JPH09301951A - Production of amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and advantageously produce an amide compound, capable of reducing the corrosion of an apparatus without requiring a neutralizing step with an alkali after reaction due to no use of an acid by rearranging an oxime compound in the presence of a specific rhenium compound. SOLUTION: (B) An oxime compound (preferably cyclohexanone oxime) is rearranged in the presence of (A) a rhenium compound represented by the formula [M is nitrogen, phosphorus or arsenic; R<1> to R<3> are each H, a (substituted)alkyl, an aryl or an aralkyl] to afford an amide compound. The compound is preferably a salt comprising a perrhenic acid and a nitrogen- containing heterocyclic compound and, e.g. the component A is used in an amount of about 0.1-20mol% based on the component B in the rearrangement. The reaction is preferably carried out in the presence of an inert gas such as nitrogen in a solvent such as tetrahydrofuran at 100-220 deg.C reactional temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amide compound by rearrangement of an oxime compound.

[0002]

BACKGROUND ART The rearrangement reaction of an oxime compound to an amide compound is known as the Beckmann rearrangement reaction. For example, in industrial production of ε-caprolactam by rearrangement of cyclohexanone oxime, fuming sulfuric acid is used as a catalyst. A phased reaction is employed. However, in this method, in order to separate and recover the amide compound, it is usually necessary to neutralize a strong acid such as sulfuric acid with ammonia, and a large amount of ammonium sulfate is by-produced, and there are also problems in the process such as corrosion of the equipment. There are many expectations for the development of efficient rearrangement catalysts.

As a Beckmann rearrangement reaction in a liquid phase under relatively mild reaction conditions, a method using an ion pair (bismeier complex) obtained by the reaction of N, N-dimethylformamide and chlorosulfonic acid as a catalyst (MAKira and
YM Shaker, Egypt. J. Chem., 16, 55 (1990)), a method of rearrangement of cyclohexanone oxime with phosphoric acid in a heptane solvent (JP-A-62-149665), in the presence of a strong acid or a derivative thereof. , A method of rearranging an oxime compound using perrhenate as a catalyst (JP-A-5-513)
No. 66) is proposed.

[0004]

However, in these methods, since an acid is coexisted, the produced ε-caprolactam is oligomerized or polymerized, and a neutralization step with an alkali is required after the reaction. However, there is a problem that a large amount of catalyst is required.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventor was able to cause Beckmann rearrangement of an oxime compound even in the presence of a specific rhenium compound and in the absence of a strong acid. Therefore, the present invention has been achieved by finding that the amide compound can be produced industrially advantageously with a small amount.

That is, the gist of the present invention is the following general formula (I)
In the method for producing an amide compound, the oxime compound is rearranged in the presence of a rhenium compound represented by

[0007]

[R 2¹R^TwoR^ThreeMH]⁺[ReO_Four]^- (I) (In the formula, M represents nitrogen, phosphorus, or arsenic. R¹, R^Two,
R^ThreeIs hydrogen, an alkyl group which may have a substituent,
Represents an aryl group or an aralkyl group, and R ¹, R^Two,
R^ThreeAt least one of them is other than hydrogen. Also,
R¹, R^Two, R^ThreeAnd M are partially or wholly connected to each other.
Together, they may form 1 to 4 5- to 7-membered rings. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The present invention is characterized by using the perrhenate represented by the general formula (I) as a catalyst. General formula (I)
In the above, M is nitrogen (N), phosphorus (P) or arsenic (As), preferably nitrogen and phosphorus. R ¹ ,
Preferred as R ² and R ³ are a hydrogen atom and a carbon number of 1 to
They are an alkyl group having 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. These alkyl group, aryl group and aralkyl group may be substituted with an alkoxy group having 1 to 4 carbon atoms, a halogen atom or the like. Further, R ¹ , R ² and R ³ may be different from each other. The method for obtaining this perrhenate is not particularly limited, but a rhenium compound (for example, Re ₂ O ₇ , HORe) is used.
O ₃ ) and a compound represented by R ¹ R ² R ³ M are dissolved in a suitable solvent, and if necessary heated and stirred to synthesize.

Perrhenium represented by the above general formula (I)
As the acid salt, specifically, [Me _ThreeNH]⁺[Re
O_Four]^-, [Et_ThreeNH]⁺[ReO_Four]^-, [N-Pr_ThreeN
H]⁺[ReO_Four]^-, [I-Pr_ThreeNH]⁺[ReO_Four]^-,
[N-Bu_ThreeNH]⁺[ReO_Four]^-, [I-Bu_ThreeNH]⁺[R
eO_Four]^-, [T-Bu_ThreeNH]⁺[ReO_Four]^-, [Me_TwoN
H_Two]⁺[ReO_Four]^-, [Et_TwoNH_Two]⁺[ReO_Four]^-,
[N-Pr_TwoNH_Two]⁺[ReO_Four]^-, [I-Pr_TwoNH_Two]
⁺[ReO_Four]^-, [N-Bu_TwoNH_Two]⁺[ReO_Four]^-, [I-
Bu _TwoNH_Two]⁺[ReO_Four]^-, [T-Bu_TwoNH_Two]⁺[Re
O_Four]^-, [MeNH_Three]⁺[ReO_Four]^-, [EtNH_Three]⁺
[ReO_Four]^-, [NPrNH_Three]⁺[ReO_Four]^-, [I-P
rNH_Three]⁺[ReO_Four]^-, [NBuNH_Three]⁺[ReO_Four]
^-, [IBuNH_Three]⁺[ReO_Four]^-, [TBuNH_Three]
⁺[ReO_Four]^-, [Ph_ThreeNH] + [ReO_Four]^-, [Ph_Two
NH_Two]⁺[ReO_Four]^-, [PhNH_Three]⁺[ReO_Four]^-,
[(PhCH_Two)_ThreeNH]⁺[ReO_Four]^-, [(PhC
H_Two)_TwoNH_Two]⁺[ReO_Four]^-, [(PhCH_Two) NH_Three]
⁺[ReO_Four]^-Ammonium perrhenate, such as [M
e_ThreePH]⁺[ReO_Four]^-, [Et_ThreePH]⁺[Re
O_Four]^-, [N-Pr_ThreePH]⁺[ReO_Four]^-, [IPr_ThreeP
H]⁺[ReO_Four]^-, [N-Bu_ThreePH]⁺[ReO_Four]^-,
[I-Bu_ThreePH]⁺[ReO_Four]^-, [T-Bu_ThreePH]⁺[R
eO_Four]^-, [Me_TwoPH_Two]⁺[ReO_Four]^-, [Et_TwoPH
_Two]⁺[ReO_Four]^-, [N-Pr_TwoPH_Two]⁺[ReO_Four]^-,
[I-Pr_TwoPH_Two]⁺[ReO_Four]^-, [N-Bu_TwoPH_Two]
⁺[ReO_Four]^-, [IBu_TwoPH_Two]⁺[ReO_Four]^-, [T-
Bu_TwoPH_Two]⁺[ReO_Four]^-, [MePH_Three]⁺[Re
O_Four]^-, [EtPH_Three]⁺[ReO_Four]^-, [N-PrP
H_Three]⁺[ReO_Four] ^-, [I-PrPH_Three]⁺[ReO_Four]^-,
[N-BuPH3]⁺[ReO_Four]^-, [I-BuPH3]⁺[R
eO_Four]^-, [T-BuPH3]⁺[ReO_Four]^-, [Ph_ThreeP
H]⁺[ReO_Four]^-, [Ph_TwoPH_Two]⁺[ReO_Four]^-,
[PhPH_Three]⁺[ReO_Four]^-, [(PhCH_Two)_ThreePH]
⁺[ReO_Four]^-, [(PhCH_Two)_TwoPH_Two]⁺[ReO_Four]
^-, [(PhCH_Two) PH_Three]⁺[ReO_Four]^-Excess Renyu
Phosphonium mumate, [Me_ThreeAsH]⁺[ReO_Four]^-,
[Et_ThreeAsH]⁺[ReO_Four]^-, [N-Pr_ThreeAsH]
⁺[ReO_Four]^-, [I-Pr_ThreeAsH]⁺[ReO_Four]^-, [N
-Bu_ThreeAsH]⁺[ReO_Four]^-, [I-Bu_ThreeAsPH]⁺
[ReO_Four]^-, [T-Bu_ThreeAsH]⁺[ReO_Four]^-, [M
e_TwoAsH_Two]⁺[ReO_Four]^-, [Et_TwoAsH_Two]⁺[Re
O_Four]^-, [N-Pr_TwoAsH_Two]⁺[ReO_Four]^-, [I-Pr_Two
AsH_Two]⁺[ReO_Four]^-, [N-Bu _TwoAsH_Two]⁺[Re
O_Four]^-, [I-Bu_TwoAsH_Two]⁺[ReO_Four]^-, [T-Bu_Two
AsH_Two]⁺[ReO_Four]^-, [MeAsH_Three]⁺[Re
O_Four]^-, [EtAsH_Three]⁺[ReO_Four]^-, [N-PrAs
H3]⁺[ReO_Four]^-, [I-PrAsH3]⁺[Re
O_Four]^-, [N-BuAsH_Three]⁺[ReO_Four]^-, [I-BuA
sH_Three]⁺[ReO_Four]^-, [T-BuAsH_Three]⁺[Re
O_Four]^-, [Ph_ThreeAsH]⁺[ReO_Four]^-, [Ph_TwoAs
H_Two]⁺[ReO_Four]^-, [PhAsH_Three]⁺[ReO_Four]^-,
[(PhCH_Two)_ThreeAsH]⁺[ReO_Four]^-, [(PhC
H_Two)_TwoAsH_Two]⁺[ReO_Four]^-, [(PhCH_Two) As
H_Three]⁺[ReO_Four]^-Arsinium perrhenate such as
No. In the chemical formula shown above,
Me is a methyl group, Et is an ethyl group, Pr is a propyl group,
Bu represents a butyl group and Ph represents a phenyl group.

Further, as the perrhenate represented by the general formula (I), R ¹ , R ² , R ³ and M are partially or wholly bonded to each other to form a 5- to 7-membered ring. It may be a salt composed of 4 to 4 compound cations and a perrhenate anion. In this case, the compound cation is preferably a proton adduct of a nitrogen-containing heterocyclic compound. That is,
One of the preferable rhenium compounds represented by the general formula (I) is a salt composed of perrhenic acid and a nitrogen-containing heterocyclic compound.

The nitrogen-containing heterocyclic compound has one or more, usually 1 to 4, nitrogen as a hetero atom in the heterocycle. The nitrogen-containing heterocyclic compound is usually composed of 1 to 4 heterocyclic rings and 5 to 7 membered homocyclic rings. Examples of the heterocycle include a 5-membered ring such as a pyrrole ring, an imidazole ring, a pyrazole ring and a triazole ring, a monocyclic compound containing a 6-membered ring such as a pyridine ring, a pyrimidine ring and a triazine ring, an indole ring and a benzimidazole ring. It may be a multi-ring compound containing a ring, a benztriazole ring, a quinoline ring, a bipyridyl ring or a phenanthroline ring. Further, a homocyclic ring composed only of carbon having aromaticity such as a benzene ring or a naphthalene ring may be condensed with these heterocycles. Among the above nitrogen-containing heterocyclic compounds, those having aromaticity are particularly preferable, and a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, an indole ring, a quinoline ring, a bipyridyl ring,
Examples thereof include nitrogen-containing heterocyclic compounds containing a phenanthroline ring and the like. Further, the nitrogen-containing heterocycle may have a substituent such as an alkyl group, a hydroxyl group or a cyano group.

Specific examples of the monocyclic compound include pyridine derivatives such as pyridine, pyrimidine, pyridazine and pyrazine, pyrrole derivatives such as pyrrole and pyrazole, imidazole derivatives such as imidazole and 1-methylimidazole, 1H-1,2. , 3-triazole, 2H-1,
Examples thereof include triazole derivatives such as 2,3-triazole, 2H-1,2,4-triazole and 4H-1,2,4-triazole. In addition, as the polycyclic compound, indole, isoindole, 1H-indazole, 2H-
Indole, indole derivatives such as purines, benzimidazole, benzimidazole derivatives such as 1-methylbenzimidazole, benzotriazole, benztriazole derivatives such as 1-methylbenzotriazole, quinoline, isoquinoline, phthalazine, cinnoline, quinazoline, quinoxaline, 1, Quinoline derivatives such as 8-naphthyridine and pteridine, 2,2′-dipyridyl, 2,
3'-dipyridyl, 2,4'-dipyridyl, 3,3'-
Examples include bipyridyl derivatives such as dipyridyl, acridine, phenazine, phenanthroline derivatives such as 1,10-phenanthroline, and the like.

The amount of the rhenium compound represented by the above general formula (I) used as a catalyst is based on the oxime compound.
It is usually 0.01 to 50 mol%, preferably 0.1 to 20 mol%. The type of the oxime compound as the reaction raw material in the present invention is not particularly limited, but specifically,
Cyclohexanone oxime, cyclopentanone oxime, cyclododecanone oxime, acetone oxime, 2
-Butanone oxime, acetophenone oxime, benzophenone oxime and the like. Of these, cyclohexanone oxime and cyclopentanone oxime are particularly common in consideration of the industrial use of the resulting amide compound.

The rearrangement reaction of the present invention is usually carried out in the liquid phase in the presence of a solvent. Examples of the solvent include tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether,
Methanol, ethanol, propanol, butanol,
Alcohols such as pentanol, hexanol, cyclohexanol, octanol, halogenated aliphatic hydrocarbons such as 1,2,3-trichloropropane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, 1,2-dichloroethane , Cyclohexane, hexane, octane and other aliphatic hydrocarbons, benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, nitrobenzene, squalane and other aromatic hydrocarbons,
N, N-dimethylformamide, N, N, N ', N'-
Amides such as tetramethylurea, dimethyl sulfoxide, sulfoxides such as sulfolane, acetonitrile,
Nitriles such as propanenitrile and benzonitrile, and esters such as ethyl acetate, methyl propionate, methyl enanthate, methyl linoleate and methyl stearate are used. Of these solvents, ether solvents such as tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether are particularly preferable. The amount of the above solvent is usually 0.01 to 20 for the catalyst.
The amount is a concentration of weight%.

The rearrangement reaction of the present invention is usually carried out by dissolving the oxime compound and the rhenium compound represented by the general formula (I) in a suitable solvent and then heating. The reaction is usually carried out in the presence of air or a gas inert to the rearrangement reaction,
It is preferably carried out in the presence of a gas inert to the rearrangement reaction. Examples of the gas inert to the rearrangement reaction include nitrogen, helium, argon and the like. The reaction temperature is usually 10 to 300.
℃, preferably 80-250 ℃, more preferably 100
２２０220 ° C. Further, when a high boiling solvent is used, the reaction can be carried out in an open system, but when a low boiling solvent is used, for example, when the reaction is carried out in a closed system such as an autoclave, sublimation of the oxime compound in the reaction or solvent Evaporation can be prevented.

[0016]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The reaction product was analyzed by gas chromatography (GC), and the oligomer by-produced in the reaction was analyzed by gel filtration chromatography (GPC). The "catalyst turnover number (TOF)" shown in the reaction results of the following examples is the number of moles of ε-caprolactam produced per hour from 1 g atom of rhenium, and is synonymous with the reaction rate. It is a thing.

Example 1 Pyridinium perrhenate 0.05 mmol and cyclohexanone oxime 2.5 m were placed in a 100 ml glass flask.
mol, diethylene glycol dimethyl ether 20m
1 was charged and reacted at 160 ° C. for 0.5 hours. As a result, the conversion of cyclohexanone oxime was 94.6%, ε
-Caprolactam yield is 73.7%, catalyst turnover number (TOF) is 73.7 (mol-lactam / mol-Re.
hr). The amount of by-product oligomer at this time was 1.8% by weight based on the charged cyclohexanone oxime. The above results are summarized in Table 1.

Example 2 A 100 ml glass flask was charged with quinolinium perrhenate (0.05 mmol), quinoline (0.1 mmol), cyclohexanone oxime (2.5 mmol) and diethylene glycol dimethyl ether (20 ml) at 160 ° C.
The reaction was performed for 5 hours. The results are shown in Table 1.

Example 3 Pyridinium perrhenate (0.05 mmol), quinoline (0.1 mmol), cyclohexanone oxime (2.5 mmol) and diethylene glycol dimethyl ether (20 ml) were charged in a 100 ml glass flask, and the mixture was dried at 160 ° C.
The reaction was performed for 5 hours. The results are shown in Table 1.

Example 4 Triethylammonium perrhenate ([Et ₃ NH] ⁺ [ReO ₄ ] ^- ) 0.05 m in a 100 ml glass flask.
mol, cyclohexanone oxime 2.5 mmol, and diethylene glycol dimethyl ether 20 ml were charged and reacted at 160 ° C. for 0.5 hours. The results are shown in Table 1.

Example 5 Diphenylammonium perrhenate ([Ph ₂ NH ₂ ] ⁺ [ReO ₄ ] ^- ) 0.05 was put in a 100 ml glass flask.
mmol, cyclohexanone oxime 2.5 mmol,
20 ml of diethylene glycol dimethyl ether was charged and reacted at 160 ° C. for 0.5 hours. The results are shown in Table 1.

Example 6 Tri-n-propylphosphonium perrhenate ([n-Pr ₃ PH] ⁺ [ReO ₄ ] ^- ) was placed in a 100 ml glass flask.
0.05 mmol, cyclohexanone oxime 2.5 m
mol, diethylene glycol dimethyl ether 20m
1 was charged and reacted at 160 ° C. for 0.5 hours. The results are shown in Table 1.

Example 7 A 100 ml glass flask was charged with tripheny perrhenate.
Ruphosphonium [Ph _ThreePH]⁺[ReO4]^-0.05m
mol, cyclohexanone oxime 2.5 mmol, di
Charge 20 ml of ethylene glycol dimethyl ether
And reacted at 160 ° C. for 0.5 hours. The results are shown in Table-1.
Show.

Comparative Example 1 In a 100 ml glass flask, dirhenium heptaoxide (Re ₂
O ₇ ) 0.05 mmol, cyclohexanone oxime 2.5 mmol, and diethylene glycol dimethyl ether 20 ml were charged and reacted at 160 ° C. for 0.5 hours. The results are shown in Table 1.

Comparative Example 2 Tetraethylammonium perrhenate ([NEt ₄ ] ⁺ [ReO ₄ ] ⁻ ) 0.05 m was placed in a 100 ml glass flask.
mol, p-toluenesulfonic acid 0.05 mmol, cyclohexanone oxime 2.5 mmol, diethylene glycol dimethyl ether 20 ml were charged, and 160 ° C.
And reacted for 0.5 hours. The results are shown in Table 1.

[0026]

[Table 1]

Example 8 Quinolinium perrhenate 0.05 mmol, cyclohexanone oxime in a 70 ml microautoclave.
5 mmol, diethylene glycol dimethyl ether 2
0 ml was charged and reacted at 180 ° C. for 1 hour. Table 2 shows the results. Comparative Example 3 Dirhenium heptoxide 0.7 g in a 70 ml microautoclave.
025 mmol, cyclohexanone oxime 2.5 mm
ol, diethylene glycol dimethyl ether 10 ml
Was charged and reacted at 180 ° C. for 2 hours. Table 2 shows the results.
Shown in

[0028]

[Table 2]

[0029]

EFFECTS OF THE INVENTION According to the present invention, since an acid is not used, equipment corrosion can be reduced, and an alkali neutralization step after the reaction is unnecessary, so that an amide compound can be produced industrially advantageously. be able to.

Claims (4)

[Claims] 1. A rhenium compound represented by the following general formula (I):
Characterized by rearrangement of oxime compound in the presence of compound
And a method for producing an amide compound. [R 1¹R^TwoR^ThreeMH]⁺[ReO_Four]^- (I) (In the formula, M represents nitrogen, phosphorus, or arsenic. R¹, R^Two,
R^ThreeIs hydrogen, an alkyl group which may have a substituent,
Represents an aryl group or an aralkyl group, and R ¹, R^Two,
R^ThreeAt least one of them is other than hydrogen. Also,
R¹, R^Two, R^ThreeAnd M are partially or wholly connected to each other.
Together, they may form 1 to 4 5- to 7-membered rings. ) 2. The method according to claim 1, wherein the rhenium compound represented by the general formula (I) is a salt composed of perrhenic acid and a nitrogen heterocyclic compound. 3. The method according to claim 1, wherein the oxime compound is cyclohexanone oxime. 4. The production method according to claim 1, wherein the rearrangement of the oxime compound is carried out in a liquid phase.