JP2005170821A - Method for producing amide compounds by hydration reaction of nitrile compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an amide compound by the hydration reaction of the corresponding nitrile compound in the presence of a solid catalyst capable of improving/maintaining a catalyst activity performance, by which the amide compound can be produced in a high yield and in high selectivity. <P>SOLUTION: This method for producing the amide compound (for example, benzamide) by the hydration reaction of the nitrile production (for example, benzonitrile) is characterized by using a solid catalyst prepared by carrying at least one element (for example, ruthenium) selected from the group consisting of the groups 8, 9 and 10 elements on a metal oxide (for example, alumina). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a method for producing a corresponding amide compound by a hydration reaction of nitriles, and a solid catalyst in which at least one element selected from the group consisting of Groups 8, 9, and 10 is supported on a metal oxide The present invention relates to a method for producing an amide compound characterized in that

As a method for obtaining a corresponding amide compound by hydration reaction of nitriles in the presence of a solid catalyst, a method using Raney copper (for example, see Patent Document 1) or a method using a cobalt-based catalyst (for example, see Patent Document 2). ), A method using a catalyst in which copper oxide is supported on alumina (for example, see Patent Document 3), and the like are known. In addition, a method using a catalyst in which potassium fluoride is supported on alumina or neutral phosphate (for example, Non-Patent Documents 1 and 2) or a method using manganese dioxide (for example, see Patent Document 4) is known. Recently, a method using hydroxyapatite substituted with ruthenium (for example, Non-Patent Document 3) and a method using a catalyst in which sodium nitrate is supported on fluoroapatite (for example, Non-Patent Document 4) have also been reported.

  However, these methods have problems such as insufficient yield and selectivity of the target amide compound, and significant reduction in catalytic activity as the hydration reaction continues, leaving room for further technical innovation. there were.

Japanese Patent Publication No.49-30810 US Patent 4,329,500 US Pat. No. 6,472,561 Japanese Patent Publication No. 2853190 Synth. Commun., 1982, 12, 177. Tetrahedron. Lett., 1996, 37, 6555 Chem. Commun., 2001, 461 Tetrahedron. Lett., 2003, 44, 4031

The present invention has been made in view of the above situation, and in the production of the corresponding amide compound by the hydration reaction of nitriles, a higher yield is obtained by using a solid catalyst capable of improving and maintaining the catalytic activity. It is an object of the present invention to provide a method for producing an amide compound with high efficiency and high selectivity.

The present inventor has studied various catalysts for nitrile hydration reaction, and the solid catalyst in which at least one element selected from a specific group in the periodic table is supported on a metal oxide is a hydration of nitriles. The inventors have found that the present invention has extremely high activity and that these catalysts can be used in a recycling reaction without lowering the catalytic activity, and have conceived that the above problems can be solved brilliantly.

  That is, the present invention relates to a method for producing a corresponding amide compound by hydration reaction of nitriles, and a solid in which at least one element selected from the group consisting of Groups 8, 9, and 10 is supported on a metal oxide. It is a manufacturing method of the amide compound characterized by using a catalyst.

The present invention is described in detail below.
The catalyst used in the present invention is a solid catalyst in which at least one element selected from the group consisting of Groups 8, 9, and 10 is supported on a metal oxide, and one such catalyst may be used. Two or more kinds may be used.

  In the present invention, when the corresponding amide compound is produced by the hydration reaction of nitriles using such a catalyst, the amide compound can be produced with higher yield and higher selectivity. The corresponding amide compound here is a compound in which a nitrile group is converted into an amide group by a hydration reaction. When two or more nitrile groups are present in the molecule, at least one nitrile group is present. Those converted to amide groups are shown.

As a preferable form of the catalyst, at least one element selected from the group consisting of Group 8, Group 9, and Group 10 is at least one element selected from the group consisting of ruthenium, rhodium, palladium, iridium and platinum. It is a certain form, more preferably a form that is at least one element selected from the group consisting of ruthenium, palladium, and platinum.
“Group” means a group in the 18-group long periodic table.

  A preferable form of the catalyst is a form in which at least one element selected from the group consisting of Groups 8, 9, and 10 is supported on a metal oxide. The catalyst preferably has at least one element selected from the group consisting of Group 8, Group 9, and Group 10 and a metal oxide, and preferably contains these as main components. As long as it is effective, it may contain impurities generated in the catalyst preparation process and other components.

  Examples of the metal oxide that is an essential component of the catalyst include rare earth oxides such as alumina, cerium oxide, and lanthanum oxide, barium oxide, tungsten oxide, and composite oxides such as silica-alumina. The above can be used. Among these, it is preferable to make alumina or rare earth oxide essential.

  The content of at least one element selected from the group consisting of Group 8, Group 9, and Group 10 in the catalyst can be set as appropriate, but with respect to 100 parts by weight of the metal oxide as the support It is preferably 0.1 parts by weight or more, and preferably 50 parts by weight or less. More preferably, it is 1 part by weight or more and 40 parts by weight or less.

  As a method for preparing the catalyst, for example, it can be prepared by the method described in Angew. Chem. Int. Ed. 2003, 42, 1479.

  In the method for preparing the catalyst, as a raw material form of at least one element selected from the group consisting of Group 8, Group 9, and Group 10, both inorganic salts and organic salts can be used, preferably nitrates. , Chlorides, sulfates and acetates, more preferably chlorides.

  In the following, the reaction substrate, production conditions, etc. in the case of producing the corresponding amide compound by hydration reaction of nitriles using the above catalyst as a preferred embodiment of the present invention will be described.

  As the nitrile as the reaction substrate, a nitrile having about 1 to 20 carbon atoms is preferable. For example, aliphatic saturated nitriles such as acetonitrile, propionitrile, butyronitrile, pentanonitriledodecanonitrile, succinonitrile, adiponitrile, acrylonitrile, methacrylonitrile, crotononitrile, beta-phenylacrylonitrile, 2-cyano-2- Unsaturated aliphatic nitriles such as butene, 1-cyano-1-octene, 10-undecenonitrile, maleonitrile, fumaronitrile, benzonitrile, methylbenzonitrile, methoxybenzonitrile, fragrance such as chlorobenzonitrile, naphthonitrile, phthalonitrile, etc. Group nitriles. Heterocyclic nitrile compounds such as 4-cyanopyridine and 3-cyanothiophene, nitriles having a carbon-carbon double bond in the molecule such as cyanostyrene, and mandelonitrile such as 2-chloromandelonitrile There can be mentioned.

  The amount of the catalyst used is such that the molar ratio of nitriles as reaction substrates to at least one element selected from the group consisting of Group 8, Group 9, and Group 10 contained in the catalyst is 100,000 / 1 or more. It is preferable to make it become, More preferably, it is 10,000 / 1 or more. Moreover, it is preferable to set it as 1/10 or less, More preferably, it is 1/1 or less.

  As a solvent in the production of the amide compound, water and / or an organic solvent is used. As an organic solvent, 1 type (s) or 2 or more types can be used, The thing which does not react with the nitrile which is a reaction substrate, and the produced | generated amide compound is preferable.

  As reaction conditions for the hydration reaction, the reaction temperature is preferably 0 ° C. or higher, more preferably room temperature or higher. Moreover, 250 degrees C or less is preferable, More preferably, it is 180 degrees C or less.

The reaction time is preferably several minutes or longer, and is preferably within 150 hours. More preferably, it is within 48 hours. The reaction pressure is preferably equal to or higher than normal pressure, and is preferably 2 × 10 ⁷ Pa or lower. More preferably, it is 5 × 10 ⁶ Pa or less. The catalyst can be used in a suspended bed or a fixed bed, and adopts a flow type or batch type reaction mode.

  Since the amide compound obtained by the method of the present invention can be obtained with high yield and high selectivity, it is possible to obtain the target amide compound with high purity without any special purification operation. For example, after the reaction, after separating the solid catalyst by filtration operation, it is possible to obtain a solid matter produced by cooling the obtained filtrate or a solid matter remaining after the solvent is distilled off as a high-purity amide compound. These can also be used as organic synthetic raw materials and polymerizable monomers.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” represents “mass%” and “part” represents “part by mass”.

(Catalyst preparation)
Ru / Al ₂ O ₃
In 60 mL of an aqueous ruthenium chloride solution (8.3 × 10 ⁻³ M), 2.0 g of γ-alumina (JRC-ALO-4, BET surface area: 174 m ^{2 /} g) was added and stirred at room temperature for 15 minutes, then solid The minutes were filtered, washed with a large amount of pure water, and dried at room temperature under vacuum. The obtained solid content was added to 30 mL of pure water, the pH was adjusted to 13.2 with 1.0 M NaOH aqueous solution, stirred at room temperature for 24 hours, and then the dark green solid content was filtered. After washing, 2.1 g of Ru / Al ₂ O ₃ was obtained by drying under vacuum.

Pd / Al ₂ O ₃
Pd / Al ₂ O ₃ was obtained by the same operation as Ru / Al ₂ O ₃ described above except that ruthenium chloride was replaced with palladium chloride.

Ru / CeO ₂
Ru / CeO ₂ was obtained in the same manner as Ru / Al ₂ O ₃ described above, except that γ-alumina was replaced with cerium oxide.

(RuCl) ₂ Ca ₈ (PO ₄ ) ₆ (OH) ₂
Chem. Synthesis was performed according to the method described in Commun., 2001, 461. In 75 mL of an aqueous ruthenium chloride solution (2.67 × 10 −2 M), 1.0 g of calcium hydroxyapatite was added and stirred at 25 ° C. for 24 hours. The obtained slurry solution was filtered, washed with a large amount of water, and dried at 110 ° C. overnight to obtain (RuCl) ₂ Ca ₈ (PO ₄ ) ₆ (OH) ₂ .

_{Ru (OH) 3 · nH 2} O: Ruthenium hydroxide (III) n-hydrate (commercially available)
RuO ₂ : Ruthenium (IV) oxide anhydride (commercially available).

Example 1: Hydration reaction of benzonitrile 1 mmol of benzonitrile, Ru / Al ₂ O ₃ (Ru: 2 mol%) and 3 mL of water were added to an autoclave having an internal volume of 17.5 mL, and the reaction was carried out at 130 ° C in an air atmosphere. It was. The conversion rate of benzonitrile as a raw material and the selectivity to benzamide were calculated by gas chromatography. The reaction results after 6 hours are shown in Table 1.

Example 2: Isolation of benzamide A catalyst was separated from the reaction solution obtained in Example 1 by filtration, and the obtained filtrate was cooled to 0 ° C to precipitate white crystals of benzamide. The isolated yield of pure benzamide obtained by filtration from this solution was 90%. In the case of carrying out this reaction, after the catalyst is separated by filtration or the like, there is an excellent point that the product can be easily separated by advantageous crystallization with low energy load.

Examples 3-4: Hydration of benzonitrile Hydration of benzonitrile according to the method of Example 1 except that Pd / Al ₂ O ₃ and Ru / CeO ₂ were used instead of Ru / Al ₂ O _3. Reaction was performed. The catalyst amount was set to 2 mol% in terms of the amount of supported metal. The reaction results after 6 hours are shown in Table 1.

Comparative Examples 1-3: Hydration reaction of benzonitrile (RuCl) ₂ Ca ₈ (PO ₄ ) ₆ (OH) ₂ , Ru (OH) ₃ .nH ₂ O, RuO ₂ instead of Ru / Al ₂ O ₃ Benzonitrile was hydrated according to the method of Example 1 except that it was used. The catalyst amount was set to 2 mol% in terms of ruthenium. The reaction results after 6 hours are shown in Table 1.

Example 5: Hydration reaction of benzonitrile 1 mmol of benzonitrile, Ru / Al ₂ O ₃ (Ru: 4 mol%) and 3 mL of water were added to an autoclave having an internal volume of 17.5 mL, and the reaction was performed at 140 ° C. in an air atmosphere. It was. The conversion rate of the raw material benzonitrile and the selectivity to benzamide were calculated by gas chromatography. The reaction results are shown in Table 2.

Example 6: Hydration reaction of benzonitrile (first recycling)
After reacting for 6 hours in Example 5, the catalyst was separated by filtration, washed with hot water and aqueous NaOH, and dried. When the filtrate was analyzed by ICP (SEPS Electronics Co., Ltd. SPS4000), it was found that the filtrate did not contain ruthenium (below the detection limit). The recovered catalyst was subjected to a second reaction under the same conditions as in Example 5. The reaction results are shown in Table 2.

Example 7: Benzonitrile Hydration Reaction (Second Recycle)
After reacting for 6 hours in Example 6, the catalyst was separated by filtration, washed with hot water and aqueous NaOH, and dried. When the filtrate was analyzed by ICP, it was found that ruthenium was not contained in the filtrate (below the detection limit). The recovered catalyst was subjected to a third reaction under the same conditions as in Example 5. The reaction results are shown in Table 2.

Example 8: Hydration reaction of acrylonitrile The hydration reaction was carried out under the same conditions as in Example 5 except that acrylonitrile was used instead of benzonitrile. The reaction results are shown in Table 2.

Examples 9 to 18: Hydration reaction of various nitriles Hydration reactions were carried out under the same conditions as in Example 5 except that various nitriles were used instead of benzonitrile. The reaction results are shown in Table 2. As can be seen from this result, in this reaction, even in the compound having a double bond in the molecule (Examples 8 and 10), the hydration reaction of only the nitrile site proceeds selectively, and it corresponds with high yield and selectivity. An amide compound is obtained.

The amide compound produced in the present invention is produced with high yield and high selectivity without a decrease in catalytic activity, and is suitable as a raw material or intermediate used in the production of various industrial products. In particular, acrylamide obtained by hydration of acrylamide is used as an acrylamide polymer in papermaking chemicals, flocculants, petroleum recovery agents, and the like, and has a very wide range of uses as a raw material comonomer for various polymers.

Claims (3)

In a method for producing a corresponding amide compound by hydration reaction of nitriles, a solid catalyst in which at least one element selected from the group consisting of Group 8, Group 9, and Group 10 is supported on a metal oxide is used. A method for producing an amide compound. The method for producing an amide compound according to claim 1, wherein at least one element selected from the group consisting of Group 8, Group 9, and Group 10 is ruthenium. 3. The method for producing an amide compound according to claim 1, wherein the metal oxide is alumina and / or rare earth oxide.