CN114716487B - 一种呋喃双酯类化合物及其制备方法和应用 - Google Patents
一种呋喃双酯类化合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN114716487B CN114716487B CN202210172645.8A CN202210172645A CN114716487B CN 114716487 B CN114716487 B CN 114716487B CN 202210172645 A CN202210172645 A CN 202210172645A CN 114716487 B CN114716487 B CN 114716487B
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- preparation
- nmr
- mites
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 15
- -1 furan diester compound Chemical class 0.000 claims abstract description 11
- 241000488581 Panonychus citri Species 0.000 claims abstract description 10
- 241000344246 Tetranychus cinnabarinus Species 0.000 claims abstract description 9
- 239000000642 acaricide Substances 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 241000238876 Acari Species 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 241000607479 Yersinia pestis Species 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002611 lead compounds Chemical class 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 239000005878 Azadirachtin Substances 0.000 description 3
- 241000207199 Citrus Species 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- VEHPJKVTJQSSKL-UHFFFAOYSA-N azadirachtin Natural products O1C2(C)C(C3(C=COC3O3)O)CC3C21C1(C)C(O)C(OCC2(OC(C)=O)C(CC3OC(=O)C(C)=CC)OC(C)=O)C2C32COC(C(=O)OC)(O)C12 VEHPJKVTJQSSKL-UHFFFAOYSA-N 0.000 description 3
- FTNJWQUOZFUQQJ-IRYYUVNJSA-N azadirachtin A Natural products C([C@@H]([C@]1(C=CO[C@H]1O1)O)[C@]2(C)O3)[C@H]1[C@]23[C@]1(C)[C@H](O)[C@H](OC[C@@]2([C@@H](C[C@@H]3OC(=O)C(\C)=C/C)OC(C)=O)C(=O)OC)[C@@H]2[C@]32CO[C@@](C(=O)OC)(O)[C@@H]12 FTNJWQUOZFUQQJ-IRYYUVNJSA-N 0.000 description 3
- FTNJWQUOZFUQQJ-NDAWSKJSSA-N azadirachtin A Chemical compound C([C@@H]([C@]1(C=CO[C@H]1O1)O)[C@]2(C)O3)[C@H]1[C@]23[C@]1(C)[C@H](O)[C@H](OC[C@@]2([C@@H](C[C@@H]3OC(=O)C(\C)=C\C)OC(C)=O)C(=O)OC)[C@@H]2[C@]32CO[C@@](C(=O)OC)(O)[C@@H]12 FTNJWQUOZFUQQJ-NDAWSKJSSA-N 0.000 description 3
- 235000020971 citrus fruits Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000001018 virulence Effects 0.000 description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004166 bioassay Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 240000005343 Azadirachta indica Species 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 241000488585 Panonychus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及杀螨剂领域,具体是一种呋喃双酯类化合物及其制备方法和应用,所述呋喃双酯类化合物的通式为式中:R选自烷氧基;R1选自烷基和苯基。该化合物溶解性强、活性高、合成方法简单、生产生本低,对柑橘全爪螨和朱砂叶螨有较好的防治效果。
Description
技术领域
本发明涉及杀螨剂领域,具体涉及一种呋喃双酯类化合物及其制备方法和应用。
背景技术
目前,对害螨的防治仍以化学防治为主。由于害螨较其他害虫活动范围小,发育周期短,世代多,产卵量大且卵突变率高,在一定范围内受药剂选择淘汰作用机会相对较多,抗性因子积累相对较快,造成该螨抗药性产生极为迅速。研究表明,柑橘全爪螨已经对有机磷类、有机氯类、菊酯类等多种农药产生了不同程度的抗药性,且抗药性问题愈演愈烈。近年来,有关柑橘全爪螨和朱砂叶螨的抗性监测在国内外逐渐受到重视。
印楝素是从印楝树种里提取的一种生物杀虫剂,可防治200多种农、林、仓储和室内卫生害虫,是世界公认广谱、高效、低毒、易降解、无残留的杀虫剂。贾仁勇等使用硅胶柱层析法和丙酮重结晶法从印楝素中获得了具有杀柑橘全爪螨活性的先导化合物:十八碳酸-3,4-四氢呋喃二酯,初步的构效关系研究结果表明该先导化合物结构的链长短影响其活性和稳定性,合成过程中得到的中间体也具有杀螨的活性(贾仁勇,杜永华,殷中琼,等.4种中药单体物质的体外杀螨活性[J].中国兽医学报,2014,34(1):136-130.);但该先导化合物存在溶解性较差,活性有待提高等缺点。为了得到溶解性改善、活性增强的呋喃二酯类化合物,在此基础上对结构进行改造,促进以呋喃二酯结构模型为基础的新型杀螨农药的出现。目前未见呋喃双酯类化合物用于农业害虫病害杀柑橘全爪螨和朱砂叶螨活性物质的相关报道。
发明内容
本发明的目的在于克服现有技术的不足,提供一种呋喃双酯类化合物,以至少达到溶解性强、活性高、合成方法简单、生产生本低,对柑橘全爪螨和朱砂叶螨有较好的防治效果。
本发明的目的是通过以下技术方案来实现的:
式(I)的化合物、或其立体异构体、手性异构体或其盐作为杀螨剂活性成分的用途,所述化合物(I)的结构式如下:
式中:
R选自烷氧基;
R1同时选自烷基或苯基。
进一步的,
R选自戊氧基、庚氧基、苄氧基、甲氧基或乙氧基中的一种;
R1选自正丁基、苯基、甲基或长碳链的烷基中的一种;
以上所述的烷基包括十六碳、十四碳和十八碳烷基。
进一步的所述化合物的制备方法,其特征在于,包括以下步骤:
1)取化合物A进行氧化加成反应,得到化合物B;
2)取所述化合物B与卤化烷进行取代反应,得到化合物C;
3)取所述化合物C进行水解反应,得到化合物D;
4)取所述化合物D与酸酐进行酯化反应,得到式(I)所述化合物(I);
所述化合物A为:
;
所述化合物B为:
;
所述化合物C的通式为:
;
所述化合物D的通式为:
。
进一步的,所述氧化加成反应具体为:
①将所述化合物A溶于有机溶剂,然后加入氧化剂a进行氧化反应,待反应完全后调节pH至6.0~7.0,然后过滤得到淡黄色油状滤液;
②将所述滤液加入还原剂b进行还原反应,反应完全后调节pH至6.0~7.0;
③调节pH后再加入氧化剂c进行氧化反应,反应完全后调节pH至6.0~7.0,然后萃取即得到所述化合物B。
进一步的,步骤1)中:
所述有机溶剂为丙酮;
所述氧化剂a为氧化性酸,优选的,所述氧化剂a为浓硫酸;
所述还原剂b为四氢硼酸盐,优选的,所述还原剂b为硼氢化钠;
所述氧化剂c为高碘酸盐,优选的,所述氧化剂c为高碘酸钠。 进一步的,步骤2)中,所述取代反应具体为:
将化合物B溶于有机溶剂,然后依次加入强碱和卤化烷,反应完全后萃取得到化合物C;
所述取代反应在无氧环境下进行。
进一步的,步骤2)中:
所述有机溶剂为N,N-二甲基甲酰胺;
所述强碱为氢化钠;
所述卤化烷包括溴戊烷、溴庚烷。
进一步的,步骤3)中,所述水解反应具体为:
将所述化合物C溶于有机溶剂,然后加酸进行反应,反应结束后调节pH为中性,得到所述化合物D;
优选的,所述酸为稀盐酸。
进一步的,步骤4)中 所述的酯化反应具体为:
将所述化合物D溶于有机溶剂,然后加入酸酐和缚酸剂进行反应,反应完全后加入淬灭剂进行淬灭,然后调整pH至6.0~7.0进行萃取即得到式(I)所述化合物(I)。
进一步的,步骤4)中:
所述有机溶剂为甲醇;
所述酸酐包括戊酸酐、苯甲酸酐、乙酸酐;
所述缚酸剂为吡啶;
所述淬灭反应的淬灭剂为稀盐酸。
进一步的,所述杀螨剂用于防治柑橘全爪螨和朱砂叶螨。
本发明的有益效果是:
(1)本发明的化合物对多种螨虫具有良好的防治效果,溶解性强,可作为杀螨剂的活性成分;
(2)本发明的化合物结构简单,易于合成,反应快速,生产成本低,实际应用前景广泛。
附图说明
图1为实施例1的核磁共振图谱;
图2为实施例1的碳谱图;
图3为实施例2的核磁共振图谱;
图4为实施例2的碳谱图;
图5为实施例3的核磁共振图谱;
图6为实施例3的碳谱图;
图7为实施例4的核磁共振图谱;
图8为实施例4的碳谱图;
图9为实施例5的核磁共振图谱;
图10为实施例5的碳谱图;
图11为实施例6的核磁共振图谱;
图12为实施例6的碳谱图;
图13为所述化合物(I)的通式。
具体实施方式
下面结合附图进一步详细描述本发明的技术方案,但本发明的保护范围不局限于以下所述。
实施例1
制备戊氧基-2-戊酸-3,4-四氢呋喃二酯:
详细制备方法如下:
(1)化合物2的合成:
取反应圆底烧瓶(2 L),加入化合物1(380 mmol,57 g,1.0 equiv)、丙酮溶液(1 L无水硫酸镁干燥并且静置24 h),置于冰浴中,预冷片刻后缓慢滴加浓硫酸(6 ml)。冰浴下反应30 min后,恢复室温反应。TLC监测反应进程,待反应完全,加入氢氧化钙调pH至中性。随后用铺有厚厚一层硅藻土的布氏漏斗过滤,冰浴条件下旋干滤液,得到淡黄色油状液体。
接着将上一步得到的淡黄色油状液体溶于水(1 L)中,置于冰浴条件下,预冷片刻后,分批加入硼氢化钠(760 mmol,29 g,2.0 equiv),室温下反应且TLC监测反应进程。反应完全后,置于冰浴条件下,加入冰乙酸调pH至6.0,再加入高碘酸钠(380 mmol,81 g,1.0equiv),室温继续反应。反应完全后,加入碳酸钠调溶液pH至中性,乙酸乙酯萃取,合并有机相,无水硫酸镁干燥、浓缩、柱色谱即得化合物36.72 g化合物2,产率为60%。
(2)化合物3的合成:
取反应双颈瓶(250 mL),氮气保护下加入化合物2(19 mmol,3 g,1.0 equiv),接着量取N,N-二甲基甲酰胺(90 mL用氢化钙干燥),置于冰浴条件下预冷片刻后加入氢化钠(38 mmol,1.5 g,2.0 equiv)。冰浴搅拌10 min后,缓慢滴加溴戊烷(29 mmol,3.5 mL,1.5equiv),恢复室温继续搅拌反应。待反应完全,加入饱和氯化铵溶液淬灭,乙酸乙酯萃取,合并有机相,无水硫酸镁干燥、浓缩、柱色谱即得到同分异构化合物3,即上点2.01 g,产率为46.0%;下点为1.16 g,产率为27%。
(3)化合物4的合成:取反应圆底烧瓶(100 mL),加入化合物3上点(8 mmol,1.8 4g,1.0 equiv)、1M HCl (4 mmol,4 mL,0.5 equiv)以及甲醇溶液(40 mL),55℃搅拌反应,TLC监测反应进程。反应结束后用饱和碳酸氢钠溶液调pH至中性,旋干反应液,柱色谱即得到249.6 mg化合物4,产率为16%。
(1)化合物5的合成:
取反应试管(15 ml),加入化合物4(0.5 mmol,95.11 mg,1.0 equiv)、戊酸酐(1.5mmol,312.9 mg 3.0 equiv)、吡啶(3.0 mmol,265.8 mg,6.0 equiv)以及二氯甲烷溶液(5mL),室温下搅拌反应。待反应完全,先加入1M HCl冰浴下淬灭反应,再加入碳酸氢钠调pH至中性,乙酸乙酯萃取,合并有机相,无水硫酸镁干燥、浓缩、柱色谱即得到165.2 mg化合物5,产率为92%。化合物为黄色油状物。
核磁共振图谱图如说明书附图1所示:
1H NMR and 13C NMR Spectra for Compound example1 :1165.2 mg, 92 %, ayellow oil, 1H NMR (400 MHz, CDCl3) δ 5.44 (td, J = 5.8, 4.3 Hz, 1H), 5.18(dd, J = 5.4, 1.6 Hz, 1H), 5.02 (d, J = 1.5 Hz, 1H), 4.23 (dd, J = 9.8, 6.1Hz, 1H), 3.86 (dd, J = 9.8, 4.3 Hz, 1H), 3.66 (dt, J = 9.5, 6.8 Hz, 1H), 3.40(dt, J = 9.5, 6.6 Hz, 1H), 2.41 – 2.26 (m, 4H), 1.62 – 1.58 (m, 3H), 1.55 (d,J = 4.0 Hz, 1H), 1.45 – 1.23 (m, 10H), 0.91 (td, J = 7.1, 3.5 Hz, 9H). 13C NMR(100 MHz, CDCl3): δ = 173.0, 172.6, 105.3, 75.3, 71.4, 69.6, 68.2, 33.7,33.7, 29.2, 28.2, 26.9, 26.9, 22.4, 22.2, 14.0, 13.7, 13.7.
实施例2
制备庚氧基-2-苯酸-3,4-四氢呋喃二酯:
制备方法同实施例1。不同点为用溴庚烷和苯甲酸酐替代实施例1中的溴戊烷和戊酸酐,制备获得目标化合物。最终得到187.4 mg的产物,产率为88%,化合物为黄色油状物。
核磁共振图谱图如说明书附图2所示:
1H NMR and 13C NMR Spectra for Compound example 2:187.4 mg, 88 %, ayellow oil, 1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J = 8.2, 1.5 Hz, 2H), 7.88(dd, J = 8.2, 1.5 Hz, 2H), 7.69 – 7.54 (m, 1H), 7.52 – 7.37 (m, 3H), 7.34 –7.20 (m, 2H), 5.77 (td, J = 6.3, 3.1 Hz, 1H), 5.39 (d, J = 4.4 Hz, 1H), 5.19(dd, J = 6.7, 4.5 Hz, 1H), 4.39 (dd, J = 10.5, 6.1 Hz, 1H), 4.16 (dd, J =10.5, 3.1 Hz, 1H), 3.81 (dt, J = 9.3, 6.1 Hz, 1H), 3.44 (dt, J = 9.4, 6.4 Hz,1H), 1.58 (s, 1H), 1.54 (d, J = 6.7 Hz, 1H), 1.28 – 1.08 (m, 8H), 0.80 (t, J= 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 166.1, 165.6, 133.2, 133.1,130.0, 129.8, 128.4, 128.3, 100.0, 72.3, 69.8, 69.5, 68.4, 31.8, 29.8, 29.1,26.1, 22.5, 14.1.
实施例3
制备庚氧基-2-戊酸-3,4-四氢呋喃二酯:
制备方法同实施例1。不同点为用溴庚烷替代实施例1中的溴戊烷,制备获得目标化合物。最终得到166.7 mg的产物,产率为91%,化合物为黄色油状物。
核磁共振图谱图说如明书附图3所示:
1H NMR and 13C NMR Spectra for Compound example 3:166.7 mg, 91 %, ayellow oil, 1H NMR (400 MHz, CDCl3) δ 5.44 (td, J = 5.7, 4.2 Hz, 1H), 5.18(dd, J = 5.3, 1.6 Hz, 1H), 5.02 (d, J = 1.6 Hz, 1H), 4.23 (dd, J = 9.8, 6.1Hz, 1H), 3.86 (dd, J = 9.8, 4.3 Hz, 1H), 3.66 (dt, J = 9.5, 6.7 Hz, 1H), 3.41(dt, J = 9.5, 6.6 Hz, 1H), 2.38 – 2.28 (m, 4H), 1.62 – 1.57 (m, 4H), 1.38 –1.26 (m, 14H), 0.96 – 0.88 (m, 9H). 13C NMR (100 MHz, CDCl3): δ = 172.9,172.5, 105.3, 75.3, 71.4, 69.6, 68.2, 33.7, 31.8, 29.5, 29.0, 26.9, 26.9,26.0, 22.6, 22.2, 14.1.
实施例4
制备戊氧基-2-戊酸-3,4-四氢呋喃二酯:
制备方法同实施例1。不同点为下点中间化合物替代了实施例1中的上点中间化合物,制备获得目标化合物。最终得到161.4 mg的产物,产率为90%,化合物为黄色油状物。
核磁共振图谱图如说明书附图4所示:
1H NMR and 13C NMR Spectra for Compound example 4:161.4 mg, 90 %, ayellow oil, 1H NMR (400 MHz, CDCl3) δ 5.35 (td, J = 6.6, 3.8 Hz, 1H), 5.17(d, J = 4.5 Hz, 1H), 4.89 (dd, J = 7.0, 4.6 Hz, 1H), 4.20 (dd, J = 10.2, 6.4Hz, 1H), 3.89 (dd, J = 10.2, 3.9 Hz, 1H), 3.70 (dt, J = 9.7, 6.7 Hz, 1H),3.42 (dt, J = 9.7, 6.6 Hz, 1H), 2.38 – 2.32 (m, 4H), 1.65 – 1.58 (m, 4H),1.42 – 1.23 (m, 10H), 0.95 – 0.87 (m, 9H). 13C NMR (100 MHz, CDCl3): δ =172.9, 172.5, 105.3, 75.3, 71.4, 69.6, 68.2, 33.7, 33.7, 29.2, 28.2, 26.9,26.9, 22.4, 22.2, 14.0, 13.7, 13.7.
实施例5
制备庚氧基-2-乙酸-3,4-四氢呋喃二酯:
制备方法同实施例1。不同点为溴庚烷、乙酸酐和下点中间化合物替代了实施例1中的溴戊烷、戊酸酐和上点中间化合物,制备获得目标化合物。最终得到110.7 mg的产物,产率为92%,化合物为黄色油状物。
核磁共振图谱图如说明书附图5所示:1H NMR and 13C NMR Spectra forCompound example 5:110.7 mg, 92 %, a yellow oil, 1H NMR (400 MHz, CDCl3) δ5.31 (td, 1H), 5.16 (d, J = 4.6 Hz, 1H), 4.91 (dd, J = 7.1, 4.5 Hz, 1H), 4.21(dd, J = 10.2, 6.4 Hz, 1H), 3.89 (dd, J = 10.3, 4.0 Hz, 1H), 3.70 (dt, J =9.9, 6.8 Hz, 1H), 3.47 (dt, J = 9.9, 6.7 Hz, 1H), 2.11 (s, 6H), 1.64 – 1.55(m, 4H), 1.36 – 1.21 (m, 6H), 0.92 – 0.84 (m, 3H). 13C NMR (100 MHz, CDCl3): δ= 170.6, 170.1, 99.7, 71.2, 69.5, 68.6, 68.5, 31.9, 29.5, 29.0, 25.9, 22.6,20.8, 20.6, 14.1.
实施例6
制备庚氧基-2-戊酸-3,4-四氢呋喃二酯:
制备方法同实施例1。不同点为溴庚烷和下点中间化合物替代了实施例1中的溴戊烷和上点中间化合物,制备获得目标化合物。最终得到138.2 mg的产物,产率为89%,化合物为黄色油状物。
核磁共振图谱图如说明书附图6所示:
1H NMR and 13C NMR Spectra for Compound example 6:110.7 mg, 92 %, ayellow oil, 1H NMR (400 MHz, CDCl3) δ 5.35 (td, 1H), 5.17 (d, J = 4.5 Hz, 1H),4.89 (dd, J = 7.0, 4.5 Hz, 1H), 4.19 (dd, J = 10.2, 6.4 Hz, 1H), 3.89 (dd, J= 10.2, 3.9 Hz, 1H), 3.70 (dt, J = 9.7, 6.7 Hz, 1H), 3.42 (dt, J = 9.6, 6.5Hz, 1H), 2.43 – 2.30 (m, 4H), 1.63 – 1.57 (m, 4H), 1.39 – 1.25 (m, 14H), 0.98– 0.84 (m, 9H). 13C NMR (100 MHz, CDCl3): δ = 173.3, 172.8, 99.7, 71.2, 69.5,68.4, 68.4, 33.9, 33.6, 31.9, 29.6, 29.1, 27.0, 26.9, 26.0, 22.6, 22.2, 22.2,14.1.
以上实施例有上点、下点之分是因为在整个合成路线中,合成化合物C时由于构型不同会有同分异构体,通过薄层色谱分析法监测,发现该化合物C的两个产物点在板上的分布为上点和下点。
选择以上的实施例进行保护是因为以上化合物是在室内毒力测定预试验的基础上所筛选出杀螨活性突出的化合物。
分别对实施例1-6中的呋喃双酯类化合物进行螨虫抑制性测定。生物测定参照联合国粮农组织(FAO)推荐的害螨生物测定的标准方法—玻片浸渍法并加以改进。
将供试药剂用0.1%吐温、2%二甲亚砜2%在预备试验的基础上将实施例1~6每个实施例和对照组药剂配置成20 mg/ml、5 mg/ml、1.25 mg/ml、0.3 mg/ml、0.08 mg/ml的5个浓度的杀螨剂。将双面胶带剪成2 cm长贴在载玻片的一端,用毛笔挑选健康的柑橘全爪成螨,将其背部黏在载玻片的双面胶带上,不要粘住螨的口器、足和须,保证螨足能够自由活动,每块载玻片40头。将玻片带螨的一端浸入药液中,轻轻摇动5 s后取出,迅速用吸水纸吸干螨体及其周围多余的药液,室温晾干后置于温度为(25 ± 1)℃、 RH=75%左右的光照培养箱中,24 h后于双筒解剖镜下观察死亡螨数并作记录。另以印楝素中获得了具有杀柑橘全爪螨活性的先导化合物:十八碳酸-3,4-四氢呋喃二酯为对照药剂,每处理重复3次,所得数据在Excel和SPSS上进行处理,求出毒力直线回归方程和致死中浓度LD50值。对柑橘全爪螨的室内毒力测定结果如表1所示,对朱砂叶螨的室内毒力测定结果如表2所示。
表1
由表1可知:实施例1-6制备的呋喃双酯类化合物对柑橘全爪螨的抑制作用比对照组(十八碳酸-3,4-四氢呋喃二酯)效果好,对照组的LD50为1767.8855 μg/mL说明通过对其结构改造能够有效的提升杀螨活性。并且实验例5相比其余5个实施例LD50值低,抑制效果最好,其浓度为508.3610 μg/mL,药物的杀螨活性强弱为实施例5>实施例2>实施例4>实施例1>实施例6>实施例3。
表2
CK a 表示十八碳酸-3,4-四氢呋喃二酯的对照组。
由表2可知:实施例1-6通过结构改造制备的四氢呋喃双酯类化合物对朱砂叶螨也具有一定抑制作用,同上对照药剂(十八碳酸-3,4-四氢呋喃二酯)对朱砂叶螨的防治效果不如表2中的实施例1-6,对照药剂的抑制LD50为2380.9913 μg/mL。其中实验例5相比其余5个实验例LD50值低,抑制效果最好,其浓度为593.1262 μg/mL,药物的杀螨活性强弱为实施例5>实施例2>实施例6>实施例4>实施例1>实施例3。以上所述仅是本发明的优选实施方式,应当理解本发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围,则都应在本发明所附权利要求的保护范围内。
Claims (1)
1.式(I)的化合物或其盐在制备杀螨剂中的用途,其特征在于,所述化合物(I)的结构式如下:
式中:
R选自戊氧基和庚氧基中的一种;
R1选自正丁基、苯基或甲基中的一种;
所述螨为柑橘全爪螨和朱砂叶螨。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210172645.8A CN114716487B (zh) | 2022-02-24 | 2022-02-24 | 一种呋喃双酯类化合物及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210172645.8A CN114716487B (zh) | 2022-02-24 | 2022-02-24 | 一种呋喃双酯类化合物及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114716487A CN114716487A (zh) | 2022-07-08 |
CN114716487B true CN114716487B (zh) | 2024-03-08 |
Family
ID=82235220
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210172645.8A Active CN114716487B (zh) | 2022-02-24 | 2022-02-24 | 一种呋喃双酯类化合物及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114716487B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115028607A (zh) * | 2021-03-06 | 2022-09-09 | 四川农业大学 | 一种具有杀螨活性的化合物、制作方法及应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001040228A1 (fr) * | 1999-12-03 | 2001-06-07 | Kyoto Pharmaceutical Industries, Ltd. | Composes de carbapenem, leur utilisation et leurs intermediaires |
CN1628773A (zh) * | 2004-08-31 | 2005-06-22 | 吴成奎 | 植物源印楝油杀精制剂 |
CN102633745A (zh) * | 2012-04-05 | 2012-08-15 | 南开大学 | 一类α-甲氧亚氨基-4-甲基-1,2,3-噻二唑-5-甲基羧酸酯衍生物及其制备方法和用途 |
WO2016095662A1 (zh) * | 2014-12-15 | 2016-06-23 | 苏州旺山旺水生物医药有限公司 | (2S,3R,4R)-3,5-二取代-2-脱氧-2-羟基-2-甲基-D-核糖-γ-内酯的制备方法及其中间体 |
CN109232550A (zh) * | 2018-11-07 | 2019-01-18 | 青岛科技大学 | 一种含3-氯-5-三氟甲基吡啶基-1,3,4-噁二唑-2-酮类化合物及其应用 |
CN112209906A (zh) * | 2019-07-10 | 2021-01-12 | 中国科学院宁波材料技术与工程研究所 | 一种呋喃二癸酯的制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105859590B (zh) * | 2010-10-12 | 2018-01-02 | 日本曹达株式会社 | 芳氧基脲化合物及有害生物防除剂 |
RU2576316C2 (ru) * | 2010-11-03 | 2016-02-27 | ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи | Пестицидная композиция, способ контроля вредителей, способ контроля эндопаразитов, эктопаразитов или обоих и способ усиления жизнестойкости растений |
-
2022
- 2022-02-24 CN CN202210172645.8A patent/CN114716487B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001040228A1 (fr) * | 1999-12-03 | 2001-06-07 | Kyoto Pharmaceutical Industries, Ltd. | Composes de carbapenem, leur utilisation et leurs intermediaires |
CN1628773A (zh) * | 2004-08-31 | 2005-06-22 | 吴成奎 | 植物源印楝油杀精制剂 |
CN102633745A (zh) * | 2012-04-05 | 2012-08-15 | 南开大学 | 一类α-甲氧亚氨基-4-甲基-1,2,3-噻二唑-5-甲基羧酸酯衍生物及其制备方法和用途 |
WO2016095662A1 (zh) * | 2014-12-15 | 2016-06-23 | 苏州旺山旺水生物医药有限公司 | (2S,3R,4R)-3,5-二取代-2-脱氧-2-羟基-2-甲基-D-核糖-γ-内酯的制备方法及其中间体 |
CN109232550A (zh) * | 2018-11-07 | 2019-01-18 | 青岛科技大学 | 一种含3-氯-5-三氟甲基吡啶基-1,3,4-噁二唑-2-酮类化合物及其应用 |
CN112209906A (zh) * | 2019-07-10 | 2021-01-12 | 中国科学院宁波材料技术与工程研究所 | 一种呋喃二癸酯的制备方法 |
Non-Patent Citations (5)
Title |
---|
Structural modification of octadecanoic acid-3,4-tetrahydrofuran diester and the acaricidal activity and mechanism of its derivatives against Sarcoptes scabiei var. Cuniculi;Li LX,等;FRONTIERS IN PHARMACOLOGY;第第13卷卷;第1-11页 * |
刘涛,等.十八碳酸-3,4-四氢呋喃二酯衍生物杀螨活性研究.中国畜牧兽医学会兽医药理毒理学分会第十五次学术讨论会论文集.2019,第37页"摘要". * |
十八碳酸-3,4-四氢呋喃二酯衍生物杀螨活性研究;刘涛,等;中国畜牧兽医学会兽医药理毒理学分会第十五次学术讨论会论文集;第37页"摘要" * |
十八碳酸-3,4-四氢呋喃二酯衍生物的合成及其体外杀螨活性研究;周迅;中国优秀硕士学位论文全文数据库农业科技辑(第第04期期);第17-21页 * |
含呋喃环双酰肼类化合物的合成及杀虫活性研究;崔紫宁;王振;李映;周心玉;凌云;杨新玲;;有机化学(10);第1300-1304页 * |
Also Published As
Publication number | Publication date |
---|---|
CN114716487A (zh) | 2022-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017067500A1 (zh) | 一种联苯类化合物及其应用 | |
EP1155616B1 (en) | Process for the preparation of (N-phenylacetyl-N-2,6-xylil)methyl alaninate | |
JP2016535004A (ja) | 有害生物防除化合物の調製法 | |
DE69629387T2 (de) | Dimere indan verbindungen und ihre pharmazeutische verwendung | |
CN114716487B (zh) | 一种呋喃双酯类化合物及其制备方法和应用 | |
JP2633377B2 (ja) | 4―アシルオキシキノリン誘導体及びこれを有効成分として含有する殺虫、殺ダニ剤 | |
EP1860103A1 (en) | Anticancer compound, intermediate therefor, and processes for producing these | |
US4983630A (en) | 2,2-difluorocyclopropylethane derivatives, processes for their preparation and their use as pesticides | |
DE4327365A1 (de) | Verwendung von Phenolen und Phenolderivaten als Arzneimittel mit fibrinogensenkender Wirkung | |
CN110551148B (zh) | 含硅酰基乙腈化合物及其制备方法与应用 | |
CN109942427B (zh) | 一种单萜酚类衍生物及其合成方法和在农药中的应用 | |
JPS6055075B2 (ja) | ピラゾ−ル系リン酸エステル類、その製造法および殺虫殺ダニ剤 | |
US5990322A (en) | Alpha-tocopherol cyclopropylates, the new vitamin E derivatives and method for producing the same | |
US6214882B1 (en) | Benzenesulphonamide derivatives, preparation thereof and therapeutical uses thereof | |
CN113943238B (zh) | 一种取代的苯硫醚类化合物及其应用 | |
JP2597687B2 (ja) | 有害生物防除剤 | |
US4275068A (en) | Lipid lowering alkylene glycols and ester derivatives thereof | |
KR101206123B1 (ko) | 스틸벤 골격을 갖는 화합물의 합성방법 | |
CN106431977B (zh) | 一种不饱和肟醚类化合物及其用途 | |
US20050054877A1 (en) | Enantiomerically selective cyclopropanation | |
GB2143814A (en) | Quinazolines | |
KR19980083587A (ko) | 플루오르비닐기를 갖는 신규의 프로페노익 에스테르 및 아미드 유도체 | |
CN111269180B (zh) | 含有三氟甲基茚并苯并六元杂环结构化合物在防治植物病虫害中的应用 | |
JP4685742B2 (ja) | 4−キノリノール誘導体及びこれを有効成分として含有する農園芸用殺菌剤 | |
EP1035120B1 (en) | Alpha-tocopherol cyclopropylates, the new vitamin E derivatives, and method for producing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |