Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
  • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated

Definitions

• the present invention relates to a novel process for preparing substituted anthranilic acid derivatives of the formula (I)
• R 1 , R 3 and R 4 radicals are each as defined above and
• R 6 and R 7 are each as defined above.
• substituted anthranilic acid derivatives of the formula (I) require the availability of the corresponding substituted anthranilic acid derivatives of the general formula (VII).
• substituted anthranilic acid derivatives of the general formula (VII) are either known or can be prepared by known organic chemistry methods. Some of these substituted anthranilic acid derivatives of the general formula (VII), however, can be prepared only in a complex manner, in multiple stages and at high cost, which can lead to uneconomically high costs for the end products as a result of unavoidable yield losses.
• Substituted anthranilic acid derivatives of the formula (I) are of high interest as compounds having known insecticidal efficacy (see, for example, Bioorg. & Med. Chem. Lett. 15 (2005) 4898-4906; Biorg. & Med. Chem. 16 (2008) 3163-3170). Further, it is already known, that substituted anthranilic acid derivatives of the general formula (VII) can be obtained by reacting substituted anthranilic acid derivatives of the general formula (IX) with carbon monoxide in the presence of a palladium catalyst, of a ligand, of a primary amine and a base (WO 2012/103436). However, it is not known whether anthranilic acid amides of the general formula (IV) can be used correspondingly.
• R 6 and R 7 are each as defined above to give the substituted anthranilic acid derivatives of the general formula (I).
• the present invention likewise provides novel compounds of the general formula (IV)
• R 1 , R 3 , R 4 and X radicals are each as defined above.
• Alkyl groups substituted by one or more fluorine or chlorine atoms are selected, for example, from trifluoromethyl (CF 3 ), difluoromethyl (CHF 2 ), CCl 3 , CFCl 2 , CF 3 CH 2 , ClCH 2 , CF 3 CCl 2 .
• Alkyl groups in the context of the present invention are linear or branched hydrocarbyl groups.
• alkyl and C 1 -C 12 -alkyl encompasses, for example, the meanings of methyl, ethyl, n-, isopropyl, n, iso-, sec- and t-butyl, n-pentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl.
• Aryl radicals in the context of the present invention are aromatic hydrocarbyl radicals which may have one, two or more heteroatoms selected from O, N, P and S and may optionally be substituted by further groups.
• Alkylaryl groups (alkaryl groups) and alkylaryloxy groups in the context of the present invention are, respectively, aryl groups and aryloxy groups which are substituted by alkyl groups, may have a C 1-8 -alkylene chain and may have, in the aryl skeleton or aryloxy skeleton, one or more heteroatoms selected from O, N, P and S.
• Anthranilic acid derivatives of the formula (IV) can be prepared as follows:
• the reaction time may, according to the batch size and the temperature, be selected within a range between 1 hour and several hours.
• Process step 1 can optionally be performed in the presence of a catalyst.
• a catalyst examples include 4-dimethylaminopyridine or 1-hydroxybenzotriazole.
• the amount of palladium catalyst used in the process according to the invention is 0.001 to 20 mole percent, based on substituted anthranilic acid derivative of the general formula (IV) used. Preferably 0.005 to 10 mole percent is used, more preferably 0.01 to 5 mole percent.
• phosphine ligands include chelating bisphosphines. Examples of these include 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphino)butane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and 1,1′-bis(diphenylpho sphino)ferrocene.
• Preferred phosphine ligands are trialkylphosphines such as tri-tert-butylphosphine and triadamantylphosphine, and also triarylphosphines such as triphenylphosphine, tri(ortho-tolyl)phosphine or tri(para-methoxyphenyl)phosphine. Particular preference is given to triphenylphosphine.
• phosphine 1-20 molar equivalents of phosphine are used, based on the amount of palladium used. Preferably 2-15 molar equivalents are used.
• Process step 2 of the process according to the invention is performed in the presence of carbon monoxide (CO).
• CO carbon monoxide
• the carbon monoxide is typically introduced in gaseous form, and so the reaction is usually performed in an autoclave. It is customary to work at CO pressure 0.1 to 50 bar, preferably at 1 to 25 bar.
• carbon monoxide in the form of suitable metal carbonyl complexes, for example dicobalt octacarbonyl or molybdenum hexacarbonyl. Preference is given to working with gaseous carbon monoxide.
• Process step 2 is generally performed in the presence of a base.
• Suitable bases are organic bases such as trialkylamines, alkylpyridines, phosphazenes and 1,8-diazabicyclo[5.4.0]undecene (DBU).
• organic bases such as triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, alkylpyridines, for example 2,6-dimethylpyridine, 2-methyl-5-ethylpyridine or 2,3-dimethylpyridine.
• the compounds of the general formula (V) or (VI) required for preparation of the substituted anthranilic acid derivatives of the general formula (I) are typically used in an excess, based on the substituted anthranilic acid derivative of the general formula (IV). It is also possible to use the compounds of the general formula (V) or (VI) in such an amount that they simultaneously serve as solvents.
• the autoclave After closure, the autoclave is purged with carbon monoxide and heated to 110° C., and a carbon monoxide pressure of 10 bar is maintained After 18 hours, the mixture is allowed to cool to room temperature, the autoclave is depressurized, the reaction mixture is stirred with methylene chloride and filtered through kieselguhr, and the filtrate is washed, first with dilute hydrochloric acid and then with water, dried over sodium sulphate and concentrated under reduced pressure. This gives 1.14 g of the title compound.
• the reaction mixture is stirred at room temperature for one hour and at 40° C. for 1 hour and cooled to room temperature, water and methylene chloride are added thereto, and the organic phase is removed, washed with dilute hydrochloric acid, dried and concentrated.
• the crude product thus obtained is purified by chromatography on silica gel (cyclohexane/ethyl acetate). This gives 1.30 g of the title compound as a pale beige solid.
• the autoclave After closure, the autoclave is purged with carbon monoxide and heated to 110° C., and a carbon monoxide pressure of 10 bar is maintained. After 18 hours, the mixture is allowed to cool to room temperature, the autoclave is depressurized, the reaction mixture is stirred with methylene chloride and filtered through kieselguhr, and the filtrate is washed, first with dilute hydrochloric acid and then with water, dried over sodium sulphate and concentrated under reduced pressure. This gives 0.49 g of the title compound.
• the autoclave After closure, the autoclave is purged with carbon monoxide and heated to 110° C., and a carbon monoxide pressure of 10 bar is maintained. After 18 hours, the mixture is allowed to cool to room temperature, the autoclave is depressurized, the reaction mixture is stirred with methylene chloride and filtered through kieselguhr, and the filtrate is washed, first with dilute hydrochloric acid and then with water, dried over sodium sulphate and concentrated under reduced pressure. This gives 0.475 g of the title compound.

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• Chemical & Material Sciences (AREA)
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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 2013
  • 2013-02-06 TW TW102104496A patent/TWI644888B/zh not_active IP Right Cessation
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  • 2013-02-06 JP JP2014555260A patent/JP2015511229A/ja not_active Withdrawn
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