Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P15/00—Biocides for specific purposes not provided for in groups A01P1/00 - A01P13/00
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

• Nitrogen is an essential element for plant health.
• bound nitrogen for plant nutrition can be present in the form of ammonium compounds or nitrates.
• the ammonium form of nitrogen is preferred because it is readily incorporated into plants.
• nitrate nitrogen must be reduced to ammonium by the plant before it can be used – an energetically costly process.
• Ammonium nitrogen, having a positive charge, is tightly bound to growing media.
• Nitrogen in the form of nitrate is negatively charged, water soluble, not tightly bound to growing media and is readily washed out.
• Ammonia-oxidizing bacteria of the genera Nitrosomonas and Nitrobacter oxidize ammonium nitrogen to nitrate nitrogen via nitrite nitrogen. This process is known as nitrification. The extent of nitrification is dependent on the temperature, type of growing medium, pH, moisture content and biological activity. The nitrification process leads to ammonium nitrogen loss and nitrate nitrogen creation. As much as half of applied nitrogen fertilizer is lost within a year, and an undesirable concentration of nitrate in the groundwater is promoted by this process.
• the inhibition of nitrification is particularly important, and is generally considered to consist in selective inhibition of the growth of the above-mentioned bacteria strains.
• the incorporation of certain chemical compounds in critical quantities into growing media are known to have a pronounced effect on nitrification – the conversion of reduced nitrogen such as ammonia or ammonium ions into higher oxidized forms, particularly into the nitrate form.
• Prevention of such nitrification in growing media is known to be beneficial and desirable from the economic and agronomic points of view since it enhances plant health, enhances crop yields, and lessens nitrate runoff.
• nitrification inhibitors including linoleic acid, a-linoleic acid, methyl-p- coumarate, methyl ferulate, MHPP, Karanjin, brachialacton, 2-chloro-6-trichloromethylpyridine (nitrapyrin), dicyandiamide, 3,4-dimethylpyrazole phosphate, 4-amino-1,2,4-triazole hydrochloride, 1-amido-2-thiourea, 2-amino-4-chloro-6-methylpyrimidine, 5-ethoxy-3- trichloromethyl-1,2,4-thiodiazole, 2-sulfanilamidethiazole, 3,5-dimethyltetrahydro-1,3,5- thiadiazine-2-thione (dazomet).
• Nitrification inhibition has been disclosed in the following publications: US 3,494,757 and US 3,635,690, German Laid Open Application DOS 2,745,833 and GB 1,592,516. See also U.S. 3,050,380 Goring; GB 970,663 Watkins; US 3,533,774 Nault; US 4,673,429 Rieber, et al; US 4,925,476 Wagner et al; US 2015/0052960 Makin et al; US 2017/0036969 Nave et al; US 2020/0352162 Cunningham et al; WO 2015/158853 Nave et al; WO 2020/002472 Cunningham et al; WO 2020/020765 Nesvadba et al; WO 2020/020777 Nesvadba et al.
• nitrification inhibitors lack traits that are beneficial to their users.
• dazomet is known to have a very non-specific action and attack non-target bacteria in growing media, especially in soil.
• Nitrification inhibition is also useful for lowering the production of nitrate in growing media – particularly in soil – thereby reducing the amount unwanted nitrate in groundwater.
• Methods of employing the compounds include applying to and/or incorporating into growing media (e.g., soil) an effective amount of nitrification-inhibiting alkynyl heterocycle.
• growing media e.g., soil
• Preferred compounds include an ethynyl-thiazole, an ethynyl-oxazole, an ethynyl-isoxazole, or mixtures thereof.
• growing medium and growing media are defined as materials in which plants grow.
• Exemplary growing media include, but are not limited to, soil, perlite, pumice, vermiculite, zeolite, compost, peat moss, coconut coir, sand, silt, clay, water, bark, sawdust, water, and limestone.
• Exemplary growing media may be outdoor-soil-based or hydroponic.
• alkyl refers to a C 1 – C 6 branched or unbranched group consisting of carbon and hydrogen atoms.
• Alkyl groups include for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, s-butyl, t-butyl and the like.
• alkoxy refers to a O-C 1 – C 6 group where the oxygen atom is connected to a C 1 – C 6 branched or unbranched alkyl group.
• Alkoxy groups include for example methoxy, ethoxy, propoxy, iso-propoxy, butoxy, iso-butoxy, sec-butoxy, tert-butoxy and the like.
• thioalkyl refers to a S-C 1 – C 6 group, branched or unbranched, where the sulfur atom is connected to a C 1 – C 6 alkyl group.
• Thioalkyl groups include for example thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl, thioisobutyl, thiosecbutyl, thiotertbutyl, and the like.
• cycloalkyl refers to a C3 – C6 group where the carbon atoms form a carbocyclic ring.
• Cycloalkyl groups include for example cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like.
• alkenyl refers to a C 2 – C 6 to a branched or unbranched group consisting of carbon and hydrogen atoms and having one or more double bonds between carbon atoms.
• Alkenyl groups include for example ethylene, propene, 1-butene, 2-butene, isobutene and the like.
• cycloalkenyl refers to a C 3 – C 6 where the carbon atoms for a carbocyclic ring and contain one or two double bonds.
• Cycloalkenyl groups include for example cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclopentadiene, 1,4-cyclohexadiene and the like.
• halo refers to halogen atoms such as F, Cl, Br, and I.
• haloalkyl refers to a C 1 – C 6 branched or unbranched alkyl group where one or more hydrogen atoms has been replaced with a halogen atom.
• Haloalkyl groups include for example fluoromethyl, difluoromethyl, trifluoromethyl, chloroethyl, bromoethyl, iodobutyl, dichloroethyl, and the like.
• haloalkoxy refers to a C 1 – C 6 group where the oxygen atom is connected to a C 1 – C 6 branched or unbranched alkyl group where one or more hydrogen atoms has been replaced with a halogen atom.
• Halolkoxy groups include for example trifluoromethoxy, difluoroethoxy, chloropropoxy, bromo-iso-propoxy, dibromobutoxy, and the like.
• haloalkenyl refers to a C 2 – C 6 to a branched or unbranched group consisting of carbon and hydrogen atoms where one or more hydrogen atoms has been replaced with a halogen atom and having one or more double bonds between carbon atoms.
• Haloalkenyl groups include for example 1-chloroethylene, 3,3-difluoropropene, 4-bromo-1-butene, and the like.
• N-oxide includes any compound which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides may be formed for example through oxidation of tertiary amines, such as pyridine, by hydrogen peroxide.
• salts and agriculturally acceptable salts include hydrofluorides, hydrochlorides, hydrobromides, hydroiodides, nitrates, hydrogensulfates, sulfates, dihydrogenphosphates, hydrogenphosphates, phosphates, carbonates, bicarbonates, oxalates, and C 1 – C 6 branched or unbranched alkanoates – such as formates, acetates, n-propionates, i-propionates, and the like.
• carrier includes a liquid or solid carrier.
• a carrier may include an organic or inorganic carrier.
• Exemplary liquid carriers include, but are not limited to: water; petroleum fractions or hydrocarbons, such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils, such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethyl hexyl stearate, n- butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono, di and polycarboxylic acids and the like; toluene;
• Exemplary solid carriers include, but are not limited to: silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, pyrophyllite clay, attapulgus clay, kieselguhr, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, cereal meal, tree bark meal, wood meal, nutshell meal, cellulose powders, and mixtures thereof.
• Fertilizers including but limited to, fertilizers comprising ammonia may be used as carriers.
• exemplary fertilizers comprise, but are not limited to, anhydrous ammonium, ammonium salts such as ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; organic ammonia sources, such as manure, biogas, worm castings, compost, seaweed or guano; urea-containing fertilizers such as, urea, formaldehyde urea, urea ammonium nitrate solution, urea sulfur, urea ammonium sulfate, or other urea-based fertilizers.
• surfactant or surfactants include, but are not limited to: the alkali metal salts, alkaline earth metal salts and ammonium salts of fatty acids or of aromatic sulfonic acids (e.g., lignosulfonic acids, phenolsulfonic acids, naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid); alkyl- and alkylarylsulfonates; alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates; salts of sulfated hexa-, hepta- and octadecanols; salts of fatty alcohol glycol ethers; condensates of sulfonated naphthalene and its derivatives with formaldehyde; condensates of naphthalen
• adjuvant includes agriculturally acceptable adjuvants.
• exemplary agriculturally acceptable adjuvants include, but are not limited to, antifreeze agents, antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, colorants, odorants, penetration aids, wetting agents, spreading agents, dispersing agents, thickening agents, freeze point depressants, antimicrobial agents, crop oil (concentrates), adhesives (for instance, for use in seed treatment formulations), surfactants, protective colloids, emulsifiers, tackifiers, and mixtures thereof.
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, crop oil concentrates (e.g., 85% mineral oil + 15% emulsifiers); nonylphenol ethoxylates; benzylcocoalkyldimethyl quaternary ammonium salts; blends of petroleum hydrocarbon, alkyl esters, organic acids, and anionic surfactants; C 9 -C 11 alkylpolyglycoside; phosphate alcohol ethoxylates; natural primary alcohol (C 12 -C 16 ) ethoxylate; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrates; emulsified methylated seed oils; tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO); tallow amine ethoxylates (e.g., 15 EO); and PEG(
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, thickening agents (i.e., thickeners).
• Exemplary thickeners include, but are not limited to, polysaccharides (e.g., xanthan gum), organic and inorganic sheet minerals, and mixtures thereof.
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifoam agents.
• Exemplary antifoam agents include, but are not limited to, silicone emulsions, long-chain alcohols, fatty acids, fatty acid salts, organofluorine compounds, and mixtures thereof.
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifreeze agents.
• Exemplary antifreeze agents include, but are not limited to ethylene glycol, propylene glycol, urea, glycerol, and mixtures thereof.
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, colorants.
• Exemplary colorants include, but are not limited to, the dyes known under the names Rhodamine B, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108, and mixtures thereof.
• Exemplary agriculturally acceptable adjuvants include, but are not limited to, adhesives.
• Exemplary adhesives include, but are not limited to, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, and mixtures thereof.
• an agriculturally effective amount of compound is an amount of compound that produces a measurable effect on one or more of: ammonium nitrogen, nitrification inhibition, nitrate formation, increased plant health, increased plant growth, increased plant or crop yield, bacteria of the genera Nitrosomonas and Nitrobacter.
• compound or “compounds” comprise chemicals defined by molecular structure formulas and/or chemical names as well as their tautomers, salts, N-oxides, and stereoisomers.
• Compounds described herein are nitrification inhibitors.
• One or more compounds described herein may be incorporated into a composition comprising other ingredients such as carriers, surfactants, and adjuvants.
• the composition optionally may include a source of ammonia.
• Sources of ammonia include anhydrous ammonia, urea, urea-ammonium nitrate, and manure.
• the compound or composition may be mixed directly with the ammonia source.
• the mixture of compound or composition and ammonia source may be applied directly to a growing medium, such as soil.
• the compound or composition and the ammonia source may be applied separately to the growing medium, such as soil.
• the compound or composition and the ammonia source may be applied separately and simultaneously.
• a compound or composition may be applied before planting or after planting.
• a compound or composition may be applied pre- emergence or post-emergence.
• a nitrification inhibiting composition or method provided herein comprises one or more of the following compounds and agriculturally acceptable salts, tautomers, stereoisomers, and N-oxides thereof: R 1 R 1 R 1 N O N R N S 4 N R3 R2 R3 R2 R 3 R 2 Formula I Formula II Formula III, where R 1 -R 4 are independently H, ethynyl, trimethylsilyl-ethynyl, C 1 – C 6 alkoxy, C 1 – C 6 thioalkyl, C 1 – C 6 alkyl, C 3 – C 6 cycloalkyl, C 1 – C 6 alkenyl, C 3 – C 6 cycloalkenyl, C 1 – C 6 haloalkyl, C 1 – C 6 haloalkenyl, C 1 – C 6 haloal
• R 11 and R 14 are independently C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 11 and R 14 is C ⁇ C or C ⁇ C-TMS.
• R 12 – R 13 are H.
• R 21 and R 24 are independently C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 21 and R 24 is C ⁇ C or C ⁇ C-TMS.
• R 22 , R 23 , and R 25 are H.
• R 32 R N 33 R 31 N R34 Formula VI where R 31 and R 33 are independently C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 31 and R 33 is C ⁇ C or C ⁇ C-TMS.
• R32, and R34 are H.
• R 42 N R 43 R 41 N R44 Formula VII where R 41 and R 43 are independently C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 41 and R 43 is C ⁇ C or C ⁇ C-TMS.
• R 42 and R 44 are H.
• R 51 R 52 Formula VIII, where R 51 , R 52 , and R 53 are independently H, C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 51 , R 52 , or R 53 is C ⁇ C or C ⁇ C-TMS.
• R 63 R 61 R 62 Formula IX where R 61 , R 62 , and R 63 are independently H, C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 61 , R 62 , or R 63 is C ⁇ C or C ⁇ C-TMS.
• R 71 N N R 72 R 74 R 73 Formula X where R 71 , R 72 , R 73 , and R 74 are independently H, C ⁇ C, C ⁇ C-TMS, C ⁇ CMe, OEt, OMe, OCF 3 , OH, I, Cl, F, methyl, ethyl, cyclopropyl, propyl, SMe, CN, benzyl, acetyl, vinyl, wherein at least one of R 71 , R 72 , R 73 , or R 74 is C ⁇ C or C ⁇ C-TMS.
• a nitrification inhibiting compound, composition, or method provided herein comprises a compound selected from the group consisting of Si N O N O , , O O Si N O N O , , O O N N N S , S O , S , S N S , , S N ⁇ y E / o N, PO ⁇ I — ( o / ⁇ ⁇ N ⁇ H ⁇ V i A / ⁇ , , , , , , , , , S N O N O O O N N , , , , H Cl , , , , , , , , , , , , Sa , H N" UL , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,
• a nitrification inhibiting compound, composition, or method provided herein comprises a compound selected from the group consisting of S N O N O N , , , , and agriculturally acceptable salts, N-oxides, stereoisomers, and tautomers thereof.
• a nitrification inhibiting compound is selected from the group consisting of compounds in Table 1, and agriculturally acceptable salts, N-oxides, stereoisomers, and tautomers thereof.
• Application of Nitrification Inhibitor Compounds to Soil In certain aspects provided herein one or more nitrification inhibitor compounds or compositions are mixed with a source of ammonia.
• Sources of ammonia include, but are not limited to, anhydrous ammonium, ammonium salts, such as ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; organic ammonia sources, such as manure, biogas, worm castings, compost, seaweed or guano; urea-containing fertilizers such as, urea, formaldehyde urea, urea ammonium nitrate solution, urea sulfur, urea ammonium sulfate, or other urea-based fertilizers.
• anhydrous ammonium such as ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate
• organic ammonia sources such as manure, biogas, worm castings, compost, seaweed or guano
• one or more of the nitrification inhibitor compounds or compositions are mixed with anhydrous ammonia, which is then injected into the soil.
• the compound or composition is injected separately into the growing medium at the time of anhydrous ammonia application.
• the amount of compound or composition present in the anhydrous ammonia mixture, or directly injected, may be adjusted so that an agriculturally effective amount of the nitrification-inhibiting compound or composition is spread.
• the nitrification inhibitor compound or composition is mixed with fertilizers such as urea-ammonium nitrate solution to form a urea-ammonium nitrate nitrification-inhibitor mixture.
• mixtures may also include other ingredients such as herbicides, insecticides, fungicides, and safeners.
• Such mixtures may be applied at rates of from about 10 to about 70 gallons per acre depending on the fertilizer strength and concentration as well as the target amount of nitrogen per acre.
• the amount of compound or composition present in the treated mixture may be adjusted so that an agriculturally effective amount of the compound or composition is spread.
• the nitrification compound or composition is impregnated on dry urea. The amount of compound or composition impregnated will depend upon the application rate of the urea. For example, urea may be spread at a rate of from about 200 to about 700 pounds per acre.
• An amount of compound or composition may be impregnated on dry urea so that the compound or composition is spread at an agriculturally effective amount.
• the compound or composition is spread as part of a manure slurry mixture.
• the compound or composition may be mixed with manure prior to application or may be separately applied.
• the amount of compound or composition present in a manure slurry may be adjusted so that an agriculturally effective amount of compound or composition is spread.
• a compound or composition may be applied to a growing medium at a rate of from about 50 grams per acre to about 4 kilograms per acre.
• a compound may be applied to a growing medium at the following rates: 50-60 grams/acre; 60-70 grams/acre; 70-80 grams/acre; 80-90 grams/acre; 90-100 grams/acre; 100-120 grams/acre; 120-140 grams/acre; 140-160 grams/acre; 160-180 grams/acre; 180-200 grams/acre; 200-225 grams/acre; 225-250 grams/acre; 250-275 grams/acre; 275-300 grams/acre; 300-350 grams/acre; 350-400 grams/acre; 400-450 grams/acre; 450-500 grams/acre; 500-550 grams/acre; 550-600 grams/acre; 600-650 grams/acre; 650-700 grams/acre; 700-750 grams/acre; 750-800 grams/acre; 800-850 grams/acre; 850-900 grams/acre; 900-950 grams/acre; 950-1000 grams/acre; 1.0-1.1 kilograms/acre; 1.1-1.2 kilograms/acre; 1.2-1.3 kilograms/acre; 1.3-1.4 kilograms/acre;
• reaction mixture was cooled to RT, EtOAc (30 mL) was added, filtered through a pad of celite, the filtrate was washed with brine (20 mL), dried over anhydrous Na 2 SO 4 , filtered, and concentrated under reduced pressure.
• reaction mixture was cooled to RT, EtOAc (30 mL) was added, filtered through a pad of celite, the filtrate was washed with brine (20 mL), dried over anhydrous Na 2 SO 4 , filtered, and concentrated under reduced pressure.
• reaction mixture was cooled to RT, EtOAc (150 mL) was added and filtered through pad of celite and filtrate was washed with brine (20 mL), dried over anhydrous Na 2 SO 4 , filtered, and concentrated under reduced pressure.
• Furan-2-carbaldehyde SM-C (0.5 g, 6.41 mmol) was then added into the reaction mixture at -78 °C and stirred for 5h at RT. After completion of the reaction, the reaction mixture was quenched with aq. NH 4 Cl (10 mL) and extracted with EtOAc. The combined organic layers were dried over Na 2 SO 4 , filtered, and concentrated under reduced pressure.
• the vial was placed in a heating block that was warmed to 80 oC and the solution was stirred for 20 h. After the reaction time, the vial was opened to air and aqueous Na 2 CO 3 was added (4 mL). The crude product was extracted with CH 2 Cl 2 and purified by flash chromatography on silica gel.
• General Procedure F To a 20 mL vial, sodium alkoxide (1.0 equiv.) was charged. Then a solution of aryl halide (1.0 equiv.) in THF (0.2 M concentration of substrate) was added. The vial was placed in a heating block that was warmed to 50 oC and the solution was stirred for 20 h.
• the contents were sealed and degassed with nitrogen and the overall reaction concentration was 0.2M. With stirring, ethynyltrimethylsilane (2 equiv) was added neat and the contents were heated to 60 o C overnight for 18 hours. The reaction was quenched with AcOH (10 equiv), the product mass was observed by LCMS. The contents were diluted with EtOAc and partitioned between 2.5 M KHCO3 (2 x) and brine then dried over MgSO 4 . The contents were condensed by rotoary evaporation and the residue was purified by silica-gel chromatography eluting with hexanes/EtOAc 10-100% over 10 minutes to yield the product.
• Biological Testing Compound Preparation Compounds were dissolved in DMSO at 0.1 mM concentrations.
• Soil Slurry Preparation Two different soils were sourced from Kalamazoo, Michigan (loamy fine sand) and Windfall, Indiana (clay loam). After collection soils were sieved at 2 mm and stored at 4 °C for no more than 6 months.
• the slurry is prepared by weighing out 143 grams of field moist soil per liter of nitrification media with a chlorate block (0.8 ⁇ M K 2 HPO 4 ; 0.1 ⁇ M KH 2 PO 4 ; 0.5 ⁇ M(NH 4 ) 2 SO 4 ; 10 ⁇ M NaClO 3 ) and stirring it in a Pyrex dish for 5 minutes.
• Experimental Approach While stirring, 900 ⁇ L of slurry was pipetted into a 96 deep well plate. After slurry addition, 9 ⁇ L of 0.1 mM stock solution of a compound or solvent control (i.e., DMSO) was immediately added to the designated well to bring the final concentration to 0.1 ⁇ M.
• a compound or solvent control i.e., DMSO
• a sealing mat was placed on top of the plate and mixed by inverting the plates three times. Plates were incubated for 48 hours at 28°C while shaking sideways at 225 rpm. After 48 hours the plate was spun down at 3,000 rpm for 15 minutes and the supernatant was analyzed for nitrite concentrations using the colorimetric Griess assay. Nitrification rates were determined by the total amount of nitrite formed over the incubation period. Nitrification inhibition was determined by normalizing the nitrification rate by the DMSO control. The relative inhibition of tested compounds was additionally normalized to the reference nitrification inhibitor nitrapyrin. Results are shown in Table 3. Table 3 Inhibition of Soil Nitrification.

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