CN106397422A - 含手性噁唑啉的烟酰胺类化合物及作为农用杀菌剂的用途 - Google Patents
含手性噁唑啉的烟酰胺类化合物及作为农用杀菌剂的用途 Download PDFInfo
- Publication number
- CN106397422A CN106397422A CN201610762194.8A CN201610762194A CN106397422A CN 106397422 A CN106397422 A CN 106397422A CN 201610762194 A CN201610762194 A CN 201610762194A CN 106397422 A CN106397422 A CN 106397422A
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- CN
- China
- Prior art keywords
- oxazoline
- compound
- compound containing
- nicotinamide
- carbon
- 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.)
- Granted
Links
- -1 Nicotinamide compound Chemical class 0.000 title claims abstract description 32
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 235000005152 nicotinamide Nutrition 0.000 title claims abstract description 28
- 239000011570 nicotinamide Substances 0.000 title claims abstract description 26
- 229960003966 nicotinamide Drugs 0.000 title claims abstract description 26
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 19
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000575 pesticide Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 8
- 239000005740 Boscalid Substances 0.000 claims description 7
- 241000813090 Rhizoctonia solani Species 0.000 claims description 7
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 claims description 7
- 229940118790 boscalid Drugs 0.000 claims description 7
- 201000010099 disease Diseases 0.000 claims description 7
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000000417 fungicide Substances 0.000 claims description 6
- 241000221696 Sclerotinia sclerotiorum Species 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 2
- 150000005480 nicotinamides Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- ZMYFCFLJBGAQRS-IRXDYDNUSA-N (2R,3S)-epoxiconazole Chemical compound C1=CC(F)=CC=C1[C@@]1(CN2N=CN=C2)[C@H](C=2C(=CC=CC=2)Cl)O1 ZMYFCFLJBGAQRS-IRXDYDNUSA-N 0.000 claims 1
- AMNAZJFEONUVTD-KEWDHRJRSA-N (2s,3s,4s,5r,6r)-6-(4-amino-2-oxopyrimidin-1-yl)-4,5-dihydroxy-3-[[(2s)-3-hydroxy-2-[[2-(methylamino)acetyl]amino]propanoyl]amino]oxane-2-carboxamide Chemical compound O1[C@H](C(N)=O)[C@@H](NC(=O)[C@H](CO)NC(=O)CNC)[C@H](O)[C@@H](O)[C@@H]1N1C(=O)N=C(N)C=C1 AMNAZJFEONUVTD-KEWDHRJRSA-N 0.000 claims 1
- BKBSMMUEEAWFRX-NBVRZTHBSA-N (E)-flumorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(F)=CC=1)=C\C(=O)N1CCOCC1 BKBSMMUEEAWFRX-NBVRZTHBSA-N 0.000 claims 1
- QNBTYORWCCMPQP-JXAWBTAJSA-N (Z)-dimethomorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(Cl)=CC=1)=C/C(=O)N1CCOCC1 QNBTYORWCCMPQP-JXAWBTAJSA-N 0.000 claims 1
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims 1
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 claims 1
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 claims 1
- 239000005730 Azoxystrobin Substances 0.000 claims 1
- 239000005747 Chlorothalonil Substances 0.000 claims 1
- 239000005757 Cyproconazole Substances 0.000 claims 1
- 239000005760 Difenoconazole Substances 0.000 claims 1
- 239000005761 Dimethomorph Substances 0.000 claims 1
- 239000005767 Epoxiconazole Substances 0.000 claims 1
- FEACDOXQOYCHKU-UHFFFAOYSA-N Gougerotin Natural products CNCC(=O)NC1=NC(=O)N(C=C1)C2OC(C(O)C(NC(=O)C(N)CO)C2O)C(=O)N FEACDOXQOYCHKU-UHFFFAOYSA-N 0.000 claims 1
- 239000005802 Mancozeb Substances 0.000 claims 1
- 239000005807 Metalaxyl Substances 0.000 claims 1
- 239000005818 Picoxystrobin Substances 0.000 claims 1
- 239000005822 Propiconazole Substances 0.000 claims 1
- 239000005825 Prothioconazole Substances 0.000 claims 1
- 239000005869 Pyraclostrobin Substances 0.000 claims 1
- 239000005839 Tebuconazole Substances 0.000 claims 1
- 239000005857 Trifloxystrobin Substances 0.000 claims 1
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical group CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 claims 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 claims 1
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- WLPCAERCXQSYLQ-UHFFFAOYSA-N isotianil Chemical compound ClC1=NSC(C(=O)NC=2C(=CC=CC=2)C#N)=C1Cl WLPCAERCXQSYLQ-UHFFFAOYSA-N 0.000 claims 1
- ZQEIXNIJLIKNTD-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alaninate Chemical compound COCC(=O)N(C(C)C(=O)OC)C1=C(C)C=CC=C1C ZQEIXNIJLIKNTD-UHFFFAOYSA-N 0.000 claims 1
- 239000004530 micro-emulsion Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- IBSNKSODLGJUMQ-SDNWHVSQSA-N picoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1COC1=CC=CC(C(F)(F)F)=N1 IBSNKSODLGJUMQ-SDNWHVSQSA-N 0.000 claims 1
- WHHIPMZEDGBUCC-UHFFFAOYSA-N probenazole Chemical compound C1=CC=C2C(OCC=C)=NS(=O)(=O)C2=C1 WHHIPMZEDGBUCC-UHFFFAOYSA-N 0.000 claims 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 claims 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 claims 1
- 239000000375 suspending agent Substances 0.000 claims 1
- WOSNCVAPUOFXEH-UHFFFAOYSA-N thifluzamide Chemical compound S1C(C)=NC(C(F)(F)F)=C1C(=O)NC1=C(Br)C=C(OC(F)(F)F)C=C1Br WOSNCVAPUOFXEH-UHFFFAOYSA-N 0.000 claims 1
- VJQYLJSMBWXGDV-UHFFFAOYSA-N tiadinil Chemical compound N1=NSC(C(=O)NC=2C=C(Cl)C(C)=CC=2)=C1C VJQYLJSMBWXGDV-UHFFFAOYSA-N 0.000 claims 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 claims 1
- 239000004562 water dispersible granule Substances 0.000 claims 1
- 239000004563 wettable powder Substances 0.000 claims 1
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 241000894006 Bacteria Species 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- 241000209094 Oryza Species 0.000 description 8
- 235000007164 Oryza sativa Nutrition 0.000 description 8
- 235000009566 rice Nutrition 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- FDLSEUGNQNFTFX-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)aniline Chemical compound NC1=CC=CC=C1C1=NCCO1 FDLSEUGNQNFTFX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 241000209140 Triticum Species 0.000 description 6
- 235000021307 Triticum Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 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 5
- 241000123650 Botrytis cinerea Species 0.000 description 5
- 241000223218 Fusarium Species 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 125000004076 pyridyl group Chemical group 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 241000227653 Lycopersicon Species 0.000 description 4
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 4
- 208000031888 Mycoses Diseases 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 241000233616 Phytophthora capsici Species 0.000 description 4
- 241000233622 Phytophthora infestans Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 241000222199 Colletotrichum Species 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- IBRSSZOHCGUTHI-UHFFFAOYSA-N 2-chloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Cl IBRSSZOHCGUTHI-UHFFFAOYSA-N 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 2
- 241000213004 Alternaria solani Species 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 2
- 241000223195 Fusarium graminearum Species 0.000 description 2
- 241000251511 Holothuroidea Species 0.000 description 2
- 241001330975 Magnaporthe oryzae Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 2
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 2
- 239000006013 carbendazim Substances 0.000 description 2
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- ULWOJODHECIZAU-UHFFFAOYSA-N n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)C ULWOJODHECIZAU-UHFFFAOYSA-N 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- BKMMTJMQCTUHRP-GSVOUGTGSA-N (2r)-2-aminopropan-1-ol Chemical group C[C@@H](N)CO BKMMTJMQCTUHRP-GSVOUGTGSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WPJQSSOGCLGFDI-SSDOTTSWSA-N 2-[(4R)-4-methyl-4,5-dihydro-1,3-oxazol-2-yl]aniline Chemical compound C[C@@H]1COC(=N1)c1ccccc1N WPJQSSOGCLGFDI-SSDOTTSWSA-N 0.000 description 1
- USNRYBPPOQLMAB-AWEZNQCLSA-N 2-[(4R)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]aniline Chemical compound C1(=CC=CC=C1)[C@H]1N=C(OC1)C1=C(N)C=CC=C1 USNRYBPPOQLMAB-AWEZNQCLSA-N 0.000 description 1
- XTDZGXBTXBEZDN-UHFFFAOYSA-N 3-(difluoromethyl)-N-(9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl)-1-methylpyrazole-4-carboxamide Chemical compound CC(C)C1C2CCC1C1=C2C=CC=C1NC(=O)C1=CN(C)N=C1C(F)F XTDZGXBTXBEZDN-UHFFFAOYSA-N 0.000 description 1
- 239000005737 Benzovindiflupyr Substances 0.000 description 1
- 241001290235 Ceratobasidium cereale Species 0.000 description 1
- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241001149475 Gaeumannomyces graminis Species 0.000 description 1
- 239000005799 Isopyrazam Substances 0.000 description 1
- CCCGEKHKTPTUHJ-UHFFFAOYSA-N N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC2=C1C1CCC2C1=C(Cl)Cl CCCGEKHKTPTUHJ-UHFFFAOYSA-N 0.000 description 1
- XQJQCBDIXRIYRP-UHFFFAOYSA-N N-{2-[1,1'-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methyl-1pyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1C(C2CC2)C1 XQJQCBDIXRIYRP-UHFFFAOYSA-N 0.000 description 1
- 241000576755 Sclerotia Species 0.000 description 1
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 1
- 239000005834 Sedaxane Substances 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 244000000004 fungal plant pathogen Species 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ATBIAJXSKNPHEI-UHFFFAOYSA-N pyridine-3-carbonyl chloride Chemical compound ClC(=O)C1=CC=CN=C1 ATBIAJXSKNPHEI-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C07D413/12—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 linked by a chain containing hetero atoms as chain links
-
- 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
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Abstract
本发明涉及一类新颖的含手性噁唑啉的烟酰胺类化合物，以及该类化合物作为农用杀菌剂的用途，该类化合物的化学结构式如下式(I)所示，式中的各基团的意义见说明书，此类化合物的手性对抑菌活性有显著影响：
Description
技术领域
本发明涉及一类新的含手性噁唑啉的烟酰胺类化合物及作为农用杀菌剂的用途；特别是指该类化合物在植物真菌病害防治中的应用，属于农药技术领域。
背景技术
从分子水平角度讲，农药分子在生物体内发挥药效是一个手性识别过程，配体和受体的匹配性将关系到活性大小和安全性，手性的重要性在现代农药开发中也越来越得到凸显，目前商品化手性农药在农药市场中已超过三分之一(Lamberth，C.，et al.，Science，2013，341，742-746.)。手性农药创制使化学品的精准高效使用成为可能，符合绿色新农药创制的要求。
酰胺类化合物在药物化学与农药化学领域中扮演着重要的角色，是农用杀菌剂开发领域经典且充满活力的一类。较具有代表性的酰胺杀菌剂就是琥珀酸脱氢酶抑制剂(SDHIs)，目前开发成功且商品化的已有18种，并且构建出这类杀菌剂的药效团模型(Sierotzki，H.and Scalliet，G.，.Phytopathology 2013，103(9)，880-887.；Xiong，L.；etal.ACS Symposium Series，2015，1204，Chapter 13，175-194.)。这类杀菌剂多为芳香化的平面结构，且均没有涉及到立体构型，典型的代表为2003年巴斯夫(BASF)开发的杀菌剂啶酰菌胺(Boscalid)；近期由先正达开发成功的琥珀酸脱氢酶抑制剂(SDHIs)类杀菌剂，如吡唑萘菌胺(isopyrazam)、氟唑环菌胺(sedaxane)和苯并烯氟菌唑(benzovindiflupyr)等，虽然在结构上均表现出部分去芳香化的特征，但仍没有涉及到立体构型对药效的影响。近期针对烟酰胺杀菌剂啶酰菌胺的结构优化取得了不错的进展，如引入芳醚单元(Wen，F.；etal..Pesticide Biochemistry and Physiology，2010，98(2)，248-253)或者多样的杂环单元(Du，S.；etal.Molecules，2015，20(5)，8395-8408.)。但目前针对琥珀酸脱氢酶抑制剂(SDHIs)类杀菌剂中的啶酰菌胺均没有涉及到手性问题，也没有噁唑啉单元的引入。
本发明设计合成了含有手性噁唑啉的烟酰胺类化合物，发现其对植物真菌病害有强烈的抑制作用，手性对抑菌活性有显著影响。这类化合物的比啶酰菌胺易于合成且成本低，这对新农药的创制有积极意义。
发明内容
本发明要解决的技术问题是提供含有手性噁唑啉的烟酰胺类化合物的制备方法及其在防治植物真菌病害中的应用。本发明的含有手性噁唑啉的烟酰胺类化合物表现出很好的抑制真菌病害的作用，并且噁唑啉环的手性(立体构型)对抑菌活性有显著的影响。
本发明提供的含有手性噁唑啉的烟酰胺类化合物具有如下通式(I)所示结构。
通式(I)中噁唑啉环上手性碳的立体构型为R或者S。
取代基R1分别代表：氢、卤素、甲基，羟基，氨基，1-6碳烷氧基、1-6碳烷氨基、芳香氧基、芳香氨基、二氟甲基、三氟甲基、二氟甲氧基、三氟甲氧基。以及同时含有2～3个R1所代表的取代基。
取代基R2分别代表：氢、甲基、羟亚甲基、1-4碳烷基、芳香基和芳香基亚甲基。
其中芳香基是指苯基类和杂环类取代基；
苯基类取代基包括苯基；和卤素、羟基、氨基、1-6碳烷氧基、1-6碳烷氨基取代的苯基；
杂环类取代基包括：吡啶基和卤素、羟基、氨基、1-6碳烷氧基、1-6碳烷氨基取代的吡啶基；吲哚基和有卤素、羟基、氨基、1-6碳烷氧基、1-6碳烷氨基取代的吲哚基；咪唑基和N原子上有1-16碳烃基取代的咪唑基、N原子上有苄基或者苯基取代的咪唑基。
本发明还包括如通式(I)所示的含有手性噁唑啉的烟酰胺类化合物在农药化学上可以接受的盐。
本发明涉及的化合物可以根据如下合成路线来进行化学完成。
本发明所涉及的含有手性噁唑啉的烟酰胺类化合物，以廉价易得的邻氨基苯腈为起始原料来进行合成，其特征在于包括以下两个步骤：
步骤(1)，将邻氨基苯腈和手性氨基醇溶于无水氯苯中，加入10mol％的无水氯化锌作催化剂，回流反应72小时，减压下蒸除溶剂，用氢氧化钠溶液淬灭反应后，乙酸乙酯或者二氯甲烷萃取，无水硫酸钠干燥，柱层析分离获得邻(4，5-二氢-2-噁唑-基)苯胺中间体A。
步骤(2)，方法一：在氮气保护下，将邻(4，5-二氢-2-噁唑-基)苯胺中间体A溶于无水二氯甲烷或者二氯乙烷中，加入1.4倍量的缚酸剂三乙胺(亦可以用二乙胺，二乙基异丙基胺代替)，冰浴条件下，向其中缓慢加入烟酰氯的二氯甲烷溶液(或者二氯乙烷溶液)，体系自然升至室温，饱和氯化铵溶液淬灭反应，水洗，脱溶，柱层析分离得目标物。
方法二：在氮气保护下，将邻(4，5-二氢-2-噁唑-基)苯胺中间体A和烟酸溶于无水二氯甲烷或者二氯乙烷中，加入1.1倍量的缩合剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDCI)，随后加入1.5倍量的缚酸剂三乙胺(亦可以用二乙胺，二乙基异丙基胺代替)以及催化量(10mol％)的4-二甲氨基吡啶(DMAP)，室温下搅拌反应，饱和氯化铵溶液淬灭反应，水洗，脱溶，柱层析分离得目标物。
本发明所提供的含有手性噁唑啉的烟酰胺类化合物的合成具有原料廉价易得、合成步骤少及易于操作的特点。
本发明所涉及的含有手性噁唑啉的烟酰胺类化合物，优选如下化合物：
本发明所涉及的化合物还包括由通式(I)所示的含有手性噁唑啉的烟酰胺类化合物在农药学上可以接收的盐。
本发明所提供的含有手性噁唑啉的烟酰胺类化合物对植物病原真菌的活性，包括水稻纹枯病菌(Rhizoctonia solani)，小麦纹枯病菌(Rhizoctonia cerealis)，油菜菌核病菌(Sclerotinia scleotiorum)，小麦赤霉病菌(Fusarium graminearum)，小麦全蚀病菌(Gaeumanomyce graminis)，番茄灰霉病菌(Botrytis cinerea)，马铃薯晚疫病菌(Phytophthora infestans)，辣椒疫霉病菌(Phytophthora capsici)，番茄早疫病菌(Alternaria solani)，水稻恶苗病菌(Fusarium fujikuroi)，马铃薯干腐病菌(Fusariumsulphureum)，黄瓜炭疽病菌(Colletotrichum lagenarium)，水稻稻瘟病菌(Phyriculariacerealis)。
具体实施方式
通过下述实施例和生测实验结果，可进一步说明和理解本发明，但并不意味着限制本发明。
实施例一：(R)-2-氯-N-(2-(4-苯基-4，5-4，5-二氢-2-噁唑基)苯基)烟酰胺I-8a的合成
步骤(1)将邻氨基苯腈(1.18g，10mmol)和(R)-2-氨基-2-苯乙醇(1.65g，12mmol)溶于15mL无水氯苯中，加入10mol％的无水氯化锌(0.136g)作催化剂，回流反应72小时，减压下蒸除溶剂，向其中加入15％氢氧化钠溶液(15mL)淬灭反应，用二氯甲烷萃取(15mLX3)，合并有机相，无水硫酸钠干燥，减压蒸除溶剂，硅胶柱层析(200～300目，石油醚/乙酸乙酯＝2∶1)分离，获得(R)-2-(4-苯基-4，5-二氢-2-噁唑基)苯胺A-I-8a，1.69g，产率71％。LC-MS(ESI+)m/z：Calcd.for[M+H：C15H15N2O]：239.12，Found：239.21。
步骤(2)称取邻(4，5-二氢-2-噁唑基)苯胺中间体A-I-8a(1mmol，0.238g)和2-氯烟酸(0.165g，1.05mmol)于干净干燥的schlenk反应瓶中，在氮气保护下，溶于加入10mL无水二氯甲烷溶解，加入缩合剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDCI，0.211g，1.1mmol)，随后加入1.5倍量的缚酸剂三乙胺(0.21mL，1.5mmol)以及催化量的4-二甲氨基吡啶(DMAP，0.012g，0.1mmol)，室温下搅拌反应，反应完毕后，向体系中加入10mL饱和氯化铵溶液淬灭反应，分液，用二氯甲烷萃取(10mL X 2)，合并有机相，无水硫酸钠干燥，减压蒸除溶剂，硅胶柱层析(200～300目，石油醚/乙酸乙酯＝4∶1～2∶1)分离，得目标物(R)N-(2-(4-苯基-4，5-4，5-二氢-2-噁唑基)苯基)烟酰胺I-8a。白色固体，279mg，产率74％。熔点95.6～96.7℃。LC-MS(ESI+)m/z：Calcd.for[M+H：C21H17ClN3O2]：378.10 and 380.10，Found：378.17 and 380.17。
实施例二：(R)-N-(2-(4-甲基-4，5-4，5-二氢-2-噁唑基)苯基)烟酰胺的合成
步骤(1)制备方法同实施例一步骤(1)，用(R)-2-氨基-1-丙醇代替(R)-2-氨基-2-苯乙醇，产率74％。LC-MS(ESI+)m/z：Calcd.for[M+H：C10H13N2O]：177.10，Found：177.17。
步骤(2)制备方法同实施例一步骤(1)，用烟酸代替2-氯烟酸，用(R)-2-(4-甲基-4，5-二氢-2-噁唑基)苯胺代替邻(4，5-二氢-2-噁唑基)苯胺中间体A-I-8a；得(R)-N-(2-(4-甲基-4，5-二氢-2-噁唑基)苯基)烟酰胺，
白色固体，产率79％，熔点m.p.88.1～88.4℃，1H-NMR(CDCl3，400MHz)δ：1.47(d，J＝5.08Hz，3H，CH3)，3.97(dd，J1＝5.92Hz，J2＝5.76Hz，1H，1H in OCH2)，4.52～4.61(m，2H，1H in OCH2 and 1H in CHN-CH3)，7.17(ddd，1H，J1＝6.32Hz，J2＝5.88Hz，J3＝0.84Hz，1H，aromatic H in phenyl ring)7.53～7.57(m，2H，aromatic H in phenyl ring andPyridyl ring)，7.92(dd，J1＝6.32Hz，J2＝1.24Hz，1H，aromatic H in phenyl ring)，8.53(m，1H，aromatic H in Pyridyl ring)，8.79(dd，J1＝3.88Hz，J2＝1.08Hz，1H，aromatic Hin phenyl ring)，8.90(dd，J1＝6.20Hz，J2＝0.56Hz，1H，aromatic H in Pyridyl ring)，9.37(d，1H，J＝1.40Hz，aromatic H in Pyridyl ring)，13.41(s，1H，NH).13C-NMR andDEPT135(CDCl3，100MHz)δ：21.6(CH3)，61.9(CH)，72.9(OCH2)，113.8(C)，119.9(CH)，123.1(CH)，124.1(CH)，129.4(CH)，131.7(C)，132.8(CH)，137.2(CH)，139.7，147.5(CH)，150.6(CH)，163.2(C)，163.9(C).Elemental anal.calcd for C16H15N3O2：C，68.31；H，5.37；N，14.94；Found：C，68.42；H，5.41；N，14.96.ESI-MS，Calcd for[M+H，C16H16N3O2]282.12，found282.19.
实施例三：含有手性噁唑啉的烟酰胺类化合物的抑菌活性测定
采用平板抑制菌丝生长速率法进行离体抑菌活性评价，选取测试菌株于PDA平板进行活化，包括水稻纹枯病菌(Rhizoctonia solani)，小麦纹枯病菌(Rhizoctoniacerealis)，油菜菌核病菌(Sclerotinia scleotiorum)，小麦赤霉病菌(Fusariumgraminearum)，小麦全蚀病菌(Gaeumanomyce graminis)，番茄灰霉病菌(Botrytiscinerea)，马铃薯晚疫病菌(Phytophthora infestans)，辣椒疫霉病菌(Phytophthoracapsici)，番茄早疫病菌(Alternaria solani)，水稻恶苗病菌(Fusarium fujikuroi)，马铃薯干腐病菌(Fusarium sulphureum)，黄瓜炭疽病菌(Colletotrichum lagenarium)，水稻稻瘟病菌(Phyricularia cerealis)。将化合物配置成系列梯度浓度的PDA含药平板，将测试菌株制成5mm直径菌饼置于含药培养皿中央，25℃恒温培养至空白对照皿的测试菌株长至接近培养皿边缘时，用十字交叉法测量各含药平板的菌落直径，计算化合物对菌丝生长的抑制率，对病害的抑制率按照如下公式计算：
使用统计软件SPSS20.0计算抑制率为50％时化合物的浓度，即EC50值。重复3次取平均值。以多菌灵(carbendazim)为阳性对照，各化合物对植物病原菌的EC50值(mg/L)。
表1 含有手性噁唑啉的烟酰胺类化合物的抑菌活性
从表中可以看出，含有手性噁唑啉的烟酰胺类化合物对植物病害有较好的抑制作用。且噁唑啉环上4位取代基的体积和立体构型对抑菌活性有显著影响。有取代基对活性提高时必须的，但空间体积不宜过大。4位取代基的体积对抑菌活性的影响有如下趋势Ph＜Bu＜Pr＜Et。一般而言，噁唑啉环上4位的立体构型为R构型时，抑菌活性要好于S构型的对映异构体。
当噁唑啉环上4位为乙基取代基，且构型为R时，抑菌活性最为明显，对水稻纹枯病菌、番茄灰霉病菌和油菜菌核病菌的抑制中浓度分别低至0.58mg/L，0.43mg/L和2.07mg/L。其对水稻纹枯病菌、番茄灰霉病菌的活性明显高于阳性对照啶酰菌胺。有望作为一类新型的杀菌剂候选化合物或者直接作为杀菌剂使用，对新农药创制将有重要意义。
本发明所涉及的含有手性噁唑啉的烟酰胺类化合物作为农用杀菌剂的用途已经通过具体的实例进行了描述，本领域技术人员可借鉴本发明内容，适当改变原料、工艺条件等环节来实现相应的其它目的，其相关改变都没有脱离本发明的内容，所有类似的替换和改动对于本领域技术人员来说是显而易见的，都被视为包括在本发明的范围之内。
Claims (6)
1.如下通式(I)所示的含手性噁唑啉的烟酰胺类化合物，及其农药上可以接受的盐。
其中，
通式(I)中噁唑啉环上手性碳的立体构型为R或者S。
取代基R1分别代表：氢、卤素、甲基，羟基，氨基，1-6碳烷氧基、1-6碳烷氨基、芳香氧基、芳香氨基、二氟甲基、三氟甲基、二氟甲氧基、三氟甲氧基。以及同时含有2～3个R1所代表的取代基。
取代基R2分别代表：氢、甲基、羟亚甲基、1-4碳烷基、芳香基和芳香基亚甲基。
2.权利要求1通式(I)所示的化合物，其特征在于，包括以下化合物：
3.权利要求1所示的含手性噁唑啉的烟酰胺类化合物在防治农业植物病害上的应用。
4.如权利3所要求的应用，其特征在于，所述的农业病害为油菜菌核病菌(Sclerotiniascleotiorum)，水稻纹枯病菌(Rhizoctonia solani)和番茄灰霉病菌(Botrytiscinerea)。
5.根据权利3和4的用途，所述化合物可以加工成乳油、水乳剂、微乳剂、可湿性粉剂、水分散粒剂、悬浮剂和其他适宜剂型。
6.权利要求1和2所述含手性噁唑啉的烟酰胺类化合物在防治植物病害中的应用，其特征在于，它和商品化杀菌剂中的一种或多种组合在制备复配杀菌剂中的用途；商品化杀菌剂选自嘧菌酯、吡唑醚菌酯、丙硫菌唑、肟菌酯、环菌唑、代森锰锌、氟环唑、戊唑醇、啶酰菌胺、甲霜灵、啶氧菌酯、苯醚甲环唑、丙环唑、百菌清、噻酰菌胺、甲噻诱胺、异噻菌胺、宁南霉素、烯丙异噻唑、氟吗啉、烯酰吗啉。
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| CN113788790A (zh) * | 2021-10-18 | 2021-12-14 | 华东理工大学 | 一种芳香杂环酰胺衍生物及其应用 |
| CN114213353A (zh) * | 2022-01-20 | 2022-03-22 | 贵州大学 | 一种芳基-噁唑-噁唑啉类化合物及其制备方法和应用 |
| CN114436988A (zh) * | 2020-11-05 | 2022-05-06 | 江西仰立新材料有限公司 | 一种1,3-双(4,5-二氢-2-噁唑基)苯的制备方法及其应用 |
| CN114736170A (zh) * | 2022-05-20 | 2022-07-12 | 贵州大学 | 含噻(噁)唑啉的芳基酰胺类化合物及其制备方法和制备杀菌剂的应用 |
| CN115433141A (zh) * | 2022-09-06 | 2022-12-06 | 贵州大学 | 一种α-肟基苯乙酰胺类化合物及其制备方法和作为农用杀菌剂的应用 |
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| CN114436988A (zh) * | 2020-11-05 | 2022-05-06 | 江西仰立新材料有限公司 | 一种1,3-双(4,5-二氢-2-噁唑基)苯的制备方法及其应用 |
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| CN114213353A (zh) * | 2022-01-20 | 2022-03-22 | 贵州大学 | 一种芳基-噁唑-噁唑啉类化合物及其制备方法和应用 |
| CN114736170A (zh) * | 2022-05-20 | 2022-07-12 | 贵州大学 | 含噻(噁)唑啉的芳基酰胺类化合物及其制备方法和制备杀菌剂的应用 |
| CN115433141A (zh) * | 2022-09-06 | 2022-12-06 | 贵州大学 | 一种α-肟基苯乙酰胺类化合物及其制备方法和作为农用杀菌剂的应用 |
| CN115433141B (zh) * | 2022-09-06 | 2023-08-22 | 贵州大学 | 一种α-肟基苯乙酰胺类化合物及其制备方法和作为农用杀菌剂的应用 |
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