CN116058376B - Modified tea saponin molluscicide and preparation method thereof - Google Patents
Modified tea saponin molluscicide and preparation method thereof Download PDFInfo
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- CN116058376B CN116058376B CN202310113197.9A CN202310113197A CN116058376B CN 116058376 B CN116058376 B CN 116058376B CN 202310113197 A CN202310113197 A CN 202310113197A CN 116058376 B CN116058376 B CN 116058376B
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- tea saponin
- molluscicide
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- modified tea
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- 239000001397 quillaja saponaria molina bark Substances 0.000 title claims abstract description 87
- 229930182490 saponin Natural products 0.000 title claims abstract description 87
- 150000007949 saponins Chemical class 0.000 title claims abstract description 87
- 241001122767 Theaceae Species 0.000 title claims abstract description 86
- 230000002013 molluscicidal effect Effects 0.000 title claims abstract description 49
- 239000003750 molluscacide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims abstract description 21
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- -1 azodicarboxylic acid ester Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000002608 ionic liquid Substances 0.000 claims description 17
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical group O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- FYXPKOPFEGFWHG-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 FYXPKOPFEGFWHG-UHFFFAOYSA-N 0.000 claims description 3
- YKHFNYFQEJHRBA-UHFFFAOYSA-N 4-dinaphthalen-1-ylphosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC2=CC=CC=C12 YKHFNYFQEJHRBA-UHFFFAOYSA-N 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- NCBFTYFOPLPRBX-UHFFFAOYSA-N dimethyl azodicarboxylate Substances COC(=O)N=NC(=O)OC NCBFTYFOPLPRBX-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- NCBFTYFOPLPRBX-AATRIKPKSA-N methyl (ne)-n-methoxycarbonyliminocarbamate Chemical compound COC(=O)\N=N\C(=O)OC NCBFTYFOPLPRBX-AATRIKPKSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 229940057950 sodium laureth sulfate Drugs 0.000 claims description 3
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- ALDGWBIKTNGIKV-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-(2,4,5-trimethylphenyl)phosphoryl]phenol Chemical compound C1=C(C)C(C)=CC(C)=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 ALDGWBIKTNGIKV-UHFFFAOYSA-N 0.000 claims description 2
- YCBHQMFKTMZNIF-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-naphthalen-1-ylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(O)C=C1 YCBHQMFKTMZNIF-UHFFFAOYSA-N 0.000 claims description 2
- LMBQOLBVWODAFG-UHFFFAOYSA-N 4-bis(4-hydroxyphenyl)phosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 LMBQOLBVWODAFG-UHFFFAOYSA-N 0.000 claims description 2
- IHASAJAGQUQZSU-UHFFFAOYSA-N 4-bis(4-phenoxyphenyl)phosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(OC=2C=CC=CC=2)=CC=1)C(C=C1)=CC=C1OC1=CC=CC=C1 IHASAJAGQUQZSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229940105289 carbon black Drugs 0.000 claims description 2
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 2
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- KBABHAOMYBQXAD-UHFFFAOYSA-N 1-methyl-3-octyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.CCCCCCCCN1CN(C)C=C1 KBABHAOMYBQXAD-UHFFFAOYSA-N 0.000 claims 1
- 241000251468 Actinopterygii Species 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 241000565675 Oncomelania Species 0.000 abstract description 4
- 230000002147 killing effect Effects 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 241000534460 Ampullaria Species 0.000 abstract description 2
- 241000143060 Americamysis bahia Species 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000032050 esterification Effects 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 241000237858 Gastropoda Species 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 4
- 125000003147 glycosyl group Chemical group 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 2
- 241000237852 Mollusca Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000636 lethal dose Toxicity 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical class OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 1
- BCVMAYRUJBXMAP-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCCCC[N+]=1C=CN(C)C=1 BCVMAYRUJBXMAP-UHFFFAOYSA-M 0.000 description 1
- TWCMVXMQHSVIOJ-UHFFFAOYSA-N Aglycone of yadanzioside D Natural products COC(=O)C12OCC34C(CC5C(=CC(O)C(O)C5(C)C3C(O)C1O)C)OC(=O)C(OC(=O)C)C24 TWCMVXMQHSVIOJ-UHFFFAOYSA-N 0.000 description 1
- 235000015911 Amorpha canescens Nutrition 0.000 description 1
- PLMKQQMDOMTZGG-UHFFFAOYSA-N Astrantiagenin E-methylester Natural products CC12CCC(O)C(C)(CO)C1CCC1(C)C2CC=C2C3CC(C)(C)CCC3(C(=O)OC)CCC21C PLMKQQMDOMTZGG-UHFFFAOYSA-N 0.000 description 1
- 244000107780 Capraria biflora Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000013629 Lippia javanica Nutrition 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- FHICGHSMIPIAPL-HDYAAECPSA-N [2-[3-[6-[3-[(5R,6aS,6bR,12aR)-10-[6-[2-[2-[4,5-dihydroxy-3-(3,4,5-trihydroxyoxan-2-yl)oxyoxan-2-yl]ethoxy]ethyl]-3,4,5-trihydroxyoxan-2-yl]oxy-5-hydroxy-2,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,7,8,8a,10,11,12,13,14b-tetradecahydropicene-4a-carbonyl]peroxypropyl]-5-[[5-[8-[3,5-dihydroxy-4-(3,4,5-trihydroxyoxan-2-yl)oxyoxan-2-yl]octoxy]-3,4-dihydroxy-6-methyloxan-2-yl]methoxy]-3,4-dihydroxyoxan-2-yl]propoxymethyl]-5-hydroxy-3-[(6S)-6-hydroxy-2,6-dimethylocta-2,7-dienoyl]oxy-6-methyloxan-4-yl] (2E,6S)-6-hydroxy-2-(hydroxymethyl)-6-methylocta-2,7-dienoate Chemical compound C=C[C@@](C)(O)CCC=C(C)C(=O)OC1C(OC(=O)C(\CO)=C\CC[C@](C)(O)C=C)C(O)C(C)OC1COCCCC1C(O)C(O)C(OCC2C(C(O)C(OCCCCCCCCC3C(C(OC4C(C(O)C(O)CO4)O)C(O)CO3)O)C(C)O2)O)C(CCCOOC(=O)C23C(CC(C)(C)CC2)C=2[C@@]([C@]4(C)CCC5C(C)(C)C(OC6C(C(O)C(O)C(CCOCCC7C(C(O)C(O)CO7)OC7C(C(O)C(O)CO7)O)O6)O)CC[C@]5(C)C4CC=2)(C)C[C@H]3O)O1 FHICGHSMIPIAPL-HDYAAECPSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000001205 effect on erythrocytes Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- PFOARMALXZGCHY-UHFFFAOYSA-N homoegonol Natural products C1=C(OC)C(OC)=CC=C1C1=CC2=CC(CCCO)=CC(OC)=C2O1 PFOARMALXZGCHY-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical class OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- DQAKJEWZWDQURW-UHFFFAOYSA-N pyrrolidonecarboxylic acid Chemical compound OC(=O)N1CCCC1=O DQAKJEWZWDQURW-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930182493 triterpene saponin Natural products 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P9/00—Molluscicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dentistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a modified tea saponin molluscicide and a preparation method thereof, wherein the modified tea saponin molluscicide comprises the following raw materials in parts by mass: 100 parts of filler, 18-24 parts of modified tea saponin, 6-10 parts of dispersing agent, 1-3 parts of disintegrating agent and 10-15 parts of wetting agent; the modified tea saponin is a product obtained by esterifying tea saponin and pyrrolidone carboxylic acid. The invention carries out structural modification based on tea saponin to prepare the efficient, low-toxicity and pesticide-hazard-free modified tea saponin molluscicide, has good killing effect on ampullaria gigas and oncomelania, has no influence on fishes, shrimps and the like, and is a novel efficient and pollution-free tea saponin molluscicide.
Description
Technical Field
The invention belongs to the technical field of tea saponin and pesticides, and particularly relates to a modified tea saponin molluscicide and a preparation method thereof.
Background
Tea saponin is a natural plant molluscicide, is a pentacyclic triterpene saponin mixture, and mainly comprises aglycone, sugar body and organic acid. However, the unmodified tea saponin has insufficient molluscicidal activity, and particularly has a significantly lower molluscicidal effect on adult molluscs than young molluscs, and a large amount of tea saponin is needed to achieve the effective molluscicidal effect, so that the utilization efficiency of the tea saponin raw material is low. It is generally prepared in the form of a derivative in order to desirably enhance molluscicidal activity. For example, tea saponin is used as raw material to prepare effective molluscicide-spirowei. The molluscicidal effect of the spirocarb is remarkable, but the literature reports that the spirocarb has side effects including ecological damage of farmlands caused by toxicity and pesticide residue problems, such as certain damage effect on erythrocytes of fishes and shrimps.
Therefore, development of a novel tea saponin-based molluscicide is desired, which is low in toxicity and side effects while improving molluscicidal activity.
In addition, the structural modification of tea saponin is generally carried out by alkali hydrolysis and/or acid hydrolysis, and then the modification of groups is carried out, so that the physiological function of glycosyl is maintained, and when the structural modification is carried out, the hydroxyl on the glycosyl needs to be protected firstly, and then the structural modification is carried out. However, the protection and deprotection of the hydroxyl group are time-consuming and laborious, and increase the manufacturing cost, and there is still room for improvement in terms of industrialization. The inventors' prior patent CN202211592954.7 disclosed an esterification reaction of tea saponin in an ionic liquid with an organic acid in the presence of a condensing agent (a mixture containing a hydroxyphenylphosphine oxide derivative and an azodicarbonate). The method for synthesizing the tea saponin derivative is simple, effective and low in cost by utilizing the difference of the activities of the primary hydroxyl and the secondary hydroxyl and selectively carrying out esterification reaction on the primary hydroxyl of the tea saponin under the condition of not protecting the glycosyl dosage form. The invention is based on the research, and a novel modified tea saponin molluscicide is prepared according to the synthesis strategy.
Disclosure of Invention
In order to overcome the problems of insufficient activity or high toxicity of the molluscicide based on the tea saponin in the prior art, the invention is based on the tea saponin for structural modification to prepare the efficient, low-toxicity and pesticide-free modified tea saponin molluscicide, has good killing effect on ampullaria gigas and oncomelania, has no influence on fishes, shrimps and the like basically, and is a novel efficient and pollution-free tea saponin molluscicide.
The aim of the invention is achieved by the following technical scheme:
the modified tea saponin molluscicide comprises the following raw materials in parts by mass: 100 parts of filler, 18-24 parts of modified tea saponin, 6-10 parts of dispersing agent, 1-3 parts of disintegrating agent and 10-15 parts of wetting agent; the modified tea saponin is a product obtained by esterifying tea saponin and pyrrolidone carboxylic acid.
Further, the dispersing agent is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium laureth sulfate, sodium sorbitol, alkylphenol ethoxylates and fatty alcohol polyoxyethylene ether; the filler is at least one selected from calcium bicarbonate, kaolin, talcum powder, bentonite, lignin, white carbon black, hydrotalcite and sodium alginate; the disintegrating agent is at least one selected from sodium carboxymethyl starch, sodium carboxymethyl cellulose, ammonium sulfate and sodium chloride; the wetting agent is at least one selected from ethanol and ethylene glycol.
Preferably, the dispersing agent is a compound of sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene ether according to a mass ratio of 1-3:1-3; more preferably, the dispersing agent is the compound of sodium dodecyl benzene sulfonate and polyoxyethylene nonylphenol ether according to the mass ratio of 1-2:1-2.
Further, the modified tea saponin is prepared by a preparation method comprising the following steps: dissolving tea saponin in ionic liquid, adding pyrrolidone carboxylic acid and a photo-delay reaction reagent, and reacting for 2-3h at 130-150 ℃ under the protection of inert atmosphere and vacuum degree of 0.01-0.05 MPa.
Further, the molar ratio of pyrrolidone carboxylic acid to tea saponin is 2-2.2:1. the activity of the primary hydroxyl groups of the tea saponin is much higher than that of the secondary hydroxyl groups, the tea saponin contains 2 primary hydroxyl groups, pyrrolidone carboxylic acid with the molar weight of 2-2.2 times of that of the tea saponin is added, the 2 primary hydroxyl groups participate in the esterification reaction, and the secondary hydroxyl groups do not substantially participate in the reaction.
The light-delay reaction reagent is phenyl phosphine oxide derivative containing hydroxyl and azodicarboxylic acid ester according to the mol ratio of 1-1.2:1-1.2, wherein the dosage of the condensing agent is 1-3% of the mass of the tea saponin; the ionic liquid is imidazole ionic liquid and/or pyridine ionic liquid. Preferably, the hydroxyl-containing phenylphosphine oxide derivative is selected from at least one of bis (4-hydroxyphenyl) phenylphosphine oxide, tris (4-hydroxyphenyl) phosphine oxide, bis (4-hydroxyphenyl) (1-naphthyl) phosphine oxide, bis (1-naphthyl) (4-hydroxyphenyl) phosphine oxide, bis (4-phenoxyphenyl) (4-hydroxyphenyl) phosphine oxide, bis (4-hydroxyphenyl) (2, 4, 5-trimethylphenyl) phosphine oxide; the azodicarboxylic acid ester is at least one selected from dimethyl azodicarboxylate, diethyl azodicarboxylate, dimethyl azodiisobutyrate and diisopropyl azodicarboxylate.
Such imidazole-based ionic liquids and pyridine-based ionic liquids are well known in the art. Examples of imidazole-based ionic liquids include, but are not limited to, at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium triflate; examples of pyridine-based ionic liquids include, but are not limited to, at least one of N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate, N-butylpyridine tetrafluoroborate, N-butylpyridine hexafluorophosphate.
In the casting reaction, triphenylphosphine and azodicarboxylic acid ester are generally adopted as casting reagents, the configuration of carbon atoms where hydroxyl groups are located is inverted, and the reaction requires the triphenylphosphine with equivalent reaction weight. The inventors have unexpectedly found that the esterification of the primary hydroxyl groups of tea saponin can be efficiently accomplished in ionic liquids as solvents with catalytic amounts of hydroxyl-containing phenylphosphine oxide derivatives and azodicarbonates as casting reagents. The cost and risk problems of using large amounts of triphenylphosphine and azodicarboxylic acid esters are avoided.
According to the invention, after pyrrolidone carboxylic acid esterification modification is carried out on tea saponin, the molluscicidal activity is unexpectedly increased. Pyrrolidone carboxylic acid is an amino acid derivative and is widely used in the cosmetic field as a humectant. The esterified product of tea saponin and pyrrolidone carboxylic acid has low toxic and side effects, can be used as an effective field molluscicide, and cannot damage the field ecological environment.
The invention also provides a preparation method of the modified tea saponin molluscicide, which comprises the following steps: weighing filler, modified tea saponin, dispersant and disintegrating agent in proportion, adding into a stirrer, uniformly mixing, adding wetting agent, uniformly stirring, oven drying, pulverizing, and sieving to obtain the modified tea saponin molluscicide.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a modified tea saponin molluscicide, which is prepared by modifying primary hydroxyl of tea saponin through esterification reaction of pyrrolidone carboxylic acid, has obviously improved molluscicide activity, has no toxic or side effect, reduces harm to fields, and is environment-friendly.
2. The preparation of the modified tea saponin is carried out by esterifying and modifying, avoiding protecting hydroxyl on glycosyl, carrying out esterification reaction of pyrrolidone carboxylic acid in the presence of ionic liquid and specific light delay reaction reagent, and enabling active primary hydroxyl to react and secondary hydroxyl not to participate in reaction basically.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
The parts in the embodiments of the present invention are parts by mass unless otherwise specified; unless otherwise specified, "%" is mass percent.
Tea saponin is obtained from Jiangxi Xinzhong wild tea industry Co.Ltd and has purity of 95.2%.
Preparation examplePreparation of modified tea saponin
Preparation example 1
Under the protection of nitrogen, 1 mole part of tea saponin is dissolved in 1-hexyl-3-methylimidazole hexafluorophosphate, 2.2 mole parts of pyrrolidone carboxylic acid and a condensing agent with the mass of 1% of the tea saponin are added, the condensing agent is a mixture of bis (4-hydroxyphenyl) phenylphosphine oxide and diisopropyl azodicarboxylate according to the molar ratio of 1:1, the mixture is reacted for 3 hours at the vacuum degree of 0.05MPa and the temperature of 130 ℃, and the mixture is naturally cooled to the room temperature, so that the pyrrolidone carboxylic acid esterification modified tea saponin is obtained.
Preparation example 2
Under the protection of nitrogen, 1 mole part of tea saponin is dissolved in 1-butyl-3-methylimidazole tetrafluoroborate, 2.1 mole parts of pyrrolidone carboxylic acid and 3% of condensing agent by mass of the tea saponin are added, the condensing agent is a mixture of bis (1-naphthyl) (4-hydroxyphenyl) phosphine oxide and dimethyl azodicarboxylate according to the molar ratio of 1:1, the mixture is reacted for 2 hours at the vacuum degree of 0.05MPa and the temperature of 150 ℃, and the mixture is naturally cooled to the room temperature, so that the pyrrolidone carboxylic acid esterification modified tea saponin is obtained.
Example 1
Preparation of modified tea saponin molluscicide: 60 parts by mass of talcum powder, 40 parts by mass of light calcium bicarbonate, 18 parts by mass of pyrrolidone carboxylic acid esterification modified tea saponin prepared in preparation example 1, 6 parts by mass of sodium dodecyl benzene sulfonate and 3 parts by mass of sodium carboxymethyl cellulose are uniformly mixed in a stirrer, 20 parts of ethanol is added, the mixture is uniformly stirred and mixed, vacuum drying is carried out at the temperature of 0.2MPa and 60 ℃, and the dried solid is crushed by using a jet mill and is screened to obtain the modified tea saponin molluscicide with the average particle size of 70 mu m.
Example 2
Preparation of modified tea saponin molluscicide: 70 parts of hydrotalcite, 30 parts of light calcium bicarbonate, 24 parts of pyrrolidone carboxylic acid esterification modified tea saponin prepared in preparation example 2, 10 parts of sodium laureth sulfate and 1 part of sodium carboxymethylcellulose are uniformly mixed in a stirrer, 15 parts of ethanol is added, the mixture is uniformly stirred and mixed, vacuum drying is carried out at the temperature of 60 ℃ under the pressure of 0.2MPa, the dried solid is crushed by using a jet mill, and the crushed solid is screened to obtain the modified tea saponin molluscicide with the average particle size of 70 mu m.
Example 3
Other conditions and operations were the same as in example 1 except that 13 parts by mass of tea saponin was used for the esterification modification of pyrrolidone carboxylic acid.
Example 4
Other conditions and operations were the same as in example 1 except that the dispersant was nonylphenol polyoxyethylene ether NP-10.
Example 5
Other conditions and operations are the same as in example 1, except that the dispersant is a mixture of sodium dodecyl benzene sulfonate and polyoxyethylene nonylphenol ether NP-10 in a mass ratio of 1:1.
Comparative example 1
Other conditions and operations were the same as in example 1 except that pyrrolidone carboxylic acid-esterified modified tea saponin was replaced with equal quality unmodified tea saponin.
Application example 1 molluscicidal Activity experiment
(1) The Poyang county is filled with the strong-activity oncomelania to form the snail for standby.
(2) The molluscicides of the above examples and comparative examples were diluted to 5mg/mL (low dose), 10mg/m (high dose) with dechlorinated tap water.
3) Under the room temperature condition, 50 snails are grouped into a group by adopting a snail immersing method, and are respectively immersed into 3000mL of the low-dose and high-dose molluscicide liquid for 24 hours and 48 hours, and are fished out for flushing by clear water, and the death rate of the snails is tested by adopting a knocking method. Clear water was used as a blank control group and 45% of baipirocin was used as a positive control group. The results are shown in Table 1 below.
Table 1 test of molluscicide activity against oncomelania
As can be seen from the data in Table 1, the modified tea saponin molluscicide provided by the invention has very excellent molluscicide activity, the death rate of 24 hours reaches more than 80% and the death rate of 48 hours reaches more than 90% under the low dosage concentration of 5mg/mL, and the death rates of 24 hours and 48 hours of a negative control group (clear water) are respectively 0% and 4%. At high dosage, the death rate of the modified tea saponin molluscicide disclosed by the embodiment of the invention reaches 100%. And compared with the positive control group, the molluscicidal activity is higher than that of the hundred molluscicides.
In addition, the inventor also discovers that the modified tea saponin molluscicide prepared by taking the combination of the anionic surfactant and the nonionic surfactant as a dispersing agent has the optimal effect.
Unmodified tea saponin has low toxicity to prawns and is often used in shrimp ponds, but even at very dilute concentrations, it has greater toxicity to fish. The half lethal dose of tea saponin to Ding Ban fish is 3.8mg/L, and the half lethal dose of the modified tea saponin obtained in preparation example 1 of the invention to Ding Ban fish is 18.7mg/L. The reason is presumably that the modified tea saponin has reduced permeability to fish red blood cells. The tea saponin modified by pyrrolidone carboxylic acid esterification improves molluscicidal activity and reduces toxicity to fish. The device is more suitable for killing snails in farmlands, and cannot cause pollution or harm.
Claims (7)
1. The modified tea saponin molluscicide is characterized by comprising the following raw materials in parts by mass: 100 parts of filler, 18-24 parts of modified tea saponin, 6-10 parts of dispersing agent, 1-3 parts of disintegrating agent and 10-15 parts of wetting agent; the modified tea saponin is a product obtained by esterifying tea saponin and pyrrolidone carboxylic acid;
the modified tea saponin is prepared by a preparation method comprising the following steps: dissolving tea saponin in ionic liquid, adding pyrrolidone carboxylic acid and a photo-delay reaction reagent, and reacting for 2-3 hours at 130-150 ℃ under the protection of inert atmosphere and vacuum degree of 0.01-0.05 MPa; the molar ratio of pyrrolidone carboxylic acid to tea saponin is 2-2.2:1, a step of; the light-delay reaction reagent is phenyl phosphine oxide derivative containing hydroxyl and azodicarboxylic acid ester according to the mol ratio of 1-1.2:1-1.2, wherein the dosage of the light-delay reaction reagent is 1-3% of the mass of the tea saponin; the ionic liquid is imidazole ionic liquid and/or pyridine ionic liquid.
2. The modified tea saponin molluscicide according to claim 1, wherein the dispersant is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium laureth sulfate, sodium sorbitol, alkylphenol ethoxylates, fatty alcohol polyoxyethylene ether; the filler is at least one selected from calcium bicarbonate, kaolin, talcum powder, bentonite, lignin, white carbon black, hydrotalcite and sodium alginate; the disintegrating agent is at least one selected from sodium carboxymethyl starch, sodium carboxymethyl cellulose, ammonium sulfate and sodium chloride; the wetting agent is at least one selected from ethanol and ethylene glycol.
3. The modified tea saponin molluscicide according to claim 1, wherein the dispersant is a compound of sodium dodecyl benzene sulfonate and alkylphenol ethoxylates according to a mass ratio of 1-3:1-3.
4. The modified tea saponin molluscicide according to claim 1, wherein the dispersant is a compound of sodium dodecyl benzene sulfonate and polyoxyethylene nonyl phenyl ether according to a mass ratio of 1-2:1-2.
5. A modified tea saponin molluscicide according to claim 1, wherein the hydroxyl-containing phenyl phosphine oxide derivative is selected from at least one of bis (4-hydroxyphenyl) phenyl phosphine oxide, tris (4-hydroxyphenyl) phosphine oxide, bis (4-hydroxyphenyl) (1-naphthyl) phosphine oxide, bis (1-naphthyl) (4-hydroxyphenyl) phosphine oxide, bis (4-phenoxyphenyl) (4-hydroxyphenyl) phosphine oxide, bis (4-hydroxyphenyl) (2, 4, 5-trimethylphenyl) phosphine oxide; the azodicarboxylic acid ester is at least one selected from dimethyl azodicarboxylate, diethyl azodicarboxylate, dimethyl azodiisobutyrate and diisopropyl azodicarboxylate.
6. A modified tea saponin molluscicide according to claim 1, wherein the imidazole ionic liquid is selected from at least one of 1-butyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole tetrafluoroborate, 1-octyl-3-methylimidazole trifluoromethane sulfonate; the pyridine ionic liquid is at least one selected from N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate, N-butylpyridine tetrafluoroborate and N-butylpyridine hexafluorophosphate.
7. The method for preparing the modified tea saponin molluscicide according to any one of claims 1 to 6, comprising the following steps: weighing filler, modified tea saponin, dispersant and disintegrating agent in proportion, adding into a stirrer, uniformly mixing, adding wetting agent, uniformly stirring, oven drying, pulverizing, and sieving to obtain the modified tea saponin molluscicide.
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| CN101524067A (en) * | 2009-03-30 | 2009-09-09 | 浙江久晟茶业发展有限公司 | Usage of botanical molluscicide and tea saponin thereof |
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
| CN113980750A (en) * | 2021-10-27 | 2022-01-28 | 深圳市洁王精细化工科技有限公司 | Kitchen detergent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101524067A (en) * | 2009-03-30 | 2009-09-09 | 浙江久晟茶业发展有限公司 | Usage of botanical molluscicide and tea saponin thereof |
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
| CN113980750A (en) * | 2021-10-27 | 2022-01-28 | 深圳市洁王精细化工科技有限公司 | Kitchen detergent and preparation method thereof |
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