Europaisches Patentamt C19J European Patent Office ® Publication number: 0 304 409 Office europeen des brevets A1
EUROPEAN PATENT APPLICATION
@ Application number: 88870135.6 © int. ci.*: C 07 D 413/04 C 07 D 498/10, A 01 N 25/32, © Date of filing: 12.08.88 A 01 N 47/32, A 01 N 43/76
© Priority: 13.08.87 US 84786 01.07.88 US 212621 Inventor: Brinker, Ronald Joseph 12815 Glenbernie Lane © Date of publication of application: St. Louis Missouri 63146 (US) 22.02.89 Bulletin 89/08 Massey, Steven Marc 2459 Pheasant Run © Designated Contracting States: Maryland Heights Missouri 63043 (US) AT BE CH DE ES FR GB GR IT LI LU NL SE Bussler, Brett Hayden © Applicant: MONSANTO COMPANY 12 Suncrest Drive Patent Department 800 North Lindbergh Boulevard St. Peters Missouri 63376 (US) St. Missouri 63166 Louis, (US) Williams, Eric Lee 130 Timberbrook St. Peters Missouri 63376 (US)
(74) Representative : Lunt, John Cooper et al Monsanto Europe S.A. Patent Department Avenue de Tervuren 270-272 Letter Box No 1 B-1 150 Brussels (BE)
© 5-Heterocyclic-substituted oxazolidine dihaloacetamides. © The disclosure herein relates to a new family of haloalkyl oxazolidinyl derivatives as antidotal compounds to reduce injury to crop plants by a variety of herbicides. The antidotal compounds are characterized particularly by having hetero- cyclyl or spiroheterocyclyl radicals attached to the 5-position of haloalkyl oxazolidine compounds and are especially useful as in-can antidotes against injury by acetanilide and thiocarbamate herbicides to corn, sorghum, soybeans, wheat, rice and other crops.
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Description
5-HETEROCYCLIC-SUBSTITUTED OXAZOLIDINE DIHALOACETAMIDES
5 FIELD OF THE INVENTION
Herbicide antidotes are well-known crop protection chemicals. Of particular interest herein is a class of certain 5-heterocyclic-substituted oxazolidine and thiazolidine dihaloacetamide compounds found effective as 10 antidotes for protecting crop plants from herbicide injury.
BACKGROUND OF THE INVENTION
15 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 an 20 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 patents describe 25 such dihaloacyl oxazolidinyl compounds having as substituents on the oxazolidinyl ring hydrogen, alkyl, cycloalkyl, spirocycloalkyl, alkoxyalkyl, alkanol, heterocycyl, 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, 0,147,365, 190,105 and 30 0,234,036, None of the above patents or any other known to the inventors herein disclose any dihaloacyl 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 dichloroacetyl oxazolidine antidotes in that patent. The EP 35 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 both, in 40 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 identification of an antidote which safens 45 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; and the antidote compound itself. Moreover, the 50 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 55
A novel family of compounds useful as antidotes against herbicide injury to crops is provided by 5-heterocyclic-substituted oxazolidine dihaloacetamide compounds embraced by the general formula:
60
2 EP 0 304 409 A1
R4 R5
0 T R6
R - C N 3
- 0 10
and agriculturally-acceptable salts thereof wherein 15 R is haloalkyl; Ri is C1-4 alkyl, haloalkyl or phenyl; R2-R5 are H or C1-4 alkyl; R6 is a saturated or unsaturated C5-10 heterocyclic radical containing 1 or 2 oxygen, nitrogen or sulfur atoms, optionally substituted with a C1-4 alkyl or haloalkyl radical or halogen atom or with oxygen on a ring nitrogen 20 atom; and R5 and R6 may be combined to form a spiroheterocyclic ring as defined for the R6 radical. The term "haloalkyl" embraces radicals wherein any one or more of the carbon atoms, preferably 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 groups 30 such as trifluoromethyl and perfluoroethyl groups. Preferred haloalkyl R members aredihalomethyl, 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 and ethyl. 35 Also included in this invention are the stereo and optical isomers of compounds within the class defined by the above formula. The heterocyclic R6 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 contains five to ten ring members of which at least one member is a heterocyclic oxygen, nitrogen or sulfur atom. The 40 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 R6 member per se the heterocyclic ring must be attached directly to the 5-position of the oxazolidinone ring without any intervening moieties therebetween, 45 e.g., an alkylene group. It is further within the purview of this invention that in alternative embodiments, the oxazolidinyl radical may be substituted with a heterocyclic or spiroheterocyclic ring at the 2- and/or 4- carbon atoms, as described above for such substitutions on the 5- position carbon atom. By "agriculturally-acceptable salts" of the compounds defined by the above formula is meant a salt or salts 50 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 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 55 of a herbicide, preferably by at least 10% or 15%, but naturally the greater the reduction in herbicidal injury the better. 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 60 commercially significant suppression of weed growth can occur at much lower levels, particularly with some 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
3 EP 0 304 409 A1
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 5 to denote a composition containing as the active ingredients, a herbicide-antidote combination which 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. 10 As further detailed infra, while not necessary, the composition containing the herbicide-antidote combination may also contain other additaments, e.g., biocides such as insecticides, fungicides, nematocides, 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 15 phenoxypyrazoles), imidazolinones, pyridines, and sulfonylureas. It is within the purview of this 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 20 plants such as corn, grain sorghum (milo), and cereals such as wheat, rice, barley, 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: 25 cis-/trans-2,3-dichloroallyl-diisopropylthiolcarbamate (common name "diallate"); ethyl dipropylthiocarbamate (common name "EPTC"); S-ethyl diisobutyl (thiocarbamate) (common name "butylate"); S-propyl dipropyl(thiocarbamate) (common name "vernolate"); 2,3,3-trichloroallyl-diisopropylthiolcarbamate (common name "triallate")' 30 Examples of important acetamide herbicides are the following: 2-chloro-N-isopropylacetanilide (common name "propachlor"); 2-chloro-1',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-acetoluidide (common name "acetochlor"); 35 ethyl ester of N-chloroacetyl-N-(2,6-diethylphenyl)glycine (common name "diethatyl ethyl"); 2-chloro-N-(2,6-dimethyIphenyl)-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-pyrazol-1-ylmethyl)-acetanilide (common name "metazachlor"); 40 2-chloro-N(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)acetamide; 2-chloro-6'-trifluoromethyl-N-(isopropoxymethyl)acetanilide; 2-chloro-2'-methyl-6'trifluoromethyl-N-(ethoxymethyl)acetanilide; 2-chIoro-2'-ethyl-6'-trifluoromethyl-N-(1-pyrazolyl-1-ylmethyl)acetanilide; 2- chloro-N-isopropyl-1-(3,5,5,-trimethylcyclohexen-1-yl)acetamide (common name "trimexachlor" 45 Examples of important pyridine herbicides include: 3- pyridinecarboxylic acid, 2-(difluoromethyl)-5-(4,5-dihydro-2-thiazolyl)-4-(2-methylpropyl)-6-(trifluoro- methyl)-, methyl ester; 3-pyridinecarboxylic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-5-(1H-pyrazol-1-ylcarbonyl)-6-(trifluoro- methyl)-, methyl ester; 50 3,5-pyridine dicarbothioic acid, 2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-, S,S-dirnethyl ester; 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-ethoxycarbonyl]-ethoxy-4'-nitrophenoxy)-1-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-methoxy-4'-nitrophenoxy)-1-methylpyrazole; 55 5-(trifluoromethyl)-4-chloro-3(3'-t1-butoxycarbonyi]-ethoxy-4'-nitrophenoxy)-4-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-methylsulfonoylcarbonyl propoxy-4'-nitrophenoxy)-4-methylpyrazol; 5-(trifluoromethyl)-4-chloro-3-(3'-propoxycarbonylmethyloxime-4'-nitrophenoxy)-1-methylpyrazole; (± )-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid (9CI). Examples of important sulfonylureas include: 60 Benzenesulfonamide, 2-chloro-N-[[(4-methoxy-6-methyl-1, 3, 5-triazin-2-yl) amino] carbonyl]; Benzoic acid, 2-[[[[(4-chloro-6-methoxy-2-pyrinidinyl) aminojcarbonyl] amino] sulfonyl]-ethyl ester; 2-thiophenecarboxylic acid, 3-[[[[(4,6-dimethoxy-1 ,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-, methyl ester; Benzoic acid, 2-[[[[(4, 6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl ester; 65 Benzenesulfonamide, 2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1, 3, 5-triazin-2-yl) amino] carbonyl];
4 EP 0 304 409 A1
Benzoic acid, 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino]carbonyl] amino]sulfonyl]-methyl ester; Examples of important imidazolinone herbicides include: 3-Quinolinecarboxylic acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-; 3-pyridinecarboxylic acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-; Benzoic Acid, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2- yl]-4(or 5)-methyl-; 5 3-pyridinecarboxylic acid, 5-ethyl-2-[4-methyl-4-(1-methylethyl)-5-oxo-1H-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. Examples of other important herbicides include: 2-Chloro-4-(ethylamino)-6-(isopropylamino)-sym-triazine; 10 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-; 2- Pyrrolidinone, 3-chloro-4-(chloromethyl)-1-[3-(trifluoromethyl) phenyl], trans-; 3- lsoxazolidinone, 2-[(2-chlorophenyl) methyl]-4, 4-dimethyl-; 15 2-lmidazolidinone, 3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-methyI-; 2-Chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine; 2-Methoxy-3, 6-dichlorobenzoic acid, dimethylamine salt; Methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate; l'-(Carboethoxy) ethyl 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitrobenzoate; 20 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 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 25 determined of commercial utility, alachlor, acetochlor, butachlor, metolachlor, 30 metazochlor, 2-chloro-2'-methyl-6'-methoxy-N-(isopropoxymethyl)acetanilide, 2-chloro-2'-methyl-6'-trifluoromethyl-N-(ethoxymethyl)acetanilide, and 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 35 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 more of the herbicide compounds mentioned herein. Of particular importance and preference herein, a number of the antidotal compounds of the invention have 40 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-fu- ranyl)-2,2-dimethyl-; oxazolidine, 3-(dichloroacetyl)-5-(3-pyridyl)-2,2-dimethyl- and oxazolidine, 3-(dichlo- roacetyl)-5-(2-thienyl)-2,2-dimethyl-, to reduce the phytotoxicity of alachlor (active ingredient in LASSO® herbicide) in corn and grain sorghum. The just-named antidotes have similarly been found to be particularly 45 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, 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 50 various plants because of the sensitivity of the plant to the herbicide. Thus, e.g., although certain crops 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 55 herbicide. 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 60 degrees of crop protective effect against different herbicides in different crops. Accordingly, as will 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 65
5 EP 0 304 409 A1
given herbicide in a different crop or against a different herbicide in the same crop. This is an expected phenomenon.
DETAILED DESCRIPTION OF THE INVENTION
10 Antidote Compound Preparation
The antidote compounds of the invention may be prepared by the following exemplary general procedures described in Examples 1-38. 15 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. Table I sets forth analytical data for 38 specific compounds prepared in accordance with these procedures.
20 Example 1
Preparation of 3-(Dichloroacetyl)-2,2-Dimethyl-5-(2-Thienyl)-Oxazolidine 25 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 1.5 torr) yielding 50.9g (96°/o) of a pale yellow oil. 30 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 sodium sulfate was added and the mixture was filtered through celite. The filter cake was rinsed with THF and the filtrate was 35 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 mixture was concentrated giving an oil which was distilled to give 12.33g (80%) of 2,2-dimethyl-5-(2-thienyl)-oxazolidine, as 40 a pale yellow oil (BP 102-105° 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 separated. The aqueous layer was extracted with CH2CI2 and the combined organic layers dried over anhydrous magnesium 45 sulfate (MgS04). 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 104-105° C.
50 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 55 identified by structure and physical properties in Table 1 herein.
Example 6
60 Example 6 is prepared using the same basic procedure as Example 1 with the following modifications. 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 11.2 grams (0.067 mol) 2,2-dimethyl- 65 5-(3-furan)-oxazolidine in methylene chloride at 0°C with 9.5 g (0.094 mol) triethylamine and adding dropwise
6 EP 0 304 409 A1
11.8 grams (0.08 mol) dichloroacetyl chloride. The reaction mixture is washed with water and the organics dried with MgSCU- Concentration and chromatography with 10% ethylacetate-hexanes gives 5.1 grams (65%) of white solid; m.p. 90-91 °C.
5 Examples 7-12
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 w structure and physical properties in Table 1 herein.
Example 13 15
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.
20 Examples 14 and 15
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, respectively, for 25 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) 1-furanmethanol alpha-(aminomethyl)- and 1.8 grams (0.04 mol) acetaldehyde in methylene chloride in the presence of MgS04 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 30 over MgS04. Concentration and chromatography with 10% ethyl acetate-hexanes gives 2.0 grams (19%) of colorless oil.
Example 16 35
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. 40
Example 17
In similar manner, when the procedure of Example 14 was repeated using benzaldehyde instead of 45 acetaldehyde, there was obtained the product of Example 17 as identified in Table 1.
Examples 18 and 19 50
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 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. 55
Example 20
60
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 carboxaldehyde. The reaction was 65
7 EP 0 304 409 A1
stirred for 3 hours at 0°C then warmed to ambient temperature. Concentration yielded crude 1 -(3-pyridyl)-2-nitroethanoi. 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. 5 Filtration through celite and concentration yielded a crude 2-(3-pyridyl)-2-hydroxy-1-aminoethane. 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 10 0°C in CH2CI2. 12.9 grams (0.088 mol) dichloroacetyl chloride were added dropwise and the reaction mixture was stirred for 30 minutes at 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-hex- anes gave 70/0 overall yield of the title compound (1.8 grams, cream colored solid, M.P. 111-113°C). 15 The product of this example can also be prepared according to the procedure of Example 1 .
Example 21
20 Three (3) grams (0.01 mol) of the product of Example 20 and 1.1 gram (0.013 mol) of NaHCOa were 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 MgS04. The MgS04 was filtered and the CH2CI2 was removed to yield a white solid. Flash chromatography using 20% methanol, 30% 25 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, 2.5 grams, 82% yield). The product was identified as pyridineoxide, 2-[3-(dichloroacetyl)2,2-dimethyl-5-oxazolidinyl]-.
30 Example 22
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 35 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 trifluorometh- ane 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 (4.1.2.10) 45 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 CHCI3 (3 x 150 mis) and then the organics were dried using MgS04. After filtration and concentration, 21 grams of 83% enantiomerically pure oil, 2-(1-hydroxy-2-cyanoethyl)-furan (S) was collected. 50 Optical rotation [a]2D' = +28.5° (C = 5, chloroform; Lit value [a]" = +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 milliliters of H2O and 5 milliliters of 10% NaOH (aq). The mixture was filtered and concentrated to give 4 grams of colorless 55 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]" = -23.6° (C = 5, chloroform; Lit value [a]" = -28° C = 5, chloroform) 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 60 milliliters of H2O 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). 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. 1 7 grams (0.01 9 mol) of dichloroacetyl chloride was effected and the reaction was stirred for an additional 30 65 minutes at 0°C. The reaction was warmed to room temperature, washed with water and the organics were
8 EP 0 304 409 A1 dried with NaaSCU- Filtration and concentration yielded 5.0 grams of dark oil which was 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]* = +10.8° (C=5, chloroform). 5
Example 24
Six grams (0.05 mol) of 2-(1-hydroxy-1-aminoethyl)-furan, 2.8 grams (0.05 mol) acetic acid and 10.6 grams w (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 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 75 refluxed in toluene for 4 hours. The reaction mixture was concentrated and flash chromatography was 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°-100cC. as a mixture of diasteroisomers. 20
Examples 25 and 26
Following substantially the same procedure described in Example 24, but substituting 2-(1-hydroxy-1-ami- 25 noethyl)-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 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 30 modeling.
Example 27 35
This example describes the preparation of an antidotal compound according to the invention wherein the R5 and R6 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 40 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 137-139°C, which was identified as 1-oxa-8-thia-3-azaspiro [4.5]-decane, 3-(dichloroacetyl)-2,2-dimethyl-.
45 Example 28
This example describes the preparation of an antidotal compound wherein the R5 and R6 members of the above generic formula are combined with the 5-carbon atom of the oxazolidinyl ring to form a 5-membered 50 spiroheterocyclic radical. The process according to Example 6 was repeated, except the 3-furaldehyde of that example was 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 128-139°C, was recovered. The compound was identified as 1-oxa-7-thia-3-azaspiro [4.4]-nonane, 3-(dichloroacetyl)-2,2-dimethyl-. 55
Example 29
60 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 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-. 65
9 EP 0 304 409 A1
Example 30
5 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-methyk
10 Example 31
This example describes the preparation of an antidotal compound according to the invention, characterized 15 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 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 20 identified as oxazolidine, 3-(3-di-chloroacetyl)-5-(2-furanyl)-2,2,4-trimethyk
Example 32
25 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-pyrazinecarboxalde- hyde for the 3-pyridinecarboxaldehyde of Example 20. 30 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, 3-[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 (0.1 1 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. 40 A solution of 10.2g (0.10 mol) of tetrahydrofurfural alcohol in 100 mL of anhydrous 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 45 anhydrous magensium sulfate and concentrated ( > 1 0° C, 1 00 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 trimethylsilylcy- anide 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 50 lithium aluminum hydride solution in ether. The 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 55 was dissolved in 100 mL of acetone. 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 was vigorously stirred for 45 minutes. The layers were then separated and the organic 60 phase was dried over anhydrous magnesium sulfate. Thin layer chromatography (ethyl acetate :hex- anes = 1 ;1 ) 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 isolated : (A) 3.46 g of the less polar isomer was isolated as a yellow oil njf = 1 .4991 . Anal, calc'd for C11H17CI2NO3: C.46.82; H.6.07; Cl.25.13. Found: C.46.52; H.6.01; Cl.25.01. (B) 2.00g of the more 65 polar isomer as a yellow oil vig= 1.5021. Anal. Calc'd for C11H17CI2NO3: C.46.82; H.6.07; CI25.13. Found:
10 EP 0 304 409 A1
C.46.58; H.6.00; Cl.24.97. The overall yield for the fix steps is 190/o. The product was identified as 3-(dichloroacetyl)-2,2-dimethyl-5-(tetrahydro-2-furanyl)-oxazolidine.
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. 10
Example 35
Following the procedure of Example 6, but substituting trichloroacetyl chloride in the last step of the 15 reaction there was prepared oxazolidine, 5-(2-furanyl)-2,2-dimethyl-3-(trichloracetyl)-.
Example 36 20
Using the same procedure as Example 6, but substituting 2-thiophene-methanol for tetrahydro furfuralalcohol and using monofluoroacetyl chloride in the last step, the compound oxazolidine, 3-(fluoroacetyl) 2,2-dimethyl-5-(2-thienyl) was prepared. MP 65-67° C. 25
Example 37
The compound oxazolidine, 3-(dichloracetyl)-5-(2-thienyl- was prepared using the same basic procedure as 30 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 (MgSCU). Filtration and concentration gave a crude product which was acetylated with dichloroacetyl chloride to give the above 35 compound.
Example 38 40
The same basic procedure as in example 6 was repeated with the following modifications: the 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 (MgSCU) . Filtration and concentration gave a crude product that was acetylated 45 to yield oxazolidine, 5-(2-benzofuranyl)-3-(dichloroacetyl)-2, 2-dimethyl- MP115°-117°C. Various other compounds within the above generic formula and analogs thereof are specifically contemplated as within the scope of the invention. For example, compounds according to the above formula where the oxygen atom of the oxazolidinyl radical is replaced by a sulfur atom (to form the thiazolidinyl analog) and the R-R6 members are as defined above may be found to have varying degrees of antidotal activity against 50 various herbicides in various crops. Particularly contemplated are such thiazolidinyl compounds wherein R is dichloromethyl, the R1-R5 members hydrogen or C1 4 alkyl and the R6 member is a thienyl, furanyl, pyranyl, pyrazinyl or pyridinyl radical or the 5,5-spiro analogs thereof. Exemplary species include thiaziolidine, 3-(dichloroacetyl)-5-(2-furanyl)-2,2-dimethy[-; thiazolidine, 3-(dichloroacetyl)-5-(2-thienyl)-2,2-dimethyl-; thia- zolidine, 3-(dichloroacetyl-2,2-dimethyl-5-(1-methyl-1H-pyrrol-2-yl)-; thiazolidinyl, 3-(dichloroacetyl)-5-(3-pyri- 55 dyl)-2,2-dimethyl- and thiazolidinyl, 3-(dichloroacetyl)-5-(2-pyrazyl)-2,2-dimethyl-. As with the oxazolidinyl analogs, the foregoing thiazolidinyl compounds and analogs thereof may be characterized as having H or other lower alkyl groups in the R1-R5 positions. The antidotal compounds prepared in accordance with the foregoing working examples are listed in Table 1 . The specific compounds are listed in the first column by example/antidote number ("Ex./Antidote No.") 60 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.
65
11
M in m
13 0*< CO " 0) US2 ti3 o I— I 3*1 I PS w w w ; us o o 2** P ctn CI 1—1 I—I i— i v v cn cn \ / \ I i K W « W W <; CO CN LD < cr. w o r- cj\CJ\ i—i—l < cmcn r~~ r~~ r-i CTlcti \o IT)m Ii P-|P-l /— *» I Ii • LO S CJ O U0 >—i—lI r-t O Ci i—i w O CM f=JO ; i —I 0) • O 00 COO0 •h +j4-i r-r oo oo co //— — «v N 1I P0CO *p-p p p r— I 0) in i~- * PS W h5K Sw £TJ»t* ^3& to H PSpT K W « K coCO PS £S ss £sps £* CO CO CO cmCM K K SS PS CJ CJ scM oCJ I I I CO CO coCO PS G cj KPS Gcj i i i CM IN CO r— I r-l PS ' — I CJ CJ CJ CJ K £5 K CJ CJ CJ CJ II I I I •H • 4J O CS S3 < 01 uo 1— oo • 4-1 CO CO CO CO ><; o 19 EP 0 304 409 A1 Biological Evaluation 5 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 application to the plant growing medium, such as soil, as well as to the seeds, emerging seedlings, roots, stems, leaves, or other plant parts. 10 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 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 15 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. 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 20 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 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 25 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 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- 30 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 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 35 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. 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 40 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 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 45 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 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 50 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 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. 55 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 (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 60 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 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 65 upon the species of weeds to be controlled and the crop to be protected. 20 EP 0 304 40& A1 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 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 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 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 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 No . Name 1. 2 , 3 , 3-trichloroallyl-N,N-diisopropyl- thiocarbamate ( triallate ) ' 1 2. 2-chloro-2 , 6 -diethyl -N- (methoxymethyl ) - acetanilide (alachlor) ' 1 3. 2-chloro-2 , 6 -diethyl-N- (butoxymethyl )- acetanilide (butachlor) 4. 2-chloro-2 1 -methyl-6 ' -methoxy-N- ( iso- propoxymethyl ) acetanilide 5. 3 , 5-pyridinecarboxylic acid, 2- (difluoro- methyl ) -4- ( 2-methylpropyl ) -6-trif luoro- methyl, dimethyl ester 6. ethyl dipropyl thiocarbamate 7. a , a , a-trifluoro-2 , 6-dinitro-N,N-dipropyl- p_-toluidine 8. 2-chloro-N- (2-methoxyethyl ) -o , o-aceto- xylidide 9. 2-chloro-N- ( 2 -methoxy-1 -methyl ethyl ) - 6 ' -ethyl-o-acetotoluide 21 EP 0 304 409 A1 1 ' 10 . 2-chloro-2 , 6 -dime thy 1-N- ( 1-pyrazol- 1-ylmethyl ) acetanilide 1 1 11 . 2-chloro- 2 -methyl-6 -trif luoromethyl-N- ( ethoxymethyl ) acetanilide 12. 2-pyrrolidinone, 3-chloro-4-(chloro- methy 1 ) - 1- [ 3 - ( tr i f luor omethy 1 ) phenyl ] - , trans - ' 13 . 2-chloro-N- ( ethoxymethyl ) -6 -ethyl -o- acetotoluide 14. cis-trans-2 , 3-dichloroallyl N-benzyl- di thiocarbamate 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 < > = X 100 Example 39 The following procedure shows interaction between the herbicide and antidote when the antidote is 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 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 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. 22 EP 0 304 409 A1 Table 2 % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 1 .56 1 .28 90 95 ( 5) 1 .56 2 .28 85 95 ( 10) 1 .56 3 .28 95 95 ( 0) 1 .56 4 .28 80 95 ( 15) 1 .56 5 .28 80 95 ( 15) 1 .56 13 .28 95 95 ( 0) 1 .56 6 .28 95 100 ( 5) 2 2.24 1 .28, 25 95 15 60 ( 73) ( 75) 23 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 2 2.24 2 .28 15 100 30 70 ( 85) ( 57) 2 2.24 3 .28 55 95 85 100 ( 42) ( 15) 2 2.24 4 .28 45 95 50 70 ( 52) ( 28) 2 2.24 5 .28 15 95 10 65 ( 84) ( 84) 2 2.24 13 .28 35 100 50 85 ( 65) ( 41) 2 2.24 6 .28 35 95 90 95 ( 63) ( 5) 2 2.24 27 .28 45 95 ( 52) 2 2.24 7 .28 35 95 ( 63) 2 2.24 28 .28 25 95 ( 73) 24 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 2 2.24 8 .28 10 95 ( 89) 2 2.24 29 .28 30 100 ( 70) 2 2.24 14 .28 20 100 ( 80) 2 2.24 30 .28 60 100 ( 40) 2 2.24 15 .28 30 100 ( 70) 2 2.24 16 .28 25 100 ( 75) 2 2.24 9 .28 40 100 ( 60) 2 2.24 10 .28 15 100 ( 85) 2 2.24 11 .28 15 85 ( 82) 25 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB . DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 2 2.24 17 .28 20 90 ( 77) 2 2.24 20 .28 15 90 ( 83) 2 2.24 12 .28 50 95 ( 47) 2 2.24 18 .28 35 97 ( 63) 2 2.24 24 .28 50 98 ( 48) 2 2.24 19 .28 35 98 ( 64) 2 2.24 22 .28 95 92 ( 0) 3 4.48 1 .28 0 80 (100) 3 4.48 2 .28 50 95 ( 47) 26 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 3 4.48 3 .28 85 95 ( 10) 3 4.48 4 .28 70 95 ( 26) 3 4.48 5 .28 90 95 ( 5) 3 4.48 13 .28 55 85 ( 35) 3 4.48 6 .28 90 95 ( 5) 4 2.24 1 .28 30 40 5 95 ( 25) ( 94) 4 2.24 2 .28 30 70 10 95 ( 57) ( 89) 4 2.24 3 .28 95 90 5 95 ( 0) ( 94) 4 2.24 4 .28 70 80 15 80 ( 12) ( 81) 27 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANT I- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 4 2.24 5 .28 80 55 45 85 ( 0) ( 47) 4 2.24 13 .28 40 55 35 90 ( 27) ( 61) 4 2.24 6 .28 80 75 5 95 ( 0) ( 94) 5 .07 1 .28 95 100 90 100 ( 5) ( 10) 5 .14 1 .28 65 50 100 100 (0) (0) 5 .07 2 .28 100 100 90 95 (0) (5) 5 .14 2 .28 55 55 85 95 ( 0) ( 10) 5 .07 3 .28 50 90 95 95 ( 44) ( 0) 5 .14 3 .28 40 75 95 95 ( 46) ( 0) 28 EP 0 304 409 At Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 5 .07 4 .28 90 65 95 95 (0) (0) 5 .14 4 .28 70 60 95 95 (0) (0) 5 .07 5 .28 95 80 95 90 (0) (0) 5 .14 5 .28 65 60 95 85 (0) (0) 5 .07 13 .28 85 80 35 85 ( 0) ( 58) 5 .14 13 .28 45 45 55 90 ( 0) ( 38) 5 .07 6 .28 90 95 95 95 (5) (0) 5 .14 6 .28 75 90 95 95 ( 16) ( 0) 5 .07 27 .28 95 100 75 90 ( 5) ( 16) 29 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 5 .14 27 .28 60 50 95 95 (0) (0) 5 .07 7 .28 95 100 95 90 (5) (0) 5 .14 7 .28 65 50 95 95 (0) (0) 5 .07 28 .28 100 100 95 90 (0) (0) 5 .14 28 .28 20 50 95 95 ( 60) ( 0) 5 .07 8 .28 100 95 95 90 (0) (0) 5 .14 8 .28 60 80 90 95 ( 25) ( 5) 5 .07 29 .28 100 95 95 95 (0) (0) 5 .14 29 .28 85 85 95 95 (0) (0) 30 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 5 .07 14 .28 90 95 95 95 (5) (0) 5 .14 14 .28 65 75 95 95 ( 13) ( 0) 5 .07 30 .28 95 95 95 95 (0) (0) 5 .14 30 .28 40 75 95 95 ( 46) ( 0) 5 .07 15 .28 100 95 95 95 (0) (0) 5 .14 15 .28 75 75 95 95 (0) (0) 5 .07 16 .28 100 95 95 95 (0) (0) 5 .14 16 .28 70 85 95 95 ( 17) ( 0) 5 .07 9 .28 100 100 95 95 (0) (0) 31 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 5 .14 9 .28 65 70 95 95 (7) (0) 5 .07 10 .28 95 100 85 95 ( 5) ( 10) 5 .14 10 .28 55 50 75 95 ( 0) ( 21) 5 .07 11 .28 100 95 30 95 ( 0) ( 68) 5 .14 11 .28 30 50 95 85 ( 40) ( 0) 5 .07 17 .28 100 100 70 100 ( 0) ( 30) 5 .14 17 .28 25 70 85 90 ( 64) ( 5) 5 .07 20 .28 100 100 90 100 ( 0) ( 10) 5 .14 20 .28 65 70 100 90 (7) (0) 32 EP 0 304 409 A1 Table 2 (continued) % PLANT INHIBITION AND % SAFENING EFFECT ( ) ANTI- HERB. DOTE Sorghum Wheat Rice Soybean Corn NO. RATE NO. RATE W WO W WO W WO W WO W WO 5 .07 12 .28 95 95 65 95 ( 0) ( 31) 5 .14 12 .28 15 80 70 95 ( 81) ( 26) Example 40 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 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 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 the test. Plant response was observed about three weeks after initial treatment. Results are reported in Table 3. 33 o o o i—i o r—i m o inm T—r—tI o o o o o o Oo inm Oo r~-r-» w^— > ~cf- o o o o o r—h * i/iIT! i—Hi 1/1m m in w cn ^ CT\ w -3" v£)*-0 vO -3" CMcm Oo in CMcm ONon CM 00 CNCM 00 I —I I —I I— III I —I 1—4 • VO m m inmoo o o cn r- \ as i — ^ ^ asOS \@> oO <~-s oO //— —@> o oa o i-i o i—ih min i—i1—1 min min m o inm asOl ^vv oiOl ^—->@ ' ooCO "— ^' oO v—•' ascr.OS ^v—w ^ i—ii—l CM /—v CO ' — s o o\as CO o v—< — ' o S— "s in in v—' OIVJv ' in in min o o asa\ as ^——. as s-^ o /— \* o o od r-ii—i i-Hh m i—i—i •' inm i-i i-i-i CM in in min inm inm oo ^ oo v —-j •* r-i—r~ ' cp,asen wv— ' ctnv_/ctnon v_>v_ ' vo vo •<)• vo vo l t-hi CO CO co CO CO CO 1 CMI vo vo vovO -ct ) vo! voVO vovO vovO VOvO vovO 35 U-5 in as /— > a\ ^ o o in min OA O O O CM CM CM - in in asOA <— asOA .—n-—n i—i vo CM ^CM m o vo cooocococoooooco co co coCO ooOO o o CM CM vOvOvOCMCMCMvOvOVO VO CM CM CM VO VO oococor-r-r^inu")oo co r- r-r^- r-» in in OO CO OO vOVO vO vOVO vOvOvOvOvOvOvOvOvO vO vO vO vO voVO vo 36 o o o /—A O / \ O /-A O /—/""A \ O <—1 O n in I-HrH Oo o in o v ' O v—/ OA v_/ Oo v—v— '' rH rH O O O CM CM o o o ^-n O O ^> oO <-a' — v rH rH in rH m I-HH If)if) CM m in in OA OA v —' OA v— ' vo-d-vovo-a-vovo-a-vo vo -a- vo vo o- mcMOAincMOAincMoa in cm oa in cm CM CO CM CO CM ooooooooo o o o o o CMCMCMCMCMCMCMCMCM CM CM CM CM CM vOVOvOvOvOvOvOvOvo vO vo VO vo vO 37 —@ ' • "— ' ' ' ' — • ' 1 * l r i * , f % r—I O i—I O i— I O i—I O i— < O o o o o o O v—' ow o v_ / ow o w r- 1 rH rH r-" I i-H 4-1 0) X u O O 3: CN CO O CO /—a o 3: oa •h on m o o o m OA /—a O f~\ CD s-~> O /—a OA /~\ m i— i o t— 1 o I—i in o o o o m in OA v_ ' O v—' O W OA a—' CAW f— I rH AOao ao i —' i —i t —t ! —i on CO CM CN CAJ CO CN rH rH rH CAJ o o o i ^ O <—a O /-a o -~a IO rH O rH O rH O ooooooooI O O O —' O av O a—' O v— ' O vj O i a —'' oO a—/v— ' oO a—s —' oO 1— ' r-ir^t—lr-tr-^^r-~iT—^I rH i—t rH LnooomLOLnoLnoooLnLnmo) LD lO O —> OA ''—A O ' — ^ O /~"A O •'—A OAv OA /"^./-^. OA ' — \n O **""A**""a 3 inrHinrHOrHO LO AO OrHinO rH m CMCN oinoooomini o in in —/ oiavOlAV oawCAW ow ow oawV w r-wr- v— OAWOA w OAWOA w rH i-H AOAO-*AOAO- cocococooooo) o o o CMI COCMCMCMCOCOCOCMCO CM CM CM CO) CO CO CM CM ' — 1i rH i —Ii CAJCM1 CNCM CMCAJCN rH T-^ i—t rH T— 39 ld o oo o /-A OA^~. OA <^ O /— v o o i—i o o r-rH < oO 4-1 0) x u O O O 3= 0- w ow ow O w 1—t l-H 1—I CU O C\( 00 /-> o o r—• I —I \0 u0 CM oooinooooooooinooooooo o o o CD / — \a OA / — a% OA /—a O / — av O /"a O /-a O /—a Oo /~a/""a oO /~a/""a rH O O O irHO —' O rHQ rHOrHrHo O Hrn in Hrt mU1 rHrHOr-io O ooomoooininocoinoooininoo m m o CD A—/w OA A_/a_/ OA Aw/a_/ O A/a—' Oo A—/a—/ Ooow Aw/ OA01 Avvv — ' QAOAoaw A/w Oo Aw/a—/a_ ' I-H rH rH rH rH cAjincoimcoi — cAji—oomCAjr-~oomr-- o o m rH rH rH rH aOaOAOaOaOaOaOaOaOAOaOaOaoaOaOaOaOAO AO AO AO Lnininininininininininininininininm m in in CNCA!Ca1CA1CMCA)CA1CA|i^JCAlOlCAlCMCAlCAlCAll^JCA) CAJ CAl I^J 41 o in o o /—A O /""*A OA / A O ^ \ O / A co cu 3s i—io i—i in o t—* o rti— *in in o i—ilo n in f—*o x u o in o o loin in in o 0 0 3: O a—' oaaw/ o^— ' O W' OAoa a— ' OlAVOia/ OAoaa— Aw/ / o - rjLiL| i—I—»1 i1 — '1 i1 — i1 i1 — " 0)u o CJJ 3: •rH-i Cwy 3: T33 Sh CO0 M O >>i inw 3 d3 co S-iH U co0 O 3-3: CQ O C3 3: w O cjJ 3= 4->-i O CO0 3= U 3S 3:3= S= r--OCOCOOOOCOI--OCOCOOOOCOo o o CO 33 Oo r-/~>/— a AO^-Aao^-a O0/-Aoo/-a OA^-Aoa^-a/—\ AOAO/-^ao /-^ oa^~aOA^~aoa^-a 00O0^-aoo^-a ^-a caCA-— > jw3:OAOinOACOCMCOOw3:OAOinOACOCMCOOOA CO CM CO O ooso OAor-oooor-OAOoo oo r~ oa o sj- o i—1i o o o o m in m o •* O3 3: Aw> CM A ' CM A ' I—I1—1 A^ r-i Aw*"@—> CM Aw/ Aw/ Aw/A/ co0 WaOaOaOaOaOaOaOaOAO AO AD AO HmE-iininmininininin mm in mmm in in in <•••••••• Cw m"-i W • I — I i —I i—* i —I 2S O 255 <=c oa ryjW AO AOaO AO AO AO AO^ ^AO AO^ E—iin m m m in in in in <•••••••• Cw CO03 • CwCwOCM O CM CM CM CM CM CM CM CM w z 42 iOOloOOOOOOOlOOOOOOo o o o i /—a-A OAoa <— Aa Oo /—A/—a OAoa /"A/"a Oo -—A-—a Oo oO /-^/"^ Oo Oo f~\'^ar—\ 1 O"3 O rHO O 1—1— IOI O Hi —t 1/1LO rHOi —' O rHQi — iO rH@—' — '> O ILOOOOLOOOOLOOOOLOOOOin o o o > a— S' OAoa "- —' Oo Av— ' Oo Aa — ' Oo Wa—/ OA A— 1 LOLniOlOLOLOLOLOLO LO LO IO LO UO LO LO LO - / — -a a CO / — Aa OA /—a N AO Ii — a OO i — Aa OA //—A — Aa COOO /—A/—a/-A OA /, — > OA / — Aa COor~-aAOA-cf- (AOaOaOaoaOaOaOaOaOaOaOaoaOaOaOaOAO AO AO AO )U0lOlOlOLOlOlOlolOlOlOlOLOlOuOloLO LO LO LO \ rH rH rH rHr-H rH'rHt-H't—I —t " 1— 1i rH rH iaOaOaOaOaOaOaOAOAOaOaOaoaOaOaOaOAO AO AO AO ILOlolOlOlOlOlOlolOlolOlOlOlOlOloLO LO LO UO JCaJCaICaICaICAJCAJCaJCaJCaJCaICNCaJCAJCAJCaJCaJCA] CAJ CAJ CAJ 43 CO o ' — > oa - —< oa /-^ o /-^ o ' — a o v oa /-a o ' — > o ^\ 0)3: @—'in o C h in h in n in O rn lO r— ♦ ot 0) s-iinininininininino J3 OA w ' OA ' — ' OA1— CAW OA W CAW CAW CAW Ow/ i— • o 3: 3: en O w 3: CO u -3 3: O 3: 3= 3= ooooomooinm O > oa /—v oo /-a ca^-v CO N OA /-a OJ A 00/^ oa/— A 3:mcO'-' f£J AO AO AO AO AO AO AO AO AO E-iiommmmmmmm < ...... b ;s WaOaOaOaOaOaOaOaOaO r-mmmmmmmmm <••••••••• DSOCAl CN CAI OJ CAI CAJ CN CAJ CAJ @-a 2; 44 o o o o OA -—A OA /~A O •'""A O /""A/—A O /""A O /' — »A O /^A o o i-i Oo Hi—i LOin it-i — ! Oo rtr-i LOm rHi—i Oo in m o inin o m o OA A ' OA A_V O AV OA A—- O A_/ CA A_V O A ' i—l rH l—lrH o oO -"A. rHr-l O oO O wA—' T"H ommoLninoino in in o m CO /~A LO / A OA /—\ r-»l~» A OA /—A/"A OA /—A CO ' VA OA /—/—AA A0C0OL0C0 AOaOaOaoaOaOaOaOAO AO A£> AO AO inininLoinLnLoinm m in in in rH i-H i—I I—i— i1 I—i— 1 l—lrH t-Ht— f i —1I ao ao ao AOao AOao ao AO AOao AOao lOlOlOlOlOlolOlOin m in in m CMCMCMCMCaJCaICMCMCN caI CAI CN CM 45 iOiOOOOOOOlO co oa /—v oa ^"a o / o /"a o /—a o /—a o -~a o ' a oa /"a (D 3=3 O O i-l<— O 3: 3: O 3= 3: LOLOOcnu-iLnrA-cNicoLOLnocoininrA-cMoo O 00 /—A I1 -—A OA /—A OA ^ASS OA /—A 00oo -—A-—a OA /"A COco -—A.—a lOin —A—a 3=r-~AOAOOooooAi~-o -d"aCT AO AO CO AO O AO COooo O m in o min o o @—i• o o o @—•— 3: aJavaJAV oajav(N AV cowC1AV aoa_-a£>a_, oo00 a—' wW ooa_/COW CAJWcajn— wA_x WAOAOACAOAOAO MaOaOaOaOaOvOaOaOaOMAO AO AO AO AO AO AO AO A£) £^LOuoininLninininioE-HinuoininLOinininuo iSOCAlOCAJCAJOAlCAJ^JCAlCAJCNCAJ CAJ OAl CAJ CA| CA| CAJ CA| CAJ d 2 46 o o o o o OA / —v O /@— > O / — a O <—< O /-a O //-"a — a O -/— —a O /-a O rHO rHOO rHO rHO r-Hr-l 1 LOin i—rHOi-H<0 O rHOrH O i—l1—1 OOOOOOLOOOo o LO o o CJ\ A_- O A—/ O A_/A ' OOA— A— ' Ooa— A ' coCO00 a—A—*w > oa—O A—w ' oa_/O A_/a_/ 1 — 1 1— 1 i1 — i1 i1 — i1 i1rH — iiI 1rH —i1 LocMinrA-oomcor- o O o loLO oo00 CM /—A aJ- ,—a OA /"/— A \ OA /"Ar- \ OA i—^/-^*\ OA /-a//"A — A OA /> — A v OA /—A/~-a/~A ocorA-cocor-ACOAOI-- oo co i r-Ar-~ co ao cm lo -J co r-Ar-r-» r-~r- -J->cr •^t-A^-Aj-^i-Ajr-.j-^t^r- I—IrHrHrHrHrHi—tr— i —ii — l irH — l irH —ii r—— 1i AO AO AO AO AO AO AO AO LOLOLOLOLOLOLOLOLO LO LO LO LO CNCNCMCNCNCMCNCNCM CM CN CM CMOA) CMCN 47 inooLTiOLnoooo ! o on ' — a o / a o on / — > a / a cn o o ' — A» Oo /—A 3 a rH o rn o o h in o h m "-ho 3 t—i— < Oo i imoomLommooc 1 3 ON W OW OW ON W ON w ON W ON w OW OW rH rH rH rH o 3: I O i 3: l t I 3: O 3= 3= § 3= LnLnoooinininLn O . ON / — < l~» /~N ON /— > CO /—-. OO'-A ON/ — CO -\N ON /—AN ^oooocnr-AAjcncNA-tv \or--i-ncocovOvOincN@) on ooinmooinoin 3: cnw cnw ct-' !—)•—/ co< — ' cnw -3-- — ' w w 1 • ] vO E-Hininunininininininu-) <;...... as 5 @ I O CN CN CN CN CN CN CN CN CN 1 25 48 -OOOlOOloOOloOOlOOlOOOlOLO O O LO oa /—a/"a o >@/"~a a o >-~a oa a o /—as oaON ' — - oO '.-"A a oO /"a a onOAoa /"a/—A LO rHO Hrl LO O rHO O rHrHO O rHrHO O O rH OOlOlOOOOOlOOlOlOOOOOlOo o o lo CJN A—-a —' Oo A—-a_/ OA AV qjAOA sA — - qaCA A-V Oo aA— ' oO awA_>a— / Oo a_>a—A—^ oacaQA 1A—— ' rHi-H irH —t irH —I1 rH OOlOlOlOOOOlOOOlOlOlOOOOlOOOO O LO o ro / — a oa •/ — a oa , — . lo f' — >a co <— a ACfA^-<)-<:j-<). I —Ii I —Ii — ll'I —ii — Ii rH— li rH —t, rH— I,1, rH —, •OvovOvOvOvovOvOvOvovOvOvOvovOvOvOVO AO VO AO -OlOlOlOlololOlOlolOlOlOlololOlOloLO LO LO LO rAlCMCMCMCMCMCMCMCMCMCNCMCMCMCMCMCMCM CM CM CM 49 O C O O 3 /—a -a O ---a--"a O 0/—>0/-~> O /-a @> LO Z3 <—r—to< O n inm 1 i 4J LOn LOlo Oo LOlo -a o>3a /— -. oaoa- ' — . o0/-a -—a r-r~ >a d 00oo vTvj i-ii—i uOm oo O AO OA 00 OA OO uOlO uOlO LOlo 00 w r- 1 A_, A_/ i——' r—I i—i"rH r-H AOO AO AO AO LOO LO LOlO LO ONN OAlCN OMOaI OAl 13 O LO oO D ' — v CJ\ / — s CJN O LO O LO 3N . CO / a ONON/ /— . 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