CN116041166B - 3, 6-Diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol, preparation method and application - Google Patents
3, 6-Diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol, preparation method and application Download PDFInfo
- Publication number
- CN116041166B CN116041166B CN202211721122.0A CN202211721122A CN116041166B CN 116041166 B CN116041166 B CN 116041166B CN 202211721122 A CN202211721122 A CN 202211721122A CN 116041166 B CN116041166 B CN 116041166B
- Authority
- CN
- China
- Prior art keywords
- benzenediol
- copper
- cyclohexanone
- dialkyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 7
- -1 aromatic o-diphenol compound Chemical class 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 33
- 230000001580 bacterial effect Effects 0.000 claims description 29
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 241000207199 Citrus Species 0.000 claims description 19
- 201000010099 disease Diseases 0.000 claims description 18
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 235000020971 citrus fruits Nutrition 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 240000007594 Oryza sativa Species 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 235000013399 edible fruits Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 244000144730 Amygdalus persica Species 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 claims description 4
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 claims description 4
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 claims description 4
- 244000241235 Citrullus lanatus Species 0.000 claims description 4
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims description 4
- 240000008067 Cucumis sativus Species 0.000 claims description 4
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 4
- 240000003768 Solanum lycopersicum Species 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 239000003139 biocide Substances 0.000 abstract description 2
- 230000000855 fungicidal effect Effects 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 32
- 239000003995 emulsifying agent Substances 0.000 description 23
- 239000004495 emulsifiable concentrate Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000003814 drug Substances 0.000 description 21
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000375 suspending agent Substances 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 10
- 231100000674 Phytotoxicity Toxicity 0.000 description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 9
- 208000025865 Ulcer Diseases 0.000 description 7
- 239000003899 bactericide agent Substances 0.000 description 7
- 230000003902 lesion Effects 0.000 description 7
- 239000000575 pesticide Substances 0.000 description 7
- 241000589634 Xanthomonas Species 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- JJKSAEHNIHMQKQ-UHFFFAOYSA-N copper;quinoline Chemical compound [Cu].N1=CC=CC2=CC=CC=C21 JJKSAEHNIHMQKQ-UHFFFAOYSA-N 0.000 description 5
- 238000011835 investigation Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 241000047982 Axonopus Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 241001600126 Acidovorax citrulli Species 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 241000588701 Pectobacterium carotovorum Species 0.000 description 2
- KHGNFPUMBJSZSM-UHFFFAOYSA-N Perforine Natural products COC1=C2CCC(O)C(CCC(C)(C)O)(OC)C2=NC2=C1C=CO2 KHGNFPUMBJSZSM-UHFFFAOYSA-N 0.000 description 2
- 239000005869 Pyraclostrobin Substances 0.000 description 2
- 241000520892 Xanthomonas axonopodis Species 0.000 description 2
- 241000907138 Xanthomonas oryzae pv. oryzae Species 0.000 description 2
- 241000626572 Xanthomonas oryzae pv. oryzicola Species 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- JLOULEJYJNBUMX-UHFFFAOYSA-L copper;quinoline-2-carboxylate Chemical compound [Cu+2].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 JLOULEJYJNBUMX-UHFFFAOYSA-L 0.000 description 2
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- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229930192851 perforin Natural products 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
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- 231100000397 ulcer Toxicity 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OPFTUNCRGUEPRZ-UHFFFAOYSA-N (+)-beta-Elemen Natural products CC(=C)C1CCC(C)(C=C)C(C(C)=C)C1 OPFTUNCRGUEPRZ-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N (-)-beta-elemene Chemical compound CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- 208000018380 Chemical injury Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000589615 Pseudomonas syringae Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000985670 Xanthomonas arboricola pv. pruni Species 0.000 description 1
- 241000589636 Xanthomonas campestris Species 0.000 description 1
- 241000589655 Xanthomonas citri Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 230000001338 necrotic effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000036269 ulceration Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- 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
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol with a structural formula I, a preparation method and application thereof, and belongs to the technical field of biocides containing organic compounds. The 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol or 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) prepared by the invention has the characteristics of extremely low toxicity, excellent sterilization effect and good safety. Can be used in a manner similar to that of a conventional fungicidal composition, and can exert a more excellent control effect than a conventional composition. The amount of the present invention to be applied may vary within a considerably wide range depending on the application season, place and method, etc.
Description
Technical Field
The invention relates to the technical field of biocides containing organic compounds, in particular to 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol, a preparation method and application thereof.
Background
Citrus canker is caused by xanthomonas carpet grass (Xanthomonas campestris pv. Citri (Hasse) Dye), the most unfavorable and extensive disease affecting citrus crops. In the growth process of citrus twigs and fruits, xanthomonas carpet grass is attached and grown on the surface of the leaf to form a biological film structure, so that more favorable environmental conditions for growth and survival are obtained. Rainfall and wind are favorable for the infection of the xanthomonas carpet, when free water appears at ulcer lesions, the xanthomonas carpet can exude and disperse, and lesions are caused at multiple positions of citrus. Typical symptoms of citrus canker are necrotic ulceration lesions on fruits, stems and leaves. Peeling, shoot thinning and premature fruit drop are the main causes of reduced fruit quality and yield.
The formation of the flavomonas carpet is closely related to the development of citrus canker virus and citrus canker, and the interference of the formation of the biological film helps to improve the resistance of citrus plants to canker. Formulations containing copper ions help to inhibit the formation of xanthomonas carpet biofilm.
The invention discloses a pyraclostrobin-quinoline copper microcapsule suspension-suspension agent and a preparation method thereof, wherein pyraclostrobin-quinoline copper is taken as an active ingredient, and a capsule wall material, a capsule core solvent, an emulsifying agent, a thickening agent, a dispersing agent, an antifreezing agent, a preservative, a pH regulator and water are matched to form the pyraclostrobin-quinoline copper microcapsule suspension-suspension agent. The pyraclostrobin-oxine copper microcapsule suspension-suspending agent can reduce the addition amount of harmful solvents in old products and improve the environmental protection performance of the preparation; the compound of the pyraclostrobin and the copper quinolinate has a synergistic effect, the control effect is obviously improved, and the pesticide usage amount is reduced; long lasting period, saving the times of pesticide application and reducing labor cost. The invention also discloses a preparation method of the pyraclostrobin-quinoline copper microcapsule suspension-suspension agent. The method has simple process, can realize mass production, and has extremely high application value.
The Chinese patent application CN115067344A provides a pesticide suspending agent compounded by copper quinolinate and kasugamycin, which comprises the following raw materials in percentage by weight: 1 to 60 percent of quinoline copper raw medicine, 1 to 60 percent of kasugamycin raw medicine, 1 to 10 percent of dispersing agent, 1 to 10 percent of wetting agent, 0.1 to 3 percent of thickening agent, 0.1 to 0.5 percent of preservative, 1 to 8 percent of antifreezing agent, 0.1 to 1 percent of defoaming agent and 100 percent of water, wherein the dispersing agent is selected from one or more of hydrophobic group modified carboxylic acid copolymer and macromolecular amphiphilic anionic nonionic surfactant compound; the wetting agent is selected from alkylphenol polyoxyethylene ether phosphate. The suspending agent disclosed by the invention can effectively prevent the degradation of pesticide active ingredients, further avoid long-term layering of a solution, be beneficial to improving the suspension stability of the suspending agent, and can be stably present for a long time in a lower pH environment.
Copper bactericides used in the prior art can play a certain role in preventing and treating citrus canker, but the repeated use of copper bactericides also has certain defects, such as induction of resistance in xanthomonas carpet grass population, possible phytotoxicity and increase of negative ecological effects in soil.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol with good control effect on citrus canker, and a preparation method and application thereof.
The invention provides 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol with a structural formula I:
preferably, each R 1、R2 is independently H, C 1-12 alkanyl.
Preferably, each R 3、R4 is independently H, C 1-4 alkanyl.
The invention also discloses a preparation method of the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol, which comprises the following steps:
1) Adding an aromatic o-diphenol compound with a structural formula IV into a mixed solution formed by an alcohol solvent and water, continuously adding an aliphatic carbonyl compound with a structural formula III, uniformly mixing, adding an inorganic acid, carrying out reflux reaction at 50-100 ℃ for 3-5 hours, and distilling to remove redundant reactants and solvents to obtain an addition product with a structural formula II;
2) The addition product of the structural formula II is uniformly mixed with cyclohexanone and organic acid, reflux reaction is carried out for 3-5 hours at the temperature of 80-150 ℃, redundant reactants and solvents are distilled off, a crude product is obtained, and the crude product is washed by water to remove the organic acid, so that 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol of the structural formula I is obtained.
Preferably, the aromatic o-diphenol compound of the structural formula IV is used in an amount of 80-120 parts by weight, the alcohol solvent is used in an amount of 100-200 parts by weight, the water is used in an amount of 30-80 parts by weight, the aliphatic carbonyl compound of the structural formula III is used in an amount of 100-300 parts by weight, and the inorganic acid is used in an amount of 10-30 parts by weight; the dosage of the cyclohexanone is 200-300 parts, and the dosage of the organic acid is 10-30 parts.
Preferably, the alcohol solvent is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, propylene glycol, 1, 3-butanediol and 1, 4-butanediol.
Preferably, the inorganic acid is any one of hydrochloric acid, sulfuric acid and phosphoric acid.
Preferably, the organic acid is any one of sulfamic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trichloroacetic acid, and trifluoroacetic acid.
The preparation method of the 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) comprises the following steps in parts by weight:
Adding 20-80 parts of inorganic salt of bivalent copper into 50-200 parts of water to obtain copper salt aqueous solution; adding 30-120 parts of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol into 10-50 parts of aqueous alkali to obtain an alkaline aqueous solution of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol; adding 80-120 parts of the alkaline aqueous solution of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH to 3-8, and continuously stirring for 10-60 minutes at 20-80 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II).
The chemical structural formula of the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) is as follows:
preferably, the inorganic salt of divalent copper is any one of copper chloride, copper sulfate and copper nitrate.
Preferably, the aqueous alkali solution is an aqueous sodium hydroxide solution having a concentration of 20 to 50 wt%.
In the process of regulating the pH value of the mixture to 3-8 after the uniform mixing, an acid-base regulator commonly used in the field can be adopted; in the acid-base modifier, the acid liquid is preferably 10wt% sulfuric acid aqueous solution, and the alkali liquid is preferably 10wt% sodium hydroxide aqueous solution.
The invention discloses a 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate, which comprises the following components in percentage by weight:
The invention also discloses a preparation method of the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate, which comprises the steps of adding 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifying agent, anhydrous 500# ammonium salt and 601# emulsifying agent, and uniformly stirring to obtain the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate.
The invention provides an application method of the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate, which is prepared by diluting the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate according to a proportion by using water; and uniformly spraying the crops by using spraying equipment.
Preferably, the dilution ratio of the bactericidal agent is 500 to 1500 times.
The invention provides an application of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) in crop disease control. The crop diseases are bacterial leaf blight of rice (Xanthomonas oryzae pv. Oryzae), bacterial wilt of peanut (Pseudomanas solanacearum Smith), bacterial fruit blotch of watermelon (Acidovorax avenae subsp. Citrulli), soft rot of chinese cabbage (Erwinia carotovora), bacterial leaf blotch of rice (Xanthomonas oryzae pv. Oryzicola), citrus canker (Xanthomonas axonopodis pv. Citr, xac), bacterial angular leaf blotch of cucumber (Pseudomonas syringae), bacterial perforin disease of peach tree (Xanthomonas campestris pv. Prun), bacterial wilt of tomato (Pseudomanas solanacearum Smith)
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the beneficial effects that:
the 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol or 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) prepared by the invention has the characteristics of extremely low toxicity, excellent sterilization effect and good safety. Can be used in a manner similar to that of a conventional fungicidal composition, and can exert a more excellent control effect than a conventional composition. The amount of the copper-based bactericide to be applied according to the present invention may vary within a considerably wide range depending on the season, place and method of application, etc. Taking citrus canker as an example, 5wt% of 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol copper (II) emulsifiable concentrate preparation is usually diluted by 1000-1500 times, namely has excellent leaf protection and prevention effect, and the lower the dilution ratio is, the better the leaf protection and prevention effect is, and 1000-1500 times is recommended to be used. .
Drawings
FIG. 1 is an infrared spectrum of 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol prepared in example 1;
FIG. 2 is an infrared spectrum of 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol and copper (II) 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol prepared in example 1.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The comparative example and the examples of the present invention have the following parameters of part of raw materials:
40% of pyraclostrobin copper quinoline, suspending agent and brand: shanghai Hu Liubao, shanghai Hu Liu biological pharmaceutical industry (Xiayi) Co., ltd.
36% Of Chunlei copper quinoline, suspending agent and brand: security, weifang, gaobao agricultural services Inc.
Example 1
3, 6-Diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzene diphenol, which is prepared by the following method:
1) Adding 10.0kg of 4, 5-dihexyl catechol of the structural formula IV into a mixed solution formed by 15.0kg of absolute ethyl alcohol and 5.5kg of water, continuously adding 20.0kg of 3-pentanone of the structural formula III, uniformly mixing, adding 2.0kg of hydrochloric acid with the concentration of 37wt% and carrying out reflux reaction at the temperature of 75 ℃ for 4 hours, and distilling to remove redundant reactants and solvents to obtain an organic matter of the structural formula II;
2) Uniformly mixing the organic matter of the structural formula II obtained in the step 1) with 25.0kg of cyclohexanone and 2.0kg of trifluoroacetic acid, carrying out reflux reaction for 4 hours at 115 ℃, distilling off redundant reactants and solvents to obtain a crude product, and washing the crude product to remove the trifluoroacetic acid to obtain the 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol of the structural formula I.
The 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzene diphenol copper (II) is prepared by the following method:
Adding 5.0kg of copper chloride into 12.5kg of water to obtain copper salt aqueous solution; adding 7.5kg of 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol into 3.0kg of aqueous sodium hydroxide solution with concentration of 40wt percent to obtain alkaline aqueous solution of 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol; adding 10.0kg of the alkaline aqueous solution of 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH value to 5.5, and continuously stirring for 35 minutes at 50 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol copper (II).
The 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzene diphenol copper (II) emulsifiable concentrate comprises 5wt% of 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzene diphenol copper (II), 15wt% of cyclohexanone, 3wt% of EO/PO block polyether emulsifier, 5wt% of anhydrous 500# ammonium salt, 10wt% of 601# emulsifier and the balance 200# solvent oil, and is prepared by the following method:
Adding 3, 6-diisoamyl cyclohexanone-4, 5-dialkyl-1, 2-benzene diphenol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifier, anhydrous 500# ammonium salt and 601# emulsifier, and uniformly stirring to obtain 3, 6-diisoamyl cyclohexanone-4, 5-dialkyl-1, 2-benzene diphenol copper (II) emulsifiable concentrate.
The 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzene diphenol copper (II) emulsifiable concentrate is diluted by 500 times by water to obtain the bactericidal agent.
Example 2
This example is substantially identical to example 1, except that the dilution ratio of the 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol copper (II) emulsifiable concentrate in this example with water is 1000 times.
Example 3
This example is substantially identical to example 1, except that the dilution ratio of the 3, 6-diisoamyl cyclohexanone-4, 5-dihexyl-1, 2-benzenediol copper (II) emulsifiable concentrate in this example with water is 1500 times.
Example 4
3, 6-Diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzene diphenol, which is prepared by the following method:
1) Adding 10.0kg of 4, 5-dimethanoyl catechol of the structural formula IV into a mixed solution formed by 15.0kg of absolute ethyl alcohol and 5.5kg of water, continuously adding 20.0kg of acetone of the structural formula III, uniformly mixing, adding 2.0kg of hydrochloric acid with the concentration of 37wt% and carrying out reflux reaction at the temperature of 75 ℃ for 4 hours, and distilling to remove redundant reactants and solvents to obtain an organic matter of the structural formula II;
2) Uniformly mixing the organic matter of the structural formula II obtained in the step 1) with 25.0kg of cyclohexanone and 2.0kg of trifluoroacetic acid, carrying out reflux reaction for 4 hours at 115 ℃, distilling off redundant reactants and solvents to obtain a crude product, and washing the crude product to remove the trifluoroacetic acid to obtain the 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzenediol of the structural formula I.
3, 6-Diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzene diphenol copper (II) is prepared by the following method:
Adding 5.0kg of copper chloride into 12.5kg of water to obtain copper salt aqueous solution; adding 7.5kg of 3, 6-diisopropylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol into 3.0kg of 40wt% sodium hydroxide aqueous solution to obtain an alkaline aqueous solution of 3, 6-diisopropylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol; adding 10.0kg of the alkaline aqueous solution of 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH value to 5.5, and continuously stirring for 35 minutes at 50 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisopropylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II).
The 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II) emulsifiable concentrate comprises 5 weight percent of 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II), 15 weight percent of cyclohexanone, 3 weight percent of EO/PO block polyether emulsifier, 5 weight percent of anhydrous 500# ammonium salt, 10 weight percent of 601# emulsifier and the balance 200# solvent oil, and is prepared by the following method:
Adding 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzene diphenol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifier, anhydrous 500# ammonium salt and 601# emulsifier, and uniformly stirring to obtain 3, 6-diisopropyl cyclohexanone-4, 5-dimethyl-1, 2-benzene diphenol copper (II) emulsifiable concentrate.
Example 5
3, 6-Diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzene diphenol is prepared by the following method:
1) Adding 10.0kg of 4, 5-didodecyl catechol of the structural formula IV into a mixed solution formed by 15.0kg of absolute ethyl alcohol and 5.5kg of water, continuously adding 20.0kg of acetone of the structural formula III, uniformly mixing, adding 2.0kg of hydrochloric acid with the concentration of 37wt% and carrying out reflux reaction at the temperature of 75 ℃ for 4 hours, and distilling to remove redundant reactants and solvents to obtain an organic matter of the structural formula II;
2) Uniformly mixing the organic matter of the structural formula II obtained in the step 1) with 25.0kg of cyclohexanone and 2.0kg of trifluoroacetic acid, carrying out reflux reaction for 4 hours at 115 ℃, distilling off redundant reactants and solvents to obtain a crude product, and washing the crude product to remove the trifluoroacetic acid to obtain the 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzenediol of the structural formula I.
The 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) is prepared by the following method:
Adding 5.0kg of copper chloride into 12.5kg of water to obtain copper salt aqueous solution; adding 7.5kg of 3, 6-diisopropylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol into 3.0kg of 40wt% sodium hydroxide aqueous solution to obtain an alkaline aqueous solution of 3, 6-diisopropylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol; adding 10.0kg of the alkaline aqueous solution of 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH value to 5.5, and continuously stirring for 35 minutes at 50 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisopropylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II).
The 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) emulsifiable concentrate comprises 5 weight percent of 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II), 15 weight percent of cyclohexanone, 3 weight percent of EO/PO block polyether emulsifier, 5 weight percent of anhydrous 500# ammonium salt, 10 weight percent of 601# emulsifier and the balance 200# solvent oil, and is prepared by the following method:
adding 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzene diphenol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifier, anhydrous 500# ammonium salt and 601# emulsifier, and uniformly stirring to obtain 3, 6-diisopropyl cyclohexanone-4, 5-didodecyl-1, 2-benzene diphenol copper (II) emulsifiable concentrate.
Example 6
3, 6-Diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol is prepared by the following method:
1) Adding 10.0kg of 4, 5-dimethanoyl catechol of the structural formula IV into a mixed solution formed by 15.0kg of absolute ethyl alcohol and 5.5kg of water, continuously adding 20.0kg of 5-nonone of the structural formula III, uniformly mixing, adding 2.0kg of hydrochloric acid with the concentration of 37wt% and carrying out reflux reaction at the temperature of 75 ℃ for 4 hours, and distilling to remove redundant reactants and solvents to obtain an organic matter of the structural formula II;
2) Uniformly mixing the organic matter of the structural formula II obtained in the step 1) with 25.0kg of cyclohexanone and 2.0kg of trifluoroacetic acid, carrying out reflux reaction for 4 hours at 115 ℃, distilling off redundant reactants and solvents to obtain a crude product, and washing the crude product to remove the trifluoroacetic acid to obtain the 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol of the structural formula I.
The 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II) is prepared by the following method:
Adding 5.0kg of copper chloride into 12.5kg of water to obtain copper salt aqueous solution; adding 7.5kg of 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol into 3.0kg of 40wt% sodium hydroxide aqueous solution to obtain an alkaline aqueous solution of 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol; adding 10.0kg of the alkaline aqueous solution of 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH to 5.5, and continuously stirring for 35 minutes at 50 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II).
The 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II) emulsifiable concentrate comprises 5wt% of 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II), 15wt% of cyclohexanone, 3wt% of EO/PO block polyether emulsifier, 5wt% of anhydrous 500# ammonium salt, 10wt% of 601# emulsifier and the balance 200# solvent oil, and is prepared by the following method:
Adding 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifier, anhydrous 500# ammonium salt and 601# emulsifier, and uniformly stirring to obtain 3, 6-diisononylcyclohexanone-4, 5-dimethyl-1, 2-benzenediol copper (II) emulsifiable concentrate.
Example 7
3, 6-Diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol is prepared by the following method:
1) Adding 10.0kg of 4, 5-didodecyl catechol of the structural formula IV into a mixed solution formed by 15.0kg of absolute ethyl alcohol and 5.5kg of water, continuously adding 20.0kg of 5-nonone of the structural formula III, uniformly mixing, adding 2.0kg of hydrochloric acid with the concentration of 37wt% and carrying out reflux reaction at the temperature of 75 ℃ for 4 hours, and distilling to remove redundant reactants and solvents to obtain an organic matter of the structural formula II;
2) Uniformly mixing the organic matter of the structural formula II obtained in the step 1) with 25.0kg of cyclohexanone and 2.0kg of trifluoroacetic acid, carrying out reflux reaction for 4 hours at 115 ℃, distilling off redundant reactants and solvents to obtain a crude product, and washing the crude product to remove the trifluoroacetic acid to obtain the 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol of the structural formula I.
The 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) is prepared by the following method:
Adding 5.0kg of copper chloride into 12.5kg of water to obtain copper salt aqueous solution; adding 7.5kg of 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol into 3.0kg of 40wt% sodium hydroxide aqueous solution to obtain an alkaline aqueous solution of 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol; adding 10.0kg of the alkaline aqueous solution of 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, adjusting the pH to 5.5, and continuously stirring for 35 minutes at 50 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II).
The 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) emulsifiable concentrate comprises 5 weight percent of 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II), 15 weight percent of cyclohexanone, 3 weight percent of EO/PO block polyether emulsifier, 5 weight percent of anhydrous 500# ammonium salt, 10 weight percent of 601# emulsifier and the balance 200# solvent oil, and is prepared by the following method:
adding 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) into cyclohexanone and 200# solvent oil, sequentially adding EO/PO block polyether emulsifier, anhydrous 500# ammonium salt and 601# emulsifier, and uniformly stirring to obtain 3, 6-diisononylcyclohexanone-4, 5-didodecyl-1, 2-benzenediol copper (II) emulsifiable concentrate.
Comparative example 1
Diluting 40% of the pyraclostrobin-quinoline copper suspending agent by 1500 times with water to prepare pyraclostrobin-quinoline copper liquid medicine.
Comparative example 2
The 36% spring mine and quinoline copper suspending agent is diluted 1500 times by water to prepare the spring mine and quinoline copper liquid medicine.
Test example 1
The drug effect of the drug solution prepared by the invention on the citrus canker prevention and treatment drug of citrus plants is tested by field test. The test crop is WoGAN, and is in early summer stage and uniform in growth vigor during application. The control objects are citrus canker, and sporadic occurrence is mainly caused by the generation of lesions on old and new leaves of the tip-extracted branches. The test is carried out in the Wu Ming district of the Guangxi Zhuang autonomous region nan Ning, the soil fertility of the test field is consistent, the normal farming operation is carried out during the test period, and other pesticides are not applied before the pesticide. The test agents were the liquid medicines prepared in examples 1 to 3 and comparative examples 1 to 2, and clear water was used as a blank.
The test is carried out in three times, and the first test field is located in ancient elemene in Wuming district, 9:30 am in 14 days of 4 months of 2022; the second test field is carried out in Yu Wuming east Jiang Tangan, 4 months 2022 and 14 afternoon at 4:30; the third test field was conducted at day 18 of 5, 2022, by guangxi Shang Nong company, wu Ming. The liquid medicines of the examples, the control examples and the blank control were uniformly sprayed by using a backpack type electric sprayer. The first test and the second test are applied once, and the third test only has sporadic disease spots before the drug, so the drug is applied for multiple times according to the occurrence condition of the disease. In the actual test, the drug was applied once every 7 days, three times in succession, and the disease data was investigated before each application.
Investigation, recording and measurement were performed as follows after administration.
Test 1: the number of leaves of each disease grade was investigated on day 2022, 04, 14 and 4, 28; test 2: the leaf numbers of each disease grade were investigated on day 2020, 14 on 04 month and 28 on 4 months; test 3: the number of leaves at each disease level was investigated before the first administration for 2022, month 05 and 18; the number of leaves at each grade was investigated before the second administration for 2022, 25 days of 05-month; the number of leaves of each disease grade was investigated before the third administration of 2022, 5 months and 31 days, and the number of leaves of each disease grade was investigated 12 days after the third administration of 6 months and 12 days.
Each formula is used for treating 1 whole tree, 5 positions in southeast, northwest and northwest are selected for each treatment tree during investigation, 5 leaves are investigated for each position, and 25 leaves are investigated in total. And calculating the disease leaf rate, the disease index, the leaf protection effect and the leaf protection control effect according to the investigation data.
The calculation formula is as follows:
the classification method is as follows:
level 0: the whole leaf has no disease spots;
Stage 1: 1-3 lesions are formed on the leaf;
3 stages: 4-7 lesions are formed on the leaf;
5 stages: 8-11 lesions are formed on the leaf;
7 stages: more than 11 disease spots are arranged on the leaf blade;
Stage 9: the diseased leaves fall off.
Post-drug investigation: the investigation method is the same as above.
Safety: observing whether the medicament has phytotoxicity to crops, and recording symptoms, types and extent of phytotoxicity. The method for classifying the phytotoxicity comprises the following steps:
-: no chemical injury exists;
+: slight phytotoxicity does not affect the normal growth of crops;
++: moderate phytotoxicity, can recover, and can not cause crop yield reduction;
+++: severe phytotoxicity affects normal growth of crops, and causes a certain loss of crop yield and quality;
++++: serious phytotoxicity, hindered crop growth, serious crop yield and quality loss and must compensate economic loss.
The test data of two places of test of ancient olive and Dongjiang sugar factories in Wuming area of 4 months 2022 are shown in tables 1 and 2 respectively; the data of 3 consecutive administrations at Guangxi Shangdong agricultural company in the Wuming region at 5 months 2022 are shown in tables 3 to 5.
Table 1: data sheet 14 days after Wu Minggu olive canker test drug
Table 2: data sheet 14 days after Wu Mingdong Jiang Tangan ulcer test drug
As can be seen from the test results in tables 1 and 2, the 5%3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate medicament has the control effect on Wobbe ulcer disease obviously better than 1000 times and 1500 times when diluted by 500 times in 14 days after medicament administration, the control effect is better when diluted by 1000 times, and the actual use cost and the control effect are considered to suggest that the 5%3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate medicament is recommended to be 1000 times, and the later-stage illness state is heavier and can be used by 500 times.
Table 3: data sheet 7 days after first administration of Wankan ulcer disease of Guangxi Shangnong Co at Wu Ming
Table 4: data sheet 6 days after second application of Wankan ulcer disease in Guangxi Shangnong Co at Wu Ming
Table 5: data sheet 12 days after third application of drug for Wankan ulcer disease of Guangxi Shangnong Co at Wu Ming area
As can be seen from the control results in tables 3 to 5, under the condition of 3 times of continuous use, the 5%3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) emulsifiable concentrate has ideal leaf-protecting effect and control effect under the condition of 1000 and 1500 times of dosage, and can better control citrus canker, which is equivalent to or slightly better than the conventional medicament 40% pyraclostrobin-quinoline copper suspending agent and 36% chunlar-quinoline copper suspending agent by 1500 times.
All the above tests are that the phytotoxicity phenomenon occurs.
Test example 2
The infrared absorption spectrum of the 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol sample prepared in example 1 was measured after tabletting with KBr. As can be seen from FIG. 1,3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol has a strong absorption peak at 1710cm -1, which is a C=O stretching vibration peak of ketone. The absorption peak at 1480cm -1 is strong and is the bending vibration peak of-CH 2 -of ketone and fat side chains. 2850cm -1、2940cm-1 is the telescopic vibration peak of ketone and fatty side chain-CH 2 -. The characteristic absorption peak of benzene ring is 1600cm -1, the telescopic vibration peak of C-O bond on benzene ring is 1250cm -1, and the absorption peak of phenolic hydroxyl is 3430cm -1. The absorption peak at 750cm -1 is ortho-position double-substituted peak of benzene ring, and the absorption peak at 850cm -1 is para-position double-substituted peak of benzene ring.
3, 6-Diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzene diphenol is complexed with cupric salt to prepare the bactericidal agent, and the infrared absorption spectrum of the sample is measured after KBr tabletting. As can be seen from FIG. 2, after complexing the 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol molecule with copper ions, the absorption peak of the complex in the range of 750-850 cm -1 is significantly reduced, corresponding to the characteristic vibration absorption band of benzene rings and substituents, due to the influence of Cu 2+ on the vibration mode by coupling with the 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol ligand. Compared with the infrared absorption spectrum of the 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-dihydroxybenzene ligand, the absorption peak of the complex corresponding to the C-O stretching vibration mode at 1250cm -1 is obviously weakened, which indicates that O atoms participate in bonding and coordinate with Cu 2+. Further, the absorption spectrum was observed, and it was found that an OH - characteristic absorption peak of water molecules appears near the wave number 3430cm -1, indicating that the complex contains crystal water.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Test example 3
The bioassay example test of the invention reference standard NY/T1156.16-2008, section 16 of pesticide indoor bioassay test criteria Bactericide: the specific method and the steps in the turbidity method for the test of inhibiting the bacterial growth are carried out. The test agent was copper (II) 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol of example 1; in the test, 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol is complexed with manganese and zinc ions respectively to form 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol manganese (II) and 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol zinc (II) which are used as reference medicaments. The types of cases tested were rice bacterial leaf blight (Xanthomonas oryzae pv. Oryzae), peanut bacterial wilt (Pseudomanas solanacearum Smith), watermelon bacterial fruit blotch (Acidovorax avenae subsp. Citrulli), chinese cabbage soft rot (Erwinia carotovora), rice bacterial leaf streak (Xanthomonas oryzae pv. Oryzicola), citrus canker (Xanthomonas axonopodis pv. Citr, xac), cucumber bacterial angular leaf spot (Pseudomonas syringepv. Lachrymans), peach bacterial perforin (Xanthomonas campestris pv. Pruni), tomato bacterial wilt (Pseudomanas solanacearum Smith). The test results are shown in Table 6 and Table 7.
Table 6: biological measurement example result data table
Table 7: biological measurement example result data table
From the test results, the divalent metal complex formed by 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol has high antibacterial activity on bacterial leaf blight of rice, bacterial leaf spot of peanut, bacterial fruit spot of watermelon, soft rot of Chinese cabbage, bacterial leaf spot of rice and citrus canker, bacterial angular leaf spot of cucumber, bacterial perforation of peach tree and bacterial wilt of tomato.
Claims (10)
1. 3, 6-Diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol of formula I:
Wherein:
Each R 1、R2 is independently H, C 1-12 alkanyl;
each R 3、R4 is independently H, C 1-4 alkanyl.
2. A process for the preparation of 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol of formula I according to claim 1, characterized in that it comprises the steps of:
Wherein:
Each R 1、R2 is independently H, C 1-12 alkanyl;
Each R 3、R4 is independently H, C 1-4 alkanyl;
1) Adding an aromatic o-diphenol compound with a structural formula IV into a mixed solution formed by an alcohol solvent and water, continuously adding an aliphatic carbonyl compound with a structural formula III, uniformly mixing, adding an inorganic acid, carrying out reflux reaction at 50-100 ℃ for 3-5 hours, and distilling to remove redundant reactants and solvents to obtain an addition product with a structural formula II;
2) The addition product of the structural formula II is uniformly mixed with cyclohexanone and organic acid, reflux reaction is carried out for 3-5 hours at the temperature of 80-150 ℃, redundant reactants and solvents are distilled off, a crude product is obtained, and the crude product is washed by water to remove the organic acid, so that 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol of the structural formula I is obtained.
3. The method according to claim 2, characterized in that: the aromatic o-diphenol compound of the structural formula IV is 80-120 parts by weight, the alcohol solvent is 100-200 parts by weight, the water is 30-80 parts by weight, the aliphatic carbonyl compound of the structural formula III is 100-300 parts by weight, the inorganic acid is 10-30 parts by weight, the cyclohexanone is 200-300 parts by weight, and the organic acid is 10-30 parts by weight.
4. A method according to claim 2 or 3, characterized in that: the alcohol solvent is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, propylene glycol, 1, 3-butanediol and 1, 4-butanediol.
5. A method according to claim 2 or 3, characterized in that: the inorganic acid is any one of hydrochloric acid, sulfuric acid and phosphoric acid.
6. A method according to claim 2 or 3, characterized in that: the organic acid is any one of sulfamic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trichloroacetic acid and trifluoroacetic acid.
7. 3, 6-Diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II) of formula I 'or formula I':
Wherein:
Each R 1、R2 is independently H, C 1-12 alkanyl;
each R 3、R4 is independently H, C 1-4 alkanyl.
8. Process for the preparation of 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (ii) according to claim 7, characterized in that it comprises the following steps, in parts by weight:
Adding 20-80 parts of inorganic salt of bivalent copper into 50-200 parts of water to obtain copper salt aqueous solution; adding 30-120 parts of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol into 10-50 parts of aqueous alkali to obtain an alkaline aqueous solution of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol; adding 80-120 parts of the alkaline aqueous solution of 3, 6-diisoalkyl cyclohexanone-4, 5-dialkyl-1, 2-benzenediol into the copper salt aqueous solution, uniformly mixing, regulating the pH value of the mixture to 3-8, and continuously stirring for 10-60 minutes at 20-80 ℃; after stopping stirring, standing for layering, removing supernatant, collecting a lower crude product, adding water for washing to remove salt, and distilling under negative pressure to remove water to obtain 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol copper (II).
9. The method according to claim 8, wherein: the inorganic salt of bivalent copper is any one of cupric chloride, cupric sulfate and cupric nitrate.
10. Use of the copper 3, 6-diisoalkylcyclohexanone-4, 5-dialkyl-1, 2-benzenediol (ii) according to claim 7 for controlling crop diseases, characterized in that: the crop diseases are bacterial leaf blight of rice, bacterial wilt of peanut, bacterial fruit blotch of watermelon, soft rot of Chinese cabbage, bacterial leaf spot of rice, citrus canker, bacterial angular leaf spot of cucumber, bacterial perforation of peach tree and bacterial wilt of tomato.
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