NL8500277A - NEW PHOSPHATES AND PHOSPHONATES AND METHODS FOR PREPARING AND USING THESE COMPOUNDS. - Google Patents
NEW PHOSPHATES AND PHOSPHONATES AND METHODS FOR PREPARING AND USING THESE COMPOUNDS. Download PDFInfo
- Publication number
- NL8500277A NL8500277A NL8500277A NL8500277A NL8500277A NL 8500277 A NL8500277 A NL 8500277A NL 8500277 A NL8500277 A NL 8500277A NL 8500277 A NL8500277 A NL 8500277A NL 8500277 A NL8500277 A NL 8500277A
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- NL
- Netherlands
- Prior art keywords
- formula
- compound
- ch2ch3
- compounds
- ethyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 81
- 238000000034 method Methods 0.000 title claims description 23
- 229910019142 PO4 Inorganic materials 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title 1
- 239000000460 chlorine Chemical group 0.000 claims description 57
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 241000196324 Embryophyta Species 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 230000002363 herbicidal effect Effects 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 229910052731 fluorine Chemical group 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- -1 dinitroanilides Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000004480 active ingredient Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000012447 hatching Effects 0.000 description 7
- 238000012746 preparative thin layer chromatography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 240000006995 Abutilon theophrasti Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000207890 Ipomoea purpurea Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 241000209504 Poaceae Species 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KPJJKEJKPLBXBP-UHFFFAOYSA-N 2-chloro-n-[[chloro(ethyl)phosphoryl]methyl]-5-nitroaniline Chemical compound CCP(Cl)(=O)CNC1=CC([N+]([O-])=O)=CC=C1Cl KPJJKEJKPLBXBP-UHFFFAOYSA-N 0.000 description 2
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 2
- WYFCZWSWFGJODV-MIANJLSGSA-N 4-[[(1s)-2-[(e)-3-[3-chloro-2-fluoro-6-(tetrazol-1-yl)phenyl]prop-2-enoyl]-5-(4-methyl-2-oxopiperazin-1-yl)-3,4-dihydro-1h-isoquinoline-1-carbonyl]amino]benzoic acid Chemical compound O=C1CN(C)CCN1C1=CC=CC2=C1CCN(C(=O)\C=C\C=1C(=CC=C(Cl)C=1F)N1N=NN=C1)[C@@H]2C(=O)NC1=CC=C(C(O)=O)C=C1 WYFCZWSWFGJODV-MIANJLSGSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000219198 Brassica Species 0.000 description 2
- 240000008853 Datura stramonium Species 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000007126 N-alkylation reaction Methods 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 235000005775 Setaria Nutrition 0.000 description 2
- 241000232088 Setaria <nematode> Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 240000006394 Sorghum bicolor Species 0.000 description 2
- 235000007230 Sorghum bicolor Nutrition 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 1
- UKTZKQLYBYWWIT-UHFFFAOYSA-N (2-chloro-5-nitroanilino)methyl-ethylphosphinic acid Chemical compound CCP(O)(=O)CNC1=CC([N+]([O-])=O)=CC=C1Cl UKTZKQLYBYWWIT-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- MDTUWBLTRPRXBX-UHFFFAOYSA-N 1,2,4-triazol-3-one Chemical class O=C1N=CN=N1 MDTUWBLTRPRXBX-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 1
- WSFGOLVWRKEQOW-UHFFFAOYSA-N 2-amino-n,n-dimethylpropanamide Chemical compound CC(N)C(=O)N(C)C WSFGOLVWRKEQOW-UHFFFAOYSA-N 0.000 description 1
- KWIXNFOTNVKIGM-UHFFFAOYSA-N 2-chloro-5-nitroaniline Chemical compound NC1=CC([N+]([O-])=O)=CC=C1Cl KWIXNFOTNVKIGM-UHFFFAOYSA-N 0.000 description 1
- WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 description 1
- WTSXVIMLKCKWIW-UHFFFAOYSA-N 3h-1,3,4-oxadiazol-2-one Chemical compound O=C1NN=CO1 WTSXVIMLKCKWIW-UHFFFAOYSA-N 0.000 description 1
- HCCNBKFJYUWLEX-UHFFFAOYSA-N 7-(6-methoxypyridin-3-yl)-1-(2-propoxyethyl)-3-(pyrazin-2-ylmethylamino)pyrido[3,4-b]pyrazin-2-one Chemical compound O=C1N(CCOCCC)C2=CC(C=3C=NC(OC)=CC=3)=NC=C2N=C1NCC1=CN=CC=N1 HCCNBKFJYUWLEX-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- 241000219318 Amaranthus Species 0.000 description 1
- 240000005528 Arctium lappa Species 0.000 description 1
- 235000003130 Arctium lappa Nutrition 0.000 description 1
- 235000008078 Arctium minus Nutrition 0.000 description 1
- 235000007320 Avena fatua Nutrition 0.000 description 1
- 241000209764 Avena fatua Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000749615 Boechera canadensis Species 0.000 description 1
- 235000011331 Brassica Nutrition 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 244000178993 Brassica juncea Species 0.000 description 1
- 235000011332 Brassica juncea Nutrition 0.000 description 1
- 235000014700 Brassica juncea var napiformis Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OTECONGKECEUHO-UHFFFAOYSA-N C(C)P(=O)(CNC1=C(C=C(C(=C1)[N+](=O)[O-])F)Cl)Cl Chemical compound C(C)P(=O)(CNC1=C(C=C(C(=C1)[N+](=O)[O-])F)Cl)Cl OTECONGKECEUHO-UHFFFAOYSA-N 0.000 description 1
- DGLXNOJGOHKWTN-UHFFFAOYSA-N CCCP(O)=O Chemical compound CCCP(O)=O DGLXNOJGOHKWTN-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 244000277285 Cassia obtusifolia Species 0.000 description 1
- 235000006719 Cassia obtusifolia Nutrition 0.000 description 1
- 241000233838 Commelina Species 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- 241000192043 Echinochloa Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241001000287 Helvetia Species 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 240000007930 Oxalis acetosella Species 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- 244000088461 Panicum crus-galli Species 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000002634 Solanum Nutrition 0.000 description 1
- 241000207763 Solanum Species 0.000 description 1
- 235000000208 Solanum incanum Nutrition 0.000 description 1
- 241001506766 Xanthium Species 0.000 description 1
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical compound C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 1
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical class NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940127573 compound 38 Drugs 0.000 description 1
- 229940127271 compound 49 Drugs 0.000 description 1
- 229940126545 compound 53 Drugs 0.000 description 1
- 229940127113 compound 57 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- QXUYUOORAMVQSV-UHFFFAOYSA-N ethyl diazinane-1-carboxylate Chemical compound CCOC(=O)N1CCCCN1 QXUYUOORAMVQSV-UHFFFAOYSA-N 0.000 description 1
- SZIKRGHFZTYTIT-UHFFFAOYSA-N ethyl piperidine-2-carboxylate Chemical compound CCOC(=O)C1CCCCN1 SZIKRGHFZTYTIT-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VXGABWCSZZWXPC-UHFFFAOYSA-N methyl 2-(methylamino)acetate Chemical compound CNCC(=O)OC VXGABWCSZZWXPC-UHFFFAOYSA-N 0.000 description 1
- SBVISLHSHRMINS-UHFFFAOYSA-N methyl 2-[(2-chloro-5-nitroanilino)methyl-ethylphosphoryl]oxyacetate Chemical compound COC(=O)COP(=O)(CC)CNC1=CC([N+]([O-])=O)=CC=C1Cl SBVISLHSHRMINS-UHFFFAOYSA-N 0.000 description 1
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-M methylphosphinate Chemical compound CP([O-])=O BCDIWLCKOCHCIH-UHFFFAOYSA-M 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- NJTMPILFXWNYAH-UHFFFAOYSA-N n-carbamoyl-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC(N)=O NJTMPILFXWNYAH-UHFFFAOYSA-N 0.000 description 1
- JOWMUPQBELRFRZ-UHFFFAOYSA-N n-carbamoylformamide Chemical compound NC(=O)NC=O JOWMUPQBELRFRZ-UHFFFAOYSA-N 0.000 description 1
- GWWNCLHJCFNTJA-UHFFFAOYSA-N nicandrenone-2 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC23C)C1C3CCC2(O)C(C)C1OC(O)C2(C)OC2(C)C1 GWWNCLHJCFNTJA-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical compound COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
- A01N57/32—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/36—Amides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4403—Amides thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4407—Amides of acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
-
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/59—Hydrogenated pyridine rings
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
- C07F9/65068—Five-membered rings having the nitrogen atoms in positions 1 and 3 condensed with carbocyclic rings or carbocyclic ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
- C07F9/65306—Five-membered rings containing two nitrogen atoms
- C07F9/65312—Five-membered rings containing two nitrogen atoms having the two nitrogen atoms in positions 1 and 2
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
Landscapes
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Description
IkI
Nieuwe fosfinaten en fosfonaten en werkwijzen voor het bereiden en toepassen van deze verbindingen.Novel phosphinates and phosphonates and methods of preparing and using these compounds.
De onderhavige uitvinding heeft betrekking op nieuwe 5 5-(gesubstitueerde amino)anilinoalkyl-fosfinaten en -fosfonaten, synthesen ervan, tussenprodukten ervoor en op het gebruik van deze nieuwe verbindingen voor het bestrijden van onkruidsoorten.The present invention relates to new 5- (substituted amino) anilinoalkyl phosphinates and phosphonates, syntheses thereof, intermediates therefor and to the use of these new compounds to control weeds.
De nieuwe verbindingen volgens de uitvinding worden in het bijzonder weergegeven door formule 1, waarin 10 W een groep met formule W1, W2, W3, W4, W5 of W6, IQ N of CH, elk van de substituenten X en Y, onafhankelijk van elkaar, een waterstof- of halogeenatoom, Z 0 of NH, 15 elk van de substituenten R en Rj, onafhankelijk van elkaar, een waterstofatoom of een alkylgroep met 1-8 koolstof atomen, een alkylgroep met 1-8 koolstofatomen of een ‘ alkoxygroep met 1-8 koolstofatomen, 20 een waterstofatoom, een alkylgroep met 1-8 I koolstofatomen, een alkenylgroep met 2-8 koolstofatomen, een cycloalkylgroep met 3-8 koolstofatomen, een C^_g alkoxy- alkylgroep, een C£_g alkylthioalkylgroep, een C^_g alkoxycarbonyl- alkylgroep of een dialkylaminocarbonylalkylgroep en 25 elk van de substituenten R. , Rc, Rc , R,, R, en 4 5 5a 6 6a R^, onafhankelijk van elkaar, een waterstofatoom of een alkylgroep met 1-8 koolstofatomen voorstellen.The novel compounds of the invention are particularly represented by formula 1, wherein 10 W is a group of formula W1, W2, W3, W4, W5 or W6, IQ N or CH, each of the substituents X and Y, independently of each other , a hydrogen or halogen atom, Z 0 or NH, each of the substituents R and R 1, independently, a hydrogen atom or an alkyl group with 1-8 carbon atoms, an alkyl group with 1-8 carbon atoms or an alkoxy group with 1 -8 carbon atoms, a hydrogen atom, an alkyl group with 1-8 I carbon atoms, an alkenyl group with 2-8 carbon atoms, a cycloalkyl group with 3-8 carbon atoms, a C 1-8 alkoxyalkyl group, a C 1-8 alkylthioalkyl group, a C 1-8 alkoxycarbonylalkyl group or a dialkylaminocarbonylalkyl group and each of the substituents R, Rc, Rc, R, R, and 4 5a 6 6a R 4, independently, represent a hydrogen atom or an alkyl group of 1-8 carbon atoms.
De aanduiding "een alkenylgroep met 2-8 koolstofatomen" duidt op een alkenylgroep met een of twee dubbele 30 bindingen.The designation "an alkenyl group with 2-8 carbon atoms" refers to an alkenyl group with one or two double bonds.
De aanduiding halogeen geeft een fluor-, chloor-of broomatoom, in het bijzonder een fluor- of chlooratoom, aan.The term halogen denotes a fluorine, chlorine or bromine atom, in particular a fluorine or chlorine atom.
De uitvinding verschaft eveneens werkwijzen voor het bereiden van een verbinding met formule I, welke omvat 35 a) het bereiden van een verbinding met formule Ia, 8500277The invention also provides methods of preparing a compound of formula I, which comprises a) preparing a compound of formula Ia, 8500277
BAD ORIGINALBAD ORIGINAL
- 2 - waarin W' gekozen wordt uit de hiervoor gedefinieerde groepen W1, W2 en W4, en X, Y, R, Rj, Rg, Rg en Z de hiervoor gedefinieerde betekenissen hebben, door reaktie van een verbinding met formule II, waarin X, Y, R, Rj, Rg, Rg eh Z de hiervoor 5 gedefinieerde betekenissen hebben, met een verbinding met formulella, III of IV, waarin R^, Rg, Rg en Q de hiervoor gedefinieerde betekenissen hebben en Rg een alkylgróep met 1-5 koolstofatomen voorstelt, of b) het bereiden van een verbinding met formule Ib, 10 waarin Wf* gekozen wordt uit de groepen W2 of W3, en X, Y, R, Rj, R2> Rg en Z de hiervoor gedefinieerde betekenissen hebben, door intramolekulaire ringsluiting van een verbinding met formule V, waarin X, Y, R, Rj, R2> Rg en Z de hiervoor gedefinieerde betekenissen hebben en W'’1 gekozen wordt uit de groepen met formules 15 VI of VII waarin Q en R„ de hiervoor gedefinieerde betekenissen- 2 - wherein W 'is selected from the previously defined groups W1, W2 and W4, and X, Y, R, Rj, Rg, Rg and Z have the previously defined meanings, by reaction of a compound of formula II, wherein X , Y, R, Rj, Rg, Rg eh Z have the meanings defined above, with a compound of formulella, III or IV, wherein R ^, Rg, Rg and Q have the meanings previously defined and Rg has an alkyl group with 1- Represents 5 carbon atoms, or b) preparing a compound of formula Ib, wherein Wf * is selected from the groups W2 or W3, and X, Y, R, Rj, R2> Rg and Z have the meanings defined above, by intramolecular cyclization of a compound of formula V, wherein X, Y, R, Rj, R2> Rg and Z have the previously defined meanings and W'1 is selected from the groups of formulas VI or VII wherein Q and R'de meanings defined above
OO
hebben, of c) het bereiden van een verbinding met formule Ic, waarin X, Y, R, Rj, R2» Rg, Rg en Z de hiervoor gedefinieerde betekenissen hebben, door reaktie van een verbinding met formule 20 VIII, waarin X, Y, R, Rj, R2> Rg, Rg en Z de hiervoor gedefinieerde betekenissen hebben, met fosgeen of een reaktief funktioneel derivaat daarvan, of d) het bereiden van een verbinding met formule ld, waarin R, R., R„, R,, Rc , R, , X, Y en Z de hiervoor gedefi-1 Δ3 d a ba 25 nieerde betekenissen hebben, door reaktie van een verbinding met formule IX, waarin X, Y, R, Rj, Rg, Rg en Z de hiervoor gedefinieerde betekenissen hebben, met een verbinding met formule X, waarin R^^ een hiervoor gedefinieerde betekenisor c) preparing a compound of formula Ic, wherein X, Y, R, Rj, R 2, Rg, Rg and Z have the previously defined meanings, by reacting a compound of formula 20 VIII, wherein X, Y , R, Rj, R2> Rg, Rg and Z have the meanings defined above, with phosgene or a reactive functional derivative thereof, or d) preparing a compound of formula Id, wherein R, R., R, R, , Rc, R,, X, Y and Z have the meanings defined above-1 Δ3 da ba 25 by reaction of a compound of formula IX, wherein X, Y, R, Rj, Rg, Rg and Z have the previously defined have meanings, with a compound of formula X, wherein R ^ ^ has a previously defined meaning
NN
heeft, desgewenst gevolgd door N-alkylering van de aldus ver-30 kregen 1,2,4-triazool-5-onen op de 4-plaats.optionally followed by N-alkylation of the thus obtained 1,2,4-triazol-5-ones in the 4-position.
De reaktie volgens werkwijze a) wordt geschikt bij een temperatuur boven kamertemperatuur, bijvoorbeeld 100° C of de terugvloeitemperatuur, uitgevoerd. Indien de reaktie-deelnemer een anhydride is (een verbinding met formule II of IV), 35 wordt de reaktie geschikt in aanwezigheid van een zuur, zoals 8500277The reaction according to method a) is suitably carried out at a temperature above room temperature, for example 100 ° C or the reflux temperature. If the reaction participant is an anhydride (a compound of formula II or IV), the reaction becomes suitable in the presence of an acid, such as 8500277
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- 3 - azijnzuur, uitgevoerd, waarbij dit tevens als oplosmiddel voor de reaktie kan dienen.- 3 - acetic acid, which can also serve as a solvent for the reaction.
De intramolekulaire ringsluiting van de verbindingen met formule V volgens werkwijze b) kan onder zure omstan-W 5 digheden geschieden, bijvoorbeeld in aanwezigheid van waterstof- chloride. De verbindingen met formule V worden geschikt in deThe intramolecular cyclization of the compounds of formula V according to method b) can be effected under acidic conditions, for example in the presence of hydrogen chloride. The compounds of formula V are suitable in the
Ivorm van een zuuradditiezout in reaktie gebracht, bijvoorbeeld als hydrochloride, en in een oplosmiddel, dat onder de omstandigheden inert is, bijvoorbeeld een alkohol, zoals ethanol.An acid addition salt is reacted, for example, as hydrochloride, and in a solvent which is inert under the conditions, for example, an alcohol such as ethanol.
10 Een geschikte reaktietemperatuur ligt tussen kamertemperatuur en de terugvloeitemperatuur.A suitable reaction temperature is between room temperature and the reflux temperature.
De reaktie volgens werkwijze c) wordt geschikt uitgevoerd in een oplosmiddel dat onder de reaktieomstandigheden inert is, zoals dioxan, en bij een temperatuur boven kamertem-15 peratuur. Een reaktief, funktioneel derivaat van fosgeen dat bijzonder geschikt is om bij deze reaktie te worden toegepast is trichloormethylchloorformiaat, bij voorkeur in aanwezigheid van een organische base, zoals triethylamine.The reaction according to method c) is suitably carried out in a solvent that is inert under the reaction conditions, such as dioxane, and at a temperature above room temperature. A reactive, functional derivative of phosgene which is particularly suitable for use in this reaction is trichloromethyl chloroformate, preferably in the presence of an organic base, such as triethylamine.
De reaktie volgens werkwijze d) kan volgens de 20 methode van Gold-Aubert of modificaties daarvan worden uitge-x voerd. Een geschikt oplosmiddel is decahydronaftaleen, terwijl I een geschikte reaktietemperatuur een temperatuur boven kamer- temperatuur, bijvoorbeeld de terugvloeitemperatuur, is.The reaction according to method d) can be carried out according to the Gold-Aubert method or modifications thereof. A suitable solvent is decahydronaphthalene, while a suitable reaction temperature is a temperature above room temperature, for example the reflux temperature.
I De daarnavolgende N-alkylering kan volgens op 25 zichzelf bekende methoden geschieden. Geschikte alkylerings- I middelen zijn alkylhalogeniden met 1-8 koolstofatomen of * reaktieve, funkionele derivaten daarvan, zoals bijvoorbeeld CI^^.The subsequent N-alkylation can be carried out by methods known per se. Suitable alkylating agents are alkyl halides with 1-8 carbon atoms or reactive, functional derivatives thereof, such as, for example, C 1-4.
De verbindingen met formule I kunnen door opwerken -Γ volgens bekende methoden uit het reaktiemengsel waarin ze zijn 30 gevormd worden gewonnen.The compounds of formula I can be recovered from the reaction mixture in which they are formed by working-up according to known methods.
De verbindingen volgens de onderhavige uitvinding bezitten een of een aantal asymmetrische koolstofatomen. De onderhavige uitvinding omvat elk van de optisch aktieve isomeren en racemische mengsels daarvan. In de hiernavolgende voorbeelden 35 wordt de verbinding in de vorm van een racemisch mengsel ver- 8500277The compounds of the present invention have one or more asymmetric carbon atoms. The present invention includes any of the optically active isomers and racemic mixtures thereof. In the following Examples 35, the compound is prepared in the form of a racemic mixture. 8500277
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- 4 - kregen, tenzij anders is aangegeven.- 4 - unless stated otherwise.
Voorbeelden van geschikte reaktieschema’s voor het bereiden van verschillende verbindingen met formule II zijn weergegeven onder X op het formuleblad, waarin Hal een 5 halogeenatoom, R^' een lage alkylgroep, een waterstofatoom of een lage alkylgroep en Alk een lage alkylgroep voorstellen en X, Y, R, Rj, R^, R^ en Z de hiervoor gedefinieerde betekenissen hebben.Examples of suitable reaction schemes for preparing various compounds of formula II are shown under X on the formula sheet, where Hal represents a halogen atom, R 1 'a lower alkyl group, a hydrogen atom or a lower alkyl group, and Alk represents a lower alkyl group, and X, Y , R, Rj, R ^, R ^ and Z have the previously defined meanings.
De verbindingen met formule IX worden verkregen 10 door reaktie van een verbinding met formule II met natrium- nitriet en daarna met stannochloride in HC1 bij een temperatuur lager dan kamertemperatuur. De reaktie van verbindingen met formule IX met R^COCl in aanwezigheid van een base, zoals tri-ethylamine en een oplosmiddel , zoals methyleenchloride en 15 bij kamertemperatuur of een lagere temperatuur verschaft verbindingen met formule VIII.The compounds of formula IX are obtained by reacting a compound of formula II with sodium nitrite and then with stannous chloride in HCl at a temperature below room temperature. The reaction of compounds of formula IX with R 2 COCl in the presence of a base such as triethylamine and a solvent such as methylene chloride and at room temperature or lower temperature provides compounds of formula VIII.
De bij de hiervoor beschreven werkwijzen toegepaste uitgangsmaterialen en reagentia zijn bekend of, voor zover ze niet bekend zijn, kunnen op analoge wijze aan de hierin beschre-20 ven werkwijzen of aan bekende werkwijzen worden bereid.The starting materials and reagents used in the above-described methods are known or, if not known, can be prepared analogously to the methods described herein or to known methods.
De nieuwe verbindingen met formule I zijn bruikbaar voor het bestrijden van onkruidsoorten, onder toepassing van behandelingen voor en/of na het uitkomen. Het aanbrengen van een verbinding volgens de onderhavige uitvinding geschiedt 25 volgens gebruikelijke methoden voor de onkruidsoorten van het gebied, onder toepassing van een herbicidaal doeltreffende hoeveelheid van de verbindingen, gewoonlijk van ongeveer 100 g tot 10 kg/ha.The new compounds of formula I are useful for weed control, using treatments before and / or after hatching. Application of a compound of the present invention is by conventional methods for the weeds of the area, using a herbicidally effective amount of the compounds, usually from about 100 g to 10 kg / ha.
Het optimale gebruik van een verbinding volgens de 30 onderhavige uitvinding kan gemakkelijk door een deskundige, onder toepassing van een routineonderzoek, zoals een onderzoek in een kas of op een klein terrein, worden bepaald. In het algemeen worden echter gewoonlijk bevredigende resultaten verkregen indien de verbinding wordt aangebracht in een hoeveelheid tussen 35 ongeveer 0,1-5 kg/ha, bijvoorbeeld 0,1 of 0,33 pounds/acre).The optimal use of a compound according to the present invention can be easily determined by a person skilled in the art, using a routine examination, such as an investigation in a greenhouse or in a small area. In general, however, satisfactory results are usually obtained when the compound is applied in an amount between about 0.1-5 kg / ha (e.g. 0.1 or 0.33 pounds / acre).
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I Hoewel de verbindingen volgens de onderhavige uit vinding een werking op grasachtige onkruidsoorten uitoefenen, vertonen de verbindingen in het algemeen een grotere mate van herbicide werking op breedbladige planten. Onder·breedbladige 5 planten (onkruid) soorten waarop de verbindingen volgens de % onderhavige uitvinding een doeltreffende herbicide werking I uitoefenen vallen mosterd (Brassica spp.), melganzevoet (Amaranthus spp.), kameresdoorn (Abutilon theophrasti), doornappel (Datura stramonium), klis (Xanthium spp.), Arabis Canadensis 10 (Cassia obtusifolia) en éénjarige dagbloem (Ipomoea purpurea), doch zijn hiertoe niet beperkt.Although the compounds of the present invention exert an effect on grassy weeds, the compounds generally exhibit a greater degree of herbicidal activity on broadleaf plants. Broad-leaved plants (weeds) species on which the compounds according to the present invention exert an effective herbicidal effect I include mustard (Brassica spp.), Melgan foot (Amaranthus spp.), Room maple (Abutilon theophrasti), thorn apple (Datura stramonium), burdock (Xanthium spp.), Arabis Canadensis 10 (Cassia obtusifolia) and annual day flower (Ipomoea purpurea), but are not limited thereto.
Het het oog op hun herbicide werking met breed spektrum op breedbladige onkruidsoorten kunnen de verbindingen volgens de onderhavige uitvinding geschikt met herbiciden voor 15 grasachtige onkruidsoorten voor het met een breed spektrum bestrijden van onkruid na het uitkomen in de meeste grasachtige gewassen worden gecombineerd. Voorbeelden van herbiciden die met een verbinding volgens de onderhavige uitvinding kunnen worden gecombineerd omvatten die gekozen uit carbamaten, thio- 20 carbamaten, chlooraceetamiden, dinitroaniliden, benzoezuren, y- ... .In view of their broad spectrum herbicidal action on broadleaf weeds, the compounds of the present invention may be suitably combined with herbicides for grassy weeds for broad spectrum weed control after hatching in most grassy crops. Examples of herbicides that can be combined with a compound of the present invention include those selected from carbamates, thio-carbamates, chloroacetamides, dinitroanilides, benzoic acids, y- ....
glycerolethers, pyndazmonen, uracil- en ureumverbindingen, ter bestrijding van een breed spektrum van onkruidsoorten.glycerol ethers, pyndazmones, uracil and urea compounds, to combat a wide spectrum of weeds.
De hierin gebruikte uitdrukking "herbicide'’ duidt op een aktief bestanddeel dat de groei van planten door 25 fytotoxische of plantengroeiregulerende eigenschappen, ter vertraging van de groei van planten of het in voldoende mate schade toebrengen aan de plant waardoor deze sterft, modifi-· ceert.The term "herbicide" as used herein refers to an active ingredient that modifies the growth of plants by phytotoxic or plant growth regulating properties, to slow down the growth of plants or to cause sufficient damage to the plant causing it to die. .
I Aanbevolen verbindingen met formule 1 bezitten een 30 of een aantal van de volgende kenmerken: V is NI, W2, W3, W5 of W6, in het bijzonder W1 of W5, bij voorkeur W1, X is H, F of Cl, vooral H, Y is F, Cl, Br, vooral F of Cl, bij voorkeur Cl,Recommended compounds of formula 1 have some or all of the following characteristics: V is N1, W2, W3, W5 or W6, especially W1 or W5, preferably W1, X is H, F or Cl, especially H , Y is F, Cl, Br, especially F or Cl, preferably Cl,
35 R is H of Cj_^alkyl, vooral HR is H or C 1-4 alkyl, especially H
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- 6 - Q is CH,- 6 - Q is CH,
Rj is H of Cj_^alkyl, in het bijzonder H of Cj^alkyl, bij voorkeur Cj_3alkyl, R2 is Cj ^alkyl of Cj_^alkoxy, vooral C^^alkyl, 5 R^ is Cj_^alkyl, C^^alkenyl, Cj_^alkoxy-carbonyl-R 1 is H or C 1-6 alkyl, in particular H or C 1-6 alkyl, preferably C 1-6 alkyl, R 2 is C 1-6 alkyl or C 1-6 alkoxy, especially C 1-6 alkyl, R 1 is C 1-6 alkyl, C 1-6 alkenyl, Cj_ ^ alkoxy-carbonyl-
Cj_^.alkyl, C j^alkoxy-Cj^alkyl, C^^alkylthio-C^^alkyl, C3_g“ cycloalkyl, (di-Cj_2alkylamino)carbonyl-Cj_^alkyl, vooral Cj^alkyl, C^alkoxycarbonyl-C^alkyl of di-C^alkylamino-carbonyl-C1_2alkyl, in het bijzonder Cj^alkyl, 10 R^ is H, R^, R^, Rg en Rga» onafhankelijk van elkaar, zijn waterstof of een alkylgroep met 1-4 koolstofatomen, R^ is H of Cj_^alkyl, vooral t-C^Hg, Z is 0.C 1-4 alkyl, C 1-4 alkoxy-C 1-6 alkyl, C 1-6 alkylthio-C 1-6 alkyl, C 3-8 cycloalkyl, (di-C 12alkylamino) carbonyl-C 1-6 alkyl, especially C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-4 alkyl or di-C 1-6 alkylamino-carbonyl-C 1-2 alkyl, especially C 1-6 alkyl, R 10 is H, R 1, R 2, R 9 and R 8 independently, are hydrogen or an alkyl group of 1-4 carbon atoms, R ^ is H or C1-4 alkyl, especially tC ^ Hg, Z is 0.
1515
De verbindingen met formule I kunnen geschikt tezamen met op.landbouwgebied aanvaardbare verdunningsmiddelen als, herbicide preparaten worden toegepast. Dergelijke preparaten maken eveneens deel uit van de uitvinding. Behalve een 20 of een aantal verbindingen met formule I als aktief bestanddeel kunnen ze tevens andere aktieve middelen, zoals herbiciden, bevatten. Ze kunnen zowel in vaste als vloeibare vorm, bijvoorbeeld in de vorm van een bevochtigbaar poeder of een emul-geerbaar concentraat, waarin gebruikelijke verdunningsmiddelen 25 aanwezig zijn, worden toegepast. Dergelijke preparaten kunnen op een gebruikelijke wijze worden bereid of vervaardigd, bijvoorbeeld door het aktieve bestanddeel met een verdunnings-middel en desgewenst andere verwerkende bestanddelen, zoals oppervlakteaktieve middelen, te mengen.The compounds of the formula I can be suitably used as herbicidal compositions together with acceptable agricultural diluents. Such preparations are also part of the invention. In addition to a 20 or a number of compounds of the formula I as active ingredient, they may also contain other active agents, such as herbicides. They can be used in either solid or liquid form, for example in the form of a wettable powder or an emulsifiable concentrate, in which conventional diluents are present. Such compositions can be prepared or prepared in a conventional manner, for example, by mixing the active ingredient with a diluent and, if desired, other processing ingredients, such as surfactants.
30 De hierin gebruikte uitdrukking verdunningsmiddel duidt op elk vloeibaar of vast, voor landbouwdoeleinden geschikt, materiaal, dat aan het aktieve bestanddeel kan worden toegevoegd teneinde dit in een gemakkelijkere of verbeterde toepasbare vorm, respektievelijk in een gebruikelijke of gewenste 35 mate van aktiviteit, te brengen. Het kan bijvoorbeeld talk, 8500277The term diluent used herein refers to any liquid or solid agricultural material which can be added to the active ingredient to bring it into a more convenient or improved usable form, or a conventional or desired degree of activity, respectively. . For example, it can be talc, 8500277
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- 7 - kaoline, diatomeënaarde, xyleen of water zijn.7 - kaolin, diatomaceous earth, xylene or water.
In het bijzonder preparaten die in sproeivormen, zoals in water dispergeerbare, geconcentreerde produkten of bevochtigbare poeders, moeten worden aangebraeht, kunnen cpper-1¾ 5 vlakteaktieve middelen, zoals bevochtigende middelen of disper- igeermiddelen, bijvoorbeeld het condensatieprodukt van formaldehyde met naftaleensulfónaat, een alkylarylsulfonaat, een ligninesulfonaat, een hoger alkylsulfaat, een geethoxyleerde alkylfenol en een geethoxyleerde hogere alkohol., bevatten.In particular, preparations to be applied in spray forms, such as water-dispersible, concentrated products or wettable powders, cpper-1¾ 5 surfactants, such as wetting agents or dispersants, for example the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate a lignin sulfonate, a higher alkyl sulfate, an ethoxylated alkyl phenol, and an ethoxylated higher alcohol.
10 In het algemeen zullen in de preparaten 0,01-90 gew.% aktief bestanddeel, 0-20 gew.% van een op landbouwgebied aanvaardbaar oppervlakteaktief middel en 9.9,99-10 gew.% (vaste of vloeibare) verdunningsmiddel(en) aanwezig zijn, waarbij het aktieve bestanddeel hetzij tenminste een verbinding met formule I, 115 hetzij mengsels daarvan met andere aktieve bestanddelen^is.Generally, in the compositions will be 0.01-90 wt% active ingredient, 0-20 wt% of an agriculture acceptable surfactant, and 9.9.99-10 wt% (solid or liquid) diluent (s). the active ingredient is either at least one compound of formula I, 115 or mixtures thereof with other active ingredients.
Geconcentreerde vormen van de preparaten bevatten in het algemeen ongeveer 2-90 gew.%, bij voorkeur ongeveer 5-70 gew.%, aktief bestanddeel. De toepassingsvormen van het preparaat kunnen bijvoorbeeld 0,01-20 gew.%, bij voorkeur 0,01-5 gew.%, 20 aktief bestanddeel bevatten.Concentrated forms of the compositions generally contain about 2-90% by weight, preferably about 5-70% by weight, of the active ingredient. The use forms of the preparation may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight, of the active ingredient.
De in de hiernavolgende voorbeelden vermelde delen en percentages zijn respektievelijk gewichtsdelen en gewichts-percentages. RT is kamertemperatuur.The parts and percentages mentioned in the following examples are parts by weight and percentages by weight, respectively. RT is room temperature.
125 Preparaatvoorbeelden125 Sample Preparations
Voorbeeld A - Emulgeerbaar geconcentreerd preparaat.Example A - Emulsifiable concentrated preparation.
Men mengde 13 delen van een verbinding met formule I, 30 bijvoorbeeld het hiemavermelde voorbeeld 37, met 10 delen van een emulgator (bijvoorbeeld 5 delen Atlox 3404 F en 5 delen Atlox 8916 TF, dat mengsels van anionogene en niet-ionogene emulgatoren van ICI America zijn) en 77 delen van een organisch oplosmiddel (bijvoorbeeld xyleen of Tenneco 500-100, een mengsel 35 van trimethylbenzeen en xyleenoplosmiddelen van Tenneco Corpora- 85 0 0 2 7 713 parts of a compound of formula I, for example the example 37 mentioned above, were mixed with 10 parts of an emulsifier (for example 5 parts of Atlox 3404 F and 5 parts of Atlox 8916 TF, which are mixtures of anionic and non-ionic emulsifiers of ICI America and 77 parts of an organic solvent (for example, xylene or Tenneco 500-100, a mixture of trimethylbenzene and xylene solvents from Tenneco Corpora 85 0 0 2 7 7
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- 8 - tion), innig, totdat een homogene oplossing werd verkregen. Voorbeeld B - Bevochtigbaar poeder.- 8 - tion), intimately, until a homogeneous solution is obtained. Example B - wettable powder.
5 Men mengde 25 delen van een verbinding met formule I, bijvoorbeeld de hiernavermelde verbinding 34, 70 delen kaoline-klei, 4 delen natriumlignosulfonaat en 1 deel natriumdialkyl-naftaleensulfonaat (bijvoorbeeld Sellogen HR van Diamond Shamrock) en maalde in een hamermolen totdat de deeltjesgrootte kleiner 10 dan 325 ^u was.25 parts of a compound of formula I, for example the compound 34 mentioned below, 70 parts of kaolin clay, 4 parts of sodium lignosulfonate and 1 part of sodium dialkyl naphthalene sulfonate (for example Sellogen HR from Diamond Shamrock) were mixed and ground in a hammer mill until the particle size became smaller. 10 then 325 ^ u.
Voorbeeld C - Korrelvormig preparaat.Example C - Granular preparation.
Men loste 2 delen dipropyleenglycol op in 10 delen 15 van een vloeibare verbinding met formule I, bijvoorbeeld de hiernavermelde verbinding 38 en impregneerde het mengsel door sproeien op 88 delen van een gecalcineerde, korrelvormige attapulgietklei^ zoals Attapulgus Granular LVM van Engelhard Minerals en Chemicals.2 parts of dipropylene glycol were dissolved in 10 parts of a liquid compound of formula I, for example the compound 38 mentioned below, and the mixture was impregnated by spraying onto 88 parts of a calcined granular attapulgite clay such as Attapulgus Granular LVM from Engelhard Minerals and Chemicals.
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Verbindingen volgens de uitvinding.Compounds of the invention.
Voorbeeld 1 N-£3-(diethylfosfono-1-ethylamino)-4-chloorfeny 17~tetrahydro- 25 f taalimideExample 1 N-3- (diethylphosphono-1-ethylamino) -4-chloropheny-17-tetrahydrofalimide
Men loste 1,20 g (3,9 m.mol) diethyl l-(2-chloor-5-aminoanilino)ethylfosfonaat, op in 0,5 ml ijsazijn. Daarna voegde men 774 mg (5,1 m.mol) 3,4,5,6-tetrahydroftaalzuuranhydride 30 aan de oplossing toe en verhitte het mengsel 15 uren onder terugvloeiing. Vervolgens verwijderde men het azijnzuur en de overmaat anhydride onder verminderde druk en zuiverde het verkregen ruwe produkt door preparatieve dunnelaagchromatoagrafie, waardoor de in de titel genoemde 'verbinding (verbinding 1, tabel 35 A) werd verkregen.1.20 g (3.9 moles) of diethyl 1- (2-chloro-5-aminoanilino) ethylphosphonate were dissolved in 0.5 ml glacial acetic acid. Then 774 mg (5.1 mmol) of 3,4,5,6-tetrahydrophthalic anhydride 30 was added to the solution and the mixture was refluxed for 15 hours. The acetic acid and excess anhydride were then removed under reduced pressure and the crude product obtained was purified by preparative thin layer chromatography to obtain the title compound (Compound 1, Table 35 A).
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^Hi' Η ^ nmr (CDCl^Y 8,74 (t, 6H, P-OCH2CH3), 8,40 (d, 3H, 7 Hz, NHCH(CH3)), 8,24 (m, 4H, CH2C=CCH2), 7,64 (m, ,4H, CH2CH2), I 5,87 (m, 6H, NHCH(CHJ), £3,40 (dd, 1H), 3,32 (s, 1H), 2,75 (d, B j 1H, 8Hz) aromatische h7· ^ Voorbeeld 2 I Analoog aan de werkwijze volgens voorbeeld 1 werden de verbindingen 2-48 met formule Ie verkregen door reaktie van 10 3,4,5,6-tetrahydroftaalzuuranhydride met de overeenkomstige aminoanilinoverbinding met formule II (tabel A).^ Hi 'Η ^ nmr (CDCl ^ Y 8.74 (t, 6H, P-OCH2CH3), 8.40 (d, 3H, 7Hz, NHCH (CH3)), 8.24 (m, 4H, CH2C = CCH2), 7.64 (m, .4H, CH2CH2), I 5.87 (m, 6H, NHCH (CHJ), £ 3.40 (dd, 1H), 3.32 (s, 1H), 2, 75 (d, B j 1H, 8Hz) aromatic h7. EXAMPLE 2 I Analogous to the method of example 1, compounds 2-48 of formula Ie were obtained by reacting 3,4,5,6-tetrahydrophthalic anhydride with the corresponding aminoanilino compound of formula II (Table A).
Voorbeeld 3 3-^5-(ethyl P-methylfosfino-l-propylamino)-4-chloor-2-fluor- 115 fenyl7~l,5-tetramethyleenhydrantoine.Example 3 3- (5- (ethyl P-methylphosphino-1-propylamino) -4-chloro-2-fluoro-115-phenyl-1,5-tetramethylene-hydrantoin.
Men loste 3,2 m.mol 5-ethyl P-methyl-l-£2-chloor-4-fluor-5-(2-ethoxycarbonyl-1-hexahydropyridinylcarboxamido)-anilino/propylfosfinaat op in 15 ml ethanol. Daarna voegde men 20 aan het reaktiemengsel 20 ml 2 N zoutzuur toe en verhitte de oplossing eerst 5 uren onder terugvloeiing en daarna een nacht bij 90° C. Men verwijderde de ethanol onder verminderde druk, verdunde het verkregen residu met water en extraheerde drie I malen met methyleenchloride. De samengevoegde extrakten werden 25 gedroogd en drooggedampt. Het ruwe produkt werd gezuiverd door preparatievë dunnelaagchromatografie, waardoor de in de titel genoemde verbinding (verbinding 49) werd verkregen.3.2 moles of 5-ethyl P-methyl-1- 2-chloro-4-fluoro-5- (2-ethoxycarbonyl-1-hexahydropyridinylcarboxamido) -anilino / propylphosphinate were dissolved in 15 ml of ethanol. 20 ml of 2N hydrochloric acid were then added to the reaction mixture and the solution was first refluxed for 5 hours and then at 90 ° C overnight. The ethanol was removed under reduced pressure, the resulting residue was diluted with water and extracted three times. with methylene chloride. The combined extracts were dried and evaporated to dryness. The crude product was purified by thin layer preparative chromatography to give the title compound (compound 49).
Voorbeeld 4 I Analoog aan de werkwijze van voorbeeld 3 werden de volgende verbindingen met formule Ib bereid door intramolekulaire ringsluiting van een verbinding met formule V, waarin Rg de ethylgroep voorstelt.Example 4 Analogous to the method of Example 3, the following compounds of formula Ib were prepared by intramolecular cyclization of a compound of formula V, wherein Rg represents the ethyl group.
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Verb in- ding W' ’ X Y R Rj R2 ZR3 50 W3 Cl Cl H C2H5 CH3 OC^ 51 W3 F Cl H C2H5 CH3 OC^ 5 52 W2(Q=N) F Cl H 0£Η CH3 0C2H5Connection input W '' X Y R Rj R2 ZR3 50 W3 Cl Cl H C2H5 CH3 OC ^ 51 W3 F Cl H C2H5 CH3 OC ^ 5 52 W2 (Q = N) F Cl H 0 £ Η CH3 0C2H5
Voorbeeld 5 2- t-butyl-4-t5-methyl P-ethylfosfinomethylamino)-4-chloor-2-fluorfenyl7~ Δ ~1 ,3,4-oxadiazoline-5-on.Example 5 2-t-butyl-4-t5-methyl β-ethylphosphinomethylamino) -4-chloro-2-fluorophenyl-Δ ~ 1,3,4-oxadiazoline-5-one.
1010
Men verhitte 3,2 m.mol methyl P-ethyl-£2-chloor-4-fluor-5-(N’-pivaloylhydrazino)anilino7methylfosfinaat, 3,9 m.mol trichloormethylchloorformiaat en 3,5 m.mol triethylamine in 50 ml dioxan gedurende 3,5 uren. Daarna verwijderde men de 15 dioxan onder verminderde druk. Het produkt werd verdund met methyleenchloride, gewassen, gedroogd, drooggedampt en gezuiverd door preparatieve dunnelaagchromatografie, waardoor de in de titel genoemde verbinding (verbinding 53) werd verkregen.3.2 moles of methyl P-ethyl-2-chloro-4-fluoro-5- (N'-pivaloylhydrazino) anilino-7-methylphosphinate, 3.9 moles of trichloromethylchloroformate and 3.5 moles of triethylamine in 50 ml were heated dioxane for 3.5 hours. The dioxane was then removed under reduced pressure. The product was diluted with methylene chloride, washed, dried, evaporated to dryness and purified by preparative thin layer chromatography to obtain the title compound (compound 53).
20 Voorbeeld 6 2-t-butyl-4-/5-0nethyl P-ethyl-fosfino-l-ethylamino)-4-chloorfenyl7-2 A, -1,3,4-oxadiazoline-5-on.Example 6 2-t-butyl-4- / 5-O-ethyl P-ethyl-phosphino-1-ethylamino) -4-chlorophenyl-7-2 A, -1,3,4-oxadiazolin-5-one.
Volgens de methode van voorbeeld 5 werd een 25 mengsel van 0,62 g (1,6 m.mol)methyl P-ethyl-l-£2-chloor-5-(N'-pivaloylhydrazino)anilinq7ethylfosfinaat en 0,39 g (2,0 m.mol) · trichloormethylchloorformiaat in 8 ml-dioxan ongeveer 8 uren verhit op 60° C, waardoor, na verwijderen van het oplosmiddel en " zuiveren, de in de titel genoemde verbinding MS m/e 401 30 (M+) (verbinding 54) werd verkregen.According to the method of Example 5, a mixture of 0.62 g (1.6 mmol) of methyl P-ethyl-1-2-chloro-5- (N'-pivaloylhydrazino) anilinethylphosphinate and 0.39 g ( 2.0 m.mol) trichloromethyl chloroformate in 8 ml dioxane heated at 60 ° C for about 8 hours, whereby, after solvent removal and purification, the title compound MS m / e 401 30 (M +) ( compound 54) was obtained.
Voorbeeld 7 3- t-buty1-1-£5-(methyl P-methylfosfino-1-propylamino)-2,4-dichloor- 2 fenyl7~ Δ -1,2,4-triazoline-5-on.Example 7 3-t-butyl-1 - 5- (methyl β-methylphosphino-1-propylamino) -2,4-dichloro-2-phenyl-Δ-1,2,4-triazolin-5-one.
35 850027735 8500277
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Men verhitte een mengsel van 9,6 m.mol methyl P-methyl-l-(2,4-dichloor-5-hydrazinoanilino)-propylfosfinaat en 9,6 m.mol pivaloylureum in 12 ml decahydrohaftaleen (decaline) ongeveer 8 uren onder roeren onder terugvloeiing, volgens de 5 methode van Gold-Aubert en med., Helvetia Chimica Acta 47(5): 1188 (1964), waardoor, na zuiveren, de in de titel genoemde verbinding (verbinding 55) werd verkregen.A mixture of 9.6 moles of methyl P-methyl-1- (2,4-dichloro-5-hydrazinoanilino) propyl phosphinate and 9.6 moles of pivaloylurea in 12 ml of decahydrohaphthalene (decalin) was heated for about 8 hours under stirring under reflux, according to the method of Gold-Aubert et al., Helvetia Chimica Acta 47 (5): 1188 (1964), whereby, after purification, the title compound (compound 55) was obtained.
^ Voorbeeld 8 : 10 l-/Ï5-methyl P-ethylfosfinomethylamino)-4-chloor-2-fluorfenyl/- I A ^-1,2,4-triazoline-5-on.EXAMPLE 8: 10 1- (5-methyl β-ethylphosphinomethylamino) -4-chloro-2-fluorophenyl / -1 A -1,2,4-triazolin-5-one.
I Volgens de methode van voorbeeld 7 liet men methyl H P-ethyl(2-chloor-4-fluor-hydrazinoanilino)-methylfosfinaat |g 15 met formylureum reageren tot de in de titel genoemde verbinding (verbinding 56).According to the method of Example 7, methyl H P-ethyl (2-chloro-4-fluoro-hydrazinoanilino) -methylphosphinate 15 was reacted with formyl urea to give the title compound (compound 56).
I Voorbeeld 9 4-methyl-1-/5-(methyl-P-ethylfosfinomethylamino)-4-chloor-2-20 fluorfenyl7~A ^-1,2,4-triazoline-5-on.Example 9 4-Methyl-1- / 5- (methyl-P-ethylphosphinomethylamino) -4-chloro-2-20 fluorophenyl-7-1,2,4-triazolin-5-one.
Men voegde aan verbinding 56 3,0 m.mol methylchloride, 2,5 m.mol natriumhydride en 15 ml dimethylformamide toe. Daarna3.0 mole mole methyl chloride, 2.5 mmole sodium hydride and 15 ml dimethylformamide were added to compound 56. Afterwards
Is verhitte men het mengsel 2 uren op 80° C. Na afkoelen tot I 25 kamertemperatuur goot men het reaktiemengsel uit in water en f extraheerde met methyleenchloride. De samengevoegde extrakten I werden gewassen met water, gedroogd, drooggedampt en gezuiverd I door preparatieve dunnelaagchromatografie, waardoor men de in I de titel genoemde verbinding (verbinding 57) verkreeg.The mixture was heated at 80 ° C for 2 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted with methylene chloride. The combined extracts I were washed with water, dried, evaporated to dryness and purified by preparative thin layer chromatography to obtain the title compound (compound 57).
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-12-Tabel A-12-Table A
Verbindingen met formule IeCompounds of Formula Ie
Verbin- MS m/e ding X Y R Z ^ (M* + 1) 1 H Cl H CH3 0CH2CH3 0 CH2CH3 441 2 H Cl H CH3 CH2CH3 0 CH3 411 3 H Cl Η H CH2CH3 0 C»3 397 4 H Cl H CH2CH3 CH2CH3 0 CH3 425 5 Cl Cl H CH3 CH2CH3 0 - CH3 6 F Cl H CH3 CH2CH3 0 CH-j 7 F F H CH3 CH2CH3 0 CH3 8 Cl Br H CH3 CH2CH3 0 CH3 9 H Cl Η H CH3 0 CH2CH3 10 H Cl Η H CH2CH(CH3)2 0 CH2CH3 11 H Cl Η H CH2(CH3)2 0 CH3 12 H Cl Η H 0CH3 0 CH3 13 H Cl Η H CH2CH3 0 CH(CH3)2 14 H Cl Η H CH2CH3 ' 0 CH2CH(CH3)2 15 H Cl Η H CH2CH3 0 CH2CH2CH(CH3)2 16 H Cl Η H CH2CH3 0 CH2C(0)0CH3 17 H Cl Η H CH2CH3 0 CH(CH3)C(0)0CH2CH3 18 H Cl Η H CH3 0 CH2C(0)0CH3 19 H Cl H Of CH2CH3 O CH2C(0)0CH3 20 F Cl Η H CH2CH3 O CH2C(0)0CH3 21 H Cl Η H CH2CH3 O CH2CH=CH2 22 H Cl Η H CH2CH3 O CH2CH20CH3 23 H Cl Η H CH2CH3 O CH-CHg ch2 24 H Cl Η H CH2CH3 O CH2CH2SCH3 25 F Cl Η H CH2CH3 NH CH2CH2CH3 26 F Cl Η H CH2CH3 NH CH2CH2CH(CH3)2 27 F C1 H H CH2CH3 NH CH(CH3)C(0)N(CH3)2 8500277Connection MS m / e XYRZ ^ (M * + 1) 1 H Cl H CH3 0CH2CH3 0 CH2CH3 441 2 H Cl H CH3 CH2CH3 0 CH3 411 3 H Cl Η H CH2CH3 0 C »3 397 4 H Cl H CH2CH3 CH2CH3 0 CH3 425 5 Cl Cl H CH3 CH2CH3 0 - CH3 6 F Cl H CH3 CH2CH3 0 CH-j 7 FFH CH3 CH2CH3 0 CH3 8 Cl Br H CH3 CH2CH3 0 CH3 9 H Cl Η H CH3 0 CH2CH3 10 H Cl Η H CH2CH (CH3) 2 0 CH2CH3 11 H Cl Η H CH2 (CH3) 2 0 CH3 12 H Cl Η H 0CH3 0 CH3 13 H Cl Η H CH2CH3 0 CH (CH3) 2 14 H Cl Η H CH2CH3 '0 CH2CH (CH3) 2 15 H Cl Η H CH2CH3 0 CH2CH2CH (CH3) 2 16 H Cl Η H CH2CH3 0 CH2C (0) 0CH3 17 H Cl Η H CH2CH3 0 CH (CH3) C (0) 0CH2CH3 18 H Cl Η H CH3 0 CH2C ( 0) 0CH3 19 H Cl H Or CH2CH3 O CH2C (0) 0CH3 20 F Cl Η H CH2CH3 O CH2C (0) 0CH3 21 H Cl Η H CH2CH3 O CH2CH = CH2 22 H Cl Η H CH2CH3 O CH2CH20CH3 23 H Cl Η H CH2CH3 O CH-CHg ch2 24 H Cl Η H CH2CH3 O CH2CH2SCH3 25 F Cl Η H CH2CH3 NH CH2CH2CH3 26 F Cl Η H CH2CH3 NH CH2CH2CH (CH3) 2 27 F C1 HH CH2CH3 NH CH (CH3) C (0) N ( CH3) 2 8500277
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I* VI * V
(vervolg) Tabel A(continued) Table A
128 H Cl H CH2CH3 0CH3 0 CH3 427 29 H Cl H CH3 0CH3 0 CH3 413 30 H Cl H CH3 0CH(CH3)2 0 _ CH(CH3)2 469 ’ 31 H Cl Η H 0CH(CH3)2 0 CH(CH3)2 455 32 H Cl H CH3 CH2CH2CH3 0 CH2CH3 439 33 H Cl H CH2CH2CH3 CH2CH3 0 CH2CH3 453 34 H Cl H CH2'CH2CH3 CH3 0 c H *39 135 H Cl H CH2CH2CH3 CH3 0 CH3 5 425 36 H Cl H CH2CH2CH3 CH2CH3 0 CH3 439 37 H Cl H CH(CH3)2 CHgCH-j 0 CH3 439 38 H Cl H CH(CH3)2 CH3 0 CH3 425 39 H Cl H CH(CH3)2 CH3 0 CH2CH3 439 40 H Cl H CH(CH3)2 CH2CH3 0 CH2CH3 453 41 H Cl H CH3 CH3 0 CH3 397 42 H Cl H CH2CH3 CH3 0 CH3 411 43 H Cl H CH3 CH3 0 CH2CH3 411 44 H Cl H CH2CH3 CH3 0 CH2CH3 425 45 H Cl Η H CH2CH3 0 CH2CH3 411 46 H Cl H CH3 CH2CH3 0 CH2CH3 425 ; 47 H Cl H CH2CH3 CH2CH3 0 CH2CH3 439 148 Cl F H CH2CH3 CH3 O CH2CH3 443 8500277128 H Cl H CH2CH3 0CH3 0 CH3 427 29 H Cl H CH3 0CH3 0 CH3 413 30 H Cl H CH3 0CH (CH3) 2 0 _ CH (CH3) 2 469 '31 H Cl Η H 0CH (CH3) 2 0 CH ( CH3) 2 455 32 H Cl H CH3 CH2CH2CH3 0 CH2CH3 439 33 H Cl H CH2CH2CH3 CH2CH3 0 CH2CH3 453 34 H Cl H CH2'CH2CH3 CH3 0 c H * 39 135 H Cl H CH2CH2CH3 CH3 0 CH3 5 425 36 H Cl H CH2CH2CH3 CH2CH3 0 CH3 439 37 H Cl H CH (CH3) 2 CHgCH-j 0 CH3 439 38 H Cl H CH (CH3) 2 CH3 0 CH3 425 39 H Cl H CH (CH3) 2 CH3 0 CH2CH3 439 40 H Cl H CH (CH3) 2 CH2CH3 0 CH2CH3 453 41 H Cl H CH3 CH3 0 CH3 397 42 H Cl H CH2CH3 CH3 0 CH3 411 43 H Cl H CH3 CH3 0 CH2CH3 411 44 H Cl H CH2CH3 CH3 0 CH2CH3 425 45 H Cl Η H CH2CH3 0 CH2CH3 411 46 H Cl H CH3 CH2CH3 0 CH2CH3 425; 47 H Cl H CH2CH3 CH2CH3 0 CH2CH3 439 148 Cl F H CH2CH3 CH3 O CH2CH3 443 8500277
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VV
% - -14-% - -14-
De selektie van de verbindingen van tabel A werd door het kernspinresonantiespektrum als volgt gekarakteriseerd:The selection of the compounds of Table A was characterized by the nuclear magnetic resonance spectrum as follows:
Verbinding no.Connection no.
2 NMR (C0C13) r 7.84-9.17 (m, 12H, PCH2CH3, NHCH(CH3), CH2C=CCH2), 7.64 (m, 4H, CH2CH2), 6,25 (d, 3H, 10Hz, P0CH3), 6,30 (m, 1H, NHCH(CH3)), 5,14 (m, 1H, NH), [3,40 (dd, 1H)., 3,32 (s, 1H), 2,75 (d, 1H, 8Hz) aromatische 3 NMR (C0Cl3)r 9,00, 8,70 (tt, 3H, PCH2CH3), 8,24 (m, 4H, CH2C=CCH2), 7.64 (m, 4H, CH2CH2), 6,50 (tt, 2H, NHCHg), 6,25 (s, 3H, P0CH3), 5,37 (m, 1H, NH), [3,40 (dd, 1H, 2Hz), 3,32 (s, 1H), 2,75 (d, 1H, 8Hz) aromatische 4 NMR (C0C13) X 9,00, 8,70 (tt, 3H, PCH2CH3), 8,97 (t, 3H, NHCH(CH2 CH3)),-8,24 (m, 4H, CHgC-CCHg), 7,94 (sextet, 2H, PCHgCH-g), 7,64 (m, 4H, CH2CH2), 6,30 (m, 1H, NHCH), 6,25 (d, 3H, 10Hz, P0CH3), 5,54 (m, 1H, NH), [3,40 (dd, 1H, 2Hz), 3,32 (s, 1H), 2,75 (d, 1H, 8Hz) aromati sche 33 NMR (CDC13) X 9,07 (m, 6H, (CH2)2-CH3, P-CH2CH3), 8,68 (t, 3H, P-0CH2CH3), 8,19 (ui, 4H, CHgCHgCHg), 7,59 (m, 4H, Ct^OCCHg), 6,34 (m, 1H, NH-C.H-P), 5,87 (m, 2H, P-0CH2CH3), 5,48 (dd, 1H, NH) [3,34 (d, 1H), 3,28 (s, 1H), 2,70 (d, 1H) fenyl H].2 NMR (COCl3) r 7.84-9.17 (m, 12H, PCH2CH3, NHCH (CH3), CH2C = CCH2), 7.64 (m, 4H, CH2CH2), 6.25 (d, 3H, 10Hz, P0CH3), 6, 30 (m, 1H, NHCH (CH 3)), 5.14 (m, 1H, NH), [3.40 (dd, 1H)., 3.32 (s, 1H), 2.75 (d, 1H .8Hz) aromatic 3 NMR (C0Cl3) r 9.00, 8.70 (tt, 3H, PCH2CH3), 8.24 (m, 4H, CH2C = CCH2), 7.64 (m, 4H, CH2CH2), 6.50 (tt, 2H, NHCHg), 6.25 (s, 3H, POCH3), 5.37 (m, 1H, NH), [3.40 (dd, 1H, 2Hz), 3.32 (s, 1H) , 2.75 (d, 1H, 8Hz) aromatic 4 NMR (COCl3) X 9.00, 8.70 (tt, 3H, PCH2CH3), 8.97 (t, 3H, NHCH (CH2 CH3)), - 8 .24 (m, 4H, CHgC-CCHg), 7.94 (sextet, 2H, PCHgCH-g), 7.64 (m, 4H, CH2CH2), 6.30 (m, 1H, NHCH), 6.25 (d, 3H, 10Hz, P0CH3), 5.54 (m, 1H, NH), [3.40 (dd, 1H, 2Hz), 3.32 (s, 1H), 2.75 (d, 1H, 8Hz) aromatic 33 NMR (CDCl3) X 9.07 (m, 6H, (CH2) 2-CH3, P-CH2CH3), 8.68 (t, 3H, P-0CH2CH3), 8.19 (µL, 4H , CHgCHgCHg), 7.59 (m, 4H, Ct ^ OCCHg), 6.34 (m, 1H, NH-CH-P), 5.87 (m, 2H, P-0CH2CH3), 5.48 (dd , 1H, NH) [3.34 (d, 1H), 3.28 (s, 1H), 2.70 (d, 1H) phenyl H].
34 NMR (CDC13) V 9^,08 (t, 3H, (CH2)2-CH3), 8,72 (t, 3H, P-0CH2CH3), 8,53 (d, 3H, P-CHg), 8,20 (m, 4H, CHgCH^Hj), 7,60 (m, 4H, C^C-CCHg), 6,32 (m, 1H, NH-CH-P), 5,90 (m, 2H, P-OCHgCH^, 5,57 (dd, 1H, NH) en [3,34 (d, 1H), 3,22 (s, 1H), 2,66 (d, 1H) fenyl H]. .34 NMR (CDCl 3) V 9 ^, 08 (t, 3H, (CH 2) 2 -CH 3), 8.72 (t, 3H, P-0CH 2 CH 3), 8.53 (d, 3H, P-CHg), 8 .20 (m, 4H, CH 2 CH 2 Hj), 7.60 (m, 4H, C 1 C-CCHg), 6.32 (m, 1H, NH-CH-P), 5.90 (m, 2H, P-OCHgCH2, 5.57 (dd, 1H, NH) and [3.34 (d, 1H), 3.22 (s, 1H), 2.66 (d, 1H) phenyl H].
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I verbin- 35 NMR (CDC13) Tr 10 (t, 3H, (CH2-CH3), 8,54 {d, 3H, P-CH3), 8,20 (m, 4H, CH2-CH2-CH3), 7,60 (m, 4H, CH2C=CCH2), 6,34 (m, 1H, NHCH-P), 6,26 (d, 3H, P-OCf^), 5,60 (m, 1H, NH) en [3,3Ö (d, 1H), 3,30 (s, 1H), 2,70 (d, 1H) fenyl H].I compound 35 NMR (CDCl 3) Tr 10 (t, 3H, (CH 2 -CH 3), 8.54 {d, 3H, P-CH 3), 8.20 (m, 4H, CH 2 -CH 2 -CH 3), 7 .60 (m, 4H, CH2C = CCH2), 6.34 (m, 1H, NHCH-P), 6.26 (d, 3H, P-OCf ^), 5.60 (m, 1H, NH) and [3.3O (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].
37 NMR (CD 13) ΐ 8,92 (m, 9H, CH()2, P-CH2CH3), 7,58 (m, 4H, 6,32 (m, 1H, NH-CH-P), 6,24 (dd, 3H, P-0CH3), 5,27 (dd, 1H, NH), en [3,36 (d, 1H), 3,30 (s, 1H), 2,70 (d, 1H) fenyl H].37 NMR (CD 13) ΐ 8.92 (m, 9H, CH () 2, P-CH2CH3), 7.58 (m, 4H, 6.32 (m, 1H, NH-CH-P), 6, 24 (dd, 3H, P-0CH3), 5.27 (dd, 1H, NH), and [3.36 (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].
I’“ 38 NMR (CDC13)^ 8,90 (m, 6H, CH(CH3)2), 8,54 (d, 3H, P-CH-j), 7,59 I (m, 4H, CH^C^C-CHg), 6^,34 (m, 1H, NH-CH-P), 6.26 (d, 3H, P-OC^), 5,33 (dd, 1H, NH) en [1,34 (d, 1H), 3,30 (s, 1H), 2,70 (d, 1H) fenyl H].38 NMR (CDCl3) ^ 8.90 (m, 6H, CH (CH3) 2), 8.54 (d, 3H, P-CH-j), 7.59 I (m, 4H, CH ^) C ^ C-CHg), 6 ^, 34 (m, 1H, NH-CH-P), 6.26 (d, 3H, P-OC ^), 5.33 (dd, 1H, NH) and [1.34 (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].
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-16--16-
Tussenprodukten.Intermediates.
Voorbeeld 10Example 10
Diethyl l-(2-chloor-5-nitroanilino)ethylfosfonaat.Diethyl 1- (2-chloro-5-nitroanilino) ethyl phosphonate.
55
Men verhitte een mengsel van 1,20 g (6,9 m.mol) 2-chloor-5-nitroaniline, 1,7 ml aceetaldehyde, 3,46 g (20,8 m.mol) triethylfosfiet, 0,4 ml boriumtrifluoride in ether en 30,0 ml tolueen 2 uren onder terugvloeiing, waarna men het 10 reaktiemengsel afkoelde en uitgoot in waterige natriumbicarbonaat. Daarna extraheerde men de oplossing met ether. De ether-extrakten werden samengevoegd, gewassen met water, gedroogd en drooggedampt. Het ruwe produkt werd gezuiverd door prepara-tieve dunnelaagehromatografie, waardoor de in de titel ge-15 noemde verbinding (kristallijn) werd verkregen.A mixture of 1.20 g (6.9 mole) of 2-chloro-5-nitroaniline, 1.7 ml of acetaldehyde, 3.46 g (20.8 mole) of triethyl phosphite, 0.4 ml of boron trifluoride was heated in ether and 30.0 ml of toluene under reflux for 2 hours, after which the reaction mixture was cooled and poured into aqueous sodium bicarbonate. The solution was then extracted with ether. The ether extracts were combined, washed with water, dried and evaporated to dryness. The crude product was purified by preparative thin layer chromatography to give the title compound (crystalline).
Voorbeeld 11Example 11
Analoog aan de werkwijze van voorbeeld 10, werd 20 het uitgangsmateriaal met formule XI voor de verbindingen 2-15 en 28-48 van tabel A en voor de verbindingen 49-52 verkregen door reaktie van het overeenkomstige aniline, aldehyde en fosfiet of fosfoniet.Analogous to the procedure of Example 10, the starting material of formula XI for compounds 2-15 and 28-48 of Table A and for compounds 49-52 was obtained by reaction of the corresponding aniline, aldehyde and phosphite or phosphonite.
Op dezelfde wijze werden methyl P-ethyl-2-chloor-4-25 fluor-5-nitroanilinomethylfosfinaat (uitgangsmateriaal voor de verbindingen 20, 53, 56 en 57) en methyl P-ethyl-l-(2,4-dichloor- 5-nitroanilino)-propylfosfinaat (het uitgangsmateriaal voor verbinding 55) verkregen.Similarly, methyl P-ethyl-2-chloro-4-25 fluoro-5-nitroanilinomethylphosphinate (starting material for compounds 20, 53, 56 and 57) and methyl P-ethyl-1- (2,4-dichloro-5 nitroanilino) propyl phosphinate (the starting material for compound 55).
30 Voorbeeld 1230 Example 12
Methoxycarbonylmethyl P-ethyl-2-chloor-5-nitroanilinomethyl-fosfinaat.Methoxycarbonylmethyl P-ethyl-2-chloro-5-nitroanilinomethyl phosphinate.
Men voegde 8 ml thionylchloride toe aan methyl P-35 ethyl-2-chloor-5-nitroanilinomethylfosfinaat en liet het mengsel 85 0 0 2 7 78 ml of thionyl chloride was added to methyl P-35 ethyl-2-chloro-5-nitroanilinomethyl phosphinate and the mixture was left to 85 0 0 2 7 7
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Η een nacht staan bij kamertemperatuur. Daarna verwijderde men de overmaat thionylchloride, waardoor P-ethyl-2-chloor-5-nitro - anilinomethylfosfinezuurchloride werd verkregen. Dit zuurchloride werd behandeld met 2,0 g natriumhydroxyde in 100 ml water. Daar- 5 na zuurde men de waterige oplossing aan en extraheerde met B ether, droogde de samengevoegde etherextrakten en dampte droog, ? waardoor P-ethyl-2-chloor-5-nitroanilinomethylfosfinezuurStaan stand overnight at room temperature. The excess thionyl chloride was then removed to give P-ethyl-2-chloro-5-nitroanilinomethylphosphinic acid chloride. This acid chloride was treated with 2.0 g of sodium hydroxide in 100 ml of water. The aqueous solution was then acidified and extracted with B ether, the combined ether extracts dried and evaporated. giving P-ethyl-2-chloro-5-nitroanilinomethylphosphinic acid
Iwerd verkregen.I was obtained.
Men verhitte een mengsel van 5,59 m.mol van het 10 hiervoor genoemde fosfinezuur, 0,9 g kaliumcarbonaat, 1,2 g (0,74 ml, 7,80 m.mol) methylbroomacetaat en 20 ml aceton een nacht onder terugvloeiing. Daarna liet men het reaktiemengsel afkoelen tot kamertemperatuur en filtreerde het en concentreerde het filtraat. Het residu werd geextraheerd in methyleenchloride 15 en de samengevoegde extrakten werden gewassen, gedroogd enA mixture of 5.59 moles of the aforementioned phosphinic acid, 0.9 g of potassium carbonate, 1.2 g (0.74 ml, 7.80 moles) of methyl bromoacetate and 20 ml of acetone was heated under reflux overnight . The reaction mixture was then allowed to cool to room temperature and filtered and the filtrate concentrated. The residue was extracted into methylene chloride and the combined extracts were washed, dried and
Idrooggedampt, waardoor de in de titel genoemde verbinding werd verkregen. De uitgangsmaterialen met formule XI voor de verbindingen 1.7, .18, 19 en 20 werden op dezelfde wijze verkregen.Evaporated to dryness to give the title compound. The starting materials of formula XI for compounds 1.7, 18, 19 and 20 were obtained in the same manner.
Voorbeeld 13Example 13
Men combineerde 1,0 g P-ethyl-2-chloor-5-nitro- I anilinomethylfosfinezuurchloride, 1,3 g 2-propenyl en 10 ml 25 methyleenchloride en liet dit mengsel 2 uren staan bij kamertemperatuur, waarna men in waterig milieu opwerkte, waardoor men 2-propenyl P-ethyl-2-chloor-5-nitroanilinomethylfosfinaat verkreeg.1.0 g of P-ethyl-2-chloro-5-nitro-anilinomethylphosphinic acid chloride, 1.3 g of 2-propenyl and 10 ml of methylene chloride were combined and this mixture was allowed to stand at room temperature for 2 hours, after which it was worked up in an aqueous medium, to obtain 2-propenyl P-ethyl-2-chloro-5-nitroanilinomethyl phosphinate.
De uitgangsmaterialen met formule XI voor de ver-30 bindingen 22, 23 en 24 (tabel A) werden op dezelfde wijze I verkregen onder toepassing van respektievelijk methoxyethanol, cyclopropanol en methylthioethanol als alkohol.The starting materials of formula XI for compounds 22, 23 and 24 (Table A) were similarly obtained using methoxyethanol, cyclopropanol and methylthioethanol as alcohol, respectively.
85002778500277
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-18--18-
Voorbeeld 14Example 14
Men voegde 1,5 g P-ethyl-2-chloor-4-fluor-5-nitro-anilinomethylfosfinezuurchloride, 2,2 g irpropylamine, 2,0 g 5 triethylamine en 10 ml methyleenchloride samen en liet dit reaktiemengsel 3 uren staan bij kamertemperatuur, waarna men in waterig milieu opwerkte, waardoor men n-propyl P-ethyl-2-chloor-4-fluor-5-nitroanilinomethylfosfinamide verkreeg.1.5 g of P-ethyl-2-chloro-4-fluoro-5-nitro-anilinomethylphosphinic acid chloride, 2.2 g of irpropylamine, 2.0 g of triethylamine and 10 ml of methylene chloride were combined and this reaction mixture was left for 3 hours at room temperature and worked up in an aqueous medium to give n-propyl P-ethyl-2-chloro-4-fluoro-5-nitroanilinomethylphosphinamide.
De uitgangsmaterialen met formule XI voor de ver- 10 bindingen 26 en 27 (tabel A) werden op dezelfde wijze, onder toepassing van respektievelijk 3-methylbutylamine en l-(dimethyl-aminocarbonyl)ethylamine als amine verkregen.The starting materials of formula XI for compounds 26 and 27 (Table A) were obtained in the same manner, using 3-methylbutylamine and 1- (dimethyl-aminocarbonyl) ethylamine as amine, respectively.
Voorbeeld 15 15 Diethyl l-(2-chloor-5-aminoanilino)ethylfosfonaat.Example 15 Diethyl 1- (2-chloro-5-aminoanilino) ethyl phosphonate.
Men verhitte een mengsel van 1,74 g (5,7 m.mol) diethyl l-(2-chloor-5-nitroanilino)ethylfosfonaat, 0,30 g (5,7 m.mol) ammoniumchloride en 1,26 g (22,7 m.mol) ijzer in 20 16,0 ml ethanol en 8,0 ml water ongeveer een uur onder terug- vloeiing. Daarna werd het reaktiemengsel gefiltreerd en het filtraat werd drooggedampt. Het residu werd opgenomen in methyleenchloride, gewassen met een natriumchlorideoplossing, gedroogd en drooggedampt, waarbij na zuivering door prepara- 25 tieve dunnelaagchromatografie, de in de titel genoemde verbin ding werd verkregen.A mixture of 1.74 g (5.7 mole) of diethyl 1- (2-chloro-5-nitroanilino) ethylphosphonate, 0.30 g (5.7 mole) of ammonium chloride and 1.26 g ( 22.7 moles) iron in 16.0 ml ethanol and 8.0 ml water under reflux for about an hour. The reaction mixture was then filtered and the filtrate was evaporated to dryness. The residue was taken up in methylene chloride, washed with sodium chloride solution, dried and evaporated to give the title compound after purification by preparative thin layer chromatography.
Voorbeeld 16 30 De uitgangsmaterialen met formule II voor de ver bindingen 1-15 en 17-57 werden op analoge wijze verkregen door hydrogeneren van de overeenkomstige nitroverbinding met formule XI.Example 16 The starting materials of formula II for compounds 1-15 and 17-57 were obtained in an analogous manner by hydrogenation of the corresponding nitro compound of formula XI.
35 850027735 8500277
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-19--19-
Voorbeeld 17Example 17
Methoxycarbonylmethyl P-ethyl-2-chloor-5-amino-anilinomethyl-fosfinaat.Methoxycarbonylmethyl P-ethyl-2-chloro-5-amino-anilinomethyl phosphinate.
5 Men suspendeerde methoxycarbonylmethyl P-ethyl-2- chloor-5rnitroanilinomethylfosfinaat in 50 ml 5 % azijnzuur en voegde 2,0 g ijzerpoeder toe. Daarna verhitte men het mengsel 1 uur onder terugvloeiing. Na afkoelen tot kamertemperatuur filtreerde men het reaktiemengsel en extraheerde het 10 filtraat met methyleenchloride. De samengevoegde extrakten werden gedroogd boven magnesiumsulfaat en drooggedampt, waarna, na zuiveren door preparatieve dunnelaagchromatografie, de in de titel genoemde verbinding werd verkregen.Methoxycarbonylmethyl P-ethyl-2-chloro-5-nitroanilinomethylphosphinate was suspended in 50 ml of 5% acetic acid and 2.0 g of iron powder was added. The mixture was then heated under reflux for 1 hour. After cooling to room temperature, the reaction mixture was filtered and the filtrate was extracted with methylene chloride. The combined extracts were dried over magnesium sulfate and evaporated to dryness, after which, after purification by preparative thin layer chromatography, the title compound was obtained.
15 Voorbeeld 1815 Example 18
Ethyl P-methy1-1-/2-chloor-4-fluor-5-(2-ethoxycarbony1-1-hexa-hydropyridinylcarboxamido)anilinQ7propylfosfinaat.Ethyl P -methyl-1- / 2-chloro-4-fluoro-5- (2-ethoxycarbony1-1-hexa-hydropyridinylcarboxamido) anilinQ7propylphosphinate.
Men verhitte een mengsel van 3,2 m.mol ethyl P-methy1-20 l-(2-chloor-4-fluor-5-aminoanilino)-propylfosfinaat en 0,76 g (0,46 ml, 3,9 m.mol) trichloormethylchloorformiaat. in 50 ml dioxan en 0,36 g (0,49 ml, 3,5 m.mol) triethylamine gedurende 3 uren. Daarna verwijderde men de dioxan onder verminderde druk, waardoor men het overeenkomstige isocyanaat verkreeg, waarvan het 25 residu werd opgenomen in 35 ml methyleenchloride. Men voegde 0,754g (0,75 ml, 4,8 m.mol) ethylpipecolinaat toe en.roerde het mengsel een nacht bij kamertemperatuur. Tenslotte verdunde men het mengsel met methyleenchloride, waste met water, droogde en dampte droog, waardoor men de in de titel genoemde verbinding 30 verkreeg.A mixture of 3.2 moles of ethyl P-methyl-1-20-1- (2-chloro-4-fluoro-5-aminoanilino) -propylphosphinate and 0.76 g (0.46 ml, 3.9 m) was heated. mol) trichloromethyl chloroformate. in 50 ml of dioxane and 0.36 g (0.49 ml, 3.5 mole) of triethylamine for 3 hours. The dioxane was then removed under reduced pressure to obtain the corresponding isocyanate, the residue of which was taken up in 35 ml of methylene chloride. 0.754g (0.75ml, 4.8mol) ethyl pipecolinate was added and the mixture was stirred at room temperature overnight. Finally, the mixture was diluted with methylene chloride, washed with water, dried and evaporated to dryness to give the title compound 30.
Voorbeeld 19Example 19
Analoog aan de werkwijze van voorbeeld 18 werd het 35 uitgangsmateriaal met formule V voor de verbindingen 50, 51 en 52 85 0 0 2 77Analogous to the method of Example 18, the starting material of formula V for compounds 50, 51 and 52 was 85 0 0 2 77
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-20- verkregen door reaktie van het overeenkomstige isocyanaat met respektievelijk methylmethylaminoacetaat HCl/NiC^H^)^ en N-ethoxycarbonylhexahydropyridazine.HCl/NCC^H^)^.-20- obtained by reaction of the corresponding isocyanate with methyl methylaminoacetate HCl / NiC 2 H 3) and N-ethoxycarbonylhexahydropyridazine HCl / NCC 2 H 3), respectively.
5 Voorbeeld 205 Example 20
Methyl P-ethyl-Z2-chloor-5-fluor-5-(N,-pivaloylhydrazino)-am.linQ?-methylfosfinaat.Methyl P-ethyl-Z2-chloro-5-fluoro-5- (N, -pivaloylhydrazino) -am.linQ-methylphosphinate.
a) Men loste 3,4 m.mol methyl P-ethyl-(2-chloor-4- 10 fluor-5-aminoanilino)-methylfosfinaat op in 10 ml 6 N zoutzuur.a) 3.4 moles of methyl P-ethyl- (2-chloro-4-10 fluoro-5-aminoanilino) methylphosphinate were dissolved in 10 ml 6N hydrochloric acid.
De temperatuur van de oplossing werd tussen -15 en -20° C gehouden wanneer 0,24 g (3,5 m.mol) natriumnitriet in 2 ml water werd toegedruppeld. Het mengsel werd verwarmd tot 0° C en 1 uur bij 0° C geroerd. Daarna voegde men snel een met ijs gekoelde 15 oplossing van stannochloride.2 H^O in 2 ml geconcentreerd zoutzuur aan het mengsel toe en roerde nog 2,5 uren bij 0° C.The temperature of the solution was kept between -15 and -20 ° C when 0.24 g (3.5 moles) of sodium nitrite were added dropwise into 2 ml of water. The mixture was heated to 0 ° C and stirred at 0 ° C for 1 hour. An ice-cooled solution of stannous chloride. 2 H 2 O in 2 ml of concentrated hydrochloric acid was then quickly added to the mixture and stirred at 0 ° C for an additional 2.5 hours.
Het reaktiemengsel werd geneutraliseerd met verzadigde natriumbicarbonaat en met een methyleenchloride geextraheerd. De samengevoegde extrakten- werden gewassen met water, gedroogd, 20 drooggedampt en gezuiverd door preparatieve dunnelaagchromato-grafie, waardoor methyl P-ethyl-(2-chloor-4-fluor-5-hydrazino-anilino)-methylfosfinaat werd verkregen.The reaction mixture was neutralized with saturated sodium bicarbonate and extracted with methylene chloride. The combined extracts were washed with water, dried, evaporated to dryness and purified by preparative thin layer chromatography to give methyl P-ethyl (2-chloro-4-fluoro-5-hydrazino-anilino) -methylphosphinate.
b) Aan het hiervoor genoemde fosfinaat (2,5 m.mol) 25 in 10 ml methyleenchloride werd 3,0 m.mol pivaloylchloridé en 3,0 m.mol triethylamine toegevoegd. Het mengsel werd 4 uren geroerd bij kamertemperatuur, waarna het werd gewassen met water, gedroogd en drooggedampt, waardoor de in de titel genoemde verbinding werd verkregen.b) To the aforementioned phosphinate (2.5 mole) 25 in 10 ml methylene chloride, 3.0 mole pivaloyl chloride and 3.0 mole triethylamine were added. The mixture was stirred at room temperature for 4 hours, after which it was washed with water, dried and evaporated to give the title compound.
30 Het uitgangsmateriaal met formule VIII voor verbin ding 54 werd op analoge wijze verkregen. Het uitgangsmateriaal met formule IX voor de verbindingen 55, 56 en 57 werd analoog aan de werkwijze van voorbeeld 20a) verkregen.The starting material of formula VIII for compound 54 was obtained in an analogous manner. The starting material of formula IX for compounds 55, 56 and 57 was obtained analogous to the method of example 20a).
35 850027735 8500277
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I, «* iI, «* i
Beoordeling van de herbicide werking.Assessment of the herbicidal action.
Voorbeeld 21 5 De herbicide werking voor het uitkomen van gekozen I verbindingen volgens de onderhavige uitvinding werd als volgt | bepaald: Zaden van gekozen onkruidsoorten werden geplant en de aarde werd gedrenkt met een oplossing van water (17 %), oppervlakteaktief middel (0,17 %) en de te onderzoeken verbin-i 10 ding in een hoeveelheid equivalent aan 1,12 g/m^. De beoor- ! deling geschiedde twee weken na de behandeling. De grassoorten (GR) Setaria vividis, Echinochloa, crus-galli, Sorghum bicolor en Avena fatua en de breedbladige gewassen (BL) Ipomoea purpurea, IBrassica juncea, . Solanum spp. en Abutilon theophrasti werden 15 behandeld. De gemiddelde werking voor het uitkomen van de verbindingen is weergegeven in de hiernavolgende tabel B.Example 21 The herbicidal action for hatching of selected I compounds of the present invention was as follows determined: Seeds of selected weeds were planted and the soil was soaked with a solution of water (17%), surfactant (0.17%) and the compound to be tested in an amount equivalent to 1.12 g / m ^. The evaluation! division occurred two weeks after treatment. The grasses (GR) Setaria vividis, Echinochloa, crus-galli, Sorghum bicolor and Avena fatua and the broadleaf crops (BL) Ipomoea purpurea, IBrassica juncea,. Solanum spp. and Abutilon theophrasti were treated. The average performance for hatching of the compounds is shown in Table B below.
Voorbeeld 22 t i ! 20 De herbicide werking na het uitkomen van gekozen verbindingen werd als volgt bepaald: Zaailingen van gekozen onkruidsoorten werden besproeid met een oplossing van een I mengsel van gelijke delen water en aceton, oppervlakteaktief middel (0,5 %) en de te onderzoeken verbinding in een hoeveel-25 heid equivalent aan 1,12 g/m^. De beoordeling geschiedde 2 ' weken na het sproeien. De grassoorten (GR) Setaria vividis,Example 22 t i! The herbicidal activity after hatching of selected compounds was determined as follows: Seedlings of selected weeds were sprayed with a solution of a mixture of equal parts water and acetone, surfactant (0.5%) and the test compound in a amount equivalent to 1.12 g / m 2. The evaluation was made 2 weeks after spraying. The grass species (GR) Setaria vividis,
Echinochloa crus-galli, Sorghum bicolor*lfiPin:eedbladige gewassen (BL) Ipomoea purpurea, Brassica juncea, glycine max en Abutilon theophrasti werden onderzocht. De gemiddelde werking 30 na het uitkomen van de verbindingen is weergegeven in de hierna-I volgende tabel B.Echinochloa crus-galli, Sorghum bicolor * lfiPin: oval-leaved crops (BL) Ipomoea purpurea, Brassica juncea, glycine max and Abutilon theophrasti. The average activity 30 after hatching of the compounds is shown in Table B below.
35 850027735 8500277
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22
-22-Tabel B-22-Table B
het percentage herbicide werking bij 1,12 g/m 5 voor het uitkomen na het uitkomenthe percentage of herbicidal activity at 1.12 g / m 5 before hatching
verbinding GR_BL GR_BLconnection GR_BL GR_BL
4 100 100 95 100 32 100 100 96 100 10 33 100 100 100 100 34 100 100 91 100 35 100 100 91 100 37 100 100 100 100 38 100 100 95 100 15 39 100 100 100 100 40 100 100 100 100 42 100 100 100 100 43 100 100 98 100 1 S 5 0 ö 2 7 74 100 100 95 100 32 100 100 96 100 10 33 100 100 100 100 34 100 100 91 100 35 100 100 91 100 37 100 100 100 100 38 100 100 95 100 15 39 100 100 100 100 40 100 100 100 100 42 100 100 100 100 43 100 100 98 100 1 S 5 0 ö 2 7 7
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Claims (7)
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US57974984A | 1984-02-13 | 1984-02-13 | |
US57974984 | 1984-02-13 |
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JP (1) | JPS60188392A (en) |
AU (1) | AU3860185A (en) |
BE (1) | BE901697A (en) |
BR (1) | BR8500621A (en) |
CS (1) | CS250679B2 (en) |
DE (1) | DE3504051A1 (en) |
DK (1) | DK62785A (en) |
FR (1) | FR2559489A1 (en) |
GB (1) | GB2154239A (en) |
HU (1) | HUT39335A (en) |
IL (1) | IL74299A0 (en) |
IT (1) | IT1199944B (en) |
NL (1) | NL8500277A (en) |
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EP0078536A3 (en) * | 1981-11-02 | 1983-07-27 | Sandoz Ag | Phosphinates and phosphonates and their use in the control of weeds |
AU557324B2 (en) * | 1981-12-25 | 1986-12-18 | Sumitomo Chemical Company, Limited | Tetrahydro phthalimide compounds |
HUT36688A (en) * | 1983-07-29 | 1985-10-28 | Sandoz Ag | Herbicide containing phenoxi-alkyl-phosphinate- and phenoxi-alkyl-phosphonate-derivatives as agent and process for the production of the agents |
-
1985
- 1985-02-01 HU HU85395A patent/HUT39335A/en unknown
- 1985-02-01 NL NL8500277A patent/NL8500277A/en not_active Application Discontinuation
- 1985-02-07 FR FR8501872A patent/FR2559489A1/en not_active Withdrawn
- 1985-02-07 DE DE19853504051 patent/DE3504051A1/en not_active Withdrawn
- 1985-02-11 GB GB08503485A patent/GB2154239A/en not_active Withdrawn
- 1985-02-11 AU AU38601/85A patent/AU3860185A/en not_active Abandoned
- 1985-02-11 PT PT79948A patent/PT79948B/en unknown
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- 1985-02-11 DK DK62785A patent/DK62785A/en not_active Application Discontinuation
- 1985-02-11 IL IL74299A patent/IL74299A0/en unknown
- 1985-02-12 JP JP60026141A patent/JPS60188392A/en active Pending
- 1985-02-12 CS CS85990A patent/CS250679B2/en unknown
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DE3504051A1 (en) | 1985-08-14 |
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BR8500621A (en) | 1985-09-24 |
GB8503485D0 (en) | 1985-03-13 |
GB2154239A (en) | 1985-09-04 |
DK62785D0 (en) | 1985-02-11 |
CS250679B2 (en) | 1987-05-14 |
BE901697A (en) | 1985-08-12 |
ZA851089B (en) | 1986-09-24 |
IT1199944B (en) | 1989-01-05 |
HUT39335A (en) | 1986-09-29 |
IT8547657A0 (en) | 1985-02-08 |
IT8547657A1 (en) | 1986-10-18 |
DK62785A (en) | 1985-08-14 |
IL74299A0 (en) | 1985-05-31 |
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AU3860185A (en) | 1985-08-22 |
PT79948A (en) | 1985-03-01 |
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