), blends of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols, (Tritons X-l5l, X-l6l, and X-l7l e.g., about equal parts of sodium kerylbenzene sulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl aryl sulfonates and polyethoxylated vegetable oils (Agrimul N 8). It will be understood, of course, that the sulfate andsulfonate surfactants suggested above will preferably be used in the form of their soluble salts, for example, their sodium salts. All of these surfactants are capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1 percent or less. The dispersible powder compositions can be formulated with a mixture of surfactants of the types indicated if desired.  
  A suitable dispersible powder formulation is obtained by blending and milling 235 lbs. of Georgia Clay, 5.5 lbs&#39;. of isooctylphenoxy polyethoxy ethanol. (Triton X- as a wetting agent, 9.5 lbs. of a polymerized sodium salt of substituted benzoid longchain sulfonic acid Active ingredient 50 7c lsooctylphenoxy polyethoxy ethan Polymerized sodium salt of substituted benzoid long-chain sulfonic acid Georgia Clay The formulation, when dispersed in water at the rate of 10 lbs. per 100 gals, gives a spray formulation containing about 0.6 percent (6000 ppm) active ingredient which can be applied to soil, plant growth media, growing plants, e.g., turf at the rate of 40 gals per acre to give a total application of active ingredient of 2 lbs. per  
 acre.  
  The compounds of this invention can be applied to soil, plants, plant growth media, growing plants, e.g., turf in aqueous sprays without a solid carrier. However. since the compounds themselves are relatively insoluble in water they are preferably dissolved in a suitable inert organic solvent carrier. Advantageously, the solvent carrier is immiscible with water so that an emulsion of the solvent carrier in water can be prepared. If, for example, a watermiscible solvent carrier such as acetone is used the solvent carrier will disolve in the water and any excess according to Formula I will be thrown out of solution. In an emulsion. the solvent phase is dispersed in the water phase and the active ingredient is held in solution in the dispersed phase. In this way, uniform distribution of active ingredient with an aqueous spray can be achieved A solvent carrier in which the compounds are highly soluble is desirable so that relatively high concentrations of active ingredient can be obtained Sometimes, one or more solvent carriers with or without a cosolvent can be used in order to obtain concentrated solutions of the active ingredient, the main consideration being to employ a water-immiscible solvent for the active ingredient that will hold the compound in solution over the range of concentrations useful for preventing germination of undesired seeds and controlling growth of plants.  
  The emulsifiable concentrates of the invention are prepared by dissolving the active ingredient and a surfactant is a substantially water-immiscible solvent carrier (i.e., a solvent carrier which is soluble in water to the extent of less than 2.5 percent by volume at temperatures of the order of to C. for example, cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and highboiling petroleum hydrocarbons such as kerosene, diesel oil, and the like. If desired, a co-solvent such as methyl ethyl ketone, acetone, and the like can be included with the solvent carrier in order to enhance the solubility of the active ingredient. Aqueous emulsions are then prepared by mixing with water to give any desired concentration of active ingredient. The surfactants which ca be employed in the aqueous emulsions of the invention are those types noted above. Mixtures of surfactants can be employed if desired.  
  Advantageously, the concentration of active ingredient in the emulsifiable concentrates can range from about 5 percent to about 50 percent by weight, preferably from about 10 to percent. A concentrate comprising 20% (by weight) of the compound dissolved in a water-immiscible solvent of the kind noted above can be admixed with an aqueous medium in the proportions of 13 ml. of concentrate with 1 gal. of medium to give a mixture containing 700 parts of active ingredient per million parts of liquid carrier. Similarly, I gt. of a 20 percent concentrate mixed with 40 gals. of water provides about 1200 ppm of active ingredient. In the same manner. more concentrated solutions of active ingredient can be prepared.  
  The concentrate compositions of the invention which are intended for use in the form of aqueous dispersions or emulsions can also comprise a humectant, that is to say, an agent which will delay the drying of the composition in contact with material to which it has been applied. Suitable humectants include solubilized lignins, such as calcium lignosulfonate, and the like.  
  Further in accordance with this invention, certain formulations of m-aminobenzaldoxime derivatives with oil are particularly efficacious, and herbicidal action of the compound is improved. Any petroleum oil can be used so long as it is not so viscous as to be too difficult to disperse. A non-phytotoxic coil is satisfactory.  
  Advantageously, a 50 percent wettable powder of the herbicidal active ingredient is mixed with about 38 gals. water and 2 gals. oil for spray applications. Alternatively, about 2 gals. oil and a 50 percent wettable powder are premixed and then dispersed in aabout 38 gals. water for spray application. In field tests, oil formulations of the foregoing type have given improved herbicidal action.  
  The rates of application to soils, plant growth media, growing plants, e.g., turf to be protected from noxious weeds will depend upon the species of vegetation to be controlled, the presence or absence of desirable species, the stage of plant developments, the season of year at which treatment is undertaken, and the method and efficiency of application. In general, selective herbicidal activity is obtained when the compounds are applied at the rate of about 1.0 to about 15 lbs. per acre, preferably at the rate of about 1.0 to about 8 lbs. per  
 acre.  
  The compositionscontaining m-aminobenzaldoxime derivatives can be applied to soil, plant growth media, growing plants, e.g., turf by conventional methods. For example, an area of soil can be treated prior to or after seeding by spraying wettable powder suspensions, emulsions or solutions from boom-type power sprayers or from hand-operated knapsack sprayers. Dusts can be applied by power clusters, or by hand-operated dusters. Dusts and granular formulations can also be applied at the time of seeding in bands spanning the seeded rows.  
  Further, the compounds of this invention are efficacious as plant growth regulants when applied at low rates such as 0.1 lb per acre. For example, significant increases in crop weight were obtained from forage sorghum, red top grass, peanuts, beans, peas and other crops, using compounds of Formula I.  
 We claim: I  
  l. The method of selectively controlling plant growth by applying thereto a controlling amount of the compound of H l C=N -0-R N-C-Y I ll H X where R, H or nitrophenyl, X O or S,  
  R Y N 2 \R3 or 0R R2 H Or R3 R alkyl of from 1 to 8 carbon atoms, inclusive. alkenyl of from 3 to 8 carbon atoms, inclusive, aralkyl of from 7 to 13 carbon atoms, inclusive. aryl of from 6 to 10 carbon atoms, inclusive. (provided both R, and R are not aryl at the same time).  
 2. The method in accordance with claim I in which said compound is applied in the form of an aqueous 0| to 15 pounds of said compound per acre.  
  4. The method in accordance with claim 1 in which said compound is applied in the form of granules containing from 0.25 to percent by weight of said compound and said application is in the range of 0.] to 15 pounds of said comound per acre.