GB2234509A - Intermediates for the preparation of insecticidally active compounds - Google Patents
Intermediates for the preparation of insecticidally active compounds Download PDFInfo
- Publication number
- GB2234509A GB2234509A GB9018329A GB9018329A GB2234509A GB 2234509 A GB2234509 A GB 2234509A GB 9018329 A GB9018329 A GB 9018329A GB 9018329 A GB9018329 A GB 9018329A GB 2234509 A GB2234509 A GB 2234509A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- phenoxyphenyl
- fluoro
- prop
- nmr
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000543 intermediate Substances 0.000 title abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- -1 halide anion Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052736 halogen Chemical group 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract 2
- DTMXOLQBAQULLC-SNAWJCMRSA-N 4-[(e)-3-chloroprop-1-enyl]-1-fluoro-2-phenoxybenzene Chemical compound FC1=CC=C(\C=C\CCl)C=C1OC1=CC=CC=C1 DTMXOLQBAQULLC-SNAWJCMRSA-N 0.000 claims description 6
- UEEXSKUQFMMNML-IERUDJENSA-M [(e)-3-(4-fluoro-3-phenoxyphenyl)prop-2-enyl]-triphenylphosphanium;chloride Chemical compound [Cl-].C1=C(OC=2C=CC=CC=2)C(F)=CC=C1\C=C\C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UEEXSKUQFMMNML-IERUDJENSA-M 0.000 claims description 5
- BFXRXGRUCURCGC-FNORWQNLSA-N 1-[(e)-3-chloroprop-1-enyl]-3-phenoxybenzene Chemical compound ClC\C=C\C1=CC=CC(OC=2C=CC=CC=2)=C1 BFXRXGRUCURCGC-FNORWQNLSA-N 0.000 claims description 4
- FTLCSCOMAQFCHL-BACBYAOASA-M [(e)-3-(3-phenoxyphenyl)prop-2-enyl]-triphenylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C(C=1)=CC=CC=1OC1=CC=CC=C1 FTLCSCOMAQFCHL-BACBYAOASA-M 0.000 claims description 4
- GFIWENSXVCDTKC-BNSHTTSQSA-M [(e)-3-[3-(4-chlorophenoxy)phenyl]prop-2-enyl]-triphenylphosphanium;chloride Chemical compound [Cl-].C1=CC(Cl)=CC=C1OC1=CC=CC(\C=C\C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 GFIWENSXVCDTKC-BNSHTTSQSA-M 0.000 claims description 4
- UZRFBWDHVIEVAQ-FNORWQNLSA-N 1-[(e)-3-bromoprop-1-enyl]-3-phenoxybenzene Chemical compound BrC\C=C\C1=CC=CC(OC=2C=CC=CC=2)=C1 UZRFBWDHVIEVAQ-FNORWQNLSA-N 0.000 claims description 3
- CFEIUJYRYSRJJF-DUXPYHPUSA-N 1-chloro-4-[3-[(e)-3-chloroprop-1-enyl]phenoxy]benzene Chemical compound ClC\C=C\C1=CC=CC(OC=2C=CC(Cl)=CC=2)=C1 CFEIUJYRYSRJJF-DUXPYHPUSA-N 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 55
- 239000000203 mixture Substances 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 101150041968 CDC13 gene Proteins 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000004293 19F NMR spectroscopy Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001793 charged compounds Chemical class 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- CPHXLFKIUVVIOQ-UHFFFAOYSA-N 2-(trifluoromethoxy)benzaldehyde Chemical group FC(F)(F)OC1=CC=CC=C1C=O CPHXLFKIUVVIOQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 238000007239 Wittig reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001030 gas--liquid chromatography Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- NZTDDZUMHYFRGR-UHFFFAOYSA-N 1-fluoro-2-phenoxy-4-[5,5,5-trifluoro-4-[4-(trifluoromethoxy)phenyl]penta-1,3-dienyl]benzene Chemical compound C1=C(OC=2C=CC=CC=2)C(F)=CC=C1C=CC=C(C(F)(F)F)C1=CC=C(OC(F)(F)F)C=C1 NZTDDZUMHYFRGR-UHFFFAOYSA-N 0.000 description 2
- FTLCSCOMAQFCHL-UHFFFAOYSA-M 3-(3-phenoxyphenyl)prop-2-enyl-triphenylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC=CC(C=1)=CC=CC=1OC1=CC=CC=C1 FTLCSCOMAQFCHL-UHFFFAOYSA-M 0.000 description 2
- UEEXSKUQFMMNML-UHFFFAOYSA-M 3-(4-fluoro-3-phenoxyphenyl)prop-2-enyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=C(OC=2C=CC=CC=2)C(F)=CC=C1C=CC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UEEXSKUQFMMNML-UHFFFAOYSA-M 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004438 haloalkoxy group Chemical group 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- XMNCVUFULWGDHK-UHFFFAOYSA-N 1-(4-fluoro-3-phenoxyphenyl)prop-2-en-1-ol Chemical compound C=CC(O)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 XMNCVUFULWGDHK-UHFFFAOYSA-N 0.000 description 1
- NUBWJTCIWOUPAY-UHFFFAOYSA-N 1-[1,1-difluoro-5-(3-phenoxyphenyl)penta-2,4-dien-2-yl]-4-ethoxybenzene Chemical compound C1=CC(OCC)=CC=C1C(C(F)F)=CC=CC1=CC=CC(OC=2C=CC=CC=2)=C1 NUBWJTCIWOUPAY-UHFFFAOYSA-N 0.000 description 1
- BXFHQTIFPVRTQU-UHFFFAOYSA-N 1-[1,1-difluoro-5-(3-phenoxyphenyl)pentan-2-yl]-4-(trifluoromethoxy)benzene Chemical compound C=1C=C(OC(F)(F)F)C=CC=1C(C(F)F)CCCC(C=1)=CC=CC=1OC1=CC=CC=C1 BXFHQTIFPVRTQU-UHFFFAOYSA-N 0.000 description 1
- LGHAOPKAYGCSCS-UHFFFAOYSA-N 1-[1,1-difluoro-5-(3-phenoxyphenyl)pentan-2-yl]-4-ethoxybenzene Chemical compound C1=CC(OCC)=CC=C1C(C(F)F)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 LGHAOPKAYGCSCS-UHFFFAOYSA-N 0.000 description 1
- MIFKZMITESRWAB-UHFFFAOYSA-N 1-[1-chloro-1,1-difluoro-5-(3-phenoxyphenyl)penta-2,4-dien-2-yl]-4-ethoxybenzene Chemical compound C1=CC(OCC)=CC=C1C(C(F)(F)Cl)=CC=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MIFKZMITESRWAB-UHFFFAOYSA-N 0.000 description 1
- OZVMTGZZXACPAV-UHFFFAOYSA-N 1-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-ol Chemical compound C=CC(O)C1=CC=CC(OC=2C=CC(Cl)=CC=2)=C1 OZVMTGZZXACPAV-UHFFFAOYSA-N 0.000 description 1
- IEXQWUOBLHIYFV-UHFFFAOYSA-N 1-chloro-4-[3-[5,5,5-trifluoro-4-[4-(trifluoromethoxy)phenyl]pentyl]phenoxy]benzene Chemical compound C1=CC(OC(F)(F)F)=CC=C1C(C(F)(F)F)CCCC1=CC=CC(OC=2C=CC(Cl)=CC=2)=C1 IEXQWUOBLHIYFV-UHFFFAOYSA-N 0.000 description 1
- TYNZKFRDFCQCCH-UHFFFAOYSA-N 1-fluoro-2-phenoxy-4-[5,5,5-trifluoro-4-[4-(trifluoromethoxy)phenyl]pentyl]benzene Chemical compound C1=C(OC=2C=CC=CC=2)C(F)=CC=C1CCCC(C(F)(F)F)C1=CC=C(OC(F)(F)F)C=C1 TYNZKFRDFCQCCH-UHFFFAOYSA-N 0.000 description 1
- UTAMHACNJHAETP-UHFFFAOYSA-N 1-phenoxy-3-[4-[4-(trifluoromethoxy)phenyl]pentyl]benzene Chemical compound C=1C=C(OC(F)(F)F)C=CC=1C(C)CCCC(C=1)=CC=CC=1OC1=CC=CC=C1 UTAMHACNJHAETP-UHFFFAOYSA-N 0.000 description 1
- RTONLFPQGZSPLG-UHFFFAOYSA-N 1-phenoxy-3-[5,5,5-trifluoro-4-[4-(trifluoromethoxy)phenyl]pentyl]benzene Chemical compound C1=CC(OC(F)(F)F)=CC=C1C(C(F)(F)F)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 RTONLFPQGZSPLG-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- XSFFZLMYUGMVBS-UHFFFAOYSA-N 4-[5-chloro-5,5-difluoro-4-[4-(trifluoromethoxy)phenyl]penta-1,3-dienyl]-1-fluoro-2-phenoxybenzene Chemical compound C1=C(OC=2C=CC=CC=2)C(F)=CC=C1C=CC=C(C(F)(F)Cl)C1=CC=C(OC(F)(F)F)C=C1 XSFFZLMYUGMVBS-UHFFFAOYSA-N 0.000 description 1
- JDICMOLUAHZVDS-UHFFFAOYSA-N 4-fluoro-3-phenoxybenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1OC1=CC=CC=C1 JDICMOLUAHZVDS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UGVBQVMXIDTORY-JQIJEIRASA-N [(e)-3-(3-phenoxyphenyl)prop-2-enyl]-triphenylphosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C(C=1)=CC=CC=1OC1=CC=CC=C1 UGVBQVMXIDTORY-JQIJEIRASA-N 0.000 description 1
- GFIWENSXVCDTKC-UHFFFAOYSA-M [Cl-].C1=CC(Cl)=CC=C1OC1=CC=CC(C=CC[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 Chemical compound [Cl-].C1=CC(Cl)=CC=C1OC1=CC=CC(C=CC[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 GFIWENSXVCDTKC-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- 150000004794 vinyl magnesium halides Chemical class 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
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Abstract
Diphenyl ether compounds, useful as intermediates for the preparation of insecticidally active compounds, have the formula: <IMAGE> and geometric isomers thereof, wherein W is hydrogen or halogen, and X is hydrogen or fluoro, and either Y represents chlorine, bromine or iodine, or Y is selected from a group of formula: -P<+)<R<2>)3 Hal<-> and a group of formula: <IMAGE> wherein R<2> represents alkyl of up to six carbon atoms or aryl, and Hal<-> represents a halide anion selected from chloride, bromide and iodide.
Description
INTERMEDIATES FOR THE PREPARATION OF
INSECTICIDALLY ACTIVE COMPOUNDS
This invention relates to a process for the preparation of insecticidally active compounds and to novel styrene derivatives useful as intermediates therein.
The applicant's copending UK Patent Application No.
2,187,452 describes insecticidally active diphenyl ether derivatives of formula (I):
Wherein X is selected from hydrogen and fluoro, W is selected from hydrogen and halo, Z is selected from halo, alkyl of up to six carbon atoms, alkoxy of up to six carbon atoms, haloalkoxy of up to six carbon atoms and haloalkyl of up to six carbon atoms, and Q is a group of formula -(CF2)nRl where R1 represents hydrogen, chloro or fluoro and n has a value selected from one and two-. Preferred insecticidal compounds of formula (I) are those wherein Q represents the trifluoromethyl group.
The compounds of formula (I) may be prepared according to the process described in the UK Patent Application No.
2,187,452 by reduction of the corresponding compound of formula (II):
The applicants have now developed an improved process for the preparation of compounds of formula (I) and formula (II). In a first aspect, therefore, the invention provides a process for the preparation of a compound of formula (I)
wherein W is hydrogen or halogen, X is hydrogen or fluoro,
Q is a group of formula -(CF2)nRl where R1 is hydrogen, fluoro or chloro and n has a value selected from one and two, and Z is halo, alkyl of up to six carbon atoms, alkoxy of up to six carbon atoms, haloalkyl of up to six carbon atoms or haloalkoxy of up to six carbon atoms, which comprises the step of (i) Wittig reaction between either (a) a phosphonium
salt of formula (III)
or (b) a phosphonate of formula (IV)
wherein X and X have any of the meanings given hereinbefore, R2 represents alkyl of up to six carbon atoms or aryl, preferably methyl, ethyl or phenyl, and Hal represents a halide anion, and a ketone of formula (VII)
wherein 0 and Z have any of the meanings given hereinbefore, in the presence of a strong base, for example n-butyllithium, to produce a diene of formula (II) ::
followed by the step of (ii) reaction of the diene of formula (II) with a
reducing agent to produce the corresponding
compound of formula (I) The preparation of ketones of formula (VII) is fully described in UK Patent Application No. 2,187,452.
The phosphonium salts of formula (III) and the phosphonates of formula (IV) may be prepared from the corresponding compounds of formula (V)
wherein W and X have any of the meanings given hereinbefore and Hal represents chlorine, bromine or iodine. In a further aspect therefore, the invention provides a process as described hereinbefore for the preparation of a compound.
of formula (I) wherein the phosphonium salt of formula (III) is prepared by a process which comprises reaction of a compound of formula (V) with a trisubstituted phosphine of formula P(R)3, wherein R represents alkyl of up to six carbon atoms or aryl; in a preferred aspect, the trisubstituted phosphine is triphenylphosphine. In a further aspect the invention provides a process as described hereinbefore for the preparation of a compound of formula (I) wherein the phosphonate of formula (IV) is prepared by a process which comprises reaction of a compound of formula (V) with a trisubstituted phosphite of formula P(OR2)3, wherein R2 represents alkyl of up to six carbon atoms or aryl; in a preferred aspect, the trisubstituted phosphite is trimethyl phosphite or triethyl phosphite.
The invention also provides a process as described hereinbefore for the preparation of a phosphonium salt of fqrmula (III) or a phosphonate of formula (IV) wherein the compound of formula (V) is prepared by a process which comprises the step of (i): (i) Reaction between an aldehyde of formula:
wherein W and X have any of the meanings given hereinbefore, and an organometallic vinylating agent, for example vinyllithium or a vinylmagnesium halide of formula:
H2C=CH-Mg-Hal wherein Hal represents a halogen atom, preferably bromine, to produce a compound of formula (VI)
followed by the step of (ii) reaction of the compound of formula (VI) with a
hydrogen halide selected from hydrogen chloride,
hydrogen bromide and hydrogen iodide, to produce
the corresponding compound of formula (V).
The reaction of the compound of formula (VI) with a hydrogen halide may be conveniently performed using an inert solvent, for example diethyl ether, previously saturated with gaseous hydrogen chloride, or alternatively in a water miscible solvent, for example tetrahvdrorur r., in the presence of a concentrated aqueous solution of a hydrogen halide selected from hydrochloric acid, hydrobromic acid and hydroiodic acid.
The processes described herein are summarised, by way of example only, in Schemes A and B. Further details of the processes are given in the Examples.
Scheme A
(III, R=Ph, Hal-=Cl-)
Scheme B
Key: n-BuLi = n-butyllithium
H2/Pd/C = hydrogenation over a catalyst of Palladium
on charcoal.
The compounds of formula (V), (III) and (IV) may exhibit geometric isomerism, and when prepared by the processes of the invention are formed predominantly in the form of the E isomer. Subsequent Wittig reaction to form the compounds of formula (II) retains the initial configuration at the existing carbon-carbon double bond, but may result in a mixture of E and Z configurations at the double bond formed during the Wittig reaction step. In the Examples given hereinafter, the observed ratios of the (E,E) and (E,Z) iosmers of compounds of formula (II) are recorded where they have been determined.
The reduction of compounds of formula (II) to give the compounds of formula (I) may be conveniently carried out by passing hydrogen gas under a pressure of from 1.5 to 20 atmospheres, preferably from 2 to 5 atmospheres, into a solution of the compound of formula (II) in a suitable solvent such as a lower alkanol, for example methanol or ethanol. The presence of an asymmetric carbon atom in the compounds of formula (I) leads to the possibiiLt of stereoisomerism. Reduction of the compounds of formula (II) by hydrogenation as described herein usualy produces a racemic mixture of the R and S enantiomers of the corresponding compound of formula (I).
Enantiomeric excess of one enantiomer may result from the use of a chiral catalytic reducing agent. In those compounds of formula (I) where the group R1 represents hydrogen or chloro, hydrogenation may lead to the formation of side products resulting from competing reductive dehalogenation in the group Q.
Examples of the compounds of formula (I) which may be prepared by the processes of the Invention are Given in
Table I.
TABLE I
COMPOUND NO. W X Q Z 1 H H CF3 OC2H5 2 H F CF3 OC2H5 3 H H CF3 C(CH3)3 4 H H CF3 OCF3 5 H H C2F5 OC2H5 6 Cl H CF3 Cl 7 F H CF3 OC2H5 8 H H CF3 CF3 9 H F CF3 CF3 10 H F CF3 OCF3 11 Cl F CF3 CF3 12 0 Br F CF3 OC2H5 13 H H F CF2H OCF3 14 H H CF2Cl OCF3 15 H H CF2H OC2H5 16 H H CF2H OCF3
TABLE I (cont)
COMPOUND NO. W X Q Z 17 Cl H CF3 OC2H5 18 Cl H CF3 OCF3 19 Cl F CF3 OC2H5 20 Cl F CF3 OCF3 21 H H CF3 Cl 22 Cl F CF3 Cl 23 H F CF3 Cl The intermediates of formulae (III), (IV) and (V) are believed to be novel.In a further aspect, therefore, the invention provides compounds of formula:
and geometric isomers thereof, wherein W and X have any of the meanings given hereinabove, and Y represents chlorine, bromine or iodine, or Y is selected from a group of formula: -P+(R2)3 Hal and a group of formula
wherein R represents alkyl of up to six carbon atoms or aryl and Hal represents a halide anion.Specific examples of compounds of formulae (III), (IV) and (V) provided by the invention include
E-3-(3-phenoxyphenyl)-1-chloroprop-2-ene, E-3-(3-phenoxyphenyl)-l-bromoprop-2-ene, E-3-(4-fluoro-3-phenoxyphenyl)-1-chloroprop-2-ene,
E-3-[3-(4-chlorophenoxy)phenyl]-1-chloroprop-2-ene,
E-3-(3-phenoxyphenyl)prop-2-en-l-yl triphenyl phosphonium chloride, E-3-(4-fluoro-3-phenoxyphenyl)prop-2-en-l-yl triphenyl phosphonium chloride, E-3-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-yl triphenyl phosphonium chloride, dimethyl E-3-(4-fluoro-3-phenoxyphenyl)prop-2-en-l-yl phosphonate.
The following Examples illustrate various aspects of this invention. In the Examples the products were usually identified and characterised by means of nuclear magnetic reasonance spectroscopy and infra red spectroscopy. In each case where a product is specifically named its spectral characteristics are consistent with the assigned structure. Except where stated otherwise, exemplified compounds having one or more asymmetrically substituted carbon atoms were prepared in racemic formt In the Examples, 1H Nuclear Magnetic Resonance (NMR) spectrometry was performed at a frequency of 270 MHz.on a
Jeol FX 270 NMR spectrometer, unless otherwise indicated.
90 MHz, 60 MHz and 400 MHz 1H NMR spectrometry were performed using Jeol FX 90Q, Jeol PMX 60SI and Jeol GX400 spectrometers respectively.
19F NMR spectrometry was performed on a Jeol FX90Q spectrometer at a frequency of 84.26 MHz. All NMR shi- values (i ) are quoted in ppm relative to a standard (TMS or CFCl3).
Molecular Ion (M+) peaks were determined on one of three mass spectrometers: Jeol DX303, Kratos MS80 or Hewlett Packard HP 5992.
EXAMPLE 1
This Example illustrates the stages in the preparation of E-3-(4-fluoro-3-phenoxyphenyl)prop-2-en-l- yl triphenyl phosphonium chloride.
Stage 1 Preparation of l-(4-fluoro-3-phenoxyphenyl)prop- 2-en-l-ol
A solution of 4-fluoro-3-phenoxybenzaldehyde (35g) in arv tetrahydrofuran (100 cm3) was added slowly to stirred
vinyl magnesium bromide, commercially available from the
Aldrich Chemical Co Ltd, Gillingham, Dorset, England, (162 cm3 of a 1.0 molar solution in tetrahydrofuran) under an
atmosphere of nitrogen at the ambient temperature (ca
200C); a moderate exotherm was noted, raising the
temperature of the mixture to 400C. On completion. of the
addition, the mixture was stirred for a further 2 hours,
then poured into water and acidified with dilute
hydrochloric acid.The products were extracted three
times into ethyl acetate and the combined organic layers
were washed with water, dried over anhydrous magnesium sulphate and concentrated by evaporation under reduced
pressure to give a viscous oil (39g), characterised as 1 (4-fluoro-3-phenoxyphenyl)prop-2-en-l-ol, 97% pure by gas
liquid chromatographic analysis.
400 MHz 1H NMR (CDCl3) # (ppm) : ca 2.3 (1H, broad); 5.11
(lH,dd, J=lOHz,lHz); 5.18 (lH,dt, J=lOHz, 1Hz); 5.3
(lH,dt, J=17Hz, 1Hz); ca 5.95 (lH,m); 6.9-7.4 (8H,m).
Stages2 : Preparation of D-3-(4-fluoro-3-phenoxyphenyl)-l- chloroprop-2-ene l-(4-Fluoro-3-phenoxyphenyl)prop-2-en-l-ol (38g) was
dissolved in tetrahydrofuran (400 cm3) and concentrated
hydrochloric acid (180 cm3) was added with vigorous
stirring. Stirring was continued for a further 2 hours,
after which time, analysis of a withdrawn sample by gas
liquid chromatography showed no starting material
remaining. The mixture was diluted with water and the
products extracted into ethyl acetate. The combined organic layers were washed with water (4 times), then dried over anhydrous magnesium sulphate. Evaporation of the solvent under reduced pressure gave E-3-(4-fluoro-3phenoxyphenyl)-l-chloroprop-2-ene (44g) as a viscous oil, 98% pure by gas liquid chromatographic analysis.
An alternative preparative method is described in Stage 2 of Example 2(i). The preparation of brominated analogues is described in Example 2(ii).
1H NMR (CDC13)t (ppm) : 4.19 (2H,d); ca 6.15 (lH,dt); ca 6.55 (lH,d); 6.9-7.4 (8H,m), The E configuration was assigned after consideration of the coupling constants in the NMR spectrum.
Stage 3 : Preparation of E-3-(4-fluoro-3phenoxyphenyl)prop-2-en-l-yl triphenyl phosphonium chloride.
A mixture of E-3-(4-fluoro-3-phenoxyphenyl)-l-chloro prop-2-ene (42g), triphenylphosphine (42g) and xylene (300 cm3) was heated at the reflux temperature for 16 hours. After cooling, crystals of E-3-(4-fluoro-3 phenoxyphenyl )prop-2-en-l-yl triphenyl phosphonium chloride (68g) were filtered from the reaction mixture, washed with dry diethyl ether, dried by suction and stored in a desiccator under vacuum.
1H NMR (DMSO)-y(ppm) : ca 4.65 (2H,m); 6.0 (lH,broad m); 6.55 (lH,dd); 6.9-7.4 (8H,m); 7.7- 7.9 (15H,m).
EXAMPLE 2
The following compounds were prepared from the appropriate starting materials by procedures similar to those described in Example 1.
(i) E-3-(3-phenoxyphenyl)prop-2-en-l-yl triphenyl phosphonium chloride
Stage 1 : l-(3-phenoxyphenyl)prop-2-en-l-ol 1H NMR (CDC13) t(ppm) : 1.93 (1H, broad), 5.18 (1H, broad
s); ca 5.21 (1H, dd); 5.38 (1H, dd); 6.04 (lH, octet); 6.9-7.4
(9H, m).
Stage 2 : E-3-(3-phenoxyphenyl)-l-chloroprop-2-ene
Alternative Method l-(3-Phenoxyphenyl)prop-2-en-l-ol (0.05g) was dissolved in diethyl ether (2 cm3) which had been previously saturated with hydrogen chloride gas, and the solution was stirred at the ambient temperature for 2 hours. Water was added to the mixture and the products extracted into further diethyl ether. The combined ethereal layers were dried over anhydrous magnesium sulphate and the solvent evaporated under reduced pressure. The residual oil was purified by column chromatography on a silica gel support, eluted with hexane containing 5% by volume ethyl acetate, to give E-3-(3-phenoxyphenyl)-l-chloroprop-2-ene (0.03g).
1H NMR (CDCl3)# (ppm) : 4.21 (2H, d); 6.1-6.4 (1H, dt); ca
6.6 (1H, d); 6.8-7.45 (9H, m).
Stage 3 : E-3-(3-Phenoxyphenyl)prop-2-en-l-yl triphenyl
phosphonium chloride.
1H NMR (CDC13) (ppm) : ca 4.7 (1H, m); ca 6.1 (1H, m);
6.5 (1H, dd); 6.8-7.4 (9H, m);
7.65-7.9 (15H, m).
(ii) E-3-(3-phenoxyphenyl)-l-bromoprop-2-ene may be
prepared from l-(3-phenoxyphenyl)prop-2-en-l-ol according
to the method of Stage 2 of Example 1 using 48% aqueous
hydrobromic acid solution in place of concentrated
hydrochloric acid.
1H NMR (CDC13)4 (ppm) : ca 4.1 (2H,d,J=7Hz); 6.0-6.5 (2H,dt,J=17Hz and 7Hz); ca 6.6
(1H,d,j=17Hz) 6.8-7.5 (9H,m,
aromatic protons).
(iii) E-3-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-yl
triphenyl phosphonium chloride.
Stage 1 : 1-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-ol
1H NMR (CDCl3) # (ppm) : 1.96 (1H, broad s);ca 5.2 (2 x
1H overlapping); 5.36 (lH,d); 6.0
(lH,ddd); 6.9-7.4 (8H,m, aromatic
protons)
Stage 2 : E-3-[3-(4-chlorophenoxy)phenyl]-1-chloroprop-2- ene 1H NMR (CDCl3) # (ppm) : 4.21 (2H,d); ca 6.3 (lH,dt); 6.6
(lH,d); 6.9-7.4 (8H,m).
Stage 3 : E-3-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-yl triphenyl phosphonium chloride 1H NMR (CDC13) (ppm) : 4.7 (2H,dd); ca 6.1 (lH,m); ca.
6.53 (lH,dd); 6.8-7.4 (8H,m);
7.6-8.0 (15H,m) EXAMPLE 3
This Example illustrate the preparation of 1,1,1trifluoro-2-(4-trifluoromethoxyphenyl)-5-(3ptenoxyphenyl)penta-2,4-diene as a 6:1 mixture of the 2E,4E) and (2Z,4E) isomers.
n-Butyllithium (6.4 cm3 of a 2.5M solution in nhexane) was added dropwise to a cooled (0 C) suspension of
E-3-(3-phenoxyphenyl)prop-2-en-l-yl triphenyl phosphonium chloride- (8.2g) in dry tetrahydrofuran (100 cm3); a dark red colour developed in the reaction mixture. The reaction mixture was stirred at 0 C for a further 30 minutes, then a solution of 4-trifluoromethoxy-α,α,α- trifluoroacetophenone (3.87g) in dry tetrahydrofuran (50 cm3) was added dropwise. The mixture was allowed to stir
for a further hour and was then poured into water, and the.
products extracted into diethyl ether. The combined organic layers were washed with water, dried over anhydrous magnesium sulphate and concentrated by evaporation under reduced pressure. The residue was mixed with silica gel and diethyl ether and evaporated. The
residue was placed on top of a short plug of silica, and products were eluted by washing with n-hexane containing
10% by volume diethyl ether. Evaporation under reduced pressure gave an oil, which was purified by thigh pressure liquid chromatography, using n-hexane containing 10% by volume dichloromethane as eluent to give the title compound as a 6:1 mixture of the (2E,4E) and (2Z,4E)
isomers (4.24g). High pressure liquid chromatography using n-hexane containing 1% by volume ethyl acetate allowed separation and isolation of the major (2E,4E)
isomer of 96% purity.
NMR (CDCl3)#(ppm) for 2E,4E isomer
6.55 (lH,dd); 6.8-7.4 (15H,m).
19F NMR (CDC13) 4(ppm - relative to CFC13) for isomer mixture
-56.88 (E isomer CF3,s); -58.18 and -58.33 (CF30, 2s);
-65.2 (Z isomer CF3,s).
EXAMPLE 4
The following compounds were prepared from the
appropriate starting materials by a procedure similar to
that described in Example 3.
(i) 1,1,1-Trifluoro-2-(4-trifluoromethoxyphenyl)-5-(4fluoro-3-phenoxyphenyl)penta-2,4-diene as an 85:15 mixture of the (2E,4E) and (2Z,4E) isomers from 4-trifluoromethoxy α,α,α-trifluoroacetophenone and 3-(4-fluoro-3 phenoxyphenyl )-prop-2-en-1-yl triphenyl phosphonium chloride.
The 85:15 isomer mixture was separated by chromatography to give (A) the pure (2E,4E) isomer and (B) a 1:1 mixture of the (2E,4E) and (2Z,4E) isomers.
(A) (2E,4E) isomer : 1H NMR (CDCl3)# (ppm): 6.45 (lH,dd); 6.78 (lH,d); 6.9-7.4 (13H,m).
(B) contains extra peaks in the alkene region for the Z-isomer (ca 6.65).
(ii) 1,1-Difluoro-l-chloro-2-t4=Er-^if-luoromethoxyphenyl)-5- (4-fluoro-3-phenoxyphenyl)penta-2,4-diene as 12:1 mixture of (2E,4E) and (2Z,4E) isomers, from 4-trifluoromethoxy-α, α-difluoro-α -chloroacetophenone and 3-(4-fluoro-3phenoxyphenyl)prop-2-en-1-yl triphenyl phosphonium chloride.
1H NMR (CDCl3)#(ppm) : 6.32 (dd) and 6.77 (d). (2E,4E
isomer); 6.45 (d) and 6.7(d)
(2Z,4E isomer); 6.9-7.5 (m)
(iii) l,l-Difluoro-2-(4-ethoxyphenyl)-5-(3-phenoxy- phenyl)penta-2,4-diene, as a 3:1 mixture of the (2E,4E) and (2Z,4E) isomers, from 8-ethoxy- X,c-difluoroaceto- phenone and 3-(3-phenoxyphenyl)prop-2-en-l-yl trpr'enyl phosphonium chloride.
1H NMR (CDCl3)(ppm) (ppm) : ca 1.4 (3H,overlapping t); ca 4.1 (2H,overlapping q); 6.26
(lH,t,J=56Hz); 6.6-7.4 (16H,m) (iv) 1,1-Difluoro-1-chloro-2-(4-ethoxyphenyl)-5-(3phenoxyphenyl)penta-2,4-diene as a 4:1 mixture of the (2E,4E) and (2Z,4E) isomers, from 4-ethoxy-α,α-difluoro- α-chloroacetophenone and 3-(3-phenoxyphenyl)prop-2-en-1-yl triphenyl phosphonium chloride.
1H NMR (CDCl3)#(ppm) : ca 1.45 (3H,overlapping t);
ca 4.10 (2H,overlapping q); 6.4
7.4 (16H,m) 19F NMR (CDCl3)#(ppm - relative to CFC13) -43.9, -51.3 (CF2C1, 2s, in ratio 1:4) (NB. Product contained some unreacted acetophenone which could be removed by heating under vacuum) (v) 1,1-Difluoro-l-chloro-2-(4-trifluoromethoxyphenr~)-5- (3-phenoxyphenyl)penta-2,4-diene as a 13:1 mixture of the (2E,4E) and (2Z,4E) isomers, from 4-trifluoromethoxy-α,α- difluoro-α-chloroacetophenone and 3-(3-phenoxy phenyl)prop-2-en-l-yl triphenyl phosphonium chloride.
(2E,4E) isomer separated by high pressure liquid chromatography (93% pure) 1H NMR (CDCl3) #(ppm) : 6.44 (lH,dd); 6.8-7.4 (15H,m)
Molecular ion : 466/468 (vi) l,1,l-Trifluoro-2-(4-trifluoromethoxyphenyl)-5-[3-(4- chlorophenoxy)phenylpenta-2,4-diene as a 7.5:1 mixture of the (2E,4E) and (2Z,4E) isomers, from 4-trifluoromethoxy & α,α -trifluoroacetophenone and 3-[3-(4-chlorophenoxy)phenyl]prop-2-en-l-yl triphenyl phosphonium chloride.
1H NMR (CDC13) 4(ppm) : Olefinic and aromatic protons in
range of 6.5-7.4 19F NMR (CDC13) S (ppm - relative to CFC13) -58.2 (CF30,s,Z-isomer); -58.4 (CF30,s,E-isomer); -65.3 (CF3,s,Z-isomer); -56.9 (CF3,s,E-isomer)
Integration shows ratio of (2E,4E) and (2Z,4E) isomers to be 7.5:1
EXAMPLE 5
This Example illustrates the preparatIon of dimethyl E-3-(4-fluoro-3-phenoxyphenyl)prop-2-en-l-yl phosphonate.
A mixture of E-3-(4-fluoro-3-phenoxyphenyl)-l-chloroprop-2-ene (lg) and trimethyl phosphite (0.95g) was heated at 1250C under an atmosphere of nitrogen for 6 hours.
Analysis by gas liquid chromatography showed complete reaction at this stage. The mixture was cooled and poured into water, and the products were extracted into chloroform. The combined organic layers were washed twice with water, dried over anhydrous magnesium sulphate and
concentrated to leave dimethyl E-3-(4-fluoro-3
phenoxyphenyl)prop-2-en-1-yl phosphonate as an oil (1.3g).
1H NMR (CDC13)4 (ppm) : 2.73 (2H,dd and fine coupling);
3.74 (6H,d); 6.0 (lH,m); 6.42 (lH,dd); 6.9-7.4 (8H,m).
EXAMPLE 6
This Example describes the preparation of 1,1
difluoro-l-chloro-2-(4-trifluoromethoxyphenyl)-5-(3
phenoxy-4-fluorophenyl)penta-2,4-diene as a 2:1 mixture of
the (2E,4E) and (2Z,4E) isomers.
n-Butyllithium (0.24 cm3 of a 2.5 molar solution in
hexane) was added dropwise to a solution of dimethyl E-3
(4-fluoro-3-phenoxyphenyl)prop-2-en-l-yl phosphonate
(0.2g) in dry tetrahydrofuran (5 cm3) at the ambient
temperature, under an atmosphere of nitrogen; a deep red colouration was produced. After stirring for 2 hours at
the ambient temperature, a solution of 4-trifluoromethoxy , .-difluoro- > -chloroacetophenone (0.164g) in
tetrahydrofuran (2 cm3) was added dropwise. Gas liquid
chromatography after 30 minutes showed no starting
materials present. The mixture was quenched with water
and the products extracted into chloroform.The organic
layers were dried and concentrated by evaporation under
reduced pressure to give a mixture of two isomers of the
title compound, confirmed by comparison with an authentic
sample of the title compound produced by an alternative
route as the (2E,4E) and (2Z,4E) isomers in a 2:1 ratio.
EXAMPLE 7
This Example illustrates the preparation of 1,1,1trifluoro-2-(4-trifluoromethoxyphenyl)-5-(3phenoxyphenyl)pentane.
The (2E, 4E) isomer of l,1,l-trifluoro-2-(4-tri- fluoromethoxyphenyl)-5-(3-phenoxyphenyl)penta-2,4-diene (2.7g) in ethanol (80 cm3) in the presence of a hydrogenation catalyst (10% palladium on charcoal, 200 mg) was stirred under an atmosphere of hydrogen at a pressure of 3.7 atmospheres for 1 hour. The reaction mixture was filtered through celite to remove the catalyst and the celite washed with further ethanol. The combined filtrates were concentrated by evaporation of the ethanol under reduced pressure to yield l,l,l-trifluoro-2-(4-trifluoromethoxyphenyl)-5-(3-phenoxyphenyl)pentane (2.09g) as a colourless oil.
1H NMR (CDC13)S: ca 1.48 (2H, m); 1.84 and 2.0 (2H, broad
m); 2.56 (2, m); 3.22 (1H, broad m);
6.7-7.4 (13H, m).
19F NMR (CDCl3) (ppm - relative to CFC13) -58.33 (CF3O, s), -70.41 (CF3, d).
EXAMPLE 8
The following compounds were prepared from the appropriate alkadiene by a procedure similar to that described in Example 7.
(i) 1,1,1-Trifluoro-2-(4-trifluoromethoxyphenyl)-5-(4
fluoro-3-phenoxyphenyl)pentane, from 1,1,1-tri
fluoro-2-(4-trifluoromethoxyphenyl)-5-(4-fluoro-3 phenoxyphenyl ) penta-2, 4-diene.
1H NMR (CDCl3)# (ppm) : ca 1.5 (2H, m); 1.8, 2.0 (2H, broad, m); 2.55 (2H, m); 3.2 (1H, m); .7-7.4 (12H, m).
19F NMR (CDCl3)#(ppm - relative to CFC13)-: -58.35 (CF30, s); -70.45 (CF3, d); -135.2 (1F, m).
(ii) l,l-Difluoro-2-(4-trifluoromethoxyphenyl)-5-(4
fluoro-3-phenoxyphenyl)pentane from l,l-difluoro-l
chloro-2-(4-trifluoromethoxyphenyl)-5-(4-fluoro-3
phenoxyphenyl)penta-2,4-diene.
Hydrogenation of l,l-difluoro-1-chloro-2-(4- trifluoromethoxyphenyl)-5-(4-fluoro-3-phenoxy
phenyl)penta-2,4-diene at a hydrogen pressure of 4
atmospheres for 5 hours produced a multi-component
mixture of products, one of which was identified as
the title compound following reductive removal of
the chlorine atom. The products were separated by
analytical high pressure liquid chromatography on a
Dupont silica column eluted with hexane containing 1%
by volume ethyl acetate.
Details for title compound
1H NMR (CDCl3)#(ppm) : 1.46 (2H,m); ca 1.7, 1.9
(each lH, broad m); 2.52
2H,m); 2.96 (lH,m);5.77
(lH,dt, J=5Hz and 56Hz); 6.8
7.4 (12H,m).
19F NMR (CDCl3) (ppm - relative to CFC13) -58.37 (CF30,s); ca -121.24 (CF2H,m); -135.28 (lF,m) (iii) 1,1-Difluoro-2-(4-ethoxyphenyl)-5-(3-phenoxyphenyl)- pentane from 1,1-difluoro-2-(4-ethoxyphenyl)-5-(3-phenoxy phenyl )penta-2, 4-diene.
lH NMR (CDCl3)# # (ppm) : 1.41 (3H,t); 1.5 (2H,m); 1.6-1.9 (2H,m); 2.55 (2H,m); 2.9 (lH,m);
4.02 (2H,q); 5.75 (lH,dt, J=57Hz
and 5Hz); 6.7-7.4 (13H,m).
(iv) 1,l-Difluoro-l-chloro-2-(4-ethoxyphenyl)-5-(3phenoxyphenyl)pentane from l,l-difluoro-l-chloro-2-(4 ethOxyphenyl)-5-(3-phenoxyphenyl)penta-2,4-diene.
1H NMR (CDC13) s (ppm) : 1.3-1.6 (5H,m); 1.8-2.1 (2H,m); 2.55 (2H,m); 3.27 (lH,dq); 4.02
(2H,q); 6.7-7.4 (13H,m).
Molecular ion : 430, 432 (two peaks due to chlorIne isotopes).
In this case, hydrogenation for 4d hours at 3.5 atmospheres using a Rhodium on alumina catalyst, produced a complex mixture including partially reduced materials. Further hydrogenation (4 hours at 3 atmospheres) of the mixture produced two main components which were separated by high pressure liquid chromatography to give the title product and a further reduction product characterised as 1,1 disluoro-2-(4-ethoxyphenyl)-5-(3-phenoxyphenyl)-pentane, resulting from reductive dechlorination. The dechlorinated product was identical with the product obtained in Example 8(iii) above.
(v) 1,1,1-Trifluoro-2-(4-trifluoromethoxyphenyl)-5-[3-(4 chlorophenoxy)phenyl]pentane, from l,l,l-trifluoro-2-(4 trifluoromethoxyphenyl)-5-[3-(4-chlorophenoxy)phenyl]- penta-2,4-diene 1H NMR (CDCl3) # (ppm) : 1.5 (2H, broad m); 1.85 and 2.04
(2H, broad m); 2.58 (2H,m); 3.25
(1H,m); 6.7-7.35 (12H,m)
Molecular ion : 488/490 (vi) 2-(4-Trifluoromethoxyphenyl)-5-(3-phenoxyphenyl)pentane. This compound was produced by reductive defluorination as the major product during the hydrogenation of l,l-difluoro-2-(4-trifluoromethoxyphenyl)5-(3-phenoxyphenyl)-penta-2,4-diene (palladium on charcoal catalyst, 4.3 atmospheres, 2.5 hours). The difluoro and the monofluoro reduction products were identified as minor products.
Characteristic data for major product 1H NMR (CDCl3)# # (ppm) : 1.22 (3H,d); 1.4-1.65 (4H,m); 2.55 (2H,m); 2.9 (lH,q); 6.8-7.4
(13H,m) 19F NMR (CDCl3)# { (ppm - relative to CFCl3 -58.4 (CF30,s)
Molecular ion : 400
Characteristic data for 1,1-difluoro-2-(4-trifluoromethoxy- phenyl)-5-(3-phenoxyphenyl)pentane 1H NMR (CDCl3) s (ppm) : 1.5 (2H,m); 1.7-2.0 (2H,m); 2.56
(2H,m); 3.0 (lH,m); 5.8 (1H,dt); 6.7-7.4 (13H,m) 19F NMR (CDCl3)# (ppm relative to CFCl3) : -58.4 (CF3O,S); -121.2 (CHF2,m)
Claims (2)
- CLAIZIS 1. A compound of formula :and geometric isomers thereof, wherein W is hydrogen or halogen, and X is hydrogen or fluoro, and either Y represents chlorine, bromine or iodine, or Y is selected from a group of formula: - P+(R2)3 Hal and a group of formula:wherein R2 represents alkyl of up to six carbon atoms or aryl, and Hal represents a halide anion selected from chloride, bromide and iodide.
- 2. A compound as claimed in claim 1 selected from the group of compounds consisting of E-3-(3-phenoxyphenyl)-1-chloroprop-2-ene, E-3-(3-phenoxyphenyl)-1-bromoprop-2-ene, E-3-(4-fluoro-3-phenoxyphenyl)-1-chloroprop-2-ene, E-3-[3-(4-chlorophenoxy)phenyl]-1-chloroprop-2-ene, E-3-(3-phenoxyphenyl)prop-2-en-1-yl triphenyl phosphonium chloride, E-3-(4-fluoro-3-phenoxyphenyl)prop-2-en-1-yl triphenyl phosphonium chloride, E-3-[3-(4-chlorophenoxy)phenyl]prop-2-en-1-yl triphenyl phosphonium chloride and dimethyl E-3-(4-fluoro-3-phenoxy-phenyl)prop-2-en-1-yl phosphonate.
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GB878703653A GB8703653D0 (en) | 1987-02-17 | 1987-02-17 | Preparation of insecticidally active compounds |
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Citations (2)
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---|---|---|---|---|
GB2187452A (en) * | 1986-03-04 | 1987-09-09 | Ici Plc | Insecticidal fluoroalkyl benzene derivatives |
EP0279531A2 (en) * | 1987-02-17 | 1988-08-24 | Imperial Chemical Industries Plc | Process and intermediates for the preparation of insecticidally active compounds |
-
1990
- 1990-08-21 GB GB9018329A patent/GB2234509B/en not_active Revoked
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2187452A (en) * | 1986-03-04 | 1987-09-09 | Ici Plc | Insecticidal fluoroalkyl benzene derivatives |
EP0279531A2 (en) * | 1987-02-17 | 1988-08-24 | Imperial Chemical Industries Plc | Process and intermediates for the preparation of insecticidally active compounds |
Non-Patent Citations (1)
Title |
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Chemical Abstracts 108 (11) : 94163d (and J. Med. Chem., 31 (3), 499-500 * |
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CN113861240A (en) * | 2021-10-20 | 2021-12-31 | 中国科学院大学 | Trifluoromethyl reagent and synthesis method and application thereof |
CN113861240B (en) * | 2021-10-20 | 2023-10-31 | 中国科学院大学 | Trifluoromethyl reagent and synthetic method and application thereof |
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GB2234509B (en) | 1991-07-31 |
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