CN111574466A - Novel allyl benzoate compound containing triazole as well as preparation method and application thereof - Google Patents
Novel allyl benzoate compound containing triazole as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN111574466A CN111574466A CN202010504490.4A CN202010504490A CN111574466A CN 111574466 A CN111574466 A CN 111574466A CN 202010504490 A CN202010504490 A CN 202010504490A CN 111574466 A CN111574466 A CN 111574466A
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- Prior art keywords
- triazole
- formula
- arh
- phenyl
- reaction
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Links
- -1 allyl benzoate compound Chemical class 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 25
- 125000001424 substituent group Chemical group 0.000 claims abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 13
- 230000005764 inhibitory process Effects 0.000 claims abstract description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 5
- 241000221696 Sclerotinia sclerotiorum Species 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000005711 Benzoic acid Substances 0.000 claims description 30
- 235000010233 benzoic acid Nutrition 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- RXGNQUOYJPSWRW-UHFFFAOYSA-N 1-phenyl-2-(1,2,4-triazol-1-yl)ethanone Chemical compound C=1C=CC=CC=1C(=O)CN1C=NC=N1 RXGNQUOYJPSWRW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical class C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PEUPUKDBCPLDIH-UHFFFAOYSA-N 1,2,4-triazole Chemical group C1=NC=N[N]1 PEUPUKDBCPLDIH-UHFFFAOYSA-N 0.000 claims description 7
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 6
- AMSRANWZOYZEKJ-LFIBNONCSA-N (E)-1,3-diphenyl-2-(1,2,4-triazol-1-yl)prop-2-en-1-one Chemical compound C1=CC=C(C=C1)/C=C(\C(=O)C2=CC=CC=C2)/N3C=NC=N3 AMSRANWZOYZEKJ-LFIBNONCSA-N 0.000 claims description 5
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000000417 fungicide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 4
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 45
- 239000000575 pesticide Substances 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract 1
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 description 55
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 52
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- ODSNCZIFTQVJLF-UHFFFAOYSA-N prop-2-enyl 3-nitrobenzoate Chemical compound [O-][N+](=O)C1=CC=CC(C(=O)OCC=C)=C1 ODSNCZIFTQVJLF-UHFFFAOYSA-N 0.000 description 9
- JUZUVYLOVZGXAN-UHFFFAOYSA-N prop-2-enyl 4-methoxybenzoate Chemical compound COC1=CC=C(C(=O)OCC=C)C=C1 JUZUVYLOVZGXAN-UHFFFAOYSA-N 0.000 description 8
- 229940045860 white wax Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- ZJVOQVIQHLGYNO-LFIBNONCSA-N (E)-1,3-diphenyl-2-(1,2,4-triazol-1-yl)prop-2-en-1-ol Chemical compound C1=CC=C(C=C1)/C=C(\C(C2=CC=CC=C2)O)/N3C=NC=N3 ZJVOQVIQHLGYNO-LFIBNONCSA-N 0.000 description 4
- YTRZIGHLUAGZLF-MHWRWJLKSA-N (E)-1-phenyl-2-(1,2,4-triazol-1-yl)-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-ol Chemical compound C1=CC=C(C=C1)C(/C(=C\C2=CC=C(C=C2)C(F)(F)F)/N3C=NC=N3)O YTRZIGHLUAGZLF-MHWRWJLKSA-N 0.000 description 4
- GRUJFKXNBSECHW-MHWRWJLKSA-N (E)-1-phenyl-2-(1,2,4-triazol-1-yl)-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-one Chemical compound C1=CC=C(C=C1)C(=O)/C(=C\C2=CC=C(C=C2)C(F)(F)F)/N3C=NC=N3 GRUJFKXNBSECHW-MHWRWJLKSA-N 0.000 description 4
- ATCRIUVQKHMXSH-UHFFFAOYSA-N 2,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1Cl ATCRIUVQKHMXSH-UHFFFAOYSA-N 0.000 description 4
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 4
- YNWVFADWVLCOPU-MDWZMJQESA-N (1E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical group C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MDWZMJQESA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000005788 Fluxapyroxad Substances 0.000 description 3
- 241000233616 Phytophthora capsici Species 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SXSGXWCSHSVPGB-UHFFFAOYSA-N fluxapyroxad Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1=CC(F)=C(F)C(F)=C1 SXSGXWCSHSVPGB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- QAPRPPQBBCRDKG-UHFFFAOYSA-N prop-2-enyl 2-chlorobenzoate Chemical compound ClC1=CC=CC=C1C(=O)OCC=C QAPRPPQBBCRDKG-UHFFFAOYSA-N 0.000 description 3
- WJTFPKSSYSADRW-UHFFFAOYSA-N prop-2-enyl 3-methylbenzoate Chemical compound CC1=CC=CC(C(=O)OCC=C)=C1 WJTFPKSSYSADRW-UHFFFAOYSA-N 0.000 description 3
- GGJIQHHMXJIVPF-UHFFFAOYSA-N prop-2-enyl 4-methylbenzoate Chemical compound CC1=CC=C(C(=O)OCC=C)C=C1 GGJIQHHMXJIVPF-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RMOGWMIKYWRTKW-UONOGXRCSA-N (S,S)-paclobutrazol Chemical compound C([C@@H]([C@@H](O)C(C)(C)C)N1N=CN=C1)C1=CC=C(Cl)C=C1 RMOGWMIKYWRTKW-UONOGXRCSA-N 0.000 description 2
- QAOJBHRZQQDFHA-UHFFFAOYSA-N 2,3-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1Cl QAOJBHRZQQDFHA-UHFFFAOYSA-N 0.000 description 2
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 2
- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 2
- ATZHGRNFEFVDDJ-UHFFFAOYSA-N 4-propylbenzoic acid Chemical compound CCCC1=CC=C(C(O)=O)C=C1 ATZHGRNFEFVDDJ-UHFFFAOYSA-N 0.000 description 2
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 2
- 241001530056 Athelia rolfsii Species 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 2
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 2
- 241000223221 Fusarium oxysporum Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000005985 Paclobutrazol Substances 0.000 description 2
- 241000233622 Phytophthora infestans Species 0.000 description 2
- 239000005822 Propiconazole Substances 0.000 description 2
- 241000813090 Rhizoctonia solani Species 0.000 description 2
- 241001558929 Sclerotium <basidiomycota> Species 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- MXNBDFWNYRNIBH-UHFFFAOYSA-N 3-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC(F)=C1 MXNBDFWNYRNIBH-UHFFFAOYSA-N 0.000 description 1
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 1
- 241000213004 Alternaria solani Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000123650 Botrytis cinerea Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020323 ClF3 Inorganic materials 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000223195 Fusarium graminearum Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- 241000315044 Passalora arachidicola Species 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 239000005846 Triadimenol Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008686 ergosterol biosynthesis Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Abstract
The invention discloses a novel allyl benzoate compound containing triazole and a preparation method and application thereof, wherein the structural formula of the novel allyl benzoate compound containing triazole is shown as a formula (I):
in formula (I): substituent R1Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R2Is hydrogen or trifluoromethyl. The novel allyl benzoate compound containing triazole disclosed by the invention is a novel compound with bactericidal activity, and can kill rape bacteria at a concentration of 50ppmThe sclerotinia sclerotiorum has better inhibition rate, and provides a foundation for the research and development of new pesticides.
Description
Technical Field
The invention relates to a novel allyl benzoate compound containing triazole and a preparation method and application thereof.
Background
The nitrogen-containing heterocyclic compound has wide biological activity, and is therefore significant in the process of pesticide preparation. The triazole fungicide belongs to an organic heterocyclic nitrogen compound, is an ergosterol synthesis inhibitor and has good control effect on most fungal diseases harmful to the growth of crops. Over the last several decades, triazole bactericides occupy a huge market due to the advantages of high efficiency, broad spectrum, low toxicity and the like, and due to the fact that most triazole bactericides have the plant growth regulating function, research on triazole antifungal medicines is concerned. To date, several tens of thousands of triazole compounds have been synthesized one after another, and most of them are 1,2, 4-triazole compounds, and the varieties that have been commercialized are more than 40, such as triadimefon (triadimifon), triadimenol (triadiminol), propiconazole (propiconazole), Paclobutrazol (Paclobutrazol), and the like. With the frequent use of triazole fungicides in agriculture, some disadvantages are revealed, and the single active site of the triazole fungicides loses high efficiency due to the fact that the triazole fungicides are more and more resistant to the fungi due to the frequent use.
The design and synthesis of the novel triazole bactericide have important significance for developing novel pesticides with high efficiency, low toxicity and low residue.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a novel allyl benzoate compound containing triazole as well as a preparation method and application thereof. The invention designs and synthesizes triazole series compounds based on that an uniconazole structure is taken as a matrix, a benzene ring, a triazole ring and a carbon-carbon double bond of the uniconazole are kept unchanged, chlorine on the benzene ring is replaced by hydrogen and trifluoromethyl, a tert-butyl group of the uniconazole is replaced by the benzene ring, an ester group and an aromatic ring are introduced on a hydroxyl group to synthesize an ester compound so as to investigate the influence on the biological activity of the compound.
The novel allyl benzoate compound containing triazole is characterized in that the structural formula is shown as the formula (I):
in formula (I): substituent R1Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R2Is hydrogen or trifluoromethyl.
The novel allyl benzoate compound containing triazole is characterized in that R in the formula (I)1Is one of the following: phenyl, 2-methylphenyl, 2-chlorophenyl, 2, 4-dichlorophenyl, 3-methoxyphenyl, 2, 6-dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-methylphenyl, 2, 3-dichlorophenyl, 4-tert-butylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 3-methylphenyl, 4-fluorophenyl, 3-nitrophenyl, 3-chlorophenyl.
The preparation method of the novel allyl benzoate compound containing triazole is characterized by comprising the following steps:
1) alpha-bromoacetophenone and 1,2, 4-triazole are mixed in an organic solvent A, the temperature is controlled to be below 0 ℃, triethylamine is dropwise added, the mixture is stirred at room temperature for reaction, and the reaction process is tracked by TLC; after the reaction is finished, filtering to remove triethylamine hydrochloride generated in the reaction, and after desolventizing the filtrate, recrystallizing the filtrate by using an organic solvent B to prepare 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethane-1-ketone shown in a formula (II);
2) heating 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) obtained in the step 1), benzaldehyde or p-trifluoromethylbenzaldehyde and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; after the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, washing with water, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and carrying out column chromatography separation and purification treatment on the concentrate to obtain the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III);
3) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) obtained in the step 2) in an organic reagent D, adding PEG600 and sodium borohydride, stirring and reacting under the ice bath condition of 0 ℃, and tracking the reaction process by TLC; after the reaction is finished, desolventizing the reaction solution, dropwise adding 0.5-2N hydrochloric acid solution into the desolventized concentrate, extracting by using an organic reagent E, combining organic phases, drying by using anhydrous sodium sulfate, filtering, and treating by using a spin-dried solvent to obtain a (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as a formula (IV);
4) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding DMAP, EDC and substituted benzoic acid, stirring at room temperature for reaction, and tracking the reaction process by TLC; after the reaction is finished, washing with water, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain the novel allyl benzoate compound containing triazole as shown in the formula (I);
wherein, R is1Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R2Is hydrogen or trifluoromethyl.
The preparation method of the novel allyl benzoate compound containing triazole is characterized in that the organic solvent A in the step 1) is a ketone solvent, preferably acetone; the organic solvent B is an alcohol solvent, preferably isopropanol; the organic solvent C in the step 2) is a benzene solvent, preferably toluene; the organic reagent D in the step 3) is an alcohol solvent, preferably methanol; the organic reagent E in the step 3) and the organic solvent F in the step 4) are both dichloromethane.
The preparation method of the novel allyl benzoate compound containing triazole is characterized in that in the step 1), the feeding molar ratio of the alpha-bromoacetophenone to the 1,2, 4-triazole is 1: 1.1-1.5; in the step 2), the feeding molar ratio of 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) to (p-trifluoromethyl) benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) to the sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as the formula (IV) to the substituted benzoic acid is 1: 1.1-1.5.
The preparation method of the novel allyl benzoate compound containing triazole is characterized in that the volume usage of the organic solvent A in the step 1) is 1-2 mL/mmol based on the mass of alpha-bromoacetophenone, the volume usage of the organic solvent C in the step 2) is 1-1.5 mL/mmol based on the mass of 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethane-1-ketone shown in the formula (II), the volume usage of the organic solvent D in the step 3) is 2-3 mL/mmol based on the mass of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III), the volume usage amount of the organic solvent F in the step 4) is 6-8 mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol compound shown in the formula (IV).
The preparation method of the novel allyl benzoate compound containing triazole is characterized in that eluant for column chromatography separation in the steps 2) and 4) adopts a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 0.5-2.
The novel allyl benzoate compound containing triazole is applied to preparation of bactericides.
Furthermore, the novel allyl benzoate compound containing triazole is used for preparing a bactericide for inhibiting sclerotinia sclerotiorum.
The synthesis process route of the novel allyl benzoate compound containing triazole is as follows:
compared with the prior art, the invention has the following beneficial effects: the invention provides a novel allyl benzoate compound containing triazole, a preparation method thereof and application thereof in preparing a bactericide, wherein the preparation method is simple and convenient to operate, the obtained compound has the best inhibition activity on sclerotinia sclerotiorum under the effective concentration of 50ppm, and the inhibition rate reaches 71.4%.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
EXAMPLE 1 preparation of (E) -1, 3-Diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl benzoate
1) Synthesis of 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (II):
alpha-bromoacetophenone (19.90g,0.10mol) and 1,2, 4-triazole (7.60g,0.11mol) are sequentially added into a 500mL three-neck flask, 150mL of acetone is added as a solvent, an ice salt bath is used for controlling the temperature below 0 ℃, and triethylamine (11.13g,0.11mol) is slowly dropped through a constant-pressure dropping funnel. After the addition, the reaction was continued for 1h, the ice bath was removed, stirring was continued for 1h at room temperature, TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, filtering to remove triethylamine hydrochloride generated by the reaction, leaching the triethylamine hydrochloride with acetone, combining leacheate and filtrate, desolventizing to obtain red oily matter, cooling and solidifying, and recrystallizing with 20mL of isopropanol to obtain 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II);
2) synthesis of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one (III-1):
1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (5.62g,30.00mmol) represented by the formula (II), benzaldehyde (3.50g,33.00mmol) were added in one portion to a 100mL three-necked flask equipped with a water separator, a thermometer and a condenser, 30mL of toluene was added as a solvent, piperidine (0.20g,2.35mmol) was added dropwise as a catalyst, and the mixture was heated under reflux for 6 hours and TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, carrying out water washing, layering, washing an organic phase twice with saturated saline solution (the volume of the saturated saline solution adopted in each washing is 20mL), drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove a solvent, and carrying out column chromatography separation and purification on a concentrated residue (eluent is petroleum ether and ethyl acetate in a volume ratio of 1: 1) to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one shown in a formula (III-1);
3) synthesis of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol (IV-1):
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one (1.93g,7.00mmol) represented by the formula (III-1) was added to a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, the temperature in ice bath was controlled at 0 ℃, PEG600(0.50g,0.83mmol) was added, then sodium borohydride (0.42g,11.00mmol) was added in portions under stirring, and reaction was carried out for 4 hours in ice bath at 0 ℃ by TLC (V-1)EA/VPE1/2, v/v) followed the progress of the reaction. After the reaction is finished, desolventizing the reaction solution, dropwise adding 1N hydrochloric acid solution into the desolventized concentrate, extracting with dichloromethane for three times (15 mL of dichloromethane is used for each extraction), combining organic phases, drying by anhydrous sodium sulfate, filtering, and spin-drying the solvent to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol shown as a formula (IV-1);
4) synthesis of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl benzoate (C1):
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) propan-2-en-1-ol (0.20g, 0.72mmol) represented by the formula (IV-1), benzoic acid (0.10g, 0.80mmol), DMAP (0.09g, 0.72mmol), EDC (0.28g, 1.44mmol) were added to 5mL of dichloromethane, reacted at room temperature for 4 hours, and then the reaction solution was transferred to a separatory funnel, washed with water (3X 5mL), washed with saturated brine (2X 5mL), dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated to remove the solvent, and the concentrated residue was purified by separation with an eluent of petroleum ether and ethyl acetate at a volume ratio of 1:1 to obtain a compound (C1).
Wherein the substituent R in the structural formulas of the formula (III) and the formula (IV)2Are both hydrogen, and form the molecular structures of formula (III-1) and formula (IV-1), respectively.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl benzoate: yellow oil, yield 52.36%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),7.68(s,1H,triazole-H),7.60-7.56(m,1H,ArH),7.48-7.42(m,5H,ArH),7.38-7.33(m,4H,ArH),7.21-7.17(m,3H,ArH),7.03(s,1H,CH),6.95(s,1H,＝CH),6.84-6.79(m,2H,ArH).HRMS(ESI)for C24H19N3O2m/z:Calculated,382.1550,Found,382.1556[M+H]+.
example 2 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-methylbenzoate (C2)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 2-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C2).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-methylbenzoate: yellow oil, yield 42.62%;1H NMR(500MHz,CDCl3):8.09(s,1H,triazole-H),7.98(d,J＝7.8Hz,1H,ArH),7.66(s,1H,triazole-H),7.45-7.42(m,2H,ArH),7.41-7.31(m,4H,ArH),7.27-7.21(m,2H,ArH),7.20-7.15(m,3H,ArH),7.02(s,1H,CH),6.93(s,1H,＝CH),6.82-6.79(m,2H,ArH),2.56(s,3H,CH3).HRMS(ESI)for C25H21N3O2m/z:Calculated,396.1707,Found,396.1712[M+H]+.
example 3 preparation of (E) -1, 3-Diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-chlorobenzoate (C3)
The procedure of example 1 was otherwise the same as that of example 1 except that the benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 2-chlorobenzoic acid, to obtain a compound (C3).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-chlorobenzoate: yellow oil, yield 60.21%;1H NMR(500MHz,CDCl3):8.09(s,1H,triazole-H),7.87(dd,J＝7.8,1.3Hz,1H,ArH),7.67(s,1H,triazole-H),7.48-7.41(m,4H,ArH),7.38-7.31(m,4H,ArH),7.23-7.17(m,3H,ArH),7.03(s,1H,CH),6.98(s,1H,＝CH),6.84-6.77(m,2H,ArH).HRMS(ESI)forC24H18ClN3O2m/z:Calculated,416.1160,Found,416.1166[M+H]+.
EXAMPLE 4 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 4-dichlorobenzoate (C4)
The compound (C4) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 4-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 4-dichlorobenzoate: white oil, yield 42.17%;1H NMR(500MHz,CDCl3):8.09(s,1H,triazole-H),7.85(d,J＝8.5Hz,1H,ArH),7.64(s,1H,triazole-H),7.48(d,J＝2.0Hz,1H,ArH),7.44-7.40(m,2H,ArH),7.39-7.33(m,3H,ArH),7.32(dd,J＝8.5,2.0Hz,1H,ArH),7.23-7.17(m,3H,ArH),7.02(s,1H,CH),6.96(s,1H,＝CH),6.84-6.77(m,2H,ArH).HRMS(ESI)for C24H17Cl2N3O2m/z:Calculated,450.0771,Found,450.0776[M+H]+.
example 5 preparation of (E) -1, 3-Diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methoxybenzoate (C5)
The compound (C5) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-methoxybenzoic acid and the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methoxybenzoate: white wax, yield 25.35%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),8.06-8.02(m,2H,ArH),7.69(s,1H,triazole-H),7.44-7.40(m,2H,ArH),7.37-7.31(m,3H,ArH),7.21-7.16(m,3H,ArH),7.00(s,1H,CH),6.95(s,1H,＝CH),6.94-6.91(m,2H,ArH),6.83-6.79(m,2H,ArH),3.83(s,3H,OCH3).HRMS(ESI)for C25H21N3O3m/z:Calculated,412.1656,Found,412.1661[M+H]+.
EXAMPLE 6 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 6-dichlorobenzoate (C6)
The compound (C6) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 6-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 6-dichlorobenzoate: yellow oil, yield 47.66%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),7.78(s,1H,triazole-H),7.52-7.49(m,2H,ArH),7.46-7.41(m,1H,ArH),7.39-7.35(m,3H,ArH),7.30-7.25(m,2H,ArH),7.21-7.17(m,3H,ArH),7.12(s,1H,CH),6.87(s,1H,＝CH),6.82-6.78(m,2H,ArH).HRMS(ESI)for C24H17Cl2N3O2m/z:Calculated,450.0771,Found,450.0776[M+H]+.
example 7 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-fluorobenzoate (C7)
The compound (C7) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2-fluorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-fluorobenzoate: yellow oil, yield 56.35%;1HNMR(500MHz,CDCl3):8.07(s,1H,triazole-H),8.00-7.92(m,1H,ArH),7.72(s,1H,triazole-H),7.55-7.47(m,1H,ArH),7.46-7.40(m,2H,ArH),7.38-7.29(m,3H,ArH),7.22-7.10(m,5H,ArH),7.04(s,1H,CH),7.02(s,1H,＝CH),6.86-6.78(m,2H,ArH).HRMS(ESI)for C24H18FN3O2m/z:Calculated,400.1456,Found,400.1461[M+H]+.
example 8 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-fluorobenzoate (C8)
The compound (C8) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-fluorobenzoic acid and performing the same procedures as in example 1.
(E) 1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-fluorobenzoate as a yellow oil in a yield of 58.34%;1H NMR(500MHz,CDCl3):8.09(s,1H,triazole-H),7.90-7.85(m,1H,ArH),7.79-7.74(m,1H,ArH),7.65(s,1H,triazole-H),7.46-7.40(m,3H,ArH),7.39-7.33(m,3H,ArH),7.31-7.26(m,1H,ArH),7.23-7.17(m,3H,ArH),7.02(s,1H,CH),6.94(s,1H,＝CH),6.88-6.78(m,2H,ArH).HRMS(ESI)for C24H18FN3O2m/z:Calculated,400.1456,Found,400.1461[M+H]+.
example 9 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methylbenzoate (C9)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 4-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C9).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methylbenzoate as white oil, yield 44.72%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),7.97(d,J＝8.2Hz,2H,ArH),7.69(s,1H,triazole-H),7.45-7.40(m,3H,ArH),7.36-7.32(m,4H,ArH),7.22-7.16(m,3H,ArH),7.01(s,1H,CH),6.95(s,1H,＝CH),6.84-6.78(m,2H,ArH),2.40(s,3H,CH3).HRMS(ESI)for C25H21N3O2m/z:Calculated,396.1707,Found,396.1712[M+H]+.
EXAMPLE 10 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 3-dichlorobenzoate (C10)
The compound (C10) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 3-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 3-dichlorobenzoate: yellow oil, yield 30.33%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),8.03(d,J＝8.3Hz,2H,ArH),7.71(s,1H,triazole-H),7.50-7.45(m,3H,ArH),7.35-7.31(m,3H,ArH),7.21-7.15(m,3H,ArH),7.02(s,1H,CH),6.95(s,1H,＝CH),6.84-6.78(m,2H,ArH).HRMS(ESI)forC24H17Cl2N3O2m/z:Calculated,450.0771,Found,450.0776[M+H]+.
example 11 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-tert-butylbenzoate (C11)
The same operation as in example 1 was carried out except that benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 4-tert-butylbenzoic acid, to obtain a compound (C11).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-tert-butylbenzoate: white wax, yield 44.20%;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),7.67(dd,J＝7.8,1.5Hz,1H,ArH),7.64(s,1H,triazole-H),7.62(dd,J＝8.0,1.5Hz,1H,ArH),7.44-7.41(m,2H,ArH),7.41-7.32(m,4H,ArH),7.29(d,J＝7.9Hz,1H,ArH),7.24-7.20(m,3H,ArH),7.02(s,1H,CH),6.94(s,1H,＝CH),6.83-6.80(m,2H,ArH),1.56(s,9H,t-Bu).HRMS(ESI)forC28H27N3O2m/z:Calculated,438.2176,Found,438.2182[M+H]+.
example 12 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-n-propylbenzoate (C12)
The compound (C12) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-n-propylbenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-n-propylbenzoate: white wax, yield 48.96%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),8.00(d,J＝8.2Hz,2H,ArH),7.69(s,1H,triazole-H),7.45-7.41(m,2H,ArH),7.36-7.31(m,3H,ArH),7.26(d,J＝8.4Hz,2H,ArH),7.22-7.17(m,3H,ArH),7.01(s,1H,CH),6.95(s,1H,＝CH),6.81(dd,J＝7.8,1.4Hz,2H,ArH),2.65(t,J＝7.5Hz,2H,CH2),1.71-1.59(m,2H,CH2),0.94(t,J＝7.3Hz,3H,CH3).HRMS(ESI)for C27H25N3O2m/z:Calculated,424.2020,Found,424.2025[M+H]+.
example 13 preparation of (E) -1, 3-Diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methoxybenzoate (C13)
The compound (C13) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-methoxybenzoic acid and the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methoxybenzoate: white wax, yield 27.43%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),8.06-8.02(m,2H,ArH),7.69(s,1H,triazole-H),7.42(d,J＝7.0Hz,2H,ArH),7.36-7.29(m,3H,ArH),7.20-7.15(m,3H,ArH),7.00(s,1H,CH),6.95(s,1H,＝CH),6.92(d,J＝8.9Hz,2H,ArH),6.83-6.79(m,2H,ArH),3.82(s,3H,OCH3).HRMS(ESI)for C25H21N3O3m/z:Calculated,412.1656,Found,412.1661[M+H]+.
example 14 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methylbenzoate (C14)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 3-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C14).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methylbenzoate: white oil, yield 55.64%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),7.89(d,J＝7.6Hz,2H,ArH),7.70(s,1H,triazole-H),7.46-7.41(m,2H,ArH),7.36-7.30(m,5H,ArH),7.20-7.15(m,3H,ArH),7.03(s,1H,CH),6.95(s,1H,＝CH),6.83-6.78(m,2H,ArH),2.38(s,3H,CH3).HRMS(ESI)for C25H21N3O2m/z:Calculated,396.1707,Found,396.1712[M+H]+.
example 15 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-fluorobenzoate (C15)
The compound (C15) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-fluorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-fluorobenzoate:yellow oil, yield 47.25%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),7.66(s,1H,triazole-H),7.44-7.39(m,3H,ArH),7.38-7.31(m,4H,ArH),7.21-7.15(m,3H,ArH),7.13-7.09(m,2H,ArH),7.02(s,1H,CH),6.95(s,1H,＝CH),6.83-6.79(m,2H,ArH).HRMS(ESI)for C24H18FN3O2m/z:Calculated,400.1456,Found,400.1461[M+H]+.
EXAMPLE 16 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-nitrobenzoate (C16)
The compound (C16) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-nitrobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-nitrobenzoate: yellow wax, yield 15.16%;1H NMR(500MHz,CDCl3):8.95-8.89(m,1H,ArH),8.47-8.43(m,1H,ArH),8.41-8.38(m,1H,ArH),8.11(s,1H,triazole-H),7.68(t,J＝8.0Hz,1H,ArH),7.63(s,1H,triazole-H),7.44-7.37(m,5H,ArH),7.25-7.20(m,3H,ArH),7.07(s,1H,CH),6.94(s,1H,＝CH),6.84-6.81(m,2H,ArH).HRMS(ESI)for C24H18N4O4m/z:Calculated,427.1401,Found,427.1406[M+H]+.
EXAMPLE 17 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-nitrobenzoate
1) Synthesis of 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (II):
alpha-bromoacetophenone (19.90g,0.10mol) and 1,2, 4-triazole (7.60g,0.11mol) are sequentially added into a 500mL three-neck flask, 150mL of acetone is added as a solvent, an ice salt bath is used for controlling the temperature below 0 ℃, and triethylamine (11.1g,0.11mol) is slowly dropped through a constant-pressure dropping funnel. After the addition, the reaction was continued for 1h, the ice bath was removed, stirring was continued for 1h at room temperature, TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, filtering to remove triethylamine hydrochloride generated in the reaction, leaching the triethylamine hydrochloride with acetone, combining leacheate and filtrate, desolventizing to obtain red oily matter, cooling and solidifying, and adding 20mL of isopropanolRecrystallizing to obtain 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethan-1-one shown in formula (II);
2) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one (III-2):
a100 mL three-necked flask equipped with a water separator, a thermometer and a condenser was charged with 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (5.62g,30.00mol) represented by the formula (II), p-trifluoromethylbenzaldehyde (5.75g,33.00mmol), 30mL toluene as a solvent, piperidine (0.20g,2.35mmol) as a catalyst, and the mixture was heated under reflux for 7 hours and TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, washing with water, then layering, washing an organic phase with saturated saline twice (the volume of the saturated saline adopted in each washing is 20mL), drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove a solvent, and purifying a concentrated residue by column chromatography (eluent is petroleum ether and ethyl acetate in a volume ratio of 1: 1) to obtain (E) -1-phenyl-2- (1H-1,2, 4-triazole-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one shown in a formula (III-2);
3) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-ol (IV-2):
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one (2.40g,7.00mmol) represented by the formula (III-2) was charged into a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, temperature was controlled at 0 ℃ in ice bath, PEG600(0.50g,0.83mmol) was added, then sodium borohydride (0.42g,11.0mmol) was added in portions under stirring, and reaction was carried out for 4 hours in ice bath at 0 ℃ by TLC (V-2)EA/VPE1/2, v/v) followed the progress of the reaction. After the reaction is finished, desolventizing the reaction solution, dropwise adding 1N hydrochloric acid solution into the desolventized concentrate, extracting with dichloromethane for three times (15 mL of dichloromethane is used for each extraction), combining organic phases, drying through anhydrous sodium sulfate, filtering, and spin-drying the solvent to obtain (E) -1-phenyl-2- (1H-1,2, 4-triazole-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-ene-1-ol shown as a formula (IV-2);
4) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl benzoate (B1):
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) propan-2-en-1-ol represented by the formula (IV-2) (0.25g, 0.72mmol), benzoic acid (0.10g, 0.80mmol), DMAP (0.09g, 0.72mmol), EDC (0.28g, 1.44mmol) were added to 5mL of dichloromethane, reacted at room temperature for 4 hours, and then the reaction mixture was transferred to a separatory funnel, washed with water (3X 5mL), washed with saturated brine (2X 5mL), dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated to remove the solvent, and the concentrated residue was purified by column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 1: 1) to obtain a compound of the formula (B1).
Wherein the substituent R in the structural formulas of the formula (III) and the formula (IV)2Are trifluoromethyl groups, and respectively form the molecular structures of a formula (III-2) and a formula (IV-2).
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl benzoate: yellow oil, yield 46.37%;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),8.09-8.07(m,2H,ArH),7.67(s,1H,triazole-H),7.59(t,J＝7.5Hz,1H,ArH),7.49-7.42(m,6H,ArH),7.40-7.33(m,3H,ArH),7.04(s,1H,CH),6.99(s,1H,＝CH),6.96(d,J＝8.3Hz,2H,ArH).HRMS(ESI)for C25H18F3N3O2m/z:Calculated,450.1424,Found,450.1423[M+H]+.
example 18 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-methylbenzoate (B2)
The compound (B2) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2-methylbenzoic acid and the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-methylbenzoate: yellow oil, yield 58.38%;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),8.01-7.94(m,1H,ArH),7.65(s,1H,triazole-H),7.48-7.42(m,5H,ArH),7.39-7.33(m,3H,ArH),7.26(t,J＝7.4Hz,2H,ArH),7.03(s,1H,CH),6.96(s,2H,ArH),6.94(s,1H,＝CH),2.57(s,3H,CH3).HRMS(ESI)for C26H20F3N3O2m/z:Calculated,464.1580,Found,464.1577[M+H]+.
example 19 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-fluorobenzoate (B3)
The compound (B3) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2-fluorobenzoic acid and the same procedures used in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-fluorobenzoate: yellow oil, yield 72.35%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),8.01-7.94(m,1H,ArH),7.69(s,1H,triazole-H),7.61-7.52(m,1H,ArH),7.48-7.42(m,4H,ArH),7.38-7.32(m,3H,ArH),7.23(t,J＝7.6Hz,1H,ArH),7.20-7.14(m,1H,ArH),7.07(s,1H,CH),7.04(s,1H,＝CH),6.96(d,J＝8.2Hz,2H,ArH).HRMS(ESI)for C25H17F4N3O2m/z:Calculated,468.1330,Found,468.1327[M+H]+.
example 20 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-tert-butylbenzoate (B4)
The compound (B4) was obtained in the same manner as in example 17 except that the benzoic acid in step 4) of example 17 was replaced with an equimolar amount of 4-tert-butylbenzoic acid.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-tert-butylbenzoate: white wax, yield 55.16%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),8.05-8.01(m,2H,ArH),7.68(s,1H,triazole-H),7.50-7.48(m,2H,ArH),7.47-7.42(m,4H,ArH),7.38-7.32(m,3H,ArH),7.03(s,1H,CH),6.98(s,1H,＝CH),6.95(d,J＝8.3Hz,2H,ArH),1.34(s,9H,t-Bu).HRMS(ESI)for C29H26F3N3O2m/z:Calculated,506.2050,Found,506.2061[M+H]+.
example 21 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-chlorobenzoate (B5)
The procedure of example 17 was otherwise the same as that of example 17 except that the benzoic acid in step 4) of example 17 was replaced with an equimolar amount of 3-chlorobenzoic acid, to obtain a compound (B5).
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-chlorobenzoate: yellow oil, yield 48.75%;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),8.04(t,J＝1.8Hz,1H,ArH),7.98-7.94(m,1H,ArH),7.64(s,1H,triazole-H),7.59-7.55(m,1H,ArH),7.46(d,J＝8.3Hz,2H,ArH),7.43-7.36(m,6H,ArH),7.04(s,1H,CH),6.97(s,2H,ArH),6.95(s,1H,＝CH).HRMS(ESI)for C25H17ClF3N3O2m/z:Calculated,484.1034,Found,484.1028[M+H]+.
example 22 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-n-propylbenzoate (B6)
The compound (B6) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 4-n-propylbenzoic acid and conducting the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-n-propylbenzoate: white wax, yield 55.32%;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),8.00(d,J＝8.2Hz,2H,ArH),7.72(s,1H,triazole-H),7.58(t,J＝7.4Hz,2H,ArH),7.45-7.41(m,3H,ArH),7.40-7.32(m,4H,ArH),7.02(s,1H,CH),6.99(s,1H,＝CH),6.96(d,J＝8.2Hz,2H,ArH),2.65(t,J＝7.5Hz,2H,CH2),1.70-1.61(m,2H,CH2),0.94(t,J＝7.3Hz,3H,CH3).HRMS(ESI)for C28H24F3N3O2m/z:Calculated,492.1893,Found,492.1861[M+H]+.
example 23 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-methoxybenzoate (B7)
The compound (B7) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 4-methoxybenzoic acid and the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-methoxybenzoate: white wax, yield 44.10%;1H NMR(500MHz,CDCl3):8.08(s,1H,triazole-H),8.06-8.03(m,2H,ArH),7.67(s,1H,triazole-H),7.46(d,J＝8.3Hz,2H,ArH),7.43-7.40(m,2H,ArH),7.38-7.33(m,3H,ArH),7.00(s,1H,CH),6.98(s,1H,＝CH),6.97-6.94(m,4H,ArH),3.86(s,3H,OCH3).HRMS(ESI)for C26H20F3N3O3m/z:Calculated,480.1530,Found,480.1530[M+H]+.
example 24 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 4-dichlorobenzoate (B8)
The compound (B8) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2, 4-dichlorobenzoic acid and carrying out the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 4-dichlorobenzoate as a yellow oil in 66.16% yield;1H NMR(500MHz,CDCl3):8.10(s,1H,triazole-H),7.85(d,J＝8.5Hz,1H,ArH),7.63(s,1H,triazole-H),7.49-7.45(m,3H,ArH),7.39-7.35(m,4H,ArH),7.34-7.31(m,2H,ArH),7.04(s,1H,CH),7.01(s,1H,＝CH),6.95(d,J＝8.2Hz,2H,ArH).
EXAMPLE 25 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-nitrobenzoate (B9)
The compound (B9) was obtained by substituting benzoic acid in step 4) of example 17 with the equimolar amount of 3-nitrobenzoic acid and performing the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-nitrobenzoate as white wax in 23.17% yield;1H NMR(500MHz,CDCl3):8.93-8.89(m,1H,ArH),8.48-8.43(m,1H,ArH),8.40(d,J＝7.9Hz,1H,ArH),8.13(s,1H,triazole-H),7.70(t,J＝8.0Hz,1H,ArH),7.67(s,1H,triazole-H),7.49-7.39(m,7H,ArH),7.09(s,1H,CH),6.99(s,1H,＝CH),6.98(d,J＝8.3Hz,2H,ArH).HRMS(ESI)for C25H17F3N4O4m/z:Calculated,495.1275,Found,495.1271[M+H]+.
example 26 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 3-dichlorobenzoate (B10)
The compound (B10) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2, 3-dichlorobenzoic acid and carrying out the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 3-dichlorobenzoate: yellow oil, yield 33.25%;1H NMR(500MHz,CDCl3):8.11(s,1H,triazole-H),7.67(dd,J＝7.8,1.6Hz,1H,ArH),7.64(s,1H,triazole-H),7.47(d,J＝8.3Hz,2H,ArH),7.45-7.42(m,2H,ArH),7.41-7.36(m,3H,ArH),7.31-7.27(m,2H,ArH),7.04(s,1H,CH),6.99(s,1H,＝CH),6.95(d,J＝8.3Hz,2H,ArH).HRMS(ESI)for C25H16Cl2F3N3O2m/z:Calculated,518.0644,Found,518.0644[M+H]+.
example 27 bactericidal Activity test
Test subjects: tomato early blight (Alternaria solani), wheat scab (Gibberella zeae), potato late blight (Phytophthora infestans), Phytophthora capsici (Phytophthora capsici), sclerotium napellum (Sclerotinia sclerotiorum), cucumber gray mold (Botrytis cinerea), Rhizoctonia solani (Rhizoctonia solani), cucumber Fusarium oxysporum (Fusarium oxysporum), peanut brown spot (Cercospora arachidicola), and apple ring rot (Phycospora piricola).
The compounds represented by the formulae (C1) to (C16) prepared in examples 1 to 16 were labeled as test compounds for bactericidal activity test in the following manner, and the compounds represented by the formulae (B1) to (B10) prepared in examples 17 to 26 were labeled as test compounds:
and (3) test treatment: each test compound was dissolved in DMSO to 1% EC stock solution for use. The indoor bactericidal activity of the compound to be tested to the test target under the dosage of 50ppm is evaluated by adopting a bacteriostatic ring method, and a solvent clean water control (QCK) and a fluxapyroxad control (YCK) with the effective content of 50ppm are additionally arranged.
The test method comprises the following steps: 150 microliter of the prepared EC mother liquor is absorbed by a pipette gun and dissolved in 2.85mL of Tween water to prepare a liquid medicine with the effective concentration of the compound to be detected being 500 ppm. Sucking 1mL of the liquid medicine by using a pipette, putting the liquid medicine into a sterilized culture dish, putting 9mL of PDA culture medium into the culture dish, shaking up, and cooling. And (3) beating the round bacterial cake by using a puncher, picking the round bacterial cake to the center of a culture dish by using an inoculating needle, then placing the culture dish in an incubator at 27 ℃ for culture, and measuring the diameter of a bacterial colony after 48-72 hours. The pure growth amount of the bacterial colony is the difference value between the average diameter of the bacterial colony and the diameter of the bacterial cake, and the bacteria inhibition rate (%) calculation method is calculated according to the following formula.
The pure growth amount of the control colony in the above calculation formula refers to the pure growth amount of the colony under the test of the clear water control (QCK).
The bactericidal activity test results are shown in table 1.
Table 150 ppm fungicidal Activity of Compounds (% control)
As can be seen from the table, the C series compounds show good inhibition rate on the sclerotium rolfsii, and most of the compounds have the inhibition rate of over 60 percent, wherein the inhibition rates of C1, C7 and C14 on the sclerotium rolfsii are over 70 percent, the inhibition rates of C8 and C13 on rice sheath blight are over 60 percent, and the inhibition rates of C7, C11, C13 and C16 on apple ring rot are 58.3 percent, but not as good as that of a control medicament fluxapyroxad.
As shown in the table, the compounds of the B series all show certain activity, wherein the inhibition rates of the compounds B1, B2, B3, B5, B6, B7, B8 and B9 on sclerotium of rape are all over 50 percent, the inhibition rate of the compounds B7 on gibberellic disease of wheat is over 50 percent, the prevention and control rates of the compounds B1, B3, B6 and B7 on rice sheath blight are over 50 percent, the bactericidal activity of the B series is not ideal overall, compared with a control medicament fluxapyroxad, the prevention and control rate on phytophthora capsici is higher than that of fluxad, and the prevention and control rate on gibberellic disease of wheat is higher than that of the fluxad for part of the compounds.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A novel allyl benzoate compound containing triazole is characterized in that the structural formula is shown as the formula (I):
in formula (I): substituent R1Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R2Is hydrogen or trifluoromethyl.
2. The novel triazole-containing allylbenzoate compound of claim 1, wherein R in formula (I)1Is one of the following: phenyl, 2-methylphenyl, 2-chlorophenyl, 2, 4-dichlorophenyl, 3-methoxyphenyl, 2, 6-dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-methylphenyl, 2, 3-dichlorophenyl, 4-tert-butylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 3-methylphenyl, 4-fluorophenyl, 3-nitrophenyl, 3-chlorophenyl.
3. The process for producing a novel triazole-containing allylbenzoate compound according to claim 1 or 2, comprising the steps of:
1) alpha-bromoacetophenone and 1,2, 4-triazole are mixed in an organic solvent A, the temperature is controlled to be below 0 ℃, triethylamine is dropwise added, the mixture is stirred at room temperature for reaction, and the reaction process is tracked by TLC; after the reaction is finished, filtering to remove triethylamine hydrochloride generated in the reaction, and after desolventizing the filtrate, recrystallizing the filtrate by using an organic solvent B to prepare 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethane-1-ketone shown in a formula (II);
2) heating 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) obtained in the step 1), benzaldehyde or p-trifluoromethylbenzaldehyde and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; after the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, washing with water, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and carrying out column chromatography separation and purification treatment on the concentrate to obtain the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III);
3) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) obtained in the step 2) in an organic reagent D, adding PEG600 and sodium borohydride, stirring and reacting under the ice bath condition of 0 ℃, and tracking the reaction process by TLC; after the reaction is finished, desolventizing the reaction solution, dropwise adding 0.5-2N hydrochloric acid solution into the desolventized concentrate, extracting by using an organic reagent E, combining organic phases, drying by using anhydrous sodium sulfate, filtering, and treating by using a spin-dried solvent to obtain a (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as a formula (IV);
4) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding DMAP, EDC and substituted benzoic acid, stirring at room temperature for reaction, and tracking the reaction process by TLC; after the reaction is finished, washing with water, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain the novel allyl benzoate compound containing triazole as shown in the formula (I);
wherein, R is1Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R2Is hydrogen or trifluoromethyl.
4. The process for preparing a novel triazole-containing allylbenzoate compound according to claim 3, wherein the organic solvent A in step 1) is a ketone solvent, preferably acetone; the organic solvent B is an alcohol solvent, preferably isopropanol; the organic solvent C in the step 2) is a benzene solvent, preferably toluene; the organic reagent D in the step 3) is an alcohol solvent, preferably methanol; the organic reagent E in the step 3) and the organic solvent F in the step 4) are both dichloromethane.
5. The method for preparing the novel triazole-containing allyl benzoate compound of claim 3, wherein in the step 1), the molar ratio of the alpha-bromoacetophenone to the 1,2, 4-triazole is 1: 1.1-1.5; in the step 2), the feeding molar ratio of 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) to (p-trifluoromethyl) benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) to the sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as the formula (IV) to the substituted benzoic acid is 1: 1.1-1.5.
6. The method according to claim 3, wherein the volume of the organic solvent A used in step 1) is 1 to 2mL/mmol based on the amount of the alpha-bromoacetophenone, the volume of the organic solvent C used in step 2) is 1 to 1.5mL/mmol based on the amount of the 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one represented by formula (II), the volume of the organic solvent D used in step 3) is 2 to 3mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one represented by formula (III), the volume usage amount of the organic solvent F in the step 4) is 6-8 mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol compound shown in the formula (IV).
7. The method for preparing the novel triazole-containing allyl benzoate compound as claimed in claim 3, wherein the eluent for column chromatography separation in step 2) and step 4) is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1: 0.5-2.
8. The use of a novel triazole-containing allylbenzoate compound as claimed in claim 1 or 2 for the preparation of a bactericide.
9. The use according to claim 8, characterized in that the novel triazole-containing allylbenzoate compounds are used for the preparation of fungicides for the inhibition of sclerotinia sclerotiorum.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59186964A (en) * | 1983-04-05 | 1984-10-23 | Sumitomo Chem Co Ltd | Production of alcoholic compound |
| CN101445488A (en) * | 2007-11-27 | 2009-06-03 | 西南大学 | Triazoles compounds with antimicrobial activity and preparation method and pharmaceutical use thereof |
| CN104370892A (en) * | 2014-10-27 | 2015-02-25 | 湖南大学 | 1-(7-methoxybenzofuran-5-yl)-3-(2-methoxyphenyl)-2-(1,2,4-triazole-1-yl) allyl alcohol |
| CN104557888A (en) * | 2015-01-23 | 2015-04-29 | 邵阳学院 | Application of furan phenol allyl alcohol derivative used as herbicide |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59186964A (en) * | 1983-04-05 | 1984-10-23 | Sumitomo Chem Co Ltd | Production of alcoholic compound |
| CN101445488A (en) * | 2007-11-27 | 2009-06-03 | 西南大学 | Triazoles compounds with antimicrobial activity and preparation method and pharmaceutical use thereof |
| CN104370892A (en) * | 2014-10-27 | 2015-02-25 | 湖南大学 | 1-(7-methoxybenzofuran-5-yl)-3-(2-methoxyphenyl)-2-(1,2,4-triazole-1-yl) allyl alcohol |
| CN104557888A (en) * | 2015-01-23 | 2015-04-29 | 邵阳学院 | Application of furan phenol allyl alcohol derivative used as herbicide |
Non-Patent Citations (2)
| Title |
|---|
| YONG KI MIN,等: "New Lead Compounds for Brassinosteroid Biosynthesis Inhibitors", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| 李春芳，等: "新型含氟三唑类化合物的合成及生物活性研究", 《青岛科技大学学报( 自然科学版)》 * |
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