NZ500579A - Use of hydroxylamine derivatives, and method and preparations for increasing the tolerance of field crops against weather stresses - Google Patents
Use of hydroxylamine derivatives, and method and preparations for increasing the tolerance of field crops against weather stressesInfo
- Publication number
- NZ500579A NZ500579A NZ500579A NZ50057998A NZ500579A NZ 500579 A NZ500579 A NZ 500579A NZ 500579 A NZ500579 A NZ 500579A NZ 50057998 A NZ50057998 A NZ 50057998A NZ 500579 A NZ500579 A NZ 500579A
- Authority
- NZ
- New Zealand
- Prior art keywords
- general formula
- substituted
- hydroxy
- tolerance
- plant
- Prior art date
Links
- 150000002443 hydroxylamines Chemical class 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 29
- 230000001965 increasing effect Effects 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title description 17
- 244000037666 field crops Species 0.000 title description 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 125000005843 halogen group Chemical group 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 17
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000003277 amino group Chemical group 0.000 claims abstract description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical group O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008030 elimination Effects 0.000 claims abstract description 5
- 238000003379 elimination reaction Methods 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 83
- 239000013543 active substance Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 25
- 238000005507 spraying Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 230000035784 germination Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- CHRDOERYBYSMEV-UHFFFAOYSA-N n'-phenyl-n-(3-piperidin-1-ylpropoxy)benzenecarboximidamide;hydrochloride Chemical compound Cl.C1CCCCN1CCCONC(C=1C=CC=CC=1)=NC1=CC=CC=C1 CHRDOERYBYSMEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- -1 hydroxylamine derivative compounds Chemical class 0.000 abstract description 5
- 241000196324 Embryophyta Species 0.000 description 100
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 239000003795 chemical substances by application Substances 0.000 description 44
- 235000011468 Albizia julibrissin Nutrition 0.000 description 32
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- 238000002474 experimental method Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 229940093499 ethyl acetate Drugs 0.000 description 16
- 235000019439 ethyl acetate Nutrition 0.000 description 16
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- 238000011282 treatment Methods 0.000 description 14
- 240000008042 Zea mays Species 0.000 description 13
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 13
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 13
- 235000009973 maize Nutrition 0.000 description 13
- IAJRBASJKPAYBJ-UHFFFAOYSA-N 3-nitro-n-(3-piperidin-1-ylpropoxy)benzenecarboximidoyl chloride;hydrochloride Chemical compound Cl.[O-][N+](=O)C1=CC=CC(C(Cl)=NOCCCN2CCCCC2)=C1 IAJRBASJKPAYBJ-UHFFFAOYSA-N 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 244000068988 Glycine max Species 0.000 description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000010469 Glycine max Nutrition 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
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- RRSNDVCODIMOFX-MPKOGUQCSA-N Fc1c(Cl)cccc1[C@H]1[C@@H](NC2(CCCCC2)[C@@]11C(=O)Nc2cc(Cl)ccc12)C(=O)Nc1ccc(cc1)C(=O)NCCCCCc1cccc2C(=O)N(Cc12)C1CCC(=O)NC1=O Chemical compound Fc1c(Cl)cccc1[C@H]1[C@@H](NC2(CCCCC2)[C@@]11C(=O)Nc2cc(Cl)ccc12)C(=O)Nc1ccc(cc1)C(=O)NCCCCCc1cccc2C(=O)N(Cc12)C1CCC(=O)NC1=O RRSNDVCODIMOFX-MPKOGUQCSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
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- FCRACOPGPMPSHN-UHFFFAOYSA-N desoxyabscisic acid Natural products OC(=O)C=C(C)C=CC1C(C)=CC(=O)CC1(C)C FCRACOPGPMPSHN-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
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- 125000004076 pyridyl group Chemical group 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical class CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
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- OEBZFKIPXIUMRM-UHFFFAOYSA-N ethyl n-ethyl-n-(2-hydroxy-3-piperidin-1-ylpropoxy)carbamate Chemical compound CCOC(=O)N(CC)OCC(O)CN1CCCCC1 OEBZFKIPXIUMRM-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 150000002465 imidoyl halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MVLOQULXIYSERZ-UHFFFAOYSA-N n'-(2-hydroxy-3-piperidin-1-ylpropoxy)pyridine-3-carboximidamide Chemical compound C1CCCCN1CC(O)CONC(=N)C1=CC=CN=C1 MVLOQULXIYSERZ-UHFFFAOYSA-N 0.000 description 1
- ATIGGIJEVHORCN-UHFFFAOYSA-N n-(2-hydroxy-3-piperidin-1-ylpropoxy)-2-nitrobenzenecarboximidoyl chloride;hydrochloride Chemical compound Cl.C1CCCCN1CC(O)CON=C(Cl)C1=CC=CC=C1[N+]([O-])=O ATIGGIJEVHORCN-UHFFFAOYSA-N 0.000 description 1
- HPNBPCVAJIMXAR-UHFFFAOYSA-N n-(2-hydroxy-3-piperidin-1-ylpropoxy)benzenecarboximidoyl chloride;hydrochloride Chemical compound Cl.C1CCCCN1CC(O)CON=C(Cl)C1=CC=CC=C1 HPNBPCVAJIMXAR-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000008121 plant development Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000037039 plant physiology Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940084879 selective beta blocking agent Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
-
- 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
- A01N43/10—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 sulfur 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
- A01N43/60—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
- A01N43/88—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 six-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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
- C07C259/18—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines having carbon atoms of hydroxamidine groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Dentistry (AREA)
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- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The use of hydroxylamine derivative compounds of formula (I) wherein: R1 represents phenyl, N-heteroaryl, S-heteroaryl or a naphthyl group which may be substituted with one or more halo, alkyl, alkoxy, haloalkyl or nitro, an unsubstituted or substituted phenylamino or alkylamino or lower alkyl; X represents halo, amino or an unsubstituted or substituted phenylamino group, or amino substituted with one or two lower alkyl or a hydroxy group provided that if R1 is unsubstituted or substituted phenylamino, alkylamino or lower alkoxy, then X may not be a halo; Y represents hydrogen, hydroxy or acyloxy, or longer alkanoyloxy, or if Y represents hydroxy, the molecule may contain a dioxazine ring closed at the carbon atom carrying the X group formed by formal XH elimination; R2 and R3, independently represent hydrogen or lower alkyl group provided that R2 and R3 may not be hydrogen simultaneously; R2 and R3 along with the adjacent nitrogen atom form a 5- to 7-membered saturated hetero ring; to increase the tolerance of cultivated plants against weather condition stresses, such as cold, frost and drought.
Description
500579
Use of Hydroxylamine Derivatives, and Method and Preparation for Increasing the Tolerance of Field Crops against Weather Stresses
TECHNICAL FIELD
This invention relates to the use of hydroxylamine derivatives of general formula (I)
X
R1 C
/ R2-
^ /
N— 0— CH— CH — CH — N
Y R3--''
I
/
wherein
R1 represents phenyl, N-heteroaryl, S-heteroaryl or a naphthyl group which may be substituted with one or more 20 halo, alkyl, alkoxy, haloalkyl or nitro, an unsubstituted or substituted phenylamino or alkylamino or lower alkoxy, X represents halo, preferably chloro or bromo, amino or an unsubstituted or substituted phenylamino group, or amino substituted with one or two lower alkyl or a hydroxy group 25 provied that if R1 represents unsubstituted or substituted phenylamino, alkylamino or lower alkoxy, then X may not represent halo,
Y represents hydrogen, hydroxy or acyloxy, preferably longer alkanoyloxy, or if Y represents hydroxy, the molecule may 30 contain a dioxazine ring closed at the carbon atom carrying the X group formed by a formal XH elimination,
R2 and R3, independently from each other, represent hydrogen or lower alkyl group provided that R2 and R3 may not represent hydrogen simultaneously,
R2 and R3 along with the adjacent nitrogen atom form a 5 to 7-membered saturated hetero ring,
and the method and preparation for increasing the tolerance of cultivated plants against weather condition stresses.
intellectual property office of nz
1 o SEP 2001
Received
2
BACKGROUND ART
Damages to cultivated plants by weather stresses, such as cold, 5 frost and drought cause significant losses for the agriculture. These factors, within this invention briefly referred to as weather stresses, may occur in any period of the growth or vegetation of the plant. Although they affect the plants in various ways and the plants react to them differently according to species and type, the effect is usually 10 connected to the water metabolism of the plants. The protection of plants against weather stresses is made more difficult by the widely varied distribution of the time, strength and length of these stresses present at most agricultural regions.
In the present invention a temperature is considered cold if it is 15 less than the minimum temperature necessary for normal physiological functioning of the individuals belonging to a given plant species or type, but greater than the freezing point of the water. Generally its effect may not be determined immediately by simple observation. The damage caused by the cold appears later, after warming up, such as the 20 decrease in plant growth, the withering or fading (chlorosis), or in the most severe cases, death of the plant.
The frost, i.e. the temperature below zero degree centigrade does not necessarily cause the plant to perish. After it is gone, the plant may be regenerated but the irreversible cell damages caused by the frost will 25 strain its development, which will decrease its yield in the end.
While the cold and the frost usually appears at an early stage of plant development and hence damages the germinating or developing plant, the drought damages the fully developed plant and endangers the further stage of development. Decreasing the evaporation level of
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the plant may render the reduction of the losses. For example there exists a method, when the surface of the plant is coated with a polymer film in order to physically limit the transpiration of the plant in the case of drought. For this purpose polyetoxylated polyoxypropylene 5 copolymers described m the US Patent No. 4828602 are applied. The disadvantage of the method is that it requires a local application of the coating material, which may be done only by investing a great amount of manual labour. A durable transpiration inhibition is not desirable anyway; the system-effect transpiration inhibitors are more favourable 10 with respect to plant physiology.
Thorough research related to the effects of the weather stresses on plants has been performed to reduce the damages of the cold, frost and drought, and a great number of scientific publications deal with the plant physiological relevance of cold, frost and drought tolerance. 15 Since plants react to these weather stresses very differently according to their botanical characteristics, a theoretically satisfactory explanation of the mechanism of the cold, frost and drought tolerance has not yet been given, and hence the methods developed for application in practice to improve the tolerance of plants against weather stresses are 20 very diverse.
For example, it is known in the art that growth, regulating materials, which are compounds of hormonal activity, affect the cold, frost and drought tolerance of plants positively, and therefore they are applied for the treatment of cultivated plants. A typical example is 25 abscisic acid, which is a growth regulating hormone. Abscisic acid itself is difficult to synthesise and hence it is not applied in agriculture. However, materials analogous to abscisic acid chemically and in their effect are used, which have identical or stronger effect than the abscisic acid itself , especially when combined with other compounds, which
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ensures a synergetic increase in the effect. For example, the PCT publication WO No. 9608481 A1 describes that plants are treated with epoxycyclohexane derivatives so as to make their development and yield more favourable and to increase their tolerance against cold and 5 drought. Besides these compounds, brassidosteroids are also used as synergetic auxiliarys. The EP No. 327309 A1 describes a compound that contains a poly-substituted cyclohexenyl-acetylene derivative as effective agent, and a diversely and multi-substituted phenyl-benzyl-urea derivative as synergetic auxiliary. With the help of this substance 10 of hormonal activity, the tolerance of the plant against drought may be improved.
Compounds of hormonal activity are without any doubt significant, because they have an intense effect even when applied in small quantity, however their disadvantage is that they affect the metabolic 15 processes taking place in the plants to a large extent, modify the hormnonal equlibrium of the plants, which may result in unpredictable physiological changes. Therefore such compounds and products must be applied with care in practice. Before application, it is essential to perform preliminary experiments related to a given plant species or type 20 in order to determine the suitability and optimal application circumstances of the product in a given agricultural region, which limits their use in agricultural practice.
To avoid the above mentioned disadvantages of substances of hormonal activity, researchers turned to simpler, hormonally indiffer-25 ent substances to find a suitable effective agent to improve the tolerance of plants against cold, frost and drought. According to the PCT publication WO No. 92/08350 A1 tetrahydro-furfuryl-alcohol, tetrahy-dro-furfuryl-amine, or the combination of these compounds is applied to improve the tolerance of plants against cold. These effective agents
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lack the mentioned disadvantages of substances of hormonal activity, their production is easier, and hence they are more economical, but in view of the practice they are not favourable. This is because, according to the paper cited above, it is recommended to spray the plants more 5 than once with the solution of the effective agent in order to achieve a satisfactory extent of regeneration of the cold-effected plants, and to repeat the treatment after the cold is gone, but the most expedient way is to spray the plants regularly. A treatment of the whole surface is considered important to ensure the contact of the effective agent on the 10 entire surface of the plant. Therefore, thorough or repeated spraying is recommended. This requirement may be fulfilled only by investing a great amount of manual labour.
According to Hungarian Patent No. 181241, secondary or tertiary P-hydroxyethyl-ammes or respective quaternary ammonium salts, 15 preferably 2-hydroxy-ethyl-amines and trimethyl-P-hydroxy-ethyl-ammonium-chloride (choline-chloride) and, in certain cases, combinations of these may be applied to improve the tolerance of plants against cold and frost. Primarily, the effective agent is applied to the plant by spraying. It may be concluded from the experimental section of the 20 Patent that the effective agent is aimed at changing the phospholipid composition of the membrane of plant cells, and thus the fluidity of the membrane. Hence the mentioned effective agents may be applied for the treatment of fully developed plants only. This was supported by the experimental results as well. The treatment of seedlings and seeds, 25 which is mentioned in the Patent may not be effective with these effective agents since the plants lack the parts with the necessary membrane. An exception of is the choline-chloride, the application of which for treatment of seeds is known from the publication JP No. 62161701. In this case, however, the general growth regulating effect of
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WO 98/47362 , PCT/HU98/00039
Or
Is n -i m c o£
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"7 70
zo
N "O • rn TO
the substance is utilised, as described in the above mentioned paper, and this effect causes among others the improved tolerance of the sprouting plant against cold. However, the growth regulating substances of hormonal activity possess all of the disadvantages described above.
To sum up the above, we may conclude that several different attempts have been published in Patent literature aimed at improving the tolerance of cultivated plants against weather stresses. The effective agents and products of these Patents are, however, suitable for direct agricultural application only with the mentioned limiting conditions.
Our research was aimed at finding effective agents, which increase the cold, frost and drought tolerance of plants but are hor-monally neutral, non-toxic, the limits of their application being the smallest possible, and which are suitable not only for the treatment of fully developed plants but also of seedlings and seeds. A further aim is to at least provide a useful alternative to know agents.
DISCLOSURE OF INVENTION
It was found that the hydroxylamine derivatives of general formula (I), wherein
X
/ R1—
R~S, /
N—0—CH—CH —CHi—N
1 R3--
\
s
N
/
/
R1 represents phenyl, N-heteroaryl, S-heteroaryl or a naphthyl group which may be substituted with one or more halo, alkyl, alkoxy, haloalkyl or nitro, an unsubstituted or
(Followed by page 6a)
00579
substituted phenylamino or alkylamino or lower alkoxy, X represents halo, preferably chloro or bromo, amino or an unsubstituted or substituted phenylamino group, or amino substituted with one or two lower alkyl or a hydroxy group provided that if R1 represents unsubstituted or substituted phenylamino, alkylamino or lower alkoxy, then X may not represent halo,
(Followed by page 7)
intellectual property office of m 7
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Received
7
then X may not represent halo,
Y represents hydrogen, hydroxy or acyloxy, preferably longer alkanoy-
loxy, or if Y represents hydroxy, the molecule may contain a dioxazine ring closed at the carbon atom carrying the X group formed by formal
XH elimination,
2 3
R and R , independently from each other, represent hydrogen or
2 3
lower alkyl group provided that R and R may not represent hydrogen simultaneously,
2 3
R and R along with the adjacent nitrogen atom form a 5 to 7-10 membered saturated hetero ring,
show the required effect and satisfy the mentioned requirements.
These compounds act in an inductive manner, i.e. they increase the level of hardiness if the plant faces environmental stresses, as when the above mentioned weather stresses affect the plant. The inducted 15 metabolic processes result in an improved tolerance against cold, frost and drought.
Based on this observation, this invention relates to the use of
1 2
hydroxylamine derivatives of general formula (I), where R , X, Y, R
3
and R are as above, for the improvement of the tolerance of cultivated 20 plants against weather stresses.
In general formula (I), a lower alkyl group contains preferably 1-6 carbon atoms, most preferably 1-4 carbon atoms, and a lower alkoxy group contains 1-6, preferably 1-4 carbon atoms. In compounds of general formula (I), where R1 is a substituted phenyl or phenylamino 25 group, the alkyl groups attached to the phenyl ring as substituents are preferably lower 1-6 carbon atom alkyl groups. The alkoxy substituents of the phenyl ring preferably contain 1-6 carbon atoms. The haloalkyl substituents of the phenyl ring contain preferably alkyl, most preferably Ci-6 alkyl. Most preferable haloalkyl substituent is the trifluoro-
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70
Z
—i _ m o !=
m o
m
^5
CO
m ~o
•T! m
O —1 m c o£
<
m o r-o
C3 <=>
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zO
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—t -<
methyl group. If R^" represents alkylamino, it preferably contains at most 12 carbon atoms. If R^ represents N-heteroaryl, it is preferably pyridyl or pyrazinyl group, while if R1 represents an S-heteroaryl group, it is preferably tzenyl. Finally, if Y represents a long carbon chain alkanoyloxy, it preferably contains 12-20 carbon atoms.
Some of the hydroxylamine derivatives of general formula (I) are known compounds. Those compounds of general formula (I) in which
R* represents phenyl or pyridyl or naphtyl which may be substituted with halo or alkoxy, X represents amino and Y represents hydroxy, are known from Hungarian Patent No. 177.578, which also describes the process of, preparation of these compounds, as well as the different possibilities for synthesis. These compounds, as selective beta-blocking agents, may be applied in the therapy of angiopathy, primarily diabetic angiopathy. Those compounds of general formula (1), in which R1
represents phenyl or alkoxyphenyl or pyridyl or naphtyl, X represents halo and Y is hydroxy, as well as their preparation are known from
International Application WO 90/04584. These compounds may also be applied in the therapy of angiopathy. Those compounds of general formula (I) , in which R1 represents naphtyl or haloalkylphenyl, X is hydroxy and Y represents hydroxy, are known from published Hungarian Patent Publication T/66350. These compounds have antiisschemic and antianginal effect, and hence may be applied particularly in the therapy of heart diseases. Those compounds of general formula (I), in which R* represents phenyl or phenyl group substituted by the above listed substituents or a pyridyl group, X represents halo and Y is a hydrogen atom, are known from the PCT publication WO No. 95/30649 Al. The same document describes the preparation of these compounds. These compounds have antiischemic effect and hence may be applied in the therapy of diabetic angiopathy. Furthermore, those compounds of
WO 98/47362 9 PCT/HU98/00039
general formula (I) are also known, in which R* represents phenylamino which is unsubstituted or substituted with alkyl, alkoxy, halo, haloalkyl or nitro, or an alkoxy or alkylamino group, X represents hydroxy and Y is hydrogen, hydroxy or alkanoyloxy. Their description may be found in the PCT publication WO No. 97/00251, which describes the preparation of these compounds as well. These compounds have antiischemic effect and hence may be applied in the therapy of o
heart and blood vessel diseases. Note that in the known compounds R
O
and R represent the same as defined above, and therefore these two substituents are not described in detail.
It should also be noted that in certain compounds of general formula (I) tautomery may occur, i.e. they may appear in a tautomeric structure different from but corresponding to the formula (I). In particular, this is the case when compounds of general formula (I) contain a hydroxy group as X, where the tautomeric version containing a -(CO}-NH- molecule part not appearing m the structural formula is more stable.
The remaining compounds of general formula (I) form the subject matter of our pehdin patent application.
New compounds are those hydroxylamine derivatives of general formula (I), in which X represents halo, Y is hydroxy, and R* represents a group that is different from the ones described in the International Application WO 90/04584 dealing with these kinds of compounds, for example phenyl substituted with alkyl, haloalkyl or nitro. These substances are prepared analogously to the cited description by diazotating the corresponding compound containing a NH2 group in place of X. The necessary starting amino compounds are produced also by know method, by the coupling reaction of the corresponding amidoxime anda 3-amino-2-propanol derivative, for intellectual property office of nz.
1 0 SEP 2001 RECEIVED
example according to the method described in the Hungarian Patent No. 177.578.
N-substiteud amidoximes of general formula (I), wherein R1 represents an aromatic group and X represents a substituted amino group, are also novel compounds, and maybe produced by the coupling reaction of a suitable imidoyl-halide of general formula (1 )y
NR'
R1— z! (D
\
Hal wherein Hal represents a halo and R1 is above, while R* is the substituent of the amino group of X, and a l-amino-3-aminooxypropane derivative of general formula (2)?
Y
W'R3 (2)
where R2, R3 and Y are as above. The reactions should be performed in a neutral solvent, for example in chlorinated hydrocarbon, at room temperature and after extraction separation, the product is isolated as a salt with a suitable organic or inorganic acid.
Other novel compounds of general formula (I) are N-hydroxy-guanidine derivatives in which both R1 and X are substituted nitrogen atoms. These derivatives are produced by the acylation of a suitable aminooxy compound of general formula (2) , if the acylating agent is haloformamidine of general formula (3)
NR'R"
R'N=C^ (3)
Hal intellectual property office of nz
1 0 SEP 2001
received
(Followed by page 10a)
10a where Hal represents halogen, R1 is as above, R' and R^' are substituents of the amino group appearing as X in the product. The reaction is performed in a two phase system, in the mixture of some organic solvent not mixable with water and a aqueous base, preferably aqueous sodium-carbonate solution. The product is isolated in this case also by extraction separation and, if possible, by salt-formation .
(Followed by page 11)
intellectual property office of nz
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11
As acylating agent, acid halides, active esters or other usual reagents applicable for O-acylation may be used. The reactions can be performed in a neutral solvent, usually at room temperature and if necessary in the presence of a suitable acid-binding agent, such as an organic or inorganic base, for example triethylamine or solid sodium-carbonate. For acylating agent, the acid chlorides are preferable, where the compound itself may behave as acid-binding agent, and hence usually the product may be easily isolated in the form of hydrochloride by simple ethereal crystallisation after evaporation. When using less reactive acylating agents, Schotten-Baumann acylation may also be applied. The products are generally isolated in the form of their salt with a organic or an inorganic acid.
With respect to the application of the invention, most preferable compounds were the following ones of general formula (I): N-[2-hydroxy-3-( 1 -piperidinyl)propoxy]-benzimidoyl-chloride hydrochloride (Compound 1)
N-[2-hydroxy-3-( 1, l-dimethylethyl-amino)propoxy]-3-tnfluoromethyl-benzamide monohydrochloride (Compound 2)
N- [2-palmitoyloxy-3 - (1 -piperininyl)propoxy] - 3-pyridinecarboximidamide monohydrochloride (Compound 3)
N-[3-(l-piperidinyl)propoxy]-3-nitro-benzimidoyl-chloride monohydrochloride (Compound 4)
N-[2-hydroxy-3-(l-piperidinyl)propoxy]-2-nitro-benzimidoyl-chloride monohydrochloride (Compound 5)
N-[[3-(l,l-dimethylethyl)-amino]-2-hydroxypropoxy]-N'-phenyl-benzamidine hydrochloride (Compound 6)
N-N '-dimethyl-N -phenyl-N"- [3- (1 -piperidinyl) propoxy ] -guanidine hydrochloride (Compound 7)
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12
N- [3-( 1 -piperidinyl)propoxy] -pirazine-carboximidoylchloride monohydrochloride (Compound 8)
3-(3-piridyl)-5-diethylaminomethyl-5,6-dihydro-1,4,2-dioxazine hydrochloride (Compound 9)
N-[2-hydroxy-3-(l-piperidinyl)propoxy]-l-naphtalene-carboxamide (Compound 10)
N-[2-hydroxy-3-(l-piperidinyl)propoxy]-ethylurethane (Compound 11) N-hexyl-N'-[2-hydroxy-3-(l-piperidinyl)propoxy]-urea (Compound 12) N,N-dimethyl-N'-phenyl-N"-[2-hydroxy-3-( 1 -piperidinyl)propoxy]-guanidme hydrochloride (Compound 13)
N-[3-( 1 -piperidinyl)propoxy]-tiophene-2-carboximidoylchloride hydrochloride (Compound 14)
N-[3-( l-piperidinyl)propoxy]-N'-phenyl-benzamidine hydrochloride (Compound 15)
Compounds of general formula (I) are favourable with respect to application in the cultivation of plants because they are suitable for treating both the fully developed plant and the seed or the seedling.
These compounds may be applied to the plants using any of the usual procedures widely used in plant-protection.
Based on the above, the invention relates to a procedure to increase the tolerance of cultivated plants against weather stresses.
According to the invention, the protected plant or its seed is treated with a hydroxylamine derivative of general formula (I), where R*, X, Y, 2 3
R and R are as above. Preferably an aqueous solution of the compound of general formula (I) is used for the treatment, but alternatively a preparation containing the usual carriers and the hydroxylamine derivative of general formula (I) as effective agent may be applied.
The dose and the concentration of the effective agent of general formula (I) is dependent on the protected plant species or type and on
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13
the method of the application.
If the procedure according to the invention is aimed at improving the tolerance of the plant against cold and frost, preferably the seed of the plant should be treated with a hydroxylamine derivative of general
formula (I), where
1 2 3
R , X, Y, R and R are as above. The seed of the plant must be covered with the proper product containing the active agent and suitable for coating, preferably pearled, in certain cases dressed, or the aqueous solution of the effective agent may simply be used.
The preferable method is to soak the seed of the plant in an aqueous solution of a compound of general formula (I). For this purpose a 1-200 mg/1 concentration of the compound of general formula (I) in aqueous solution is prepared.
The procedure according to the invention may be performed by 15 coating the seed of the plant with a solution containing a hydroxylamine derivative of general formula (I). The compounds of general formula (I) may be combined with dressing agents in certain cases.
For the coating of the seeds preferably pearling agents are applied, which contain compounds of general formula (I) in a concen-20 tration of 0.1-10 g/1 along with the usual pearling and auxiliary materials. The pearling agents may contain other effective agents beside the mentioned effective agent as well, such as fungicides or additives promoting germination, for example microelements. The pearling agent is applied in a small volume. For example, when treating bean, soybean 25 or maize seeds, only 1 ml or less amount of pearling agent is used for 100 seeds, which is dried on the seeds uniformly while constantly stirring.
Furthermore, this invention relates to a procedure for improving the tolerance of cultivated plants against cold, where the plant is
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14
sprayed before or at the time when the cold season sets in with a spray preparation containing a hydroxylamine derivative of general formula (I) as effective agent.
The spraying is performed with a 1-500 mg/litre concentration 5 aqueous solution of the effective agent, which may occasionally contain spraying auxiliary materials, such as surface active material (detergent). In certain cases, compounds of general formula (I) may be combined and sprayed to the plant to be protected with other effective agents such as fungicides.
The spraying is to be performed at the beginning of the period hazardous in terms of cold temperature. If more than one period is to be taken into consideration, then the plants must be sprayed at the beginning of each such period.
According to the invention, to improve the tolerance of cultivated 15 plants the plant must be sprayed before or at the time when the diy season sets in with a spray preparation containing a hydroxylamine derivative of general formula (I) as effective agent.
The spraying is performed using a 1-500 mg/1 aqueous solution of the active agent. The plants to be protected are sprayed before or at 20 the beginning of the period when there is a risk of drought. In every case, the characteristics of the given plant species or type determine the applicable quantity of the active agent. If more than one drought period is to be taken into consideration, then the spraying must be repeated at the beginning of each such period.
For the above listed treatments, a simple aqueous solution of the hydroxylamine derivatives of general formula (I), but preferably such preparations are used which contain proper auxiliary materials beside the active agent, for improving the spraying, distribution and the absorption of the active agent.
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The composition of the invention for improving the tolerance of cultivated plants against weather stresses contains 0.001-95 m/m% hydroxylamine derivative of general formula (I), in which R1, X, Y, R2 and R3 are as above, beside the solid or liquid carriers and possible 5 auxiliary materials suitable for agricultural application.
The composition preferably contains water as liquid vehicle agent. The aqueous solution of the active agent is a concentrate, which should be diluted before application in order to prepare the proper concentration mentioned above. Preferably, the aqueous solutions 10 contain surfactants, those solutions for treating the seed contain dressing and pearling auxiliary materials, such as film forming materials. The sprays contain an adhesion improving agent, a substance to improve spreading, light protecting agent, if required, a stabilising agent and other additives beside the detergents. For spraying purposes 15 ULV concentrates, emulsifiable concentrates, hydrophyl powders, soluble granulates or microgranulates dilutable with water may be applied. These products contain anionic or non-anionic detergents in order to help the dilution with water. The solid products may contain kaolin, diatomite or dolomite as vehicle, but may also contain any other 20 solid vehicle agent widely applied in such products. Preferably, perlite is used as vehicle agent for the production of microgranulate.
The compositions of the invention may be combined or simultaneously applied with other pesticides, if the active agent of the latter is compatible with the active agent of the composition of the invention. In 25 these cases, the spraying of the composition of the invention does not require a separate process, it can be performed along with the usual pesticide treatment of the cultivated plants.
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BEST MADE OF CARRYING OUT THE INVENTION
The invention is demonstrated by the following examples without limiting the scope of the invention.
Example 1:
N-[2-palmitoyloxy-3-( 1 -piperidinyl)propoxy]-3-
pyridinecarboximidamide monohydrochloride (Compound 3)
14.7 g (52.8 mmol) of N-[2-hydroxy-3-(l-piperidinyl) propoxy]-3-pyridine-carboximidamide is dissolved in 160 ml of chloroform. 7.7 ml (55 mmol) of triethylamine is added, followed by the dropwise addition of a solution of palmitoyl chloride (14.7 g; 56.5 mmol) in 85 ml of 15 chloroform. The mixture is stirred overnight at room temperature. The next day, a further 3.8 ml of triethylamine and 7.4 g of palmitoylchlo-ride are added, and the stirring is continued for one more day. Then the solution is extracted with water, 5 V/V% acetic acid and water, successively, dried over anhydrous sodium sulphate, and evaporated to 20 dryness.
The residue (28.2 g oil) is dissolved in ethyl acetate, and the product is precipitated by addition of 30 ml of 1 N HCl/ethyl acetate. The thick, white precipitate is filtered off, washed with ethyl acetate and dried. Yield: 10.9 g (37%)
Mp.: 110-113 °C
Example 2.
N-[2-hydroxy-3-( 1 -piperidinyl)propoxy]-2'-nitro-
benzenecarboximidoyl chloride monohydrochloride (Compound 5)
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17
6.0 g (16.7 mmol) of N-[2-hydroxy-3-(l-piperidinyl) propoxy]-2'-nitro-benzene-carboximidamide monohydrochloride is dissolved in 21 ml of water, then 48 ml of concentrated hydrochloric acid is added. The solution is cooled to -5 °C, then a cold solution of 2.1 g (33.3 mmol) of sodium nitrite in 9 ml of water is added dropwise. Throughout the reaction the internal temperature is maintained at 0°C. When the addition is completed, the mixture is stirred for a further four hours and cooled overnight. The product is filtered off, washed with cold water and dried.
Yield: 3.9 g (63%). Mp.: 159-162 °C
IR(KBr): 3298, 2983, 2932, 2746, 1593, 1574, 1535, 1445, 1391, 1354, 1317, 1288, 1242, 1198, 1117, 1092, 1069, 1020, 968, 947, 914, 852, 793, 756, 708, 577 cnr1
Example 3
N-[[3-( 1,1-dimethylethyl)-amino]-2-hydroxypropoxy]-N-phenyl-
benzamidine hydrochloride (Compound 6)
4 g (24.7 mmol) of benzanilide-imide-chloride is dissolved in 45 ml of chloroform. Then 5.32 g (24.7 mmol) of 1 -aminooxy-3-[( 1,1-dimethyl-ethyl)-amino]-2-hydroxy-propane dissolved in 45 ml of chloroform is added dropwise to the resulting solution. The reaction mixture is stirred at room temperature for 3 hours, and then washed with 25 ml of 1 M aqueous sodium-carbonate solution. The chloroform phase is dried over sodium-sulphate, filtered and evaporated. The evaporation residue is cnstallysed with hexane. The resulting base is dissolved in (5.33 g) 50 ml of ethyl-acetate and then 3.35 ml of 3.67 N hydrochloric acid/ethyl-acetate is added. The isolated crystals are
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18
filtered off, washed with ethyl-acetate and dried.
Yield: 2.97 g (72%). M.p.: 140-143 °C
!H-NMR (solvent: CDCb; reference: CDCI3 [ppm]): 9.7 (m,lH) and 8.1 (m,lH,NH2+); 7.8 (s,lH,NH-0); 6.7-7.4 (m,10H,2xPh); 5.7 (d,lH,OH); 4.5 5 (m,lH,CH); 4.25 (d,2H,OCH2); 3.1 (m,2H,NCH2); 1.25 (s^H^Bu).
Example 4
N-N'-dimethyl-N'-phenyl-N"-[3-(l-piperidinyl)propoxy]-guanidine hydrochloride (Compound 7) j
ml of 1 M aqueous sodium-carbonate solution is added to 1,040 g (6.5 mmol) of "l-aminooxy-3-(l-piperidinyl)propane dissolved m 10 ml of ether. While intensely stirring, 1200 ml (6.5 mmol) of N,N-dimethyl-N'-phenyl-chloroformamidine dissolved in 10 ml of ether is 15 added. After 2 hours of stirring, further 20 mg (0.1 mmol) of N,N-dimethyl-N'-phenyl-chloroformamidme is added. After further 3 hours of stirring, the phases are separated and the ethereal phase is dned over sodium-sulphate, filtered and evaporated. The residue (1700 mg of yellow oil) is dissolved in 10 ml of ethyl acetate. 10.5 ml of 0.54 M 20 hydrochloric acid/ethyl-acetate is added, and then the product is cooled and the isolated crystals are filtered off. The raw product is crystallised from methanol-ether mixture to give 847 mg of white crystalline material.
Yield: 847 mg (38%). M.p.: 138-139 °C (methanol-ether)
!H-NMR (solvent: CDCI3; reference: CDCI3 [ppm]): 7.2 (t,2H,Ph-m); 7.1 (d,2H,Ph-o); 6.9 (t,lH,Ph-p); 6.6 (m,lH,NH+); 4.0 (t,2H,OCH2); 3.5 (m,2H); 3.0 (t,2H,CH2); 2.6 (s,6H,2xNCH3); 2.2-2.5 (m,6H,3xNCH2); 1.8 (m,4H) and 1.3 (m,2H,piperidine).
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19
The product crystallised from isopropanol melts at 213-216°C.
Example 5
N-[3-( 1 -piperidinyl)propoxy]-N'-phenyl-benzamidine hydrochloride (Compound 15)
0.8 g (5 mmol) of l-aminooxy-3-(l-piperidinyl)propane is dissolved in 7.5 ml of chloroform. 1.08 g (5 mmol) of benzanilide-imide-chloride dissolved in 7.5 ml of chloroform is added dropwise and then the reaction mixture is stirred for 3 hours. Then it is washed with two times 10 ml of water, and the chloroform phase is dried over sodium-sulphate, filtered and evaporated. The evaporation residue is dissolved in 20 ml of 2 N aqueous sodium-hydroxide solution and the solution is extracted with 20 ml of ethyl-acetate. The ethyl-acetate phase is dried over sodium-sulphate and filtered, and then 0.8 ml of 3.45 M hydrochloric acid/ethyl acetate is added. The isolated precipitate is filtered and dried.
Yield: 0.8 g (46%). M.p.: 164-166 °C (crystallised from ethyl-acetate) C13-NMR (solvent: CDC13; reference: CDC13 [ppm]): 157.55 (C-amidine); 135.75 (N-Ph-ipso); 132.84 (C-Ph-ipso); 128.95 (N-Ph-m); 128.84 (C-Ph-m); 126.66 (N-Ph-p); 125.34 (N-Ph-p); 124.0 (C-Ph-p); 74.02 (O.CH2); 54.20 (NCH2); 53.30 (2.6 piperidine); 23.19 (CH2); 22.63 (3.5 piperidine); 21.76 (4 piperidine).
Example 6
N,N-dimethyl-N'-phenyl-N"-[2-hydroxy-3-(l-piperidinyl)propoxy]-
guanidine hydrochloride (Compound 13)
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1,150 mg (6.58 mmol) l-aminooxy-2-hydroxy-3-(l-piperidinyl)-propane] is dissolved in 20 ml of ether and to this solution 20 ml of 1 M sodium carbonate solution is added, then 1,206 mg (6.58 mmol) of N,N-dimethyl-N'-phenyl-chloroformamidine dissolved in 10 ml of ether is 5 added. After two hours, 22 mg (0.11 mmol) of N,N-dimethyl-N-phenyl-chloroformamidine is also added to the reaction mixture. After stirring for further 3 hours, the layers are separated, the ether layer is dried over sodium-sulphate, filtered and evaporated. The residual 1,800 mg of yellow oil is taken in 10 ml of'ethyl acetate, and to this solution 10 10.46 ml of 0.54 M HCl/ethyl acetate is added, cooled and the yellow crystals are filtered off. Impurities are removed by recrystallization first in acetone, then in ethyl acetate.
Yield: 674 mg (28%) pale yellow powder. Mp.: 127-129 °C (ethyl acetate)
1H-NMR (solvent: CDCI3; reference: CDCI3 [ppm]): 7.1-7.4 (m,5H,Ph); 5,9 (m,lH,OH); 4.6 (m,lH,CH); 4,1 (m,2H,OCH2); 3.6 (m,4H,2-6 piperidine); 3.4 (m,2H); 3.2 (m,lH,NH); 1.8 (m,4H,3-5 piperidine); 1.4 (m,2H,4 piperidine)
Example 7
Increasing chilling tolerance by treating seeds
In this experiment the tolerance of maize, soybean and pepper seeds treated with the active agent against cold was tested. This test 25 imposed temperature and oxygen deficiency stresses on the seeds and was carried out according to Barla-Szabo and Dolinka CSVT (Complex Stressing Vigour Test). For a single test, two hundred seeds were soaked for 48 hours at 25°C and another 48 hours at 5°C in 150 ml distilled water containing the active agent in 10 mg/1 concentration.
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21
Following the 96 hours of soaking, the seeds were further germinated between rolled wet paper for 96 hours at 25°C. There were 25 seeds in each roll, the rolls were placed vertically into containers and covered with a plastic bag in order to reduce evaporation. During the whole 5 procedure the seeds were kept in darkness.
At the end of the experiment the number of normally developing and ungerminated seeds were recorded. The length of the normal seedlings was measured and the average length of the five longest seedlings was calculated. Seedlings longer than 0.33 times the average io length of the five longest seedlings were considered to be of high vigour, and low vigour seedlings were shorter than this length.
In experiments with maize, it was found that the tested active agents did not influence the germination and development of the Mo 17 inbred maize line germinated in optimal circumstances, at 25°C. Under 15 the circumstances of the CSVT test, however, they proved to be effective, as it is shown in Table 1.
Table 1.
Active agent
Ratio of high
Compound 1
38*
Compound 2
29*
Compound 9
33*
Compound 11
24
Compound 3
47*
Compound 12
23*
Compound 4
28*
Compound 5
32*
Compound 6
*
Compound 7
36*
Control
19
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22
Results marked with * are significant compared to the control, if P<0.05.
Using the same experimental method for the HMv09 inbred maize line compounds, shown in Table 2., proved to be effective, the ratio of plants of high vigour increased significantly.
Table 2.
Active agent Ratio of high vigour plants (%)
Compound 2 49*
Compound 10 52*
Compound 4 40*
Compound 6 57*
Compound 13 56*
Compound 14 45*
Compound 15 53*
Control 33
Results marked with * are significant compared to the control, if
P<0.05.
In the case of a further experiment with maize of low chilling tolerance (LT) and high chilling tolerance (HT) populations [Ref: P. 15 Landi, E. Frascaroli, A Lovato; EUPHYTICA 64 21-29 (1992)], the following positive effects were found (Table 3.).
Printed from Mimosa 10/26/1999 15:31:55 page -24-
WO 98/47362 ^ PCT/HU98/00039
Table 3.
Active agent Ratio of high vigour plants (%)
HT LT
Compound 2 98* 94*
Compound 3 92* 86*
Compound 4 94* 88*
Compound 5 96* 92*
Control 84 74
Results marked with * are significant compared to the control, if P<0.05.
Experiments with McCall soybeans also showed that the active agents have no effect on the germination and development of the plants under normal conditions. When applying the CSVT test, the following results were obtained (Table 4.).
Table 4.
Active agent Ratio of high vigour plants (%)
Compound 2 43*
Compound 4 46*
Compound 8 47*
Control 38
Results marked with * are significant compared to the control, if. 15 It was further observed that Compound 8 decreased the number of ungerminating seeds by 50% (control: 33%, treated: 17%, significant at P<0 05).
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WO 98/47362 24 PCT/HU98/00039
Experiments with green peppers showed similarly that the active agents have no effect under normal circumstances, do not influence the germination of the seeds and the development of the plants kept at 25°C. Under the circumstances of the CSVT test, they increased the 5 length of the sprouts and the roots along with the proportion of the high vigour seedlings The ratio of the ungerminating seeds decreased by 30% on average due to the treatment with the active agents. The results are demonstrated in Table 5.
Table 5
Active agent Ratio of high vigour plants (%)
Compound 2 47*
Compound 4 45*
Control 36
Results marked with * are significant compared to the control, if P<0.05.
In order to make the results more comprehensible, it should be 15 noted that the CSVT procedure is developed to predict the expected minimal ratio of sprouting seeds under environmental stresses. In a given set of seeds, the ratio of those seeds that safely sprout and properly germinate in cold spring weather is 90% for seeds which proved to be of high vigour m the CSVT test, while the ratio of those 20 seeds which safely sprout and properly germinate m cold spring weather is only 60% for seeds that proved to be of low vigour in the test. Hence, if an active agent improves the vigour of the seedlings, it in the end improves the sprouting ratio under open field conditions in the case of ground temperature colder than optimal.
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WO 98/47362 PCT/HU98/00039
The above experiments prove that the compounds of general formula (I) are able to improve the vigour of the seedlings and hence improve the chance of sprouting, if unexpectable weather stresses occur after the sowing.
Example 8
Pearling of soybean seeds
Soybean seeds are treated with a pearling agent, which contains 1 10 mg/ml of N-[3-(l-piperidinyl)propoxy]-3-nitro-benzimidoyl-chlonde monohydrochloride (Compound 4) m a 5% aqueous polyvinylalcohol solution. 100 seeds and 1 ml of pearling agent are filled into a glass vessel and while the vessel is rotated, the seeds are coated with the agent and then it is left to dry. For seeds treated this way, we obtained 15 the following results when placed under the conditions of the CSVT test described in Example 7.
Table 6.
Treatment untreated control pearled with PVA pearled with PVA and Compound 4
Ratio of high vigour plants (%)
sprout root
47 40
52 49
63* 58*
Results marked with * are significant compared to the control, if P<0.05.
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WO 98/47362 26 PCT/HU98/00039
PVA slightly increased the ratio of high vigour plants. The PVA solution containing Compound 4 proved to be such a pearling agent which was able to increase the ratio of high vigour plants significantly under the experimental conditions, increasing the length of both the 5 sprouts and the roots.
In a further CSVT experiment also using McCall soybeans, polyvinylalcohol (PVA) was applied for pearling the seeds. The 2.5 mg doses of the active agents were dissolved in 1 ml of 2.5% PVA solution, and this quantity was applied to 100 pieces of seeds. The improvement 10 of the chilling tolerance is observed by the significant elongation of the germ and the roots. The results are demonstrated in Table 7.
Table 7.
Active agent
Compound 2 Compound 9 Compound 3 Compound 5 Compound 6
Relative length germ 106 110 133 116 127
(control=100) root 128 131 150 135 152
The experiments show clearly that, according to the results of the vigour test, the chances of sprouting of the plants increased after pearling with the active agent.
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27
Example 9
Increasing the drought tolerance of beans
Based on the experiences of our prelimmaiy experiments, the plants were hardened before the application of the active agent; by withholding the water for a few days, until the first signs of withering appeared. Then the plants were watered and the active agent was either dissolved in the water, or sprayed to the plants directly. Afterwards, the 10 plants were subjected to different periods of drought according to the given experiment, watered again, and after a week-long regeneration period, the survival ratio was determined.
a) Seaway bean cultivar was hardened for 5 days by withholding the water. Afterwards the plantlets were watered for two days nor-15 mally. During this time, a 10 mg/litre and 100 mg/litre concentration solution of the active agent was applied two times a day dissolved in water or by direct spraying. Then the water was withheld for 7 days, and after a week-long regeneration period, the survival ratio was determined. The results are summarised in Table 8.
Table 8
Active agent Watering (10mg/l) Watering (100mg/l) Spraying (100mg/l)
survival (%)
Control
17
17
0
Compound 2
*
41*
71*
Compound 6
*
36*
-
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WO 98/47362 PCT/HU98/00039
Zo
Results marked with * are significant compared to the control, if P<0.05.
b) In this experiment, bean plants (cv. Seaway) were hardened for 5 7 days instead of the 5 days described m Part a. Then a 10 mg/litre and 100 mg/litre concentration solution of the active agent was applied two times a day for two days. Then 7 days without water followed, and after a week-long regeneration period, the results of the experiment were evaluated. The results are summarised in Table 9.
Table 9.
Active agent Survival (%)
Compound 2 14*
Compound 4 39*
Control 0
Results marked with * are significant compared to the control, if P<0.05.
Example 10
Increasing the drought tolerance of soybeans
Soybeans of soybean cv. Bolyi 44 were hardened for 6 days by 20 withholding the water. This was followed by two days of watering, and the active agent was applied m the water. The concentration of the solution of the active agent was 50 mg/litre. After a 4-day-long cease of watering and a one week regeneration period, the number of surviving plants was recorded. The results are listed in Table 10.
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29
Active agent Compound 2 Compound 4 Control
Table 10.
Survival (%) 25*
33*
18
Results marked with * are significant compared to the control, if 5 P<0.05.
Watering was ceased for 10 days for a certain group of plants in the experiment. It was observed that almost every plant perished. Each of the 4 surviving plants had previously been treated with the active 10 agent.
Example 11
Increasing the frost tolerance of beans
Seedlings of bean cv. Seaway were cultivated under normal conditions for the first two weeks, then they were treated with 10 mg/litre and 100 mg/litre concentration solutions of the examined active agents 2 and 1 days before the initiation of the frost tolerance experiments. In the experiment, the plants were kept at -2°C for 8 20 hours, then grew under normal conditions for 1 week, and the survival ratio was determined. 4 trays were used for each experiment and 6 seeds were planted in each tray. The compounds in Table 11. significantly increased the survival ratio.
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Table 11.
Active agent Treatment Survival (%)
Compound 2 spraying, 100 mg/1 40*
Control spraying 25
Compound 2 watering, 10 mg/1 25*
Compound 4 watering, 10 mg/1 40*
Control watering 18
Results marked with * are significant compared to the control, if P<0.05.
Example 12
Increasing the chilling tolerance of maize in a gradient chamber
The experiment was performed using the Mo 17 maize inbred 10 line. The seeds were coated with a 2% solution of the examined compound dissolved in 2 ml polyvinylalcohol before germination, where the above quantity of solution is applied for 100 seeds. The seeds were germinated for 3 days wrapped in wet filter paper, they were sown and then cultivated in gradient chamber for 6 weeks. In the gradient 15 chamber, the temperature was maintained on a scale between 18 and 12°C, with differences of 1°C. This was followed by a one week regeneration at 23/20°C temperature.
In the experiment, the length of the plants was measured 16, 31 and 43 days after the sowing, and at the end of the experiment the 20 fresh weight of the plants was measured. The experiment was performed on 4 plants at each temperature and by each treatment. The results demonstrate the increased germination potential of the examined maize inbred line, and the imrovement of the early development of
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31
the seedlings compared to the untreated control. The experimental results are summarized in Table 12.
Table 12.
Increasing the chilling tolerance of maize in gradient chamber with
Compounds 2, 5 and 6
Control Compound 2 Compound 5 Compound 6
Temp Time Length FW Length FW Length FW Length FW
(days) (cm) (g) (cm) (g) (cm) (g) (cm) (g)
18 °C 16 12.9 - 13.2 - 15.0 - 14.6
31 22.0 - 28.4 - 28.4 - 25.0
43 35.0 5.3 37.0 6.0 38.0 6.2 39.0 7.6
17 °C 16 13.1 - 17.0 - 19.7 - 17.8
31 22.9 - 27.7 - 31.2 - 29.9
43 36.0 4.8 36.5 5.5 37.3 6.6 44.3 9.7
16 °C 16 10.2 - 15.2 - 15.4 - 12.4
31 20.6 - 24.8 - 26.8 - 26.4
43 33.1 4.2 32 3 4.5 34.5 5.0 42.3 7.7
°C 16 9 2 - 10 0 - 10.2 - 9.5
31 15.0 - 17.7 - 21.3 - 22.2
43 21.2 2.0 28.5 3.6 32.3 4.4 34.0 5.4
14 °C 16 5.2 - 7.6 - 9.7 - 5.8
31 10.8 - 15 4 - 17.2 - 11.6
43 20.3 1.6 25.9 2.7 25.1 2.9 20.3 1.3
13 °C 16 5.0 - 6.0 - 7.4 - 4.7
31 10.8 - 10.1 - 13.1 - 10.0
43 17.2 1.0 16 0 1.0 23.8 2.1 18.5 1.1
12 °C 16 5.4 - 5.0 - 5.8 - 4.5
31 8.7 - 7.9 - 11.3 - 10.9
43 17.8 0.9 18.9 1.2 20.1 1.5 25.5 2.0
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32
In the following examples, results of field experiments are shown, which were arranged with early sowing in order to determine the effect of the hydroxylamine derivatives of the invention on the development and yield of the plants in this case under natural conditions.
Example 13
Increasing the yield of field soybean cultivation
The experiment was performed using soybean cv. Bolyi 44. Before 10 sowing, the seeds were treated with Rhyzobium Japonicum nitrogen-binding bacterium, which forms a root nodule providing 50-70% of the nitrogen demand of the plant.
The examined compounds were applied by pearling the seeds; 1 ml of pearling agent containing 1 mg of active agent in a 5% aqueous 15 PVA solution was used for 100 seeds.
The plants were sown after soil preparation in the autumn, using a crop rotation system, 3-5 cm deep in the ground, with a 45-50 cm row distance, a 5 cm plant distance and 450,000-500,000 plant/ha density. The date of sowing was April 15, 1997. During the develop-20 ment of the plant, the usual cultivation procedures were followed and the usual pesticides were used. The harvest took place in September -October, with the water content of the grains being between 16-18%. The results are listed m Table 13.
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33
Active agent
Control Compound 6 Compound 5 Compound 2
Table 13.
Weight of the crop (kg/m2) Improvement compared to the control (%)
0.45
0.52 15.5
0.50 11.1
0.55 22.2
Example 14
Increasing the yield of maize m field cultivation
The experiments were perfomed on the Mo 17 and AMO 406 lines. Before sowing, the seeds were dressed with fungicides, insecticides and rodent-control agents, and, at the same time, the tested compounds were applied in the form of a 2.5 mg/ml concentration 10 solution in a 2% PVA solution; 2 ml of solution was used for 100 seeds.
The plants were sown after soil preparation in the autumn, using a crop rotation system, 4-8 cm deep in the ground, with a 45 cm row distance, a 30 cm plant distance and 60,000-80,000 plant/ha density. The date of the sowmg was April 15, 1997. During the development of 15 the plant, the usual cultivation procedures were followed, and the usual pesticides were applied. Harvest took place when the water content of the grains decreased below 28%. At harvest, the weight of the plants and of the crop were determined. The results are listed in Table 14. and 15.
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34
Table 14.
Field cultivation of the Mo 17 maize line
Active agent Weight of the crop (kg/m2) Ratio to the control
(Compound No.)
Control
1st
1.55
100%
0.09
100%
2nd
1.42
100%
0.088
100%
6
1st
2.03
130.9%
0.101
112.2%
2nd
2.0
-140.8%
0.11
125%
1st
1.97
127%
0.109
121.1%
2nd
0.093
105.6%
2
1st
1.85
119.3%
0.108
120%
2nd
2.0
140.8%
0.111
126.1%
Table 15.
Field cultivation of the AMO 406 maize line
Active agent Weight of the crop (kg/m2) Ratio to the control
(Compound No.)
Control
1st
1.65
100%
0.097
100%
2nd
1.13
100%
0.075
100%
6
1st
2.2
133.3%
0.115
118.5%
2nd
1 75
154.8%
0.097
129.3%
1st
1.8
109%
0.1
103.0%
2nd
1.8
159.2%
0.1
133.3.6%
2
1st
2.35
140.6%
0.16
164.9%
2nd
1.25
110.6%
0.089
118.6%
Printed from Mimosa 10/26/1999 15:31:55 page -36-
Example 15 Foliar spray
The foliar spray is prepared with the following composition (proportions by weight):
Compound 2 20
sodium-lauryl-sulphate 3
sodium-lignine-sulphonate 6
water 63
kaolin 8
Example 16
Foliar spray
Foliar spray is prepared with the following composition (proportions by weight):
Compound 4 20
alkyl-aryl-sulphonate 5
water 75
Example 17
Pearling agent
Pearling agent is prepared with the following composition (proportions by weight):
Compound 3 0.25
2 % aqueous solution of polyvinylalcohol 9.75
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36
The pearling agent must be applied as active agent in a quantity of 0.01-0.02 m/m% with respect to the weight of the seed.
Example 18 Granulate
Granulate is prepared (proportions by weight): Compound 13 limestone-powder ethylene-glykol high dispersity silicic acid sodium-ligninesulphonate water with the following composition
64
3
4 4 15
The mixture of the components must be ground m a hammer mill until it reaches the particle size of 5 micron.
Example 19 Powder preparation
Powder preparation is prepared with the following composition (proportions by weight):
Compound 6 50
poly-vinyl-pyrrolidon 10
silicon-dioxide 25
china-clay (kaolin) 15
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37
Example 20 Powder preparation
Powder preparation is prepared with the following composition
(proportions by weight):
Compound 1 50
calcium-ligninesulphonate 5
isopropyl-naphtalene-sulphonate 1
silicon-dioxide 4
filler (kaolin) 40
Printed from Mimosa 10/26/1999 15:31:55 page -39-
38
, /
R C
\
\
\ I
i / /
/
Claims (28)
1. The use of a hydroxylamine derivative of general formula (i), x rV / - N—0—CH—CH —CH,— N I \ Y R3--'' wherein ||j R1 represents phenyl, N-heteroaryl, S-heteroaryl or a naphthyl group which may be substituted with on or more halo, alkyl, alkoxy, haloalkyl or nitro, an unsubstituted or substituted phenylamino or alkylamino or lower alkyl, X represents halo, amino or an unsubstituted or substituted phenylamino group, or amino substituted with or two lower alkyl or a hydroxy group provided that if R1 represents unsubstituted or substituted phenylamino, alkylamino or lower alkoxy, then X may not represent halo, Y represents hydrogen, hydroxy, acyloxy, or longer alkanoyloxy, or if Y represents hydroxy, the molecule may contain a dioxazine ring closed at the carbon atom carrying the X group formed by a formal XH elimination, R2 and R3, independently from each other, represent hydrogen or lower alkyl group provided that R2 and R3 may not represent hydrogen simultaneously, R2 and R3 along with the adjacent nitrogen atom from a 5 to 7-membered saturated hetero ring, to increase the tolerance of cultivated plants against weather condition stresses.
2. The use according to claim 1, wherein X is chloro or bromo.
3. The use according to claim 1 or claim 2, wherein Y is longer alkanoyloxy. 'NTomS'oV^EI"Y 1 0 sep 2001 Received 39
4. Method for increasing the tolerance of cultivated plants against weather condition stresses, comprising treating the plant or its seed with a hydroxylamine derivative of general formula (I), where R1, R2, R3, X and Y are as in any one of claims 1 to 3.
5. Method for increasing the tolerance of cultivated plants against cold and frost, comprising treating the seed of the plant with a compound of general formula (I) , where R1, R2, R3, X and Y as as in any one of claims 1 to 3.
6. Method according to Claim 5, comprising treating the seed of the plant with the aqueous solution of a hydroxylamine derivative of general formula (I), wherein R1, R2, R3, X and Y are as in any one of claims 1 to 3.
7. Method according to Claim 6, comprising soaking the seed of the plant in the aqueous solution of a hydroxylamine derivative of general formula (I), wherein R1, R2, R3, X and Y are as in any one of Claims 1 to 3.
8. Method according to Claim 5, comprising coating the seed of the plant with a product containing a hydroxylamine derivative of general formula (I) , wherein R1, R2, R3, X and Y are as in any one of Claims 1 to 3 and optionally other active agents and/or germination improving auxiliary materials.
9. Method for increasing the tolerance of cultivated plants against cold, comprising spraying the plant with a solution containing a hydroxylamine derivative of general formula (I), where R1, R2, R3, X and Y are as in any one of Claims 1 to 3 as active agent, before or when the cold season sets in.
10. Method for increasing the tolerance of cultivated plants against drought, comprising spraying the plant with a solution containing a intellectual property office of n7. 1 0 SEP 2001 RECEIVED 50 0^7 hydroxylamine derivative of general formula (I), where R1, R2, R3, X and Y are as in any of Claims 1 to 3, as active agent, before or when the drought period sets in.
11. Composition for increasing the tolerance of cultivated plants against weather stresses, comprising as active ingredient a hydroxylamine derivative of general formula (I), where R1 represents phenyl, N-heteroaryl, S-heteroaryl or a napthyl group which may be substituted with one or more halo, alkyl, alkoxy, haloalkyl or nitro, X represents unsubstituted or substituted phenylamino group, or amino substituted with one or two lower alkyl, Y represents hydrogen, hydroxy, acyloxy, or alkanoyloxy, or if Y represents hydroxy, the molecule may contain a dioxazine ring closed at the carbon atom carrying the X group formed by formal XH elimination, R2 and R3, independently from each other, represent hydrogen or lower alkyl group provided that R2 and R3 may not represent hydrogen simultaneously, R2 and R3 along with the adjacent nitrogen atom form a 5 to 7-membered saturated hetero ring.
12. The composition according to claim 11, when Y in the hydroxylamine derivative of general formula (I) is longer alkanoyloxy.
13. The composition of claim 11 or claim 12 which also comprises solid or liquid carriers and optionally auxiliary materials suitable for agricultural use.
14. The composition according to claim 11 wherein -R1 is unsubstituted or substituted phenyl, X is unsubstituted or substituted phenylamino and R2, R3 and Y are as defined in claim 1.
15. The composition according to claim 14 which comprises N-{[3-(1, 1-dimethyl-ethyl)-amino]-2-hydroxy-propoxy}-N'-phenyl-benzamidine hydroxhloride as active compound. 'NTOTSUAiPR°«ry I 1 0 SEP 2001 / Received i
16. The composition according to claim 14 which comprises N-[3-(l-piperidinyl)-propoxy]-N'-phenyl-benzamidine hydrochloride as active ingredient.
17. A hydroxylamine derivative of the general formula (I) wherein R1 is phenyl which is unsubstituted or substituted with one or more selected from halo, alkyl, alkoxy, haloalkyl and nitro, X is unsubstituted or substituted phenylamino, Y is hydrogen, hydroxy, acyloxy, or longer alkanoyloxy, R2 and R3 independently from each other are H or lower alkyl provided that at least one of them is not hydrogen, or R2 and R3 together with the nitrogen adjacent thereto, form a 5 to 7-membered saturated hetero ring, or a salt thereof.
18. A hydroxylamine derivative according to claim 17, wherein Y is longer alkanoyloxy.
19 . N-{[3-(1,1-dimethyl-ethyl)-amino]-2-hydroxy-propoxy}-N'-phenyl-benzamidine hydrochloride.
20 . N-[3-(1-piperidinyl)-propoxy]-N'-phenyl-benzamidine hydrochloride.
21. The use according to claim 1, substantially as herein described with reference to any one of the Examples.
22. The use according to any one of claims 1 to 3, substantially as herein described.
23. Method according to any one of claims 4, 5, 9 or 10, substantially as herein described with reference to any Example thereof. 2 SO O!
24. Method according to any one of claims 4 to 10, substantially a» herein described. J ° ° c/> ££ < S " § mS O • | 42
25. Composition according to claim 11, substantially as herein described with reference to any one of Examples 15 to 20.
26. Composition according to any one of claims 11 to 16, substantially as herein described.
27. A hydroxylamine derivative according to claim 17, substantially as herein described with reference to any one of Examples 1 to 6.
28. A hydroxylamine derivative according to any one of claims 17 to 20, substantially as herein described. BIOREX KUTATO ES FEJLESZTO RT By ifs Attorneys LDWIN SHELSTON WATERS
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HU9700792A HU9700792D0 (en) | 1997-04-22 | 1997-04-22 | Hydroxil-amine derivatives, preparation and use thereof, composition containing these compounds as active ingredients and same use for plants protection against extremity weather conditions |
HU9702365A HUP9702365A3 (en) | 1997-04-22 | 1997-12-05 | Application of hydroxilamin-derivatives, as well as process and composition for increase of weather extreme resistent by cultivated plants |
PCT/HU1998/000039 WO1998047362A1 (en) | 1997-04-22 | 1998-04-21 | Use of hydroxylamine derivatives, and method and preparations for increasing the tolerance of field crops against weather stresses |
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NZ500579A true NZ500579A (en) | 2001-10-26 |
Family
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EP (1) | EP1018876A1 (en) |
JP (1) | JP2002514216A (en) |
AR (1) | AR012482A1 (en) |
AU (1) | AU748367B2 (en) |
BR (1) | BR9808976A (en) |
CA (1) | CA2288075A1 (en) |
CO (1) | CO5040008A1 (en) |
HR (1) | HRP980217A2 (en) |
HU (1) | HUP9702365A3 (en) |
ID (1) | ID20187A (en) |
IL (1) | IL132509A0 (en) |
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WO2003076375A1 (en) * | 2002-03-14 | 2003-09-18 | National Institute Of Agrobiological Sciences | Novel diterpenoids imparting stress resistance to plants |
JP5687490B2 (en) * | 2007-06-29 | 2015-03-18 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Strobilurin for increasing plant tolerance to abiotic stress |
EP2597697A1 (en) | 2011-11-28 | 2013-05-29 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Sealed thin-film device as well as method of repairing, system for repairing and computer program product |
KR20240075869A (en) * | 2021-09-28 | 2024-05-29 | 제브라 덴마크 에이/에스 | Dioxazine and its use in the treatment of GBA-related diseases |
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-
1997
- 1997-12-05 HU HU9702365A patent/HUP9702365A3/en unknown
-
1998
- 1998-04-21 JP JP54531498A patent/JP2002514216A/en active Pending
- 1998-04-21 AR ARP980101827A patent/AR012482A1/en not_active Application Discontinuation
- 1998-04-21 AU AU70703/98A patent/AU748367B2/en not_active Ceased
- 1998-04-21 CA CA002288075A patent/CA2288075A1/en not_active Abandoned
- 1998-04-21 BR BR9808976-5A patent/BR9808976A/en not_active IP Right Cessation
- 1998-04-21 WO PCT/HU1998/000039 patent/WO1998047362A1/en not_active Application Discontinuation
- 1998-04-21 IL IL13250998A patent/IL132509A0/en unknown
- 1998-04-21 NZ NZ500579A patent/NZ500579A/en unknown
- 1998-04-21 EP EP98917479A patent/EP1018876A1/en not_active Withdrawn
- 1998-04-22 HR HRP9702365A patent/HRP980217A2/en not_active Application Discontinuation
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HRP980217A2 (en) | 1998-12-31 |
AR012482A1 (en) | 2000-10-18 |
HUP9702365A2 (en) | 1999-01-28 |
AU748367B2 (en) | 2002-06-06 |
AU7070398A (en) | 1998-11-13 |
EP1018876A1 (en) | 2000-07-19 |
ID20187A (en) | 1998-10-22 |
IL132509A0 (en) | 2001-03-19 |
CA2288075A1 (en) | 1998-10-29 |
WO1998047362A1 (en) | 1998-10-29 |
JP2002514216A (en) | 2002-05-14 |
HUP9702365A3 (en) | 1999-09-28 |
HU9702365D0 (en) | 1998-03-02 |
CO5040008A1 (en) | 2001-05-29 |
BR9808976A (en) | 2000-08-01 |
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