JP2000302739A - Production of amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an amide compound in a high conversion and in a high yield, without forming ammonium sulfate as a by- product, and inhibiting formation of by-products, such as high boiling point substances. SOLUTION: This method for producing an amide compound comprises carrying out Beckmann rearrangement reaction of an oxime compound in a liquid phase, wherein the reaction is carried out in the presence of a catalyst containing a structure expressed by the formula: MZs [M is an element selected from groups comprising 1 to 15 group of the periodical table; Z is an anion expressed by the formula of OSO2R; R is an alkyl group in which the carbon atom at alpha-position bonds to at least two fluorine atoms, or a part of a fluorinated polymer in which the carbon atoms at alpha- and beta-positions to the sulfonate group bond together to at least four fluorine atoms; and (s) is a natural number not more than the maximum oxidation number of M].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amide compound. Specifically, the present invention relates to a method for efficiently producing an amide compound by performing a Beckmann rearrangement reaction of an oxime in a liquid phase.

[0002]

2. Description of the Related Art ε-Caprolactam is usually produced by a Beckmann rearrangement reaction of cyclohexanone oxime. As the Beckmann rearrangement reaction, a liquid phase reaction using a strong acid such as concentrated sulfuric acid or fuming sulfuric acid is currently industrially employed. However, in such a method, it is usually necessary to neutralize sulfuric acid with ammonia in order to separate ε-caprolactam, and there is a problem that a large amount of ammonium sulfate is by-produced.

[0003] Various studies have been made on the Beckmann rearrangement without using sulfuric acid. As a promising method, a method of performing a Beckmann rearrangement reaction in the gas phase in the presence of a solid acid catalyst can be considered. As the solid acid catalyst, for example, a silica-alumina catalyst (UK Patent No. 8)
81,927), solid phosphoric acid catalyst (UK Patent No. 88)
1,276), titania-polya catalyst (JP-B-46-1)
2125), boron-based catalyst (German Patent No. 1092)
0, “Applied Catalysts” vol.
29, p-107 (1987)), a hydrous niobium oxide catalyst (JP-A-60-44039), a high silica zeolite catalyst ("Catalyst" vol. 31, No. 2, p-136)
1989)). It has also been reported that hydrous tantalum oxide can be used as a solid acid catalyst having an excellent Beckmann rearrangement reaction (JP-A-63-519).
45).

As a Beckmann rearrangement reaction in a liquid phase where the reaction conditions are relatively mild, a method using an ion pair (Bismeyer complex) obtained by the reaction of N, N-dimethylformamide and chlorosulfonic acid as a catalyst (M. A. Ki
ra and Y. M. Shaker, Egypt.
J. Chem. , 16, 55 (1990)), a method of rearranging cyclohexanone oxime with phosphoric acid in a heptane solvent (JP-A-62-149665), using perrhenate as a catalyst in the presence of a strong acid or a derivative thereof. Method for rearranging an oxime compound (Japanese Patent Laid-Open No. 5-51)
No. 366) has been proposed.

On the other hand, it has been reported by Osamu Kobayashi that rare earth metal triflates and specific metal triflates are called new Lewis acids and can be applied to various organic synthesis reactions without losing activity in the presence of water or amine ( Organic Synthetic Chemistry Association, Vol. 56, No. 5 (1998), The Chemical Society of Japan 76th Spring Annual Meeting 3C107, etc.). In addition, various metal triflates have been synthesized, and application to, for example, ring-opening polymerization of tetrahydrofuran has been reported (Japanese Patent Application Laid-Open No. 8-502531, Du Pont). However, there is no known example of using these triflates in a Beckmann rearrangement reaction having a completely different reaction mechanism.

[0006]

However, in the above-described method of performing a Beckmann rearrangement reaction in a gas phase using a solid acid catalyst, side reactions such as thermal decomposition and polymerization are likely to occur, and amines, amides, and cyanides are likely to occur. Separation of by-products such as tar-like high-boiling substances and the like becomes complicated, and it is difficult to obtain ε-caprolactam in a sufficient yield. There is also a problem that the activity of the catalyst component is significantly reduced due to the volatilization of the catalyst component over time.
In the method of performing the Beckmann rearrangement reaction in the liquid phase described above, since an acid is present, oligomerization and polymerization of the generated ε-caprolactam occur,
After the reaction, there is a problem that a neutralization step with an alkali is required or a large amount of a catalyst is required.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that when a compound having a triflate structure containing a specific element is used as a catalyst for a liquid phase Beckmann reaction, an amide having a high conversion rate can be obtained. The inventors have found that a compound can be obtained, and have reached the present invention. That is, the gist of the present invention is characterized in that in producing an amide compound by performing a Beckmann rearrangement reaction of an oxime compound in a liquid phase, the reaction is carried out in the presence of a catalyst having a structure represented by the general formula MZs. A method for producing an amide compound, wherein
Is an element selected from the group consisting of 1 to Group 15 of the Periodic Table, Z is the formula ^- is an anion represented by OSO ₂ R, R is carbon at least two alpha-position S is M, which is an alkyl group bonded to a fluorine atom, or a fluorinated polymer in which the carbon atoms alpha and beta to the sulfonate group are bonded together to at least 4 fluorine atoms. Is a natural number less than or equal to the highest oxidation number of ).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The catalyst used in the present invention has a general formula MZs (M is an element selected from Groups 1 to 15 of the periodic table, and Z is
^- it is an anion represented by OSO ₂ R, R is either carbon of at least the alpha-position is an alkyl group bonded to at least two fluorine atoms, or carbon atoms of the alpha and beta-position with respect to the sulfonate group Part of a fluorinated polymer bonded together to at least 4 fluorine atoms, where s is a natural number less than or equal to the highest oxidation number of M. ), Which are produced by various known methods (eg, J. Org. Chem. 1).
987, 52, 1017-1021 and Tokuhyo Hei 8-502
531) or a commercially available product (available from Aldrich). Specifically, as the type of the element M,
Sc, La, Pr, Nd, Sm, Eu, Tb, Dy, H
o, Er, Lu, Y, Yb, Zr, Hf, Cu, Ag,
Examples thereof include Zn, Pb, and Cd, and among them, an element selected from Groups 3, 4, and 11 to 14 of the periodic table is preferable, and a Group 3 metal is particularly preferable.

When R in the catalyst of the present invention is an alkyl group, specific examples include an alkyl group having 1 to 3 carbon atoms such as a trifluoromethyl group and a pentafluoroethyl group. Further, the catalyst of the present invention may contain a neutral ligand such as CO or cyclopentadiene in addition to the above-mentioned MZs structure. The raw material oxime compound used in the Beckmann rearrangement reaction of the present invention can be applied to known oxime compounds without any limitation. Specific examples of the oxime compound include cyclohexanone oxime, cyclopentanone oxime, cyclododecanone oxime, acetone oxime, 2-butanone oxime, acetophenone oxime, benzophenone oxime, and 4'-hydroxyacetophenone oxime. Especially, it is preferably applied to cyclic oxime compounds such as cyclohexanone oxime, cyclopentanone oxime and cyclododecanone oxime.

The amount of the catalyst used in the present invention is not particularly limited, but when the reaction is a homogeneous system, it is usually used in an amount of 0.001 mol% to 50 mol% based on the oxime compound. The Beckmann rearrangement of the oxime of the present invention can also be performed in the presence of a solvent. Although the solvent is not particularly limited, for example, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethers such as tetraethylene glycol dimethyl ether, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol and octanol, 2,
3-trichloropropane, tetrachloroethylene, 1,
Halogenated aliphatic hydrocarbons such as 1,2,2-tetrachloroethane and 1,2-dichloroethane, cyclohexane,
Aliphatic hydrocarbons such as hexane and octane, benzene, toluene, xylene, mesitylene, monochlorobenzene,
Aromatic hydrocarbons such as dichlorobenzene, nitrobenzene, and squalane; N, N-dimethylformamide;
Amides such as N, N ', N'-tetramethylurea, sulfoxides such as dimethylsulfoxide and sulfolane, nitriles such as acetonitrile, propanenitrile and benzonitrile, ethyl acetate, methyl propionate, methyl enanthate and linoleic acid Esters such as methyl and methyl stearate are used. Above all, when a compound having a cyano group such as benzonitrile, acetonitrile, adiponitrile or the like is used as a solvent, the yield is particularly improved because it is improved. The amount of the solvent to be used is not particularly limited, but is usually 1 to 10,000 times the weight of the oxime compound.

The coexistence of a nitrile compound different from the solvent in the reaction system using the above solvent is preferable in that the yield of the amide compound is improved. In this case, although not particularly limited, the nitrile compound is added to the oxime compound at a concentration of 0.1%.
It is preferable that 1 mol% or more coexist. In this reaction,
Performing the reaction in the coexistence of water is preferable in that the coloring of the reaction solution is suppressed and the generation of high boiling components is suppressed. Although the amount of water in the reaction system is not particularly limited, it is preferable to carry out the reaction while maintaining the amount of water at 50 ppm or more. The Beckmann rearrangement of the oxime of the present invention is preferably carried out in a two-layer system of an organic solvent and water. In this case, the amount of the catalyst can be used up to a saturated dissolution amount of the catalyst in water. Further, in this system, the catalyst separation is simplified, and the process is advantageous.

The reaction temperature is not particularly limited, but the reaction is carried out at 0 ° C to 200 ° C, preferably at 70 ° C to 160 ° C.
The reaction type, residence time, and the like of this reaction are not particularly limited. For example, the shape of the catalyst may be any of a fixed bed, a flow bed and a suspension bed. In the case of a batch reaction, the residence time can usually be set to about 0.1 to 24 hours. Also in the case of a continuous reaction, the residence time can be set to about 0.01 to 24 hours. Among them,
Industrially, it is preferable to use a continuous flow reaction system.

[0013]

EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Example 1 102 mg of cyclohexanone oxime dissolved in 15 ml of dehydrated benzonitrile (0.
901 mmol). Next, 27.0 mg of lanthanum trifluoromethanesulfonate (0.046 mmol)
l) was added. The reaction was performed at 130 ° C. for 3 hours. The reaction solution after the reaction was analyzed by gas chromatography. The oxime conversion was 93%, and the yield of ε-caprolactam was 48%.

Example 2 Cyclohexanone oxime 10 dissolved in 15 ml of dehydrated benzonitrile was placed in a flask.
0 mg (0.884 mmol) was charged. Next, water 47
mg and lanthanum trifluoromethanesulfonate 26.
1 mg (0.045 mmol) was added. The reaction was performed at 130 ° C. for 3 hours. The reaction solution after the reaction was analyzed by gas chromatography. The conversion of oxy was 88%, and the yield of ε-caprolactam was 66%.

Example 3 Cyclohexanone oxime 10 dissolved in 15 ml of dehydrated benzonitrile was placed in a flask.
0 mg (0.901 mmol) was charged. Then 1g of water
And lanthanum trifluoromethanesulfonate 27.1m
g (0.046 mmol) was added. The reaction was performed at 130 ° C. for 3 hours. The reaction solution after the reaction was analyzed by gas chromatography. The conversion of the oxime was 74%, and the yield of ε-caprolactam was 48%.

Example 4 Cyclohexanone oxime 10 dissolved in 15 ml of dehydrated benzonitrile in a flask
2 mg (0.901 mmol) were charged. 22.0 mg of scandium trifluoromethanesulfonate (0.
045 mmol) was added. Reaction was performed at 130 ° C. for 3 hours. The reaction solution after the reaction was analyzed by gas chromatography. The conversion of the oxime was 85%, and the yield of ε-caprolactam was 48%.

Example 5 Cyclohexanone oxime 10 dissolved in 15 ml of dehydrated benzonitrile was placed in a flask.
0 mg (0.884 mmol) was charged. Then water 48
mg and 29.0 mg (0.047 mmol) of ytterbium trifluoromethanesulfonate. 13
Reaction was performed at 0 ° C. for 3 hours. The reaction solution after the reaction was analyzed by gas chromatography. 94% oxime conversion, ε-
The yield of caprolactam was 65%.

[0018]

By performing the Beckmann rearrangement reaction of the oxime compound using the triflate having the specific element of the present invention as a catalyst, there is no by-product of ammonium sulfate unlike the conventional method, and there is no secondary product such as high boiling substances. An amide compound can be produced at a high conversion rate and a high selection yield while suppressing production.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Makoto Tezuka 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Institute Yokohama Research Laboratory (72) Inventor Takahiko Takewaki 1000-Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Laboratory (72) Inventor Toru Setoyama 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 4C034 DE03 4H006 AA02 AC27 AC53 BA05 BA07 BA08 BA11 BA28 BA29 BA52 BS10 BV21 4H039 CA42 CA71 CJ10

Claims (7)

[Claims] 1. An amide compound produced by performing a Beckmann rearrangement reaction of an oxime compound in a liquid phase, wherein the amide compound is reacted in the presence of a catalyst having a structure represented by the general formula MZs. A method for producing a compound.
(Wherein, M is an element selected from the group consisting of 1 to Group 15 of the Periodic Table, Z is the formula ^- is an anion represented by OSO ₂ R, R is the alpha-position carbon Is an alkyl group bonded to at least two fluorine atoms, or a part of a fluorinated polymer in which the carbon atoms alpha and beta to the sulfonate group are bonded together to at least four fluorine atoms. And s is a natural number less than or equal to the highest oxidation number of M.) 2. In the general formula MZs, M is 3 of the periodic table.
The method for producing an amide compound according to claim 1, which is an element selected from the group consisting of Group 4, Group 4, and Group 11 to 14. 3. The method according to claim 2, wherein M in the general formula MZs is an element selected from the group consisting of Sc, Y, rare earth metals, Zr, Hf, Cu, Zn, Ag, Cd, and Pb. A method for producing the amide compound as described above. Wherein all Z in the general formula MZs has the formula ^- OSO
Method for producing an amide compound according to claim 1, characterized in that the anion represented by ₂ CF _3. 5. The method for producing an amide compound according to claim 1, wherein the reaction is carried out in the presence of a compound having a cyano group. 6. The method for producing an amide compound according to claim 1, wherein 50 ppm or more of water is allowed to coexist in the reaction system. 7. The method for producing an amide compound according to claim 1, wherein the oxime is cyclohexanone oxime and the amide is ε-caprolactam.