EP0032948A1 - Spirooxazolidines et thiazolidines comme antidotes herbicides - Google Patents

Spirooxazolidines et thiazolidines comme antidotes herbicides

Info

Publication number
EP0032948A1
EP0032948A1 EP80901619A EP80901619A EP0032948A1 EP 0032948 A1 EP0032948 A1 EP 0032948A1 EP 80901619 A EP80901619 A EP 80901619A EP 80901619 A EP80901619 A EP 80901619A EP 0032948 A1 EP0032948 A1 EP 0032948A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
oxygen
carbon atoms
sulfur
inclusive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP80901619A
Other languages
German (de)
English (en)
Inventor
Eugene G. Teach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stauffer Chemical Co
Original Assignee
Stauffer Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Publication of EP0032948A1 publication Critical patent/EP0032948A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions

Definitions

  • U.S. Patents 3,859,292 and 3,881,908 disclose cartain N-haloacyl(2-spirocycloaliphatic) oxazolidines useful as herbicides. There is no teaching or disclosure of herbicidal antidote activity. The monochloro acetyl compounds are specifically disclosed.
  • cultivated crop plants can be protected against injury by thiolcarbamate-type herbicides or haloacetanilide-type herbicides, and said injury can be decreased when the thiolcarbamate-type herbicides or haloacetanilide-type herbicides, each alone or in mixtures or combination with other compounds, are applied in a variety of ways.
  • the tolerance of the plants, to these herbicides can be substantially increased by adding to the soil an antidote compound of the type N-haloacyl oxazolidine or thiazolidine substituted in the 2-position with the spiro cyclohexyl group.
  • the present invention also includes a two-part herbicide system comprising a first-part of one or more thiolcarbamate herbicides or haloacetanilide herbicides and a second-part of an effective antidote compound therefore, said antidote compounds corresponding to the following formula
  • X oxygen or sulfur
  • R is lower haloalkyl having 1 to 6 carbon atoms, inclusive, and halo is at least one of chlorine, fluorine or bromine
  • R 1 is hydrogen or lower alkyl having 1 to 6 carbon atoms, inclusive
  • R 2 is hydrogen or phenyl.
  • thiolcarbamate herbicides the present invention includes compounds of the formula
  • R 3 is selected from the group consisting of alkyl 1-6 carbon atoms and alkenyl 2-6 carbon atoms;
  • R 4 is selected from the group consisting of alkyl 1-6 carbon atoms, alkenyl 2-6 carbon atoms, cyclohexyl, phenyl and benzyl; or
  • R 3 and R 4 taken together with the nitrogen atom to which they are attached form an alkylene ring substituted and unsubstituted 2-9 carbon atoms;
  • R 5 is selected from the group consisting of alkyl 1-6 carbon atoms, haloalkyl 1-6 carbon atoms; alkenylene ring 5-10 carbon atoms, phenyl, substituted phenyl, benzyl and substituted benzyl.
  • haloacetanilide herbicides the present invention includes compounds of the formula
  • X, Y and Z are independently selected from the group consisting of hydrogen, alkyl 1-4 carbon atoms and alkoxy 1-4 carbon atoms;
  • R 6 is selected from the group consisting of alkyl 1-6 carbon atoms, alleylalkoxy 2-10 carbon atoms, acetoxy 2-6 carbon atoms and dioxane; and R 7 is selected from the group consisting of chlorine, bromine and iodine.
  • the unacylated oxazolidine and thiazolidine intermediates for preparing the subject compounds can be synthesized conveniently by reacting substituted amino alkanols or mercaptans with a suitable aldehyde or with ketone.
  • a suitable aldehyde or with ketone A substantial list of these compounds is given in the review article "THE OXAZOLIDINES", E. D. Bergman, Chem. Rev., 53; 309 (1953).
  • the amino alcohol or mercaptan and the ketone or aldehyde are heated together in an inert hydrocarbon solvent, and by-product water is separated from the condensed azeotropic mixture of hydrocarbon and water in a Dean-Stark water separator.
  • the solvent is then evaporated and the product purified by distillation under reduced pressure.
  • Suitable reaction solvents are water immiscible hydrocarbons such as benzene, toluene and the like.
  • a preferred solvent is benzene because of its low boiling point.
  • the N-haloacyl oxazolidines and thiazolidines of this invention can be synthesized by reacting the corresponding intermediate oxazolidine or thiazoli'dine. with the desired haloalkylcarbonyl chloride (also described as a haloacyl chloride) at a temperature in the range of about 50°C. in the presence of an acid-acceptor.
  • the reaction is preferably carried out in an organic solvent, inert under the conditions of the reaction.
  • the acid-acceptor is generally a basic substance which forms water soluble by-products easily separable from the main reaction product.
  • the acid-acceptor can sometimes be an alkali metal salt of a weak acid, such as sodium or potassium carbonate, or acetate, it is preferable to use a tertiary amine.
  • Useful and common tertiary amines are, for example, triethylamine and pyridine; frequently the crystalline hydrohalide formed as a by-product is insoluble in the reaction solvent and easily removed by filtration.
  • the product When a hydrocarbon solvent is used the product is frequently completely soluble in the reaction solvent and workup is conveniently carried out by filtering the by-product amine hydrohalide, washing the remaining organic phase with water, and removing the reaction solvent by evaporation or distillation. Thereafter, the product can usually be purified by conventional distillation procedures including ones at subatmospheric pressure.
  • the herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with little or no discrimination between desirable and undesirable species.
  • the method of controlling vegetation comprises applying an herbicidally effective amount of the herein described herbicidal compounds to the area or plant locus where control is desired.
  • An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like.
  • plants it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.
  • herbicide antidote or antidotal amount is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the seed, soil or furrow in which a crop is planted. Hitherto, there have been no systems employing the antidotes of the present invention which have been satisfactory for this purpose.
  • the compounds of this invention may interfere with the normal herbicidal action of the thiolcarbamate-type or haloacetanilide-type or other herbicides to render them selective in their action.
  • the observation noted with the presence of the herein described antidote is a decrease in phytotoxicity with respect to various crops. The phytotoxicity is otherwise observed when various thiolcarbamate or haloacetanilide herbicides are used for weed control.
  • Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiolcarbamate or haloacetanilide against weed species present with the crop, with the accompanying selective. decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.
  • Corn Seed Treatment Test Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five- gallon cement mixer where the soil was mixed as the herbicides were applied using a predetermined amount of a stock solution containing 936 milligrams of 75.5% active ingredient to 100 milliliters of water. One milliliter of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One milliliter of stock solution contained 7 milligrams of herbicide which equals 1 pound per acre when applied to the soil in the flats. After the herbicide incorporation, the soil was placed back into the flats.
  • Seeds were treated by either (1) placing 50 milligrams of the antidote compound with 10 grams of corn seed in a suitable container and shaking them until the seeds were uniformly covered with the compound; or (2) preparing a stock solution by dissolving 50 milligrams of the antidote compound in 5 milliliters of acetone, then using 0.5 milliliters of the solution to treat 10 grams of corn seed (0.05% w/w).
  • Antidote compounds were also applied a liquid slurries and powders or dusts. In some cases, acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.
  • the herbicide was applied alone, in combination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity.
  • the untreated adjacent row was employed to observe any beneficial lateral movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control.
  • compound number 1 reduced injury to corn from 80 percent to 30 percent; and compound number 2 reduced injury to corn from about 80 percent to 20 percent.
  • compound number 3 was used at 5 lb/A preplant incorporated with EPTC at 1/2 lb/A preplant incorporated, barley was reduced in injury from 50 percent to 10 percent.
  • compound number 3 was used at 5 lb/A preplant incorporated and EPTC at 5 lb/A preplant incorporated, injury to oil seed rape was reduced from 75 percent to 30 percent.
  • the herbicide and the antidote of each test group were incorporated into the soil as a tank mix using a five-gallon rotary mixer.
  • Control flats contained crops treated with herbicides only at the various rates and method of application.
  • the treated crops initially screened for reduced herbicidal injury were milo (Ml), wheat (Wh), cotton (Ct), rice (Rc), barley (Ba), corn (Cn) and soybeans (Soy). Those compounds which showed substantial crop injury reduction were further tested at reduced rates.
  • VERNAM ® S-propyl N,N-dipropylthiocarbamate as described in U.S. Patent No. 2, 913,324
  • VERNAM ® vernolate - S-propyl dipropyl thiolcarbamate
  • the antidotes were applied at 5 lb/A preemergence surface tank mixed with the herbicide (PES-TM); 0.5% seed treatment (ST); 5 lb/A in-furrow (IF) and 5 lb/A preplant incorporated tank-mixed with the herbicide (PPI-TM).
  • the herbicides were applied preemergence surface or preplant incorporated.
  • the soil was transferred from the mixer back into the flat where it was prepared for seeding.
  • the initial step in planting was to remove a one pint sample of soil from each flat to be retained and used to cover the seeds after planting.
  • the soil was then leveled and rows 1/4 inch deep were made in each flat.
  • the flats were seeded with the crops Milo - Ml [Sorghum vulgare] Wheat - Wh [Triticum aestivum] Cotton - Ct [Gossypium hirsutum] Barley - Ba [Hordeium vulgare (L.)] Soybeans - Soy [Glycine max]
  • the flats were placed on greenhouse benches where the temperature was maintained between 70-90°F.
  • the soil was watered by sprinkling to assure good plant growth.
  • the percent injury was determined by a comparison with the control flats not treated with the antidote compounds and with blank flats with neither herbicide or antidote additive.
  • the antidote compounds and compositions of the present invention can be used in any convenient form.
  • the antidote compounds can be formulated into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form.
  • a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil.
  • the crop seed itself can be treated with a non- phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide.
  • the addition of the antidote compound does not effect the herbicidal activity of the herbicides except to render the activity selective with respect to beneficial crops.
  • the amount of antidote compound present can range between about 0.01 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non- phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein.

Landscapes

  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Des N-haloacyle oxazolidines ou thiazolidines substituees en position 2 avec le groupe spiro cyclohexyle inclus dans un systeme herbicide a deux parties comprenant une premiere partie d'un ou plusieurs herbicides thiolcarbamate ou herbicides haloacetanilide et une seconde partie d'un compose antidote d'oxazolidine ou thiazolidine effectif de formule: (FORMULE) ou X est l'oxygene ou le soufre, R est un haloalkyle inferieur, R1 est l'hydrogene ou un alkyle inferieur et R2 est l'hydrogene ou le phenyl; methodes d'utilisation.
EP80901619A 1979-08-03 1981-02-24 Spirooxazolidines et thiazolidines comme antidotes herbicides Withdrawn EP0032948A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6363579A 1979-08-03 1979-08-03
US63635 1979-08-03

Publications (1)

Publication Number Publication Date
EP0032948A1 true EP0032948A1 (fr) 1981-08-05

Family

ID=22050511

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80901619A Withdrawn EP0032948A1 (fr) 1979-08-03 1981-02-24 Spirooxazolidines et thiazolidines comme antidotes herbicides

Country Status (8)

Country Link
EP (1) EP0032948A1 (fr)
ES (1) ES493981A0 (fr)
IL (1) IL60745A0 (fr)
IT (1) IT8049414A0 (fr)
NZ (1) NZ194503A (fr)
PT (1) PT71633B (fr)
WO (1) WO1981000406A1 (fr)
ZA (1) ZA804735B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2164934B (en) * 1984-09-29 1988-10-05 Stc Plc Optical fibres
US5225570A (en) * 1987-08-13 1993-07-06 Monsanto Company 5-heterocyclic-substituted oxazolidine dihaloacetamides
US5328635A (en) * 1990-12-04 1994-07-12 Angus Chemical Company Iminoalcohol-oxazolidine mixtures and their use
US5527762A (en) * 1990-12-12 1996-06-18 Zeneca Limited Antidoting herbicidal 3-isoxazolidinone compounds
US5395816A (en) * 1990-12-12 1995-03-07 Imperial Chemical Industries Plc Antidoting herbicidal 3-ixoxazolidinone compounds

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3185720A (en) * 1962-08-21 1965-05-25 Stauffer Chemical Co Asymmetric thiolcarbamates
US3442945A (en) * 1967-05-22 1969-05-06 Monsanto Co Phytotoxic alpha-halo-acetanilides
US3989503A (en) * 1972-10-13 1976-11-02 Stauffer Chemical Company Herbicidal antidote compositions with substituted oxazolidines and thiazolidines
US3859292A (en) * 1972-08-15 1975-01-07 Scm Corp N-haloacyl (2-spirocycloaliphatic) oxazolidines
US3881908A (en) * 1972-08-15 1975-05-06 Scm Corp Herbicidal N-haloacyl (2-spirocycloaliphatic) oxazolidines
US4124372A (en) * 1973-05-02 1978-11-07 Stauffer Chemical Company Herbicidal antidote compositions with substituted oxazolidines and thiazolidines
US3959304A (en) * 1974-07-01 1976-05-25 Stauffer Chemical Company Certain 3-haloacyl-2,2,5-trimethyl-oxazolidines
US4072688A (en) * 1975-02-14 1978-02-07 Stauffer Chemical Company Haloacyl and thiohaloacyl aryl-substituted oxazolidines and thiazolidines-herbicidal antidotes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8100406A1 *

Also Published As

Publication number Publication date
ZA804735B (en) 1981-06-24
ES8106303A1 (es) 1981-08-01
PT71633B (en) 1981-06-11
WO1981000406A1 (fr) 1981-02-19
IT8049414A0 (it) 1980-08-04
ES493981A0 (es) 1981-08-01
IL60745A0 (en) 1980-10-26
PT71633A (en) 1980-09-01
NZ194503A (en) 1983-03-15

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Legal Events

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19810401

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RIN1 Information on inventor provided before grant (corrected)

Inventor name: TEACH, EUGENE G.