JP2004051485A - Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient - Google Patents
Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient Download PDFInfo
- Publication number
- JP2004051485A JP2004051485A JP2002195879A JP2002195879A JP2004051485A JP 2004051485 A JP2004051485 A JP 2004051485A JP 2002195879 A JP2002195879 A JP 2002195879A JP 2002195879 A JP2002195879 A JP 2002195879A JP 2004051485 A JP2004051485 A JP 2004051485A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen atom
- lower alkyl
- alkyl group
- group
- cinnamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001851 cinnamic acid derivatives Chemical class 0.000 title claims abstract description 24
- 239000004480 active ingredient Substances 0.000 title claims abstract description 20
- 239000000417 fungicide Substances 0.000 title abstract description 6
- 239000004599 antimicrobial Substances 0.000 title abstract 4
- 230000000855 fungicidal effect Effects 0.000 title abstract 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 53
- 239000003899 bactericide agent Substances 0.000 claims description 25
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 241000233866 Fungi Species 0.000 claims description 9
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 7
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 7
- 241000223199 Humicola grisea Species 0.000 claims description 7
- 229930016911 cinnamic acid Natural products 0.000 claims description 7
- 235000013985 cinnamic acid Nutrition 0.000 claims description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 7
- 101100505672 Podospora anserina grisea gene Proteins 0.000 claims description 3
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 claims description 2
- NITWSHWHQAQBAW-QPJJXVBHSA-N (E)-4-coumaric acid methyl ester Chemical compound COC(=O)\C=C\C1=CC=C(O)C=C1 NITWSHWHQAQBAW-QPJJXVBHSA-N 0.000 claims description 2
- BYHBHNKBISXCEP-UHFFFAOYSA-N 3-(4-acetyloxyphenyl)prop-2-enoic acid Chemical compound CC(=O)OC1=CC=C(C=CC(O)=O)C=C1 BYHBHNKBISXCEP-UHFFFAOYSA-N 0.000 claims description 2
- QFIJQJNGZZITLH-UHFFFAOYSA-N 3-(4-propanoyloxyphenyl)prop-2-enoic acid Chemical class CCC(=O)OC1=CC=C(C=CC(O)=O)C=C1 QFIJQJNGZZITLH-UHFFFAOYSA-N 0.000 claims description 2
- ZOQCEVXVQCPESC-UHFFFAOYSA-N ethyl 3-(4-hydroxyphenyl)prop-2-enoate Chemical compound CCOC(=O)C=CC1=CC=C(O)C=C1 ZOQCEVXVQCPESC-UHFFFAOYSA-N 0.000 claims description 2
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 claims description 2
- DZLOUWYGNATKKZ-VMPITWQZSA-N (e)-3-(4-ethoxyphenyl)prop-2-enoic acid Chemical compound CCOC1=CC=C(\C=C\C(O)=O)C=C1 DZLOUWYGNATKKZ-VMPITWQZSA-N 0.000 claims 1
- DZLOUWYGNATKKZ-UHFFFAOYSA-N 4-ethoxycinnamic acid Natural products CCOC1=CC=C(C=CC(O)=O)C=C1 DZLOUWYGNATKKZ-UHFFFAOYSA-N 0.000 claims 1
- 230000002101 lytic effect Effects 0.000 abstract description 18
- 241001121156 Humicola grisea var. grisea Species 0.000 abstract description 4
- 244000053095 fungal pathogen Species 0.000 abstract 1
- 241000894007 species Species 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 230000009089 cytolysis Effects 0.000 description 13
- 201000010099 disease Diseases 0.000 description 12
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 244000052769 pathogen Species 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- -1 —OH Chemical group 0.000 description 7
- 229920001817 Agar Polymers 0.000 description 6
- 229920000298 Cellophane Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 101000962469 Homo sapiens Transcription factor MafF Proteins 0.000 description 6
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 6
- 102100039187 Transcription factor MafF Human genes 0.000 description 6
- 239000008272 agar Substances 0.000 description 6
- 244000052616 bacterial pathogen Species 0.000 description 6
- MMUFAGXJPKNAHT-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1 MMUFAGXJPKNAHT-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 241000221785 Erysiphales Species 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003042 antagnostic effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 241000223218 Fusarium Species 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 206010039509 Scab Diseases 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000002021 butanolic extract Substances 0.000 description 3
- 125000001589 carboacyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 210000000805 cytoplasm Anatomy 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001420 bacteriolytic effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 244000000004 fungal plant pathogen Species 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000743339 Agrostis Species 0.000 description 1
- 201000004384 Alopecia Diseases 0.000 description 1
- 241001621841 Alopecurus myosuroides Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000052363 Cynodon dactylon Species 0.000 description 1
- 240000004585 Dactylis glomerata Species 0.000 description 1
- 241000234642 Festuca Species 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 244000025221 Humulus lupulus Species 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000209082 Lolium Species 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 244000070406 Malus silvestris Species 0.000 description 1
- 241001459558 Monographella nivalis Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241000209049 Poa pratensis Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000589540 Pseudomonas fluorescens Species 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000040738 Sesamum orientale Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 244000152045 Themeda triandra Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001086 cytosolic effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 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 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BCTQJXQXJVLSIG-UHFFFAOYSA-N mepronil Chemical compound CC(C)OC1=CC=CC(NC(=O)C=2C(=CC=CC=2)C)=C1 BCTQJXQXJVLSIG-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000020183 skimmed milk Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
Landscapes
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、植物病原菌類に対し強い溶菌作用を有するケイ皮酸誘導体を有効成分とする農業用抗菌・殺菌剤に関するものである。さらに、ケイ皮酸誘導体及び糸状菌フミコーラ グリセア バル グリセアＭ６８３４を有効成分とする農業用抗菌・殺菌剤に関するものである。
【０００２】
【従来の技術】
雪腐病は、寒冷地の積雪地帯における芝草に特有の病害であり、これらの病原菌の被害を受けた芝草は、積雪下で菌が繁殖し、雪どけ直後茎葉が熱湯をかけたように水浸状淡緑色になって腐敗し、乾燥すると灰白色から淡桃色を呈し枯れる。原因となる病原菌の種類に応じ、雪腐褐色小粒菌核病、雪腐黒色小粒菌核病、雪腐大粒菌核病、紅色雪腐病、褐色雪腐病などの種類が知られている。
【０００３】
これらの雪腐病菌の防除剤としては、従来より８−ヒドロキシキノリン銅などを有効成分とした有機銅剤、３’−イソプロポキシ−２−メチルベンズアニリドを主成分とするメブロニル剤、３−ヒドロキシ−５−メチルイソキサゾールカリウムを主成分とするヒドロキシイソキサゾール剤などが用いられてきた。しかし、これらの薬剤は、人体や動物に対する毒性が強く、環境汚染を引き起こすと共に、継続的に使用すると耐性菌が出現するという問題があった。
【０００４】
これまで病害防除の方法は農薬に大きく依存していたが、近年環境保護の観点より農薬から脱却し、拮抗微生物を有効利用しようとする研究が盛んになってきている。
【０００５】
例えば、特開平７−２８９２４２号公報には、芝草雪腐病の病原菌に対する拮抗菌として、Ｐｓｅｕｄｏｍｏｎａｓ ｆｌｕｏｒｅｓｃｅｎｓ Ａ−１１菌株が開示されている。
【０００６】
また、国際公開ＷＯ９６／２８９７７号公報には、雪腐病原菌に対して拮抗作用を有する糸状菌として、フミコーラ グリセア バル グリセアＭ６８３４（Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ ６８３４）菌株（ＦＥＲＭ ＢＰ−５４５２）が開示されている。しかし、このＭ６８３４菌株が産生していると考えられる、雪腐病の防除機構を発現する物質が抽出、単離されたという報告例はない。
【０００７】
他方、ケイ皮酸誘導体が、各種雪腐病原菌に対する溶菌作用を有し、雪腐病の防除機構を有することはこれまで知られていない。
【０００８】
【発明が解決しようとする課題】
本発明は、各種雪腐病原菌に対し高い溶菌活性を有するケイ皮酸誘導体を有効成分とする農業用抗菌・殺菌剤を提供することを目的とする。さらに、該ケイ皮酸誘導体及び糸状菌フミコーラ グリセア バル グリセアＭ６８３４を有効成分とする農業用抗菌・殺菌剤をも提供することを目的とする。
【０００９】
【課題を解決するための手段】
本発明の発明者らは、Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ ６８３４菌株が、植物病原菌の菌糸に対して何らかの拮抗作用を示す物質を産生し、この物質が各種雪腐病の防除機構に関与していると考えた。発明者らは、鋭意研究の結果、このＭ ６８３４菌株が産生する、各種雪腐病原菌に対し強い溶菌活性を有する物質を抽出、単離することに成功し本発明を完成するに至った。
【００１０】
本発明は、一般式（Ｉ）：
【００１１】
【化６】
（式中、Ｒ１は水素原子又は−ＯＲ５で示される基、Ｒ５は水素原子、低級アルキル基又は低級アルカノイル基、Ｒ２は水素原子又は低級アルキル基、Ｒ３は水素原子又は低級アルキル基、Ｒ４は水素原子又は低級アルキル基を表す）
で示されるケイ皮酸誘導体又はその塩を有効成分とする農業用抗菌・殺菌剤を提供する。
【００１３】
【発明の実施の形態】
本発明の農業用抗菌・殺菌剤は、化合物（Ｉ）で示されるケイ皮酸誘導体を有効成分とするものである。
【００１４】
化合物（Ｉ）において、Ｒ２、Ｒ３、Ｒ４又はＲ５で示される低級アルキルとしては、例えば、炭素数１〜６の直鎖状又は分岐鎖状のアルキルが挙げられ、とりわけ炭素数１〜４の直鎖状又は分岐鎖状のアルキルが挙げられる。具体的には、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル等が挙げられる。
【００１５】
化合物（Ｉ）において、Ｒ５で示される低級アルカノイルとしては、例えば、例えば、炭素数１〜６の直鎖状又は分岐状のアルカノイルが挙げられる。好ましくは、炭素数１〜４の直鎖状又は分岐状のアルカノイルが挙げられ、より好ましくは、ホルミル、アセチル、プロピオニル、ｎ−ブチリル、ｉ−ブチリル、バレリル、ピバロイル等が挙げられる。
【００１６】
好ましいＲ１としては、例えば、水素原子、−ＯＨ、メトキシ、エトキシ、ｎ−プロピルオキシ、ホルミルオキシ、アセチルオキシ、プロピオニルオキシ等が挙げられ、より好ましくは、水素原子、−ＯＨが挙げられる。
【００１７】
好ましいＲ２としては、例えば、水素原子、メチル、エチル等が挙げられ、より好ましくは、水素原子が挙げられる。
【００１８】
好ましいＲ３としては、例えば、水素原子、メチル、エチル等が挙げられ、より好ましくは、水素原子が挙げられる。
【００１９】
好ましいＲ４としては、例えば、水素原子、メチル、エチル、ｎ−プロピル等が挙げられ、より好ましくは、水素原子が挙げられる。
【００２０】
化合物（Ｉ）のうち好ましいものとしては、例えば、一般式（Ｉ−ａ）：
【００２１】
【化７】
（Ｒ１又はＲ４は、前記で定義される通りである）
で示されるケイ皮酸誘導体が挙げられる。
【００２３】
化合物（Ｉ）うちより好ましいものとしては、例えば、ケイ皮酸、ｐ−ヒドロキシケイ皮酸、ｐ−ヒドロキシケイ皮酸メチルエステル、ｐ−ヒドロキシケイ皮酸エチルエステル、ｐ−メトキシケイ皮酸、ｐ−エトキシケイ皮酸、ｐ−アセチルオキシケイ皮酸、ｐ−プロピオニルオキシケイ皮酸等が挙げられる。また、これらからなる群より選ばれる少なくとも１個のケイ皮酸誘導体が挙げられる。
【００２４】
化合物（Ｉ）うち最も好ましいものとしては、ケイ皮酸、ｐ−ヒドロキシケイ皮酸が挙げられる。
【００２５】
化合物（Ｉ）は、二重結合の幾何異性体（シス体又はトランス体、或いはＺ体又はＥ体）を有するが、化合物（Ｉ）は、それらのうちいずれか１個の異性体又はその混合物のいずれをも含むものである。
【００２６】
化合物（Ｉ）は、遊離の形でも、その塩の形でも本発明の用途に用いることができる。塩としては、例えば、リチウム、ナトリウム、カリウム等のアルカリ金属塩、カルシウム等のアルカリ土類金属塩等が挙げられる。
【００２７】
化合物（Ｉ）又はその塩は、溶媒和物（例えば、水、エタノール等）であってもよい。
【００２８】
化合物（Ｉ）は、例えば、次のようにして製造することができる。
【００２９】
【化８】
（Ｒ１、Ｒ２、Ｒ３、及びＲ４は前記で定義される通りである）
化合物（ＩＩ）と化合物（ＩＩＩ）を酢酸ナトリウム等の塩基の存在下で縮合させ、さらに必要に応じ常法によりエステル化することにより化合物（Ｉ）を製造できる。本製造方法は、例えば、Ｊ． Ｒ． Ｊｏｈｎｓｏｎ， Ｏｒｇ． Ｒｅａｃｔ． １， ２１０ （１９４２）等に準じて実施できる。
【００３１】
化合物（Ｉ）は、病原菌（雪腐病菌： Ｆｕｓａｒｉｕｍ ｎｉｖａｌｅ ＭＡＦＦ １０１０４９菌株及びＭｉｃｒｏｎｅｃｔｒｉｅｌｌａ ｎｉｖａｌｉｓ ＭＡＦＦ ３０５０３１菌株）に対し、公知の抗菌作用を有する８−ハイドロキシキノリン銅と同等又はそれ以上の溶菌活性を示すことから、化合物（Ｉ）は、農薬として用いることができる。特に、農業用抗菌・殺菌剤として用いることができる。
【００３２】
本発明の農業用抗菌・殺菌剤は、例えば、芝草の雪腐病（例えば、雪腐褐色小粒菌核病、雪腐黒色小粒菌核病、雪腐大粒菌核病、紅色雪腐病、褐色雪腐病等）、斑点落葉病、葉腐病（例えば、ラージパッチ、ブラウンパッチ等）、疑似葉腐病（例えば、イエローパッチ、象の足跡、春ハゲ病）、フザリウム病、ダラースポット病、ピシウム病、赤焼病、カーブラリア葉枯病、ヘルミントスポリウム葉枯病、さび病、炭疽病；イネのいもち病、ごま葉枯病、苗立枯病；ムギ類の赤かび病、赤さび病、黄さび病、黒さび病、うどんこ病；甘薯の黒斑病等の植物病害に防除効果を有する。
【００３３】
また、本発明の農業用抗菌・殺菌剤は、各種植物の病原菌を防除対象とすることができる。例えば、オーチャードグラス（雪腐病等）、ライグラス（雪腐病等）、ケンタッキーブルーグラス（雪腐病等）、フェスク（雪腐病等）、ベントグラス（葉腐病、雪腐病等）、セントオーガスチングラス（雪腐病等）、ブルーグラス（雪腐病等）、シバ（葉腐病、雪腐病等）、コウライシバ（雪腐病等）、バミューダグラス（カーブラリア葉枯病等）等の牧草用植物；ソラマメ（さび病等）、エンドウ（うどんこ病等）、ホウレンソウ（立枯病等）、セロリ（葉枯病等）、キュウリ（うどんこ病等）、イチゴ（うどんこ病等）、ホップ（灰色かび病等）、リンゴ（赤星病等）、ナシ（黒星病等）、モモ（黒星病等）、カキ（うどんこ病等）、バラ（うどんこ病等）等の農業用植物等が挙げられる。防除対象となる植物病原菌は、上記例示したものに限定されることはない。とりわけ、芝生等の牧草用植物における雪腐病、葉腐病及び疑似葉腐病の防除剤として極めて有効である。
【００３４】
化合物（Ｉ）は、それ自体で農業用抗菌・殺菌剤として用いることができるが、公知の農薬補助剤を含んだ組成物の形態で農業用抗菌・殺菌剤として用いることが好ましい。その形態は、例えば、乳剤、水和剤、水溶剤、懸濁剤（フロアブル剤）、油剤等の液剤；粉剤、微粒剤、粒剤、錠剤、マイクロカプセル剤等の固形剤；くん煙剤；くん蒸剤等の形態の組成物が好適である。農薬用補助剤は、例えば、効果の向上、安定化、分散性の向上等の目的で使用することができ、具体的には、担体（希釈剤）、展着剤、乳化剤、湿展剤、分散剤、崩壊剤等を挙げることができる。
【００３５】
液体担体としては、例えば、水、メタノール、エタノール、ブタノール、グリコール等のアルコール類、アセトン等のケトン類、ジメチルスルホキシド等のスルホキシド類、メチルナフタレン、シクロヘキサン、動植物油、脂肪酸等を挙げることができる。
【００３６】
固体担体としては、例えば、クレー、カオリン、タルク、珪藻土、シリカ、炭酸カルシウム、モンモリナイト、ベントナイト、長石、石英、アルミナ、鋸屑、ニトロセルロース、でんぷん、アラビアゴム等を用いることができる。
【００３７】
乳化剤、分散剤としては、通常の界面活性剤を使用することができ、例えば、高級アルコール硫酸ナトリウム、ステアリルトリメチルアンモニウムクロライド、ポリオキシエチレンラウリルエーテル等の展着剤；ポリオキシエチレンノニルフェニルエーテル、ジアルキルスルホサクシネート等の湿展剤；カルボキシメチルセルロース、ポリビニルアルコール等の固着剤；リグニンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等の崩壊剤を用いることができる。
【００３８】
農業用抗菌・殺菌剤に配合される化合物（Ｉ）の含有量は、特に限定されず、農業用抗菌・殺菌剤の形態、使用の目的及び使用方法等の条件に応じて適宜選択することが可能である。例えば、粉剤、水和剤及び乳化剤等では、農業用抗菌・殺菌剤の全重量に対して、０．００１〜２０重量％程度、好ましくは０．０３〜１０重量％程度の範囲から選択することができる。
【００３９】
農業用抗菌・殺菌剤の形態、製造方法、並びに使用方法は、公知の方法に基づき当業者が適宜選択可能である。
【００４０】
本発明の農業用抗菌・殺菌剤は、有効成分である化合物（Ｉ）以外に、他の殺菌剤、殺虫剤、殺ダニ剤、除草剤、昆虫生育調製剤、肥料、土壌改良剤等の有効成分を任意に配合してもよい。
【００４１】
本発明の農業用抗菌・殺菌剤の施用対象及び施用形態は、特に限定されないが、例えば、茎葉処理（液剤散布、粉剤散布、煙霧等）、種子処理（浸漬、粉衣、塗抹等）、土壌処理（粉剤散布、灌注、混和、くん蒸等）、水面施用（粒剤散布等）等のいずれでもよい。例えば、茎葉散布の場合、１〜１０００ｐｐｍ程度の溶液を１アールあたり１０〜１００Ｌ程度の施用量で用いればよく、水面施用の場合は、通常、有効成分が１〜２０％程度の粒剤では、１アールあたり０．１〜１ｋｇ程度であればよい。
【００４２】
更に、本発明の農業用抗菌・殺菌剤は、農業用抗菌・殺菌剤として使用しうる濃度の範囲では、人体への悪影響を及ぼすことがなく低毒性であり、生分解性がよく安全性が高いという特長をも有する。
【００４３】
本発明の農業用抗菌・殺菌剤は、また、化合物（Ｉ）で示されるケイ皮酸誘導体及びそれを産生する糸状菌であるフミコーラ グリセア バル グリセアＭ６８３４（Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ ６８３４）菌株（ＦＥＲＭ ＢＰ−５４５２）を有効成分とするものである。
【００４４】
糸状菌フミコーラ グリセア バル グリセアＭ６８３４（以下、「Ｍ６８３４」と呼ぶ）は、国際公開ＷＯ９６／２８９７７号公報に記載のように、動植物に対し無害であり、上述した雪腐病原菌をはじめとする他の植物病原菌にも高い拮抗作用を有し、低温に対しても耐性を有し、活動又は増殖が可能であって、土壌に対する定着性も好ましい。
【００４５】
上記公報の記載に従い製造されるＭ６８３４を含有する雪腐病害防除微生物資材と化合物（Ｉ）で示されるケイ皮酸誘導体とを合わせたものを、対象植物に対して施用してもよい。また、該雪腐病害防除微生物資材と化合物（Ｉ）で示されるケイ皮酸誘導体とを、別々に対象植物に対して施用してもよい。ここで、化合物（Ｉ）で示されるケイ皮酸誘導体は、上述のようにそれ自体で用いても農業用補助剤を含んだ組成物の形態で用いてもよい。
【００４６】
糸状菌Ｍ６８３４を含む雪腐病害防除微生物資材と化合物（Ｉ）の配合量、施用量は、特に限定はなく、糸状菌Ｍ６８３４については上記公報に記載の範囲で、また化合物（Ｉ）については上述に記載の範囲で、任意に選択することができる。この併用による病害防除効果は極めて大きい。
【００４７】
【実施例】
以下、本発明の具体例（実施例）を示すが、これにより本発明が限定されるものではない。
【００４８】
実施例１（Ｍ６８３４菌株が産生する溶菌物質の同定）
米糠液体培地の長期低温培養ろ液中でＭ６８３４菌株が産生する溶菌物質を単離同定した。
（１）供試菌株
溶菌観察用として、Ｆｕｓａｒｉｕｍ ｎｉｖａｌｅ （Ｆｒｉｅｓ） Ｃｅｓａｔｉ ＭＡＦＦ １０１０４９菌株、Ｍｉｃｒｏｎｅｃｔｒｉｅｌｌａ ｎｉｖａｌｉｓ （Ｓｃｈｆｆｎｉｔ） ＭＡＦＦ ３０５０３１菌株、及びＨｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ．ｇｒｉｓｅａ Ｍ６８３４菌株を用いた。
（２）溶菌観察用の病原菌の調製
予め２５℃で７日〜１４日間ジャガイモグルコース寒天培地（ＰＤＡ）上で伸長させた菌の菌層先端を、直径３ｍｍのコルクボーラーで打ち抜いた。２％のグルコースを加えた素寒天培地（ＷＡ）上に７ｍｍ四方のセロファンを敷き、含菌寒天の半分がセロファンにかかるように置床した後、２５℃で１〜２日間伸長させた。このとき、各菌の伸長は、セロファンから菌糸先端が出てしまわない程度であった。
（３）溶菌観察用の溶液の調製
溶菌試験を行う各画分の物質を、１％ＤＭＳＯの滅菌水中に溶解させ濃度を３×１０−４ｇ／ｍｌ（＝３００ｐｐｍ）とした。具体的には、各画分の物質をＤＭＳＯに溶かし、このＤＭＳＯ溶液に滅菌水の加えて、滅菌水中のＤＭＳＯの濃度を１％とした。なお、１％ＤＭＳＯ水溶液は、溶菌には影響を与えない濃度である。また、セロファンを浮かべたマルチサンプルケースの１セルには、３００μｌの溶液を入れた。
（４）溶菌の観察方法
上記（３）で得られる溶液に、上記（２）で得られる菌糸を伸ばしておいたセロファンを浮かべ、３℃で４８時間静置した。セロファンをスライドグラス上に取り出し、０．０５％のコットンブルー（ｃｏｔｔｏｎ ｂｌｕｅ）で菌糸を染色後、光学顕微鏡で観察した。菌糸の染色具合により溶菌の程度を評価した（図１参照）。すなわち、下記に示した３タイプの染色度合い（Ａ、Ｂ及びＣ）を示す菌糸細胞を、合計が１００となるように計測し、各割合を下記式にあてはめ溶菌率（％）として求めた。
【００４９】
【式１】
濃青色の細胞（Ａ）：菌糸細胞質が健全で変化がなく、菌糸細胞が完全に染まっているもの。
【００５１】
淡青色の細胞（Ｂ）：菌糸細胞に変化が生じ菌糸細胞がうっすらとしか染まらないもの、又は細胞質凝固により細胞全体が完全に染まりきらないもの。
【００５２】
無色の細胞（Ｃ）：細胞質が完全に消失し、菌糸細胞が全く染まらないもの。
（５）Ｍ６８３４の培養
予め２５℃で７日〜１４日間ジャガイモグルコース寒天培地（ＰＤＡ）上で伸長させたＭ６８３４の菌層先端を、７ｍｍのコルクボーラーで打ち抜き、含菌寒天を米糠液体培地（米糠；３０ｇ、スキムミルク；２０ｇ、グルコース；１０ｇ、蒸留水；１Ｌ）３００ｍｌに１０片接種した。２５℃、１２０ｒｐｍで２日間回転培養した後、３℃で３０日間以上静置培養した。
（６）長期低温培養ろ液からの溶菌活性化合物の抽出・分画（図２参照）
上記（５）で得られる長期低温培養液を吸引ろ過し、培養ろ液（５０Ｌ）をｎ−ＢｕＯＨで抽出した後、濃縮し濃縮物（５３．８４ｇ）を得た。これに水を加えて懸濁させ、ＥｔＯＡｃ、ｎ−ＢｕＯＨの順で再抽出し、ＥｔＯＡｃ抽出物（１２．４２ｇ）、ｎ−ＢｕＯＨ抽出物（２１．４５ｇ）、及び水抽出物（１９．９７ｇ）を得た。各抽出物の溶菌活性を調べたところ、ｎ−ＢｕＯＨ抽出物に溶菌活性が認められた。
【００５３】
【表１】
ｎ−ＢｕＯＨ抽出物を、ＣＨ２Ｃｌ２−ＭｅＯＨ系の溶媒を用いてシリカゲルカラムクロマトグラフィーで分離して、画分１〜４を得た。画分１（５．１５ｇ）に溶菌活性が認められた。
【００５５】
【表２】
次に、画分１を、Ｈｅｘａｎｅ−ＥｔＯＡｃ系の溶媒を用いてシリカゲルカラムクロマトグラフィーで分離して、さらに画分５〜７を得た。画分６（１２４１ｍｇ）に溶菌活性が認められた。
【００５７】
【表３】
次に、画分６を、Ｈｅｘａｎｅ−ＥｔＯＡｃ系の溶媒を用いてシリカゲルカラムクロマトグラフィーで分離して溶菌活性化合物を単離した。溶菌活性化合物のＲｆ値は０．５２（ＥｔＯＡｃ＝１００）であった。
【００５９】
【表４】
溶菌活性化合物の機器分析データ：
ＥＩ−ＭＳ ｍ／ｚ： １６４， １４７， １１９， ９１， ６５， ６３；
ＩＲνｍａｘ ｃｍ−１：３２４０， ２９２６， ２８５４， ２３５３， １６９７， １６０４， １５１６， １２７４， ９８４， ６６６；
トランス体： １Ｈ−ＮＭＲ （５００．００ＭＨｚ， ＣＤＣｌ３， ＴＭＳ内部標準） δｐｐｍ：６．２５（１Ｈ， ｄ， Ｊ＝１４．５Ｈｚ）， ６．６１（１Ｈ， ｂｒｓ）， ６．８５（２Ｈ， ｄｄｄ， Ｊ＝８．０， ３．０， １．０Ｈｚ）， ７．４１（２Ｈ， ｄｄｄ， Ｊ＝８．０， ３．０， １．０Ｈｚ）， ７．５１（１Ｈ， ｄ， Ｊ＝１４．５Ｈｚ）， １０．７５（１Ｈ， ｂｒｓ）；
シス体：１Ｈ−ＮＭＲ （５００．００ＭＨｚ， ＣＤＣｌ３， ＴＭＳ内部標準） δｐｐｍ：５．８１ （１Ｈ， ｄ， Ｊ＝９．１Ｈｚ）， ６．５２（１Ｈ， ｂｒｓ）， ６．６５（２Ｈ， ｄｄｄ， Ｊ＝８．０， ３．０， １．０Ｈｚ）， ６．７５（２Ｈ， ｄｄｄ， Ｊ＝８．０， ３．０， １．０Ｈｚ）， ７．６３（１Ｈ， ｄ， Ｊ＝９．１Ｈｚ）， １１．１０（１Ｈ， ｂｒｓ）．
ＭＳ、ＩＲ及びＮＭＲの機器分析により、上記溶菌活性化合物の同定を試みた。ＭＳから親イオンとして１６４（ベースピーク）が検出された。その他のフラグメンテーションのパターン等からベンゼン環を有する安定な構造からなる化合物であると考えられた。ＩＲスペクトラムからは、３４００ｃｍ−１と１２７３ｃｍ−１にフェノール性水酸基の吸収がみられ、１７００ｃｍ−１の吸収等から共役カルボニル基の存在が示唆された。また、２５８４ｃｍ−１にベンゼン環に共役したオレフィンに基づく吸収がみられた。ＮＭＲスペクトラムからは、５．８１ｐｐｍ及び６．２５ｐｐｍのシグナルから、ベンゼン環に共役したオレフィンの２つのプロトンの存在が確認された。以上より、この化合物の化学構造はｐ−ヒドロキシケイ皮酸の幾何異性体の混合物であると決定された。単離したｐ−ヒドロキシケイ皮酸のトランス体とシス体の比は、ＮＭＲのオレフィンプロトンの積分比（トランス体：６．２５ｐｐｍ、シス体：５．８１ｐｐｍ）より、約５：１であった。
【００６１】
実施例２（溶菌活性化合物と８−ヒドロキシキノリン銅との溶菌活性の比較）
（１）供試菌株
溶菌観察用として、紅色雪腐病を引き起こす、Ｆｕｓａｒｉｕｍ ｎｉｖａｌｅ （Ｆｒｉｅｓ） Ｃｅｓａｔｉ ＭＡＦＦ １０１０４９菌株、Ｍｉｃｒｏｎｅｃｔｒｉｅｌｌａ ｎｉｖａｌｉｓ （Ｓｃｈｆｆｎｉｔ） ＭＡＦＦ ３０５０３１菌株を用いた。
（２）溶菌観察用の病原菌の調製
溶菌観察用の病原菌の調製は、実施例１の（２）に準じて行った。
（３）溶菌観察用の溶液の調製
溶菌活性化合物と８−ヒドロキシキノリン銅の水溶液の濃度調製は、実施例１の（３）に準じて行った。なお、ｐ−ヒドロキシケイ皮酸（カタログＮｏ． １２１０９−１Ａ；関東化学（株）製）、ケイ皮酸（カタログＮｏ． ０３５−０３４１２；和光純薬工業（株）製）は、いずれもトランス体が９８％以上の試薬を用いた。
（４）溶菌の観察方法
溶菌の観察方法は、実施例１の（４）に準じ、各物質の濃度を１００ｐｐｍ、３００ｐｐｍ及び５００ｐｐｍに設定して行った。測定結果を表５及び表６に示す。
【００６２】
【表５】
【表６】
表５よりＦ． ｎｉｖａｌｅ １０１０４９に対し、ｐ−ヒドロキシケイ皮酸及びケイ皮酸は８−ヒドロキシキノリン銅と同等又はそれ以上の溶菌活性を示すことが分かった。また、表６よりＭ． ｎｉｖａｌｉｓ ３０３０５１に対し、ｐ−ヒドロキシケイ皮酸及びケイ皮酸は８−ヒドロキシキノリン銅と同等又はそれ以上の溶菌活性を示すことが分かった。
【００６５】
【発明の効果】
Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ６８３４菌株は雪腐病に対する拮抗作用を有する糸状菌であることは知られていたが、今回、Ｍ６８３４菌株が産生するｐ−ヒドロキシケイ皮酸が雪腐病菌に対する溶菌活性物質であることをつきとめた。
【００６６】
本発明の農業用抗菌・殺菌剤であるｐ−ヒドロキシケイ皮酸、ケイ皮酸等は、８−ヒドロキシキノリン銅と同等又はそれ以上の各種雪腐病原菌に対する溶菌活性を有する。従って、ｐ−ヒドロキシケイ皮酸は、農業用抗菌・殺菌剤、病害防除剤として用いることができる。特に、雪腐病の防除剤として有効に用いることができる。
【００６７】
本発明の農業用抗菌・殺菌剤は低毒性であり、生分解性がよく安全性が高いという特長をも有する。
【００６８】
更に、本発明は、化合物（Ｉ）で示されるケイ皮酸誘導体及び糸状菌Ｍ６８３４を有効成分とする農業用抗菌・殺菌剤をも提供し、高い病害防除効果を発揮する。
【図面の簡単な説明】
【図１】菌糸の細胞質を０．０５％コットン ブルーで染色したときの光学顕微鏡による観察図である。
【図２】Ｈ．Ｍ６８３４の培養ろ液から溶菌活性化合物を単離精製する工程を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an agricultural antibacterial / bactericidal agent containing a cinnamic acid derivative having a strong bacteriolytic action against plant pathogenic fungi as an active ingredient. Further, the present invention relates to an antibacterial and bactericidal agent for agricultural use comprising a cinnamic acid derivative and a filamentous fungus Humicola grisea var glycea M6834 as active ingredients.
[0002]
[Prior art]
Snow rot is a disease peculiar to turfgrass in a snowy region in a cold region, and turfgrass damaged by these pathogens grows under snowfall, and is flooded immediately after snowing as if the foliage was exposed to boiling water. It rots in a pale green state, and when dried, it changes from grayish white to pale pink and withers. Depending on the type of causative pathogenic bacteria, types such as snow rot brown sclerotium, snow rot black sclerotium rot, snow rot large sclerotium, red snow rot and brown snow rot are known.
[0003]
As a controlling agent for these snow rot fungi, an organic copper agent containing 8-hydroxyquinoline copper as an active ingredient, a mebronyl agent containing 3′-isopropoxy-2-methylbenzanilide as a main component, a 3-hydroxy compound, Hydroxyisoxazole agents containing -5-methylisoxazole potassium as a main component have been used. However, these drugs have a problem that they are highly toxic to the human body and animals, cause environmental pollution, and that when used continuously, resistant bacteria appear.
[0004]
Until now, the method of disease control has largely relied on pesticides, but in recent years, studies have been actively conducted to break away from pesticides and effectively utilize antagonistic microorganisms from the viewpoint of environmental protection.
[0005]
For example, JP-A-7-289242 discloses a Pseudomonas fluorescens A-11 strain as an antibacterial agent against pathogens of turfgrass snow rot.
[0006]
In addition, International Publication WO 96/28977 discloses a Humicola grisea var. Grisea M6834 (FERM BP-5452) strain as a filamentous fungus having an antagonistic action against snow rot pathogens. ing. However, there is no report that a substance expressing a mechanism for controlling snow rot, which is considered to be produced by the M6834 strain, was extracted and isolated.
[0007]
On the other hand, it has not been known that cinnamic acid derivatives have a bacteriolytic action against various snow rot pathogens and have a mechanism for controlling snow rot.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide an antibacterial and bactericidal agent for agricultural use comprising a cinnamic acid derivative having high lytic activity against various snow rot pathogens as an active ingredient. Another object of the present invention is to provide an antibacterial and antibacterial agent for agricultural use containing the cinnamic acid derivative and the filamentous fungus Humicola grisea var glycea M6834 as active ingredients.
[0009]
[Means for Solving the Problems]
The inventors of the present invention provide Humicola grisea var. grisea M 6834 strain produced a substance showing some antagonistic action against hyphae of plant pathogenic fungi, and it was considered that this substance was involved in the control mechanism of various snow rots. As a result of intensive studies, the inventors succeeded in extracting and isolating substances having a strong lytic activity against various snow rot pathogens produced by this M 6834 strain, and completed the present invention.
[0010]
The present invention provides a compound represented by the general formula (I):
[0011]
Embedded image
(Wherein, R 1 is a hydrogen atom or a group represented by —OR 5 , R 5 is a hydrogen atom, a lower alkyl group or a lower alkanoyl group, R 2 is a hydrogen atom or a lower alkyl group, and R 3 is a hydrogen atom or a lower alkyl group. Group, R 4 represents a hydrogen atom or a lower alkyl group)
And an agricultural antibacterial and bactericide comprising a cinnamic acid derivative represented by the formula (1) or a salt thereof as an active ingredient
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The agricultural antibacterial / bactericide of the present invention comprises a cinnamic acid derivative represented by the compound (I) as an active ingredient.
[0014]
In the compound (I), examples of the lower alkyl represented by R 2 , R 3 , R 4, or R 5 include straight-chain or branched-chain alkyl having 1 to 6 carbon atoms. And 4 straight-chain or branched-chain alkyls. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl and the like.
[0015]
In the compound (I), examples of the lower alkanoyl represented by R 5 include linear or branched alkanoyl having 1 to 6 carbon atoms. Preferably, a linear or branched alkanoyl having 1 to 4 carbon atoms is used, and more preferably, formyl, acetyl, propionyl, n-butyryl, i-butyryl, valeryl, pivaloyl and the like are used.
[0016]
Preferred examples of R 1 include a hydrogen atom, —OH, methoxy, ethoxy, n-propyloxy, formyloxy, acetyloxy, propionyloxy, and the like, and more preferably a hydrogen atom and —OH.
[0017]
Preferred R 2 include, for example, a hydrogen atom, methyl, ethyl and the like, and more preferred is a hydrogen atom.
[0018]
Preferred R 3 include, for example, a hydrogen atom, methyl, ethyl and the like, and more preferably a hydrogen atom.
[0019]
Preferred R 4 include, for example, a hydrogen atom, methyl, ethyl, n-propyl and the like, and more preferred is a hydrogen atom.
[0020]
Preferred examples of the compound (I) include, for example, a compound represented by the general formula (Ia):
[0021]
Embedded image
(R 1 or R 4 is as defined above)
And cinnamic acid derivatives represented by
[0023]
More preferable compounds (I) include, for example, cinnamic acid, p-hydroxycinnamic acid, p-hydroxycinnamic acid methyl ester, p-hydroxycinnamic acid ethyl ester, p-methoxycinnamic acid, p-methoxycinnamic acid -Ethoxycinnamic acid, p-acetyloxycinnamic acid, p-propionyloxycinnamic acid and the like. In addition, at least one cinnamic acid derivative selected from the group consisting of these is cited.
[0024]
Among the compounds (I), most preferred are cinnamic acid and p-hydroxycinnamic acid.
[0025]
Compound (I) has a double bond geometric isomer (cis or trans form, or Z or E form), and compound (I) is any one of them or a mixture thereof. Both of these are included.
[0026]
Compound (I) can be used in the present invention in a free form or a salt thereof. Examples of the salt include alkali metal salts such as lithium, sodium, and potassium, and alkaline earth metal salts such as calcium.
[0027]
Compound (I) or a salt thereof may be a solvate (eg, water, ethanol, and the like).
[0028]
Compound (I) can be produced, for example, as follows.
[0029]
Embedded image
(R 1 , R 2 , R 3 , and R 4 are as defined above)
Compound (I) can be produced by condensing compound (II) and compound (III) in the presence of a base such as sodium acetate and, if necessary, esterifying the compound by a conventional method. This production method is described in, for example, R. Johnson, Org. React. 1, 210 (1942).
[0031]
Compound (I) has a bactericidal activity against pathogenic bacteria (snow rot fungi: Fusarium nivare MAFF 101049 strain and Micronectriella nivaris MAFF 305031 strain) which is equivalent to or higher than 8-hydroxyquinoline copper having a known antibacterial action. The compound (I) can be used as an agricultural chemical. In particular, it can be used as an agricultural antibacterial / bactericide.
[0032]
The agricultural antibacterial and fungicidal agents of the present invention include, for example, snow rot of turfgrass (for example, snow rot brown sclerotium, snow rot black sclerotium, snow rot large sclerotium, red snow rot, brown rot) Snow rot, spot leaf rot, leaf rot (eg, large patch, brown patch, etc.), pseudo-leaf rot (eg, yellow patch, elephant footprint, spring baldness), fusarium disease, dollar spot disease, Pycium disease, red blight, carburaria leaf blight, hermint sporium leaf blight, rust, anthrax; rice blast, sesame leaf blight, seedling blight; wheat rust, red rust It has an effect of controlling plant diseases such as yellow rust, black rust and powdery mildew;
[0033]
Further, the agricultural antibacterial / bactericide of the present invention can control pathogenic bacteria of various plants. For example, orchard grass (snow rot, etc.), ryegrass (snow rot, etc.), Kentucky blue grass (snow rot, etc.), fescue (snow rot, etc.), bentgrass (leaf rot, snow rot, etc.), cent Pasture such as Augustingrass (snow rot), bluegrass (snow rot), grass (leaf rot, snow rot, etc.), blackgrass (snow rot, etc.), bermudagrass (carburaria leaf wilt, etc.) Plants: Broad bean (rust, etc.), pea (powdery mildew, etc.), spinach (root blight, etc.), celery (leaf blight, etc.), cucumber (powdery mildew, etc.), strawberry (powdery mildew, etc.), Agricultural plants such as hops (grey mold), apples (scab), pears (scab), peaches (scab), oysters (powder), roses (powder), etc. Is mentioned. The plant pathogenic bacteria to be controlled are not limited to those exemplified above. In particular, it is extremely effective as an agent for controlling snow rot, leaf rot and pseudo-leaf rot in grassy plants such as lawns.
[0034]
The compound (I) itself can be used as an agricultural antibacterial / bactericide, but is preferably used as an agricultural antibacterial / bactericide in the form of a composition containing a known agricultural chemical adjuvant. Examples of the form include liquids such as emulsions, wettable powders, aqueous solvents, suspensions (flowables), and oils; solids such as powders, fine granules, granules, tablets, and microcapsules; Compositions in the form of fumigants and the like are preferred. Auxiliary agents for pesticides can be used, for example, for the purpose of improving effects, stabilizing, improving dispersibility, and the like. Specifically, carriers (diluents), spreading agents, emulsifiers, wetting agents, Dispersants, disintegrants and the like can be mentioned.
[0035]
Examples of the liquid carrier include water, alcohols such as methanol, ethanol, butanol, and glycol, ketones such as acetone, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animal and vegetable oils, and fatty acids.
[0036]
As the solid carrier, for example, clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.
[0037]
As the emulsifier and the dispersant, ordinary surfactants can be used, for example, spreading agents such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene lauryl ether; polyoxyethylene nonylphenyl ether, dialkyl Wetting agents such as sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium ligninsulfonate and sodium lauryl sulfate can be used.
[0038]
The content of the compound (I) to be added to the agricultural antibacterial / bactericide is not particularly limited, and can be appropriately selected according to conditions such as the form, purpose of use, and method of use of the agricultural antibacterial / bactericide. It is possible. For example, in the case of powders, wettable powders, emulsifiers, etc., the amount is selected from the range of about 0.001 to 20% by weight, preferably about 0.03 to 10% by weight, based on the total weight of the agricultural antibacterial / bactericide. Can be.
[0039]
The form, production method, and use method of the antibacterial and bactericide for agricultural use can be appropriately selected by those skilled in the art based on known methods.
[0040]
The agricultural antibacterial / bactericide of the present invention can be used as an active ingredient other than the compound (I) as an effective ingredient such as other fungicides, insecticides, acaricides, herbicides, insect growth regulators, fertilizers, soil conditioners and the like. The components may be optionally blended.
[0041]
The application object and application form of the agricultural antibacterial / bactericide of the present invention are not particularly limited. For example, foliage treatment (liquid spray, dust spray, fume, etc.), seed treatment (immersion, powder coating, smear, etc.), soil Any of treatment (spraying powder, irrigation, admixing, fumigation, etc.), surface application (spraying granules, etc.) may be used. For example, in the case of foliage application, a solution of about 1 to 1000 ppm may be used at an application rate of about 10 to 100 L per are, and in the case of water application, in the case of granules having an active ingredient of about 1 to 20%, It may be about 0.1 to 1 kg per 1 are.
[0042]
Furthermore, the agricultural antibacterial / bactericide of the present invention has a low toxicity without adverse effects on the human body, and has good biodegradability and safety within a range of concentrations that can be used as an agricultural antibacterial / bactericide. It also has the feature of being expensive.
[0043]
The antibacterial and antibacterial agent for agricultural use of the present invention also includes a cinnamic acid derivative represented by the compound (I) and a fungus producing the same, a strain of Humicola grisea var. Grisea M6834 (FERM). BP-5452) as an active ingredient.
[0044]
As described in International Publication WO96 / 28977, the filamentous fungus Humicola grisea bal glycea M6834 (hereinafter referred to as “M6834”) is harmless to animals and plants and other plants including the above-described snow-rot pathogens. It also has a high antagonism against pathogenic bacteria, has resistance to low temperatures, can be active or multiplied, and has good fixation to soil.
[0045]
A combination of the microbial material for controlling snow rot disease containing M6834 and the cinnamic acid derivative represented by the compound (I), which is produced according to the description in the above publication, may be applied to the target plant. Further, the snow rot disease controlling microorganism material and the cinnamic acid derivative represented by the compound (I) may be separately applied to a target plant. Here, the cinnamic acid derivative represented by the compound (I) may be used by itself or in the form of a composition containing an agricultural auxiliary as described above.
[0046]
The compounding amount and application amount of the compound (I) and the snow rot disease controlling microbial material containing the filamentous fungus M6834 are not particularly limited, and the filamentous fungus M6834 is in the range described in the above-mentioned publication, and the compound (I) is described above. Can be arbitrarily selected within the range described in. The disease control effect by this combination is extremely large.
[0047]
【Example】
Hereinafter, specific examples (examples) of the present invention will be described, but the present invention is not limited thereto.
[0048]
Example 1 (Identification of lysate produced by strain M6834)
A lysate produced by the M6834 strain was isolated and identified in a long-term low-temperature culture filtrate of rice bran liquid medium.
(1) For observation of the lysis of the test strain, Fusarium nivale (Fries) Cesati MAFF 101049 strain, Micronectriella nivaris (Schffnit) MAFF 305031 strain, and Humicola grisea var. grisea M6834 strain was used.
(2) Preparation of Pathogenic Bacteria for Observation of Lysis The tip of the bacterial layer that had been elongated on a potato glucose agar medium (PDA) at 25 ° C. for 7 to 14 days was punched out with a cork borer having a diameter of 3 mm. A 7 mm square cellophane was spread on a plain agar medium (WA) to which 2% glucose was added, and half of the agar-containing agar was placed on the cellophane so that it was allowed to elongate at 25 ° C for 1 to 2 days. At this time, the elongation of each bacterium was such that the mycelium tip did not come out of cellophane.
(3) Preparation of Solution for Observation of Bacteria The substance of each fraction to be subjected to the lysis test was dissolved in sterile water of 1% DMSO to a concentration of 3 × 10 −4 g / ml (= 300 ppm). Specifically, the substance in each fraction was dissolved in DMSO, and sterilized water was added to this DMSO solution to make the concentration of DMSO in the sterilized water 1%. The 1% DMSO aqueous solution has a concentration that does not affect lysis. Further, 300 μl of the solution was placed in one cell of the multi-sample case with cellophane floating thereon.
(4) Method of Observing Lysis Cellophane from which the hyphae obtained in (2) above had been stretched was floated on the solution obtained in (3) above, and allowed to stand at 3 ° C. for 48 hours. Cellophane was taken out on a slide glass, stained with 0.05% cotton blue, and observed with an optical microscope. The degree of lysis was evaluated by the degree of staining of the hypha (see FIG. 1). That is, the mycelium cells showing the three types of staining degree (A, B and C) shown below were measured so that the total would be 100, and each ratio was determined by applying the following formula to the lysis rate (%).
[0049]
(Equation 1)
Dark blue cells (A): those with healthy and unchanged mycelial cytoplasm and completely stained mycelial cells.
[0051]
Light blue cells (B): those in which the hyphal cells are altered and the mycelial cells are slightly stained, or those in which the whole cells are not completely stained by cytoplasmic coagulation.
[0052]
Colorless cells (C): those in which the cytoplasm is completely lost and the mycelium cells are not stained at all.
(5) Cultivation of M6834 The tip of the bacterial layer of M6834, which had been elongated on a potato glucose agar medium (PDA) at 25 ° C. for 7 to 14 days, was punched out with a 7 mm cork borer, and the bacterial agar was added to a rice bran liquid medium (rice bran). 30 g, skim milk; 20 g, glucose; 10 g, distilled water; 1 L). After rotating culture at 25 ° C. and 120 rpm for 2 days, static culture was performed at 3 ° C. for 30 days or more.
(6) Extraction and fractionation of lytic compounds from long-term low-temperature culture filtrate (see Fig. 2)
The long-term low-temperature culture solution obtained in the above (5) was subjected to suction filtration, the culture filtrate (50 L) was extracted with n-BuOH, and then concentrated to obtain a concentrate (53.84 g). This was suspended by adding water, re-extracted with EtOAc and n-BuOH in that order, and extracted with EtOAc (12.42 g), n-BuOH extract (21.45 g), and water extract (19.97 g). ) Got. When the lytic activity of each extract was examined, the lytic activity was observed in the n-BuOH extract.
[0053]
[Table 1]
The n-BuOH extract was separated by silica gel column chromatography using a CH 2 Cl 2 -MeOH-based solvent to obtain fractions 1 to 4. Bactericidal activity was observed in fraction 1 (5.15 g).
[0055]
[Table 2]
Next, Fraction 1 was separated by silica gel column chromatography using a Hexane-EtOAc-based solvent to further obtain Fractions 5 to 7. Bactericidal activity was observed in fraction 6 (1241 mg).
[0057]
[Table 3]
Next, Fraction 6 was separated by silica gel column chromatography using a Hexane-EtOAc-based solvent to isolate a lytic active compound. The Rf value of the lytic active compound was 0.52 (EtOAc = 100).
[0059]
[Table 4]
Instrumental analysis data for lytic active compounds:
EI-MS m / z: 164, 147, 119, 91, 65, 63;
IRν max cm -1 : 3240, 2926, 2854, 2353, 1697, 1604, 1516, 1274, 984, 666;
Trans form: 1 H-NMR (500.00 MHz, CDCl 3 , TMS internal standard) δ ppm: 6.25 (1H, d, J = 14.5 Hz), 6.61 (1H, brs), 6.85 (2H) , Ddd, J = 8.0, 3.0, 1.0 Hz), 7.41 (2H, ddd, J = 8.0, 3.0, 1.0 Hz), 7.51 (1H, d, J) = 14.5 Hz), 10.75 (1H, brs);
Cis form: 1 H-NMR (500.00 MHz, CDCl 3 , TMS internal standard) δ ppm: 5.81 (1H, d, J = 9.1 Hz), 6.52 (1H, brs), 6.65 (2H) , Ddd, J = 8.0, 3.0, 1.0 Hz), 6.75 (2H, ddd, J = 8.0, 3.0, 1.0 Hz), 7.63 (1H, d, J) = 9.1 Hz), 11.10 (1H, brs).
Identification of the lytic active compound was attempted by instrumental analysis of MS, IR and NMR. 164 (base peak) was detected from MS as a parent ion. From other fragmentation patterns and the like, it was considered to be a compound having a stable structure having a benzene ring. From the IR spectrum, absorption of the phenolic hydroxyl group was observed at 3400 cm -1 and 1273cm -1, presence of a conjugated carbonyl group from the absorption or the like of 1700 cm -1 was suggested. Further, an absorption based on an olefin conjugated to a benzene ring was observed at 2584 cm −1 . From the NMR spectrum, signals at 5.81 ppm and 6.25 ppm confirmed the presence of two protons of the olefin conjugated to the benzene ring. From the above, the chemical structure of this compound was determined to be a mixture of geometric isomers of p-hydroxycinnamic acid. The ratio of the trans-isomer to the cis-isomer of the isolated p-hydroxycinnamic acid was about 5: 1 from the integral ratio of olefin protons in NMR (trans-isomer: 6.25 ppm, cis-isomer: 5.81 ppm). .
[0061]
Example 2 (Comparison of lytic activity between lytic active compound and 8-hydroxyquinoline copper)
(1) Fusarium nivare (Fries) Cesati MAFF 101048 strain and Micronectriella nivaris (Schffnit) MAFF 305031 strain, which cause red snow rot, were used for lysis observation of the test strain.
(2) Preparation of Pathogenic Bacteria for Observation of Lysis Pathogens for observation of lysis were prepared according to (2) of Example 1.
(3) Preparation of Solution for Observing Lysis The concentration of the aqueous solution of the lytic active compound and 8-hydroxyquinoline copper was adjusted according to (3) of Example 1. In addition, p-hydroxycinnamic acid (catalog No. 12109-1A; manufactured by Kanto Chemical Co., Ltd.) and cinnamic acid (catalog No. 035-03412; manufactured by Wako Pure Chemical Industries, Ltd.) are all trans-forms. Used a reagent of 98% or more.
(4) Method of Observing Lysis The method of observing lysis was performed according to (4) of Example 1, with the concentration of each substance set to 100 ppm, 300 ppm, and 500 ppm. Tables 5 and 6 show the measurement results.
[0062]
[Table 5]
[Table 6]
From Table 5, F.I. It was found that p-hydroxycinnamic acid and cinnamic acid exhibited a lytic activity equal to or higher than that of copper 8-hydroxyquinoline for Nivale 104949. Also, from Table 6, M.P. It was found that p-hydroxycinnamic acid and cinnamic acid exhibited a lytic activity equivalent to or higher than that of 8-hydroxyquinoline copper with respect to Nivalis 303051.
[0065]
【The invention's effect】
Humicola grisea var. grisea M6834 was known to be a filamentous fungus having an antagonistic action against snow rot, but this time it was determined that p-hydroxycinnamic acid produced by M6834 is a lytic substance against snow rot. Was.
[0066]
The agricultural antibacterial and bactericidal agents of the present invention, such as p-hydroxycinnamic acid and cinnamic acid, have lytic activity against various snow rot pathogens equal to or higher than copper 8-hydroxyquinoline. Accordingly, p-hydroxycinnamic acid can be used as an agricultural antibacterial / bactericide and disease control agent. In particular, it can be effectively used as an agent for controlling snow rot.
[0067]
The agricultural antibacterial / bactericide of the present invention has the characteristics of low toxicity, good biodegradability and high safety.
[0068]
Further, the present invention also provides an agricultural antibacterial and bactericide containing the cinnamic acid derivative represented by the compound (I) and the filamentous fungus M6834 as active ingredients, and exhibits a high disease control effect.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view observed by an optical microscope when the cytoplasm of a hypha is stained with 0.05% cotton blue.
FIG. It is a figure which shows the process of isolating and purifying a lytic active compound from the culture filtrate of M6834.
Claims (7)
で示されるケイ皮酸誘導体又はその塩を有効成分とする農業用抗菌・殺菌剤。General formula (I):
An agricultural antibacterial / bactericide comprising a cinnamic acid derivative or a salt thereof as an active ingredient.
で示されるケイ皮酸誘導体又はその塩を有効成分とする農業用抗菌・殺菌剤。General formula (Ia):
An agricultural antibacterial / bactericide comprising a cinnamic acid derivative or a salt thereof as an active ingredient.
で示されるケイ皮酸誘導体又はその塩、及び糸状菌フミコーラ グリセア バルグリセアＭ６８３４（Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ ６８３４）菌株（ＦＥＲＭ
ＢＰ−５４５２）を有効成分とする農業用抗菌・殺菌剤。General formula (I):
And a salt thereof, and a filamentous fungus Humicola grisea var. Grisea M6834 (FERM)
An agricultural antibacterial / bactericide containing BP-5452) as an active ingredient.
で示されるケイ皮酸誘導体又はその塩を植物に適用することを特徴とする雪腐病の防除方法。General formula (I):
A method for controlling snow rot, comprising applying a cinnamic acid derivative or a salt thereof represented by the formula (1) to a plant.
で示されるケイ皮酸誘導体又はその塩、及び糸状菌フミコーラ グリセア バルグリセアＭ６８３４（Ｈｕｍｉｃｏｌａ ｇｒｉｓｅａ ｖａｒ． ｇｒｉｓｅａ Ｍ ６８３４）菌株（ＦＥＲＭＢＰ−５４５２）を植物に適用することを特徴とする雪腐病の防除方法。General formula (I):
A method for controlling snow rot, comprising applying to a plant a cinnamic acid derivative represented by the formula (I) or a salt thereof, and a fungus, Humicola grisea var.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002195879A JP2004051485A (en) | 2002-05-27 | 2002-07-04 | Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002152002 | 2002-05-27 | ||
| JP2002195879A JP2004051485A (en) | 2002-05-27 | 2002-07-04 | Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004051485A true JP2004051485A (en) | 2004-02-19 |
Family
ID=31948914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002195879A Pending JP2004051485A (en) | 2002-05-27 | 2002-07-04 | Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004051485A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190178A (en) * | 2010-03-11 | 2011-09-29 | Dainichiseika Color & Chem Mfg Co Ltd | Phytopathogenic fungus inhibitor, fertilizer composition for inhibiting phytopathogenic fungus and method for producing the same |
| CN106588662A (en) * | 2016-11-01 | 2017-04-26 | 西北农林科技大学 | (E)-cinnamate compounds and synthetic methods thereof, and medicines containing compounds and application thereof |
| CN109053431A (en) * | 2018-08-30 | 2018-12-21 | 北京清源保生物科技有限公司 | Application of the ferulic acid or derivatives thereof in prevention and treatment bacteriosis or nosomycosis |
| CN116210697A (en) * | 2023-03-02 | 2023-06-06 | 西北农林科技大学 | Application of trans-cinnamic acid in improving the resistance of apple tree rot |
| JP2024145786A (en) * | 2023-03-31 | 2024-10-15 | ブルネエズ株式会社 | Cleansing compositions and methods for producing same |
-
2002
- 2002-07-04 JP JP2002195879A patent/JP2004051485A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190178A (en) * | 2010-03-11 | 2011-09-29 | Dainichiseika Color & Chem Mfg Co Ltd | Phytopathogenic fungus inhibitor, fertilizer composition for inhibiting phytopathogenic fungus and method for producing the same |
| CN106588662A (en) * | 2016-11-01 | 2017-04-26 | 西北农林科技大学 | (E)-cinnamate compounds and synthetic methods thereof, and medicines containing compounds and application thereof |
| CN109053431A (en) * | 2018-08-30 | 2018-12-21 | 北京清源保生物科技有限公司 | Application of the ferulic acid or derivatives thereof in prevention and treatment bacteriosis or nosomycosis |
| CN116210697A (en) * | 2023-03-02 | 2023-06-06 | 西北农林科技大学 | Application of trans-cinnamic acid in improving the resistance of apple tree rot |
| JP2024145786A (en) * | 2023-03-31 | 2024-10-15 | ブルネエズ株式会社 | Cleansing compositions and methods for producing same |
| JP7705163B2 (en) | 2023-03-31 | 2025-07-09 | ブルネエズ株式会社 | Cleansing compositions and methods for producing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4416851B2 (en) | Bactericidal and fungicidal 2-methoxybenzophenones | |
| EP3520614B1 (en) | Use of grammicin as active ingredient in a nematode control method | |
| JPH07502985A (en) | Fungicide | |
| TW200808183A (en) | Azolymethyloxiranes, their use for controlling phytopathogenic fungi, and compositions comprising them | |
| JPS609748B2 (en) | 1,2-dichlorocyanovinyl compound and its use as a microbial inhibitor | |
| KR101802911B1 (en) | Composition for controlling root knot nematode comprising kojic acid as effective component and uses thereof | |
| JPH0794436B2 (en) | Fluorophthalimides, their production method, and agricultural and horticultural fungicides containing them as active ingredients | |
| KR940010036B1 (en) | Process for preparing macrocyclic compound | |
| JP2004051485A (en) | Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient | |
| KR101143033B1 (en) | Compositions for protecting Plant diseases | |
| KR20120075936A (en) | Bacillus sp. pb25 strain isolated from soil and uses thereof | |
| KR101230367B1 (en) | Composition for controlling plant diseases which comprises phloretin or Malus domestica extract containing them, and method for controlling plant diseases using the same | |
| KR900006709B1 (en) | Process for the preparation of sulf enylated acylhydrazones | |
| JP4165714B2 (en) | Solderin and its derivatives used as crop antifungal agents | |
| JPH0267208A (en) | Agricultural and horticultural germicide | |
| JPH02279670A (en) | Microbicide composite | |
| HU209950B (en) | Microbiological process for producing agriculturally acceptable active ingredients and fungicid composition containing them | |
| DE69321724T2 (en) | FUNGICIDES AND INSECTICIDAL COMPOUNDS AND COMPOSITIONS DERIVED FROM FUNGIC STRANCHES OF PYRENOPHORA TERES | |
| JPS61291582A (en) | Fungicde composition and tertiary amine compound | |
| KR100826663B1 (en) | Fungicidal composition containing bromophenol compound isolated from Odonthalia korim beeper | |
| KR101861913B1 (en) | A insecticidal composition comprising an amide | |
| JP3624209B2 (en) | Agricultural and horticultural fungicides | |
| DK179669B1 (en) | Succinimide compound | |
| KR100835677B1 (en) | Fungicidal composition containing a halysulfate compound isolated from hippospongia | |
| KR100832746B1 (en) | Polyacetylene compound or a composition for controlling plant diseases containing thistle root extract comprising the same and a plant disease control method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040512 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080402 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080827 |