~" ' MM II II II MM II MIMM II II I II J European Patent Office _ _ ^ *t\r\ w%n © Publication number: 0 304 409 B1 Office europeen, desJ brevets
© EUROPEAN PATENT SPECIFICATION
© Date of publication of patent specification: 28.10.92 © Int. CI.5: C07D 413/04, C07D 498/1 0, A01 N 25/32, A01 N 43/76 © Application number: 88870135.6
@ Date of filing: 12.08.88
The file contains technical information submitted after the application was filed and not included in this specification
5-Heterocyclic-substltuted oxazolidine haloacetamides.
© Priority: 13.08.87 US 84786 © Proprietor: MONSANTO COMPANY 01.07.88 US 212621 Patent Department 800 North Lindbergh Bou- levard @ Date of publication of application: St. Louis, Missouri 63167(US) 22.02.89 Bulletin 89/08 @ Inventor: Brlnker, Ronald Joseph © Publication of the grant of the patent: 12815 Glenbernle Lane 28.10.92 Bulletin 92/44 St. Louis, Missouri 63146(US) Inventor: Massey, Steven Marc © Designated Contracting States: 2459 Pheasant Run AT BE CH DE ES FR GB GR IT LI LU NL SE Maryland Heights, Missouri 63043(US) Inventor: Bussler, Brett Hayden (se) References cited: 12 Suncrest Drive EP-A- 0 074 255 EP-A- 0 136 016 St. Peters, Missouri 63376(US) EP-A- 0 190 105 EP-A- 0 234 036 Inventor: Williams, Eric Lee WO-A-81/00406 DE-A- 2 605 586 130 Tlmberbrook DE-A- 2 637 580 GB-A- 1 538 318 St. Peters, Missouri 63376(US) US-A- 4 072 688 US-A- 4 219 655 US-A- 4 400 200 US-A- 4 648 894 © Representative: Bosch, Henry et al CHEMICAL ABSTRACTS, vol. 95, no. 9, Au- Monsanto Services International S.A. Patent STAUF- Avenue de Tervuren 00 gust 31, 1981, Columbus, Ohio, US; Department, 270/272, FER CHEMICAL CO.: "Spirooxazolidines and Letter Box No. 21 thlazolldlnes as herbicide antidotes," page B-1150 Brussels(BE) o 787, column 2, abstract-no. 80936j o CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services EP 0 304 409 B1
Description
FIELD OF THE INVENTION
5 Herbicide antidotes are well-known crop protection chemicals. Of particular interest herein is a class of certain 5-heterocyclic-substituted oxazolidine and thiazolidine haloacetamide compounds found effective as antidotes for protecting crop plants from herbicide injury.
BACKGROUND OF THE INVENTION 70 Many herbicides injure crop plants at herbicide application rates necessary to control weed growth. Accordingly, many herbicides cannot be used for controlling weeds in the presence of certain crops. Uncontrolled weed growth, however, results in lower crop yield and reduced crop quality inasmuch as weeds compete with crops for light, water and soil nutrients. Reduction of herbicidal injury to crops without 75 an unacceptable corresponding reduction of herbicidal action on the weeds can be accomplished by use of crop protectants known as herbicide "antidotes" or "safeners". There are described in the literature various dihaloacyl oxazolidinyl and thiazolidinyl compounds containing a variety of substitutions on the oxazolidinyl or thiazolidinyl moiety, which compounds are known as antidotes, or safeners, for various herbicidal compounds in various crops. For example, a number of 20 patents describe such dihaloacyl oxazolidinyl compounds having as substituents on the oxazolidinyl ring hydrogen, alkyl, cycloalkyl, spirocycloalkyl, alkoxyalkyl, alkanol, heterocyclyl, aryl or aryloxyalkyl moieties, which compounds are used as antidotes for herbicides such as a-haloacetanilides or thiocarbamates in various crops. Typical of such patents are U.S. Patent Numbers 3,959,304, 3,989,503, 4,072,688, 4,137,070, 4,124,372, 4,186,130, 4,197,110, 4,249,932, 4,256,481, 4,618,361 and 4,708,735 and EP Nos. 0054278, 25 0,1 47,365, 1 90,1 05, 0,234,036 and 0,1 36,01 6. None of the above patents or any other known to the inventors herein disclose any haloacyl oxazolidinyl or thiazolidinyl compounds directly substituted with a heterocyclic radical in the 5-position. The above EP 190,105 discloses one dichloroacetyl oxazolidine compound having a furyl radical in the 2-position; that compound is not within the generic scope of the defined chloroacetyl oxazolidine antidotes in that patent. 30 The EP 0,234,036 discloses a great variety of dichloroacetic acid amide derivatives including various heterocyclic radicals such as 1 , 3-oxazolidines which may be further substituted in non-designated positions with any of a plurality of radicals including the pyridyl and piperidinyl radicals, but the patent fails to exemplify any such compounds. An effective herbicide must provide a relatively high level of control of grassy or broad-leaf weeds, or 35 both, in the presence of crops in addition to meeting several other criteria. For example, the herbicide should possess relatively high unit activity so that lower rates of herbicide application are feasible. Lower application rates are desirable in order to minimize exposure of the environment to the herbicide. At the same time, such herbicide must be selective in herbicidal effect so as not to injure the crops. Herbicidal selectivity can be enhanced by use of an appropriate antidote in combination with the herbicide. But 40 identification of an antidote which safens a herbicide in crops is a highly complicated task. Whether a compound or class of compounds provides efficacious antidote or safening activity is not a theoretical determination but must be done empirically. Safening activity is determined empirically by observing the complex interaction of several biological and chemical factors, namely: the type of herbicide compound; the type of weed to be controlled; the type of crop to be protected from weed competition and herbicidal injury; 45 and the antidote compound itself. Moreover, the herbicide and antidote must each possess chemical and physical properties enabling preparation of a stable formulation which is environmentally safe and easy to apply to the field.
SUMMARY OF THE INVENTION 50 A novel family of compounds useful as antidotes against herbicide injury to crops is provided by 5- heterocyclic-substituted oxazolidine haloacetamide compounds embraced by the general formula:
55
2 EP 0 304 409 B1
0 II R - C
10
and agriculturally-acceptable salts thereof wherein R is Ci-C+ haloalkyl; 15 R1 is C1-4 alkyl, C1 -C4 haloalkyl or phenyl; R2-R5 are H or C1-4 alkyl; Rg is a saturated or unsaturated heterocyclic radical which contains 5-10 ring members which may contain as many as four oxygen, nitrogen or sulfur hetero atoms optionally substi- tuted with a C1 -4 alkyl or C1 -C+ haloalkyl radical or halogen atom or with oxygen on a 20 ring nitrogen atom; and R5 and Rg may be combined to form a spiroheterocyclic ring as defined for the Rg radical. The term "haloalkyl" embraces radicals wherein any one or more of the carbon atoms, from 1 to 4 in number, is substituted with one or more halo groups, preferably selected from bromo, chloro and fluoro. Specifically embraced by the term "haloalkyl" are monohaloalkyl, dihaloalkyl and polyhaloalkyl groups. A 25 monohaloalkyl group, for example, may have either a bromo, a chloro, or a fluoro atom within the group. Dihaloalkyl and polyhaloalkyl groups may be substituted with two or more of the same halo groups, or may have a combination of different halo groups. A dihaloalkyl group, for example, may have two bromo atoms, such as a dibromomethyl group, or two chloro atoms, such as a dichloromethyl group, or one bromo atom and one chloro atom, such as a bromochloromethyl group. Examples of a polyhaloalkyl are perhaloalkyl 30 groups such as trifluoromethyl and perfluoroethyl groups. Preferred haloalkyl R members are dihalomethyl, particularly dichloromethyl, while the preferred haloalkyl R1 member is a tri-halogenated methyl radical, preferably trifluoromethyl. Where the term "alkyl" is used either alone or in compound form (as in "haloalkyl"), it is intended to embrace linear or branched radicals having up to four carbon atoms, the preferred members being methyl 35 and ethyl. Also included in this invention are the stereo and optical isomers of compounds within the class defined by the above formula. The heterocyclic Rg member, alone or combined with the R5 member to form a spiroheterocyclic radical through the 5-position carbon atom of the oxazolidinyl radical, can be saturated or unsaturated and 40 contains five to ten ring members of which at least one member is a heterocyclic oxygen, nitrogen or sulfur atom. The heterocyclic ring may contain as many as four hetero atoms which may be the same or mixtures of said hetero atoms. The heterocyclic members of preference are the furanyl, thienyl and pyridinyl radicals. The heterocyclic ring may be substituted with one or more C1 -4 alkyl or haloalkyl radicals or with a halogen, preferably chloro, atom and with oxygen on a nitrogen hetero atom. As an Rg member per se the 45 heterocyclic ring must be attached directly to the 5-position of the oxazolidinone ring without any intervening moieties therebetween, e.g., an alkylene group. By "agriculturally-acceptable salts" of the compounds defined by the above formula is meant a salt or salts which readily ionize in aqueous media to form a cation of said compounds and a salt anion, which salts have no deleterious effect on the antidotal properties of said compounds or of the herbicidal properties 50 of a given herbicide and which permit formulation of the herbicide-antidote composition without undue problems of mixing, suspension, stability, applicator equipment use, packaging, etc. By "antidotally-effective" is meant the amount of antidote required to reduce the phytotoxicity level or effect of a herbicide, preferably by at least 10% or 15%, but naturally the greater the reduction in herbicidal injury the better. 55 By "herbicidally-effective" is meant the amount of herbicide required to effect a meaningful injury or destruction to a significant portion of affected undesirable plants or weeds. Although of no hard and fast rule, it is desirable from a commercial viewpoint that 80-85% or more of the weeds be destroyed, although commercially significant suppression of weed growth can occur at much lower levels, particularly with some
3 EP 0 304 409 B1
very noxious, herbicide-resistant plants. The preferred species of antidotal compounds according to this invention are oxazolidine, 3-(dichloroacetyl)-5-(2-thienyl)-2,2-dimethyl-. oxazolidine, 3-(dichloroacetyl)-5-(2-furanyl)-2,2-dimethyl-, and 5 oxazolidine, 3-(dichloroacetyl)-5-(3-pyridyl)-2,2-dimethyl-. The terms "antidote", "safening agent", "safener", "antagonistic agent", "interferant", "crop protectant" and "crop protective", are often-used terms denoting a compound capable of reducing the phytotoxicity of a herbicide to a crop plant or crop seed. The terms "crop protectant" and "crop protective" are sometimes used to denote a composition containing as the active ingredients, a herbicide-antidote combination which io provides protection from competitive weed growth by reducing herbicidal injury to a valuable crop plant while at the same time controlling or suppressing weed growth occurring in the presence of the crop plant. Antidotes protect crop plants by interfering with the herbicidal action of a herbicide on the crop plants so as to render the herbicide selective to weed plants emerging or growing in the presence of crop plants. As further detailed infra, while not necessary, the composition containing the herbicide-antidote is combination may also contain other additaments, e.g., biocides such as insecticides, fungicides, nemato- cides, miticides, etc., fertilizers, inert formulation aids, e.g., surfactants, emulsifiers, defoamers, dyes, etc. Herbicides which may be used with benefit in combination with an antidote of the described class include preferably thiocarbamates (including dithiocarbamates), acetamides, heterocyclyl phenyl ethers (especially phenoxypyrazoles), imidazolinones, pyridines, and sulfonylureas. It is within the purview of this 20 invention that the novel class of antidotal compounds be used with other classes of herbicides, e.g., triazines, ureas, diphenyl ethers, nitroanilines, thiazoles, isoxazoles, etc., the individual members of which classes may be derivatives having one or more substituents selected from a wide variety of radicals. Such combinations can be used to obtain selective weed control with low crop injury in several varieties of monocotyledonous crop plants such as corn, grain sorghum (milo), and cereals such as wheat, rice, barley, 25 oats, and rye, as well as several varieties of dicotyledonous crop plants including oil-seed crops such as soybeans and cotton. Particular utility for the antidotal compounds of this invention has been experienced with various herbicides in corn, sorghum and soybeans. Examples of important thiocarbamate herbicides are the following: cis-/trans-2,3-dichloroallyl-diisopropylthiocarbamate (common name "diallate"); 30 ethyl dipropylthiocarbamate (common name "EPTC"); S-ethyl diisobutyl (thiocarbamate) (common name "butylate"); S-propyl dipropyl(thiocarbamate) (common name "vernolate"); 2,3,3-trichloroallyl-diisopropylthiocarbamate (common name "triallate"); Examples of important acetamide herbicides are the following: 35 2-chloro-N-isopropylacetanilide (common name "propachlor"); 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide (common name "alachlor"); 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide (common name "butachlor"); 2-chloro-N-(ethoxymethyl)-6'-ethyl-o-acetotoluidide (common name "acetochlor"); ethyl ester of N-chloroacetyl-N-(2,6-di-ethylphenyl)glycine (common name "diethatyl ethyl"); 40 2-chloro-N-(2,6-dimethylphenyl)-N-(2-methoxyethyl)acetamide (common name "dimethachlor"); 2-chloro-N-(2-methoxy-1-methylethyl)-6'-ethyl-o-acetotoluidide (common name "metolachlor"); 2-chloro-2'-methyl-6'-methoxy-N-(isopropoxymethyl)acetanilide; 2-chloro-2',6'-dimethyl-N-(1-pyrazolylmethyl)-acetanilide (common name "metazachlor"); 2-chloro-N(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-(1 H-pyrazol-1 -ylmethyl)acetamide; 45 2-chloro-6'-trifluoromethyl-N-(isopropoxymethyl)acetanilide; 2-chloro-2'-methyl-6'trifluoromethyl-N-(ethoxymethyl)acetanilide; 2-chloro-2'-ethyl-6'-trifluoromethyl-N-(1-pyrazolyl methyl)acetanilide; 2- chloro-N-isopropyl-1 -(3,5,5,-trimethylcyclohexen-1 -yl)acetamide (common name "trimexachlor"). Examples of important pyridine herbicides include: 50 3-pyridinecarboxylic acid, 2-(difluoromethyl)-5-(4,5-dihydro-2-thiazolyl)-4-(2-methylpropyl)-6-(trifluoromethyl)- , methyl ester; 3- pyridinecarboxylic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-5-(1 H-pyrazol-1 -ylcarbonyl)-6- (trifluoromethyl)-, methyl ester; 3,5-pyridine dicarbothioic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-, S,S-dimethyl ester; 55 3,5-pyridinedicarboxylic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-6-trifluoromethyl, dimethyl ester. Examples of important heterocyclyl phenyl ethers include: 5-(trifluoromethyl)-4-chloro-3-(3'-[1-ethoxycarbonylethoxy]-4'-nitrophenoxy)-1-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-methoxy-4'-nitrophenoxy)-1-methylpyrazole;
4 EP 0 304 409 B1
5-(trifluoromethyl)-4-chloro-3-(3'-[1-butoxycarbonylethoxy]-4'-nitrophenoxy)-1-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-methylsulfamoylcarbonyl propoxy-4'-nitrophenoxy)-1-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-propoxycarbonylmethyloxime-4'-nitrophenoxy)-1-methylpyrazole; (±)-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy] phenoxy]propanoic acid (9CI). 5 Examples of important sulfonylureas include: Benzenesulfonamide, 2-chloro-N-[[(4-methoxy-6-methyl-1 , 3, 5-triazin-2-yl) amino] carbonyl]; Benzoic acid, 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl) amino]carbonyl] amino] sulfonyl]-ethyl ester; 2- thiophenecarboxylic acid, 3-[[[[(4,6-dimethoxy-1 ,3,5-triazin-2-yl)amino]carbonyl] aminojsulfonyl]-, methyl ester; io Benzoic acid, 2-[[[[(4, 6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl ester; Benzenesulfonamide, 2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1 ,3, 5-triazin-2-yl) amino] carbonyl]; Benzoic acid, 2-[[[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl) aminojcarbonyl] amino] sulfonylj-methyl ester; Examples of important imidazolinone herbicides include: 3- Quinolinecarboxylic acid, 2-[4,5-dihydro-4-methyl-4-(1 -methylethyl)-5-oxo-1 H-imidazol-2-yl]-; is 3-pyridinecarboxylic acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-; Benzoic Acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2- yl] -4(or 5)-methyl-; 3-pyridinecarboxylic acid, 5-ethyl-2-[4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-; 3- pyridinecarboxylic acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-5-methyl-, am- monium salt. 20 Examples of other important herbicides include: 2- Chloro-4-(ethylamino)-6-(isopropylamino)-sym-triazine; 4- Amino-6-tertbutyl-3-(methylthio)-AS-triazine-5(4H)one; Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine; Benzeneamine, N-(1-ethylpropyl)-3, 4-dimethyl-2, 6-dinitro-; 25 2-Pyrrolidinone, 3-chloro-4-(chloromethyl)-1-[3-(trifluoromethyl) phenyl], trans-; 3- lsoxazolidinone, 2-[(2-chlorophenyl) methyl]-4, 4-dimethyl-; 2-lmidazolidinone, 3-[5-(1 ,1 -dimethylethyl)-3-isoxazolyl]-4-hydroxy-1 -methyl-; 2-Chloro-4-(1 -cyano-1 -methylethylamino)-6-ethylamino-1 ,3,5-triazine; 2-Methoxy-3, 6-dichlorobenzoic acid, dimethylamine salt; 30 Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate; 1 '-(Carboethoxy)ethyl 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoate; Ammonium-DL-homoalanin-4-yl (methyl) phosphinate; 2-(3,4-Dichlorophenyl)-4-methyl-1 ,2,4-oxadiazolidine-3,5-dione. The herbicides of particular and preferred interest in compositions with antidotes according to this 35 invention include each of the above-mentioned species from different chemical classes of compounds exemplified as important herbicides, particularly those of current commercial interest and use and those which may be determined of commercial utility. alachlor, acetochlor, 40 butachlor, metolachlor, metazochlor, 2-chloro-2'-methyl-6'-methoxy-N-(isopropoxymethyl)acetanilide, 2-chloro-2'-methyl-6'-trifluoromethyl-N-(ethoxymethyl)acetanilide, and 45 2-chloro-2',6'-dimethyl-N-(2-methoxyethyl)acetanilide. All of the above specifically-named herbicides are known in the art, except the heterocyclyl phenyl ethers which are disclosed and claimed in copending application Serial No. 07/175,460 assigned to the assignee herein. Combinations may be made of any one or more of the described antidote compounds with any one or 50 more of the herbicide compounds mentioned herein. Of particular importance and preference herein, a number of the antidotal compounds of the invention have been found to be especially versatile as "in-can" safeners or antidotes for use with a plurality of herbicides in a plurality of crops. Of special mention here is the use of the antidotes, oxazolidine, 3- (dichloroacetyl)-5-(2-furanyl)-2,2-dimethyl-; oxazolidine, 3-(dichloroacetyl)-5-(3-pyridyl)-2,2-dimethyl- and ox- 55 azolidine, 3-(dichloroacetyl)-5-(2-thienyl)-2,2-dimethyl-, to reduce the phytotoxicity of alachlor (active ingre- dient in LASSO® herbicide) in corn and grain sorghum. The just-named antidotes have similarly been found to be particularly efficacious against acetochlor (active ingredient in HARNESS® herbicide) in corn, sorghum and soybeans. And some of these antidotes, particularly the 5-(2-thienyl)oxazolidine compound,
5 EP 0 304 409 B1
have also exhibited antidotal properties against butachlor (active ingredient in MACHETE® herbicide) in rice, particularly at higher rates, e.g., 8.96 kg/ha. It will be recognized by those skilled in the art that all herbicides have varying degrees of phytotoxicity to various plants because of the sensitivity of the plant to the herbicide. Thus, e.g., although certain crops 5 such as corn and soybeans have a high level of tolerance (i.e., low sensitivity) to the phytotoxic effect of alachlor, other crops, e.g., milo (grain sorghum), rice and wheat, have a low level of tolerance (i.e., high sensitivity) to the phytotoxic effects of alachlor. The same type of sensitivity to herbicides as shown by crop plants is also exhibited by weeds, some of which are very sensitive, others very resistant to the phytotoxic effects of the herbicide. io When the sensitivity of a crop plant to a herbicide is low, whereas the sensitivity of a weed to that herbicide is high, the "selectivity factor" of the herbicide for preferentially injuring the weed while not injuring the crop is high. In an analogous manner, but more complex, an antidotal compound may, and commonly does, have varying degrees of crop protective effect against different herbicides in different crops. Accordingly, as will is be appreciated by those skilled in the art, the various antidotes of this invention, as with all classes of antidotal compounds, will have greater or lesser crop safening effects against various herbicides in various crops than in others. Thus, while a given antidotal compound may have no crop protective ability against a given herbicide in a given crop, that same antidotal compound may have a very high crop protective ability against the same given herbicide in a different crop or against a different herbicide in the same crop. This is 20 an expected phenomenon.
DETAILED DESCRIPTION OF THE INVENTION
Antidote Compound Preparation
The antidote compounds of the invention may be prepared by the following exemplary general procedures described in Examples 1-38. These examples are presented for purposes of illustration only and are not intended as a restriction on the scope of the invention. All parts are by weight unless otherwise indicated. 30 Table I sets forth analytical data for 38 specific compounds prepared in accordance with these procedures.
Example 1
35 Preparation of 3-(Dichloroacetyl)-2,2-Dimethyl-5-(2-Thienyl)-Oxazolidine
2-Thiophenecarboxaldehyde (28.3g, 0.252 mol) was added to a mixture of cyanotrimethylsilane (25 g, 0.252 mol) and zinc iodide (1 mg), and the mixture was stirred at room temperature under nitrogen for 2 hours. The resulting silylcyanohydrin was distilled directly from the pot (BP 95 °C @ 1.5 torr) yielding 50.9g 40 (96%) of a pale yellow oil. The silylcyanohydrin (0.241 mol) was taken up in 100 mL of anhydrous ether and was added dropwise to 13.7g (0.361 mol) of lithium aluminum hydride in 400 mL of anhydrous ether under nitrogen cooled in an ice bath. The green colored reaction was stirred overnight then cooled in an ice bath, and was carefully quenched with 20 mL of water followed by 20 mL of 10% NaOH. After stirring for 30 min. anhydrous 45 sodium sulfate was added and the mixture was filtered through celite. The filter cake was rinsed with THF and the filtrate was concentrated to give a solid which was recrystallized from methylene chloride - ether to give 25g (72%) of a-(aminomethyl)-2-thiophenemethanol; MP 80-82 °C. Twelve grams (12.0g, 83.8 mmol) of the product in the preceding paragraph and acetone (9.7g, 0.168 mol) in 85 mL of 1 ,2-dichloroethane were refluxed for 2 hours using a reverse water separator. Resulting 50 mixture was concentrated giving an oil which was distilled to give 12.33g (80%) of 2,2-dimethyl-5-(2- thienyl)-oxazolidine, as a pale yellow oil (BP 102-1 05 °C @ 1.5 torr). To a stirred mixture of 4.0g (21.83 mmol) of the product of the preceding paragraph in a biphasic mixture of 40 mL of methylene chloride (CH2CI2) and 20 mL of 10% NaOH cooled in an ice bath was added 2.5 mL (26.19 mmol) of dichloroacetyl chloride dropwise. The mixture was stirred for 20 min. and the layers 55 separated. The aqueous layer was extracted with CH2CI2 and the combined organic layers dried over anhydrous magnesium sulfate (MgSO+). The product was purified by chromatography on silica gel (Waters Prep. 500A, 10% ethylacetate-hexanes) and recrystallization from methylcyclohexane to give 3.87g (60%) of the title compound. MP 104-1 05 °C.
6 EP 0 304 409 B1
Examples 2-5
Following substantially the same procedure described in Example 1, but substituting the appropriate heterocyclic aldehyde, the antidotal compounds of Examples 2-5 were prepared. These compounds are 5 identified by structure and physical properties in Table 1 herein.
Example 6
Example 6 is prepared using the same basic procedure as Example 1 with the following modifications. io The starting material for Example 1, 2-thiophenecarboxaldehyde, is replaced by 3-furaldehyde. In addition, a benzene reflux is used to azeotrope water rather than 1 ,2-dichloroethane when forming the oxazolidine ring with acetone. The dichloroacetylation step is effected by placing 1 1 .2 grams (0.067 mol) 2,2-dimethyl-5-(3- furan)-oxazolidine in methylene chloride at 0°C with 9.5 g (0.094 mol) triethylamine and adding dropwise 1 1 .8 grams (0.08 mol) dichloroacetyl chloride. The reaction mixture is washed with water and the organics is dried with MgSCv Concentration and chromatography with 10% ethylacetate-hexanes gives 5.1 grams (65%) of white solid; m.p. 90-91 ° C.
Examples 7-12
20 Following the same procedure described in Example 6, but substituting the appropriate heterocyclic aldehyde, the antidotal compounds of Examples 7-12 were prepared. These compounds are described by structure and physical properties in Table 1 herein.
Example 13 25 Following the procedure described in Example 1, but substituting diethyl ketone for acetone, the compound identified as Example 13 in Table 1 was prepared and characterized.
Examples 14 and 15 30 The compounds of Examples 14 and 15 in Table 1 were prepared in accordance with the basic procedure of Example 1 above, substituting 2-furaldehyde and 3-methyl-2-thiophenecarboxaldehyde, re- spectively, for 2-thiophenecarboxaldehyde and acetaldehyde for acetone, and with the following additional modification in Example 14. In Example 14 the oxazolidine ring is formed by placing 5.0 grams (0.04 mol) 35 1-furanmethanol alpha-(aminomethyl)- and 1.8 grams (0.04 mol) acetaldehyde in methylene chloride in the presence of MgSCU for 2 hours. After filtration and then cooling to 0°C, 4.3 g (0.06 mol) pyridine was added. After the addition of 6.9 grams (0.05 mol) dichloroacetyl chloride the reaction mixture is washed with water and the organics are dried over MgSCv Concentration and chromatography with 10% ethyl acetate- hexanes gives 2.0 grams (19%) of colorless oil. 40 Example 16
Following substantially the same procedure as in Example 14, but substituting propionaldehyde instead of acetaldehyde, the product identified as Example 16 in Table 1 was produced. 45 Example 17
In similar manner, when the procedure of Example 14 was repeated using benzaldehyde instead of acetaldehyde, there was obtained the product of Example 17 as identified in Table 1. 50 Examples 18 and 19
To prepare antidotal compounds according to the invention having mixed halogen atoms at the 3- haloacyl position, the procedure of Example 6 was repeated, but substituting bromochloroacetyl chloride as 55 the acylating agent instead of dichloroacetyl chloride. In this manner, the compounds identified in Table 1 as Examples 18 and 19 were prepared and characterized.
Example 20
7 EP 0 304 409 B1
Pyridine, 3-[3-(dichloroacetyl)-2,2-dimethyl-5-oxazolidinyl]-
To a cooled stirring solution of 15 grams (0.25 mol) nitromethane and 0.35 gram (0.005 mol) diethylamine in 26 milliliters of ethanol was added dropwise 10 grams (0.093 mol) 3-pyridine carboxal- 5 dehyde. The reaction was stirred for 3 hours at 0 ° C then warmed to ambient temperature. Concentration yielded crude 1-(3-pyridyl)-2-nitroethanol. The above product was dissolved in ethyl alcohol and added to 8 grams of 10% palladium on carbon. The mixture was hydrogenated in a Parr Shaker at 45 psi until 3 mol equivalents of hydrogen were reacted. Filtration through celite and concentration yielded a crude 2-(3-pyridyl)-2-hydroxy-1-aminoethane. io The product of the preceding paragraph and 10.9 grams (0.19 mol) acetone were stirred in 150 milliliters benzene and refluxed for 4 hours in a Dean-Stark apparatus to remove water. The reaction mixture was decanted from any solid and concentrated to a crude pyridine, 3-(2,2-dimethyloxazolidinyl)-. The oxazolidinyl compound of the preceding step and 10.3 grams (0.102 mol) triethylamine were stirred at 0°C in CH2CI2. 12.9 grams (0.088 mol) dichloroacetyl chloride were added dropwise and the reaction 15 mixture was stirred for 30 minutes at 0 0 C. The reaction mixture was warmed to ambient temperature and stirred for 1 hour. The reaction was worked up by washing with water, separation and drying the organics with Na2S04. Filtration and concentration yielded crude product which when chromatographed with 60% ethylacetate-hexanes gave 7% overall yield of the title compound (1.8 grams, cream colored solid, M.P. 111-113°C). 20 The product of this example can also be prepared according to the procedure of Example 1 .
Example 21
Three (3) grams (0.01 mol) of the product of Example 20 and 1.1 gram (0.013 mol) of NaHC03 were 25 stirred in CH2CI2. To this mixture was added 2.15 grams (0.01 mol) of m-chloroperbenzoic acid in two portions and stirred for one hour. The reaction mixture was washed with water and dried with MgSO^. The MgSO^ was filtered and the CH2CI2 was removed to yield a white solid. Flash chromatography using 20% methanol, 30% ethylacetate 50% hexanes was done on the crude product. After concentration and placing under high vacuum for 24 hours at room temperature an amorphous solid was collected. (MP = 64°-70°C, 30 2.5 grams, 82% yield). The product was identified as pyridineoxide, 3-[3-(dichloroacetyl)2,2-dimethyl-5- oxazolidinyl]-.
Example 22
35 Two (2) grams (0.007 mol) of the product of Example 20 were dissolved in CH2CI2 and 1.2 gram (0.007 mol) of methyl trifluoromethyl sulfonate was added dropwise. A colorless solid precipitated after 30 minutes which was filtered and collected under nitrogen. 2.7 grams (86% yield) of product was collected (M.P. 151°-153°C) and identified as pyridinium, 3-[3-(dichloroacetyl)-2,2-dimethyl-5-oxazolidinyl]-1 -methyl-, salt of trifluoromethane sulfonic acid (1:1). 40 Example 23
Caution: This procedure uses HCN which is highly toxic and requires special handling. 19.2 grams (0.2 mol) of freshly distilled 2-furaldehyde and 40 milligrams of mandelontrile lyase 45 (4.1.2.10) were dissolved in 480 milliliters of 50% methanol-acetate buffer (pH = 5.2) 7.1 grams (0.26 mol) of HCN were added over 10 minutes with vigorous stirring to this reaction mixture. The reaction mixture was stirred for 40 minutes at room temperature and then placed under vacuum for 15 minutes to remove excess HCN. Extraction was effected using CHCb (3 x 150 mis) and then the organics were dried using MgSO+. After filtration and concentration, 21 grams of 83% enantiomerically pure oil, 2-(hydroxycyanomethyl)-furan 50 (S) was collected. Optical rotation [a ]g1 = +28.5° (C = 5, chloroform; Lit value [a ]g° = + 30.6 °C neat) Seven (7.0) grams (0.057 mol) of the above product were dissolved in anhydrous ethyl ether and added dropwise to 74 milliliters of 1M ethyl ether solution of lithium aluminum hydride (LAH) under nitrogen. The reaction mixture was stirred 5 hours and then the excess LAH was destroyed by adding dropwise 5 55 milliliters of H20 and 5 milliliters of 10% NaOH (aq). The mixture was filtered and concentrated to give 4 grams of colorless solid (55% yield). Recrystallization from ethyl acetate - hexane yielded 2-(1-hydroxy-2- aminoethyl)-furan (S) with a melting point equal to 74°-77°C. Optical rotation [a]g1 = -23.6° (C = 5, chloroform; Lit value [a]g1 = -28° C = 5, chloroform)
8 EP 0 304 409 B1
Two (2.0) grams (0.016 mol) of the product of the preceding paragraph, 1.8 grams (0.031 mol) of acetone and 50 milliliters of benzene were stirred together at reflux for 40 hours in a Dean Stark apparatus. After 0.2 milliliters of H20 was removed, the reaction was cooled and concentrated to collect 2.58 grams (96% yield) of amber oil, 2,2-dimethyl-5-(2-furyl)oxazolidine (S). 5 2.58 grams (0.015 mol) of the above oxazolidine compound was dissolved in CH2CI2 and cooled to 0° C at which time 2.18 grams (0.02 mol) of triethylamine was added in one portion with stirring. Dropwise addition of 2.17 grams (0.019 mol) of dichloroacetyl chloride was effected and the reaction was stirred for an additional 30 minutes at 0 0 C. The reaction was warmed to room temperature, washed with water and the organics were dried with Na2SCv Filtration and concentration yielded 5.0 grams of dark oil which was 10 chromatographed using 10% ethyl acetate-hexane. 2.5 grams of colorless product were collected and identified as oxazolidine, 3-(dichloroacetyl)-5-(2-furanyl)-2,2-dimethyl-, (S); (m.p. = 1160-119°C, yield = 60%). Optical rotation [a ]g1 = +10.8° (C = 5, chloroform).
15 Example 24
Six grams (0.05 mol) of 2-(1-hydroxy-2-aminoethyl)-furan, 2.8 grams (0.05 mol) acetic acid and 10.6 grams (0.1 mol) 1 ,1 ,1 -trifluoromethyl acetone were refluxed in benzene for 1.5 hours while removing water via a Dean-Stark apparatus. The reaction mixture was concentrated and the acetic acid was removed on a 20 Kugelrohr without heating, and then the product was distilled over at 80°-100°C (high vacuum). 8.4 grams of colorless oil was collected (76% yield) and identified as oxazolidine, 5-(2-furanyl)-2-methyl-2- trifluoromethyl-. One (1 .0) gram (0.005 mol) of the above oxazolidine and 0.7 gram (0.005 mol) dichloroacetyl chloride were refluxed in toluene for 4 hours. The reaction mixture was concentrated and flash chromatography was 25 run with 5% ethyl acetate-hexanes on the crude product. Three-fourth (0.75) gram (45% yield) of white solid, was collected and identified as oxazolidine, 3-(dichloroacetyl)-2-methyl-5-(2-furanyl)-2- (trifluoromethyl)-; m.p. = 97°-100°C. as a mixture of diasteroisomers.
Examples 25 and 26
Following substantially the same procedure described in Example 24, but substituting 2-(1-hydroxy-2- aminoethyl)-thiophene for the -furanyl analog, 3.3 g (5.6% yield) of white solid was separated and identified as an isomeric mixture of cis- and trans-oxazolidine,, 3-(dichloroacetyl)-2-methyl-5-(2-thienyl)-2- (trifluoromethyl)-. The disastereoisomers were separated by chromatography using 10% ethylacetate and 35 hexanes. The isomeric compounds were recovered in a ratio of 2:1 (trans-:cis-). MP of the trans-isomer, 89°-90°C and of the cis-isomer, 96°-97°C. The structures of these isomers were tentatively assigned by NMR and molecular modeling.
Example 27
This example describes the preparation of an antidotal compound according to the invention wherein the R5 and Rg members of the above generic formula are combined with the 5-carbon atom of the oxazolidine ring to form a six-membered spiroheterocyclic radical. The process of Example 6 was repeated, except the 3-furaldehyde of that example was replaced by 45 tetrahydrothiopyran-4-one as the starting heterocyclic radical donor. After reaction and workup as described in Example 6, there was recovered 4.5 g 56% yield) of a white-colored solid MP 137-1 39 °C, which was identified as 1-oxa-8-thia-3-azaspiro [4.5]-decane, 3-(dichloroacetyl)-2,2-dimethyl-.
Example 28
This example describes the preparation of an antidotal compound wherein the R5 and Rg members of the above generic formula are combined with the 5-carbon atom of the oxazolidinyl ring to form a 5- membered spiroheterocyclic radical. The process according to Example 6 was repeated, except the 3-furaldehyde of that example was 55 replaced by tetrahydrothiophene-3-one as the heterocyclic radical donor starting material. After reaction and workup as described in Example 6, 5.5g (65% yield) of a white-colored solid MP 128-1 30 °C, was recovered. The compound was identified as 1-oxa-7-thia-3-azaspiro [4.4]-nonane, 3-(dichloroacetyl)-2,2- dimethyl-.
9 EP 0 304 409 B1
Example 29
The process of Example 14 was repeated, except in this example, the starting material of Example 14 was replaced by tetrahydrothiopyran-4-one. After reaction and workup, 5.0g (65% yield) of a white-colored 5 solid, MP 109-111 °C was recovered. The compound was identified as 1-oxa-8-thia-3-azaspiro [4.5]-decane, 3-(dichloroacetyl)-2-methyl-.
Example 30
10 The process of Example 14 was followed, except the starting material of Example 14 was replaced by tetrahydrothiophene and the acetaldehyde was replaced by propionaldehyde. After workup, 5.8 g (53% yield) of a colorless oil was recovered. The compound was identified as 1-oxa-7-thia-3-azaspiro [4.4]- nonane, 3-(dichloroacetyl)-2-ethyl.
is Example 31
This example describes the preparation of an antidotal compound according to the invention, character- ized by an alkyl substitution in the 4-position and by a 5-furanyl substitution. The process of Example 20 was again repeated, except in this process 2-furaldehyde was used in place 20 of the 3-pyridinecarboxaldehyde of Example 20 and nitroethane was used instead of nitromethane in the first step of the action. After workup, 0.4 g (3% yield) of a white-colored solid, MP 128-131 °C was recovered. The compound was identified as oxazolidine, 3-(3-dichloroacetyl)-5-(2-furanyl)-2,2,4-trimethyl-.
25 Example 32
Another antidotal compound exemplary of those of this invention is characterized by substitution of a pyrazinyl radical in the 5-position of the oxazolidine ring. The process of this example followed that of Example 20, but for the substitution of 2-pyrazinecarboxal- 30 dehyde for the 3-pyridinecarboxaldehyde of Example 20. After reaction and workup, 0.9 g (5% yield) of a tan-colored solid, MP 94-96 °C was recovered. The product was identified as pyrazine, 2-[3-(dichloroacetyl)-2,2-dimethyl-5-oxazolidinyl]-.
Example 33 35 To a solution of 9.2 mL (0.105 mol) of oxalyl chloride in 200 mL of anhydrous methylene chloride under nitrogen at -78 °C was added 7.8 mL (0.11 mol) of anhydrous dimethylsulfoxide dropwise over several minutes. Following the addition the mixture was allowed to warm to -35 ° C and after five minutes was recooled to -78 °C. A solution of 10.2g (0.10 mol) of tetrahydrofurfuryl alcohol in 100 mL of anhydrous 40 methylene chloride was added. The reaction was warmed to -35 °C then 70 mL (0.50 mol) of triethylamine was added over a five minute period. The reaction was recooled to -78 °C ans was stirred at that temperature for two hours. The mixture was then filtered followed by washing the filtrate with 350 mL of 5% hydrochloric acid. The aqueous layers were backwashed with two portions of methylene chloride. The combined organic phases were dried over anhydrous magensium sulfate and concentrated (>10°C, 100 45 torr) to ca. 20 mL volume to give a mixture of the desired aldehyde and methylene chloride. This mixture is treated with 13.3 mL (0.10 mol) of trimethylsilylcyanide and 10 mg of zinc iodide. The mildly exothermic reaction is stirred under nitrogen at room temperature for one hour followed by concentration in vacuo. The resulting oily silyl cyanohydrin was taken up in 150 mL of anhydrous ether. Cooled mixture in an ice bath under nitrogen followed by the addition of 100 mL of a 1M lithium aluminum hydride solution in ether. The 50 reaction is mechanically stirred at room temperature for two hours and is then recooled with an ice bath followed by the cautious dropwise addition of 3 mL of water then 6 mL of a 10% sodium hydroxide solution. Diluted mixture with 200 mL of tetrahydrofuran and stirred at room temperature for 45 minutes. Anhydrous sodium sulfate was added to absorb excess water followed by filtration through celite and concentration in vacuo to give the amino alcohol as an amber oil. The amino alcohol was dissolved in 100 mL of acetone. 55 About 5 g of anhydrous magnesium sulfate was added followed by stirring overnight at room temperature. Filtration and concentration in vacuo gave the oxazolidine as an amber oil. The oxazolidine was dissolved in 150 mL of methylene chloride followed by the addition of 75 mL of 10% sodium hydroxide. The mixture was cooled in an ice bath and was treated with 9.6 mL (0.10 mol) of dichloroacetyl chloride. The reaction
10 EP 0 304 409 B1
was vigorously stirred for 45 minutes. The layers were then separated and the organic phase was dried over anhydrous magnesium sulfate. Thin layer chromatography (ethyl acetate:hexanes = and gas chromatography show the presence of the title product as a mixture of two diasteromers. The mixture was resolved by flash chromatography on silica gel (ethyl acetate:hexanes 1:4). The two diasteromers were 5 isolated: (A) 3.46 g of the less polar isomer was isolated as a yellow oil n^5 =1.4991. Anal, calc'd for CiiH17CI2N03: C46.82; H.6.07; Cl.25.13. Found: C.46.52; H.6.01; Cl.25.01. (B) 2.00g of the more polar isomer as a yellow oil ng5 = 1.5021. Anal. Calc'd for Ci 1 H17CI2NO3: C.46.82; H.6.07; CI25.13. Found: C.46.58; H.6.00; Cl.24.97. The overall yield for the six steps is 19%. The product was identified as 3- (dichloroacetyl)-2,2-dimethyl-5-(tetrahydro-2-furanyl)-oxazolidine. 10 Example 34
Using the same basic procedure described in Example 6, but substituting monochloroacetyl chloride in the last step, the compound oxazolidine, 3-(chloroacetyl)-5-(2-furanyl)-2, 2-dimethyl was prepared. 15 Example 35
Following the procedure of Example 6, but substituting trichloroacetyl chloride in the last step of the reaction there was prepared oxazolidine, 5-(2-furanyl)-2,2-dimethyl-3-(trichloracetyl)-. 20 Example 36
Using the same procedure as Example 6, but substituting 2-thiophene-methanol for tetrahydrofurfurylal- cohol and using monofluoroacetyl chloride in the last step, the compound oxazolidine, 3-(fluoroacetyl) 2,2- 25 dimethyl-5-(2-thienyl) was prepared. MP 65-67° C.
Example 37
The compound oxazolidine, 3-(dichloracetyl)-5-(2-thienyl)- was prepared using the same basic proce- 30 dure as Example 6 with the following modifications: the cyclization of the 2-thiophenemethanol, alpha- (aminomethyl)-, with formaldehyde to form the oxazolidine ring was effected by dissolving the 2- thiophenemethanol, alpha-(aminomethyl)-, in water and then adding the formaldehyde in one portion. The resulting oil that drops out is extracted with methylene chloride and dried with anhydrous magnesium sulfate (MgSO+). Filtration and concentration gave a crude product which was acetylated with dichloroacetyl 35 chloride to give the above compound.
Example 38
The same basic procedure as in example 6 was repeated with the following modifications: the 40 cyclization of the 2-benzofuranmethanol, alpha-(aminomethyl)-, with acetone was effected by stirring the two together at ambient temperature until a homogeneous solution resulted. After which the solution was dried with anhydrous magnesium sulfate (MgSO+). Filtration and concentration gave a crude product that was acetylated to yield oxazolidine, 5-(2-benzofuranyl)-3-(dichloroacetyl)-2, 2-dimethyl- MP1150-117°C. The antidotal compounds prepared in accordance with the foregoing working examples are listed in 45 Table 1. The specific compounds are listed in the first column by example/antidote number ("Ex./Antidote No.") followed by structural features according to the generic formula at the head of the table and by process yield and physical characteristics in the remaining columns.
50
55
11 i r-t if cs cm 9 - oo oo vo " p—4 ... 3 5 1 se 3= se :n m \o cm on E J I O Ol i—i 00 3 * N < CM CO ffi i i — 1 ... i— cn i r» EP 0 304 409 B1 CM CO CM oo CO vo m ~j VO CO CM 00 CM VO T3 oo e uxz CJ S3 55 I— I w O ON CM r- CTN VO i 0- i / — > I I s: u O U0 0 v ' o CM Q 55 N /a-* 1—( 01 • © 00 O0 00 CO T3 S c c «1 o u «1 «1 co co « 3= «1 c_> CJ I I CO co CO S3 X u u CJ I I CM i—l OS N CJ CJ 33 EC CJ CJ ■ I I I •H • 4-> O c 55 < \ O) vO 00 • +j CO CO CO CO X o Biological Evaluation Effective weed control coupled with low crop injury is a result of treatment of a plant locus with a combination of herbicide compound and antidote compound. By application to the "plant locus" is meant 19 EP 0 304 409 B1 application to the plant growing medium, such as soil, as well as to the seeds, emerging seedlings, roots, stems, leaves, or other plant parts. The phrase "combination of herbicide compound and antidote compound" embraces various methods of treatment. For example, the soil of a plant locus may be treated with a "tank-mix" composition containing 5 a mixture of the herbicide and the antidote which is "in combination". Or, the soil may be treated with the herbicide and antidote compounds separately so that the "combination" is made on, or in, the soil. After such treatments of the soil with a mixture of herbicide and antidote or by separate or sequential application of the herbicide and antidote to the soil, the herbicide and antidote may be mixed into or incorporated into the soil either by mechanical mixing of the soil with implements or by "watering in" by rainfall or irrigation. io The soil of a plant locus may also be treated with antidote by application of the antidote in a dispersible- concentrate form such as a granule. The granule may be applied to a furrow which is prepared for receipt of the crop seed and the herbicide may be applied to the plant locus either before or after in-furrow placement of the antidote-containing granule so that the herbicide and antidote form a "combination". Crop seed may be treated or coated with the antidote compound either while the crop seed is in-furrow just after is seeding or, more commonly, the crop seed may be treated or coated with antidote prior to seeding into a furrow. The herbicide may be applied to the soil plant locus before or after seeding and a "combination" is made when both herbicide and antidote-coated seed are in the soil. Also contemplated as a "combination" is a commercially-convenient association or presentation of herbicide and antidote. For example, the herbicide and antidote components in concentrated form may be contained in separate containers, but such 20 containers may be presented for sale or sold together as a "combination". Or, the herbicide and antidote components in concentrated form may be in a mixture in a single container as a "combination". Either such "combination" may be diluted or mixed with adjuvants suitable for soil applications. Another example of a commercially-presented combination is a container or antidote-coated crop seed sold, or presented for sale, along with a container or herbicide material. These containers may, or may not, be physically attached to 25 each other, but nonetheless constitute a "combination of herbicide and antidote" when intended for use ultimately in the same plant locus. In the foregoing description of various modes of application of the herbicide-antidote combinations, it is inherent that each form of application requires that in some manner, the herbicide and antidote will physically combine to form a "composition" of those agents. 30 The amount of antidote employed in the methods and compositions of the invention will vary depending upon the particular herbicide with which the antidote is employed, the rate of application of the herbicide, the particular crop to be protected, and the manner of application to the plant locus. In each instance the amount of antidote employed is a safening-effective amount, that is, the amount which reduces, or protects against, crop injury that otherwise would result from the presence of the herbicide. The amount of antidote 35 employed will be less than an amount that will substantially injure the crop plant. The antidote can be applied to the crop plant locus in a mixture with the selected herbicide. For example, where the crop seed is first planted, a suitable mixture of antidote and herbicide, whether in a homogeneous liquid, emulsion, suspension or solid form, can be applied to the surface of, or incorporated in, the soil in which the seed has been planted. Or, the herbicide-antidote mixture may be applied to the 40 soil, and then the seed thereafter "drilled" into the soil below the soil layer containing the herbicide-antidote mixture. The herbicide will reduce or eliminate the presence of undesirable weed plants. Where the herbicide would by itself injure the crop seedlings, the presence of the antidote will reduce or eliminate the injury of the crop seed caused by the herbicide. It is not essential that the application of herbicide and the antidote to the plant locus be made using the selected herbicide and antidote in the form of a mixture or 45 composition. The herbicide and the antidote may be applied to the plant locus in a sequential manner. For example, the antidote may be first applied to the plant locus and thereafter the herbicide is applied. Or, the herbicide may be first applied to the plant locus and thereafter the antidote is applied. The ratio of herbicide to antidote may vary depending upon the crop to be protected, weed to be inhibited, herbicide used, etc., but normally a herbicide-to-antidote ratio ranging from 1:25-to-60:1 50 (preferably 1:5-to-30:1) parts by weight may be employed. As indicated above, the antidote may be applied to the plant locus in a mixture, i.e., a mixture of a herbicidally-effective amount of herbicide and a safening- effective amount of an antidote, or sequentially, i.e., the plant locus may be treated with an effective amount of the herbicide followed by a treatment with the antidote or vice versa. In general, effective herbicidal amounts are in the range of about 0.1 to about 12 kilograms/hectare. The preferred range of rate of 55 application is from about 0.4 to about 10 kg/ha. Preferably, antidote application rates range from about 0.5 kg/ha down to about 0.05 kg/ha. It will be appreciated that at times amounts either below or above these ranges will be necessary to obtain the best results. The selection of the herbicide to inhibit the emergence and growth of weeds depends upon the species of weeds to be controlled and the crop to be protected. 20 EP 0 304 409 B1 The application of the antidote can be made directly to the seed before planting. In this practice, a quantity of crop seed is first coated with the antidote. The coated seed is thereafter planted. The herbicide may be applied to the soil before or after the coated seed is planted. Evaluations of safening activity of the antidote compounds of this invention were carried out using the 5 specific procedures of Examples 39-42 in greenhouse testing. Measurements of biological response as reported in Tables 2-5 were made in the following manner. A visual comparison was made between a crop plant treated with herbicide alone and crop plant having no herbicide or antidote treatment. A number was assigned to this visual comparison indicating the percent injury or inhibition to the herbicide-alone treated crop plant (column "WO" in Tables 2-5 indicating herbicide "without" antidote). Also, a visual comparison io was made between the crop plant treated with herbicide + antidote combination and the crop plant having no herbicide or antidote treatment. A number was assigned to this visual comparison indicating the percent injury or inhibition to the herbicide* antidote treated crop plant (column "W" in Tables 2-5 indicating herbicide "with" antidote). Where treatments involved weed plant species, observations of response to herbicide or herbicide* antidote were similarly recorded. The degree of reduction of herbicide injury is provided by an antidote compound is indicated by the magnitude that the plant inhibition number of column "WO" exceeds the corresponding number of column "W". Also reported in Tables 2-5 are data in parenthesis showing "safening effect" (defined below) for the herbicide + antidote combinations calculated from the plant inhibition numbers. These tables show crop or weed column headings under which there are no data. The lack of such data is not an indication of a failed test; rather it is merely an indication that the 20 particular herbicide* antidote rate combination was not tested with that crop or weed. Summarized below is key information for interpreting data reported in Tables 2-5: Herbicide Name No. 25 1. 2,3,3-trichloroallyl-N,N-diisopropylthiocarbamate(triallate) 2. 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide (alachlor) 3. 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide 30 (butachlor) 4. 2-chloro-2'-methyl-6'-methoxy-N-(isopropoxymethyl)acetan- ilide 5. 3,5-pyridinedicarboxylic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-6-trifluoromethyl, 35 dimethyl ester 6. ethyl dipropylthiocarbamate 7. a,a ,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine 8. 2-chloro-N-(2-methoxyethyl)-o,o-acetoxylidide 9. 2-chloro-N-(2-methoxy-1-methylethyl)-6'-ethyl-o-acetotolui- 40 dide 10. 2-chloro-2',6'-dimethyl-N-(1 -pyrazol-1 -ylmethyl)acetanilide 11. 2-chloro-2'-methyl-6'-trifluoromethyl-N-(ethoxymethyl)aceta- nilide 12. 2- pyrrolidinone, 45 3- chloro-4-(chloromethyl)-1-[3-(trifluoromethyl)phenyl]-, trans- 13. 2-chloro-N-(ethoxymethyl)-6'-ethyl-o-acetotoluidide 14. cis-trans-2,3-dichloroallyl N-benzyldlthiocarbamate 50 Antidote No. = Compound in corresponding Example No. Rate = kilograms/hectare (kg/ha). W = % Plant Inhibition caused by combination of herbicide and antidote. WO = % Plant Inhibition caused by herbicide alone. Data reported in parentheses = % Safening Effect 55 21 EP 0 304 409 B1 J " X 100 Example 39 The following procedure shows interaction between a herbicide and antidote when the antidote is io applied in a soil furrow containing crop seed and the herbicide is incorporated in a soil cover layer. Containers were filled and compacted with fumigated silt loam soil to a depth of about 1 .3 cm from the top of the container. A first container was designated as an untreated control, a second container was designated as a herbicide control, and a third container was designated as a herbicide + antidote test container. Each container was seeded with crop seed in marked furrows. Antidote compound, dissolved in is acetone, was applied directly to the seeded furrows of the third container. Antidote application rate was 0.55 mg active compound per inch of furrow (0.22 mg/cm). This rate was comparable to a plot application rate of 0.28 kilogram per hectare (kg/ha), based on 76 cm (30") spaced-apart furrows. Then, each of the second and third containers was filled and leveled with a cover layer of soil having incorporated therein the selected herbicide at a pre-determined concentration. The first container was filled and leveled with soil containing no 20 herbicide. The containers were then placed on a bench in a greenhouse and sub-irrigated as required for the duration of the test. Plant response was observed about three weeks after initial treatment. Results are reported in Table 2. 25 30 35 40 45 50 55 22 m in O o> /—^ os /*~\ m o 5 m o m m1 so w as w in OSv '/ — \ * n mi CMJ >w— ' 30 oo oo) rsi cm CM1 in on i—1l i—i .O so ^a- in m CMJ CMI CMI J-) in lO ,0 v 00 ON ' 00 -J- o o o —i w m • —- o> <— - J") O LO LO m ^ , — > O / > CJN / — > ON - —> —-> onON ^ -3- t—i m m cm m cnen co vo vo in .o r- n m m m in —i > —' cn - —< m <— ' » oo oo oo coCO !N CM CM CM CM n cn vo r-» oo00 i—i CM CM J- CM r> o o o — > OC ^ -iO i—i O i—i 1/1 <—i O O CM f-» vD O 00 D O iO O uO O CO w CM w -J- w —' i-i1—1 0 00 00 00 00oo M CM CM CM CM 3 IT) M3 ON »—»—ii o i-i i-H r CM LT) ON r-~ 00 CO CM ON N ON ''"^ ON ro oo oo co oo ooso CM CM CM CM -J- ON CM CM CM H CM COro o 00 ^"N T—( 00 LO 1—i o o o oo oo oo oo oo CM tN CM CM CM CO NO r—i CM »a- 1—I so oo ^a- -a- •J ^ CM CM CM ■a- -a- cm cm CM -a- LO OS ' — n o r O LO LO O w CO >« OS w I—I O LO lO1 LO ^> LO f o c VOvo -a- LO LO o VO W LO V O LO O ^> OS \ i—i O LO O5 1—I o o OS ••— ' ON n —' —' o o O ^— N O —n / — \ i—I LO 1— 1 © r -3"r LO O OS w o v—/ w I—* oo oo oo oo oo CM CM CM CM CM i-i i—1 CM CM COi r-~ LOi O LO as /— n as v oo o co lO LO LO v— / 0> ' ' LO O as >— s O vO 1—I LO LO -3- 1— - r~ v_/ I LO O as /—s as /-"s 00 O vO LO i-> I LO LO i —' as v—' r~. w lO O /—> as /s o O LO I—• LO O LO n— ' as ■*— ' as n—' oo oo oo oo CM CM CM CM CO vo vo r» i-i CM LO LO LO LO LO CT\ / — *> O LO ON %— ' o o LO LO ' — •> 00 ^v 00 /—v O lO o VO CM O O LO CM w vO w oo ' O as o o LO w as ' — ' LO -v as ^ o o o —' O w 1—I oo oo oo 00 CM CM CM CM oo co co o> CM CM LO ) LO LO i— . / — \ r — ' — n / — N vO O oo oo oo oo 00 CM CM CM CM CM O LO LO VO ON CO i—i i—i i—i LO O ON /■— N o o CT\ w 00 ^- o ^ 1—1 O O o lo r-* O -J -3" vC O lO LO CO w 0M vo n_/ LO O ON ' — n O '"^ 00 i—i o O SO OO i-i o o OO w r-~ w LO O On /—\ O ' — n O i-i O o o O v—' O 1—I 1—1 00 00 00 00 oo CM CM CM ON CM i-H i-h r** O i—i i—i i—i i—i CM r-~ <3 r-~ -J- ~-3" O i—• O i— < i—i LO EP 0 304 409 B1 ?— -s LO V- ' O ON /—V C IS vo 6m V* CM CJ O o W U S r-. w we o to O oo /-n O 0) s Z 42 00 >, LO 0) j-H 10 a W en a I— I 01 OS *h LO E-i 0Q s 3 O 20 X! S 00 i-l o 3 CO ►J Oh 25 w oo oo E-i CM CM I t-H W H H • 30 ZOO CM CM < Q Z f-. H o 35 oa • os o LO 3hi Z 40 Example 40 45 The following procedure shows interaction between herbicide and antidote when both are incorporated in a soil cover layer before emergence of crop and weed species. Containers were filled and compacted with a fumigated silt loam top soil to a depth of about 1 .3 cm from the top of the container. A first container was designated as an untreated control, a second container was designated as a herbicide control, and a third container was designated as a herbicide + antidote test container. Each of the containers was seeded 50 with a crop species. A measured amount of herbicide dispersed or dissolved in acetone was applied to a measured quantity of soil. To this same quantity of soil treated with herbicide, there was added a measured amount of antidote dispersed or dissolved in acetone. The quantity of soil treated with the herbicide and antidote was thoroughly mixed to incorporate the herbicide and antidote in the soil uniformly. The seed bed in the third container of soil was covered with the soil treated with the herbicide and antidote and the 55 container was leveled. For each test series, the seed beds of the first and second containers were likewise covered by soil layers. The cover layer of the first container was not treated with herbicide or antidote. The cover layer of the second container had a measured quantity of herbicide alone incorporated therein. The containers were then placed on a bench in a greenhouse and sub-irrigated as required for the duration of 33 :. Results ai LO LO o o o ON ' — N ON /—N —N O O O /~N o o 1—t 1—* i—i o i—i m CN m m O o m On n—' OS n— ' —' o o n—' on - —- I—I i—i o O r-. O O i—i m ON m m o ON ' — N ON ' — N ~N O c « o N o 3:_ CO p r-l 4-> •i-l CO 3: O 3= —1 LO LO LO O O C O OS ' — S OS ' N ON ' N O -* N O ' — N « D 2 o o o ho h m X M LO LO LO O LO O O 3: o^n^ o\n-> con-' on-' onn-/ CM CM CM 0) O 00 /-^ O0 /— - 00 ^ u 3: i-i o On •H 00 CO OS LO LO O 3= 1—1 Nw/ oo N—' LO ~— ' ■a u o o o CO w O O /^n O /- — v O ' — S >Nto3: hki h m i—i lo G «S U U LO LO LO Bl O 3 On ^ On w onn-/ 3Q a 3 u o ^ to 3:2 OJ £3 3: 3: S LO LO LO O O 3 O ON ' — n On /— n ON ' — ^ O ' — n O C3: O O i—i i—i in ih m 00 i—i i—i CM i-l LO lO LO LO LO o 3= ooN_xoowr^-woNN_^ONN— > x> Wv0^3-\OnO>3-nOvO^- HlOCMOnlOCMOnlOCN P£ CM 00 CM 00 CM 1 -I w . H H O «-• CO CO CO CO CO Z O Z 3 a WCMCMCMvOvOsO^-** Hr~-r~.r~LoinincMcM Q§ no vO NO CM CM OS O vO NO no vO no vO no NO 35 m min ONOn <*— Nn ON /-"v/—v oO oO LOm LOm ON w On n— '< O © O O CM CM CNCM LO LO On ^-n On i—iI—I vOno CM CM LOm Oo o. w r- *— - V0^3"v0v0^v0v0 cococooococoooco co oo co cooo o o CM CM vOvOvOCMCNCMvOvOvO vO CM CM CM vO vO cococor~-r~-r~LOinco co i — ir~- — r--r~ m min CO CO CO vO voVO vOvo nOvOvOvOvOvOnOvOvO vO vO voVO vO NOvO vO 36 a to o 4> 3: CO p "O w 3: ■i-l CO 3= O 3: m o o o •H C O On ' — n O ' — n O ' — n O ' — n BJ 0) 3= O i—t O h in i—i o 4-> 01 x u m o in o 003: Onn —' o n»—> on ' 0 s—" -U| I-l 1-H O O O CM CN ojo >■*<"- N-sT^N- ^ <0 3:s CD E m o o o 3 O ON / — s O ' — n O ' — n O A 3: i—i i—tin i—i m h in 00 CN i-i m in m m O 3: f""» n— i gs n— ' on n- ' on >— ' /i t-n ON in CN On lO CN On lo CN 0? 00 CN 00 CN 00 CN 1 HHOO o o o o o o o o Z O 55 CN CN CN CN CN CN CN CN CN < a WnO PQ • OSOnO NO no no no no no no no 37 o o o o V O O ' N O /~N O ' > ca 3: i—i o r- I i—i O r—l O i—i O i—i O «5 O c o o o o O 3: Owe O v—/' O v—' oO v—s —' O v— o ~w i-i r- i—• i—I— s 3: LO LT LO O O O LO p ov /-n o ON <—v O ' — \N O ' — nN O ^"n^"N ON 3: O lo i—i oO i—i oO hi— < mLO o lo ir o O O LO LO 3:_ on w ct ON ' — ' O *— ' Ow ' onON n_> ON w 1-H1—1 1-H vO vOVO »d"-J- vONO vONO On LO CM OnON LO 00 CM 00 rH rHr- 1 1—tI i-Hi—l CO(O 00 CM CM CM 00 CM 1-H i-Hi—I i-Hi—I CM 1-H 1-Hi-H r-< 1-H i-H i-H i-H o o o O O O O O o o ' — s o ' — N o O ' — N O ' N O ' N O ' N O ' N co 3: i-h o i-h o i—i < I-H O I-H O I-H O I-H O I-H O «5 O O O o oO oO oO o o ocs ow ow o n O N— O N— ' O N—N '' O N— / O N / OCD N / 1-H i-H i-H 1—1 1—1I 1-H r-i— 1I I—i— < 1—!—1I c 4) 3:9 V u s 3: w O co 3: « u C3 3t § 3: LO LO O O O LO lOLO LOlO O O ON ' — N ON <•— n O /■ O ' N O ' N ON ' N ON /—N ON ' N O ' — N * 3: O lo i-h l rH O 1—11-H oO LO NO O 1—i-i 1 LO CMCN LO O LO O O O O LO LO 3: on n— ' on 1— ' on n 3 v— O nN— ' onON n—N— ' ' ' ' ON —' ON ' / I-H i-HI-H s 3: -J NO NO <1"^3--3" NO NO rM On lO CM ON lO IN 00co CMcm 00oo r> coCO oO oO o o CM CM CM CM N CM 00OO 00 00 CM ph i-h CM CM CM i-h fH 1—1-H1 i-H.—I / — \ O / — V O i-h O -I *J ■4 ca o t O 3: w o v—' I—I ■i O O LO O 00 o h d o O /— N O /— n ON O ' — n ON \ O /~N a aj r* i—i O i-h O O »—i O O 1-H O O O 00 o o o ON— ' O N—' »N/ O N ' ON— ' O N^ I-H i—I i-H i-H 1-H o -V O O I-H LO LO —' ON N—' cm eo i — y-, N ON '™n —I -H D o M w 3= 3: OOOLOOOOOOO00000 O O ' N ON ' N ON ' N O ' — N O <^N<^-n O ' — Nn O ' — Nn Oo ' — ^N Oo 3: 1—IO O O 1-H O 1—tO1—I O r-H O H 1/1 H 1/1 1—1 O OOOiOOOOl/lLOOO O to lO o 3: O N ' ON » ' ON N ' O N ' O N^— ' O0 Ns— ' ON N* — ' CjNON (* —' OO^ * —' I-H 1-H i-H1-H 1-H 1-Hi-H 0 3: 3: g 3: B at s 3: cNi/icor--cNr^oOLOCN r-- O O lO O ^ ' — \ CN ^~ ^ LO ' — n on ' — CO ' — n onOn ' — n onON /—v/—v On ^-n^—n On r — ' 3:00<-ir-~oo^3:cocoo00 ^3- CO CO O OnOOOCNnOOOOOCOO\0 00 00 CO O Ol-HO O O O LO LO O Ol-HO i-h 1-H N / ,-H N ' 1-H ^—' NO SmmS V— ft] \sQ vO sO vO vOVO NO vO NO v£5 NO vONO LO LO LO LO LO 2S U ^0 \© vO vO \0NO NO NO sO NO vONO LO LO lO LO LO 3 OCNCNCNCNCNCNCNCNCNCN CN CN CN CN 53 41 to C3 o * 3 O LO O O 3 / — \ oO ' — n ON /' — v O ' — n O ' — n f-H I HO rHt-H LO O t-H H 1(1LO 1—1t-H O m 3 LO LO LO O en V 3W onON v_V— ' ON v^*— ' ON n— ' O v ' H 1-H o 0 O O O CO vO f FN /—v VOvO ' — n N ON 00 ON <*"N V ON CO CM CO O V oo oo r-~ on o O 3 O LO LO O i—iI CM v HW i-HNi-h v —' CM *- —' Nw , w 3 vO vO vO vO ~l lOLO lOLO lOLO lOLO H i-H1-H i-H i-H i-H 3 NOVO NO NO NO ~> LO LO LO LO Nl CM CM CM CM LO o o o o o ON /' — \■> O ' — s O ' — n O ' — o '^ — ^■* O ' — n O T-H O HIH i/1|/1 I-Hf-H O f—t O T-H O O O LO o o o O \sN— ' ©O n-/w OSCA 'w On-/O N— ' O *n— ' O v— ' t-H I-Hi-H t-H i-H i-HI— I lO LO LO LO LO LO O /—s 00 /»—\ CTN ^->> CO / — v OS iI — *n CTNCT\ OS <3 ^H/ ■O NO NO NO NO NO LO LO LO LO LO lO O NO NO NO NO NOnO LO LO LO LO LO LO rvl CMCN CN CNCM CMCN CNCM O O LO o o ' — ~N* O / — vN O ' — N ON / — Nv O <"-N<"-n O ' — nN LOo r—h I LOm i—h I i/iLO Oo ihrt i/iifl t-h oO LO LO ID LO oO v— h'' ON >—' onON n— <' Onon n— ' on n— ' O n ' 1-HI-H O LO 00 LO LO ' "NN 00 /"> ON /-> CM/fSl/ V 00^>00 ^> ON/- N NOSO NO NO NO NO LO LO LO LO LO NO NO NO NO VO LO LO LO LO LO CM CM CM CM CM o o o o "N O ' N O / N O O ' N 3 1—1I U-}LO t-H1-H o t—IU^I—I LO t-Ht_Ji—1 © LOUO O LO O -' ON n-1v— ' On—O w ' ON wn— ' oO n—v ' 1-H t-H o O /— > t-H O Oo O w t-H O LO LO O LO -n r~» ' — n onOn /"■">n on >— n coCO /~\/ — v onOn - —n 5 LO CO i-h COco 3 00 NO Onon 00CO r*- H O LO LO LO LO -/ 1-H N ' CO N ' N , ,_, > / r\| N /' NO NO NO NO NO LO LO LO LO LO NO NO NO NO NO LO LO LO LO LO CM CM CMCN CNCM CN oO oO oO oO loLO O / — ns O /"~s/—v ©O /' — n O ON .> O i- lo lo C-r~- cm co ' * N ON ' N 00 ON / N CO / N LO S~ N O OO00 O ONOn r~~ oO CO no O noNO CO Oo O O i-i O O O i-< »— ' CO n— WCON—-CMN — - >n —-. no no NO NO NO NO NO LO LO LO LO LO CM CM CM CM CM 3: O 3: rH 00OOOOOOO) o o o o ■H CO ON /"™"v O ' — n O ' — n O ) /—' — v n O n O /"■>' — s O ' — n O >~nN CO 41 3; O i—i O t—i O t—i O i—t—i O i—t-H'LO LO i—t-H• O i—t-H' o +J 4) rHt-H X U 00 O O O > O LO o o O C9 3 OS n_/ o n_/ o v— ' O ) ^—n«/' o vn—— /' oo00 n—/ o ^n—— /' ©O 'n_/ — / CX4 t-H t-H 1-Ht I—rHI T-HrH t-Ht—1 OJ o (J 3t •H 0:5 * >H C8 0J O w 3: C co u u (OOS c § Sh o CJ 3: to 3:9 OJ 5 3: E LOCMLor>-oOLOcoo o lo oo S O CM ' — s -J- „— ^ ON ' — >. 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CON— nOnO^nOnO^h/nOnONO -d" NO NO NO NO ONlOCMOnlOCMOnlOLO CM ON LO CM ON LO 00 CM 00 CM 00 ONONONON^a-^.^.^.ON ON ON ■*3" -a- CNCMCMCMrHrHrHrHCM CM CM rH rH rH rH nO^-J-vJ-nOnOnOO- CMCMCMCMCMCMCMCMCM CM CM CM CM CM CM 98 a 3= j 3 5 3= OOlOlOlOlOlOlOOLO i-O LO LO LO LO O 2 O O ' — n O /■ —N ON / —nN onOn /—/ — s ' ON >' — n ON /—/~*N N ON /—— -n ON //— — nN O '/~ — n ' J 3 H LO HO O O O O O LOL0<-<0 r-H O J ■ilOOOOOlOOOOO O O LO o o o 5 3t ONW Ow Ow owOnw owOn— ONWON n—' Ow onw OwOn— ' t—ti—i^j—tr-H r-H t-h r-H 1i — I1 o 3= 3 2 3 ■i 5 3= B 3= O 3= 3= lOlOlOlOlOlOlOlOOLO LO LO LO LO LO O O 00 /— n 00 / — . NO - —n' 00 '/ — n 00 '- —n NO - — n OOO0 /—/■— > NO /-N/-n ON ^— N 3=o W 3 • W-"3-NCfNONONONONONO iOCN CN CN| CM CN CN CN CN CN ! z 99 OOOOlOlOlOlOO O O LT) LO LO LO O ' — n Oo - —>- O / — - O /—n/— n ONon '/ — - ON / —- ON ^-n^—. 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