CN107311965B - N- [(3- heterocycle) acryloyl group] phenyl -3- alkoxypropionamide derivative and its preparation method and application - Google Patents
N- [(3- heterocycle) acryloyl group] phenyl -3- alkoxypropionamide derivative and its preparation method and application Download PDFInfo
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- CN107311965B CN107311965B CN201710486942.9A CN201710486942A CN107311965B CN 107311965 B CN107311965 B CN 107311965B CN 201710486942 A CN201710486942 A CN 201710486942A CN 107311965 B CN107311965 B CN 107311965B
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- aminoacetophenone
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 27
- 229960004756 ethanol Drugs 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims description 8
- 241000144210 Culex pipiens pallens Species 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 241000607479 Yersinia pestis Species 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 claims description 7
- 241000409991 Mythimna separata Species 0.000 claims description 7
- 241000344246 Tetranychus cinnabarinus Species 0.000 claims description 7
- CKQHAYFOPRIUOM-UHFFFAOYSA-N 3'-Aminoacetophenone Chemical compound CC(=O)C1=CC=CC(N)=C1 CKQHAYFOPRIUOM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 230000002265 prevention Effects 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000002917 insecticide Substances 0.000 abstract description 8
- -1 amides compounds Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 150000002611 lead compounds Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 238000005406 washing Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 235000006708 antioxidants Nutrition 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 239000002904 solvent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000003026 anti-oxygenic effect Effects 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000013642 negative control Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZIRCHXYMBFNFD-HNQUOIGGSA-N 3-(2-Furanyl)-2-propenal Chemical compound O=C\C=C\C1=CC=CO1 VZIRCHXYMBFNFD-HNQUOIGGSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- 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
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- 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
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- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The present invention relates to amides compounds and its preparation method and application, and in particular to N- [(3- heterocycle) acryloyl group] phenyl -3- alkoxypropionamide derivative and its preparation method and application.The technical problem to be solved by the present invention is to provide a kind of amides compounds that can be used as antioxidant and agricultural insecticide and use.The structural formula of the compound is as shown in formula I.The present invention splices principle using bio-active group, heterocyclic compound is introduced into amide compound, the reactive compound or active lead compound for having found some structure novels, superior activity, so that preferable basis has been established in the initiative for novel antioxidant and insecticide.
Description
Technical field
The present invention relates to amides compounds and its preparation method and application, and in particular to N- [(3- heterocycle) acryloyl
Base] phenyl -3- alkoxypropionamide derivative and its preparation method and application.
Background technique
Antioxidant effectively can delay or inhibit many substances, especially big point of the biology such as sugar, rouge, protein, nucleic acid
The oxidation deterioration of son, very extensive application is suffered from many fields: (1) in terms of food processing, antioxidant can inhibit
Oxidation of Fat and Oils prevents its rancid, frequently as food oxydating resistance additive；(2) in life science and medical domain, antioxidant energy
Interior free yl is removed, the formation of peroxidation state is slowed down, prevents and treats various diseases caused by free radical, improves machine
Body immunocompetence, to protect human health；(3) in chemical industrial field, antioxidant adds as the stability of chemical products
Add agent, improve the antioxygenic property of product, to prolong its service life.Since antioxidant is in industrial and agricultural production and daily life
Irreplaceable role is all played in work, therefore, the research and development of efficient, economic, low toxicity antioxidant have very
Important meaning.
On the other hand, long-term a large amount of use of pesticide especially insecticide not only polluted environment, destroy the ecological balance,
Also result in serious " 3R " (residual, resistance and pest resurgence) and " three cause " (carcinogenic, teratogenesis shape and mutagenesis) problem.This
A little problems cause the mankind and widely pay close attention to, and how to efficiently solve these problems is the one long-term and arduous of facing mankind
Task.In this way, being faced with huge challenge in the case where the too busy to get away pesticide of the mankind in pesticide, find to harmful organism height
Effect, to non-target organism safety, degradable in the environment and catabolite to human health and ecological environment security " environment and
Humorous pesticide " or " environment friendly agricultural " the hot spot at pesticide research and forward position.
Amides compound has extensive bioactivity, including sterilization, anti-oxidant, plant growth regulating etc..Therefore, exist
In the past few decades, it is had made extensive and intensive studies, it was found that many new and effective compounds, but also constantly
There is structure novel, mode of action uniqueness, has excellent performance, is efficient to harmful organism, is safe to non-target organism, easily dropping in the environment
It solves and catabolite reports the kind of human health and ecological environment security.
Up to the present, it yet there are no the report that amides compound is used as antioxidant and agricultural insecticide.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of amides that can be used as antioxidant and agricultural insecticide and use
Compound.
N- [(3- heterocycle) acryloyl group] phenyl -3- alkoxypropionamide derivative of the invention, structural formula is such as
Shown in formula I:
Wherein, R1ForR2For C1-C4
Alkyl；R3For hydrogen or halogen；R4For hydrogen or halogen；X is O or S.
Preferably, R1For
It is furthermore preferred that R2For ethyl.
Preferred structure formula is as shown in formula I -1 or formula I -2:
Second technical problem that the present invention solves is to provide the preparation method of above compound.
CompoundPreparation method, include the following steps:
A, in the mixture of aminoacetophenone and methylene chloride, triethylamine is added, forms solution A；
B, under conditions of stirring and ice-water bath, the mixed liquor of acryloyl chloride and methylene chloride is added drop-wise in solution A, is controlled
Reaction temperature processed is maintained at 0~5 DEG C；
C, it after the reaction was completed, washs, vacuum distillation obtains crude product, then recrystallizes to get intermediate is arrived；
D, intermediate is dissolved in dehydrated alcohol, adds the ethanol solution of NaOH, obtains solution B；
It e, is under stiring, R by structural formula1The aldehyde of-CHO and the mixed liquor of dehydrated alcohol are added drop-wise in solution B, and control is anti-
Temperature is answered to be warming up to 50 DEG C of reflux；
F, distilled water after completion of the reaction, is added, and adjusts pH value to 7, has solid Precipitation, filters, washing is tied again
Crystalline substance is to get product；
Preferably, aminoacetophenone is 4- aminoacetophenone or 3- aminoacetophenone, needs the knot according to target product
Structure selects the amino specific location of aminoacetophenone.
For this method while carrying out aldol reaction, it is anti-that also addition has occurred with C=C double bond in the ethyl alcohol in solvent
It answers, i.e., once completes two-step reaction, improve reaction efficiency.
The present invention also provides the compounds of this invention to prepare the purposes in antioxidant.
The compound of the present invention has excellent antioxygenic property, can be used as antioxidant.
The present invention also provides the compounds of this invention to kill the purposes in agricultural pests.
The compound of the present invention, it is also possible to make insecticide, have to agricultural pests such as mythimna separata, Tetranychus cinnabarinus, Culex pipiens pallens
Preferable cytotoxicity.It is therefore preferable that the agricultural pests are mythimna separata, Tetranychus cinnabarinus or Culex pipiens pallens.
The present invention splices principle using bio-active group, heterocyclic compound is introduced into amide compound, it was found that one
The reactive compound or active lead compound of a little structure novels, superior activity, to be novel antioxidant and insecticide
Preferable basis has been established in initiative.
Specific embodiment
The present invention provides structural formula such as I compound represented of formula:
Wherein, R1ForR2For C1-C4
Alkyl；R3For hydrogen or halogen；R4For hydrogen or halogen；X is O or S.
Preferably, R1ForR2For
C1-C4 alkyl.
Preferably, R1ForR2For second
Base；R3For hydrogen or halogen；R4For hydrogen or halogen；X is O or S.
Preferably, R1ForR2For ethyl.
Position on phenyl ring can be ortho position, meta position or contraposition etc., preferably meta position
Or contraposition, i.e., preferred structure formula is as shown in formula I -1 or formula I -2:
It is currently preferred some compounds below.
The compound of the present invention can be obtained using conventional preparation method.
It is preferred that working as R2When for ethyl, using following preparation method:
This method is in second step synthesis, and while carrying out aldol reaction, the ethyl alcohol in solvent is also bis- with C=C
Addition reaction has occurred in key, i.e., once completes two-step reaction, improves reaction efficiency.
Specifically, the step of this method includes the preparation of intermediate and two steps of synthesis of target product.Wherein, intermediate
The preparation method of body is specific as follows:
A, in the mixture of aminoacetophenone and methylene chloride, triethylamine is added, forms solution A；
B, under conditions of stirring and ice-water bath, the mixed liquor of acryloyl chloride and methylene chloride is added drop-wise in solution A, is controlled
Reaction temperature processed is maintained at 0~5 DEG C；
C, it after the reaction was completed, washs, vacuum distillation obtains crude product, then recrystallizes to get intermediate is arrived.
The synthetic method of target product is specific as follows:
D, intermediate is dissolved in dehydrated alcohol, adds the ethanol solution of NaOH, obtains solution B；
E, under stiring, by aldehyde (i.e. R1- CHO) and the mixed liquor of dehydrated alcohol be added drop-wise in solution B, control reaction temperature
It is warming up to 50 DEG C of reflux；
F, distilled water after completion of the reaction, is added, and adjusts pH value to 7, has solid Precipitation, filters, washing is tied again
Crystalline substance to get arrive target product.
Wherein, aminoacetophenone is 4- aminoacetophenone or 3- aminoacetophenone, needs the structure according to target product
To select the amino specific location of aminoacetophenone.
The compound of the present invention has excellent antioxygenic property, can be used as antioxidant.
The compound of the present invention, it is also possible to make insecticide, have to agricultural pests such as mythimna separata, Tetranychus cinnabarinus, Culex pipiens pallens
Preferable cytotoxicity.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
The synthesis of 1 compound 1~7 of embodiment
1, the synthetic method of compound 1
(1) it after 3- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by furfural (0.005mol) and dehydrated alcohol
The mixed liquor of (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C of reflux, and leads to
Cross thin layer silica gel plate (TLC) detection terminal.After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor, with 10%
The pH value of solution is adjusted to about 7 by HCl, there is solid Precipitation, is filtered, and washing obtains crude product again with dehydrated alcohol weight
It crystallizes to get product is arrived.
Light brown powder solid；IR(KBr)νmax(cm-1):3435,3336,1684,1662,1599,1556,1482,
1384,756,686；1H NMR(400MHz,DMSO-d6) δ (ppm): 10.21 (s, 1H), 8.29 (s, 1H), 7.95 (d, J=
1.2Hz,1H),7.91(dd,J1=1.2Hz, J2=1.2Hz, 1H), 7.76 (d, J=8.0Hz, 1H), 7.60 (d, J=
15.6Hz, 1H), 7.51 (d, J=7.6Hz, 1H), 7.47 (d, J=15.2Hz, 1H), 7.12 (d, J=3.2Hz, 1H), 6.72
(dd,J1=1.6Hz, J2=2.0Hz, 1H), 3.68 (t, J=6.0Hz, 2H), 3.48-3.42 (m, 2H), 2.58 (t, J=
6.0Hz, 2H), 1.10 (t, J=6.8Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):188.81(1C),170.16
(1C),151.50(1C),146.78(1C),140.21(1C),138.45(1C),131.04(1C),129.82(1C),123.78
(1C),123.45(1C),118.91(1C),118.85(1C),117.89(1C),113.65(1C),66.37(1C),65.87
(1C),37.72(1C),15.54(1C)；HRMS(ESI)m/z:Calcd for C18H20NO4[M+H]+:314.1387,Found:
314.1385.
2, the synthetic method of compound 2
(1) it after 3- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by thiophene -2-formaldehyde (0.005mol) and anhydrous
The mixed liquor of ethyl alcohol (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C of reflux,
And terminal is detected by thin layer silica gel plate (TLC).After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor, uses
The pH value of solution is adjusted to about 7 by 10%HCl, there is solid Precipitation, is filtered, and washing obtains crude product and uses anhydrous second again
Alcohol recrystallizes to arrive product.
Yellow powdery solid；IR(KBr)νmax(cm-1):3434,3337,1691,1656,1583,1547,1484,
1384,972,794,711；1H NMR(400MHz,DMSO-d6)δ(ppm):10.21(s,1H),8.24(s,1H),7.96–7.93
(m, 2H), 7.82-7.79 (m, 2H), 7.70 (d, J=3.2Hz, 1H), 7.52 (d, J=8.0Hz, 1H), 7.47 (d, J=
15.2Hz, 1H), 7.21 (t, J=4.4Hz, 1H), 3.68 (t, J=6.0Hz, 2H), 3.47-3.42 (m, 2H), 2.58 (t, J=
6.0Hz, 2H), 1.10 (t, J=6.8Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):188.92(1C),170.13
(1C),140.19(1C),140.15(1C),138.46(1C),137.40(1C),133.63(1C),130.94(1C),129.75
(1C),129.25(1C),123.86(1C),123.65(1C),120.67(1C),118.84(1C),66.39(1C),65.88
(1C),37.73(1C),15.54(1C)；HRMS(ESI)m/z:Calcd for C18H20NO3S[M+H]+:330.1158,
Found:330.1154.
3, the synthetic method of compound 3
(1) it after 3- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), is added in 50mL three-necked bottle,
The ethanol solution of NaOH (10%, 2.5mL) is added to the solution again.Under stiring, by 2- furylacrolein
The mixed liquor of (0.005mol) and dehydrated alcohol (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, controls reaction temperature
50 DEG C of reflux are warming up to, and terminal is detected by thin layer silica gel plate (TLC).After completion of the reaction, 3-4 times are added into mixed liquor
The pH value of solution is adjusted to about 7 with 10%HCl, there is solid Precipitation by the distilled water of volume, is filtered, washing, is obtained thick
Product is recrystallized again with dehydrated alcohol to get product is arrived.
Brown powder solid；IR(KBr)νmax(cm-1):3338,1690,1650,1578,1549,1479,1384,
999,752,682；1H NMR(400MHz,DMSO-d6)δ(ppm):10.19(s,1H),8.23(s,1H),7.87(dd,J1=
0.8Hz,J2=0.8Hz, 1H), 7.82 (d, J=1.2Hz, 1H), 7.71 (d, J=7.6Hz, 1H), 7.56-7.47 (m, 2H),
7.32 (d, J=14.8Hz, 1H), 7.11 (d, J=15.2Hz, 1H), 7.02-6.95 (m, 1H), 6.76 (d, J=3.2Hz,
1H),6.62(dd,J1=3.2Hz, J2=3.2Hz, 1H), 3.67 (t, J=6.4Hz, 2H), 3.47-3.42 (m, 2H), 2.57
(t, J=6.0Hz, 2H), 1.10 (t, J=6.8Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):189.30(1C),
170.10(1C),152.43(1C),145.33(1C),144.61(1C),140.18(1C),138.71(1C),129.66(1C),
129.10(1C),125.51(2C),123.74(1C),123.49(1C),118.77(1C),113.40(1C),113.15(1C),
66.38(1C),65.87(1C),37.70(1C),15.52(1C)；HRMS(ESI)m/z:Calcd for C20H22NO4[M+H]+:
340.1543,Found:340.1538.
4, the synthetic method of compound 4
(1) it after 4- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by furfural (0.005mol) and dehydrated alcohol
The mixed liquor of (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C of reflux, and leads to
Cross thin layer silica gel plate (TLC) detection terminal.After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor, with 10%
The pH value of solution is adjusted to about 7 by HCl, there is solid Precipitation, is filtered, and washing obtains crude product again with dehydrated alcohol weight
It crystallizes to get product is arrived.
Dark brown powder solid；IR(KBr)νmax(cm-1):3318,1658,1600,1528,1477,1384,972,
819；1H NMR(400MHz,DMSO-d6) δ (ppm): 10.34 (s, 1H), 8.07 (d, J=8.8Hz, 2H), 7.92 (d, J=
1.6Hz, 1H), 7.79 (d, J=8.8Hz, 2H), 7.56 (s, 2H), 7.10 (d, J=2.8Hz, 1H), 6.70 (dd, J1=
2.0Hz,J2=1.6Hz, 1H), 3.68 (t, J=6.0Hz, 2H), 3.47-3.42 (m, 2H), 2.61 (t, J=6.4Hz, 2H),
1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):187.45(1C),170.44(1C),151.73
(1C),146.42(1C),144.03(1C),132.62(1C),130.34(1C),130.09(2C),119.23(1C),118.96
(2C),117.04(1C),113.49(1C),66.31(1C),65.88(1C),37.85(1C),15.49(1C)；HRMS(ESI)
m/z:Calcd for C18H20NO4[M+H]+:314.1387,Found:314.1382.
5, the synthetic method of compound 5
(1) it after 4- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by thiophene -2-formaldehyde (0.005mol) and anhydrous
The mixed liquor of ethyl alcohol (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C of reflux,
And terminal is detected by thin layer silica gel plate (TLC).After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor, uses
The pH value of solution is adjusted to about 7 by 10%HCl, there is solid Precipitation, is filtered, and washing obtains crude product and uses anhydrous second again
Alcohol recrystallizes to arrive product.
Yellow powdery solid；IR(KBr)νmax(cm-1):3433,3309,1697,1655,1589,1527,1384,
965,820；1H NMR(400MHz,DMSO-d6) δ (ppm): 10.34 (s, 1H), 8.10 (d, J=8.8Hz, 2H), 7.90 (d, J
=15.2Hz, 1H), 7.80-7.78 (m, 3H), 7.69 (d, J=3.6Hz, 1H), 7.58 (d, J=15.2Hz, 1H), 7.20
(dd,J1=3.6Hz, J2=3.6Hz, 1H), 3.68 (t, J=6.4Hz, 2H), 3.47-3.42 (m, 2H), 2.61 (t, J=
6.4Hz, 2H), 1.10 (t, J=6.8Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):187.42(1C),170.45
(1C),144.05(1C),140.33(1C),136.55(1C),133.04(1C),132.55(1C),130.62(1C),130.21
(2C),129.13(1C),120.74(1C),118.88(2C),66.31(1C),65.89(1C),37.83(1C),15.51
(1C)；HRMS(ESI)m/z:Calcd for C18H20NO3S[M+H]+:330.1158,Found:330.1158.
6, the synthetic method of compound 6
(1) it after 4- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by 3- pyridine carboxaldehyde (0.005mol) and anhydrous
The mixed liquor of ethyl alcohol (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C of reflux,
And terminal is detected by thin layer silica gel plate (TLC).After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor, uses
The pH value of solution is adjusted to about 7 by 10%HCl, there is solid Precipitation, is filtered, and washing obtains crude product and uses anhydrous second again
Alcohol recrystallizes to arrive product.
Pale yellow powder shape solid；IR(KBr)νmax(cm-1):3433,3243,1688,1660,1610,1588,1535,
1481,1384,803；1H NMR(400MHz,DMSO-d6) δ (ppm): 10.37 (s, 1H), 9.04 (d, J=1.6Hz, 1H),
8.62(dd,J1=1.6Hz, J2=1.2Hz, 1H), 8.37 (d, J=8.0Hz, 1H), 8.19 (d, J=8.8Hz, 2H), 8.10
(d, J=15.6Hz, 1H), 7.81 (d, J=8.8Hz, 2H), 7.76 (d, J=15.6Hz, 1H), 7.51 (dd, J1=4.8Hz, J2
=4.8Hz, 1H), 3.68 (t, J=6.0Hz, 2H), 3.48-3.42 (m, 2H), 2.62 (t, J=6.4Hz, 2H), 1.10 (t, J
=6.8Hz, 3H)；13C NMR(100MHz,DMSO-d6)δ(ppm):187.71(1C),170.52(1C),151.34(1C),
150.76(1C),144.27(1C),140.34(1C),135.50(1C),132.39(1C),131.10(1C),130.52(2C),
124.36(1C),124.31(1C),118.85(2C),66.29(1C),65.89(1C),37.83(1C),15.52(1C)；HRMS
(ESI)m/z:Calcd for C19H21N2O3[M+H]+:325.1547,Found:325.1541.
7, the synthetic method of compound 7
(1) it after 4- aminoacetophenone (0.01mol) being dissolved in methylene chloride (10mL), is added in 50mL three-necked bottle, then
Triethylamine (3mL) is added to the solution.Under conditions of stirring and ice-water bath, by acryloyl chloride (0.015mol) and dichloromethane
The mixed liquor of alkane (5mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is maintained at 0-5 DEG C, and passes through
Thin layer silica gel plate (TLC) detects terminal.When after the reaction was completed, with hydrochloric acid (10%) and sodium hydroxide (10%) washing reaction in turn
Liquid, vacuum distillation remove solvent (methylene chloride), obtain crude product, then recrystallized to get intermediate is arrived with dehydrated alcohol.
(2) homemade intermediate (0.005mol) is dissolved in dehydrated alcohol (20mL), be added in 50mL three-necked bottle, then will
The ethanol solution (10%, 2.5mL) of NaOH is added to the solution.Under stiring, by 2- furylacrolein (0.005mol) and
The mixed liquor of dehydrated alcohol (10mL) is slowly instilled in three-necked bottle with constant pressure funnel, and control reaction temperature is warming up to 50 DEG C and returns
Stream, and terminal is detected by thin layer silica gel plate (TLC).After completion of the reaction, the distilled water of 3-4 times of volumes is added into mixed liquor,
The pH value of solution is adjusted to about 7 with 10%HCl, there is solid Precipitation, filter, washing, obtain crude product use again it is anhydrous
Ethyl alcohol recrystallization to get arrive product.
Brown powder solid；IR(KBr)νmax(cm-1):3434,3321,1658,1596,1529,1474,1384,
998,823；1H NMR(400MHz,DMSO-d6) δ (ppm): 10.33 (s, 1H), 8.02 (d, J=8.8Hz, 2H), 7.81 (d, J
=1.6Hz, 1H), 7.78 (d, J=8.8Hz, 2H), 7.53-7.40 (m, 2H), 7.08 (d, J=15.6Hz, 1H), 7.00-
6.93 (m, 1H), 6.73 (d, J=3.2Hz, 1H), 6.62 (dd, J1=1.6Hz, J2=2.0Hz, 1H), 3.68 (t, J=
6.0Hz, 2H), 3.47-3.42 (m, 2H), 2.61 (t, J=6.0Hz, 2H), 1.10 (t, J=6.8Hz, 3H)；13C NMR
(100MHz,DMSO-d6)δ(ppm):187.77(1C),170.45(1C),152.46(1C),145.20(1C),143.92
(1C),143.72(1C),132.77(1C),130.01(2C),128.57(1C),125.62(1C),125.59(1C),118.85
(2C),113.16(1C),113.11(1C),66.31(1C),65.89(1C),37.81(1C),15.51(1C)；HRMS(ESI)
m/z:Calcd for C20H22NO4[M+H]+:340.1543,Found:340.1539.
The measurement of 1 the compounds of this invention insecticidal activity of test example
1, test pest
3 instar larvae of mythimna separata, Tetranychus cinnabarinus adult mite, 3 instar larvae of Culex pipiens pallens, they be it is indoor for many generations raise throughout the year it is quick
Feel strain.
2, the measuring method of mythimna separata
Sample to be tested is dissolved in dimethyl sulfoxide and is diluted to certain concentration with 0.1% Tween-80 aqueous solution, to be not added
The corresponding solution of sample to be tested is negative control.Maize leaf is cut into the segment of 2 × 4cm, is taken after soaking 5s in solution to be measured
It opens, bottom is put into after draining and is covered in the culture dish (6cm) of filter paper, access 15 3 instar larvaes, then placing it in temperature is 22
~24 DEG C, relative humidity 60%, light application time records death condition, often to continue to raise in the laboratory of 14:10h afterwards for 24 hours
One experiment in triplicate, and calculates corrected mortality with following equation:
3, the measuring method of Tetranychus cinnabarinus
Sample to be tested is dissolved in dimethyl sulfoxide and is diluted to certain concentration with 0.1% Tween-80 aqueous solution, to be not added
The corresponding solution of sample to be tested is negative control.Acquire the big Kidney bean leaf of insect density, carefully choose make health adult mite (30~
50) it stays on blade face, it is taken away after the Kidney bean leaf with worm is immersed solution 5s to be measured, the training that bottom is covered with filter paper is put into after draining
It supports in ware (6cm), being placed on temperature is 22~24 DEG C, relative humidity 60%, and the laboratory that light application time is 14:10h relays
Continuous raising records death condition afterwards for 24 hours, and each experiment in triplicate, and calculates corrected mortality with following equation:
4, the measuring method of Culex pipiens pallens
Using the method for world health organisation recommendations, sample to be tested is dissolved in dimethyl sulfoxide and with 0.1% Tween-80 water
Solution is diluted to certain concentration, the corresponding solution of sample to be tested is not added as negative control.Take every kind of solution 1mL, respectively plus
Enter into the 118mL wax dixie cup equipped with 99mL distilled water and 20 3 instar larvaes of Culex pipiens pallens, these dixie cups are placed on temperature
It is 22~24 DEG C, relative humidity 60%, light application time records dead feelings to continue to raise in the laboratory of 14:10h afterwards for 24 hours
Condition, each experiment in triplicate, and calculate corrected mortality with following equation:
5, test result
The desinsection of the compounds of this invention the results are shown in Table 1.
Table 1
a: duplicate average value three times.
There is preferable cytotoxicity to mythimna separata, Tetranychus cinnabarinus and Culex pipiens pallens from these compounds known to upper table 1.
The measurement of the antioxygenic property of 2 the compounds of this invention of test example
1, instrument and reagent
721B type spectrophotometer, 1,1- diphenyl -2- picryl hydrazine (DPPH), 95% ethyl alcohol.
2, determination step
(1) preparation of DPPH and sample solution
0.0130 gram of DPPH is accurately weighed with assay balance, is settled in 500mL volumetric flask with 95% ethyl alcohol, obtains concentration
For the solution of 26mg/L；0.0100g sample to be tested is accurately weighed, is settled in 100mL volumetric flask with 95% ethyl alcohol, obtains concentration
For the sample solution of 100mg/L.
(2) the DPPH solution and 1mL95% ethanol solution of 4mL are sequentially added in 10mL conical flask, mix stable reaction
Afterwards, using 95% ethyl alcohol as reference solution, its absorbance value is measured at λ max=518nm, is denoted as A0。
(3) the DPPH solution and 1mL solution to be measured that 4mL is sequentially added in 10mL conical flask, shake up, react at room temperature
After 40min stablizes, using 95% ethyl alcohol as reference solution, its absorbance value is measured at wavelength X max=518nm, is denoted as AS.Often
One tests in triplicate, and the free radical scavenging activity Y (%) of antioxidant is calculated with following equation:
3, the measurement result of antioxygenic property
Measurement result is shown in Table 2.
Table 2 is when concentration is 100mg/L, clearance rate of the compound to DPPH free radical
| Compound | Clearance ratea(%) |
| Compound 1 | 88.9 |
| Compound 2 | 96.1 |
| Compound 3 | 93.5 |
| Compound 4 | 81.3 |
| Compound 5 | 82.5 |
| Compound 6 | 87.7 |
| Compound 7 | 96.9 |
a: duplicate average value three times.
From upper table 2 it is found that the compounds of this invention to the clearance rate of DPPH free radical all 81% or more, i.e., they have compared with
Good antioxygenic property.
Claims (11)
1. structural formula such as I compound represented of formula:
Wherein, R1ForR2For C1-C4 alkyl；
R3For hydrogen or halogen；R4For hydrogen or halogen；X is O or S.
2. compound according to claim 1, it is characterised in that: R1For
3. compound according to claim 1 or 2, it is characterised in that: R2For ethyl.
4. compound according to claim 1 or 2, which is characterized in that structural formula is as shown in formula I -1 or formula I -2:
5. compound according to claim 3, which is characterized in that structural formula is as shown in formula I -1 or formula I -2:
6. compound according to claim 1, which is characterized in that its structural formula is as follows:
7. the preparation method of compound described in claim 3, which comprises the steps of:
A, in the mixture of aminoacetophenone and methylene chloride, triethylamine is added, forms solution A；
B, under conditions of stirring and ice-water bath, the mixed liquor of acryloyl chloride and methylene chloride is added drop-wise in solution A, control is anti-
Temperature is answered to be maintained at 0~5 DEG C；
C, it after the reaction was completed, washs, vacuum distillation obtains crude product, then recrystallize to get intermediate；
D, intermediate is dissolved in dehydrated alcohol, adds the ethanol solution of NaOH, obtains solution B；
It e, is under stiring, R by structural formula1The aldehyde of-CHO and the mixed liquor of dehydrated alcohol are added drop-wise in solution B, control reaction temperature
Degree is warming up to 50 DEG C of reflux；
F, distilled water after completion of the reaction, is added, and adjusts pH value to 7, has solid Precipitation, filters, wash, recrystallize, i.e.,
Obtain product.
8. preparation method according to claim 7, it is characterised in that: the aminoacetophenone be 4- aminoacetophenone or
3- aminoacetophenone.
9. the described in any item compounds of claim 1~6 are preparing the application in antioxidant.
10. application of the described in any item compounds of claim 1~6 in prevention and treatment agricultural pests.
11. application of the compound according to claim 10 in prevention and treatment agricultural pests, it is characterised in that: the agricultural evil
Worm is mythimna separata, Tetranychus cinnabarinus or Culex pipiens pallens.
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| CN101792413A (en) * | 2010-01-25 | 2010-08-04 | 中国农业大学 | (E)-1-aryl-5-phenyl-2-alkene-1-pentanone compounds and synthesis and application thereof |
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