MXPA01004868A - 1,4-diaryl-2-fluoro-1-buten-3-ol compounds and their use in the preparation of 1, 4-diaryl-2-fluoro-1,3-butadiene and 1,4-diaryl-2-fluoro-2-butene compounds - Google Patents
1,4-diaryl-2-fluoro-1-buten-3-ol compounds and their use in the preparation of 1, 4-diaryl-2-fluoro-1,3-butadiene and 1,4-diaryl-2-fluoro-2-butene compoundsInfo
- Publication number
- MXPA01004868A MXPA01004868A MXPA/A/2001/004868A MXPA01004868A MXPA01004868A MX PA01004868 A MXPA01004868 A MX PA01004868A MX PA01004868 A MXPA01004868 A MX PA01004868A MX PA01004868 A MXPA01004868 A MX PA01004868A
- Authority
- MX
- Mexico
- Prior art keywords
- haloalkyl
- haloalkoxy
- halogens
- alkoxy
- combination
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims description 125
- 229910052736 halogen Inorganic materials 0.000 claims description 120
- 150000002367 halogens Chemical class 0.000 claims description 120
- 125000000217 alkyl group Chemical group 0.000 claims description 116
- 125000003545 alkoxy group Chemical group 0.000 claims description 109
- 125000001188 haloalkyl group Chemical group 0.000 claims description 94
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 85
- -1 phenoxyphenyl Chemical group 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 46
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 39
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 14
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 13
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 12
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000004305 biphenyl Chemical group 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003586 protic polar solvent Substances 0.000 claims description 8
- 150000008366 benzophenones Chemical group 0.000 claims description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N Benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 5
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 5
- MLWPJXZKQOPTKZ-UHFFFAOYSA-N benzenesulfonyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OS(=O)(=O)C1=CC=CC=C1 MLWPJXZKQOPTKZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 125000006268 biphenyl-3-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C(*)=C([H])C([H])=C1[H] 0.000 claims description 4
- OVHYIAVWHNQHSS-UHFFFAOYSA-N 4-(4-chlorophenyl)-4-cyclopropyl-3-fluoro-1-(4-fluoro-3-phenoxyphenyl)but-3-en-2-ol Chemical compound C1CC1C(C=1C=CC(Cl)=CC=1)=C(F)C(O)CC(C=1)=CC=C(F)C=1OC1=CC=CC=C1 OVHYIAVWHNQHSS-UHFFFAOYSA-N 0.000 claims description 3
- LINCLFQLZHCRHE-UHFFFAOYSA-N 4-[4-(4-chlorophenyl)-4-cyclopropyl-3-fluorobuta-1,3-dienyl]-1-fluoro-2-phenoxybenzene Chemical compound C1CC1C(C=1C=CC(Cl)=CC=1)=C(F)C=CC(C=1)=CC=C(F)C=1OC1=CC=CC=C1 LINCLFQLZHCRHE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- WDCSCGIZSMVNSU-UHFFFAOYSA-N 4-[4-(4-chlorophenyl)-4-cyclopropyl-3-fluorobut-2-enyl]-1-fluoro-2-phenoxybenzene Chemical compound C1CC1C(C=1C=CC(Cl)=CC=1)C(F)=CCC(C=1)=CC=C(F)C=1OC1=CC=CC=C1 WDCSCGIZSMVNSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 8
- 150000003462 sulfoxides Chemical class 0.000 claims 2
- 241000164466 Palaemon adspersus Species 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 125000005997 bromomethyl group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-Toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000008079 hexane Substances 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical class CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N Lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- SRTHRWZAMDZJOS-UHFFFAOYSA-N Lithium hydride Chemical compound [H-].[Li+] SRTHRWZAMDZJOS-UHFFFAOYSA-N 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N Methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal Effects 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- PDVFSPNIEOYOQL-UHFFFAOYSA-N (4-methylphenyl)sulfonyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OS(=O)(=O)C1=CC=C(C)C=C1 PDVFSPNIEOYOQL-UHFFFAOYSA-N 0.000 description 1
- WIHMGGWNMISDNJ-UHFFFAOYSA-N 1,1-dichloropropane Chemical compound CCC(Cl)Cl WIHMGGWNMISDNJ-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BQHQZFUAEAVJRE-UHFFFAOYSA-N 2-fluorobuta-1,3-diene Chemical compound FC(=C)C=C BQHQZFUAEAVJRE-UHFFFAOYSA-N 0.000 description 1
- QDKIFIYGNKHERN-UHFFFAOYSA-N 4-(bromomethyl)-1-fluoro-2-phenoxybenzene Chemical compound FC1=CC=C(CBr)C=C1OC1=CC=CC=C1 QDKIFIYGNKHERN-UHFFFAOYSA-N 0.000 description 1
- 229940010415 CALCIUM HYDRIDE Drugs 0.000 description 1
- UUGAXJGDKREHIO-UHFFFAOYSA-N Calcium hydride Chemical compound [H-].[H-].[Ca+2] UUGAXJGDKREHIO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- DTIPZKWBQBVYHL-UHFFFAOYSA-N FC=CC(CC1=CC(=C(C=C1)F)OC1=CC=CC=C1)O Chemical compound FC=CC(CC1=CC(=C(C=C1)F)OC1=CC=CC=C1)O DTIPZKWBQBVYHL-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N Fluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- IZDROVVXIHRYMH-UHFFFAOYSA-N Methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N Potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N Propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N Pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000004441 haloalkylsulfonyl group Chemical group 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000000749 insecticidal Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OCFVSFVLVRNXFJ-UHFFFAOYSA-N potassium hydride Inorganic materials [H-].[K+] OCFVSFVLVRNXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000003595 spectral Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 1
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Abstract
The present invention provides novel 1,4-diaryl-2-fluoro-1-buten-3-ol compounds of structural formula (I), a method for the preparation of those formula (I) compounds, and the use of those formula (I) compounds in the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds of formula (II) and 1,4-diaryl-2-fluoro-2-butene compounds of formula (III).
Description
r
COMPOUNDS l, 4-DIARIL-2-FLUORO-l-BUTEN-3-OL AND ITS USE IN
THE PREPARATION OF COMPOUNDS 1, 4-DIARIL-2-FLUORO-1, 3-BUTADIENE AND 1, 4-DIARIL-2-FLUORO-2-BUTHENUM
BACKGROUND OF THE INVENTION Compounds 1, 4-diaryl-2-fluoro-1,3-butadiene, the methods for their preparation and their use as intermediates in the preparation of the insecticidal agents and acaricides 1,4-diaryl-2-fluoro -2-butene are described in EP 811593-A1. The methods described in EP 811593-A1 for the preparation of the 1,4-diaryl-2-fluoro-1,3-butadiene compounds require the use of phosphonium halide compounds. However, these methods are not completely satisfactory because the necessary phosphonium halide compounds are relatively expensive and produce undesirable byproducts difficult to remove from the 1,4-diaryl-2-fluoro-1,3-butadiene compounds. Accordingly, there is a need in the art for an improved process for the preparation of the 1,4-diaryl-2-fluoro-1,3-butadiene compounds which avoids the use of the phosphonium halide compounds. Therefore, it is an object of the present invention to provide new compounds that are useful in the preparation of the compounds 1,4-diaryl-2-fluoro-1, 3-
It is also an object of the present invention to provide an improved process for the preparation of 1,4-diaryl-2-fluoro-1,3-butadiene compounds which prevent use of the phosphonium halide compounds Another object of the invention is to provide an improved process for the preparation of the 1,4-diaryl-2-fluoro-2-butene compounds.
COMPENDIUM OF THE INVENTION The present invention provides the 1,4-diaryl-2-fluoro-l-buten-3-ol compounds of the structural formula I
(I)
wherein R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy group,
1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C1-C4 alkyl groups, C1-C4 haloalkyl, C? -C alkoxy or C1-C4 haloalkoxy, or a ring five or six member heteroaromatic optionally substituted with any combination of: from one to three halogens,
• C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy groups; and Ari is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy group, phenyl optionally substituted with any combination of: from one to five halogens,
• C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy group, biphenyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C alkoxy or C 1 -C 4 haloalkoxy, phenoxypyridyl optionally substituted with
any combination of: from one to five halogens, C? -C alkyl groups, C? -C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy, benzylpyridyl optionally substituted with any combination of: from one to five halogens C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, benzylphenyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl groups, haloalkyl C? -C4, C1-C4 alkoxy or C1-C4 haloalkoxy, benzoylphenyl optionally substituted with any combination of: from one to five halogens, C1-C4 alkyl groups, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C1-C4 alkyl groups, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy, or a 5- or 6-membered heteroaromatic ring optionally substituted with any r combination of: from one to three halogens, C1-C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or
N
haloalkoxy of C? -C4. The present invention also provides a novel process for the preparation of the 1,4-diaryl-2-fluoro-1,3-butadiene compounds of structural formula II:
. { ID
wherein R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted by any combination of: from one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, 1 or 2 naphthyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or a heteroaromatic ring of five or six members optionally substituted with any
combination of: from one to three halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy; and Rx is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, optionally substituted phenyl with any combination of: from one to five halogens, C 10 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C haloalkoxy, biphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, haloalkyl
• of C? -C4, C? -C4 alkoxy or C? -C haloalkoxy, benzylpyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl , C? -C alkoxy or C? -C4 haloalkoxy, benzylphenyl optionally substituted with any combination of: from one to five halogens,
tmi? má? g? ^. *. -. ^ *? *? ? & ..Lk C? -C alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? -C haloalkoxy, benzoylphenyl optionally substituted with any combination of: from one to five halogens, alkyl groups of C? -C4, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? Alkyl groups? -C4, haloalkyl
C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy,
• or a 5- or 6-membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C haloalkoxy? -C4, whose process consists in the reaction of a 1,4-W-diaryl-2-fluoro-l-buten-3-ol compound of the structural formula I
I)
where Ar, Arx and R are as defined in the above
[ftp .._ Mfft ^ l ^ .i ~ «M .ai * ^ with a sulfonyl chloride compound or sulfonic acid anhydride and a base. The present invention also provides a novel process for the preparation of the 1,4-diaryl-2-fluoro-2-butene compounds having the structural formula III:
(III) 10 • wherein R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or
• haloalkoxy of C? -C4, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or a five or six membered heteroaromatic ring
optionally substituted with any combination of: from one to three halogens,
• C? -C4 alkyl, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy group; and 5 Arx is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenyl optionally substituted with any combination of: from one to five halogens, C? alkyl groups? -C, haloalkyl of C? -C4, alkoxy of C? -C4 or haloalkoxy of C? -C4, biphenyl optionally substituted with any combination of: from one to five halogens, 15 C? -C4 alkyl groups, haloalkyl C? ? -C, C? -C4 alkoxy or C? -C4 haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, 20 C? 4 haloalkyl, C? ? -C4 or C? -C4 haloalkoxy, benzylpyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C haloalkoxy? ? -C4, 25 benzylphenyl optionally substituted with any 10? * * ** #
combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, benzoyl phenyl optionally substituted with any combination of: from one to five halogens, C-C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? -C alkyl groups, C? -C haloalkyl, C? -C alkoxy or C? -C4 haloalkoxy, or a 5- or 6-membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, which process comprises: (a) the reaction of a compound 1, 4- diaryl-2-fluoro-l-buten-3-ol of the structural formula I
(I)
where Ar, Arx and R are as already described with a sulfonyl chloride or acid anhydride compound
• Sulfonic and a base to form a 1,4-diaryl-2-fluoro-1,3-butadiene compound of structural formula II
(b) the reaction of the compound 1,4-diaryl-2-fluoro- • 1, 3-butadiene with: (1) an alkaline earth metal in the presence of a protic solvent, or (2) an alkali metal in the presence of a protic solvent. of an aprotic solvent.
DETAILED DESCRIPTION OF THE INVENTION The present invention provides the compounds 1,4-diaryl-2-fluoro-l-buten-3-ol having the structural formula I
(I)
where Ar, Arx and R are as defined. The preferred compounds of formula I of this
invention are those in which: R is hydrogen, C? -C alkyl, C? -C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and rx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, 3 biphenyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, or 3-benzylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy. The most preferred 1,4-diaryl-2-fluoro-l-buten-3-ol compounds of this invention are those wherein: R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy. The compounds 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten-3-ol and 1- (a, a, a, -trifluoro- p-tolyl) -1-cyclopropy1-2-fluoro-4- (4-10 fluoro-3-phenoxyphenyl) -l-buten-3-ol are especially
• useful for the preparation of highly active insecticidal and acaricidal agents of the formula III. In formulas I, II and III above, the 5- and 6-membered heteroaromatic ring [sic] may conveniently be a ring containing from 1 to 4 heteroatoms selected from N, O and S, wherein the heteroaromatics may be the same or different, for example, the rings include, but are not limited to:
• pyridyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, tetrazolyl, pyrazinyl, pyridazinyl, tpazinyl, furanyl, thienyl and thiazolyl each optionally substituted as described in the above formulas II, II and III. Examples of the aforementioned "halogens" are fluorine, chlorine, bromine and iodine. The terms "haloalkyl"
fÉf * HiÉfrttlA * lft? rr nrtüf - -t- * - • "* - ^ - ^ - ^ - ^ -
of C? -C4"," C3-C6 halocycloalkyl "and" C? -C4 haloalkoxy "are defined as a C? -C4 alkyl group, a C3-C6 cycloalkyl group and a C? alkoxide group? C4 substituted with one or more halogen atoms, respectively, wherein the halogen atoms may be the same or different When used herein as a group or part of a group, the term "alkyl" includes chain alkyl groups linear or branched such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl When used herein as a group or part of a group, the term "cycloalkyl" includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl Groups containing two or more rings, such as phenoxyphenyl, phenoxypyridyl, biphenyl and benzylphenyl, which may be substituted, may be substituted on any ring unless otherwise specified herein In a preferred embodiment of the present invention, The 1,4-diaryl-2-fluoro-1,3-butadiene compounds of the formula II are prepared by reaction of a 1,4-diaryl-2-fluoro-l-buten-3-ol compound of the formula I with a sulfonyl chloride compound or sulfonic acid anhydride and a base, preferably at a temperature in
the range from about -78 ° C to 120 ° C, more preferably from about 20 ° C to 80 ° C,
• in the presence of a solvent. In another preferred embodiment of the present
In the invention, the 1,4-diaryl-2-fluoro-2-butene compounds of the formula III are prepared by the reaction of a 1,4-diaryl-2-fluoro-l-buten-3-ol compound of the formula I with a sulfonyl chloride or sulfonic acid anhydride compound and a base, preferably in a range of
temperature from about -78 ° C to 120 ° C,
• greater preference from about 20 ° C to 80 ° C, in the presence of a solvent to form a compound 1, -aryl-2-fluoro-1,3-butadiene of the formula II, and the reaction of the butadiene compound of the formula II with a
alkaline earth metal in the presence of a protic solvent. Conveniently, the present invention provides a process for the preparation of the compounds 1,4-diaryl- • 2-fluoro-1,3-butadiene which avoids the use of phosphonium halide compounds. The compounds of the formula II and III product can be isolated by diluting the reaction mixture with water and extracting the product with a solvent for convenient extraction. In the procedure of
insulation, it is possible to use the solvents for
traditional extraction such as diethyl ether, ethyl acetate, toluene, methylene chloride and the like, and mixtures thereof. Convenient sulfonyl chloride compounds for use in the present invention include, but are not limited to, unsubstituted and substituted phenylsulfonyl chlorides such as p-toluenesulfonyl chloride and the like, C? -C6 alkylsulfonyl chlorides such as methanesulfonyl and the like, and chlorides of C 10 -C haloalkylsulfonyl, such as trifluoromethanesulfonyl chloride and the like. Suitable sulfonic acid anhydrides for use in this invention include, but are not limited to, unsubstituted phenylsulfonic acid anhydrides and substituted as may be
The p-toluenesulfonic acid anhydride and the like, the C 1 -C 6 alkylsulfonic acid anhydrides such as the methanesulfonic acid anhydride and the like, and the haloalkylsulfonic acid anhydrides of C 6 -C 6
• can be trifluoromethanesulfonic acid anhydride
and similar. Suitable bases for use in the present invention include, but are not limited to, alkali metal hydrides such as sodium hydride, potassium hydride, lithium hydride and the like, alkaline earth metal hydrides such as calcium hydride and the like,
the alkali metal C? -C6 alkoxides as methoxide of
sodium, potassium t-butoxide and the like, C 1 -C 6 alkyl lithiums such as n-butyl lithium, sec-butyl lithium, methyl lithium
And the like and lithium dialkylamides such as lithium diisopropylamide, 5-lithium isopropylcyclohexylamide and the like. Preferred bases include alkali metal hydrides. Suitable solvents for use in the preparation of the compounds of formula II and III of this invention include, but are not limited to, ethers
as tetrahydrofuran, dioxane, pyran, diethyl ether, 1,2-dimethoxyethane and the like; amides of the carboxylic acid such as N, N-dimethylformamide, N, N-dimethylacetamide and the like; dialkylsulphoxides such as dimethyl sulfoxide and the like; nitriles as
acetonitrile, propionitrile and the like; aromatic hydrocarbons such as toluene, benzene, xylenes, mesitylene and the like; and the halogenated aromatic hydrocarbons such as chlorobenzene, fluorobenzene and the like; and mixtures of these. Preferred solvents for use in the
The preparation of the compounds of the formulas II and III include the ethers. Suitable protic solvents for use in this invention include, but are not limited to, C?-C6 alcohols such as methanol, ethanol, and the like. The
Preferred protic solvents include methanol and
The ethereal solvents include, but are not limited to, ammonia, and ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and the like. Use in the preparation of the compounds of the formula III include, but are not limited to, magnesium and calcium, with magnesium being preferred The alkali metals include, but are not limited to, lithium, sodium and potassium The preferred compounds of the formulas II and III which can be prepared by the processes of this invention are those in which: R is C? -C4 alkyl, C? -C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy; Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, alkyl groups C 1 -C 4, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, 3-biphenyl optionally substituted with any combination of: from one to five halogens, C alquilo alkyl groups C4, haloalkyl of C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy, or
3-benzylphenyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl groups, C 1 -C haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy. The most preferred 1,4-diaryl-2-fluoro-1,3-butadiene and 1,4-diaryl-2-fluoro-2-butene compounds that can be prepared by the processes of this invention are those wherein: R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C alkoxy or C 4 C 4 haloalkoxy; and rx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl groups, C 1 -Chaloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy. The present invention is especially useful for the preparation of: 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1,3-butadiene; 1- (, a, α-trifluoro-p-tolyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1,3-butadiene; 1- [1- (a, a, a-trifluoro-p-tolyl) -2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -2-butenyl] cyclopropane; Y
1- [1- (p-chlorophenyl) -2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -2-butenyl] cyclopropane. The present invention further provides a process for the preparation of the 1,4-diaryl-2-fluoro-l-buten-3-ol compounds of the formula I whose process consists of: (a) the reaction of an arylmethane bromide compound of structural formula IV: ArCH2Br 10 (IV) wherein Arx is as described above with a lithium (C? -Cd) alkylideurolate compound to form an intermediate compound of the structural formula V: Ar? CH2TeLi 15 (V) (b) the reaction of the intermediate compound of the formula V with an alkyl lithium compound of C? -C6 to form an intermediate compound of the structural formula VI: Ar? CH2Li; and (VI) (c) reacting the intermediate compound of formula VI with a 3-aryl-2-fluoropropene compound of structural formula VII:
where R and Ar are as defined. In a preferred embodiment of the present invention, the 1,4-diaryl-2-fluoro-l-buten-3-ol compounds of the formula I are prepared by reaction of a compound
Arylmethane bromide of the formula IV with a lithium (C? -Cd) tellurium alkyl compound, preferably in a temperature range from about -78 ° C to about 30 ° C, more preferably from about -78 ° C C to about 0 ° C, in
The presence of a solvent to form an intermediate compound of the formula V, the reaction of the intermediate compounds of the formula V in situ with a C 1 -C 6 alkyl lithium compound, preferably in a temperature range from about -78 ° C until
about 30 ° C, more preferably from about -78 ° C to 0 ° C, to form an intermediate compound having structural formula VI, and the reaction of the intermediate compound of formula VI in situ with a 3-aryl compound -2-fluoropropenal of the
Formula VII, preferably in a temperature range from about -78 ° C to about 30 ° C. ! : Suitable lithium (Cx-Cd) -lideurolate compounds for use in the present invention include, but are not limited to, lithium n-butyltelurolate, lithium sec-butyltelurolate, lithium t-butyltelurolate, n-propyltelurolate of lithium and the like. Suitable C 1 -C 6 alkyl lithium compounds for use include, but are not limited to, n-butyl lithium, sec-butyl lithium, n-propyl 10 lithium, methyl lithium and the like. Solvents useful in the preparation of the compounds of formula I of this invention include, but are not limited to, ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and the like, and
Mixtures of these, with tetrahydrofuran being preferred. To facilitate further understanding of this invention, the following examples are presented primarily for purposes of illustrating more specific details herein. The scope of the invention should not be considered as limited by the examples but includes the whole subject defined in the clauses.
EXAMPLE 1 Preparation of 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten-3-ol
• A solution of lithium n-butyltelurolate (10.5 20 mmol, n-BuTeLi), generated in situ from n-butyl lithium (4.2 ml of a 2.5 M solution in hexane, 10.5 mmol) and Te powder (1.34 g) , 10.5 mmol) in tetrahydrofuran (10 ml) at 0 ° C, treated with a solution of 3-phenoxy-4-fluorobenzyl bromide (2.81 g, 10 mmol) in tetrahydrofuran (10 ml) at 0 ° C, shake for 30
.ss? í 24
minutes, it is cooled to -78 ° C, treated with a solution of n-butyl lithium (4.2 ml of a 2.5 M solution in hexane, • 10.5 mmol), stirred for 30 minutes at -78 ° C, treated with a solution of p-chloro-β-cyclopropyl-α-5-fluorocinnamaldehyde (2.24 g, 10 mmol) in tetrahydrofuran (5 ml) is heated at room temperature with stirring for three hours, the reaction is stopped with 2N hydrochloric acid and it is extracted with ethyl acetate. The combined organic extracts are washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a residue. Flash chromatography of the residue on silica gel using a 1: 4 solution of ethyl acetate / hexanes gives the title product (3.5 g, 82% yield) which is identified by spectral analyzes of 1H, 19F and 13C NMR. Following practically the same procedure, but using p- (trifluoromethyl) -β-cyclopropyl-a-fluoro-kinnamaldehyde, 1- (a, a, a-trifluoro-p- • tolyl) -l-cyclopropyl-2-fluoro-4 is obtained. - (4-fluoro-3-phenoxyphenyl) - 20 l-buten-3-ol.
^. ^ a ^ jjÉatti ^ í ^ áa EXAMPLE 2 Preparation of 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1, 3-butadiene
A suspension of sodium hydride (6.3 mg, 0.26 mmol) in tetrahydrofuran (1 ml) is treated with a solution of 1- (p-chlorophenyl) -l-chloropropyl-2-fluoro-4- (4-fluoro-3). phenoxyphenyl) -l-buten-3-ol (106.7 mg, 0.25 mmol) in
^ Br Tetrahydrofuran (1.5 ml), is stirred at 50 ° C for 10 minutes.
minutes, it is cooled to room temperature and treated with a solution of p-toluenesulfonyl chloride (49.6 mg, 0.26 mmol) in tetrahydrofuran (1 ml), stirred at 60 ° C for one hour, the reaction is quenched with water and extracted with ethyl acetate. The organic extracts
The combined extracts are washed in sequence with water, saturated sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a residue. Flash chromatography of the residue using silica gel and a 1: 9 ethyl acetate / hexanes solution gives the title product (63 ml, 61% yield) which is identified by spectral analysis of XH, 19F and 13C NMR. Following practically the same procedure, but using 1- (a, a, α-trifluoro-p-tolyl) -l-cyclopropyl-2- A 10 fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten- 3-ol, 1- (a, a, a-trifluoro-p-tolyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1,3-butadiene is obtained.
Claims (32)
- A compound of structural formula I (I) wherein R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted by any combination of: from one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, 1 or 2 naphthyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or a heteroaromatic ring of five or Six members optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy; and • Arx is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C alkoxy or C? -C haloalkoxy, phenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, biphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C alkoxy or C 1 -C 4 haloalkoxy, benzylpyridyl optionally substituted with any combination of: from one to five halogens, C 1 alkyl groups C, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, optionally substituted benzylphenyl. with any combination of: from one to five halogens, 25 C? -C alkyl groups, C? -C4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C -haloalkoxy, benzoylphenyl optionally substituted with any • combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C haloalkoxy, 10 or • a 5- or 6-membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, alkyl groups of 15 C? -C4, C? -C4 haloalkyl, C? -C alkoxy or C? -C4 haloalkoxy.
- 2. The compound according to the claim • 1, wherein: R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, 25 C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or H¡m * nfo.fe- '-'-' ?. < * - 'ffaaafcaaaaWiaa haloalkoxy of C? -C4; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 4 C alkoxy or C 1 -C 4 haloalkoxy, 3-biphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or 3-benzylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy.
- 3. The compound according to claim 2, wherein: R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy.
- 4. The compound according to claim 1 is selected from the group consisting of: 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten-3- ol, and 1- (a, a, a-trifluoro-p-tolyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten-3-ol.
- A process for the preparation of a 1,4-diaryl-2-fluoro-1,3-butadiene compound of the formula 10 structural II • (II) wherein R is hydrogen, C? -C4 alkyl, C? -C haloalkyl, C3-C6 cycloalkyl, or C3-C6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C alkoxy or C 1 -C 4 haloalkoxy, 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or a five or six membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy; yj ^ k 10 Arx is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenyl optionally substituted with any combination of: from one to five halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, biphenyl optionally substituted with any • combination of: from one to five halogens, 20 C? -C4 alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? -C haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 33 * W «t?» Í optionally substituted benzylpyridyl with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, benzylphenyl optionally substituted with any combination of : from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C haloalkoxy, benzoyl phenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl, C? -C haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, alkyl groups of C? -C4, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C haloalkoxy, or a 5- or 6-membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, groups C? -C4 alkyl, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, the pr The process consists of the reaction of a 1,4-diaryl-2-fluoro-l-buten-3-ol compound of the structural formula I wherein Ar, Arx and R are as defined above with a sulfonyl chloride or sulfonic acid anhydride compound and a base.
- 6. The process according to claim 5, wherein the sulfonyl chloride is selected from the group • consisting of: phenylsulfonyl chloride, a substituted phenylsulfonyl chloride, an alkylsulfonyl chloride of C-C6 and a haloalkylsulfonyl chloride of C? -C6; and the sulfonic acid anhydride is selected from the group consisting of phenylsulfonic acid anhydride, a substituted phenylsulfonic acid anhydride, a C 1 -C 6 alkylsulfonic anhydride and a C 1 -C 6 haloalkylsulfonic acid anhydride.
- 7. The process according to claim 5, wherein the base is selected from the group consisting of an alkali metal hydride, an alkaline earth metal hydride, an alkali metal C 1 -C 6 alkoxide, an alkyl lithium of C? -Ce and a dialkylamide of lithium. 25 . fc »* ^ * a? > . «RtJ« at * tt.? Lti ú M • 1f
- 8. The process according to claim 7, wherein the base is an alkali metal hydride.
- 9. The process according to claim 5, wherein the compound 1,4-diaryl-2-fluoro-l-buten-3-ol reacts with the sulfonyl chloride compound or sulfonic acid anhydride and the base in the presence of a solvent.
- 10. The process according to claim 9, wherein the solvent is selected from the group consisting of an ether, carboxylic acid amide, a dialkyl sulfoxide, a nitrile, an aromatic hydrocarbon and a halogenated aromatic hydrocarbon and 15 mixtures of these.
- 11. The process according to claim 5, wherein the compound 1,4-diaryl-2-fluoro-l-buten-3-ol • reacts with the sulfonyl chloride or sulfonic acid anhydride compound and the base at a temperature in the range from about -78 ° C to about 120 ° C.
- 12. The process according to claim 5, wherein:
- R is hydrogen, C? -C alkyl, C? -C4 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C haloalkyl, C? -C alkoxy or C? -C haloalkoxy; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, haloalkyl • of C? -C4, C? -C4 alkoxy or C? -C4, 3-biphenyl haloalkoxy optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C-C4 haloalkyl , C? -C alkoxy or C? -C haloalkoxy, or 3-benzylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, haloalkyl • of C? -C, C? -C4 alkoxy or C? -C4 haloalkoxy. 13. The process according to claim 12, wherein: R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and • Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy.
- 14. The process according to claim 5 for the preparation of a compound selected from
- The group consisting of: 1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1,3-butadiene; 1- (a, a, α-trifluoro-p-tolyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -1,3-butadiene. 15. The process for the preparation of a 1,4-diaryl-2-fluoro-2-butene compound of structural formula III (III) wherein 25 R is hydrogen, C? -C4 alkyl, C? -C4 haloalkyl, C3-C6 cycloalkyl, or C3-Ce haloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2? -naphthyl optionally substituted with any combination of: from one to three halogens, C? -C alkyl groups, haloalkyl • of C -C4, C? -Calkoxy or C? -C4 haloalkoxy, or a five or six membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups , haloalkyl of C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy, and Arx is phenoxyphenyl optionally substituted with Any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, biphenyl optionally substituted with any combination of: from one to five halogensC 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C 1 alkyl groups C4, C?-C4 haloalkyl, C?-C4 alkoxy or C?-C4 haloalkoxy, benzylpyridyl optionally substituted with any combination of: from one to five halogens, C?-C alkyl, C halo-haloalkyl groups C4, C? -C4 alkoxy or C? -C4 haloalkoxy, benzylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C-C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, benzoylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? 4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, haloalkyl C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy, or a 5 or 6 membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, which process comprises: (a) the reaction of a 1,4-diaryl-2-fluoro-l-buten-3-ol compound of structural formula I (I) wherein Ar, Arx and R are as already described with a sulfonyl chloride or sulfonic acid anhydride compound and a base to form a 1,4-diaryl-2-fluoro-1,3-butadiene compound of the structural formula II F H and (II) (b) the reaction of the compound 1,4-diaryl-2-fluoro-1,3-butadiene with: (1) an alkaline earth metal in the presence of a protic solvent, or (2) a metal alkaline in the presence of an aprotic solvent,
- • The process according to claim 15, wherein the sulfonyl chloride is selected from the group consisting of: phenylsulfonyl chloride, a substituted phenylsulfonyl chloride, an alkylsulfonyl chloride of C? -Ce and a haloalkylsulfonyl chloride of C? -C6; and the sulfonic acid anhydride is selected from the group consisting of phenylsulfonic acid anhydride, a 10 substituted phenylsulfonic acid anhydride, a • C-C6 alkylsulfonic acid anhydride and a haloalkylsulfonic acid anhydride of C? -C6.
- 17. The process according to claim 15, Wherein the base is selected from the group consisting of an alkali metal hydride, an alkaline earth metal hydride, an alkali metal C? -Ce alkoxide, a C? -C6 alkyl lithium and a lithium dialkylamide.
- 18. The process according to claim 15, wherein the compound 1,4-diaryl-2-fluoro-l-buten-3-ol reacts with the sulfonyl chloride compound or sulfonic acid anhydride and the base in the presence of of a solvent. 25
- 19. The process according to claim 18, wherein the solvent is selected from the group consisting of an ether, carboxylic acid amide, a dialkyl sulfoxide, a nitrile, an aromatic hydrocarbon and a halogenated aromatic hydrocarbon and mixtures thereof.
- 20. The process according to claim 15, wherein the compound 1,4-diaryl-2-fluoro-l-buten-3-ol reacts with the sulfonyl chloride compound or sulfonic acid anhydride and the base at a temperature in the range from about -78 ° C to about 120 ° C.
- 21. The process according to claim 15, wherein the compound 1,4-diaryl-2-fluoro-1,3-butadiene reacts with the alkaline earth metal in the presence of the protic solvent.
- 22. The process according to claim 21, wherein the alkaline earth metal is magnesium.
- 23. The process according to claim 21, wherein the protic solvent is a C? -C6 alcohol.
- 24. The process according to claim 15, wherein: R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted by any combination of: from one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and fl 10 Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C alkyl groups, C? -C4 haloalkyl, C-C4 alkoxy or C? -C4 haloalkoxy, -biphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or optionally 3-benzylphenyl. substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C alkoxy or C? -C4 haloalkoxy.
- 25. The process according to claim 24, wherein: R is isopropyl or cyclopropyl; am, ^^ __! ______ Ar is phenyl optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? - haloalkoxy; C4; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy.
- 26. The process according to claim 15 for the preparation of a compound selected from the group consisting of: 1- [1- (p-chlorophenyl) -2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -2- butenyl] cyclopropane and 1- [1- (a, a, a-trifluoro-p-tolyl) -2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -2-butenyl] cyclopropane.
- 27. A process for the preparation of a compound 1,4-diaryl-2-fluoro-l-buten-3-ol of structural formula I: (I) Iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii - ^ - ^ phtafti wherein R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, f 1) - or 2-naphthyl optionally substituted with any combination of: from one to three halogens, C?-C 4 alkyl groups, C?-C 4 haloalkyl, C -C4 alkoxy or C?-C 4 haloalkoxy, or a ring five- or six-membered heteroaromatic optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and Rx is phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, optionally substituted phenyl with any combination of: from one to five halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy, biphenyl optionally substituted with any combination of: from one to five halogens, C 1 -C 4 alkyl groups , C? -C haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, phenoxypyridyl optionally substituted with any combination of: from one to five halogens, C? -C alkyl, haloalkyl groups 10 C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy, • benzylpyridyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, benzylphenyl optionally substituted with any combination of: from one to five halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, benzoyl phenyl optionally substituted with any The combination of: from one to five halogens, C? -C alkyl groups, C? -C haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 1- or 2-naphthyl optionally substituted with any combination of: from one to three 25 halogens, C? -C alkyl groups, haloalkyl of C? -C4, C? -C4 alkoxy or C? -C4 haloalkoxy, or a 5- or 6-membered heteroaromatic ring optionally substituted with any combination of: from one to three halogens, C? -C4 alkyl groups , haloalkyl of C? -C4, C? -C alkoxy or C? -C haloalkoxy, whose process consists of: (a) the reaction of a bromide compound • arylmethane of the structural formula IV: Ar? CH2Br (IV) wherein Arx is as described above with a lithium (C? -Ce) telluride compound to form an intermediate compound of the structural formula V: Ar? CH2TeLi (V) • (b) the reaction of the intermediate compound of formula V with an alkyl lithium compound of C? -Cd to form an intermediate compound of structural formula VI: Ar? CH2Li; and (VI) 25 (c) the reaction of the intermediate compound of the formula VI with a 3-aryl-2-fluoropropene compound of the structural formula VII: where R and Ar are as defined.
- 28. The process according to claim 27, wherein the compound arylmethane bromide is reacted with the lithium C?-C6 alkylcarbonate compound in the presence of a solvent to form the intermediate compound of the formula V, the reaction of the intermediate compound of the formula V in situ with the alkyl lithium compound of C? -C6 to form the intermediate compound of the formula VI, and the reaction of the intermediate compound of the formula VI in situ with the compound 3-aryl-2-fluoropropene.
- 29. The process according to claim 28, wherein the solvent is an ether.
- 30. The process according to claim 27, wherein: R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, alkyl groups of C? -C, C? -C haloalkyl, C? -C alkoxy or C? -C4 haloalkoxy; and Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C? -C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, 3- biphenyl optionally substituted with any combination of: from one to five halogens, C? -C alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? -C4 haloalkoxy, or 3-benzylphenyl optionally substituted with any combination of: from one to five halogens, C-C4 alkyl groups, C? -C4 haloalkyl, C? -C4 alkoxy or C? 4 haloalkoxy.
- 31. The process according to claim 30, wherein: R is isopropyl or cyclopropyl; Ar is phenyl optionally substituted with any combination of: from one to three halogens, C 1 -C 4 alkyl groups, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy; and F Arx is 3-phenoxyphenyl optionally substituted with any combination of: from one to six halogens, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy.
- 32. The process according to claim 27 is selected from the group consisting of: j-1- (p-chlorophenyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten- 3-ol, and 1- (a, a, a-trifluoro-p-tolyl) -l-cyclopropyl-2-fluoro-4- (4-fluoro-3-phenoxyphenyl) -l-buten-3-ol. fifteen
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/192,680 | 1998-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA01004868A true MXPA01004868A (en) | 2003-02-17 |
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