DE2125476A1 - Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agents - Google Patents
Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agentsInfo
- Publication number
- DE2125476A1 DE2125476A1 DE19712125476 DE2125476A DE2125476A1 DE 2125476 A1 DE2125476 A1 DE 2125476A1 DE 19712125476 DE19712125476 DE 19712125476 DE 2125476 A DE2125476 A DE 2125476A DE 2125476 A1 DE2125476 A1 DE 2125476A1
- Authority
- DE
- Germany
- Prior art keywords
- perfluoro
- diazahexa
- diene
- trifluoromethylimino
- oxy
- 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.)
- Pending
Links
- -1 trifluoromethylimino Chemical group 0.000 title claims description 51
- 230000002363 herbicidal effect Effects 0.000 title description 2
- 239000011814 protection agent Substances 0.000 title 1
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- NLYNXIKSYNMTLF-UHFFFAOYSA-N N,N'-bis(trifluoromethyl)ethanediimidoyl difluoride Chemical compound FC(F)(F)N=C(F)C(F)=NC(F)(F)F NLYNXIKSYNMTLF-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 abstract description 2
- 125000003341 7 membered heterocyclic group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000012442 inert solvent Substances 0.000 abstract 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 235000013024 sodium fluoride Nutrition 0.000 description 9
- 239000011775 sodium fluoride Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 125000002577 pseudohalo group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
Trifluorme thyliminove rbindungen Die Erfindung betrifft neue Trifluormethyliminoverbindungen sowie ein Verfahren zu ihrer Herstellung.Trifluoromethylimino compounds The invention relates to new trifluoromethylimino compounds and a method for their production.
Ea wurde gefunden, daß man neue Trifluormethyliminoverbindungen erhält, wenn man 1 Mol Perfluor-2,5-diazahexa-2,4-dien mit einer Verbindung der allgemeinen Formel in der X für O, S oder die Gruppierung steht und R1 und R2 gleich oder verschieden sind und für Wasserstoff, einen gegebenenfalls substituierten aliphatischen oder aromatischen Rest oder für einen gegebenenfalls substituierten heterocyclischen Rest mit 5 bis 7 Ringgliedern stehen, wobei im Fall n = 1 etwa 1 Mol, im Fall n = 2 etwa 0,5 Mol Zl< Anwendung gelangen, in Gegenwart eines Fluorwasserstoffacceptors im Temperaturbereich zwischen -100° C und +600 C umsetzt.It has been found that new trifluoromethylimino compounds are obtained if 1 mol of perfluoro-2,5-diazahexa-2,4-diene is used with a compound of the general formula in the X for O, S or the grouping and R1 and R2 are identical or different and represent hydrogen, an optionally substituted aliphatic or aromatic radical or an optionally substituted heterocyclic radical having 5 to 7 ring members, where n = 1 about 1 mol, when n = 2 about 0.5 mol Zl <use, in the presence of a hydrogen fluoride acceptor in the temperature range between -100 ° C and +600 C.
Bevorzugt wird im Temperaturbereich zwischen -70° C und +200 C gearbeitet.The temperature range between -70 ° C and +200 C is preferred.
Als aliphatische Reste (R1 und R2) seien beispielsweise geradkettige und gegebenenfalls verzweigte Alkylreste mit 1 bis 12 Kohlenstoffatomen, aber auch Alkenyl- und Alkinylreste mit bis zu 8 Kohlenstoffatomen genannt, bevorzugt Alkylreste mit 1 bis 8 Kohlenstoffatomen und Alkenyl- und Alkinylreste mit bis zu 4 Kohlenstoffatomen, insbesondere Alkylreste mit 1 bis 4 Kohlenstoffatomen, z.B. der Methyl-, Äthyl- und tert.-Butylrest.Examples of aliphatic radicals (R1 and R2) are straight-chain and optionally branched alkyl radicals having 1 to 12 carbon atoms, but also Alkenyl and alkynyl radicals with up to 8 carbon atoms, preferably alkyl radicals with 1 to 8 carbon atoms and alkenyl and alkynyl radicals with up to 4 carbon atoms, in particular alkyl radicals with 1 to 4 carbon atoms, e.g. the methyl, ethyl and tert-butyl radical.
Selbstverständlich gehören zu den aliphatischen Resten auch cycloaliphatische Reste, z.B. der Cyclopentyl- und bevorzugt der Cyclohexylrest.Of course, the aliphatic radicals also include cycloaliphatic ones Residues, e.g. the cyclopentyl and preferably the cyclohexyl radical.
Die aliphatischen Reste (R1 und R2) können auch substituiert sein, z.B. durch Halogen oder Pseudohalogen, bevorzugt Chlor.The aliphatic radicals (R1 and R2) can also be substituted, e.g. by halogen or pseudo-halogen, preferably chlorine.
Brom, Cyan, niedere Alkoxy- und Alkylmercaptogruppen mit bis zu 6, bevorzugt bis zu 3 Kohlenstoffatomen; weiterhin können sie endständig durch Arylreste mit bis zu 14 C-Atomen, vorzugsweise Phenyl substituiert sein, was besonders für aliphatische Reste mit bis zu 4 Kohlenstoffatomen, insbesondere den Methyl- und Äthylrest gilt.Bromine, cyano, lower alkoxy and alkyl mercapto groups with up to 6, preferably up to 3 carbon atoms; they can also be terminated by aryl radicals be substituted with up to 14 carbon atoms, preferably phenyl, which is particularly suitable for aliphatic radicals with up to 4 carbon atoms, especially the methyl and Ethyl radical applies.
Als aromatische Reste (R1 und R2) seine solche mit bis zu 14 Kohlenstoffatomen im Ringsystem, z.B. der Naphthyl- und der Anthranylrest, bevorzugt aber der Phenylrest verstanden.The aromatic radicals (R1 and R2) have up to 14 carbon atoms in the ring system, e.g. the naphthyl and the anthranyl radical, but preferably the phenyl radical Understood.
Diese aromatischen Reste können ebenfalls durch Halogen oder Pseudohalogen, z.B. Chlor, Brom, Jod, bevorzugt aber Cyan, die Nitrogruppe, niedere Alkyl- und Halogenalkylreste, niedere Alkoxy-, niedere Alkylmercaptoreste substituiert sein, wobei die Alkylgruppen bevorzugt 1-6, insbesondere 1-3 Kohlenstoffatome enthalten; ebenso können sie durch Arylmercaptoreste mit bis zu 14 C-Atomen, vorzugsweise Phenyl substituiert sein.These aromatic radicals can also be replaced by halogen or pseudohalogen, e.g. chlorine, bromine, iodine, but preferably cyano, the nitro group, lower alkyl and Haloalkyl radicals, lower alkoxy, lower alkyl mercapto radicals, the alkyl groups preferably containing 1-6, in particular 1-3, carbon atoms; they can also be replaced by aryl mercapto radicals with up to 14 carbon atoms, preferably phenyl be substituted.
Als 5- bis 7-gliedrige Heterocyclen (R1 und R2) kommen Heterocyclen mit einem oder mehreren Heteroatomen, z.B. O, N oder S in Betracht, z.B. Pyrrol, Pyridin, Pyrimidin, Oxazol, Oxazin, Thiazol, Thiazin, Thiophen und andere.As 5- to 7-membered heterocycles (R1 and R2) there are heterocycles with one or more heteroatoms, e.g. O, N or S, e.g. pyrrole, Pyridine, pyrimidine, oxazole, oxazine, thiazole, thiazine, thiophene and others.
Diese heterocyclischen Reste können in gleicher Weise wie die aromatischen Reste substituiert sein. Selbstverständlich können die heterocyclischen Reste auch mit einem gegebenenfalls teilweise hydrierten Benzolring anelliert sein.These heterocyclic radicals can be used in the same way as the aromatic Radicals may be substituted. Of course, the heterocyclic radicals can also be fused with an optionally partially hydrogenated benzene ring.
Die nach dem Verfahren der Erfindung erhältlichen neuen Trifluormethyliminoverbindungen entsprechen der allgemeinen Formel oder der isomeren Formel in denen X und R1 die oben angegebene Bedeutung besitzen und n für die Zahl 1 oder 2 steht.The new trifluoromethylimino compounds obtainable by the process of the invention correspond to the general formula or the isomeric formula in which X and R1 have the meaning given above and n stands for the number 1 or 2.
Nach dem Stand der Technik sind keine Kriterien für die Verbindung der allgemeinen Formel (I) bekannt, die es gestatten, vorherzusagenR welche der beiden allgemeinen Formeln (IIa) und (IIb) der nach dem erfindungsgemäßen Verfahren erhaltenen Verbindung zukommen wird; jedoch läßt sich nach erfolgter Herstellung diese Entscheidung leicht mit Hilfe der 19F-Kernresonanzspektroskopie treffen, da sich die Verbindungen der allgemeinen Formel IIa dadurch auszeichnen, daß das einzeln stehende Fluoratom im Bereich von -60 bis -80 ppm (CFDCOOH, externer Standard) absorbiert, während die Verbindung der allgemeinen Formel IIb für ihr einzeln stehendes Fluoratom eine Absorption im Bereich von -10 bis +10 ppm (CF3COOH als externer Standard) aufweisen.According to the state of the art, there are no criteria for the connection of the general formula (I), which make it possible to predict which of the both general formulas (IIa) and (IIb) according to the process according to the invention received connection will come; however, after production easily make this decision with the help of 19F nuclear magnetic resonance spectroscopy since the compounds of the general formula IIa are characterized in that the individually standing fluorine atom in the range of -60 to -80 ppm (CFDCOOH, external standard) absorbed, while the compound of the general formula IIb stands for its single fluorine atom have an absorption in the range of -10 to +10 ppm (CF3COOH as external standard).
Am Beispiel der Umsetzung von Perfluor-2,5-diazahexa-2,4-dien mit Dimethylamin sei das erfindungsgemäße Verfahren durch das folgende Formelschema wiedergegeben: Perfluor-2,5-diazahexa-2,4-dien ist bekannt (J. Amer. Chem.Using the example of the reaction of perfluoro-2,5-diazahexa-2,4-diene with dimethylamine, the process according to the invention is represented by the following equation: Perfluoro-2,5-diazahexa-2,4-diene is known (J. Amer. Chem.
Soc. 89,5007 (1967)), ebenso sind die Ausgangsmaterialien der allgemeinen Formel I bekannt oder nach bekannten Verfahren erhältlich.Soc. 89, 5007 (1967)), as are the starting materials of the general Formula I known or obtainable by known processes.
Als Fluorwasserstoffacceptoren können die üblichen Säurebindungsmittel verwendet werden. Genannt seien z.B. die Carbonate und Bicarbonate der Alkalimetalle (z.B. Natrium und Kalium), die Oxide, Carbonate und Bicarbonate der Erdalkalimetalle (z.The usual acid-binding agents can be used as hydrogen fluoride acceptors be used. The carbonates and bicarbonates of the alkali metals are mentioned, for example (e.g. sodium and potassium), the oxides, carbonates and bicarbonates of the alkaline earth metals (e.g.
B. Magnesium, Kalzium, Barium), tertiäre Amine (z.B. Triäthylamin, Dimethylanilin, Pyridin).E.g. magnesium, calcium, barium), tertiary amines (e.g. triethylamine, Dimethylaniline, pyridine).
Im allgemeinen werden aber als Fluorwasserstoffacceptoren die Alkalifluoride verwendet, wobei Natriumfluorid bevorzugt wird.In general, however, the alkali metal fluorides are used as hydrogen fluoride acceptors used, with sodium fluoride being preferred.
Gegebenenfalls kann die Umsetzung in einem Verdünnungsmittel ausgeführt werden. Hierfür kommen alle inerten organischen Lösungsmittel infrage, Z.B. Kohlenwasserstoffe, Chlorkohlenwasserstoffe, Ketone, Nitrile und Äther. Beispielsweise seien besonders genannt: Ligroin, Benzin, Benzol, Toluol, Methylenchlorid, Chloroform, Chlorbenzol, Aceton, Acetonitril und Diäthyläther.If appropriate, the reaction can be carried out in a diluent will. All inert organic solvents can be used for this, e.g. hydrocarbons, Chlorinated hydrocarbons, ketones, nitriles and ethers. For example, be special named: ligroin, gasoline, benzene, toluene, methylene chloride, chloroform, chlorobenzene, Acetone, acetonitrile and diethyl ether.
Die Ausführung des Verfahrens der Erfindung kann in an sich bekannter Weise erfolgen. Auf ein Mol Perfluor-2,5-diazahexa-2,4-dien werden 0,8 - 1 Mol, bevorzugt 0,9 Mol bis 1 Mol der Verbindung der allgemeinen Formel I im Fall n = 1 eingesetzt und 0,4 bis 0,5 Mol, bevorzugt 0,45 bis 0,50 Mol bei n = 2.The method of the invention can be carried out in a manner known per se Way. For one mole of perfluoro-2,5-diazahexa-2,4-diene, 0.8-1 mole, preferably 0.9 mol to 1 mol of the compound of the general formula I in the case n = 1 is used and 0.4 to 0.5 mol, preferably 0.45 to 0.50 mol, when n = 2.
Der Fluorwasserstoffacceptor wird mit wenigstens einem Säureäquivalent, gegebenenfalls auch im Uberschuß eingesetzt, bevorzugt wird ein Uberschuß bis zu etwa 400 96, insbesondere von etwa 100 96 bis 200 9' der wenigstens erforderlichen Menge.The hydrogen fluoride acceptor is treated with at least one acid equivalent, optionally also used in excess, preference being given to an excess of up to about 400 96, in particular from about 100 96 to 200 9 'of the least required Lot.
Zweckmäßigerweise läßt man z.3. zu einer Lösung oder Suspension aus Perfluor-2 , 5-diazahexa-2 , 4-dien, organischem Lösungsmittel und Fluorwasserstoffacceptor das Ausgangsmaterial der allgemeinen Formel I zutropfen.Appropriately, z.3. to a solution or suspension Perfluoro-2, 5-diazahexa-2, 4-diene, organic solvent and hydrogen fluoride acceptor the starting material of the general formula I is added dropwise.
Die Isolierung des Reaktionsproduktes kann nach an sich bekannten Verfahren erfolgen, z.B. filtriert man vom ausgefallenen Fluorid und überschüssigen Fluorwasserstoffacceptor ab, engt die Lösung ein und reinigt das erhaltene Rohprodukt nach an sich bekannten Verfahren, z.B. Destillation, Kristallisation.The isolation of the reaction product can be carried out according to known methods Procedures are carried out, e.g. the precipitated fluoride and excess are filtered off Hydrogen fluoride acceptor from, the solution is concentrated and the crude product obtained is purified by methods known per se, e.g. distillation, crystallization.
Die nach dem Verfahren der Erfindung erhältlichen neuen Trifluormethyliminoverbindungen sind wertvolle Ausgangsmaterialien und Zwischenprodukte für z.B. Pflanzenschutzmittel und Polymere, sie zeigen auch selbst herbizide Wirkung.The new trifluoromethylimino compounds obtainable by the process of the invention are valuable starting materials and intermediate products for e.g. pesticides and polymers, they also show herbicidal activity themselves.
Beispiel 1 Zu 23 g (0,1 Mol) Perfluor-2,5-diazahexa-2,4-dien und 10 g NaF (O,Z4 Mol) in 100 ml Äther werden 8,7 g (0,1 Mol) Morpholin, in 40 g Äther gelöst, bei -400C zugetropft. Man läßt etwa 1 Stunde bei Raumtemperatur nachrühren, filtriert von NaF, NaHF2 ab, engt das Filtrat im Vakuum ein und destilliert anschließend 26 g 3-Morpholino-perfluor-2,5-diazahexa-2,4-dien (= 87 % der Theorie).example 1 To 23 g (0.1 mol) of perfluoro-2,5-diazahexa-2,4-diene and 10 g of NaF (O, Z4 mol) in 100 ml of ether, 8.7 g (0.1 mol) of morpholine, in 40 g of ether dissolved, added dropwise at -400C. The mixture is stirred for about 1 hour at room temperature, filtered from NaF, NaHF2, the filtrate is concentrated in vacuo and 26 g of 3-morpholino-perfluoro-2,5-diazahexa-2,4-diene (= 87% of theory) are then distilled ).
Siedepunkt: 74 - 750 C/0,4 Torr.Boiling point: 74-750 C / 0.4 Torr.
Beispiel 2 Analog Beispiel 1 erhält man mit Dimethylamin 3-Dimethylaminoperfluor-2,5-diazahexa-2,4-dien vom Siedepunkt: 96 - 970 C 30 Torr; Ausbeute: 75 % der Theorie.Example 2 Analogously to Example 1, dimethylamine gives 3-dimethylaminoperfluoro-2,5-diazahexa-2,4-diene with a boiling point: 96-970 C 30 Torr; Yield: 75% of theory.
Beispiel 3 Analog Beispiel 1 erhält man mit Methanol 3-Methoxy-perfluor-2,5-diazahexa-2,4-dien vom Siedepunkt: 99 - 1000 C/760 Torr; Ausbeute: 6-5 96 der Theorie.Example 3 Analogously to Example 1, 3-methoxy-perfluoro-2,5-diazahexa-2,4-diene with a boiling point of 99-1000 C / 760 Torr is obtained with methanol; Yield: 6-5 96 of theory.
Beispiel 4 Analog Beispiel 1 erhält man mit Äthanol 3-Äthoxy-perfluor-2,5 diazaiexa-2,4-dien vom Siedepunkt: 59 - 60° C/110 Torr; Ausbeute: 85 % der Theorie.Example 4 Analogously to Example 1, 3-ethoxy-perfluoro-2,5-diazaiexa-2,4-diene with a boiling point of 59-60 ° C./110 Torr is obtained with ethanol; Yield: 85% of theory.
Beispiel 5 Zu 12 g (0,1 Mol) Caprolactam und 10 g NaF (q24 Mol) in 100 ml Acetonitril werden 23 g (0,1 Mol) Perfluor-2,5-diazahexa-2,4-dien bei -10° C zugetropft. Man läßt 1 Stunde bei Raumtemperatur nachrühren, filtriert von NaF, NaHF2 ab und engt das Filtrat im Vakuum ein. Nach Umkristallisation aus Äther/n-Hexan erhält man 25 g 1-Trifluormethyl-2-fluor-2-[(3',4',5',6'-tetrahydro-7'-2H-azipinyl)-ox]-3-trifluormethylimino-aziridin (= 78 % der Theorie).Example 5 23 g (0.1 mol) of perfluoro-2,5-diazahexa-2,4-diene are added dropwise at -10 ° C. to 12 g (0.1 mol) of caprolactam and 10 g of NaF (q24 mol) in 100 ml of acetonitrile . The mixture is stirred for 1 hour at room temperature, filtered from NaF, NaHF2 and the filtrate is concentrated in vacuo. After recrystallization from ether / n-hexane, 25 g of 1-trifluoromethyl-2-fluoro-2 - [(3 ', 4', 5 ', 6'-tetrahydro-7'-2H-azipinyl) -ox] -3 are obtained trifluoromethylimino-aziridine (= 78% of theory).
Schmelzpunkt: 65 - 660 C.Melting point: 65 - 660 C.
Beispiel 6 Zu 138 g (0,6 Mol) Perfluor-2,5-diazahexa-2,4-dien und 50 g NaF in 300 ml Aceton werden bei -400 C 60 g 2,2-(4-Hydroxyphenyl)-propan, in 200 ml Aceton gelöst, eingetropft.Example 6 To 138 g (0.6 mol) of perfluoro-2,5-diazahexa-2,4-diene and 50 g of NaF in 300 ml of acetone, 60 g of 2,2- (4-hydroxyphenyl) propane, in 200 ml of acetone dissolved, added dropwise.
Man läßt 2 Stunden bei Raumtemperatur nachrühren, filtriert von NaF, NaHF2 ab und engt das Filtrat im Vakuum ein. Nach Destillation erhält man 144 g 2,2-Bis +-(perfluor-2,5-diazahexa-2,4-dien-oxy(-3))]-phenyl-propan vom Siedepunkt: 173 -1740 C/0703 Torr; Ausbeute: 85 9' der Theorie.The mixture is stirred for 2 hours at room temperature, filtered from NaF, NaHF2 and the filtrate is concentrated in vacuo. To Receives distillation 144 g of 2,2-bis + - (perfluoro-2,5-diazahexa-2,4-dien-oxy (-3))] - phenyl-propane from Boiling point: 173-1740 C / 0703 Torr; Yield: 85 9 'of theory.
Beispiel 7 Analog Beispiel 6 erhält man mit Hexandiol-1,6 Bis-(perfluor-2,5-diazahexa-2,4-dienyl)~1,6-oxyhexan vom Siedepunkt: 108 -1100 C/0,03 Torr; Ausbeute: 82 % der Theorie.Example 7 Analogously to Example 6, 1,6-hexanediol bis (perfluoro-2,5-diazahexa-2,4-dienyl) -1,6-oxyhexane with a boiling point: 108-1100 C / 0.03 Torr is obtained; Yield: 82% of theory.
Beispiel 8 Zu 46 g (0,2 Mol) Perfluor-2,5-diazahexa-2,4-dien und 15 g NaF in 100 ml Aceton werden bei -400 C 17 g ( 0,18 Mol) Phenol in 50 ml Aceton gelöst, eingetropft. Man läßt 2 Stunden bei Raumtemperatur nachrühren, filtriert von NaF, NaHF2 ab und engt das Filtrat in Vakuum ein. Nach Destillation erhält man 51 g 3-Phenoxy-perfluor-2,5-diazahexa-2,4-dien (=85 % der Theorie) mit einem Siedepunkt von 74° C - 750 C/15 Torr.Example 8 To 46 g (0.2 mol) of perfluoro-2,5-diazahexa-2,4-diene and 15 g of NaF in 100 ml of acetone, 17 g (0.18 mol) of phenol are dissolved in 50 ml of acetone at -400 C. dripped in. The mixture is stirred for 2 hours at room temperature, filtered from NaF, NaHF2 and the filtrate is concentrated in vacuo. After distillation, 51 g of 3-phenoxy-perfluoro-2,5-diazahexa-2,4-diene (= 85% of theory) with a boiling point of 74 ° C.-750 ° C./15 torr are obtained.
Beispiel 9 Analog Beispiel 8 erhält man mit 2,4-Dichlorphenol 3-(2,4-Dichlorphenoxy)-perfluor-2, 5-diazahexa-2 , 4-dien vom Siedepunkt: 105 - 1060 C/15 Torr; Ausbeute: 78 % der Theorie.Example 9 Using 2,4-dichlorophenol, 3- (2,4-dichlorophenoxy) -perfluoro-2, 5-diazahexa-2, 4-diene with a boiling point of 105-1060 C / 15 Torr is obtained analogously to Example 8; Yield: 78% of theory.
Beispiel 10 Analog Beispiel 8 erhält man mit 4-Chlorphenol 3-p-Chlorphenoxy-perfluor-2,5-diazahexa-2,4-dien vom Siedepunkt: 95 - 960 C/ 15 Torr; Ausbeute: 83 % der Theorie.Example 10 Analogously to Example 8, 4-chlorophenol gives 3-p-chlorophenoxy-perfluoro-2,5-diazahexa-2,4-diene with a boiling point: 95-960 C / 15 Torr; Yield: 83% of theory.
Beispiel 11 Analog Beispiel 8 erhält man mit 4-Chlorthiophenol 3-(p-Chlorphenylthio)-perfluor-2,5-diazahexa-2,4-dien vom Siedepunkt: 85 - 860 C/0,02 Torr; Ausbeute: 82 % der Theorie. Beispiel 12 Analog Beispiel 8 erhält man mit 4-Nitrophenol 3-(p-Nitrophenoxy)-perfluor-2,5-diazahexa-2,4-dien vom Schmelzpunkt: 132 -1330 C; Ausbeute: 70 % der Theorie.Example 11 Analogously to Example 8, with 4-chlorothiophenol, 3- (p-chlorophenylthio) -perfluoro-2,5-diazahexa-2,4-diene is obtained with a boiling point: 85-860 C / 0.02 Torr; Yield: 82% of theory. Example 12 Using 4-nitrophenol, 3- (p-nitrophenoxy) -perfluoro-2,5-diazahexa-2,4-diene with a melting point of: 132-1330 ° C. is obtained analogously to Example 8; Yield: 70% of theory.
Beispiel 13 Analog Beispiel 8 erhält man mit Butyrolactam 3-(2'-0xo1'-pyr rolidinyl)-perfluor-2,5-diazahexa-2,4-dien vom Siedepunkt: 106 - 1080 C/0,03 Torr; Ausbeute: 69 % der Theorie.Example 13 Analogously to Example 8, 3- (2'-0xo1'-pyrrolidinyl) -perfluoro-2,5-diazahexa-2,4-diene with butyrolactam is obtained with a boiling point: 106-1080 C / 0.03 Torr; Yield: 69% of theory.
Beispiel 14 Analog Beispiel 8 erhält man mit Piperidon(2) 1-TrifluormethylS 2-fluor-2-[(2',3',4',5'-tetrahydro-6'-pyridinyl)-oxy]-3-trifluormethyl-imino-aziridin vom Schmelzpunkt: 120 - 121 °C; Ausbeute : 77 % der Theorie.Example 14 Analogously to Example 8, with piperidone (2) 1-trifluoromethylS 2-fluoro-2 - [(2 ', 3', 4 ', 5'-tetrahydro-6'-pyridinyl) -oxy] -3-trifluoromethyl-imino- aziridine of melting point: 120 - 121 ° C; Yield: 77% of theory.
Beispiel 15 - Analog Beispiel 8 erhält man mit Glycid 3-(2''3''Epoxypropyl) oxy]-perfluor-2,5-diezahexa-2,4-dien vom Siedepunkt: 53° C bis 540 C/0,2 Torr; Ausbeute: 56 % der Theorie.Example 15 - Analogously to Example 8, glycid gives 3- (2 "3" epoxypropyl) oxy] -perfluoro-2,5-diezahexa-2,4-diene with a boiling point: 53 ° C. to 540 ° C. / 0.2 Torr; Yield: 56% of theory.
Beispiel 16 Analog Beispiel 8 erhält man mit Salicylsäure 1-Trifluormethyl-2-fluor-2- ( salicyloylxy)-3-trifluormethylimino-aziridin vom Schmelzpunkt: 132 - 1330 C; Ausbeute: 87 % der Theorie.Example 16 Analogously to Example 8, 1-trifluoromethyl-2-fluoro-2- (salicyloylxy) -3-trifluoromethyliminoaziridine with a melting point of 132-1330 ° C. is obtained with salicylic acid; Yield: 87% of theory.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712125476 DE2125476A1 (en) | 1971-05-22 | 1971-05-22 | Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712125476 DE2125476A1 (en) | 1971-05-22 | 1971-05-22 | Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2125476A1 true DE2125476A1 (en) | 1972-12-07 |
Family
ID=5808646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712125476 Pending DE2125476A1 (en) | 1971-05-22 | 1971-05-22 | Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agents |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2125476A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111148733A (en) * | 2017-09-28 | 2020-05-12 | 3M创新有限公司 | Hydrofluoroformimidates and methods of making and using same |
-
1971
- 1971-05-22 DE DE19712125476 patent/DE2125476A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111148733A (en) * | 2017-09-28 | 2020-05-12 | 3M创新有限公司 | Hydrofluoroformimidates and methods of making and using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE844741C (en) | Process for the preparation of heterocyclic carbamic acid esters | |
| EP0463464B1 (en) | Process for the preparation of 2-chloro-5-methylpyridine | |
| DE2940654A1 (en) | DIMERES KETEN OF 1,2 ,, - TRIAZOL-3-CARBONIC ACID | |
| DE2125476A1 (en) | Herbicidal trifluoromethylimino cpds - as inters eg to plant protection agents | |
| EP0157270B1 (en) | Process for the preparation of tetrachloro-benzo-1,4-dioxenes | |
| EP0693466B1 (en) | Process for the preparation of aromatic fluorinated compounds and diamides | |
| CH620930A5 (en) | ||
| DE2054342A1 (en) | New 1,2,4-oxdiazoles | |
| DE1153375B (en) | Process for the preparation of benzoxazine- (1, 3) -dione- (2, 4) | |
| DE2351556C2 (en) | Process for the preparation of N-haloformyl-carbamic acid halides | |
| DE1545825C3 (en) | Process for the preparation of 3,5-dioxo-1,2,4-dithiazolidines | |
| EP0082398B1 (en) | Process for the preparation of 1,2-benzisothiazolin-3-ones | |
| DE2125474A1 (en) | Symmetrical bis (trifluoromethylimino) cpds - useful as inters | |
| DE2210882C3 (en) | Special process for the preparation of 4,5-bis-trifluoromethylimino derivatives of thiazolidines | |
| DE1225168B (en) | Process for the preparation of benzenesulfonic acid phenyl esters | |
| AT251592B (en) | Process for the production of organic imide chlorides | |
| AT344166B (en) | PROCESS FOR THE PREPARATION OF S-TRIAZOLO- (3,4-B) -BENZOTHIAZOLES | |
| DE2125477A1 (en) | Asymmetrical bis (trifluoromethylimino) cpds - useful as inters to eg plant protection agents | |
| EP0071791B1 (en) | Trichloromethylthiobenzyl halides and process for prepararing meta or para trichloromethylthiobenzyl halides | |
| DE1793287B2 (en) | METHOD FOR PREPARING N-SUBSTITUTED N-ACYLCARBAMIC ACID HALOGENIDES | |
| DE1942013C3 (en) | Thiazolo (thiono) phosphor (phosphonic) acid esters, process for their preparation and compositions containing them | |
| DE1545791A1 (en) | Process for the preparation of cyclic derivatives of phosphonic and thiophosphonic acid | |
| DE3210296C2 (en) | ||
| DE1156403B (en) | Process for the preparation of sulfonic acid amide-N-sulfenic acid chlorides | |
| DE1814251A1 (en) | Process for the preparation of nuclear halogenated alkoxy-aryl-isocyanates |