EP0596963A1 - VERFAHREN UND ZWISCHENPRODUKTE ZUR HERSTELLUNG VON SUBSTITUIERTEN 6-(3,5,6,7-TETRAHYDROPYRROLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONEN - Google Patents
VERFAHREN UND ZWISCHENPRODUKTE ZUR HERSTELLUNG VON SUBSTITUIERTEN 6-(3,5,6,7-TETRAHYDROPYRROLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONENInfo
- Publication number
- EP0596963A1 EP0596963A1 EP92916316A EP92916316A EP0596963A1 EP 0596963 A1 EP0596963 A1 EP 0596963A1 EP 92916316 A EP92916316 A EP 92916316A EP 92916316 A EP92916316 A EP 92916316A EP 0596963 A1 EP0596963 A1 EP 0596963A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- general formula
- fluoro
- radical
- alkyl radical
- benzoxazin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000013067 intermediate product Substances 0.000 title 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- -1 [1,2,4] -thiadiazol-3-ylidenamino Chemical group 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- FLLSVYRURBJWRO-UHFFFAOYSA-N 1-iminothiadiazole Chemical compound N=S1N=NC=C1 FLLSVYRURBJWRO-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical class OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- AHFWKTKIRQCWCQ-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrol-5-amine Chemical class NC1=CCCN1 AHFWKTKIRQCWCQ-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 abstract 1
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UFHAERUEUDENGS-UHFFFAOYSA-N 2-(2-acetamido-4-amino-5-fluorophenoxy)acetic acid Chemical class CC(=O)NC1=CC(N)=C(F)C=C1OCC(O)=O UFHAERUEUDENGS-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OOYHSZQSVUROMJ-UHFFFAOYSA-N 2-(2-acetamido-5-fluoro-4-nitrophenoxy)acetic acid Chemical compound CC(=O)NC1=CC([N+]([O-])=O)=C(F)C=C1OCC(O)=O OOYHSZQSVUROMJ-UHFFFAOYSA-N 0.000 description 2
- OODQURJJHQBUFM-UHFFFAOYSA-N 2-(2-acetamido-5-fluorophenoxy)acetic acid Chemical compound CC(=O)NC1=CC=C(F)C=C1OCC(O)=O OODQURJJHQBUFM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- OAEVUYAHUJWFTL-UHFFFAOYSA-N ethyl 2-[2-acetamido-4-[(6,6-dimethyl-5,7-dihydropyrrolo[2,1-c][1,2,4]thiadiazol-3-ylidene)amino]-5-fluorophenoxy]acetate Chemical compound C(C)OC(COC1=C(C=C(C(=C1)F)N=C1N2C(=NS1)CC(C2)(C)C)NC(C)=O)=O OAEVUYAHUJWFTL-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- NDTHRWDAUORQSQ-UHFFFAOYSA-N n-(4-fluoro-2-hydroxyphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(F)C=C1O NDTHRWDAUORQSQ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 2
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QXEBVQYRXDLQEY-UHFFFAOYSA-N 2-(2-acetamido-5-fluoro-4-isothiocyanatophenoxy)acetic acid Chemical compound CC(=O)NC1=CC(N=C=S)=C(F)C=C1OCC(O)=O QXEBVQYRXDLQEY-UHFFFAOYSA-N 0.000 description 1
- OHDQHPUGOMHBGZ-UHFFFAOYSA-N 2-(5-fluoro-2-nitrophenoxy)acetic acid Chemical compound OC(=O)COC1=CC(F)=CC=C1[N+]([O-])=O OHDQHPUGOMHBGZ-UHFFFAOYSA-N 0.000 description 1
- HEZCMZOIKKKUPG-UHFFFAOYSA-N 2-[2-acetamido-4-[(6,6-dimethyl-5,7-dihydropyrrolo[2,1-c][1,2,4]thiadiazol-3-ylidene)amino]-5-fluorophenoxy]acetic acid Chemical compound C(C)(=O)NC1=C(OCC(=O)O)C=C(C(=C1)N=C1N2C(=NS1)CC(C2)(C)C)F HEZCMZOIKKKUPG-UHFFFAOYSA-N 0.000 description 1
- IIDUNAVOCYMUFB-UHFFFAOYSA-N 2-amino-5-fluorophenol Chemical compound NC1=CC=C(F)C=C1O IIDUNAVOCYMUFB-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- UMTAYFACVDWHNP-UHFFFAOYSA-N 3,3-dimethyl-2,4-dihydropyrrol-5-amine;methyl hydrogen sulfate Chemical compound COS(O)(=O)=O.CC1(C)CN=C(N)C1 UMTAYFACVDWHNP-UHFFFAOYSA-N 0.000 description 1
- SPAMRUYRVYMHPV-UHFFFAOYSA-N 3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical class C1=CCCC2C(=O)NC(=O)C21 SPAMRUYRVYMHPV-UHFFFAOYSA-N 0.000 description 1
- QRCGFTXRXYMJOS-UHFFFAOYSA-N 4h-1,4-benzoxazin-3-one Chemical compound C1=CC=C2NC(=O)COC2=C1 QRCGFTXRXYMJOS-UHFFFAOYSA-N 0.000 description 1
- LWMAFJZTZAMNGG-UHFFFAOYSA-N 6-amino-7-fluoro-4h-1,4-benzoxazin-3-one Chemical compound N1C(=O)COC2=C1C=C(N)C(F)=C2 LWMAFJZTZAMNGG-UHFFFAOYSA-N 0.000 description 1
- LREXGCZCUDIQBO-UHFFFAOYSA-N 7-fluoro-4h-1,2-benzoxazin-3-one Chemical class C1C(=O)NOC2=CC(F)=CC=C21 LREXGCZCUDIQBO-UHFFFAOYSA-N 0.000 description 1
- AMGHIXJIXQAGFA-UHFFFAOYSA-N CCC(C(=O)O)OC1=C(C=C(C(=C1)F)N)NC(=O)C Chemical compound CCC(C(=O)O)OC1=C(C=C(C(=C1)F)N)NC(=O)C AMGHIXJIXQAGFA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- XICDQDGOZAJHQD-UHFFFAOYSA-N O1CC(=O)NC2=C1C=C(F)C(N=C1N3CCCC3=NS1)=C2 Chemical class O1CC(=O)NC2=C1C=C(F)C(N=C1N3CCCC3=NS1)=C2 XICDQDGOZAJHQD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- LXHDTIJGOQAZSC-UHFFFAOYSA-N ethyl 2-(2-acetamido-5-fluoro-4-nitrophenoxy)acetate Chemical compound CCOC(=O)COC1=CC(F)=C([N+]([O-])=O)C=C1NC(C)=O LXHDTIJGOQAZSC-UHFFFAOYSA-N 0.000 description 1
- NVAGNZZHZGRPMF-UHFFFAOYSA-N ethyl 2-(2-acetamido-5-fluorophenoxy)acetate Chemical compound CCOC(=O)COC1=CC(F)=CC=C1NC(C)=O NVAGNZZHZGRPMF-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
Definitions
- the invention relates to a new process and new intermediates for the preparation of substituted 6- (3,5,6,7-tetrahydropyrrolo [2,1-c] [1,2,4] - thiadiazol-3-ylidenamino) -7-fluorine -2H-1,4-benzoxazin-3 (4H) -ones of the general formula I.
- R is a C 1 -C 6 alkyl radical, a C 2 -C 6 alkenyl radical or a C 3 -C 6 alkynyl radical,
- R 2 is a hydrogen atom or a C 1 -C 4 alkyl radical
- R 3 is a hydrogen atom or a C 1 -C 4 alkyl radical
- the object of the present invention is to provide a new process which enables the compounds of the general formula I to be prepared without problems under mild reaction conditions.
- R 4 is hydrogen or a C 1 -C 4 alkyl radical, with a compound of the general
- W represents chlorine, bromine, iodine, the p-toluenesulfonyloxy radical or the methanesulfonyloxy radical, optionally with the addition of a base in a suitable solvent.
- Process stage A) is expediently carried out in such a way that the 2- (2-acetamino-4-amino-5-fluorophenoxy) acetic acid derivatives in a suitable solvent, optionally with the addition of an inorganic or organic base or a mineral acid at temperatures between 0 and 50 ° C are reacted.
- the reaction can optionally also be carried out in a two-phase mixture with water and a water-immiscible organic solvent, if appropriate with the addition of a phase transfer catalyst.
- Alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates or bicarbonates, tertiary aliphatic amines and heterocyclic bases can be used as bases.
- bases include sodium and potassium hydroxide, sodium and potassium hydrogen carbonate, calcium carbonate, triethylamine and pyridine.
- Suitable solvents are hydrocarbons such as toluene, chlorinated hydrocarbons such as methylene chloride or chloroform, ethers such as diethyl ether or tetrahydrofuran, ketones such as butanone or methyl isobutyl ketone, or water.
- the 2- (2-acetamino-5-fluoro-4-isothiocyanatphenoxy) acetic acid derivatives obtained are new and also a subject of this invention.
- Process stage B) is expediently carried out in such a way that the reactants are used in an inert solvent such as ether, methylene chloride, chloroform or ethyl acetate at a temperature of -50 ° C. and + 50 ° C., optionally with the addition of an inorganic or organic base Response.
- an inert solvent such as ether, methylene chloride, chloroform or ethyl acetate
- an inert solvent such as ether, methylene chloride, chloroform or ethyl acetate
- an inorganic or organic base Response optionally with the addition of an inorganic or organic base Response.
- the reaction time is 0.5 to 10 hours.
- R 2 , R 3 and R 4 independently of one another are hydrogen or a C 1 -C 4 -
- Alkyl radicals are thermally unstable and are therefore preferably reacted further without isolation in the next reaction. Ring formation is carried out using an oxidizing agent in an organic solvent.
- Inert solvents such as methylene chloride, chloroform, N, N-dimethylformamide or ethyl acetate are suitable as organic solvents.
- the condensation reaction with ring formation can be carried out in the presence of acid acceptors, depending on the type of oxidizing agent.
- Organic bases such as triethylamine, pyridine, dimethylaniline, inorganic bases, such as sodium hydroxide or sodium carbonate, are suitable as acid acceptors.
- Bromine, chlorine or sodium hypochlorite or others can be used as the oxidizing agent.
- the compounds of the general formula V can also be used as a salt.
- the iminothiadiazole derivatives of the formula VI obtained are new and also a subject of the invention.
- Process step C) is expediently carried out in such a way that the starting materials are reacted in a suitable solvent, optionally with the addition of an inorganic or organic base, at temperatures between -10 ° C. and 150 ° C.
- the reaction can also be carried out with the addition of a phase transfer catalyst in a two-phase system with water.
- Alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates or bicarbonates, alkali metal hydrides, tertiary aliphatic amines and heterocyclic bases can be used as bases.
- bases include sodium and potassium hydroxide, sodium and potassium hydrogen carbonate, sodium hydride, triethylamine and pyridine.
- the solvents used are hydrocarbons, such as toluene, chlorinated hydrocarbons, such as methylene chloride or chloro form, ethers, such as, for example, diethyl ether or tetrahydrofuran, ketones, such as, for example, acetone, butanone or methyl isobutyl ketone, amides, such as, for example, dimethylformamide or else nitriles, such as, for example, acetonitrile.
- hydrocarbons such as toluene
- chlorinated hydrocarbons such as methylene chloride or chloro form
- ethers such as, for example, diethyl ether or tetrahydrofuran
- ketones such as, for example, acetone, butanone or methyl isobutyl ketone
- amides such as, for example, dimethylformamide or else nitriles, such as, for example, acetonitrile.
- Process stage D) is expediently carried out in such a way that the starting materials are reacted in a suitable solvent, optionally with the addition of an inorganic or organic base, at temperatures between -10 ° C. and 160 ° C.
- the reaction can also be carried out with the addition of a phase transfer catalyst in a two-phase system with water.
- Alkali and alkaline earth metal hydroxides alkali and alkaline earth metal carbonates or bicarbonates, alkali metal hydroxides, tert. aliphatic amines and heterocyclic bases are used.
- Examples include sodium and potassium hydrogen carbonate, sodium hydride, triethylamine and
- Hydrocarbons such as toluene, chlorinated hydrocarbons such as methylene chloride or come as solvents
- Chloroform Chloroform, ethers, such as, for example, diethyl ether or tetrahydrofuran, ketones, such as, for example, acetone, butanone or methyl isobutdyl ketone, amides, such as, for example, dimethylformamide or also nitriles, such as, for example, acetonitrile.
- ethers such as, for example, diethyl ether or tetrahydrofuran
- ketones such as, for example, acetone, butanone or methyl isobutdyl ketone
- amides such as, for example, dimethylformamide or also nitriles, such as, for example, acetonitrile.
- ethyl 2- (2-acetylamino-4-amino-5-fluorophenoxy) acetic acid are dissolved in 1500 ml of ethyl acetate and 72.8 g of sodium hydrogen carbonate are added.
- 49.8 g of thiophosgene are added dropwise to the solution, which is cooled to 0.degree. C., and the mixture is stirred for a further hour at this temperature.
- the mixture is allowed to come to room temperature, the precipitated salts are filtered off with suction and washed the filter cake 2 times with 100 ml of ethyl acetate.
- the filtrate is concentrated in vacuo and the residue is recrystallized from 200 ml of ethyl acetate.
- the phases are separated and the aqueous phase is shaken out with 100 ml of dichloromethane.
- the combined organic phases are washed with 250 ml of 10% potassium bicarbonate solution and with 200 ml of water.
- the solvent is distilled off in vacuo, the oily residue is crystallized out in ethanol.
- the crystals are dried in vacuo.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914125246 DE4125246C1 (enrdf_load_stackoverflow) | 1991-07-26 | 1991-07-26 | |
| DE4125246 | 1991-07-26 | ||
| PCT/DE1992/000606 WO1993003043A1 (de) | 1991-07-26 | 1992-07-22 | VERFAHREN UND ZWISCHENPRODUKTE ZUR HERSTELLUNG VON SUBSTITUIERTEN 6-(3,5,6,7-TETRAHYDROPYRROLO[2,1-c][1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONEN |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0596963A1 true EP0596963A1 (de) | 1994-05-18 |
Family
ID=6437332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92916316A Withdrawn EP0596963A1 (de) | 1991-07-26 | 1992-07-22 | VERFAHREN UND ZWISCHENPRODUKTE ZUR HERSTELLUNG VON SUBSTITUIERTEN 6-(3,5,6,7-TETRAHYDROPYRROLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONEN |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0596963A1 (enrdf_load_stackoverflow) |
| JP (1) | JPH06509345A (enrdf_load_stackoverflow) |
| DE (1) | DE4125246C1 (enrdf_load_stackoverflow) |
| PT (1) | PT100727A (enrdf_load_stackoverflow) |
| WO (1) | WO1993003043A1 (enrdf_load_stackoverflow) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8669208B2 (en) | 2010-10-01 | 2014-03-11 | Basf Se | Herbicidal benzoxazinones |
| CA3080276A1 (en) | 2017-11-23 | 2019-05-31 | Basf Se | Herbicidal pyridylethers |
| US20200305429A1 (en) | 2017-11-23 | 2020-10-01 | Basf Se | Herbicidal phenylethers |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4640707A (en) * | 1984-07-23 | 1987-02-03 | Sumitomo Chemical Company, Ltd. | Tetrahydrophthalimides and their herbicidal use |
| US4755217A (en) * | 1987-01-15 | 1988-07-05 | Fmc Corporation | Triazinedione herbicides |
| US4734124A (en) * | 1987-01-15 | 1988-03-29 | Fmc Corporation | Tetrazolinone herbicides |
| US4877444A (en) * | 1987-08-27 | 1989-10-31 | Sumitomo Chemical Company, Limited | Tetrahydroindazolyl-benzoxazines and use |
| DE3734745A1 (de) * | 1987-10-09 | 1989-04-20 | Schering Ag | Tetrahydropyrrolo(2,1-c)(1,2,4)-thiadiazol-3-ylideniminobenzoxazinone und andere heterocyclisch substituierte azole und azine, verfahren zu ihrer herstellung und ihre verwendung als mittel mit herbizider wirkung |
| CA2026960A1 (en) * | 1989-10-12 | 1991-04-13 | Masayuki Enomoto | Benzoxazinyl-pyrazoles, and their production and use |
| EP0448188A3 (en) * | 1990-03-15 | 1992-02-26 | Schering Aktiengesellschaft | Process and intermediates for the preparation of substituted 6-(3,5,6,7-tetrahydropyrrolo-(2,1-c)(1,2,4)-thiadiazol-3-ylidenimino)-7-fluoro-2h-1,4-benzoxazin-3(4h)-ones |
-
1991
- 1991-07-26 DE DE19914125246 patent/DE4125246C1/de not_active Expired - Lifetime
-
1992
- 1992-07-22 WO PCT/DE1992/000606 patent/WO1993003043A1/de not_active Application Discontinuation
- 1992-07-22 EP EP92916316A patent/EP0596963A1/de not_active Withdrawn
- 1992-07-22 JP JP5503172A patent/JPH06509345A/ja active Pending
- 1992-07-24 PT PT10072792A patent/PT100727A/pt not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9303043A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06509345A (ja) | 1994-10-20 |
| DE4125246C1 (enrdf_load_stackoverflow) | 1993-02-04 |
| WO1993003043A1 (de) | 1993-02-18 |
| PT100727A (pt) | 1993-10-29 |
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