HERBICIDE ANTIDOTES, PRODUCTION, USE AND COMPOSITIONS THEREOF

Abstract: Certain haloalkylcarbonylamino-1,3-dioxane herbicide antidotes corresponding to the following general for­ mula: wherein R represents chloro-, bromo- or iodo- C₁-C₄ alkyl; R₁ represents hydrogen, C₁-C₄ alkyl, C₂-C₄ alkenyl or phenyl; R₂ represents hydrogen or C₁-C₄ alkyl; R₃ represents hydrogen or C₁-C₄ alkyl; and R₄ represents hydrogen or nitrophenyl; provided that one of R₃ and R₄ represents hydrogen; are disclosed, as is the production thereof. Such compounds may be formulated with inert di­ luents or carriers and or adjuvants or with herbicides, in particular thiocarbamates or acetanilides. The use of such compounds counteracts crop dam­ age caused by herbicides and hence provides a method of establishing herbicidal selectivity.

Description: "Herbicide arltidotec., production, use and compositions thereof" This invention relates to herbicide antidotes, production, use and compositions thereof; more particularly,. it relates to certain haloalkylcarbonylamino-1,3-dioxanes which are useful as herbicide antidotes. An herbicide is a compound which controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating, and dwarfing. The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. "plant growth" includes all phases of development from seed germination to natural or induced cessation of life. Herbicides are generally used to control or eradicate weed pests. They have gained a high degree of commercial success because it has been shown that such control can increase crop yield and reduce harvesting costs. The most popular methods of herbicide application include: pre-plant incorporation into the soil; infurrow application to seeds and surrounding soil; preemergence surface treatment of seeded soil, and postemergence treatment of the plant and soil. A manufacturer of an herbicide generally recommends a range of application rates and concentrations calculated to maximize weed control. The range of rates varies from approximately 0.01 to 50 pounds per acre (0.0112 to 56 kilograms per hectare (k/ha)), and is usually in the range of from 0.1 to 25 pounds per acre (0.112 to 28 kXha!. The term "herbicidally effective amount" describes an amount of an heerbicide compound which controls or modifies plant growth. The actual amount used depends upon several considerations, including particular weed susceptibility and overall cost limitations. The most important factor influencing the usefulness of a given herbicide is its selectivity towards crops. In some cases, a beneficial crop is susceptible to the effects of the herbicide. In addition, certain herbicidal compounds are phytotoxic to some weed species but not to others. To be effective, an herbicide must cause minimal damage (preferably no damage) to the beneficial crop while maximinizing damage to weed species which plague that crop. To preserve the beneficial aspects of herbicide use and to minimize crop damage, many herbicide antidotes have been prepared. These antidotes reduce or eliminate damage to the crop without substantially impairing the damaging effect of the herbicide on weed species. See U.S. Patent Nos. 4,021,224 and 4,021,229 and Belgian Patent No. 846,894. The precise mechanism by which an antidote reduces herbicidal crop injury has not been established. An antidote compound may be a remedy, interferent, protectant, or antagonist. As used herein, anti- dote" describes a compound which has the effect of establishing herbicide selectivity, i.e., continued herbicidal phytotoxicity to weed species and reduced or non-phytotoxicity to cultivated crop species. The term "antidotally effective amount" describes an amount of an antidote compound which counteracts a phytotoxic response of a beneficial crop to an herbicide. Thiocarbamate and acetanilide herbicides are particularly effective in the control of grassy tFe weeds which interfere with the cultivation of a wide variety cf crops, e.g., barley, corn, cotton, lentils, plants, peas, potatoes, soybeans, spinach, tobacco and tomatoes. Frequently the effective use of these herbicides requires the addition of an antidote compound. Description of the Invention It has now been discovered that certain haloaLkylcarbonyl- amino-l,5dioxane compounds are effective antidotes for the protection cf a variety of crops from thiocarbamate and acetanilide herbicide injuries. Such compounds have the following formula: EMI3.1 in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R1 is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitrophenyl group; and either R3 is hydrogen or R4 is hydrogen. This invention also embodies a t-vo-part herbicidal system comprised of (a) an herbicidally effective amount of a thiocarbamate com- pound of the formula EMI3.2 in which P5 is aLcJv having 1-6 carbon atoms, inclusive; P6 is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; and cyclohexyl; or R5 and R6 form indistinguishable parts of a single alkylene ring having 4-10 carbon atoms, inclusive; and R7 is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; haloakkyl wherein halo is selected from the group consisting of chlorine, bromine and iodine and alkyl has 1-6 carbon atoms, inclusive; alkenyl having 2-6 carbon atoms, inclusive; halo alkenyl wherein halo is selected fran the group consisting of chlorine, bromine and iodine and alkenyl has 2-6 carbon atoms, inclusive; benzyl; and halo-substituted benzyl, wherein halo is selected from the group consisting of chlorine, bromine and iodine; and (b) a non-phytotoxic antidotally effective amount of a compound of the formula EMI4.1 in which R is selected from the group consisting of haloaLkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; FL1 is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; is is selected from the group consisting hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitrophetyl group; and either R3 is hydrogen or R4 s hydrogen. Ey way of exemplification, the active thiocarbamate herbicides employed in the invention na. include the following: S-ethyl di- propyl thiocarbamate, S-ethyl diisc.butyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-propyl butylethylthiocarbamate, S-(2,3,3-tri chlo roally 1) diisopropyl thiocarbamate, S-ethyl N-ethyl N-cyclohexyl thiocarbamate, S-ethyl hexahyd ro- Ln-azepine-l-carbothioate, isopropyl1-hexahydro-1, 4-azepine-1-carbothioate, S-benzyl N, N-disec-butylthiolcarbamate, S-(4-chlorobenzyl) N,-diethyl thiolcarbamate and combinations thereof. This invention also embodies a two-part herbicidal system comprised of (a) an herbicidally effective amount of an acetanilide ccmpound of the formula EMI5.1 in which R8 and R10 are independently seleCted from the group consisting of hydrogen; and alkyl having 1-6 carbon atoms, inclusive; and Rg is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; alkoxy having 1-8 carbon atoms, inclusive; and carbethoxyalkyl wherein the alkyl group has 1-4 carbon atoms, inclusive; and (b) a non-phytotoxic antidotally effective amount of a compound of the formula EMI5.2 in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R1 is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitrophenyl group; and either R3 is hydrogen or R4 is hydrogen. By way of exem,plification, the active acetanilide compounds employed in the invention may include: 2-chloro-2', 6'diethyl-N- (methoxymethyl) acetanilide; 2-chloro-2'-methyl-6'-ethyl-N(methoxypropyl-(2))-acetanilide; 2-chloro-2', 6'-dimethyl-N-(methoxyethyl) acetanilide; 2-chloro-2'-methyl-6'-ethyl-N-(ethoxymethyl) acetanilide; 2-chloro-N-isopropyl acetanilide; 2-chloro-2',6'-diethyl-N-(n-butoxymethyl) acetanilide; and 2-chloro-N-carbethoxymethyl-2",6"diethyl acetanilide. This invention also includes the method of establishing herbicidal selectivity which comprises applying to the locus where protection is desired an antidotally effective amount of a compound of the formula EMI6.1 in which R Is halcaLkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R1 is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitrophenyl group: and either F3 is hydrogen or R4 i hydrogen. The locus where selectivity is desired may include soil, seeds, seedlings and vegetation. Preparation The thiocarbamates of the present composition are either corn mercially available or can be prepared by the procedures described in United States Patent Nos. 2,913,327, 2,983,747, 3,133,947, 3,185,720 and 3,198,786. The acetanilides of the present composition are either com mercially available or can be prepared > the procedures described in U.S. Patent Nos. 2,863,752; 3,442,945; 3,780,090; 3,937,730; 3,952,056; and 4,070,179. The haloalkylcarbonylamino-1,3-dioxanes of this invention can be prepared according to the following general procedures, depending upon the starting materials. In a first procedure, an appropriate haloalkylcarbonyl chlor- ide is reacted with 5-methyl-5-amino-1,3-dioxane in a basic solution. The reaction is carried out at temperatures below 35C. The reaction mixture may be stripped and the product recrystallized in ethanol/ water. structure may be confirmed by nuclear magnetic resonance (NMR) spectroscopy. In an alternate procedure, an appropriate dialkoxy compound is reacted with an appropriate dihydroxyalkyl haloacetamide in an acidic solution. The reaction is carried out at elevated temperatures. Distillate is collected at 80 C. The distillate may be cooled and washed with sodium carbonate and water. The product may be obtained by removing the solvent in vacuum. Structure may be confirmed by NMR - spectroscopy. The following examples illustrate the preparation of specific compounds according to these general methods. (Compound numbers cor respond to those in Tables I, IV and V). (Compound No. 1) Preparation of 5-methyl-5-(2',3'-dibromoproprionyl) amino-1,3-dioxane Five and nine-tenths grams (g) (0.05 mole) of 5-methyl-5amino-1,3-dioxane, 3.2 g (0.04 mole) of 50% sodium hydroxide, 8 milliliters (ml) of water and 55 ml of methylene chloride were combined in a reaction flask. The mixture was cooled to -10 C. Ten g (0.04 mole) of 2,3-dibromopropionyl chloride were added dropwise. The reaction mixture was stirred for 2 hours and then vacuum stripped. The product was recrystallized in ethanol/water. Yield was 8.7 g of 5-methyl-5-(2',3'- dibromopropionyl) amino-l,5-dioxane. m.p. = 15-119 C. Structure was confirmed by NMR spectroscopy. EXAMPLE II (Compound No. 4) Prepration of 5-(2'-bromo-3'-chloropropionyl) amino-5-ethyl-1,3-dioxene Five and two-tenths g (0.04 mole) of 5-ethyl-5-amino-1,3-di- oxane, 3.2 g (0.04 mole) of 5 sodium hydroxide, 10 ml of water, and 90 ml of methylene chloride were combined in a reaction flask. The mixture was cooled to below 35 C. Fight and two-tenths g (0.04 mole) of 2-bromo-3chloropropionyl chloride were added dropwise. The mixture was stirred for 1/2 hour, filtered, dried over magnesium sulfate, and vacuum stripped. Yield was 10.8 g of 5-(2'-bromo-3'-chloropropionyl) amino-5-ethyl-1,3-dioxane. m.p.=95-109 C. Structure was confirmed by NMR. EXAMPLE III (Compound No. 10) Preparation of 5-chloroacetylamino-5-ethyl-1,3-dioxane Five and two-tenths g (0.04 mole) of 5-ethyl-5-smino-l, 3di- oxane, 3.2 g (0.04 mole) of 50% sodium hydroxide, 10 ml of water, and 90 ml of methylene chloride were combined in a reaction flask. The mixture was cooled to below 35 C. Four and one-half g of chloroacetylchloride were added droprise. The reacticn mixture was stirred for one-half hour. washed with water and dried over magnesium sulfate. The solvent was vacuum stripped. Yield was 5.8 g of 5-chloroacetylamino-5- ethyl-l,Sdioxane. m.p. = 89-95 C. Structure was confirmed by NMR. EXAMPLE IV (Compound No. 10) Preparation of 2-vinfJl-n-methyl-,-dicKloroacetylamino-1,3-dioxane This example illustrates use of the alternate general procedure. Six and one-half grams (0.03 mole) of 2,2-(dimethoxyethyl) dichloroacetamide, 3.9 g (0.03 mole) of acrolein diethylacetal, 50 ml of acetonitrile and 0.2 g of ammonium chloride were combined in a reaction flask. The reaction mixture was stirred and refluxed through an attached packed column and variable take-off condenser. Distillate was removed to a head temperature of 78 C. The reaction mixture was cooled to 40 C and 0.1 g of crushed ammonium chloride was added. The mixture was heated to reflux and distillate was collected between 73 and 81 C. An additional 0.1 g of ammonium chloride was added and the temperature rose to 83 C. Heating was stopped and the hot reaction mixture was poured over ice and extracted twice with 75 ml of dichloromethane. The extracts were combined and washed with 100 ml of water. After drying, the solvent was removed in vacuo to yield 5.0 g of 2-vinyl-5-methyl-5-dichloroacetal amino-l,3-dioxane, an oil. n33 = 1.4980. Structure was confirmed by Nt1R spectroscopy and gas chromatography. EXAMPLE V (Compound No. 21) Preparation of 2,2-dimethyl-4-(p-nitrophenyl)-5-dichlero-1,3-dioxane This example demonstrates use of the alternate general procedure. Six grams (0.019 mole) of chloroamphenicol, 2.3 g (0.022 mole) of acetone dimethylacetal, 0.2 g cf -napthalene sulfonic acid and 60 ml of ethylene dichloride were combined in a reaction flask. The reaction mixture was stirred and refluxed through an attached packed column and variable take-off condenser. Distillate was removed to a head temperature of 80 C The distlllate was cooled and washed with water, twice with sodium carbonate and a second time with water. The mixture was dried and stripped. Yield was 6.0 g of 2,2-dimethiyl-4-(p-nitrophenyl)-5-di- chloro-1,3-dioxane. m.p.-140-143 C. Structure was confirmed my N.R. TABLE I HALOALKYLCARBONYLAMINO-1,3-DIOXANES EMI11.1 EMI11.2 Cmpd. <SEP> Physical <tb> No. <SEP> R <SEP> R1 <SEP> R2 <SEP> R3 <SEP> R4 <SEP> Chemical <SEP> Name <SEP> Constant <tb> 1 <SEP> CH2-CH <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> 5-methyl-5-(2',3'-dibromopropionyl) <SEP> m.p. <SEP> = <SEP> 115-119 C <tb> <SEP> # <SEP> # <SEP> amino-1,3-dioxane <tb> <SEP> Br <SEP> Br <tb> 2 <SEP> CH2-CH <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> 5-(2,3-dibromopropionyl)amino-2,5- <SEP> m.p. <SEP> = <SEP> 124-128 C <tb> <SEP> # <SEP> # <SEP> dimethyl-1,3-dioxane <tb> <SEP> Br <SEP> Br <tb> 3 <SEP> CH2-CH <SEP> H <SEP> H <SEP> C2H5 <SEP> H <SEP> 5-(2,3-dibromopropionyl)amino-5-ethyl <SEP> m.p. <SEP> = <SEP> 100-107 C <tb> <SEP> # <SEP> # <SEP> 1,3-dioxane <tb> <SEP> Br <SEP> Br <tb> 4 <SEP> CH2-CH <SEP> H <SEP> H <SEP> C2H5 <SEP> H <SEP> 5-(2'-bromo-3'-chloropropionyl)amino- <SEP> m.p. <SEP> = <SEP> 95-109 C <tb> <SEP> Cl <SEP> Br <SEP> 5-ethyl-1,3-dioxane <tb> 5 <SEP> Cl2CH <SEP> CH3 <SEP> C2H5 <SEP> CH3 <SEP> H <SEP> 2-ethyl-2,5-dmethyl-5-dichloroacetyl- <SEP> m.p. <SEP> = <SEP> 84-87 C <tb> <SEP> amino-1,3-dioxane <tb> 6 <SEP> ClCH2 <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> 5-chloroacetylamino-5-methyl-1,3-dioxane <SEP> m.p. <SEP> = <SEP> 116-120 C <tb> 7 <SEP> Cl2CH <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> 5-dichloroacetylamino-5-methyl-1,3- <SEP> m.p. <SEP> = <SEP> 127 C <tb> <SEP> dioxane <tb> 8 <SEP> ClCH2 <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> 5-chloroacetylamino-2,5-dimethyl-1,3- <SEP> m.p. <SEP> = <SEP> 94-97 C <tb> <SEP> dioxane <tb> 9 <SEP> Cl2CH <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> 5-dichloroacetylamino-2,5-dimethyl-1,3- <SEP> m.p. <SEP> = <SEP> 104-106 C <tb> <SEP> dioxane <tb> 10 <SEP> ClCH2 <SEP> H <SEP> H <SEP> C2H5 <SEP> H <SEP> 5-chloroacetylamino-5-ethyl-1,3-dioxane <SEP> m.p. <SEP> = <SEP> 89-94 C <tb> TABLE I (continued) EMI12.1 Cmpd. <SEP> Physical <tb> No. <SEP> R <SEP> R1 <SEP> R2 <SEP> R3 <SEP> R4 <SEP> Chemical <SEP> Name <SEP> Constant <tb> 11 <SEP> Cl2CH <SEP> H <SEP> H <SEP> C2H5 <SEP> H <SEP> 5-(dichloroacetylamino-5-ethyl-1,3- <SEP> m.p. <SEP> = <SEP> 94-96.5 C <tb> <SEP> dioxane <tb> 12 <SEP> ClCH2 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 5-methyl-5-chloroacetylamino-2,2-di- <SEP> nD30 <SEP> = <SEP> 1.4785 <tb> <SEP> methyl-1,3-dioxane <tb> 13 <SEP> Cl2CH <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 2,2,5-trimethyl-5-dichloroacetylamino- <SEP> m.p. <SEP> = <SEP> 101-104 C <tb> <SEP> 1,3-dioxane <tb> 14 <SEP> ClCH2 <SEP> CH3 <SEP> CH3 <SEP> C2H5 <SEP> H <SEP> 2,2-dimethyl-5-ethyl-5-chloroacetylamino- <SEP> m.p. <SEP> = <SEP> 67-70 C <tb> <SEP> 1,3-dioxane <tb> 15 <SEP> Cl2CH <SEP> CH3 <SEP> CH3 <SEP> C2H5 <SEP> H <SEP> 2,2-dimethyl-5-ethyl-5-dichloroacetylamino- <SEP> m.p. <SEP> = <SEP> 90-93 C <tb> <SEP> 1,3-dioxane <tb> 16 <SEP> ClCH2 <SEP> C2H5 <SEP> CH3 <SEP> CH3 <SEP> H <SEP> 2,5-dimethyl-2-ethyl-5-chloroacetylamino- <SEP> m.p. <SEP> = <SEP> 62-69 C <tb> <SEP> 1,3-dioxane <tb> 17 <SEP> ClCH2 <SEP> CH=CH2 <SEP> H <SEP> CH3 <SEP> H <SEP> 2-allyl-5-methyl-5-chloroacetylamino-1,3- <SEP> m.p. <SEP> = <SEP> 78-83 C <tb> <SEP> 1,3-dioxane <tb> 18 <SEP> Cl2CH <SEP> CH=CH2 <SEP> H <SEP> CH3 <SEP> H <SEP> 2-allyl-5-methyl-5-dichloroacetylamino- <SEP> nD30 <SEP> = <SEP> 1.4980 <tb> <SEP> 1,3-dioxne <tb> 19 <SEP> ClCH2 <SEP> # <SEP> H <SEP> CH3 <SEP> H <SEP> 2-phenyl-5-methyl-5-chloroacetylamino-1,3- <SEP> softened <SEP> above <SEP> 95 C <tb> <SEP> dioxane <tb> 20 <SEP> Cl2CH <SEP> # <SEP> H <SEP> CH3 <SEP> H <SEP> 2-phenyl-5-methyl-5-dichloroacetylamino- <SEP> m.p. <SEP> = <SEP> 145-148 C <tb> <SEP> 1,3-dioxane <tb> 21 <SEP> Cl2CH <SEP> CH3 <SEP> CH3 <SEP> H <SEP> # <SEP> 2,2-dimethyl-4-(p-nitrophenyl)-5-dichloro- <SEP> m.p. <SEP> = <SEP> 140-143 C <tb> <SEP> NO2 <SEP> acetylamino-1,3-dioxane <tb> 22 <SEP> Cl2CH <SEP> CH3 <SEP> H <SEP> H <SEP> # <SEP> 2-methyl-4-(p-nitrophenyl)-5-dichloro- <SEP> glass <tb> <SEP> NO2 <SEP> acetylamino-1,3-dioxane <tb> Testing Stock solutions of the herbicides were prepared by diluting the requisite amount of each herbicide in water. Examples of solution compositions and application rates are summarized in Table II. TABLE II Herbicide Stock Solutions Composition Herbicide Water Application Herbicide Name (mg)* (ml) ml/flat** lb/acre VEEUIS 6E S-propyl N,N- 533 400 5 1.25 diprepyl thio- 3000 500 5 6.00 carbamate EPTAM# 6E 2225 350 5 6.00 S-ethyl N,!F- dipropyl thiocarbamate * The weight is measured in terms of mg of formulated herbicide. The formulations used contain about 72% active herbicide compound. ** The flats measure 5.95 inches by 9.5 inches. Approximately four (4) mgiflat is s equal to one (1) lb/acre. The herbicide was either incorporated into the soil prior to planting or applied to the soil after planting and prior to emergence of the plants. In some cases of pre-plant incorporation, the herbicide was incorporated into the soil alone in preparation for in-furrow application of the antidote; in others the herbicide solution was tank-mixed with the antidote solution prior to incorporation. Stock solutions of each antidote compound were prepared at the desired concentraticns by diluting the requisite amount of each antidote in acetone. Examples of solution compositions, rates and application methods are slemmarized in Table III. Antidote Stock Solutions Antidote: Haloalkylcarbonylamino-1,3-dioxanes Composition Application Antidote (mg) Acetone (ml) ml/flat lb/acre Method 95 15 1.50 5.00 IF* 60 15 5.00 5.00 PPI** IF = In-furrow surface application of antidote. **PPI = Pre-plant incorporation of tank-mixed solution of herbicide and antidote The antidote solutions were applied to the soil either by in furrow surface application or by pre-plant incorporation. In all cases cf pre-plant incorporaticn, the antidote was tank-mixed with the herbicide prior to incorporation into the soil. For in-furrow application, a one pint (473 cubic centimeter (cc)) sample of soil containing the previously incorporated herbicide was removed and retained from each planting flat. After leveling and furrowing the soil, seeds of the crop or weed species were planted 1/2 inch deep (1.27 centimeter). Each flat was divided in half by a wooden barrier. A stock solution of the antidote was atomized directly onto the exposed seeds and soil in the open furrow on one side of the barrier. The seeds in the entire flat were then covered with the previ ously removed soil. The antidotally untreated sections of flats were compared for sbserr-ed differences which would indicate lateral movement of the antidote through the soil. Control flats contained crops treated with herbicide only. All flats were placed cn greenhouse benches where temperature was maintained between 70 and 900F (21.1 to 32.20C). The flats were watered by sprinkling as needed to assure good plant growth. All of the soil used in the. tests described herein was loamy sand soil treated with 50 parts per million (ppm) each of a commerci- ally available fungicide, J [(trichloromethyl ) thio]-4-cyclohexene-l, 2- dicarboximide, and 18-18-18 fertilizer, which contains 18% by weight equivalent each of nitrogen, phosphorus pentoxide, and potassium oxide. Injury ratings were taken four weeks after application of the antidote. The effectiveness of the antidote was determined by visual comparison of crop injury in the test flats to that in the control flats. The treated crops initially screened for diminution of herbicidal injury were -milo, wheat, rice, barley, corn and soybeans. Compounds which showed substantial activity were tested further. The herbicides and the most active antidote compositions were then screened on weed species. The weed species tested included watergrass (Echinochloa crusgalli), foxtail (Setaria viridis), wild oat (Avena fatua), shattercane (Sorghum bicolor), johnsongrass (Sorghum halepense) and mustard (Brasstica juncea). KEY TO TABLES IV AMD V Compound numbers in these tables correspond to the numbers and their chemical descripticn in Table I. Compounds omitted in Table V were not tested cn weed species. Herbicides VERNAM# - S-propyl N,N-dipropyl thioarbamate EPTAM# - S-ethyl N,N-dipropyl thiocarbamate RONEET# - S-ethyl N-ethyl-N-cyclohexyl thiocarbamate SUTAN# - S-ethyl N,N-diisobutyl thiocarbamate LASSO# - 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide TERIDOX# - 2-chloro-2','-dimethyl-N-(methoxymethyl) acetanilide TREFLAN# - &alpha;,&alpha;,&alpha;-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine ATRAZINE# - 2-chloro-4-ethylamino-6-isopropylamino-S-triazine Application Methods PES = Surface application of herbicide to soil after planting of seeds and prior to emergence of plants. IF = In-furrow surface application of antidote (soil previously treated with herbicide only). PPI = Pre-plant incorporation of herbicide or antidote. If both herbIcide and antidote were preplant incorporated, a tank-.mixed solution was used. = = Tank-mixed solution of herbicide and antidote. If no antidote was applied, the word "none" appears in the Antidote Fate column. The results shown on this line are the percent injuries sustained by each of the crops when treated with the herbicide only at the rate specified. All rates shown, for both herbicide and antidote, are in pounds per acre. Injury Ratings The injury to the crop (Table IV) or weeds (Table V) is shown as a percentage of damage done to the plants as compared to an evaluation of the undamaged state of the plants. The damage done to the plants is a function of the number of plants injured and the extent of injury to each plant. This rating is made four (4) weeks after application of the herbicide alone or of the herbicide in combination with the antidote. An asterisk (*) in Table Di indicates that the antidote compound is active in reducing herbicidal injury to the crop. Parentheses around a number indicate that the test has been run more than once and the results are inconclusive. Table V shows that the antidote compounds tested have no effect on weeds, i.e., herbicidal injury to the weeds is sustained even in the presence of an antidote compound. TABLE IV Antidotal Effectiveness Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 1 VERNAM 1.0 PPI none - 100 77 50 87 83 VERNAM 1.0 PPI 5.0 IF 100 *60 50 87 *20 VERNAM 6.0 PPI none - 90 100 VERNAM 6.0 PPI 5.0 IF *20 *80 VERNAM 1.0 PPI none - 60 VERNAM 1.0 PPI 1.0 IF *30 VERNAM 1.0 PPI 5.0 IF *10 VERNAM 1.0 PPI none - 100 VERNAM 1.0 PPI 1.0 IF *70 VERNAM 1.0 PPI 5.0 IF *60 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.5 PPI/TM 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *70 EPTAM 6.0 PPI 5.0 PPI *50 LASSO 3.0 PES none - 98 70 99 LASSO 3.0 PES 5.0 IF 98 70 *95 LASSO 3.0 PES none - 90 55 LASSO 3.0 PES/TM 5.0 PES/TM 90 *40 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 1 LASSO 4.0 PES none - 80 LASSO 4.0 PES/TM 5.0 PES/TM *20 TREFLAN 1.0 PPI none - 100 98 100 85 TREFLAN 1.0 PPI 5.0 IF 100 98 100 85 2 VERNAM 1.0 PPI none - 100 75 70 95 70 VERNAM 1.0 PPI 5.0 IF *80 *60 70 95 *50 VERNAM 6.0 PPI none - 80 VERNAM 6.0 PPI 5.0 IF 80 VERNAM 6.0 PPI none - 90 VERNAM 6.0 PPI 5.0 IF *50 VERNAM 1.25 PPI none - 70 VERNAM 1.25 PPI 1.0 IF *40 VERNAM 1.25 PPI 5.0 IF *30 VERNAM 1.25 PPI none - 70 VERNAM 1.25 PPI/TM 1.0 PPI/TM *50 VERNAM 1.25 PPI/TM 5.0 PPI/TM *35 LASSO 3.5 PES none - 95 70 100 70 LASSO 3.5 PES 5.0 IF *60 70 100 *50 TERIDOX 1.0 PES none - 100 70 80 100 TERIDOX 1.0 PES 5.0 IF 100 70 *55 100 3 VERNAM 1.0 PPI none - 95 70 70 95 50 VERNAM 1.0 PPI 5.0 IF 95 *30 80 95 * 0 VERNAM 6.0 PPI none - 70 55 VERNAM 6.0 PPI 5.0 IF *30 *40 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 3 VERNAM 1.25 PPI none - 95 95 80 VERNAM 1.25 PPI 1.0 IF 95 95 *60 VERNAM 1.25 PPI 5.0 IF *60 95 *40 VERNAM 5.0 PPI none - 40 VERNAM 5.0 PPI 1.0 IF 40 VERNAM 5.0 PPI 5.0 IF *30 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *10 EPTAM 6.0 PPI 5.0 PPI *30 SUTAN 5.0 PPI none - 35 SUTAN 5.0 PPI/TM 1.0 PPI/TM 35 SUTAN 5.0 PPI/TM 5.0 PPI/TM *20 LASSO 3.0 PES none - 90 55 LASSO 3.0 PES/TM 5.0 PES/TM *80 35 LASSO 4.0 PPI none - 80 LASSO 4.0 PPI 5.0 PES/TM *20 4 VERNAM 1.25 PPI none - 100 95 60 95 95 VERNAM 1.25 PPI 5.0 IF *40 *60 60 95 *20 VERNAM 6.0 PPI none - 85 60 VERNAM 6.0 PPI 5.0 IF *0 60 VERNAM 1.25 PPI none - 95 VERNAM 1.25 PPI 1.0 IF *40 VERNAM 1.25 PPI 5.0 IF *20 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 4 VERNAM 1.25 PPI none - 90 VERNAM 1.25 PPI/TM 0.25 PPI/TM 90 VERNAM 1.25 PPI/TM 0.5 PPI/TM 90 VERNAM 1.25 PPI/TM 1.0 PPI/TM *70 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *0 EPTAM 6.0 PPI 5.0 PPI *0 RONEET 3.0 PPI none - 90 RONEET 3.0 PPI 1.0 IF *60 RONEET 3.0 PPI 5.0 IF 90 LASSO 3.0 PES none - 98 70 99 LASSO 3.0 PES 5.0 IF *85 *55 99 LASSO 3.0 PES none - 95 70 100 70 LASSO 3.0 PES 5.0 IF *10 *20 100 *15 TERIDOX 1.0 PES none - 100 70 80 100 TERIDOX 1.0 PES 5.0 IF *90 *35 *35 *0 ATRAZINE 1.0 PES none - 100 70 100 ATRAZINE 1.0 PES 5.0 IF 100 70 100 ATRAZINE 0.25 PES none - 100 ATRAZINE 0.25 PES 5.0 IF 100 TREFLAN 1.0 PPI none - 100 98 100 85 TREFLAN 1.0 PPI 5.0 IF 100 *90 100 85 5 VERNAM 1.25 PPI none - 100 100 60 100 90 VERNAM 1.25 PPI 5.0 IF *75 *90 *50 *90 *70 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 5 VERNAM 6.0 PPI none - 95 60 VERNAM 6.0 PPI 5.0 IF *70 60 6 VERNAM 1.0 PPI none - 100 77 50 87 83 VERNAM 1.0 PPI 5.0 IF *60o *60 50 87 *60 VERNAM 6.0 PPI none - 90 60 VERNAM 6.0 PPI 5.0 IF *0 90 VERNAM 1.0 PPI none - 100 VERNAM 1.0 PPI 1.0 IF 100 VERNAM 1.0 PPI 5.0 IF 100 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM *(45) VERNAM 6.0 PPI/TM 2.0 PPI/TM *50 VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM (60) VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM *(0) VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *30 EPTAM 6.0 PPI 5.0 PPI *0 LASSO 3.0 PES none - 98 70 99 LASSO 3.0 PES 5.0 IF 98 70 99 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 6 ATRAZINE 0.25 PES none - 100 ATRAZINE 0.25 PES 5.0 IF 100 ATRAZINE 1.0 PES none - 100 70 100 ATRAZINE 1.0 PES 5.0 IF 100 70 100 TREFLAN 1.0 PPI none - 100 98 100 85 TREFLAN 1.0 PPI 5.0 IF 100 *95 100 *80 7 VERNAM 1.0 PPI none - 100 77 50 87 83 VERNAM 1.0 PPI 5.0 IF 100 77 *40 87 83 VERNAM 6.0 PPI none - 90 60 VERNAM 6.0 PPI 5.0 IF *40 90 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 75 8 VERNAM 1.0 PPI none - 100 75 70 95 70 VERNAM 1.0 PPI 5.0 IF *30 75 70 95 *20 VERNAM 6.0 PPI none - 80 VERNAM 6.0 PPI 5.0 IF 100 VERNAM 6.0 PPI none - 90 VERNAM 6.0 PPI 5.0 IF *0 VERNAM 1.25 PPI none - 70 VERNAM 1.25 PPI 5.0 IF 70 VERNAM 1.25 PPI 5.0 IF 70 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 8 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *30 EPTAM 6.0 PPI 5.0 PPI *0 RONEET 4.0 PPI none - 60 RONEET 4.0 PPI 1.0 IF 60 RONEET 4.0 PPI 5.0 IF *20 LASSO 3.0 PES none - 98 70 99 LASSO 3.0 PES 5.0 IF 98 70 99 LASSO 3.5 PES none - 95 70 100 70 LASSO 3.5 PES 5.0 IF 95 *60 100 70 TERIDOX 1.0 PES none - 100 70 80 100 TERIDOX 1.0 PES 5.0 IF 100 70 80 100 ATRAZINE 0.25 PES none - 100 ATRAZINE 0.25 PES 5.0 IF 100 ATRAZINE 1.0 PES none - 100 70 100 ATRAZINE 1.0 PES 5.0 IF 100 70 100 TREFLAN 1.0 PPI none - 100 98 100 98 TREFLAN 1.0 PPI 5.0 IF 100 98 100 98 9 VERNAM 1.0 PPI none - 100 75 70 95 70 VERNAM 1.0 PPI 5.0 IF *90 75 70 *50 *60 VERNAM 6.0 PPI none - 80 VERNAM 6.0 PPI 5.0 IF 95 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 9 VERNAM 6.0 PPI none - 90 VERNAM 6.0 PPI 5.0 IF *0 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 1.0 PPI/TM 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 60 VERNAM 6.0 PPI none - 60 VERNAM 6.0 PPI/TM 5.0 PPI/TM 80 EPTAM 6.0 PPI none - 80 EPTAM 6.0 PPI 0.5 PPI *70 EPTAM 6.0 PPI 5.0 PPI *45 10 VERNAM 1.25 PPI none - 80 80 70 95 70 VERNAM 1.25 PPI 5.0 IF *30 *60 *60 95 *50 VERNAM 6.0 PPI none - 90 50 VERNAM 6.0 PPI 5.0 IF *0 *30 VERNAM 5.0 PPI none - 65 VERNAM 5.0 PPI 1.0 IF *50 VERNAM 5.0 PPI 5.0 IF 80 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.05 PPI/TM 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM 90 EPTAM 6.0 PPI/TM 5.0 PPI/TM 35 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *30 EPTAM 6.0 PPI/TM 5.0 PPI/TM *20 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 10 RONEET 4.0 PPI none - 60 RONEET 4.0 PPI 1.0 IF 60 RONEET 4.0 PPI 5.0 IF 60 11 RONEET 1.25 PPI none - 80 80 70 95 70 RONEET 1.25 PPI 5.0 IF *40 *60 70 95 *50 RONEET 6.0 PPI none - 90 50 RONEET 6.0 PPI 5.0 IF *0 70 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.05 PPI/TM 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM (90) EPTAM 6.0 PPI/TM 5.0 PPI/TM *80 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *(55) EPTAM 6.0 PPI/TM 5.0 PPI/TM *25 RONEET 4.0 PPI none - 60 RONEET 4.0 PPI ---- ---- 60 RONEET 4.0 PPI ---- ---- *40 12 VERNAM 1.25 PPI none - 100 95 60 100 90 VERNAM 1.25 PPI 5.0 IF *60 *60 60 100 *60 VERNAM 6.0 PPI none - 85 70 VERNAM 6.0 PPI 5.0 IF *0 70 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.05 PPI/TM 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *80 EPTAM 6.0 PPI/TM 5.0 PPI/TM *0 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 12 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *40 EPTAM 6.0 PPI/TM 5.0 PPI/TM *10 EPTAM 6.0 PPI none - 70 EPTAM 6.0 PPI 0.5 PPI *40 EPTAM 6.0 PPI 5.0 PPI *0 13 VERNAM 1.25 PPI none - 100 90 60 95 85 VERNAM 1.25 PPI 5.0 IF 100 90 60 95 85 VERNAM 6.0 PPI none - 90 65 VERNAM 6.0 PPI 5.0 IF *65 70 14 VERNAM 1.25 PPI none - 100 95 70 100 95 VERNAM 1.25 PPI 5.0 IF 100 95 *55 100 95 VERNAM 6.0 PPI none - 90 65 VERNAM 6.0 PPI 5.0 IF *80 40 15 VERNAM 1.25 PPI none - 100 95 70 100 95 VERNAM 1.25 PPI 5.0 IF 100 95 *40 100 *80 VERNAM 6.0 PPI none - 90 65 VERNAM 6.0 PPI 5.0 IF *80 65 VERNAM 1.25 PPI none - 50 VERNAM 1.25 1.0 0.5 IF 50 VERNAM 1.25 PPI 5.0 IF *20 16 VERNAM 1.25 PPI none - 100 95 70 100 95 VERNAM 1.25 PPI 5.0 IF 100 95 70 100 100 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 16 VERNAM 6.0 PPI none - 90 65 VERNAM 6.0 PPI 5.0 IF *30 *50 EPTAM 5.0 PPI none - 85 EPTAM 5.0 PPI/TM 0.05 PPI/TM *60 EPTAM 5.0 PPI/TM 0.5 PPI/TM *0 EPTAM 5.0 PPI/TM 5.0 PPI/TM *0 17 VERNAM 1.25 PPI none - 100 100 60 100 90 VERNAM 1.25 PPI 5.0 IF *80 *95 60 100 *80 VERNAM 6.0 PPI none - 95 60 VERNAM 6.0 PPI 5.0 IF *85 60 18 VERNAM 1.25 PPI none - 90 75 55 90 60 VERNAM 1.25 PPI 5.0 IF *80 *60 55 *50 *45 VERNAM 6.0 PPI none - 90 60 VERNAM 6.0 PPI 5.0 IF *30 60 VERNAM 1.0 PPI none - 98 VERNAM 1.0 PPI 1.0 IF *60 VERNAM 1.0 PPI 5.0 IF *20 VERNAM 1.25 PPI none - 85 VERNAM 1.25 PPI 1.0 IF 85 VERNAM 1.25 PPI 5.0 IF 85 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.05 PPI/TM 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *80 EPTAM 6.0 PPI/TM 5.0 PPI/TM *0 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM *50 EPTAM 6.0 PPI/TM 5.0 PPI/TM *0 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 19 VERNAM 1.25 PPI none - 100 100 60 100 90 VERNAM 1.25 PPI 5.0 IF *80 *95 70 100 90 VERNAM 6.0 PPI none - 95 60 VERNAM 6.0 PPI 5.0 IF *60 *40 VERNAM 6.0 PPI none - 55 VERNAM 6.0 PPI 1.0 IF 55 VERNAM 6.0 PPI 5.0 IF *45 20 VERNAM 1.25 PPI none - 100 100 60 100 90 VERNAM 1.25 PPI 5.0 IF 100 100 60 *95 90 VERNAM 6.0 PPI none - 95 60 VERNAM 6.0 PPI 5.0 IF *40 60 EPTAM 5.0 PPI none - 85 EPTAM 5.0 PPI/TM 0.05 PPI/TM 85 EPTAM 5.0 PPI/TM 0.5 PPI/TM *35 EPTAM 5.0 PPI/TM 5.0 PPI/TM *15 EPTAM 6.0 PPI none - 90 EPTAM 6.0 PPI/TM 0.05 PPI/TM 90 EPTAM 6.0 PPI/TM 0.5 PPI/TM 90 EPTAM 6.0 PPI/TM 5.0 PPI/TM *30 21 VERNAM 1.25 PPI none - 80 75 60 85 65 VERNAM 1.25 PPI 5.0 IF 80 75 60 *65 *60 VERNAM 6.0 PPI none - 90 60 VERNAM 6.0 PPI 5.0 IF *60 60 TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No. Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 21 VERNAM 1.25 PPI none - 50 VERNAM 1.25 PPI 1.0 IF 50 VERNAM 1.25 PPI 5.0 IF 50 VERNAM 6.0 PPI none - 25 VERNAM 6.0 PPI 1.0 IF *10 VERNAM 6.0 PPI 5.0 IF 25 VERNAM 6.0 PPI none - 50 VERNAM 6.0 PPI/TM 1.0 PPI/TM 50 VERNAM 6.0 PPI/TM 2.0 PPI/TM 50 VERNAM 6.0 PPI/TM 5.0 PPI/TM 50 SUTAN 6.0 PPI none - 40 SUTAN 6.0 PPI/TM 1.0 PPI/TM 40 SUTAN 6.0 PPI/TM 5.0 PPI.TM 40 22 VERNAM 1.25 PPI none - 90 100 70 100 75 VERNAM 1.25 PPI 5.0 IF *60 100 70 100 75 VERNAM 6.0 PPI none - 90 40 VERNAM 6.0 PPI 5.0 IF 90 40 TABLE V Herbicidal Effectiveness Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 1 VERNAM 1.0 PPI none - 70 95 VERNAM 1.0 PPI 1.0 IF 70 95 VERNAM 1.0 PPI 5.0 IF 70 95 VERNAM 1.0 PPI none - 100 70 VERNAM 1.0 PPI 1.0 IF 100 70 VERNAM 1.0 PPI 5.0 IF 100 70 VERNAM 6.0 PPI none - 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM 5.0 PPI/TM 100 100 VERNAM 6.0 PPI none - 85 90 VERNAM 6.0 PPI/TM 1.0 PPI/TM 85 90 VERNAM 6.0 PPI/TM 5.0 PPI/TM 85 90 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 LASSO 3.0 PES none - 99 LASSO 3.0 PES 5.0 IF 99 LASSO 3.0 PES none - 100 100 LASSO 3.0 PES/TM 5.0 PES/TM 100 100 LASSO 4.0 PES none - 100 100 LASSO 4.0 PES/TM 5.0 PES/TM 100 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 2 VERNAM 1.25 PPI none - 90 100 VERNAM 1.25 PPI 1.0 IF 90 100 VERNAM 1.25 PPI 5.0 IF 90 100 VERNAM 1.25 PPI none - 85 100 VERNAM 1.25 PI/TM 1.0 PPI/TM 85 100 VERNAM 1.25 PI/TM 5.0 PPI/TM 85 100 LASSO 3.5 PPI none - 100 LASSO 3.5 PPI 5.0 IF 100 TERIDOX 1.0 PPI none - 100 TERIDOX 1.0 PPI 5.0 IF 100 3 VERNAM 1.25 PPI none - 85 VERNAM 1.25 PPI 1.0 IF 85 VERNAM 1.25 PPI 5.0 IF 85 VERNAM 5.0 PPI none - 100 100 VERNAM 5.0 PPI 1.0 IF 100 100 VERNAM 5.0 PPI 5.0 IF 100 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 3 SUTAN 5.0 PPI none - 100 100 SUTAN 5.0 PPI/TM 1.0 - 100 100 SUTAN 5.0 PPI/TM 5.0 - 100 100 LASSO 3.0 PES none - 100 100 LASSO 3.0 PES/TM 5.0 - 100 100 LASSO 4.0 PES none - 100 100 LASSO 4.0 PES/TM 5.0 - 100 100 4 VERNAM 1.25 PPI none - 100 70 VERNAM 1.25 PPI 1.0 - 100 70 VERNAM 1.25 PPI 5.0 - 100 70 VERNAM 1.25 PPI none - 70 100 VERNAM 1.25 PPI/TM 0.25 - 70 100 VERNAM 1.25 PPI/TM 0.5 - 70 100 VERNAM 1.25 PPI/TM 1.0 - 70 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 - 100 100 EPTAM 6.0 PPI 5.0 - 100 100 RONEET 3.0 PPI none - 95 100 RONEET 3.0 PPI 1.0 - 95 100 RONEET 3.0 PPI 5.0 - 95 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 4 LASSO 3.0 PES none - 99 LASSO 3.0 PES 5.0 IF 99 LASSO 3.5 PES none - 100 LASSO 3.5 PES 5.0 IF 100 TERIDOX 1.0 PES none - 100 TERIDOX 1.0 PES 5.0 IF 100 ATRAZINE 0.25 PES none - 95 100 ATRAZINE 0.25 PES 5.0 IF 95 100 6 VERNAM 1.0 PPI none - 70 100 VERNAM 1.0 PPI 1.0 IF 70 100 VERNAM 1.0 PPI 5.0 IF 70 100 VERNAM 6.0 PPI none - 100 90 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 90 VERNAM 6.0 PPI/TM 2.0 PPI/TM 100 90 VERNAM 6.0 PPI/TM 5.0 PPI/TM 100 90 VERNAM 6.0 PPI none - 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM 5.0 PPI/TM 100 100 VERNAM 6.0 PPI none - 85 90 VERNAM 6.0 PPI/TM 1.0 PPI/TM 85 90 VERNAM 6.0 PPI/TM 5.0 PPI/TM 85 90 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 6 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 LASSO 3.0 PES none - 99 LASSO 3.0 PES 5.0 IF 99 ATRAZINE 0.25 PES none - 95 ATRAZINE 0.25 PES 5.0 IF 95 7 VERNAM 6.0 PPI none - 85 90 VERNAM 6.0 PPI/TM 1.0 PPI/TM 85 90 VERNAM 6.0 PPI/TM 5.0 PPI/TM 85 90 8 VERNAM 1.25 PPI none - 90 100 VERNAM 1.25 PPI 1.0 IF 90 100 VERNAM 1.25 PPI 5.0 IF 90 100 VERNAM 6.0 PPI none - 100 100 VERNAM 6.0 PPI/TM 0.5 PPI/TM 100 100 VERNAM 6.0 PPI/TM 5.0 PPI/TM 100 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 RONEET 4.0 PPI none - 80 100 RONEET 4.0 PPI 1.0 IF 80 100 RONEET 4.0 PPI 5.0 IF 80 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 8 LASSO 3.0 PES none - 99 LASSO 3.0 PES 5.0 IF 99 LASSO 3.5 PES none - 100 LASSO 3.5 PES 5.0 IF 100 TERIDOX 1.0 PES none - 100 TERIDOX 1.0 PES 5.0 IF 100 ATRAZINE 0.25 PES none - 95 100 ATRAZINE 0.25 PES 5.0 IF 95 100 9 VERNAM 6.0 PPI none - 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM 5.0 PPI/TM 100 100 VERNAM 6.0 PPI none - 85 90 VERNAM 6.0 PPI/TM 5.0 PPI/TM 85 90 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 10 VERNAM 5.0 PPI none - 100 95 VERNAM 5.0 PPI 1.0 IF 100 95 VERNAM 5.0 PPI 5.0 IF 100 95 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 10 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 RONEET 4.0 PPI none - 80 100 RONEET 4.0 PPI 1.0 IF 80 100 RONEET 4.0 PPI 5.0 IF 80 100 11 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 RONEET 4.0 PPI none - 80 100 RONEET 4.0 PPI ---- ---- 80 100 RONEET 4.0 PPI ---- ---- 80 100 12 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 12 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI 5.0 PPI 100 100 15 VERNAM 1.25 PPI none - 90 70 VERNAM 1.25 PPI 1.0 IF 90 70 VERNAM 1.25 PPI 5.0 IF 90 70 16 EPTAM 5.0 PPI none - 98 98 EPTAM 5.0 PPI/TM 0.05 PPI/TM 98 98 EPTAM 5.0 PPI/TM 0.5 PPI/TM 98 98 EPTAM 5.0 PPI/TM 5.0 PPI/TM 98 98 18 VERNAM 6.0 PPI none - 97 85 VERNAM 6.0 PPI 1.0 IF 97 85 VERNAM 6.0 PPI 5.0 IF 97 85 VERNAM 1.25 PPI none - 90 85 VERNAM 1.25 PPI 1.0 IF 90 85 VERNAM 1.25 PPI 5.0 IF 90 85 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 18 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 19 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI 1.0 IF 100 100 EPTAM 6.0 PPI 5.0 IF 100 100 20 EPTAM 5.0 PPI none - 98 98 EPTAM 5.0 PPI/TM 0.5 PPI/TM 98 98 EPTAM 5.0 PPI/TM 0.5 PPI/TM 98 98 EPTAM 5.0 PPI/TM 5.0 PPI/TM 98 98 EPTAM 6.0 PPI none - 100 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 100 21 EPTAM 1.25 PPI none - 95 80 EPTAM 1.25 PPI 1.0 IF 95 80 EPTAM 1.25 PPI 5.0 IF 95 80 EPTAM 6.0 PPI none - 95 95 EPTAM 6.0 PPI 1.0 IF 95 95 EPTAM 6.0 PPI 5.0 IF 95 95 EPTAM 6.0 PPI none - 100 97 EPTAM 6.0 PPI/TM 1.0 PPI/TM 100 97 EPTAM 6.0 PPI/TM 2.0 PPI/TM 100 97 EPTAM 6.0 PPI/TM 5.0 PPI/TM 100 97 TABLE V (continued) Cmpd. Herbicide Antidote Antidote Water Shatter- Johnson No. Herbicide Rate Method Rate Method grass Foxtail Wild Oat cane Mustard grass 21 SUTAN 6.0 PPI none - 95 99 SUTAN 6.0 PPI/TM 1.0 PPI/TM 95 99 SUTAN 6.0 PPI/TM 5.0 PPI.TM 95 99 Test Results The compounds cf this invention show good antidotal activity for a variety of crops. The composition of thiocarbamate herbicide and antidote ccmpound was particularly effective for the reduction of herbicidal injury to corn crops. Use of the antidote compounds did not result in a reduction of herbicidal injury to weeds. Formulations A formulation is the incorporation of a formulant in a form which is directly usable on crops and weeds As defined herein, a "formulant" is the material which is to be formulated. The formulant may be either an antidote compound alone or an herbicide and antidote composition. The purpose of the formulation is to apply the formulant to the locus where it is desired to establish herbicidal selectivity by a convenient method. The "locus" may include soil, seeds, seedlings and vegetation. The formulations are commonly dusts, wettable powders, granules, solutions or emulsifiable concentrates. Thists are free-flowing powder compositions containing the formulant impregnated on a particulate carrier. The particle size of the carriers is usually in the approximate range of 30 to 50 microns. Examples of suitable carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. The composition generally contains up to 50,0 of formulant. Anti-caking and anti-static agents may also be added. Dusts may be applied by spraying from boom and hand sprayers on airplanes. Wettable powders are finely divided compositions comprising a particulate carrier impregnated with the formulant ard additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder in an aqueous medium to form stable, sprayable suspensions. A wide variety of surface active agents can be used, for example, lorg chain fatty alcohols and alkali metal salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omegasubstituted polyethylene glycols of relatively long chain lenght. A list of surface active agents suitable for use in agriculture forr.ulations can be four,d in wade Van Valkenburg, Pesticide Formulation (Marcel decker, Inc., N.Y., 1973) at pages 79-84. Granules comprise the formulant impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters (mm) in diameter. The granules can be made by spraying a solution of the foruulant in a volatile solvent onto the granular carrier. Examples of suitable carriers for the preparation of granules include clay, vermiculite, sawdust, and granular carbon. Emulsifiable concentrates consist of an oil solution of the formulant plus an emulsifying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surface tants. Other additives, such as suspending agents and thickeners, may be included in the emulsifiable concentrate. When the formulant is an antidote and herbicide composition, the proportion of antidote compound to herbicide compound generally ranges from approximately 0.001 to 30 parts by weight of the antidote compound per weight of the herbicide compound. Formulations generally contain several additives in addition to the formulant and carrier or agent. Among these are inert ingredients, diluent carriers, organic solvents, water, oil and water, water in oil emulsicns, carriers of dusts and granules, and surface active wetting, dispersing and emulsifying agents. Fertilizers, e.g., ammoni- um nitrate, urea and superphosphate, may be included. Aids to rooting and growth, e.g., compost, manure, humus and sand, may also be included. Alternatively, the antidote compounds and herbicide and antidote compositions cf this invention can be applied to a crop by addition of the fonrnilant to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed. As another alternative, the fcrmulant can be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in these formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene and aromatic petroleum fractions rich in methylated naphthalenes. Liquid solutions, like dusts, may be applied by spraying fran boan and hand sprayers on airplanes.

Claims: Claims: 1. A compound characterised in that it corresponds to the following general formula: EMI43.1 where in R represents chloro bromo- or iodo- Cl-C4 - alkyl; R1 represents hydrogen, C1-C4 alkyl, c2-C4 alkenyl or phenyl; R2 represents hydrogen or C1-C4 alkyl; R3 represents hydrogen or C1-C4 alkyl; and R4 represents hydrogen or nitrophenyl; provided that one of R3 and R4 represents hydrogen. 2. A compound as claimed in claim 1 wherein: R represents l-chloro-2-bromo; R1 represents hydrogen; R2 represents hydrogen; R3 represents ethyl; and R4 represents hydrogen. 3. A process for the production of a compound as claimed in claim 1 characterised in that it comprises reacting an appropriate haloalkylcarbonyl chloride with 5-methyl-5-amino-l , 3-dioxane. 4. A process for the production of a compound as claimed in claim 1 characterised in tat it comprises reacting an appropriate dialkoxy compound with an appropriate dihydroxyalkyl haloacetamide. 5. A composition characterised in that it compriscs a compound as claimed in claim 1 or claim 2 and an inert diluent or carrier and/or adjuvant. 6. A composition characterised in that it comprises a non-phytotoxic antidotably effective amount of a compound as claimed in claim 1 or claim 2 and a herbicidally effective amount of a thiocarbamate corresponding to the following general formula: EMI44.1 wherein R5 represents C1-C6 alkyl; R6 represents C1-C6 alkyl or cyclohexyl; or R5 and R6 together represent C4-C10 a lkylene; and R7 represents C1-C6 alkyl C2-C6 alkenyl or benzyl, all of which may optionally be chloro-, bromo- or iodo- substituted; or a herbicidally effective amount of an acetanilide corresponding to the following general formula: EMI44.2 wherein R8 represents hydrogen or C1-C6 alkyl; Rg represents Ci-C6 alkyl, C1-C8 alkoxy or carbethoxy C1-C4-alkyl; and R10 represents hydrogen or C1 -C6 alkyl. 7. it composition as claimed in claim 6 wherein: R5 represents propyl; R6 represents propyl; and R7 represents propyl; or P represents propyl; R6 represents propyl; and R7 represents ethyl; or R5 represente ethyl; R6 represents cyclohexyl; and R7 represents ethyl; or R8 represents ethyl; R9 represents methoxymethyl; and R10 represents ethyl; or R8 represents methyl; Rg represents methoxyethyl; and R10 represents methyl. 8. A method oE establishing herbicidal selectivity characterised in that it comprises applying to a locus where the said selectivity is desired a compound as claimed in claim 1 or claim 2 or a composition as claimed in any of claims 5 to 7. Claims: 1. A process for the production of a compound corresponding to the following general formula: EMI46.1 wherein R. represents chloro-, bromo- or iodo - C1-C4 - alkyl; R1 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl or phenyl; R2 represents hydrogen or C1-C4 alkyl; R3 represent hydrogen or C1-C4 alkyl; and R4 represents hydrogen or nitrophenyl; provided that one of R3 and R4 represents hydrogen; characterised in that (a) it comprises reacting an appropriate haloalkylcarbonyl chloride with 5-methyl-5-amino- 1,3-dioxane; or (b) it comprises reacting an appropriate dialkoxy compound with an appropriate dihydroxyalkyl haloacetamide 2. . A process for the production of a composition characterised in that it comprises mixing a compound produced by a process as claimed in claim 1 with an inert diluent or carrier and/or adjuvant. 3. A process for the production of a composition characterised in that it comprises mixing a non-phytotoxic antidotably effective amount of a compound produced by a process as claimed in claim 1 with a herbicidally effective amount of a thiocarbamate corresponding to the following general formula: EMI46.2 wherein P5 represents C1-C6 alkyl; R6 represente C1-C6 alkyl or cyclohexyl; or R5 and R6 together represent C4-C10 alkylene; and P7 represents C1-C6 alkyl, C2-C6 alkenyl or benzyl, all of which may optionally be chloro-, bromo- or iodo substituted; or a herbicidally effective amount of an acetanilide corresponding to the following general formula: EMI47.1 wherein R8 represents hydrogen or C1-C6 alkyl; R9 represents C1-C6 alkyl, C1-C8 alkoxy or carbethoxy C1-C4-alkyl; and R10 represents hydrogen or C1-C6 alkyl. 4. A method of establishing herbicidal selectivity characterized in that it comprises applying to a locus where the said selectivity is desired a compound produced by a process as claimed in claim 1 or a composition produced by a process as claimed in claim 2 or claim 3.

Inventors: WALKER, FRANCIS HARRY
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1982
Main classification: C07D319
IPC codes: A01N47, A01N37, A01N25, A01N43, C07D319