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5-Heterocyclic-Substituted Oxazolidine Haloacetamides

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5-Heterocyclic-Substituted Oxazolidine Haloacetamides ~" ' 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.
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