Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
  • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
  • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
  • C07C323/40—Y being a hydrogen or a carbon atom
  • C07C323/42—Y being a carbon atom of a six-membered aromatic ring

Definitions

• the invention relates to novel salts of chiral 3-HalophthalTexre derivatives, a process for their preparation, their use for the preparation of chiral Phthalcicrediamiden and a novel process for the preparation of chiral Phthalcicrediamiden.
• the present invention thus provides a process for preparing 3-halophthalic acid derivatives of the formula (I) in which
• Hal stands for halogen
• A is Ci-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Ci-C 6 -alkoxy-C r C 4 alkyl, C r C 6 alkylthio C r C 4 alkyl, (dQ-AlkyOcarbamoyl, q is O, 1 or 2,
• M is an alkali metal ion, an alkaline earth metal ion, tetra (Ci-G
• M has the meaning given above, t is 1, when M is alkali metal ion, tetra (Ci-C 4 -alkyl) ammonium or tetra (CV
• the in process (A) to be used from starting materials 3-Halophthal Acid- anhydrides are generally defined by the formula (H).
• Hal is preferably fluorine, chlorine, bromine or iodine.
• 3-Bromophthalic anhydride is obtained, for example, by diazotizing 2,3-dimethylaniline with sodium nitrite, converting the diazonium salt with potassium bromide into 2,3-dimethylbromobenzene and then adding e.g. oxidized with potassium permanganate or oxygen.
• 3-iodophthalic anhydride can be obtained analogously to 3-bromophthalic anhydride.
• 3-iodophthalic anhydride is obtained by first hydrogenating 3-nitrophthalic acid to 3-aminophthalic acid (e.g., hydrogen, nickel catalyst) and then exchanging the amino group for iodine in a Sandmeyer reaction.
• 3-aminophthalic acid e.g., hydrogen, nickel catalyst
• A is preferably methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, AUyl, propargyl, methoxymethyl or methylthiomethyl.
• A is particularly preferably methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl.
• q is preferably 0 or 2. In addition, q is preferably 1. In particular, q is more preferably 0. In addition, q is more preferably 2.
• Amines of the formula (DI) can be obtained by known processes (cf., WO 01/23350 and WO 03/099777).
• M is preferably lithium, Sodium, potassium, calcium, magnesium, barium, tetrabutylammonium, tetrabutylphosphonium, more preferably lithium, sodium, potassium, tetrabutylammonium, tetrabutylphosphonium, most preferably lithium or sodium.
• Hydroxides of formula (FV) are known synthetic chemicals.
• the process (A) according to the invention can be carried out in the presence of a suitable inert diluent.
• suitable diluents are, in particular: hydrocarbons, such as e.g. Pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, petroleum ether, ligroin, halogenated hydrocarbons, e.g.
• Dichloromethane trichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene or dichlorobenzene; Nitriles, such as acetonitrile, propionitrile, butyronitrile; Ethers, e.g. Diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DTM); Esters, e.g. Ethyl acetate, amyl acetate; Acid amides, e.g.
• Dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA).
• N-methylpyrrolidone, butyronitrile, dimethylacetamide (DMA), dioxane, 1,3-dimethyl-2-imidazolidinone are particularly preferred as diluents.
• the process (A) according to the invention can be carried out within a relatively wide temperature range.
• the reaction is preferably carried out at temperatures between -10 0 C and + 80 0 C, insbe ⁇ special between O 0 C and 30 0 C.
• the process (A) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure-generally between 0.1 bar and 50 bar, preferably between 1 bar and 10 bar.
• an amount of 1 mol of 3-halophthalic anhydride of the formula (H) is generally employed between 1 mol and 1.5 mol, preferably between 1.05 mol and 1.2 mol of amine of the formula ( DI) and further between 1 mole and 1.5 moles, preferably between 1, 05 and 1.2 moles of a hydroxide of formula (IV).
• the present invention furthermore relates to a process for the preparation of 3-halophthalic acid derivatives of the formula (Ia) in which r stands for 1 or 2 and
• the 3-halo-phthalic acid derivatives required as starting materials for carrying out the process according to the invention are generally defined by the formula (I-b).
• Hal, A and q are preferred, particularly preferably, very particularly preferably or in particular preferred, the meanings described above in connection with the description of the starting materials of the formulas (H), (IH) and (FV) these radicals have been indicated as being preferred, particularly preferred, very particularly preferred or particularly preferred.
• 3-halophthalic acid derivatives of the formula (I-b) are obtained according to the process (A) according to the invention.
• Suitable diluents for carrying out the process (B) according to the invention are the following solvents: alcohols, such as, for example, methanol, ethanol, isopropanol, trifluoroethanol; halogenated hydrocarbons, such as, for example, dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, Chlorobenzene or dichlorobenzene; Nitriles, such as acetonitrile, propionitrile, butyronitrile; Water, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA), N-methylpyrrolidone, dimethylacetamide (DMA), dioxane, 1,3-dimethyl-2-imidazolidinone, acetic acid or trifluoroacetic acid.
• alcohols such as, for example, methanol, ethanol, isopropanol, trifluoroethanol
• process (B) according to the invention is carried out in the presence of a base [preferably in the presence of an alkali metal hydroxide of the formula (TV)], the 3-halophthalic acid derivatives are obtained in the form of their salts.
• a base preferably in the presence of an alkali metal hydroxide of the formula (TV)
• the present invention further relates to the novel 3-halophthalic acid derivatives of the formula (I)
• the 3-halophthalic acid derivatives of the invention are generally defined by the formula (I).
• Hal, A, q and M are preferred, particularly preferably, very particularly preferably or in particular preferred, the meanings described above in connection with the description of the starting materials of the formulas (II), (IH) and (FV ) have been specified for these radicals as being preferred, particularly preferred, very particularly preferred or particularly preferred.
• the present invention further relates to the novel 3-halophthalic acid derivatives of the formula (I-c)
• the 3-halophthalic acid derivatives of the invention are generally defined by the formula (Ic).
• Hal, A and q are preferred, particularly preferably, very particularly preferably or in particular preferred, the meanings which have been mentioned above in connection with the description of US Pat Starting materials of the formulas (II), (IH) and (IV) for these radicals have been indicated as being preferred, particularly preferred, very particularly preferred or particularly preferred.
• the 3-halophthalic acid derivatives of the formula (I) according to the invention can be used for the preparation of chiral phthalic diamides.
• R is hydrogen or C r C 6 alkyl, Z is CY or N,
• Y is hydrogen, halogen, C, -C 6 alkyl, C r C 6 haloalkyl, C, -C 6 alkoxy, C r C 6 halo-alkoxy, Ci-C 6 alkylthio, C r C 6 - Haloalkylthio or cyano, n is 0, 1, 2, 3, 4, or 5,
• R, Z, Y and n have the abovementioned meanings, if appropriate in the presence of a diluent (for example dichloroethane) and if appropriate in the presence of an acid (for example hydrochloric acid).
• a diluent for example dichloroethane
• an acid for example hydrochloric acid
• Phthalic diamides of the formula (V) in which q is 0 or 1 can be converted in a simple manner into the sulphones, ie phthalic diamides of the formula (V) in which q is 2.
• Suitable oxidizing agents are, for example, hydrogen peroxide, peroxyacid such as peracetic acid (CH 3 COOOH), trifluoroperacetic acid (CF 3 COOOH), meta-chloroperbenzoic acid (m-CIC & HiCOOOH), potassium permanganate or oxygen.
• the isophthalimides occurring as intermediates in carrying out the process (C) according to the invention are generally defined by the formula (VI).
• Hal, A and q are preferred, particularly preferably, very particularly preferably or particularly preferably the meanings described above in connection with the description of the starting materials of the formulas (H), (IE) and (TV) for these radicals preferably, more preferably, very particularly preferably or in particular preferred.
• Isophthalimides of the formula (VI) are novel and likewise the subject of the present invention. Isophthalimides of the formula (VI) are obtained in accordance with the first step of the process (C) according to the invention and subsequent isolation (compare also the Preparation Examples). The in the implementation of the method (C) further required as starting materials arylamines are generally defined by the formula (VE). In this formula, R, Z,
• Y and n are preferred, particularly preferably or very particularly preferably indicated below.
• R is preferably hydrogen, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-
• R is particularly preferably hydrogen, methyl, ethyl, isopropyl or tert-butyl,
• R is very particularly preferably hydrogen
• Z is preferably CY or N
• Y preferably represents fluorine, chlorine, bromine, C r C 4 alkyl, C r C 3 haloalkyl, C r C 4 alkoxy, Q-Cj-haloalkoxy, Ci-C4-alkylthio, Ci-C3-haloalkylthio or cyano, Y furthermore preferably represents hydrogen
• Y is particularly preferably chlorine, methyl, ethyl, n- or iso-propyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, hexafluoroisopropyl or bromhexafluoroisopropyl
• Y furthermore particularly preferably represents hydrogen
• n is preferably 0, 1, 2, 3 or 4, n is more preferably 1, 2 or 3, n is very particularly preferably 2, n is furthermore very particularly preferably 1.
• Arylamines of the formula (VD) are known or can be obtained in a known manner (cf., EP-A 0 936 212, EP-A 1 006 102, EP-A 1 418 169, EP-A 1 418 171).
• the ring closure to the isophthalimide of the formula (VI) is carried out in the presence of a dehydrating reagent.
• a dehydrating reagent Preferably used are phosgene, thionyl chloride, POCl 3 , chloroformate and trifluoroacetic anhydride. Particular preference is given to using alkyl chloroformates such as the methyl, ethyl or propyl ester.
• reaction to the isophthalimide of the formula (VI) can be carried out in the presence of a base.
• Preferred bases are alkali metal hydroxides or carbonates, for example sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate or sodium bicarbonate, amines, for example triethylamine. amine, ethyldiisopropylamine, diazabicyclooctane (DABCO), pyridine, picoline, 4-dimethylaminopyridine. Particular preference is given to using sodium hydroxide or sodium bicarbonate.
• the reaction to the isophthalimide of the formula (VI) is carried out in the presence of a diluent.
• a diluent preferably include nitriles, e.g. Acetonitrile, propionitrile, butyronitrile; halogenated hydrocarbons, e.g. Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, dichloromethane. It is possible to use the mixtures of two or more diluents or else a two-phase system, e.g. Water / butyronitrile, water / methylene chloride, water / toluene, water / chlorobenzene.
• the reaction to form the isophthalimide of the formula (VI) can be further simplified and improved by addition of phase transfer catalysts (PTC) (eg tetramethylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, tetraphenylphosphonium bromide, 18-crown-6).
• PTC phase transfer catalysts
• the reaction with the arylamines of the formula (VH) is carried out in the presence of a diluent.
• a diluent include, preferably, nitriles, such as acetonitrile, propionitrile, butyronitrile; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, dichloromethane.
• reaction with the arylamines of the formula (VII) can be further accelerated by addition of catalytic amounts of acids, such as trifluoroacetic acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid or sulfuric acid. Also suitable is p-ToluolsuIfonklare.
• acids such as trifluoroacetic acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid or sulfuric acid.
• reaction with the arylamines of the formula (VII) is generally carried out at temperatures of 20 0 C to 8O 0 C, preferably at temperatures of 3O 0 C to 6O 0 C.
• the present invention also relates to a process for the preparation of chiral phthalic diamides of the formula (V).
• the process (C) according to the invention can be carried out in different process variants, depending on the time at which the oxidation step takes place in the reaction sequence.
• the following scheme shows two possible variants.
• Example 1 According to this general description of Example 1, the compounds listed in Examples 2 to 4 are obtained.
• Example 2 Lithium 3-bromo-2 - ( ⁇ [(7S) -l-methyl-2- (methylthio ') ethyllamino> carbonyl) benzoate Hal is bromine, M + is lithium. Yield 82%.
• Example 3 Lithium 3-chloro-2 - ( ⁇ [(JS) -l-methyl-2- (methylthio) ethynamino) carbonyl) benzoate
• Hal is chlorine, M + is lithium.
• Hal is bromine, M + is sodium.
• Example 5 According to this general description of Example 5, the compounds listed in Examples 6 to 8 are obtained.
• Example 6 3-Iodo-2- (f [(7S) -l-methyl-2- (methylsulfonyl) ethynnamino ⁇ carbonyl) benzoic acid.
• Benzoate used sodium 3-iodo-2 - ( ⁇ [(7S) -l- Methyl 2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate Yield 85%.
• Example 7 3-Chloro-2 - ( ⁇ r (7S) -l-methyl-2- (methylsulfonyl) ethylamino ⁇ carbonyl) benzoic acid
• Benzoate used Lithium 3-chloro-2 - ( ⁇ [(75) -l - Methyl 2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate Yield 88%.
• Example 8 3-Bromo-2- ( " (r (7ffM-methyl-2- (methylsulfonyl) ethyl-1-amino) carbonyl) benzoic acid.
• Benzoate used Lithium 3-bromo-2 - ( ⁇ [(iS) -l-methyl- 2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate Yield 84%.
• Example 9 3-halo-N 2 -rf; S) -l-methyl-2-methylthiocthyll-N / - (2-niethyl-4-r 2,2,2-trifluoro-1- (trifluoromethoxyethyl) -phenylphthalamide)
• Lithium 3-halo-2 - ( ⁇ [(7S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol) and sodium bicarbonate (83 mmol) are placed in 60 ml of water.
• Example 10 3-halo-N 2 -r (7S) -l-methyl-2 (N-j methylthio'lethyll -4-r2.2.2-trifluoro-l- ( 'trifluoro methyDethyUphenylphthalarnid (general method) Lithium 3 -halo-2 - ( ⁇ [(75) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol) and sodium bicarbonate (83 mmol) are initially charged in 60 ml of water ml butyronitrile to and the reaction mixture heated to 40 0 C.
• Lithium 3-halo-2 - ( ⁇ [(7iS) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol) and sodium bicarbonate (83 mmol) are placed in 60 ml of water.
• After the addition of methyl chloroformate (74 mmol) is stirred for 1 h at 4O 0 C, then cooled to room temperature and the phases separated.
• Example 13 3-Halo-N ? -r (/ S) -1-methyl-2 (methylthio) ethyl-N / (2-methyl-4-R-2,2,2-tetrafluoro-1-trifluoromethyl) -ethyl) -phenyl-phthalamide (general method)
• Lithium 3-halo-2 - ( ⁇ [(7S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol) and sodium bicarbonate (83 mmol) are placed in 60 ml of water.
• methyl chloroformate (74 mmol) is stirred for 1 h at 4O 0 C, then cooled to room temperature and the phases separated.
• the organic phase is added dropwise over 30 minutes to a solution of 2-methyl-4-heptafluoroisopropylaniline (47 mmol) in 30 ml of butyronitrile.
• the reaction mixture is stirred for 2 h at 50 0 C, the precipitate was filtered off and dried.
• Example 13 According to this general description of Example 13, the compounds listed in Examples 14 to 20 are obtained.
• Example 14 3-Bromo-N 2 -r (/ S) -1-methyl-2 (methylthio) ethyll-N y - (2-methyl-4-ri.2.2.2-tetrafluoro-1- (trifluoromethyl)
• DethyllphenvU phthalamide feedstock 3-Bromo-N 2 -r (/ S) -1-methyl-2 (methylthio) ethyll-N y - (2-methyl-4-ri.2.2.2-tetrafluoro-1- (trifluoromethyl)
• Lithium 3-iodo-2 - ( ⁇ [(7 1 S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate Yield 87%, melting point 202 ° C.
• Example 16 3-bromo-N 2 -rf75) -l-methyl-2 ( " methylthio > ) ethyn-N / 4-r2.2.2-trifluoro-1-trifluoromethoxyethyphene-4-phthalamide Feedstocks: 17 g of lithium 3 bromo-2 - ( ⁇ [(75) -1-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate, 7 g sodium bicarbonate, 7 g methyl chloroformate, 13.5 g 4- [2,2,2-trifluoro -l- (trifluoromethyl) ethyl] aniline, giving 24 g of the product.
• Example 17 3-Chloro-N-f 2 ( "7S) -l-methyl-2 (methylthio) -ethyl-N j - (2-methyl-4-r2.2.2-trifluoro-l-rtrifluor- methyl) ethyl] pheny 1) phthalamide
• Example 18 3-Chloro-N 2 -r (7S) -1-methyl-2 (methylthio) ethyl 1 -N j - (2-methyl-4-ri.2.2-trifluoro-1- ( ' trifluoromethyl) ethyl ] phenvU phthalamide
• Starting materials Lithium 3-chloro-2- ( ⁇ [(75) -1-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate, 2-methyl-4- [1, 2,2 trifluoro-1 - (trifluoromethyl) ethyl] aniline Yield 84%, m.p. 185-188 ° C.
• Example 21 S-bromo-N, N, N, C, N-methyl-sulfonylmethane-V, N-methvM-n, N'-tetrafluoro-L- (trifluoromethyl) -phenyl-4-yl-phthalamide
• Example 22 (3Z / E) -4-HaI-3-i (IS) -I-methyl-2- (methylthio) ethyl 1-imino) 2-benzofuran-1 (3H) -one (general method).
• Lithium 3-halo-2 - ( ⁇ [(/ 5) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol) and sodium bicarbonate (83 mmol) are placed in 60 ml of water , One 30 ml of butyronitrile and heated to the reaction mixture to 4O 0 C. After the addition of methyl chloroformate (74 mmol) is stirred for 1 h at 40 0 C, then cooled to room temperature and the phases separated. The organic phase is concentrated.
• Example 23 (3Z ⁇ ) -4-Iodo-3- ⁇ f (/ S) -1-methyl-2- (methylthio) ethylimino ⁇ 2-benzofuran-ir3F ⁇ -on.
• Lithium-3-iodo-2 - ( ⁇ [(7S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate. Yield: 91%, melting point 88-89 0 C.
• Example 24 (3Z / E) -4-Chloro-3- ([(JS) -1-methyl-2- (methylthio) ethyll-imino) -2-benzofuran-1 (3H) -one.
• Lithium-3-chloro-2 - ( ⁇ [(7.S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate. Yield: 93%, melting point 71-72 0 C.
• Example 25 (3Z ⁇ -4-chloro-3 - ([(7S) -l-methyl-2- (methylthio) ethyllirnino] 2-benzofuran-1 (3H [') - on lithium 3-chloro-2 ( ⁇ [(7S) -l-methyl-2- (methylthio) ethyl] amino ⁇ carbonyl) benzoate (50 mmol), sodium bicarbonate (83 mmol) and tetrabutylammonium hydrogensulfate (0.5 mmol) are initially charged in 40 ml of water The reaction mixture is stirred at room temperature for 3 hours, the organic phase is separated off and concentrated in vacuo to give 47 mmol (94% of theory) of the product with 98%

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