WO2003040085A1 - Procede de preparation d'acide carboxylique aminohydroxyaromatique - Google Patents

Procede de preparation d'acide carboxylique aminohydroxyaromatique Download PDF

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WO2003040085A1
WO2003040085A1 PCT/JP2001/009713 JP0109713W WO03040085A1 WO 2003040085 A1 WO2003040085 A1 WO 2003040085A1 JP 0109713 W JP0109713 W JP 0109713W WO 03040085 A1 WO03040085 A1 WO 03040085A1
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acid
derivative
group
carboxylic acid
amino
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PCT/JP2001/009713
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English (en)
Japanese (ja)
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Tomohiro Aoyama
Fuyuhiko Kubota
Hiroaki Taguchi
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Toyo Boseki Kabushiki Kaisha
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Priority to PCT/JP2001/009713 priority patent/WO2003040085A1/fr
Publication of WO2003040085A1 publication Critical patent/WO2003040085A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups

Definitions

  • the present invention relates to a method for producing an aminohydroxyaromatic carboxylic acid. More specifically, the amino and hydroxy groups, which are useful as monomers (AB monomer) of the high-performance heat-resistant polymer AB polybenzoxazole (AB-PBO) and various pharmaceutical intermediates, combine The present invention relates to a method for easily and inexpensively producing an amino hydroxy aromatic carboxylic acid at the ortho position and Z or a derivative thereof. Background technique
  • aminohydroxyaromatic carboxylic acids useful as monomers of AB polybenzoxazole and various pharmaceutical intermediates
  • aminohydroxyaromatic carboxylic acids have been used in the production of 3-hydroxyaminocarboxylic acids.
  • the starting material 4-hydroxybenzoic acid and its ester
  • 3-to-2 and 4-hydroxybenzoic acid and its derivatives with nitric acid.
  • a method of reducing the nitro group of the intermediate with a reducing agent such as tin and isolating it as a hydrochloride US Pat. No.
  • 3-hydroxybenzoic acid which is an isomer of 3-amino and 4-hydroxybenzoic acid and is also useful as a monomer of AB polybenzoxazole, is also 3-hydroxybenzoic acid.
  • ester can be similarly produced.
  • 3-hydroxybenzoic acid or its ester which is a raw material, is subjected to nitration with nitric acid to give 3-nitro or 4-hydroxybenzoic acid or a derivative thereof, and then the intermediate nitro
  • a reducing agent such as hydrosulfuric acid sodium and isolated as a hydrochloride
  • reaction procedures such as isolation and purification are carried out in order to avoid the danger of polynitrates formed during the dinitrogenation and to make the products suitable for polymerization. Cost increases in several stages.
  • yield is significantly reduced due to isomer formation.
  • impurities in aminohydroxyaromatic carboxylic acids hinders the production of high molecular weight and spinnable AB polybenzoxazolyl polyphosphoric acid dope. Therefore, when the aminohydroxyaromatic carboxylic acids obtained by the conventional method were sufficiently purified and then polymerized to produce AB polybenzoxazole, the resulting molded article was extremely costly. .
  • the AB monomer in the present invention refers to a monomer compound having an acid group (Acid) and a base (Base), and a polymer obtained by polymerizing the monomer compound is referred to as an AB polymer.
  • the present invention solves the above-mentioned problems and provides a method for producing high-quality aminohydroxyaromatic carboxylic acids simply and inexpensively.
  • the present inventors have intensively studied a method of producing an industrially advantageous amino hydroxyaromatic carboxylic acid, and as a result, have found that diaromatic aromatics that can be supplied industrially at low cost.
  • Amino hydrides in which the amino group and the hydroxy group are ortho to each other in a two-step reaction using a carboxylic acid and / or a derivative thereof as a new raw material and a reduction reaction and a rearrangement reaction The present inventors have found a method for producing oral xy-aromatic ruponic acid and Z or a derivative thereof, and have completed the present invention. Further, they have found that AB polybenzoxazole can be produced at low cost by heating the amino-hydroxybenzoic acid and / or its derivative obtained by this method in polyphosphoric acid.
  • FIG. 1 shows a total ion chromatogram of a target product obtained by the present invention.
  • Figure 2 shows the mass spectrum of 4-AHBA (di-TMS).
  • Figure 3 shows the mass spectrum of 4-AHBA (tri-TMS form) '. 7K in the light
  • the present invention provides, in a reaction medium, a ditoro aromatic carboxylic acid having at least one ortho position unsubstituted with respect to a nitro group represented by the formula (1) and / or a derivative thereof in a reaction medium.
  • a heat and / or acid catalyst and a no or noble metal catalyst are further obtained.
  • an aminohydroxyaromatic carboxylic acid and / or a derivative thereof in which the amino group and the hydroxyl group represented by the formula (3) are ortho to each other. is there. Equation 1
  • Ar is an aromatic group
  • X is a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms or halogen
  • R is an alkyl group having 1 to 12 carbon atoms
  • Z is A hydroxyl group or an alkoxy group having 1 to 12 carbon atoms or a halogen
  • n is an integer of 0, 1 or 2.
  • reaction medium wherein the reaction medium is a mixture of an organic solvent insoluble in all the reagents which dissolves the nitroaromatic carboxylic acid and / or its derivative and is inert to all the reagents under the reaction conditions, and an aqueous inorganic electrolyte solution.
  • the acid catalyst for the rearrangement reaction is at least one selected from the group consisting of sulfuric acid, methanesulfonic acid, trifluoroacetic acid, polyphosphoric acid, phosphoric acid, phosphorous acid, hypophosphorous acid.
  • Ar is a benzene ring
  • X is a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms
  • Z is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms.
  • the nitro group is at the para or meta position of the COX group, and in the formula (3), either the amino group or the hydroxy group is at the para position of the C ⁇ Z group.
  • the nitro group is at the para-position of the C0X group
  • the amino group is at the para-position of the C0Z group
  • Z is a hydroxyl group in the formula (3).
  • the reduction of the nitrated aromatic carboxylic acid and / or its derivative, which is the first step of the present invention, is carried out using a reducing agent in the reaction medium.
  • Suitable raw materials are unsubstituted or substituted with one or two alkyl groups, provided that at least one ortho position is unsubstituted with respect to the ditoro group.
  • Ar is an aromatic group
  • X is a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms or a halogen
  • R is alkyl having 1 to 12 carbons
  • n is an integer of 0, 1 or 2;
  • Ar is any aromatic ring and aromatic ring system, and each aromatic group may be independently a heterocyclic ring. Specifically, benzene, naphthalene, anthracene, phenanthrene, biphenyl, pyridine and the like are preferred, and benzene is preferred from the viewpoint of industrial utility and reactivity.
  • the aromatic carboxylic acid derivative is an ester, and when X is a halogen such as chlorine, bromine or iodine, it is a halogenated compound.
  • the di-to-lactated aromatic carboxylic acids and / or derivatives thereof which are preferably esters in terms of reactivity and handling, are specifically 4-nitto-benzoic acid, 4-122-tro-2-methyl-benzoic acid , 412-toro-2-ethylbenzoic acid, 412-toro-2-propylbenzoic acid, 412-to- mouth 3-Methylbenzoic acid, 412-toro-3-ethylbenzoic acid, 412 3- (3-propylbenzoic acid, 3- (2-nitrobenzoic acid), 3- (2-nitro-2-methylbenzoic acid), (3--2- (2-ethyl) benzoic acid, 3- (2-nitro-2-propylbenzoic acid) Acid, 3--2- 4-methyl benzoic acid,
  • alkyl esters and chlorides examples include methyl ester, ethyl ester, propyl ester, and butyl ester.
  • it is 412-benzobenzoic acid and / or an alkyl ester thereof, or 3-2-2-benzobenzoic acid and / or an alkyl ester thereof, and more preferably, methyl 4-412-benzobenzoate.
  • the reaction medium used is organic solvent alone or ammonium chloride. 01 09713
  • Aqueous inorganic electrolyte solution containing calcium chloride, hypophosphorous acid and its alkali metal salt, formic acid and its alkali metal salt, ammonium salt, etc. and nitrated aromatic carboxylic acid and Z or its derivatives A mixture with a dissolving organic solvent is used.
  • the mixture may be a heterogeneous system composed of two or more layers or a homogeneous system.
  • the organic solvent a solvent containing at least one selected from the group consisting of ether-based, alcohol-based, ester-based, ketone-based, carboxylic acid-based, and halogenated hydrocarbon-based organic solvents is used.
  • the amount of the reaction medium is appropriately determined by the practitioner, but is generally about 1 to 1 part by weight per 1 part by weight of the aromatic carboxylic acid and Z or its derivative.
  • the inorganic electrolyte ammonium chloride, calcium chloride, or the like is used, and the addition amount thereof is 1 to 10 times, preferably 2 to 6 times, that of the ditoro aromatic carboxylic acid and Z or a derivative thereof. Range of moles. If it is less than 1, the reduction will not proceed sufficiently, and if it is more than 6, the reaction will proceed, but the economic loss will increase.
  • the amount of addition is limited to the amount of the nitrated aromatic carboxylic acid and / or It is 1 to 4 moles, preferably 2 to 2.5 moles of the derivative.
  • the resulting reaction intermediate hydroxyaminoaminocarboxylic carboxylic acids are further reduced to produce reduced aminoamine-containing aromatic carboxylic acids, such as overreductants or dimerized azo acids.
  • Aromatic dicarboxylic acid It is necessary to control the progress of the reduction sufficiently to generate it. The present inventors diligently studied this point, and found that it is important to control the type of the reducing agent, the reaction temperature, and the equivalent ratio of the reducing agent.
  • Known reducing agents include metal powders such as zinc, iron, and tin, stannous chloride, alumina, Raney nickel, palladium / carbon, platinum carbon, platinum oxide, platinum / carbon, and ruthenium oxide. At least one is selected from carbon, hydrogen, hydrazine, hypophosphorous acid and its alkali metal salt, formic acid and its alkali metal salt and ammonium salt, and the like.
  • precious metal catalysts such as aluminum, metal catalysts such as Raney nickel, palladium / carbon, platinum carbon, platinum oxide, rhodium Z carbon and ruthenium / carbon act as catalysts for the reduction reaction, It can also be used in combination with hydrogen, hydrazine, hypophosphorous acid and its alkali metal salt, formic acid and its alkali metal salt gammonium salt.
  • the noble metal catalyst is a catalyst in which 1 to 15% of these metals are supported on carbon. Zinc powder is preferred because of its reactivity, economy, and ease of handling. Combinations of platinum oxide and hydrogen, platinum Z carbon and hydrogen, and palladium Z carbon and hydrogen are also preferred for the same reason.
  • the amount is 2 to 5 times the molar amount of the starting material, ditoxified aromatic carboxylic acid and / or its ester, in order to allow the reduction to proceed completely while suppressing overreduction. And preferably in the range of 2.5-3.5 moles. If the amount is less than 2 times, the reduction does not proceed sufficiently, and if the amount is more than 5 times, the reaction intermediate hydroxyaminoaminocarboxylic carboxylic acids formed are further reduced, and a large amount of overreduced products such as aminated aromatic carboxylic acids are generated Tend to.
  • a mixture of an inorganic electrolyte aqueous solution to which ammonium chloride, calcium chloride, or the like is added and an organic solvent that dissolves diatomalized aromatic carboxylic acid and / or its derivative is used as a reaction medium.
  • the amount of platinum / carbon or palladium / carbon is 1/1 of the weight of the raw materials, the nitrated aromatic carboxylic acid and Z or its ester. The range is from 0 to lZ5. Reduce if less than 1 Z 100 Does not proceed sufficiently, and if it exceeds 1 Z 5, the economic loss is large.
  • the amount of hydrogen absorbed is 2 to 2.5 times mol.
  • platinum / carbon or a combination of palladium / carbon and hydrogen it is preferable to use methanol or ethanol as the reaction medium.
  • JP-A-62-63548 a known method described in JP-A-62-63548 is also suitably used. That is, a heterocyclic nitrogen compound, a phosphine, a phosphite, a sulfide, and a sulfoxide are used as a reaction moderator for further suppressing the formation of a super-reductant. Preferably, it is triphenylphosphine or dimethylsulfoxide. The method of using these may be referred to the description in JP-A-62-63548. Hydrazine, a metal powder such as zinc, is gradually added while increasing the stirring intensity to promote the reduction reaction.
  • the reaction temperature should be kept as low as possible without affecting unacceptable effects, preferably below 25 ° C, in order to suppress the formation of coloring matters and overreductants due to side reactions. It is desirable to terminate the reaction in a short time by vigorous stirring while maintaining. Particularly when using metal powders such as zinc, iron and tin, and stannous chloride, the temperature is more preferably maintained at 5 ° C or lower.
  • the progress of the reaction can be confirmed by means such as high performance liquid chromatography and thin layer chromatography.
  • the reaction is preferably performed in a nitrogen atmosphere to avoid oxidation of the product.
  • the reaction medium containing the produced reaction intermediate hydroxylaminoaminoaromatic acid and / or its derivative, and the solid reducing agent and its oxide are separated into solid and liquid by a technique such as filtration. Since the product is often unstable, it is desirable to perform the reaction quickly under a nitrogen atmosphere.
  • Noble metal catalysts such as palladium Z-carbon, platinum / carbon, rhodium / carbon, ruthenium / carbon, hydrogen, hydrazine, hypophosphorous acid and its alkali metal salts, formic acid and its Metal salt If a combination of ammonium salts is used, palladium carbon, platinum
  • Noble metal catalysts such as Z-carbon, platinum oxide, rhodium Z-carbon, and ruthenium / carbon can also act as rearrangement catalysts for rearrangement reactions.
  • the second stage of the present invention, the rearrangement is carried out without performing solid-liquid separation.
  • a r is an aromatic group
  • X is a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms or a halogen
  • R is alkyl having 1 to 12 carbons
  • n is an integer of 0, 1 or 2;
  • the second step of the present invention the rearrangement of the reaction intermediate hydroxyaminoaminated aromatic carboxylic acid and / or its derivative, is carried out in a reaction medium by heating and using Z or an acid catalyst and a no or noble metal catalyst.
  • the rearrangement reaction of the reaction intermediate hydroxyaminoaminoaromatic carboxylic acid and / or X produced in the previous reduction reaction is carried out in a solid-liquid separated solution without isolating and purifying the derivative. I do.
  • the reaction medium is a mixed system composed of two or more layers, the organic layer is separated, and the rearrangement reaction is continuously performed in the aqueous layer containing the reaction intermediate. The organic layer can be recycled to the reduction reaction as it is.
  • the rearrangement reaction may be carried out as it is, or the rearrangement reaction may be carried out after distilling off the organic solvent. If the reaction medium is an organic solvent alone, it is necessary to distill off the organic solvent and replace most of it with water.
  • the acid catalyst is not particularly limited as long as it is generally used. Among them, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, polyphosphoric acid, phosphoric acid, phosphorous acid, hypophosphorous acid Phosphoric acid is preferred. These may be used in combination.
  • sulfuric acid and phosphoric acid are more preferred (the amount is 5 to 150 times the molar amount of the di-totalized aromatic carboxylic acid and / or derivative thereof, preferably 10 to 120 times). If it is less than 5 times, rearrangement does not proceed sufficiently, and if it is more than 150 times, side reactions such as dimerization and resinification progress, and the desired aminohydroxyaromatic compound
  • the reaction temperature is not particularly limited, but is preferably set by the practitioner so that the reaction proceeds under heating and reflux conditions. Is usually about 0.5 to 72 hours.
  • noble metal catalysts such as palladium Z carbon, platinum carbon, rhodium Z carbon and ruthenium z carbon can be used as the rearrangement catalyst for the rearrangement reaction.
  • heterocyclic nitrogen compounds, phosphines, phosphites, sulfides, and sulfoxides are used as reaction moderators to suppress the formation of overreduced substances. I have. Preference is given to Driphenylphosphine and dimethylsulfoxide. The method of using these may be referred to the descriptions in JP-A-62-63548, US Pat. No. 3,715,977.
  • the progress of the reaction can be confirmed by means such as high performance liquid chromatography and thin layer chromatography.
  • the reaction is preferably carried out in a nitrogen atmosphere to avoid oxidation of the product.
  • Ar is an aromatic group
  • R is alkyl having 1 to 12 carbons
  • Z is a hydroxyl group or an alkoxy group having 1 to 12 carbon atoms or a halogen
  • n is an integer of 0, 1 or 2;
  • 4-amino-3-hydroxybenzoic acid 4-amino-3-hydroxy-2-methylbenzoic acid, 4-amino-3-hydroxy-12-ethylethylbenzoic acid, 4-amino-3 —Hydroxy-2-propyl benzoic acid, 4-Amino 3-Hydroxy 5-methylbenzoic acid, 4-Amino 3-Hydroxy-5-propylbenzoic acid, 4-Amino 3-Hydroxy 6-Methylbenzoic acid, 4-Amino 3-Hydroxy-6-Propylbenzoic acid, 3-Amino 4-Hydroxybenzoic acid, 3-Amino 4-Hydroxy-1-2-Methylbenzoic acid 3-amino-4-hydroxy-2-ethylbenzoic acid, 3-amino-4-hydroxyl-2-benzopyrbenzoic acid, 3-amino-4-hydroxy-5-methylbenzoic acid.
  • 3-amino-4,1-hydroxy-5-propylbenzoic acid 3-Amino 4—Hydroxy 6-Methylbenzoic acid, 3-Amino 4-Hydroxy-1 6-propylbenzoic acid, 4-Amino 3—Hydroxynaphthalene-1 Amino 4-hydroxyhydroxynaphthalene-11-carboxylic acid, 6-amino-5-hydroxynaphthalene-12-carboxylic acid, 6-amino-7-hydroxynaphthalene1-2-carboxylic acid, etc. These alkyl esters and halides are mentioned.
  • it is 4-amino-3-hydroxybenzoic acid, 3-amino-4-hydroxybenzoic acid, and more preferably 4-amino-3-hydroxybenzoic acid.
  • the amino hydroxyaromatic carboxylic acid and / or its derivative, which is the target compound, is decomposed by light when isolated in a neutral state, and is relatively unstable, such as being oxidized by air.
  • Isolate in the form of salt Is preferred.
  • the strong acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, methanesulfonic acid, and trifluoroacetic acid. Of these, hydrochloric acid and phosphoric acid are preferred from the viewpoint of handling during polymerization.
  • the precipitated amine salt can be recovered by adding a sufficient amount of a strong acid to the reaction medium as it is or as a solution.
  • hydrochloric acid hydrogen chloride may be blown directly. It is preferable to use an antioxidant such as stannous chloride at the time of isolation. Activated carbon can be used if necessary.
  • the polybenzoxazole is produced by polymerizing the amino hydroxy aromatic carboxylic acid thus obtained and Z or a derivative thereof. Using aminohydroxyaromatic carboxylic acid and Z or a derivative thereof, 105 to 120% of polyphosphoric acid, and phosphorus pentoxide, for example, as described in U.S. Patent No. 4,533,693 By heating and mixing at 70 to 220 ° C depending on the method, AB polybenzoxazole, which has a high degree of polymerization and can withstand molding, can be obtained at a lower cost than existing methods.
  • the white powder obtained by washing with dilute hydrochloric acid and drying over phosphoric anhydride was obtained by nuclear magnetic resonance absorption spectrum in deuterated dimethyl sulfoxide and infrared absorption spectrum by KBr tablet method. It was 4-amino-3-hydroxybenzoic acid hydrochloride (4-AHBA), and the theoretical yield from methyl 4-benzoate was 73%. Purity by high performance liquid chromatography (reverse phase mode) was 98.5 % c (Examples 2, 3, and 4).
  • Example 1 In the reaction, the same operation as in Example 1 was performed except that the reduction reaction temperature, the reducing agent molar ratio, and the acid catalyst type shown in Table 1 were changed. The results are also shown in Table 1.
  • Example 1 The reaction was carried out in the same manner as in Example 1 except that the reduction reaction was carried out in the range of 25 ° C to 53 ° C without temperature control. The resulting reaction medium was colored dark red. And an insoluble oily component was found in the reaction medium. Subsequently, the rearrangement reaction was carried out in the same manner as in Example 1, and the reaction medium was analyzed by high-performance liquid chromatography. The yield of the desired 4-amino-3-hydroxybenzoic acid was about 25%. It was. The results are shown in Table 1.
  • Example 1 'The reaction was carried out in the same manner as in Example 1 except that the amount of the reducing agent was changed at the molar ratio shown in Table 1. The results are shown in Table 1.
  • Example 1 3.5 ⁇ 5 H 2 S0 4 73
  • Example 2 3.5 ⁇ 5 H 2 S0 4 63
  • Example 3 4.5 ⁇ 5 ⁇ H 2 S0 4 66
  • Example 5 3.5 25-53 H 2 S0 4 25
  • Example 6 1.2 ⁇ 5 H 2 S0 4 22
  • the solid was immediately filtered under reduced pressure, and the solid was washed with a small amount of water and furan with tetrahydrofuran.
  • the filtrate and the washing solution were combined, transferred to an Erlenmeyer flask, added with 80 parts by weight of concentrated sulfuric acid, and purged with nitrogen. Then, the mixture was heated and refluxed for 1 hour while stirring under a nitrogen stream. The solution became light brown. This was allowed to cool at room temperature, and then neutralized with an aqueous solution of sodium hydroxide under ice-cooling ( 1 part by weight of stannous chloride, 100 parts by weight of concentrated hydrochloric acid, and 5 parts by weight of powdered activated carbon were stirred. The mixture was heated at 50 ° C.
  • the activated carbon was filtered through a fluted filter paper, allowed to cool to room temperature, and the precipitated white powder crystals were filtered.
  • the white powder obtained by drying over phosphoric acid was 4-amino-13-hydroxybenzoic acid hydrochloride from nuclear magnetic resonance absorption spectrum, infrared absorption spectrum, and mass spectrometry. The theoretical yield from ditobenzoic acid was 55%. Purity by fast liquid chromatography (reverse phase mode) was 98.0%.
  • Example 2 After the rearrangement reaction in Example 1, the product obtained by neutralization was dissolved in anhydrous acetonitrile and trimethylsilylated with BSA (N, 0-pistrimethylsilyl acetamide). did. The obtained sample was analyzed by capillary gask mouth chromatography (column: HR-1) / mass spectrometry. The obtained total ion chromatogram and mass spectrum are shown in FIGS. 1, 2 and 3. In the product, in addition to the desired 4-amino-3-hydroxybenzoic acid, by-products such as 4-aminobenzoic acid were found.
  • the resulting solution was transferred to an Erlenmeyer flask, and 1 part by weight of 5% palladium carbon, 40 parts by weight of concentrated sulfuric acid, and 10 parts by weight of dimethyl sulfoxide were added, and after purging with nitrogen, the mixture was stirred under a nitrogen stream. The mixture was refluxed for 2 hours while heating. Analysis of the reaction medium by high performance liquid chromatography showed that the yield of the desired 4-amino-3-hydroxybenzoic acid was 65%. 7% of 4-aminobenzoic acid was obtained as a by-product.
  • the obtained solution was transferred to an Erlenmeyer flask, phosphoric acid (48 parts by weight) was added, the atmosphere was replaced with nitrogen, and the mixture was refluxed for 48 hours while stirring under a nitrogen stream. Analysis of the reaction medium by high performance liquid chromatography showed that the yield of the desired 4-amino-3-hydroxybenzoic acid was 71%. Further, 1 part by weight of stannous chloride, 200 parts by weight of phosphoric acid and 5 parts by weight of powdered activated carbon were added with stirring, and the mixture was heated at 50 ° C. until the deposited precipitate was dissolved. The activated carbon was filtered through a fluted filter paper, allowed to cool to room temperature, and the precipitated white powder crystals were filtered.
  • the white powder obtained by drying over anhydrous phosphoric acid was analyzed by nuclear magnetic resonance absorption spectrum, infrared absorption spectrum, mass spectrometry and elemental analysis to determine the phosphoric acid 4-amino-3-hydroxybenzoate.
  • the theoretical yield from dibenzobenzoic acid was 65%.
  • Purity by high performance liquid chromatography (reverse phase mode) was 98.7%.
  • the mixture was transferred to an ammonia flask and heated to reflux for 6 hours while stirring under a nitrogen stream in the presence of 5% palladium carbon and dimethyl sulfoxide.
  • the reaction medium was analyzed by high-performance liquid chromatography, the yield of the desired 41-amino-3-hydroxybenzoic acid was 47%.
  • the mixture was transferred to a Renmeier flask and heated to reflux for 30 hours while stirring under a nitrogen stream in the presence of 5% palladium carbon and dimethyl sulfoxide.
  • the reaction medium was analyzed by high performance liquid chromatography, the yield of the desired 4-amino-13-hydroxybenzoic acid was 63%. Also, methyl 4-amino-3-hydroxybenzoate was obtained in 5%, by-products of 9% of 4-aminobenzoic acid and 2% of methyl 4-aminobenzoate were obtained.
  • Example 2 To 16 parts by weight of the 4-amino-3-hydroxybenzoic acid hydrochloride obtained in Example 1, 34 parts by weight of polyphosphoric acid and 15 parts by weight of phosphorus pentoxide were added. Polymerization was carried out according to the method described in 693. The obtained dope of AB polybenzoxazole was a white opaque solid at room temperature. The intrinsic viscosity of the polymer in methanesulfonic anhydride and methanesulfonic anhydride at 25 ° C. was 13.5, and the polymer had a molecular weight sufficient to obtain a molded product.
  • Example 14 To 14 parts by weight of 4-amino-3-hydroxybenzoic acid phosphate obtained in Example 14 were added 10 parts by weight of polyphosphoric acid and 11 parts by weight of phosphorus pentoxide, and Polymerization was carried out according to the method described in Japanese Patent No. 49595492.
  • the obtained AB polybenzoxazole dope was a white opaque solid at room temperature.
  • the intrinsic viscosity of the polymer in methanesulfonic anhydride and methanesulfonic anhydride at 25 ° C. was 11.0, and had a molecular weight sufficient to obtain a molded product.

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Abstract

L'invention concerne un procédé de préparation d'un acide carboxylique aminohydroxyaromatique et/ou d'un dérivé de celui-ci, le groupe amino et le groupe hydroxyl étant en position ortho l'un par rapport à l'autre. Ce procédé consiste : à réduire, au moyen d'un agent de réduction, dans un milieu de réaction, un acide carboxylique nitroaromatique et/ou un dérivé de celui-ci qui est non substitué dans au moins une des positions ortho par rapport au groupe nitro, de manière à obtenir un acide carboxylique aromatique hydroxylaminé et/ou un dérivé de celui-ci comme intermédiaire; et puis à soumettre le produit obtenu à un réarrangement au moyen de chaleur et/ou d'un catalyseur acide et/ou d'un catalyseur de métal noble.
PCT/JP2001/009713 2000-05-08 2001-11-07 Procede de preparation d'acide carboxylique aminohydroxyaromatique WO2003040085A1 (fr)

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PCT/JP2001/009713 WO2003040085A1 (fr) 2000-05-08 2001-11-07 Procede de preparation d'acide carboxylique aminohydroxyaromatique

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JP7223480B2 (ja) 2020-09-14 2023-02-16 花王株式会社 ４－アミノ安息香酸水酸化活性を有するポリペプチド及びその利用

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EP0085890A1 (fr) * 1982-01-29 1983-08-17 MALLINCKRODT, INC.(a Missouri corporation) Procédé de préparation de p-aminophénol et de p-aminophénol alkyl-substitué
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