WO1998035932A1 - PROCEDE DE PRODUCTION D'ACIDE 3-NITRO-o-TOLUIQUE - Google Patents

PROCEDE DE PRODUCTION D'ACIDE 3-NITRO-o-TOLUIQUE Download PDF

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Publication number
WO1998035932A1
WO1998035932A1 PCT/JP1998/000353 JP9800353W WO9835932A1 WO 1998035932 A1 WO1998035932 A1 WO 1998035932A1 JP 9800353 W JP9800353 W JP 9800353W WO 9835932 A1 WO9835932 A1 WO 9835932A1
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WO
WIPO (PCT)
Prior art keywords
nitro
reaction
xylene
acid
bromide
Prior art date
Application number
PCT/JP1998/000353
Other languages
English (en)
Japanese (ja)
Inventor
Yoshio Ishino
Toshinobu Ono
Toshihide Suruga
Nobuyori Shibamoto
Original Assignee
Sugai Chemical Industry Co., Ltd.
Osaka-Shi
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 Sugai Chemical Industry Co., Ltd., Osaka-Shi filed Critical Sugai Chemical Industry Co., Ltd.
Publication of WO1998035932A1 publication Critical patent/WO1998035932A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups

Definitions

  • the present invention relates to a method for producing 3-nitro-o-toluic acid. More specifically, 3-nitro-10-xylene (ie, 1,2-dimethyl-3-nitrobenzene) is oxidized with oxygen or an oxygen-containing gas to produce highly selective 3-nitro-2-toluic acid. How to do. Background art
  • 3-Nitro-1-toluic acid is a compound useful as a raw material for medicines and the like.
  • the present inventors have intensively studied for the purpose of developing a method for obtaining a target substance with high selectivity.
  • the intended purpose was achieved by using a specific catalyst system in a lower aliphatic carboxylic acid-based solvent.
  • the present invention provides a 3-nitro-o-toluic acid which can obtain 3-nitro-o-toluic acid more selectively than conventional techniques in the oxidation of 3-nitro-o-xylene.
  • An object of the present invention is to provide a method for producing an acid. Disclosure of the invention
  • the present invention provides a method for producing an oxygen- or oxygen-containing gas containing 3-nitro-o-xylene in a lower aliphatic carboxylic acid solvent or a mixed solvent of a lower aliphatic carboxylic acid and an organic solvent in the presence of a heavy metal catalyst and a reaction accelerator.
  • This is a process for producing 3-nitro-2-o-toluic acid, characterized in that it is oxidized to give 3-nitro-2-o-toluic acid.
  • acetic acid, propionic acid and / or butyric acid in an amount of 5 to 100 times by weight based on 3-nitro-0-xylene;
  • bromides and hydroxides of cobalt, manganese, cerium or copper, carbonates with these heavy metals, lower aliphatic carboxylate or naphthenate, and acetyl acetate of these heavy metals It is preferable to use one or two or more selected from the group consisting of 3-nitro-o-xylene in a molar amount of 0.005 to 1.0 mol times; 1 to 2 selected from the group consisting of hydrogen hydride, cobalt bromide, ammonium bromide, alkali metal bromine compounds, tetra-n-butylammonium bromide, tetrabromoethan, bromoacetic acid and benzyl bromide
  • the present invention has the above-mentioned constitution, and the method of the present invention is represented by the following reaction formula.
  • the basic operation of the method is as follows: 3-nitro-0-xylene (1) is dissolved in a lower aliphatic carboxylic acid-based solvent. Contact with oxygen or an oxygen-containing gas in the presence of a catalyst and a reaction accelerator;
  • a mixed solvent of a lower aliphatic carboxylic acid or a lower aliphatic carboxylic acid and an organic solvent is used as the solvent.
  • lower aliphatic carboxylic acids include acetic acid, propionic acid, and butyric acid, and acetic acid is most advantageous industrially.
  • the lower aliphatic carboxylic acid is used in an amount of 5 to 100 times by weight, preferably 25 to 60 times by weight of 3-nitro-2-o-xylene. When the amount of the lower aliphatic carboxylic acid is less than 5 times by weight, the oxidation rate is small and the conversion of 3-nitro-xylene is reduced.
  • the method of the present invention can also be carried out in a mixed solvent of a lower aliphatic carboxylic acid and an organic solvent.
  • the lower aliphatic carboxylic acid include the compounds described above, and examples of the organic solvent include tetrahydrofuran, dioxane, methylene chloride, and dimethylformamide.
  • the mixing ratio of the organic solvent with respect to the lower aliphatic carboxylic acid can be appropriately selected as long as it does not adversely affect the reaction, but is preferably equal to or less than the lower aliphatic carboxylic acid.
  • the conditions when the above-mentioned lower aliphatic carboxylic acid is used can be referred to.
  • any heavy metal catalyst capable of causing the reaction of the above reaction formula to proceed can be used. These can also be used, for example, bromides and hydroxides with heavy metals such as cobalt, manganese, cerium, and copper; carbonates with these heavy metals, lower aliphatic carboxylic acids (eg, acetic acid, propionic acid, etc.). ), Naphthenic acid salts, and acetyl acetate of these heavy metals. In particular, it is preferable to use cobalt acetate in view of the selectivity of the target substance.
  • the above heavy metal catalysts may be used in combination of two or more.
  • the amount of the heavy metal catalyst used relative to 3-butene-0-xylene is 0.05 to 1.0 mole times, preferably 0.1 to 0.8 times mole, more preferably 0.3 to 0 times, 6 molar times are used. If the amount of the heavy metal catalyst used is less than 0.005 mole times, a sufficient reaction rate cannot be obtained, and if it exceeds 0 mole times, the decomposition of the reactants into carbon dioxide tends to increase, and the catalyst cost is burdened. Increases, which is economically disadvantageous. In addition, when a reaction promoting aid such as aldehydes described below is used, the amount of the heavy metal catalyst used can be reduced.
  • reaction accelerator examples include inorganic bromine compounds such as bromine, hydrogen bromide, cobalt bromide, ammonium bromide, and alkali metal bromides (eg, sodium bromide, potassium bromide, etc.) and tetra-n-butylammonium.
  • inorganic bromine compounds such as bromine, hydrogen bromide, cobalt bromide, ammonium bromide, and alkali metal bromides (eg, sodium bromide, potassium bromide, etc.) and tetra-n-butylammonium.
  • Organic bromine compounds such as mubromide, tetrabromoethane, bromoacetic acid, benzyl bromide; iodine, hydrogen iodide, ammonium iodide, alkali metal iodine compounds (eg, sodium iodide, potassium iodide, etc.) And inorganic iodine compounds such as tetra-n-butylammonium monoxide and acetic acetic acid. It is preferable to use sodium bromide from the selectivity of a special purpose substance. .
  • the above reaction accelerators may be used in combination of two or more.
  • the amount of the reaction accelerator used with respect to the heavy metal catalyst is 1.0 to 32% by weight, preferably 5 to 20% by weight, more preferably 9 to 18% by weight based on the heavy metal catalyst. If the amount of the reaction accelerator is less than 1.0% by weight, a sufficient effect cannot be obtained. If the amount exceeds 32% by weight, the contamination of the product by the reaction accelerator and the economic burden are remarkable. Is not preferred.
  • reaction accelerator for example, formaldehyde, paraformaldehyde, acetate aldehyde, paraaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, black benzaldehyde, and fluoro benzaldehyde Aldehydes such as aldehydes and benzoaldehydes; ketones such as acetone, methyl ethyl ketone, getyl ketone and benzophenone; hydrochloric acid, monochrome
  • acids such as acetic acid
  • the aldehydes, ketones and / or acids are used in an amount of 0.01 to 5.0 mole times, preferably 0.05 to 0.5 mole times, relative to 3-nitro-0-xylene. .
  • the oxygen or oxygen-containing gas used as the oxidizing agent may be any gas containing molecular oxygen, such as pure oxygen or air or any other gas containing molecular oxygen. Normal air is preferred. Oxygen or an oxygen-containing gas can be introduced at normal pressure or under pressure.
  • the best method for introducing an enzyme or an enzyme-containing gas is to blow it into the reaction solution at normal pressure, and to increase the total reaction pressure to 1 to 50 atm, preferably 2 to 10 atm under pressurized condition. It is preferable to use a method in which the oxygen concentration in the exhaust gas from the reaction vessel is in the range of 1 to 8% by volume.
  • the introduced amount of oxygen or oxygen-containing gas and the reaction time can be adjusted by checking the progress of the reaction by means such as chromatography.
  • the reaction temperature depends on the type and amount of the heavy metal catalyst used, the type and amount of the reaction accelerator, the type and amount of aldehydes, ketones, hydrochloric acid, monochloroacetic acid, etc. used in combination with the reaction accelerator, oxygen or oxygen-containing gas. It can be set as appropriate depending on the method of introduction of butane, but is generally carried out at a temperature of 70 to 250 ° C, and especially at a temperature of 100 to 160 ° C due to the reactivity of 3-nitro-o-xylene. Between is preferred.
  • the target substance can be collected from the reaction solution according to a conventional method described in the above-mentioned prior literature.
  • the unreacted material is recovered by extraction with a hydrophobic organic solvent,
  • the reaction can be carried out by acidifying the solution and subjecting the target substance to acid precipitation.
  • the recovered unreacted substances can be reused.
  • the method of the present invention is a simple method of oxygen oxidation of 3-nitro-0-xylene, and has advantages such as easy post-treatment of the reaction solution and no generation of harmful gas.
  • 3-Nitric-o-toluic acid can be obtained with selectivity. Therefore, according to the method of the present invention, 3-nitro-0-toluic acid can be industrially and economically produced.
  • the reaction was carried out in the same manner as in Example 1 except that the solvent was changed from acetic acid to butyric acid, and the reaction temperature was raised from 108 ° C to 140 ° C.
  • the obtained reaction solution was confirmed by HPL analysis. Was the reaction result.
  • the amount of sodium bromide used was 15.8 mg ( ⁇ . 16 mmol: cobalt acetate tetrahydrate
  • the reaction was carried out in the same manner as in Example 1 except that the reaction solution was reduced to 1.4% by weight).
  • the obtained reaction solution was confirmed by HPLC analysis, and the following reaction results were obtained.
  • a reaction was conducted in the same manner as in Example 1 except that 0.16 g of ammonium bromide (1.59 mmol: 14.2% by weight based on cobalt acetate tetrahydrate) was used instead of sodium bromide.
  • the obtained reaction mixture was confirmed by HPL analysis, and the following results were obtained.
  • the reaction was carried out in the same manner as in Example 1 except that ordinary air was used instead of oxygen gas.
  • the obtained reaction solution was confirmed by H.P.L.C. analysis, and the following results were obtained.
  • the mole times of the crushing of cobalt acetate, the mole times of the column for the reaction promoter and the ⁇ times of acetic acid are each 3%.
  • FfLffi% in the column of soda bromide is based on cobalt acetate.

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

Abstract

L'invention concerne un procédé de production d'acide 3-nitro-o-toluique qui consiste à oxyder du 3-nitro-o-xylène avec de l'oxygène ou un gaz oxygéné dans un solvant à base d'un acide carboxylique aliphatique inférieur, en présence d'un catalyseur à métal lourd et d'un accélérateur de réaction. Ce procédé permet d'obtenir, de façon hautement sélective, de l'acide 3-nitro-o-toluique.
PCT/JP1998/000353 1997-02-17 1998-01-29 PROCEDE DE PRODUCTION D'ACIDE 3-NITRO-o-TOLUIQUE WO1998035932A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9/49684 1997-02-17
JP4968497 1997-02-17
JP9/193192 1997-07-02
JP19319297A JP4148480B2 (ja) 1997-02-17 1997-07-02 ３−ニトロ−ｏ−トルイル酸の製造方法

Publications (1)

Publication Number Publication Date
WO1998035932A1 true WO1998035932A1 (fr) 1998-08-20

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PCT/JP1998/000353 WO1998035932A1 (fr) 1997-02-17 1998-01-29 PROCEDE DE PRODUCTION D'ACIDE 3-NITRO-o-TOLUIQUE

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JP (1) JP4148480B2 (fr)
WO (1) WO1998035932A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685280A (zh) * 2022-01-25 2022-07-01 南昌大学 一种3-硝基邻苯二甲酸的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362807B (zh) * 2020-03-30 2022-01-18 江苏永安化工有限公司 一种3-硝基-2-甲基苯甲酸的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065477A (en) * 1976-10-29 1977-12-27 Bison-Werke Bahre & Greten Gmbh & Co. Kg Process for preparing highly pure 1-nitroanthraquinone
JPS5951242A (ja) * 1982-09-14 1984-03-24 Toray Ind Inc ｍ−ニトロ安息香酸の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065477A (en) * 1976-10-29 1977-12-27 Bison-Werke Bahre & Greten Gmbh & Co. Kg Process for preparing highly pure 1-nitroanthraquinone
JPS5951242A (ja) * 1982-09-14 1984-03-24 Toray Ind Inc ｍ−ニトロ安息香酸の製造法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685280A (zh) * 2022-01-25 2022-07-01 南昌大学 一种3-硝基邻苯二甲酸的制备方法

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Publication number Publication date
JPH10287627A (ja) 1998-10-27
JP4148480B2 (ja) 2008-09-10

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