EP0596963A1 - PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA FABRICATION DE 6-(3,5,6,7-TETRAHYDROPYROLLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONES SUBSTITUES - Google Patents

PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA FABRICATION DE 6-(3,5,6,7-TETRAHYDROPYROLLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONES SUBSTITUES

Info

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Withdrawn
Application number
EP92916316A
Other languages
German (de)
English (en)
Inventor
Hartmut Seba
Klaus-Dieter Graske
Michael Ganzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Pharma AG
Original Assignee
Schering AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schering AG filed Critical Schering AG
Publication of EP0596963A1 publication Critical patent/EP0596963A1/fr
Withdrawn legal-status Critical Current

Links

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)

Abstract

L'invention concerne un nouveau procédé de fabrication de 6-(3,5,6,7-tétrahydropyrrolo[2,1-c]L1,2,4]thiadiazol-3-ylidenamino)-7-fluor-2H-1,4-benzoxazin-3(4H)-ones substitués de la formule générale (I) dans laquelle R1 désigne un résidu alcoyle C1-C6, un résidu alcényle C2-C6 ou un résidu alcynyle C3-C6; R2 désigne un atome d'hydrogène ou un résidu alcoyle C1-C4, et R3 désigne un atome d'hydrogène ou un résidu alcoyle C1-C4. Ledit procédé prend pour base de l'acide acétique de 2-(2-acétylamino-4-5-fluorphénoxy).
EP92916316A 1991-07-26 1992-07-22 PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA FABRICATION DE 6-(3,5,6,7-TETRAHYDROPYROLLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONES SUBSTITUES Withdrawn EP0596963A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914125246 DE4125246C1 (fr) 1991-07-26 1991-07-26
DE4125246 1991-07-26
PCT/DE1992/000606 WO1993003043A1 (fr) 1991-07-26 1992-07-22 PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA FABRICATION DE 6-(3,5,6,7-TETRAHYDROPYROLLO[2,1-c][1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONES SUBSTITUES

Publications (1)

Publication Number Publication Date
EP0596963A1 true EP0596963A1 (fr) 1994-05-18

Family

ID=6437332

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92916316A Withdrawn EP0596963A1 (fr) 1991-07-26 1992-07-22 PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA FABRICATION DE 6-(3,5,6,7-TETRAHYDROPYROLLO 2,1-c] 1,2,4]THIADIAZOL-3-YLIDENAMINO)-7-FLUOR-2H-1,4-BENZOXAZIN-3(4H)-ONES SUBSTITUES

Country Status (5)

Country Link
EP (1) EP0596963A1 (fr)
JP (1) JPH06509345A (fr)
DE (1) DE4125246C1 (fr)
PT (1) PT100727A (fr)
WO (1) WO1993003043A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013540113A (ja) 2010-10-01 2013-10-31 ビーエーエスエフ ソシエタス・ヨーロピア 除草性ベンゾオキサジノン
CN111356693A (zh) 2017-11-23 2020-06-30 巴斯夫欧洲公司 除草的苯基醚类
WO2019101513A1 (fr) 2017-11-23 2019-05-31 Basf Se Pyridyléthers en tant qu'herbicides

Family Cites Families (7)

* Cited by examiner, † Cited by third party
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
US4734124A (en) * 1987-01-15 1988-03-29 Fmc Corporation Tetrazolinone herbicides
US4755217A (en) * 1987-01-15 1988-07-05 Fmc Corporation Triazinedione 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 (fr) * 1989-10-12 1991-04-13 Masayuki Enomoto Benzoxazinylpyrazoles; preparation et utilisation
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9303043A1 *

Also Published As

Publication number Publication date
DE4125246C1 (fr) 1993-02-04
PT100727A (pt) 1993-10-29
JPH06509345A (ja) 1994-10-20
WO1993003043A1 (fr) 1993-02-18

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Free format text: PROCESS AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF SUBSTITUTED 6-(3,5,6,7-TETRAHYDROPYRROLO 2,1-C 1,2,4 THIADIAZOLE-3-YLIDENAMINO)-7-FLUORO-2H-1,4-BENZOXAZIN-3(4H)-ONES