Patent Publication Number: US-3877921-A

Title: Herbicidal Phenoxyalkyloxazolines

Description:
United States Patent 11 1 Timmons et a1.  
 [ HERBICIDAL PHENOXYALKYLOXAZOLINES [75] Inventors: Richard J. Timmons; William E.  
 Gallant, both of Marysville, Ohio [73] Assignee: The 0. M. Scott and Sons Company,  
 Marysville, Ohio [22] Filed: Sept. 18, 1973 [21] Appl. No.: 398,535  
 Related US. Application Data [62] Division of Ser. No. 157,711, June 28, 1971, Pat. No.  
 Primary ExaminerElbert L. Roberts Assistant ExaminerCatherine L. Mills Attorney, Agent, or Firm-Strauch, Nolan, Neale, Nies &amp; Kurz 1111 3,877,921 1451 Apr. 15, 1975 where X is hydrogen, chlorine, or methyl; Y is hydrogen or chlorine; n is 0 or 2; and R is hydrogen or methyl when n is 0 and hydrogen when n is 2. Examples of compounds with the foregoing formula are:  
  2-(2,4-Dich1or0phenoxymethyl)-2-oxazoline 2-[3-(2,4-Dichlorophenoxy)propy1]-2-oxazoline 2-[ 1-( 2,4,5-Trichlorophenoxy )ethyl]-2-oxazoline 2-[ l-( 2 Methy1-4-chlorophenoxy)ethyl]-2-oxazoline 2-(2-Methy1-4-chlorophenoxymethyl)-2-oxazoline 2-(4-Chlorophenoxymethyl)-2-oxazoline Also disclosed are methods of preparing compounds with the foregoing structural formula, methods of using such compounds as herbicides and as growth regulators, and herbicidal and growth regulator formulations including such compounds.  
 12 Claims, No Drawings HERBICIDAL PHENOXYALKYLOXAZOLINES This is a division, of application Ser. No. 157,711, filed June 28, 1971 now US. Pat. No. 3,778,445.  
  This invention relates to herbicidally active phenoxyalkyloxazolines and, more particularly, to certain novel Z-(phenoxyalkyl )-2-oxazolines and to their use as selective herbicides and as growth regulators.  
 The novel compounds we have invented are those of the formula:  
  O(CI-I CHR (I) where X is hydrogen, chlorine, or methyl; Y is hydrogen or chlorine; n is O or 2; and R is hydrogen or methyl when n is O and hydrogen when n is 2.  
  We have discovered that the foregoing compounds are selective herbicides and are particularly useful as post-emergent controls for controlling the growth of dicots in monocots.  
  As indicated above, our invention consists in one aspect of the invention of the compounds of the formula 1. Representative of these compounds are those which follow:  
 Code  
 Number Name of Compound 323 2-( 2,4-Dichlorophenoxymethyl)-2-oxazolinc 458 2-[ 3-( 2.4-Dichlorophenoxy)propyl l-2-oxazoline 400 2-[ l-( 2,4.5-Trichlorophenoxy)ethyll-Z-oxuzoline 462 2-l 1-( 2-Methyl-4-chlorophenoxy)ethyl l-2-oxazoline 468 2-( 2-Melhyl-4-chlorophcnoxymethyl )-2-oxuzoline 472 2-( 4-Chlorophenoxymethyl )-2-oxuzoline The compounds we have invented act in a manner which is typical of auxin herbicidesf For example, plants treated with these chemicals show epinasty (twisting and curling of stems and leaves). As indicated above, they give post-emergence control of dicots but have little post-emergence effect on grass species. This combination of properties makes them particularly valuable for the control of broadleaf weeds in turf.  
  Heretofore available auxin herbicides which give control of broadleaf weeds in turf all have serious drawbacks. Pyridines, such as 4-amino-3,5,6- trichloropicolinic acid (Picloram) and methoxybenzoic acids such as 2-methoxy-3,-dichlorobenzoic acid (Dicamba) are extremely mobile in the soil and are rapidly taken up by the roots of trees and shrubs. Thus, they commonly cause damage to trees and ornamentals when applied to turf.  
  The phenoxyalkanoic acids such as 2,4-dichlorophenoxyacetic acid (2,4-D) damage desirable grasses when applied at other than the specific recommended rates or under conditions when the grass does not have full vigor. For example, it is not practical to apply 2,4-D to Bermudagrass for broadleaf weed control during the dormant season because of the turf damage which will result. 1  
  Certain phenoxyalkanoic acids are also suspected of causing terratogenic effects due to contamination by highly terratogenic dioxins. An example is 2,4,5-trichlorophenoxyacetic acid.  
  The compounds of this invention do not have these disadvantages of previously known auxin herbicides. They are not readily taken up by plant roots (thus preventing tree and ornamental damage), show exceptionally good turf tolerance, and in most cases, are free of terratogenic dioxin contaminants.  
  As indicated above, certain of our novel compounds also possess growth regulator type activity. This is of course a valuable property for example, in the case of turfgrasses, mowing frequency is reduced, making turf maintenance less onerous.  
  These compounds we have invented can be synthesized by the rearrangement of aziridinyl amides with sodium iodide in acetone as shown by the following equation:  
  u NaI O(CH C1-1R-C-*N Acetone Alternately, they may be prepared by base-catalyzed cyclization of B-chloroethyl amides as shown by the reactions reproduced below:  
  f. a ucu cu oa c1 0 (CH2) CHR-C-OH Heat SOC].  
  1| (:1 0 (CH CHR-C-NHCH CH OH ---9 n c1 0(cz-r cuacuncn cu c1 ----9 2 2 2 cu oa a ct o(cu cim A related and important object of the invention resides in the provision of novel 2-(phenoxyalkyl)-2- oxazolines which are useful as selective post-emergent controls for broadleaf weeds in turfs.  
  Another object of the invention resides in the provision of novel 2-(phenoxyalkyl)-2-oxazolines which have growth regulating type activity.  
  Yet another object of the invention resides in the provision of novel herbicidally effective compositions which include compounds of formula (I).  
  Other important objects and features and additional advantages of the invention will become apparent from the appended claims and from the ensuing detailed description and discussion.  
  As indicated above, the compounds of the present invention can be made by rearranging aziridinyl amides with sodium iodide in acetone. The following examples illustrate the preparation of the aziridinyl starting compounds.  
 EXAMPLE I Preparation of N-(2,4-dichlorophenoxyacetyl) aziridine.  
  Sixteen and eight-tenths grams (16.8 g, 0.07 mole) of 2,4-dichlorophenoxyacetyl chloride was added slowly to a mixture of 85 g of crushed ice, 90 ml of benzene, 2.8 g (0.07 mole) of sodium hydroxide, and 3.0 g (0.07 mole) of aziridine while the temperature was held below 5C with an ice bath. The addition was slightly exothermic. The reaction mixture was stirred vigorously below 5 for 2 hours. The layers were separated and the aqueous layer extracted with three 35 ml portions of ether. The ether extracts were combined with the benzene layer and dried over MgSO The solvent was removed at a temperature below 40 with a rotary evaporation to give 13.2 g of a solid having a melting point of 8488.  
 Chemical Analysis:  
 Calculated for C H Cl NO c, 48.8; H, 3.69; N,  
  Found: C, 49.35; H, 3.90; N, 5.65; Cl, 26.90 Infrared Analysis:  
 5.81 p. (C=O); 7.28 p. (aziridinyl symmetrical ring breathing) EXAMPLES II V Additional aziridinyl amides were prepared in a manner analogous to that described in Example I. These compounds, their physical characteristics, and-their chemical and infrared analyses are listed below:  
 N-[4-(2,4-Dichlorophenoxy)butyryl]aziridine Light yellow viscous oil Chemical Analysis:  
 calculated for C H Cl NO Z C, H, N,  
  Found: C, 52.83; H, 4.48; N, 6.27; Cl, 25.44 Infrared Analysis:  
 5.90 p. (C=O); 7.95 ,u. (C-O) N-[2-(2,4,5-Trichlorophenoxy)propionyl]aziridine Pale yellow oil Infrared Analysis:  
 5.94 p. (C=O); 7.26 or 7.40 p. (symmetrical aziridine ring breathing) N-[2-(4-Chloro-2-methylphenoxy)propionyl]aziridine  Colorless liquid Chemical Analysis:  
 Calculated for C H CINO C, 60.2; H, 5.88; N,  
  Found: C, 60.80; H, 5.72; N, 7.13; Cl, 15.90 Infrared Analysis:  
 5.90 p. (C=O); 8.03 p. (C-O); 7.25-p. (aziridine symmetrical ring breathing) N-( 2-Chlorophenoxyacetyl )aziridine White solid, melting point 8l.583.5C Chemical Analysis:  
 Calculated for C H ClNO C, 56.75; H, 4.77; N,  
  Found: C, 56.68; H, 4.22; N, 7.29 Infrared Analysis:  
 5.85 p. (C=O); 8.00 ;.L (G0); 7.50 p.  
 (aziridine symmetrical ring breathing) The following example illustrates the conversion of the aziridine compound prepared as described in Example I to a 2-(phenoxyalkyl)-2-oxazoline, a compound of the present invention.  
 EXAMPLE VI Preparation of 2-(2,4-dichlorophenoxymethyl)-2- oxazoline,  
  0 c1 CH-/ A mixture of 6.2 g (0.025 mole) of (2,4- dichlorophenoxy)acetylaziridine and 3.0 g (0.02 mole) of sodium iodide in ml of acetone was refluxed for 20 hours. The acetone was removed with a rotary evaporator, and the residue was stirred with 15 ml of water. The insoluble material was filtered off and recrystallized from 50% aqueous ethanol. The product was dried in vacuo over P 0 at room temperature to give 4.1 g of a solid, melting point 70.9 74.9.  
 Chemical Analysis:  
 Calculated for C H CI NO C, 48.8; H, 3.69; N,  
  Found: C, 48.78; H, 4.10; N, 5.60; Cl, 27.93 Infrared Analysis:  
 3.47, 3.52 [L (C-H), 6.04 [.L (C=N) The aziridine amides of Examples II V were converted to 2-(phenoxya1kyl)-2-oxazolines of the present invention in an analogous manner. The resulting compounds are identified and their physical properties and chemical and infrared analyses are described in the following examples:  
 EXAMPLES VII X 2-[3-( 2,4-Dichlorophenoxy )propyl -2-oxazoline Off-white solid, melting point 40.5 43.5C Chemical Analysis:  
 Calculated for c,,H,,c| No,; C, 52.6; H, 4.78; N,  
  5.11; CI, 25.9 Found: C, 52.25; H, 4.09; N, 6.21; C1, 25.25 Infrared Analysis:  
  6.04 p. (C=N), 8.07 p. (C-O) 2-[ 1-( 2,4,5-Trichlorophenoxy)ethyl]-2-oxazoline Off-white solid, melting point 880&#39; 91.0C Chemical Analysis:  
 Calculated for C H Cl NO C, 44.8; H, 3.41; CI,  
  36.2 Found: C, 44.40; H, 3.70; CI, 36.73 Infrared Analysis:  
 6.04 p. (C=N), 8.07 p. 2-[ 1-(4-Chloro-2-methylphenoxy )ethyl]-2-oxazoline Yellow liquid Chemical Analysis:  
 Calculated for C H CINO C, 60.2; H, 5.88; N,  
  Found: C, 58.75; H, 5.27; N, 6.20 infrared Analysis:  
 5.97 p. (C=N); 8.05 p. (G0), 3.40 ,u. (C-H) 2-(4- Chlorophenoxymethyl )-2-oxazoline Sublimed to give a white solid, melting point 52.1  
  556C Chemical Analysis:  
 Calculated for C H CINO C, 56.75; H, 4.77; N,  
  6.68 Infrared Analysis:  
 5.97 ,u. (C=N), 8.14 p. (C-O) As indicated above, the compounds of the present invention can also be prepared from B-chloroethylamides.  
 The following examples illustrate this synthesis route:  
 EXAMPLE XI Preparation of N-( 2-Chloroethyl)-(4-chloro-2- methylphenoxy)acetamide A mixture of 1689 g (8.0 mole) of 4-chloro-2- methylphenoxyacetic acid and 489 g (8.0 mole) of 2- aminoethanol was heated for 4 hours at 160. The melt was cooled to 125 and poured slowly into 2,500 ml of benzene while stirring vigorously. To this solution was added slowly at 55 1047 g (8.8 mole) of thionyl chloride. The mixture was stirred overnight while cooling to room temperature. Excess benzene was removed with a rotary evaporator, and the residue was stirred with 2 liters of pentane. The mixture was filtered and the solid dried overnight at 45 to give 1580 g of tan solid. This crude product was recrystallized first from benzeneligroin and then from acetone-water to give 627 g of a light brown solid. Infrared Analysis:  
 3,418 cm (N-H), 1,679 cm (C=O), 1,524 cm&#34; (amide 11) Example Xll Conversion of n- 2-chloroethyl 4-chloro-2- methylphenoxy )acetamide to 2-( 4-chloro-2- methylphenoxymethyl )-2-oxazoline,  
 CL OCH Q 41] One hundred thirty-one grams (131.0 g, 0.5 mole) of n-(2-chloroethyl)-(4-chloro-2- methylphenoxy)acetamide was added to a solution of 36.5 g (0.55 mole) of 85 percent KOH in 625 ml of methanol. The mixture was heated for 4 hours at 505 5C, concentrated to half its volume, and filtered. The filtrate was poured into 650 ml of water, precipitating a tan solid. The product was filtered off and dried to give 100.6 g of solid product, melting point 60.8 633C.  
 Chemical Analysis:  
 Calculated for C H ClNO C, 58.54; H, 5.31  
  Found: C, 58,35; H, 5.84 Infrared Analysis:  
 5.97 p. (C=N); 7.99 p. (C-O) Other of the compounds of the present invention may be prepared in a manner analogous to that described in Examples X1 and X11.  
  As indicated above, the compounds of the present invention are selective post-emergence controls for broadleaf weeds in turfs. Such selectivity is shown by the following examples:  
 EXAMPLE XllI Representative compounds of the present invention were dispersed in water and sprayed on 2 X 3&#39; plots (three replications) at a rate of 10 gallons per 1,000 square feet with a hydropneumatic sprayer. The sprays provided active compound at rates of 1.5, 3.0, and 6.0 pounds per acre. Readings taken 12 to 36 days after applicat&#39;ion showed the following results:  
 TABLE 1 Percent Kill (Mean) Code Applica- Argen- No. of tion Tifway tine Com- Rate Bermuda- Cud- Dollar Bahiapound (lbs/acre) grass Weed Weed grass 323 1.5 0, 0 26.7, 36.7 80, 7O 0 3.0 0, 0 76.7, 75, 95 5 6.0 3, 0 86.7. 86.7 98, 95 7.5 400 1.5 0, 0 20 20 30, 50 0 3.0 10. 3.3 66.7, 85 60, O 6.0 30, 33 94.3, 98.3 90, 75 17.5 462 1.5 0, 1.7 16.7, 55 98, 65 I5 3.0 8.3, 6.7 43.3, 43.4 100 40 0 6.0 0, 0 73.3. 53.3 100. 75 5 468 1.5 0, 0 53.3. 76.7 100, 70 5 3.0 0, 0 96.7 100, 20 6.0 16.7, 0 8l.7,9l.7 100, 25  
  Eigl&#39;it and thirty-six days following application Twenty and thiny-six days following application &#39;lwclvc and twenty-eight days following application Twenty-eight days following application As shown by the data in the foregoing Table, the compounds of the invention exhibited a high degree of selectivity between the dicots (cudweed and dollarweed) and turfgrasses (Bermudagrass and bahiagrass) present in the plots.  
 EXAMPLE XIV In another series of tests, the same representative compounds were applied to plots containing various broadleaf weeds and bluegrass at a rate of five pounds per acre, following the procedure described in Example Xlll. The following results were obtained:  
  As shown by the foregoing Table, the compounds of the present invention also exhibit a high degree of selectivity between broadleaf weeds and the most popular of the Northern grasses.  
 EXAMPLE XV In initial field screening tests, two compounds of the present invention were dispersed in water and sprayed on 1&#39; X 2 plots which had been mowed earlier at rates providing 1 and 5 pounds of compounds ,per acre. The plots were read 14 days after application with the following results:  
  Again the compounds proved to be highly selective as between a different broadleaf weed and bluegrass turf.  
 EXAMPLES XVI In still another series of tests, Windsor, Merion, and Newport bluegrasses, fine fescue, bentgrass, St. Augustinegrass, and bahiagrass were all proved to be tolerant to a representative compound of the present invention (472), even at a rate of 16 pounds per acre. In this series of tests, the compound was applied in a spray formulation in the greenhouse. Readings were made 28 days after application. Injury to only three species was observed, and the maximum injury was only ten percent (on bahiagrass). There was no injury to any of the bluegrasses or to the fine fescue.  
 EXAMPLE XVII The compounds of the present invention can be applied in granular as well as spray form. This was demonstrated by a series of tests in which representative compounds of the present invention were made up into granular formulations with expanded vermiculite as a carrier in the manner described in US. Pats. Nos. 3,076,699 issued Feb. 5, 1963, to Victor A. Renner for GRANULAR HERBICIDAL COMPOSITION and 3,083,089 issued Mar. 26, 1963, to the same patentee for GRANULAR HERBICIDAL COMPOSITION AND METHODS, both of which are hereby incorporated by reference. These formulations were applied at rates of 2.5, 5, and pounds per acre to 2 X 3 bluegrass plots infested with broadleaf weeds (three replications). Readings were made 37 days after application. Results were not entirely consistent, but selective control of broadleaf weeds was obtained in a number of instances.  
  Specifically, there was no injury to the bluegrass turf in any of the plots to which the compounds were applied. On the other hand, compound 323 gave good control of clover at all rates (75-93 percent kill) and an 85 percent kill of dandelions at the lowest rate. Compound 400 gave good control of clover at the lowest rate (87 percent kill) while compound 462 gave a good (75 percent) kill of pigweed at the lowest rate and a good kill (88-100 percent) of clover at all rates. Compound 468 produced a 70 percent kill of pigweed and percent kill of dandelion at the 5 pound per acre 6 rate and good control of clover (88 and percent kill) at the two lower application rates. 1  
 EXAMPLE XVIII In a series of tests of the type described in Example XVII, compound 472 gave the following results (readings were taken 24 days after application):  
 TABLe 4 Application Rate Blue- Morning lbs/acre) grass Clover Chicory Pigweed Glory 5 0 I0 75 75 I 0 O 80 I00 I00 I00 This data further illustrates the high degree of selectivity which the compounds of the present invention possess. It is also indicative of the variety of broadleaf weeds which can be controlled by these compounds.  
  As indicated above, compounds of formula (I) may possess growth regulating as well as herbicidal activity. Thefollowing example demonstrates this valuable characteristic.  
 EXAMPLE XIX Compound 472 was dispersed in water as in a number of the preceding examples and applied to St. Augustinegrass as a spray and as a drench. Readings taken 30 days after application gave the following results:  
  As will be apparent from the foregoing, a high degree of growth regulation was obtained in each case. The quality of the turf uniformly remained excellent, and no injury was observed.  
 In the same series of tests, 472 was also applied as a.  
 spray at a rate of 16 pounds per acre. While inhibition was high, this application did produce moderate injury and a corresponding decrease in turf quality. However, this may have been attributable to the conditions under which the compound was applied. In a different series of tests, an identical application of the same compound to St. Augustinegrass caused only negligible injury (see Example XVI).  
  Depending on the particular compound, the type of formulation in which it is incorporated, the characteristics of the particular area to which the formulation is applied, etc., the compounds of the present invention may be applied at single application rates ranging from 1.5 to 16 or more pounds per acre for the purposes discussed above. Applications in this range will in most, if not all, cases provide excellent weed control with minimal or no turfgrass injury.  
  Also, it is within the province of our invention to use repeat applications of the compounds, normally at rates below the single application rates. Repeat applications at low rates will typically provide control of the broadleaf weeds with a minimum of turf injury in even .he most difficult circumstances.  
  Further, mixtures of the compounds of the present invention may be employed for the purposes described herein, if desired.  
  As indicated above, the compounds of the present invention can be employed in sprays and in granular formulations. They may also be applied as drenches or combined with a diluent and/or other adjuvants to make a dust and applied with conventional dusting equipment. Depending upon factors such as those discussed above in conjunction with application rates, the proportions of the ingredients in the formulation may vary over a wide range. Generally speaking, however, the proportions will fall within the following limits:  
  Appropriate carriers include organic solvents, water, vermiculite, perlite, diatomaceous earth, clay, corn cobs, and other materials such as those described in the Handbook of Dust Diluents and Carriers (2d Ed.), 1955, which is hereby incorporated by reference. For granular formulations, exfoliated vermiculite is preferred.  
  One suitable surfactant for use in the formulations described herein is Triton X-lOO, which is an octylphenoxypolyethoxy ethanol manufactured by Rohm &amp; Haas Company. Other suitable surfactants are those listed in Detergents and Emulst&#39;fiers Up-to-Date, 1968, John W. McCutcheon, Inc., which is also hereby incorporated by reference.  
  The solvent may include or be a sticking agent. Suitable solvents&#34; include Polyvis OSH (a polybutene having a molecular weight of approximately 400 manufactured by the Cosden Oil and Chemical Company) and hexylene glycol. Other suitable solvents-sticking agents are described in US Pat. Nos. 3,076,699 and 3,083,089.  
  As indicated above, the foregoing patents also disclose methods which may be employed to make granular formulations including the compounds of the present invention. That is, those compounds which are solids at room temperature may be dissolved in an appropriate solvent and adhered to a carrier in the manner disclosed in US. Pat. No. 3,083,089. Or particles of the compound may be adhered to a carrier with a suitable sticking agent as described in US. Pat. No. 3,076,699. Those compounds which are liquids can be similarly absorbed on exfoliated vermiculite as described in the foregoing patents.  
  Diluents, stabilizers, fertilizers and other plant nutrients, other pesticides, flow enhancing agents, adhesives, dyes, and other adjuvants may also be employed in formulations in which the compounds of the present invention are incorporated. This may be done, for example, to make the formulations capable of controlling formly and in accurate quantities to the area toobe treated. The abovementioned and other adjuvants which may be employed are described in Chemistry of the Pesticides (3d Ed.), Frear, D. Van Nostrand Company, Inc., New York, N.Y., 1955 and in Weed Control (2d Ed.), Robbins et al, McGraw-Hill Book Company, Inc., New York, N.Y., 1952, which are also intended to be incorporated by reference herein, along with US. Pat. No. 3,231,363, issued January 25, 1966, to Victor A. Renner for PROCESS FOR MAKING FOAMED UREAFORMALDEI-IYDE FERTILIZER, and US. Pat. Application No. 850,489, filed Aug. 15, 1969, for FOAMED FERTILIZERS AND COMBINATION PRODUCTS (now Pat. No. 3,705,794) which disclose various combination products in which the compounds disclosed herein may be incorporated and methods of preparing such formulations. (See also US. Pat. Nos. 3,076,699 and 3,083,089.) 1  
  The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. 9  
  What is claimed and desired to be secured by Letters Patent is:  
  l. A post-emergent method of selectively controlling the growth of unwanted vegetation in an area in which desirable vegetation is present comprising the step of applying to said area in an amount sufficient to be herbicidally effective to the unwanted vegetation a compound having the formula Cl O(CI-I CHR I where X is hydrogen, chlorine, or methyl; Y is hydrogen or chlorine; n is 0 or 2; and R is hydrogen or methyl when n is 0 and hydrogen when n is 2.  
  2. A post-emergent method of selectively controlling the growth of dicots in an area in which monocots are present comprising the step of applying to said area in an amount sufficient to be herbicidally effective to the dicots a compound having the formula 0 O(CH CI-IR- I V o O(CH CHR a where X is hydrogen, chlorine, or methyl; Y is hydrogen or chlorine; n is or 2; and R is hydrogen or methyl when n is 0 and hydrogen when n is 2.  
  6. The method of claim 5 wherein a compound which is applied is 2-(4-Chlorophenoxymethyl)-2-oxazoline.  
  7. The method of claim 5, wherein the plant species is a turfgrass and the growth inhibiting ingredient is applied at a rate of at least about 4 and not more than about 16 pounds per acre.  
  8. The method of claim 7, wherein the turfgrass is a St. Augustinegrass.  
  9. A formulation for selectively controlling the growth of broadleaf weeks in areas have grass therein comprising an effective amount of a herbicidally active ingredient, said ingredient being a compound of the formula Cl (CH CHR ingredient Parts by Weight Carrier 8100 Solvent-sticking agent 331-4466 Herbicidally active 301-32l3 ingredient Surfactant 0-964.  
  1 1. The formulation of claim 9, wherein the herbicidally active ingredient comprises 2-(2-Methyl-4- chlorophenoxymethyl )-2-oxazoline.  
  12. The formulation of claim 9, wherein the herbicidally active ingredient comprises 2-(4- Chlorophenoxymethyl )-2-0xazoline.