CA1147745A - M-phenoxy-benzyl esters of amino acids such as valine - Google Patents
M-phenoxy-benzyl esters of amino acids such as valineInfo
- Publication number
- CA1147745A CA1147745A CA000298515A CA298515A CA1147745A CA 1147745 A CA1147745 A CA 1147745A CA 000298515 A CA000298515 A CA 000298515A CA 298515 A CA298515 A CA 298515A CA 1147745 A CA1147745 A CA 1147745A
- Authority
- CA
- Canada
- Prior art keywords
- valine
- ester
- phenoxybenzyl
- fluoro
- compound according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 M-phenoxy-benzyl esters Chemical class 0.000 title claims abstract description 282
- 239000004474 valine Substances 0.000 title abstract description 45
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 title abstract description 43
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 title abstract description 38
- 150000001413 amino acids Chemical class 0.000 title abstract description 8
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 99
- 150000001875 compounds Chemical class 0.000 claims description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 241000238631 Hexapoda Species 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 241000238876 Acari Species 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 241000255925 Diptera Species 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 241000254173 Coleoptera Species 0.000 claims description 2
- 241000258937 Hemiptera Species 0.000 claims description 2
- 241001466007 Heteroptera Species 0.000 claims description 2
- 241000257303 Hymenoptera Species 0.000 claims description 2
- 241000255777 Lepidoptera Species 0.000 claims description 2
- 241000238814 Orthoptera Species 0.000 claims description 2
- 241000916145 Tarsonemidae Species 0.000 claims description 2
- 241001454295 Tetranychidae Species 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims 3
- 150000002148 esters Chemical class 0.000 abstract description 68
- 239000000203 mixture Substances 0.000 abstract description 57
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 3
- 150000007970 thio esters Chemical class 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 233
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 91
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- FBCHRMFAWNWJCU-JTQLQIEISA-N (2s)-2-(4-chloroanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(Cl)C=C1 FBCHRMFAWNWJCU-JTQLQIEISA-N 0.000 description 50
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 48
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 44
- UJUNUASMYSTBSK-UHFFFAOYSA-N 1-(bromomethyl)-3-phenoxybenzene Chemical compound BrCC1=CC=CC(OC=2C=CC=CC=2)=C1 UJUNUASMYSTBSK-UHFFFAOYSA-N 0.000 description 43
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000012267 brine Substances 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- AJWAECPVBMQFSX-NSHDSACASA-N (2s)-3-methyl-2-(4-methylanilino)butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C)C=C1 AJWAECPVBMQFSX-NSHDSACASA-N 0.000 description 34
- 239000011541 reaction mixture Substances 0.000 description 30
- DLULJAUWRRKBML-JTQLQIEISA-N (2s)-2-[2-fluoro-4-(trifluoromethyl)anilino]-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C(F)(F)F)C=C1F DLULJAUWRRKBML-JTQLQIEISA-N 0.000 description 26
- 229910000027 potassium carbonate Inorganic materials 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 24
- UEBARDWJXBGYEJ-UHFFFAOYSA-N 2-bromo-3-methylbutanoic acid Chemical compound CC(C)C(Br)C(O)=O UEBARDWJXBGYEJ-UHFFFAOYSA-N 0.000 description 21
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 description 16
- 235000011152 sodium sulphate Nutrition 0.000 description 16
- KZPLXTSZVZBJPO-JTQLQIEISA-N (2s)-2-(4-chloro-2-fluoroanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(Cl)C=C1F KZPLXTSZVZBJPO-JTQLQIEISA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000012259 ether extract Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 14
- 159000000000 sodium salts Chemical class 0.000 description 14
- 238000004809 thin layer chromatography Methods 0.000 description 14
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 13
- 101150041968 CDC13 gene Proteins 0.000 description 12
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 12
- NZPWGWAEKDSVFN-JTQLQIEISA-N (2s)-3-methyl-2-[4-(trifluoromethyl)anilino]butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C(F)(F)F)C=C1 NZPWGWAEKDSVFN-JTQLQIEISA-N 0.000 description 11
- 239000005457 ice water Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- CAXWIGJTXJTLLU-JTQLQIEISA-N (2s)-2-(4-bromo-2-fluoroanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(Br)C=C1F CAXWIGJTXJTLLU-JTQLQIEISA-N 0.000 description 9
- YKSHSSFDOHACTC-JTQLQIEISA-N (2s)-2-[2-chloro-4-(trifluoromethyl)anilino]-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C(F)(F)F)C=C1Cl YKSHSSFDOHACTC-JTQLQIEISA-N 0.000 description 9
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- MBRPCSKHPRLQQQ-JTQLQIEISA-N (2s)-2-anilino-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=CC=C1 MBRPCSKHPRLQQQ-JTQLQIEISA-N 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000012746 preparative thin layer chromatography Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- LYJVJCQYQYSJHU-NSHDSACASA-N (2s)-2-(2-fluoro-4-methylanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C)C=C1F LYJVJCQYQYSJHU-NSHDSACASA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005192 partition Methods 0.000 description 7
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 7
- XCAMLAFYNOLVPM-NSHDSACASA-N (2s)-2-(2,6-dimethylanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=C(C)C=CC=C1C XCAMLAFYNOLVPM-NSHDSACASA-N 0.000 description 6
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229940024606 amino acid Drugs 0.000 description 6
- 235000001014 amino acid Nutrition 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- MEFVUVHUSRMQFS-NSHDSACASA-N (2s)-2-(3-fluoro-4-methylanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C)C(F)=C1 MEFVUVHUSRMQFS-NSHDSACASA-N 0.000 description 5
- XZUCJVTXERYPQH-NSHDSACASA-N (2s)-2-(4-methoxyanilino)-3-methylbutanoic acid Chemical compound COC1=CC=C(N[C@@H](C(C)C)C(O)=O)C=C1 XZUCJVTXERYPQH-NSHDSACASA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- CSFDTBRRIBJILD-UHFFFAOYSA-N 4-chloro-2-fluoroaniline Chemical compound NC1=CC=C(Cl)C=C1F CSFDTBRRIBJILD-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XWTQCMHYIJEQPD-JTQLQIEISA-N (2s)-2-(4-chloro-3-fluoroanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(Cl)C(F)=C1 XWTQCMHYIJEQPD-JTQLQIEISA-N 0.000 description 4
- MFOQAAROVBJMNI-ZDUSSCGKSA-N (2s)-2-(4-tert-butylanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C(C)(C)C)C=C1 MFOQAAROVBJMNI-ZDUSSCGKSA-N 0.000 description 4
- ZQEXBVHABAJPHJ-UHFFFAOYSA-N 2-fluoro-4-methylaniline Chemical compound CC1=CC=C(N)C(F)=C1 ZQEXBVHABAJPHJ-UHFFFAOYSA-N 0.000 description 4
- RMXZAXNAIMJGCX-UHFFFAOYSA-N 3-[2-fluoro-4-(trifluoromethyl)phenyl]-4-propan-2-yl-1,3-oxazolidine-2,5-dione Chemical compound O=C1OC(=O)C(C(C)C)N1C1=CC=C(C(F)(F)F)C=C1F RMXZAXNAIMJGCX-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- AAOZSVIAUPQWBF-JTQLQIEISA-N (2s)-2-(2,4-difluoroanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(F)C=C1F AAOZSVIAUPQWBF-JTQLQIEISA-N 0.000 description 3
- VEMHDYZLZMGTPY-NSHDSACASA-N (2s)-2-(2-chloro-4-cyanoanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C#N)C=C1Cl VEMHDYZLZMGTPY-NSHDSACASA-N 0.000 description 3
- CQVOILYSLSWABZ-NSHDSACASA-N (2s)-2-(2-fluoro-4-methoxyanilino)-3-methylbutanoic acid Chemical compound COC1=CC=C(N[C@@H](C(C)C)C(O)=O)C(F)=C1 CQVOILYSLSWABZ-NSHDSACASA-N 0.000 description 3
- OLXMDPAVYCQLHY-NSHDSACASA-N (2s)-2-(4-cyanoanilino)-3-methylbutanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(C#N)C=C1 OLXMDPAVYCQLHY-NSHDSACASA-N 0.000 description 3
- IUKZSVHIWMVLEQ-NSHDSACASA-N (2s)-3-methyl-2-(2-methylanilino)butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=CC=C1C IUKZSVHIWMVLEQ-NSHDSACASA-N 0.000 description 3
- SNVLRKMZCYYEHD-JTQLQIEISA-N (2s)-3-methyl-2-(4-nitroanilino)butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1 SNVLRKMZCYYEHD-JTQLQIEISA-N 0.000 description 3
- WROFLMBQEAWZQE-JTQLQIEISA-N (2s)-3-methyl-2-[4-(trifluoromethylsulfanyl)anilino]butanoic acid Chemical compound CC(C)[C@@H](C(O)=O)NC1=CC=C(SC(F)(F)F)C=C1 WROFLMBQEAWZQE-JTQLQIEISA-N 0.000 description 3
- WGSBBUARHFQRMJ-UHFFFAOYSA-N 2-anilino-3-hydroxybutanoic acid Chemical compound CC(O)C(C(O)=O)NC1=CC=CC=C1 WGSBBUARHFQRMJ-UHFFFAOYSA-N 0.000 description 3
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- 241000219146 Gossypium Species 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
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- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
- FYQGBXGJFWXIPP-UHFFFAOYSA-N hydroprene Chemical compound CCOC(=O)C=C(C)C=CCC(C)CCCC(C)C FYQGBXGJFWXIPP-UHFFFAOYSA-N 0.000 description 1
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- 239000002949 juvenile hormone Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- UPRXAOPZPSAYHF-UHFFFAOYSA-N lithium;cyclohexyl(propan-2-yl)azanide Chemical compound CC(C)N([Li])C1CCCCC1 UPRXAOPZPSAYHF-UHFFFAOYSA-N 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 229940099990 ogen Drugs 0.000 description 1
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- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
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- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 229940108410 resmethrin Drugs 0.000 description 1
- VEMKTZHHVJILDY-FIWHBWSRSA-N resmethrin Chemical compound CC1(C)[C@H](C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-FIWHBWSRSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 150000003679 valine derivatives Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/44—Two oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
- C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77988677A | 1977-03-21 | 1977-03-21 | |
US82494777A | 1977-08-15 | 1977-08-15 | |
US824,947 | 1977-08-15 | ||
US05/878,091 US4243819A (en) | 1978-02-16 | 1978-02-16 | Substituted amino acids |
US779,886 | 1991-10-21 | ||
US878,091 | 1992-05-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1147745A true CA1147745A (en) | 1983-06-07 |
Family
ID=27419755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000298515A Expired CA1147745A (en) | 1977-03-21 | 1978-03-08 | M-phenoxy-benzyl esters of amino acids such as valine |
Country Status (14)
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3005201A1 (de) * | 1979-03-02 | 1980-09-11 | Zoecon Corp | Neue ester und thiolester von n-phenylsubstituierten valinderivaten |
DE2915026A1 (de) * | 1979-04-12 | 1980-10-30 | Bayer Ag | N,n-disubstituierte ethylglycin (thiol)ester, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide |
US4224330A (en) * | 1979-09-13 | 1980-09-23 | Zoecon Corporation | Esters and thiolesters of benzothienyl acids |
US4260633A (en) * | 1980-04-21 | 1981-04-07 | Zoecon Corporation | Pesticidal esters of amino acids |
US4259348A (en) | 1980-05-02 | 1981-03-31 | Zoecon Corporation | Pesticidal esters of amino acids |
US4267356A (en) * | 1980-06-09 | 1981-05-12 | Ciba-Geigy Corporation | Process for the preparation of N-(1'-alkoxycarbonylethyl)-2,6-dialkylanilines |
US4260782A (en) * | 1980-06-09 | 1981-04-07 | Ciba-Geigy Corporation | Process for the preparation of N-(1'-alkoxycarbonylethyl)-2,6-dialkylanilines |
JPS59110604A (ja) * | 1981-01-26 | 1984-06-26 | ザンドツ・アクチェンゲゼルシャフト | 新規な農薬組成物 |
ATE50244T1 (de) * | 1984-11-05 | 1990-02-15 | Sandoz Ag | Aminosaeureester. |
JPS62111903A (ja) * | 1985-11-11 | 1987-05-22 | Nippon Kayaku Co Ltd | 殺虫組成物 |
DE3737986A1 (de) * | 1987-11-09 | 1989-05-18 | Bayer Ag | Fluor und/oder chlor enthaltende trifluormethylaminobenzole und deren herstellung |
WO2023203038A1 (en) | 2022-04-19 | 2023-10-26 | Syngenta Crop Protection Ag | Insect, acarina and nematode pest control |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1065062B (it) * | 1975-08-08 | 1985-02-25 | Hoffmann La Roche | Esteri di acidi alfa arilossicar bossilici sostituiti |
DE2647368A1 (de) * | 1975-10-23 | 1977-05-05 | Ciba Geigy Ag | Alpha-(1-pyrrolyl)-carbonsaeure-3- phenoxy-benzylester, verfahren zu ihrer herstellung und ihre verwendung |
JPS5852987B2 (ja) * | 1976-02-17 | 1983-11-26 | 大日本除虫菊株式会社 | アニリノアセテ−ト誘導体 |
DE2753605A1 (de) * | 1976-12-01 | 1978-06-08 | Dainippon Jochugiku Kk | Isovaleriansaeureesterderivate sowie optische und geometrische isomere davon |
JP3108953B2 (ja) * | 1992-04-01 | 2000-11-13 | セイコーエプソン株式会社 | 光磁気信号検出器及び記録再生装置 |
JPH05291833A (ja) * | 1992-04-08 | 1993-11-05 | Yokogawa Electric Corp | ピーク値測定回路 |
-
1978
- 1978-03-07 GB GB9026/78A patent/GB1588111A/en not_active Expired
- 1978-03-08 CA CA000298515A patent/CA1147745A/en not_active Expired
- 1978-03-14 NZ NZ186688A patent/NZ186688A/xx unknown
- 1978-03-15 IL IL54293A patent/IL54293A/xx unknown
- 1978-03-16 AR AR271452A patent/AR221332A1/es active
- 1978-03-20 IE IE552/78A patent/IE46787B1/en not_active IP Right Cessation
- 1978-03-20 JP JP3226378A patent/JPS53121731A/ja active Granted
- 1978-03-20 FR FR7808047A patent/FR2405922A1/fr active Granted
- 1978-03-20 DE DE19782812169 patent/DE2812169A1/de active Granted
- 1978-03-20 CH CH302178A patent/CH632232A5/fr not_active IP Right Cessation
- 1978-03-21 NL NL7803030A patent/NL193021C/nl not_active IP Right Cessation
- 1978-03-21 DK DK127278A patent/DK154642C/da active Protection Beyond IP Right Term
- 1978-08-24 FR FR7824616A patent/FR2392959A1/fr not_active Withdrawn
-
1984
- 1984-06-12 KE KE3413A patent/KE3413A/xx unknown
-
1994
- 1994-02-14 BG BG098476A patent/BG60495B2/bg unknown
Also Published As
Publication number | Publication date |
---|---|
JPS53121731A (en) | 1978-10-24 |
IL54293A (en) | 1982-08-31 |
NL193021B (nl) | 1998-04-01 |
NL193021C (nl) | 1998-08-04 |
AR221332A1 (es) | 1981-01-30 |
DE2812169C2 (enrdf_load_html_response) | 1991-10-17 |
DK154642C (da) | 1989-06-19 |
DK154642B (da) | 1988-12-05 |
BG60495B2 (bg) | 1995-05-31 |
DE2812169A1 (de) | 1978-10-05 |
GB1588111A (en) | 1981-04-15 |
NZ186688A (en) | 1980-11-14 |
NL7803030A (nl) | 1978-09-25 |
DK127278A (da) | 1978-09-22 |
FR2392959A1 (fr) | 1978-12-29 |
FR2405922B1 (enrdf_load_html_response) | 1984-03-30 |
FR2405922A1 (fr) | 1979-05-11 |
IL54293A0 (en) | 1978-06-15 |
IE46787B1 (en) | 1983-09-21 |
JPS623146B2 (enrdf_load_html_response) | 1987-01-23 |
KE3413A (en) | 1984-07-13 |
CH632232A5 (en) | 1982-09-30 |
IE780552L (en) | 1978-09-21 |
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