CN102093306B - 2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 - Google Patents
2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 Download PDFInfo
- Publication number
- CN102093306B CN102093306B CN 201110003704 CN201110003704A CN102093306B CN 102093306 B CN102093306 B CN 102093306B CN 201110003704 CN201110003704 CN 201110003704 CN 201110003704 A CN201110003704 A CN 201110003704A CN 102093306 B CN102093306 B CN 102093306B
- Authority
- CN
- China
- Prior art keywords
- ketone
- benzoxazine
- chloro
- benzoxazin
- herbicidal activity
- 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.)
- Expired - Fee Related
Links
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000004009 herbicide Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 239000002917 insecticide Substances 0.000 claims description 4
- 239000005648 plant growth regulator Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims 1
- 239000003899 bactericide agent Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 230000002363 herbicidal effect Effects 0.000 abstract description 32
- PKUPAJQAJXVUEK-UHFFFAOYSA-N 2-phenoxyacetyl chloride Chemical compound ClC(=O)COC1=CC=CC=C1 PKUPAJQAJXVUEK-UHFFFAOYSA-N 0.000 abstract description 10
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 abstract description 10
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 abstract description 10
- RNHSRYWWLMTXNT-UHFFFAOYSA-N 2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical class N=1C2=CC=CC=C2C(=O)OC=1COC1=CC=CC=C1 RNHSRYWWLMTXNT-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000575 pesticide Substances 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000009036 growth inhibition Effects 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000002552 dosage form Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 23
- 241000196324 Embryophyta Species 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000010189 synthetic method Methods 0.000 description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 0 *c(cc1)cc(*)c1OCC(O)=O Chemical compound *c(cc1)cc(*)c1OCC(O)=O 0.000 description 4
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- NTRXZJHSUNJASA-UHFFFAOYSA-N 2-[(4-fluorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(F)=CC=C1OCC1=NC2=CC=CC=C2C(=O)O1 NTRXZJHSUNJASA-UHFFFAOYSA-N 0.000 description 3
- QRCGFTXRXYMJOS-UHFFFAOYSA-N 4h-1,4-benzoxazin-3-one Chemical class C1=CC=C2NC(=O)COC2=C1 QRCGFTXRXYMJOS-UHFFFAOYSA-N 0.000 description 3
- GQTJNDVTMOSIJP-UHFFFAOYSA-N 5-chloro-2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical compound O1C(=O)C=2C(Cl)=CC=CC=2N=C1COC1=CC=CC=C1 GQTJNDVTMOSIJP-UHFFFAOYSA-N 0.000 description 3
- NJJJARBEYMLZLA-UHFFFAOYSA-N 6,7-dimethoxy-2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical compound O1C(=O)C=2C=C(OC)C(OC)=CC=2N=C1COC1=CC=CC=C1 NJJJARBEYMLZLA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ROBSGBGTWRRYSK-SNVBAGLBSA-N (2r)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CC=C(C#N)C=C1F ROBSGBGTWRRYSK-SNVBAGLBSA-N 0.000 description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 2
- LWYRDBJQPNIMAF-UHFFFAOYSA-N 2-[(4-chlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(Cl)=CC=C1OCC1=NC2=CC=CC=C2C(=O)O1 LWYRDBJQPNIMAF-UHFFFAOYSA-N 0.000 description 2
- ZIXNXLRWPYURQS-UHFFFAOYSA-N 2-[(4-fluorophenoxy)methyl]-6-methyl-3,1-benzoxazin-4-one Chemical compound O1C(=O)C2=CC(C)=CC=C2N=C1COC1=CC=C(F)C=C1 ZIXNXLRWPYURQS-UHFFFAOYSA-N 0.000 description 2
- ADLAZIUDCGTTHI-UHFFFAOYSA-N 6-chloro-2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical compound O1C(=O)C2=CC(Cl)=CC=C2N=C1COC1=CC=CC=C1 ADLAZIUDCGTTHI-UHFFFAOYSA-N 0.000 description 2
- ARVAVIYDCJIPPM-UHFFFAOYSA-N 6-methyl-2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical compound O1C(=O)C2=CC(C)=CC=C2N=C1COC1=CC=CC=C1 ARVAVIYDCJIPPM-UHFFFAOYSA-N 0.000 description 2
- UMBWYKQBLMLMGR-UHFFFAOYSA-N 7-chloro-2-(phenoxymethyl)-3,1-benzoxazin-4-one Chemical compound C=1C(Cl)=CC=C(C(O2)=O)C=1N=C2COC1=CC=CC=C1 UMBWYKQBLMLMGR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- 244000058871 Echinochloa crus-galli Species 0.000 description 2
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SODPIMGUZLOIPE-UHFFFAOYSA-N (4-chlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1 SODPIMGUZLOIPE-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-DOMIDYPGSA-N 2-(2,4-dichlorophenoxy)acetic acid Chemical compound OC(=O)[14CH2]OC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-DOMIDYPGSA-N 0.000 description 1
- COFPOOKHLZWCDH-UHFFFAOYSA-N 2-[(2,4-dichlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound ClC1=CC(Cl)=CC=C1OCC1=NC2=CC=CC=C2C(=O)O1 COFPOOKHLZWCDH-UHFFFAOYSA-N 0.000 description 1
- CNFIUPRZNRCPLB-UHFFFAOYSA-N 2-[(4-chlorophenoxy)methyl]-6,7-dimethoxy-3,1-benzoxazin-4-one Chemical compound O1C(=O)C=2C=C(OC)C(OC)=CC=2N=C1COC1=CC=C(Cl)C=C1 CNFIUPRZNRCPLB-UHFFFAOYSA-N 0.000 description 1
- YKYKUXJXKNYWTN-UHFFFAOYSA-N 2-[(4-chlorophenoxy)methyl]-6-methyl-3,1-benzoxazin-4-one Chemical compound O1C(=O)C2=CC(C)=CC=C2N=C1COC1=CC=C(Cl)C=C1 YKYKUXJXKNYWTN-UHFFFAOYSA-N 0.000 description 1
- SFDGJDBLYNJMFI-UHFFFAOYSA-N 3,1-benzoxazin-4-one Chemical class C1=CC=C2C(=O)OC=NC2=C1 SFDGJDBLYNJMFI-UHFFFAOYSA-N 0.000 description 1
- WSPPNDPYJPDSFM-UHFFFAOYSA-N 5-chloro-2-[(2,4-dichlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound ClC1=CC(Cl)=CC=C1OCC1=NC2=CC=CC(Cl)=C2C(=O)O1 WSPPNDPYJPDSFM-UHFFFAOYSA-N 0.000 description 1
- VMHZZHQOEFROEW-UHFFFAOYSA-N 5-chloro-2-[(4-chlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(Cl)=CC=C1OCC1=NC2=CC=CC(Cl)=C2C(=O)O1 VMHZZHQOEFROEW-UHFFFAOYSA-N 0.000 description 1
- BMBFJPQKCVHKFV-UHFFFAOYSA-N 5-chloro-2-[(4-fluorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(F)=CC=C1OCC1=NC2=CC=CC(Cl)=C2C(=O)O1 BMBFJPQKCVHKFV-UHFFFAOYSA-N 0.000 description 1
- HZKBYBNLTLVSPX-UHFFFAOYSA-N 6-[(6,6-dimethyl-5,7-dihydropyrrolo[2,1-c][1,2,4]thiadiazol-3-ylidene)amino]-7-fluoro-4-prop-2-ynyl-1,4-benzoxazin-3-one Chemical compound C#CCN1C(=O)COC(C=C2F)=C1C=C2N=C1SN=C2CC(C)(C)CN21 HZKBYBNLTLVSPX-UHFFFAOYSA-N 0.000 description 1
- GOQXDMRMTBMHLG-UHFFFAOYSA-N 6-chloro-2-[(2,4-dichlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound ClC1=CC(Cl)=CC=C1OCC1=NC2=CC=C(Cl)C=C2C(=O)O1 GOQXDMRMTBMHLG-UHFFFAOYSA-N 0.000 description 1
- WTOALWZWLPQQLF-UHFFFAOYSA-N 6-chloro-2-[(4-chlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(Cl)=CC=C1OCC1=NC2=CC=C(Cl)C=C2C(=O)O1 WTOALWZWLPQQLF-UHFFFAOYSA-N 0.000 description 1
- PIBAOHBATYFLGK-UHFFFAOYSA-N 6-chloro-2-[(4-fluorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(F)=CC=C1OCC1=NC2=CC=C(Cl)C=C2C(=O)O1 PIBAOHBATYFLGK-UHFFFAOYSA-N 0.000 description 1
- SXSRWSGICKZYNW-UHFFFAOYSA-N 7-chloro-2-[(2,4-dichlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound ClC1=CC(Cl)=CC=C1OCC1=NC2=CC(Cl)=CC=C2C(=O)O1 SXSRWSGICKZYNW-UHFFFAOYSA-N 0.000 description 1
- AOCFBFDBIZYXKY-UHFFFAOYSA-N 7-chloro-2-[(4-chlorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(Cl)=CC=C1OCC1=NC2=CC(Cl)=CC=C2C(=O)O1 AOCFBFDBIZYXKY-UHFFFAOYSA-N 0.000 description 1
- NFRGGEDGLPBUJF-UHFFFAOYSA-N 7-chloro-2-[(4-fluorophenoxy)methyl]-3,1-benzoxazin-4-one Chemical compound C1=CC(F)=CC=C1OCC1=NC2=CC(Cl)=CC=C2C(=O)O1 NFRGGEDGLPBUJF-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- HXXZFWZYTBDNEU-UHFFFAOYSA-N COc(c(OC)c1)cc2c1N=C(COc(cc1)ccc1Cl)OC1OC21 Chemical compound COc(c(OC)c1)cc2c1N=C(COc(cc1)ccc1Cl)OC1OC21 HXXZFWZYTBDNEU-UHFFFAOYSA-N 0.000 description 1
- PEZPPIRMDMXAPE-UHFFFAOYSA-N Clc(cc1)ccc1OCC(O1)=Nc(cccc2)c2C1=[U] Chemical compound Clc(cc1)ccc1OCC(O1)=Nc(cccc2)c2C1=[U] PEZPPIRMDMXAPE-UHFFFAOYSA-N 0.000 description 1
- MVNLBBDPSQTXHF-UHFFFAOYSA-N Clc(cc12)ccc1N=C(COc(cc1)ccc1[Ar])OC2=[U] Chemical compound Clc(cc12)ccc1N=C(COc(cc1)ccc1[Ar])OC2=[U] MVNLBBDPSQTXHF-UHFFFAOYSA-N 0.000 description 1
- 239000005502 Cyhalofop-butyl Substances 0.000 description 1
- TYIYMOAHACZAMQ-CQSZACIVSA-N Cyhalofop-butyl Chemical group C1=CC(O[C@H](C)C(=O)OCCCC)=CC=C1OC1=CC=C(C#N)C=C1F TYIYMOAHACZAMQ-CQSZACIVSA-N 0.000 description 1
- 241000209510 Liliopsida Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 201000004681 Psoriasis Diseases 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 229940121373 acetyl-coa carboxylase inhibitor Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002269 analeptic agent Substances 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000021921 corneal disease Diseases 0.000 description 1
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical compound FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 241001233957 eudicotyledons Species 0.000 description 1
- FOUWCSDKDDHKQP-UHFFFAOYSA-N flumioxazin Chemical compound FC1=CC=2OCC(=O)N(CC#C)C=2C=C1N(C1=O)C(=O)C2=C1CCCC2 FOUWCSDKDDHKQP-UHFFFAOYSA-N 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 201000011066 hemangioma Diseases 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- -1 inorganic base sodium carbonate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- IVKNUIVDQMARCO-UHFFFAOYSA-N oxazin-4-one Chemical compound O=C1C=CON=C1 IVKNUIVDQMARCO-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229940076279 serotonin Drugs 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
通式为1的2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物,其中,R1、R2为氢、卤素;R3为氢、卤素;R4、R5为氢、卤素、烷基、烷氧基。其合成是先将苯氧乙酸转变为苯氧乙酰氯,再与邻氨基苯甲酸在溶剂和碱存在下进行关环反应得到。用NY/T 1155.1-2006标准进行室内除草活性测试表明,这些化合物有很好的除草活性,大部分在浓度100ppm和10ppm时,表现出非选择性除草活性,除草活性高于商品氰氟草酯;在浓度1ppm时,大部分表现出选择性除草活性,与商品氰氟草酯作用相反,对单子叶植物生长抑制降低,对双子叶植物保持良好的除草活性。该类化合物作为除草剂单独使用;或者与其它植保上允许的载体或稀释剂混合配制成各种剂型使用;或与其它农药复配使用或同时并用。
Description
技术领域
本发明涉及2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物的合成,以及作为除草剂的有效成份的应用。
背景技术
苯并噁嗪酮类化合物是一类具有多样性生物活性的杂环化合物,受到医药及农药研究者的关注。近年来不断有该类衍生物的合成和作为药物及农药的专利和期刊文献报道。例如,专利(US.Pat.No.5225409)报道了一类1,4-苯并噁嗪-3-酮化合物有治疗血清素紊乱的效果;专利(US.Pat.No.5281571)报道了一类苯并噁嗪酮取代的吡唑用作除草剂;专利(US.Pat.Nos.3970652;4315766)报道了2-位芳基取代的4H-3,1-苯并噁嗪-4-酮衍生物,作为除草剂应用于多种作物田地除草;专利(US.Pat.No.7049312)报道了一类1,4-苯并噁嗪-3-酮化合物有治疗癌症、关节炎、动脉粥样硬化、牛皮癣、血管瘤、角膜疾病等一系列疾病的效果;最近,专利(US 2010/0009982A1)公开了一类2-哌啶螺4H-3,1-苯并噁嗪-4-酮化合物,可作为乙酰辅酶A羧化酶抑制剂,用于人肥胖、心血管等多种疾病的治疗以及作为农药控制有害生物如杀菌、除草、杀虫等。目前,已经商品化的苯并噁嗪酮类除草剂是如下所示的丙炔氟草胺(flumioxazin)和噻二唑草胺(thidiazimin),其作用靶标为原卟啉氧化酶,在分子结构上它们属于1,4-苯并噁嗪-3-酮类化合物。
丙炔氟草胺 噻二唑草胺
苯氧乙酸类化合物同样具有多样性的生物活性,用途广泛。其本身是一种除草剂得到广泛应用,另外也可以作为植物激素、中枢兴奋药、染料、杀虫剂等的中间体。例如,4-氯苯氧乙酸可用作植物生长调节剂、落果防止剂、除草剂,可用于蕃茄、蔬菜、桃树等(Environ.Sci.Thechnol.2002,36,3030-3035)。2,4-二氯苯氧乙酸,也称2,4-滴或2,4-D,是植物生长调节剂和除草剂,对双子叶植物有选择性杀灭作用(J.H.QUASTEL.1950、244-249)。
发明内容
本发明采用活性亚结构拼接法,将苯并噁嗪酮与苯氧乙酸结构进行拼接,设计及合成了一系列新型取代的2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮类衍生物(BOZ),这类衍生物具有以下通式1结构特征:
上式中R1、R2为氢、卤素;R3为氢、卤素;R4、R5为氢、卤素、烷基、烷氧基。
本发明的通式1所表示的2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物的合成是首先将通式为2的苯氧乙酸通过酰化试剂转化为通式为3的苯氧乙酰氯,再将苯氧乙酰氯与通式为4(o-ABA)的邻氨基苯甲酸在适当的碱存在下进行关环反应,得到通式为1所表示的化合物,其合成路线如下:
上述通式2、3和4中取代基R1、R2、R3、R4、R5定义与通式1中的定义相同。
所述的通式为3的苯氧乙酰氯的制备,采用通式为2的苯氧乙酸与酰化试剂五氯化磷或氯化亚砜反应制备。
所述的苯氧乙酰氯与邻氨基苯甲酸的环化反应在碱和有机溶剂中反应,高收率得到权利要求1所述的2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物;其中,所述的碱选用有机碱三甲胺、三乙胺或N,N-二甲基哌啶,或无机碱碳酸钠、碳酸氢钠、碳酸铯或碳酸钾;所述的有机溶剂选用乙腈、丙酮,二氯甲烷,或四氢呋喃;反应温度在-20~80℃之间。
所合成化合物的结构经1H NMR及MS确证,并采用国家农业部颁布的行业标准农药室内除草剂活性测试平皿法(NY/T 1155.1-2006)进行了室内除草活性初筛。室内除草活性测试表明,这些化合物都有很好的除草活性,大部分化合物在较高浓度(100ppm和10ppm)时,表现出非选择性除草活性,并且除草活性高于对照商品化除草剂氰氟草酯;在低浓度 (1ppm)时,大部分化合物表现出选择性除草活性,与商品化除草剂氰氟草酯作用相反,对单子叶植物生长抑制降低,而对双子叶植物保持良好的除草活性。
具体实施方式
实施例1
苯氧乙酰氯合成通法
将取代苯氧乙酸在氮气保护下溶在二氯亚砜中,用油浴加热并在65~75℃下反应1~6h,直至无气体放出。减压蒸出过量的二氯亚砜得到棕黄色液体,即为取代苯氧乙酰氯。粗苯氧乙酰氯产物不需经过提纯,即可进行下一步反应。
实施例2
2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物(BOZ-1~23)合成通法
将苯氧乙酰氯溶于适量无水四氢呋喃(THF)中,在室温或冰浴、氮气保护和电磁搅拌条件下,滴加等摩尔的取代邻氨基苯甲酸(o-ABA(4))及适量三乙胺或4-二甲氨基吡啶(DMAP)溶于THF的溶液,继续在冰盐浴条件搅拌1~6小时后,自然升温至室温使反应完全。过滤,母液通过硅胶柱层析提纯,得通式为1的目标化合物2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-1~23)。
实施例3
2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-1)
将1.37g(0.01mol)的邻氨基苯甲酸和适量的4-二甲氨基吡啶(DMAP)加入250ml圆底烧瓶内,加入四氢呋喃(100mL),搅拌使其溶解,置于冰盐浴中,滴加苯氧乙酰氯2.55g(0.015mol)溶于10mL四氢呋喃的溶液,在冰盐浴条件搅拌4小时后继续室温搅拌至反应完全。过滤,母液用硅胶柱层析提纯,得2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-1),黄色固体2.16克,收率85.6%,m.p.87.9~92.1℃。
1HNMR(400MHz,CDCl3):δ5.018(s,2H,-CH2O-),7.028(d,J=17.2Hz,3H,Ar-H),7.303~7.341(m,2H,Ar-H),7.550~7.587(m,1H,Ar-H),7.668(d,J=8.4Hz,1H,Ar-H),7.819~7.857(m,1H,Ar-H),8.227(d,J=8Hz,1H,Ar-H).
EI-MS m/z,(%):145.97(100),253(M+,44).
实施例4
5-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-2)
通过与实施例3相类同的合成方法合成实施例4的化合物5-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-2),白色固体,收率87.1%,m.p.131.2-132.1℃。
1HNMR(400MHz,CDCl3):δ4.992(s,2H,-CH2O-),7.22(d,J=6.8Hz,3H,Ar-H),7.303~7.321(m,2H,Ar-H),7.571(d,J=4Hz,2H,Ar-H),7.696(d,J=4Hz,1H,Ar-H).
EI MS:m/z(%):179(100),287[M+](24).
实施例5
6-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-3)
通过与实施例3相类同的合成方法合成实施例5的化合物6-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-3),淡黄色固体,收率79.8%,m.p.113.1-115.2℃。
1HNMR(400MHz,CDCl3):δ5.011(s,2H,-CH2O-),7.027(d,J=8Hz,3H,Ar-H),7.306~7.344(m,2H,Ar-H),7.411(d,J=4.1Hz,1H,Ar-H),7.632(d,J=4Hz,1H,Ar-H),8.188(d,J=3.6Hz,1H,Ar-H).EI MS m/z(%):166(100),287[M+](39).
实施例6
7-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-4)
通过与实施例3相类同的合成方法合成实施例6的化合物7-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-4),淡黄色固体,收率85.7%,m.p.118.3-120.9℃。
1HNMR(400MHz,CDCl3):δ5.010(s,2H,-CH2O-),7.021(d,J=6.4Hz,3H,Ar-H),7.303~7.342(m,2H,Ar-H),7.516(d,J=8.8Hz,1H,Ar-H),7.660(s,1H,Ar-H),8.146(d,J=8.4Hz,1H,Ar-H).
EI MS m/z(%):179(100),287M+](33).
实施例7
6-甲基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-5)
通过与实施例3相类同的合成方法合成实施例7的化合物6-甲基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-5),粉红色固体,收率85.2%,m.p.133.3~135.1℃。
1HNMR(400MHz,CDCl3):δ2.391(s,3H,-CH3),5.000(s,2H,-CH2O-),7.035(d,J=8.4Hz,3H,Ar-H),7.296~7.335(m,2H,Ar-H),7.560(d,J=8Hz,1H,Ar-H),7.629(s,1H,Ar-H),8.016(s,1H,Ar-H).
EI MS m/z(%):146(100),267[M+](35).
实施例8
6,7-二甲氧基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-6)
通过与实施例3相类同的合成方法合成实施例8的化合物6,7-二甲氧基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮(BOZ-6),淡黄色固体,收率95.5%,m.p.156.1-157.8℃。
1HNMR(400MHz,CDCl3):δ3.995(d,J=3.2Hz,6H,-OCH3),5.000(s,2H,-CH2O-),7.036(d,J=8Hz,3H,Ar-H),7.089(s,1H,Ar-H),7.342~7.271(m,2H,Ar-H),7.531(s,1H,Ar-H).
EI MS m/z(%):192.12(100),313[M+](26).
实施例9
2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-7)
通过与实施例3相类同的合成方法合成实施例9的化合物2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-7),白色固体,收率89.1,m.p.147.5~149.2℃。
1HNMR(400MHz,CDCl3):δ4.986(s,2H,-OCH2-),6.973(d,J=9.6Hz,2H,Ar-H),7.264(d,J=16Hz,2H,Ar-H),7.577(d,J=16.8Hz,1H,Ar-H),7.645~7.664(m,1H,Ar-H),7.823~8.65(m,1H,Ar-H),8.228(d,J=9.2Hz,1H,Ar-H).
EI MS m/z(%):146(100),287[M+](33).
实施例10
5-氯-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-8)
通过与实施例3相类同的合成方法合成实施例10的化合物5-氯-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-8),白色固体,收率80.1%,m.p.144.3-145.7℃。
1HNMR(400MHz,CDCl3):δ4.591(s,2H,-CH2O-),6.953(d,J=8.8Hz,2H,Ar-H),7.216(d,J=8.4Hz,2H,Ar-H),7.296~7.389(m,2H,Ar-H),8.330(s,1H,Ar-H).
EI MS m/z(%):180(100),321[M+](5).
实施例11
6-氯-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-9)
通过与实施例3相类同的合成方法合成实施例11的化合物6-氯-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-9),浅黄色固体,收率79.5%,m.p.153.2~154.6℃。
1HNMR(400MHz,CDCl3):δ4.976(s,2H,-OCH2-),6.96(d,J=8.8Hz,2H,Ar-H),7.273(d,J=8.4Hz,2H,Ar-H),7.603(d,J=8.4Hz,1H,Ar-H),7.777(d,J=10.8Hz,1H,Ar-H),8.180(s,1H,Ar-H).
EI MS m/z(%):165(100),321[M+](25).
实施例12
7-氯-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-10)
通过与实施例3相类同的合成方法合成实施例12的化合物7-氯-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-10),淡黄色固体,收率83.3%,m.p.189.9~191.8℃。
1HNMR(400MHz,CDCl3):δ4.980(s,2H,-CH2O-),6.953(d,J=8.8Hz,2H,Ar-H),6.957(d,J=8.8Hz,2H,Ar-H),7.261(d,J=17.2Hz,2H,Ar-H),7.651(s,1H,Ar-H),8.112(d,J=4.4Hz,1H,Ar-H).
EI MS m/z(%):180(100),321[M+](32).
实施例13
6-甲基-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-11)
通过与实施例3相类同的合成方法合成实施例13的化合物6-甲基-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-11),淡黄色固体,收率92.3%,m.p.143.7~145.6℃。
1H NMR(400MHz,CDCl3):δ2.380(s,3H,-CH3),4.966(s,2H,-OCH2-),6.966(d,J=8.4Hz,2H,Ar-H),7.262(d,J=8.8Hz,2H,Ar-H),7.543(d,J=6.8Hz,1H,Ar-H),7.633(d,J=2.4Hz,1H,Ar-H),8.017(s,1H,Ar-H).
EI MS m/z(%):146(100),301[M+](28).
实施例14
6,7-二甲氧基-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-12)
通过与实施例3相类同的合成方法合成实施例14的化合物6,7-二甲氧基-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-12),白色固体,收率率90.8%,m.p.118.5~119.3℃。
1H NMR(400MHz,CDCl3):δ3.994(d,J=4Hz,6H,-OCH3),4.967(s,2H,-OCH2-),6.967(d,J=9.2Hz,2H,Ar-H),7.072(s,1H,Ar-H),7.279(d,J=4Hz,2H,Ar-H),7.528(s,1H,Ar-H).
EI MS m/z(%):192(100),347[M+](10).
实施例15
2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-13)
通过与实施例3相类同的合成方法合成实施例15的化合物2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-13),白色固体,收率93.5%,m.p.119.7~122.3℃。
1H NMR(400MHz,CDCl3):δ5.055(s,2H,-OCH2-),7.012(d,J=8.8Hz,1H,Ar-H),7.187(dJ=10Hz1H,Ar-H),7.419(s,1H,Ar-H)7.590(d,J=7.2Hz,1H,Ar-H),7.639~7.657(m,1H,Ar-H),7.825~7.846(m,1H,Ar-H),8.231~8.240(s,J=7.2Hz,1H,Ar-H).
EI MS m/z(%)::321[M+](100),323(70).
实施例16
5-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-14)
通过与实施例3相类同的合成方法合成实施例16的化合物5-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-14),白色固体,收率81.1%,m.p.161.9~163.2℃。
1HNMR(400MHz,CDCl3):δ4.6(s,2H,-OCH2-),6.859(d,J=8.4Hz,1H,Ar-H),7.154~7.245(m,1H,Ar -H),7.328(s,1H,Ar-H),7.423(d,J=8.4Hz,1H,Ar-H),7.451(d,J=1.6Hz,1H,Ar-H),8.197~8.218(m,1H,Ar-H).
EI MS m/z(%):355[M+](100).
实施例17
6-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-15)
通过与实施例3相类同的合成方法合成实施例17的化合物6-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-15),白色固体,收率87.8%,m.p.157.9-160.1℃。
1HNMR(400MHz,CDCl3):δ5.043(s,2H,-OCH2-),6.984(d,J=8.4Hz,1H,Ar-H),7.175(d,J=2.4Hz,1H,Ar-H),7.422(s,1H,Ar-H),7.597(d,J=8.4Hz,1H,Ar-H)7.764~7.791(m,1H,Ar-H),8.182~8.188(s,1H,Ar-H).
EI MS m/z(%):166(100);354[M+](9).
实施例18
7-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-16)
通过与实施例3相类同的合成方法合成实施例18的化合物7-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-16),白色固体,收率88.1%,m.p.139.6~142.5℃。
1HNMR(400MHz,CDCl3):δ5.047(s,2H,-OCH2-),6.982(d,J=6Hz,1H,Ar-H),7.175~7.258(m,2H,Ar-H),7.424(s,1H,Ar-H),7.539(d,J=8.4Hz,1H,Ar-H),7.645(s,1H,Ar-H),8.153(d,J=8.4Hz,1H,Ar-H).
EI MS m/z(%):166[M+](100),355(14).
实施例19
4,5-二甲氧基-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-17)
通过与实施例3相类同的合成方法合成实施例19的化合物4,5-二甲氧基-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-17),白色固体,收率90.2%,m.p.161.9~163.2℃。
1HNMR(400MHz,CDCl3):δ3.999(d,J=5.2Hz,6H,-OCH3),5.031(s,2H,-OCH2-),7.003(s,1H,Ar-H),7.055(s,1H,Ar-H),7.415(s,1H,Ar-H),7.421(s,1H,Ar-H),7.528(s,1H,Ar-H).
EI MS m/z(%):221[M+](100),382(89).
实施例20
2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-18)
通过与实施例3相类同的合成方法合成实施例20的化合物2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-18),白色固体,收率92.2%,m.p.112.5~114.6℃。
1H NMR(400MHz,CDCl3):δ4.9796(s,2H,-OCH2-),6.971(d,J=8.6Hz,2H,Ar-H),7.156(d,J=8Hz,2H,Ar-H),7.560~7.596(m,,1H,Ar-H),7.664(d,J=8.4Hz,1H,Ar-H),7.825~7.845(m,1H,Ar-H),8.229(d,J=8.8Hz,1H,Ar-H).
EI MS m/z(%):132(100),271[M+](53).
实施例21
5-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-19)
通过与实施例3相类同的合成方法合成实施例21的化合物5-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-19),白色固体,收率82.2%,m.p.155.9~156.7℃。
1HNMR(400MHz,CDCl3):δ4.945(s,2H,-CH2O-),6.983(d,J=2.4Hz,2H,Ar-H),6.995(d,J=8.4Hz,2H,Ar-H),7.548~7.577(m,2H,Ar-H),7.686(s,1H,Ar-H).
EI MS m/z(%):180(100),305[M+](26).
实施例22
6-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-20)
通过与实施例3相类同的合成方法合成实施例22的化合物6-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-20),白色固体,收率87.2%,m.p.159.8~161.7℃。
1HNMR(400MHz,CDCl3):δ4.963(s,2H,-OCH2-),6.5(d,J=4.2Hz,2H,Ar-H),7.010(d,J=9.6Hz,2H,Ar-H),7.609(d,J=9Hz,1H,Ar-H),7.872(d,J=9Hz,1H,Ar-H),8.183(s,1H,Ar-H).
EI MS m/z(%):166(100),305[M+](29).
实施例23
7-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-21)
通过与实施例3相类同的合成方法合成实施例23的化合物7-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-21),白色固体,收率89.8%,m.p.123.6~124.9℃。
1HNMR(400MHz,CDCl3):δ4.964(s,2H,-CH2O-),6.985(d,J=4.8Hz,2H,Ar-H),6.997(d,J=7.2Hz,2H,Ar-H),7.533(d,J=4.8Hz,1H,Ar-H),7.656(s,1H,Ar-H),8.147(d,J=8.4Hz,1H,Ar-H).
EI MS m/z(%):180(100),305[M+](38).
实施例24
6-甲基-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-22)
通过与实施例3相类同的合成方法合成实施例24的化合物6-甲基-2-(4-氟苯氧甲 基)-4H-3,1-苯并噁嗪-4-酮(BOZ-22),白色固体,收率91.4%,m.p.130.8~131.9℃。
1H NMR(400MHz,CDCl3):δ2.492(s,3H,-CH3),4.960(s,2H,-OCH2-),6.986(d,J=1.2Hz,2H,Ar-H),7.001(d,J=1.2Hz,2H,Ar-H),7.556(d,J=7.6Hz,1H,Ar-H),7.647(d,J=8.4Hz,1H,Ar-H),8.017(s,1H,Ar-H).
EI MS m/z(%):146(100),285[M+](26)。
实施例25
4,5-二甲氧基-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-23)
通过与实施例3相类同的合成方法合成实施例25的化合物4,5-二甲氧基-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮(BOZ-23),白色固体,收率96.1%,m.p.144.7~146℃。
1H NMR(400MHz,CDCl3):δ3.991(d,J=12Hz,6H,-OCH3),4.963(s,2H,-OCH2-),6.968(d,J=1.2Hz,2H,Ar-H),7.005(d,J=4Hz,2H,Ar-H),7.087(s,1H,Ar-H),7.532(s,1H,Ar-H).
EI MS m/z(%):192(100),331[M+](13).
本发明合成的通式1所表示的部分2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物列如表1。
表1 2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮1芳环上取代基
实施例26
室内除草活性
所合成化合物的除草活性采用行业标准农药室内除草剂活性测试平皿法(NY/T1155.1-2006)进行了室内除草活性初筛。以油菜为双子叶植物模式植物,以稗草为单子叶植物模式植物,对化合物BOZ-1~23进行除草活性的测试。将化合物用少许DMF溶解,吐温-80乳化,加入蒸馏水配成三个样品浓度:100ppm、10ppm和1.0ppm。培养皿直径9cm,内置两层滤纸,加入10mL配置的样品溶液,种植二十粒待测种子。在培养箱中于25℃恒温培养8天。随机选择五株油菜、五株稗草测定茎叶及根的长度。对照药选用氰氟草酯(Cyhalofop-butyl,Cyhalofop)。根据空白对照(CK)生长长度,计算抑制百分率:抑制率%=[(CK-处理)/CK]×100%。所合成化合物及对照药的除草活性数据为表2所示。
表2 2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物的除草活性
本发明的化合物在较高浓度(100ppm和10ppm)时,大部分化合物均能表现出非选择性除草活性,并且除草活性高于对照商品化除草剂氰氟草酯;在低浓度(1ppm)时,大部分化合物表现出选择性除草活性,与商品化除草剂氰氟草酯作用相反,对单子叶植物生长抑制降低,而对双子叶植物保持良好的除草活性。
本发明的化合物作为除草剂使用时,可单独或者与其它植保上允许的载体或稀释剂混合,配制成通常使用的各种剂型,如混剂、颗粒剂、水乳剂等来使用,也可以与其它农药如杀菌剂、杀虫剂、除草剂、植物生长调节剂等复配使用或同时并用。
Claims (2)
1.一类2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物,其特征是如下化合物:5-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮
6-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮
7-氯-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮
6-甲基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮
6,7-二甲氧基-2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮
2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
5-氯-2-(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6-氯-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
7-氯-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6-甲基-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6,7-二甲氧基-2--(4-氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
5-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
7-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
4,5-二甲氧基-氯-2-(2,4-二氯苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
5-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
7-氯-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
6-甲基-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
4,5-二甲氧基-2-(4-氟苯氧甲基)-4H-3,1-苯并噁嗪-4-酮
2.权利要求1所述的2-苯氧甲基-4H-3,1-苯并噁嗪-4-酮衍生物的应用,其特征是:作为除草剂单独使用,或者与其它植保上允许的载体或稀释剂混合,配制成包括混剂、颗粒剂或水乳剂来使用,或者与其它农药杀菌剂、杀虫剂、除草剂或植物生长调节剂复配使用或同时并用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110003704 CN102093306B (zh) | 2011-01-10 | 2011-01-10 | 2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110003704 CN102093306B (zh) | 2011-01-10 | 2011-01-10 | 2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102093306A CN102093306A (zh) | 2011-06-15 |
CN102093306B true CN102093306B (zh) | 2013-10-02 |
Family
ID=44126593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201110003704 Expired - Fee Related CN102093306B (zh) | 2011-01-10 | 2011-01-10 | 2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102093306B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103694255A (zh) * | 2014-01-09 | 2014-04-02 | 华中师范大学 | 吡啶并噁嗪酮和吡啶并嘧啶酮类化合物及其制备方法与应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4523942A (en) * | 1980-01-05 | 1985-06-18 | Basf Aktiengesellschaft | 4H-3,1-Benzoxazine derivatives, compositions and herbicidal use |
GB2262097A (en) * | 1991-12-06 | 1993-06-09 | Basf Ag | Manufacture of 4H-3,1-benzoxazin-4-ones |
US6337332B1 (en) * | 1998-09-17 | 2002-01-08 | Pfizer Inc. | Neuropeptide Y receptor antagonists |
-
2011
- 2011-01-10 CN CN 201110003704 patent/CN102093306B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4523942A (en) * | 1980-01-05 | 1985-06-18 | Basf Aktiengesellschaft | 4H-3,1-Benzoxazine derivatives, compositions and herbicidal use |
GB2262097A (en) * | 1991-12-06 | 1993-06-09 | Basf Ag | Manufacture of 4H-3,1-benzoxazin-4-ones |
US6337332B1 (en) * | 1998-09-17 | 2002-01-08 | Pfizer Inc. | Neuropeptide Y receptor antagonists |
Non-Patent Citations (3)
Title |
---|
STN.AN 1980:568217.《STN CAPLUS》.1984, * |
STN.AN 1989:189240.《STN CAPLUS》.1989, * |
STN.AN 1989:57612.《STN CAPLUS》.1989, * |
Also Published As
Publication number | Publication date |
---|---|
CN102093306A (zh) | 2011-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
ES2417312T3 (es) | Benzoxazinonas herbicidas | |
JP5102253B2 (ja) | 新規なベンゾイルピラゾール化合物及び除草剤 | |
JPH0381266A (ja) | ピラゾールアミド類およびこれを有効成分とする殺虫、殺ダニ剤 | |
BRPI0914217B1 (pt) | 1-substituted pyridyl-pyrazolyl amid compounds and the uses thereof | |
JPS63122673A (ja) | ピラゾ−ル誘誉体および除草剤 | |
WO2011160568A1 (zh) | 3-甲氧基吡唑酰胺类化合物及其应用 | |
CN104072455B (zh) | 6-芳氧乙酰氧基橙酮类化合物及其在农药上的应用 | |
CN102093306B (zh) | 2-苯氧甲基-4h-3,1-苯并噁嗪-4-酮衍生物的合成及生物活性 | |
CN105801513A (zh) | 具有除草活性的n-取代烷基芳氧苯氧基丙酰胺类化合物及其制备与应用 | |
WO1996014285A1 (fr) | Derive substitue de bicycloheptanedione, et herbicide | |
JPH01221371A (ja) | 環状オキシアミン誘導体の製造方法 | |
CN106831683A (zh) | 一种香豆素‑芳氧羧酸酯类化合物及其在农药上的应用 | |
CN105541745A (zh) | 具有杀菌活性的1-(芳氨基乙基)-2-芳基-3,1-苯并恶嗪类化合物及其制备和用途 | |
CN101381342B (zh) | 哌嗪衍生物及其用途 | |
CN115124477A (zh) | 一类新型嘧啶水杨酸酚酯、其合成方法及作为除草剂的应用 | |
CN105859707B (zh) | (r)-n-(噻唑-2-基)-2-[4-(喹喔啉-2-氧基)苯氧基]酰胺衍生物及其制备方法和应用 | |
CN115557855B (zh) | 多取代2-羟基二苯甲酮类化合物及其制备方法与应用 | |
JP2000178268A (ja) | トリケトン誘導体および除草剤 | |
CN110066282A (zh) | 一种吡唑并嘧啶酮类化合物及其制备方法和应用 | |
JPH02229175A (ja) | 環状アシルヒドロキシルアミン誘導体およびその製法 | |
JPH01221372A (ja) | 環状アシルヒドロキシルアミン誘導体 | |
CN1962674A (zh) | 具有杀菌活性的取代苯氧乙酰氧基呋喃基甲基膦酸酯及制备 | |
CN101863874A (zh) | 一种吡唑亚胺类化合物及其应用 | |
JPH021484A (ja) | 5,6―ジヒドロ―1,4,2―ジオキサジン誘導体および農園芸用殺菌剤 | |
JP2943778B2 (ja) | 置換ベンゼン誘導体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131002 Termination date: 20160110 |