JP2013095700A - Method for producing lactam compound and/or amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a lactam compound (III) and/or an amide compound (IV) with an excellent selectivity by converting a lactone compound (I) with an excellent conversion.SOLUTION: By making a lactone compound (I) and ammonia or an amine compound (II) react with each other in the presence of water and mesoporous silica, a lactam compound (III) and/or an amide compound (IV) represented by formulas are/is produced. The mesoporous silica is preferably MCM-41 (wherein Rrepresents a 3-7C alkylene group, and Rrepresents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group).

Description

  The present invention relates to a compound of formula (I)

（式中、Ｒ^１は、炭素数３〜７のアルキレン基を表す。）
で示されるラクトン化合物〔以下、ラクトン化合物（Ｉ）ということがある。〕と、式（ＩＩ）

(In the formula, R ¹ represents an alkylene group having 3 to 7 carbon atoms.)
A lactone compound represented by the formula [hereinafter sometimes referred to as a lactone compound (I). And formula (II)

（式中、Ｒ^２は、水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基又はヒドロキシアルキル基を表す。）
で示される化合物〔以下、アンモニア又はアミン化合物（ＩＩ）ということがある。〕とを反応させて、式（ＩＩＩ）

(Wherein R ² represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group.)
[Hereinafter, it may be referred to as ammonia or amine compound (II). And a compound of formula (III)

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるラクタム化合物〔以下、ラクタム化合物（ＩＩＩ）ということがある。〕及び／又は式（ＩＶ）

(Wherein R ¹ and R ² represent the same meaning as described above.)
A lactam compound [hereinafter, referred to as a lactam compound (III). And / or formula (IV)

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるアミド化合物〔以下、アミド化合物（ＩＶ）ということがある。〕を製造する方法に関するものである。

(Wherein R ¹ and R ² represent the same meaning as described above.)
An amide compound represented by the formula [hereinafter sometimes referred to as an amide compound (IV). ] About the method of manufacturing.

  The lactam compound (III) and the amide compound (IV) are useful as raw materials such as synthetic fibers, intermediates for the production of medical and agricultural chemicals, solvents, and the like. Conventionally, as a method for producing lactam compound (III) and / or amide compound (IV) by reacting lactone compound (I) with ammonia or amine compound (II), for example, Patent Document 1 discloses a solid catalyst. A method of reacting γ-butyrolactone with ammonia, alkylamine or ethanolamine in the presence of ZSM-5 and water in the presence of ZSM-5 is proposed.

JP 2001-302625 A

However, the conventional methods are not always satisfactory in terms of the conversion rate of the lactone compound (I) and the selectivity of the lactam compound (III) and / or the amide compound (IV).
Accordingly, an object of the present invention is to provide a method for producing a lactam compound (III) and / or an amide compound (IV) with a good selectivity by converting the lactone compound (I) with a good conversion rate. is there.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

That is, this invention consists of the following structures.
(1) Formula (I)

（式中、Ｒ^１は、炭素数３〜７のアルキレン基を表す。）
で示されるラクトン化合物と、式（ＩＩ）

(In the formula, R ¹ represents an alkylene group having 3 to 7 carbon atoms.)
A lactone compound represented by formula (II)

（式中、Ｒ^２は、水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基又はヒドロキシアルキル基を表す。）
で示される化合物とを、水及びメソポーラスシリカの存在下に反応させることを特徴とする式（ＩＩＩ）

(Wherein R ² represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group.)
The compound represented by formula (III) is reacted in the presence of water and mesoporous silica.

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるラクタム化合物及び／又は式（ＩＶ）

(Wherein R ¹ and R ² represent the same meaning as described above.)
A lactam compound represented by formula (IV)

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるアミド化合物の製造方法。
（２）前記メソポーラスシリカがＭＣＭ−４１である前記（１）に記載の製造方法。
（３）前記ＭＣＭ−４１がアルミニウムを含むものである前記（２）に記載の製造方法。
（４）式（ＩＩ）で示される化合物の使用量が、式（Ｉ）で示されるラクトン化合物１モルに対して１〜２０モルである前記（１）〜（３）のいずれかに記載の製造方法。
（５）式（ＩＩ）、（ＩＩＩ）及び（ＩＶ）におけるＲ^２が水素原子である前記（１）〜（４）のいずれかに記載の製造方法。
（６）式（Ｉ）で示されるラクトン化合物が、γ−ブチロラクトン又はε−カプロラクトンである前記（１）〜（５）のいずれかに記載の製造方法。
（７）前記反応を２００〜６００℃で行う前記（１）〜（６）のいずれかに記載の製造方法。

(Wherein R ¹ and R ² represent the same meaning as described above.)
The manufacturing method of the amide compound shown by these.
(2) The production method according to (1), wherein the mesoporous silica is MCM-41.
(3) The manufacturing method according to (2), wherein the MCM-41 contains aluminum.
(4) The amount of the compound represented by the formula (II) is 1 to 20 mol per 1 mol of the lactone compound represented by the formula (I), according to any one of the above (1) to (3) Production method.
(5) The production method according to any one of (1) to (4), wherein R ² in formulas (II), (III), and (IV) is a hydrogen atom.
(6) The production method according to any one of (1) to (5), wherein the lactone compound represented by the formula (I) is γ-butyrolactone or ε-caprolactone.
(7) The manufacturing method in any one of said (1)-(6) which performs the said reaction at 200-600 degreeC.

  According to the present invention, the lactone compound (I) can be converted at a good conversion rate, and the lactam compound (III) and / or the amide compound (IV) can be produced with a good selectivity.

  Hereinafter, the present invention will be described in detail. In the present invention, the formula (I)

（式中、Ｒ^１は、炭素数３〜７のアルキレン基を表す。）
で示されるラクトン化合物〔ラクトン化合物（Ｉ）〕と、式（ＩＩ）

(In the formula, R ¹ represents an alkylene group having 3 to 7 carbon atoms.)
A lactone compound [lactone compound (I)] represented by formula (II)

（式中、Ｒ^２は、水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基又はヒドロキシアルキル基を表す。）
で示される化合物〔アンモニア又はアミン化合物（ＩＩ）〕とを、水及びメソポーラスシリカの存在下に反応させる。

(Wherein R ² represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group.)
[Ammonia or amine compound (II)] is reacted in the presence of water and mesoporous silica.

  In formula (I), examples of the alkylene group having 3 to 7 carbon atoms include a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene group. Examples of the lactone compound (I) include γ-butyrolactone, δ-valerolactone, ε-caprolactone, ζ-enanthlactone, η-caprolactone, etc. Among them, γ-butyrolactone or ε-caprolactone is used as a raw material. In this case, the method of the present invention is advantageously employed.

  In the formula (II), the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl. Group, t-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, n-heptyl group, n-octyl group, etc. Can be mentioned. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, such as vinyl group, allyl group, 2-methylallyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3 -Butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl- Examples include 2-butenyl group, 3-methyl-2-butenyl group, 2-methyl-3-butenyl group, 2-methyl-2-pentenyl group, 3-methyl-2-pentenyl group and the like. The cycloalkyl group is preferably a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a tolyl group, and a xylyl group. Examples of the aralkyl group include benzyl group, phenethyl group, 3-phenylpropyl group, benzhydryl group, trityl group, triphenylethyl group, (1-naphthyl) methyl group, (2-naphthyl) methyl group and the like. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisobutyl group, and the like. In the method of the present invention, as ammonia or amine compound (II), among them, ammonia, methylamine, ethylamine, n-propylamine, n-octylamine, vinylamine, and ethanolamine are preferable, and ammonia and methylamine are more preferable. Ammonia is more preferred.

  1-20 mol is preferable with respect to 1 mol of lactone compounds (I), and, as for the usage-amount of ammonia or amine compound (II), 1-10 mol is more preferable.

  In the present invention, the reaction can proceed smoothly by carrying out the reaction in the presence of water. 0.1-10 mol is preferable with respect to 1 mol of lactone compounds (I), and, as for the usage-amount of water, 0.5-5 mol is more preferable.

In the present invention, by using mesoporous silica as a catalyst, the reaction can proceed smoothly. The mesoporous silica can have a so-called mesoporous structure having pores of almost uniform size of usually 2 to 50 nm, and the surface area is usually about 600 to 1500 m ² / g. Examples of such mesoporous silica include MCM-41, MCM-48, FSM-16, SBA-3, HMS, MSU-X, SBA-12, SBA-15, SBA-16 and the like. Among these, MCM-41 is preferable in that the lactone compound (I) can be converted at a good conversion rate to produce the lactam compound (III) and / or the amide compound (IV) with a good selectivity. The presence or absence of a mesoporous structure is analyzed by observation with a transmission electron microscope, pore distribution in nitrogen adsorption measurement, or presence or absence of a peak at 2θ = 0.2 to 4.0 ° in XRD (X-ray diffraction) measurement. Can be confirmed.

  The mesoporous silica contains silicon and oxygen as elements constituting the mesoporous silica, but may contain elements other than silicon and oxygen. For example, mesoporous silica substantially composed of silicon and oxygen has a skeleton. It may be a mesoporous metallosilicate that further contains other elements as elements constituting the skeleton, mesoporous silica in which other elements are incorporated in the pores, or mesoporous Other elements may be supported on the silica surface. Examples of elements other than silicon and oxygen that can be contained in the mesoporous silica include aluminum, boron, gallium, iron, chromium, nickel, and the like, and two or more of them may be contained as necessary. Among these, aluminum is preferable. In the method of the present invention, the skeleton is constituted in that the lactone compound (I) can be converted at a good conversion rate to produce the lactam compound (III) and / or the amide compound (IV) with a good selectivity. Mesoporous silicate containing aluminum as an element (mesoporous aluminosilicate) is preferably used as a catalyst, and MCM-41 containing aluminum as an element constituting the skeleton is more preferably used as a catalyst. When MCM-41 containing aluminum as an element constituting the skeleton is used as a catalyst, the content of silicon contained in MCM-41 is 5 to 500 in terms of atomic ratio (Si / Al) to aluminum. Is preferred.

  The method for preparing the mesoporous silica is not particularly limited, and a known method can be appropriately employed. The method of removing is mentioned. Preparation of mesoporous silica containing an element other than silicon and oxygen is performed by mixing a compound containing an element other than silicon and oxygen, a silicon compound, a structure directing agent and water, and removing the structure directing agent from the resulting crystal. Alternatively, it may be carried out by mixing a silicon compound, a structure directing agent and water, removing the structure directing agent from the resulting crystal, and then supporting elements other than silicon and oxygen, A structure-directing agent and water may be mixed, and after the elements other than silicon and oxygen are supported on the resulting crystal, the structure-directing agent may be removed.

  Examples of the silicon compound include amorphous silica such as colloidal silica, silica gel, and fumed silica; alkali silicates such as sodium silicate and potassium silicate; tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and the like. Depending on the situation, two or more of them can be used.

The structure directing agent means an organic compound used for forming a mesoporous structure. The mesoporous structure and pore size can be controlled by the type and molecular shape of the structure directing agent (see Zeolite Science and Engineering, Kodansha Scientific, 2000, p. 13-23). For example, when preparing MCM-41 type mesoporous silica, Nature, (USA), 1992, Vol. 359, p. As described in 710-712, a long-chain alkyl ammonium salt [C _n H _{2n + 1} N ⁺ (CH ₃ ) ₃ as a structure-directing agent. In the formula, n represents an integer. In the case of preparing MCM-48 type mesoporous silica, Microporous and Mesoporous Materials, (Netherlands), 2001, vol. 44, p. As described in 9-16, a long-chain alkyl ammonium salt [C _n H _{2n + 1} N ⁺ (CH ₃ ) ₃ as a structure-directing agent. In the formula, n represents an integer. In order to prepare FSM-16 type mesoporous silica, Bulletin of the Chemical Society of Japan, (Japan), 1996, 69th Volume, p. In the preparation of SBA-3 type mesoporous silica, a layered silicon compound is used as a raw material and a quaternary ammonium salt such as hexadecyltrimethylammonium chloride is used as a structure-directing agent as described in 1449-1457. Catalysis Communications (Netherlands), 2008, Vol. 9, No. 13, p. As described in 2287-2290, gemini surfactant as a structure-directing agent _{[C n H 2n + 1 (CH} 3) 2 N + (CH 2) s N + (CH 3) 2 C m H 2m + 1. In the formula, n, s, and m represent integers. In the preparation of HMS type mesoporous silica, Applied Catalysis A: General (Netherlands), 2008, Vol. 347, p. 133-141, long chain alkylamines [C _n H _{2n + 1} NH ₂ as structure directing agents. In the formula, n represents an integer. In the preparation of MSU-X type mesoporous silica, Microporous and Mesoporous Materials, (Netherlands), 2008, Vol. 109, p. As described in 199-209, when oleyl decaoxyethylene is selected as the structure-directing agent, and when preparing SBA-12 type mesoporous silica, Journal of Physical Chemistry B (Journal of Physical Chemistry B), (USA) USA, 2002, 106, p. As described in 3118-3123, polyethylene oxide is selected as the structure-directing agent, and when preparing SBA-15 type mesoporous silica, Science, (USA), Vol. 279, p. 548-552, Microporous and Mesoporous Materials, (Netherlands), 2006, Vol. 91, p. In the preparation of SBA-16 type mesoporous silica, a triblock copolymer (polyethylene oxide-polypropylene oxide-polyethylene oxide copolymer) is used as a structure-directing agent as described in 156-160. Porous and Mesoporous Materials (Netherlands), 2007, vol. 105, p. As described in 15-23, a triblock copolymer (polyethylene oxide-polypropylene oxide-polyethylene oxide copolymer) is selected as the structure directing agent, and when preparing SBA-16 type mesoporous silica, Porous and Mesoporous Materials (Netherlands), 2007, vol. 105, p. As described in 15-23, a triblock copolymer (polyethylene oxide-polypropylene oxide-polyethylene oxide copolymer) is selected as the structure directing agent.

  Of the above structure-directing agents, long-chain alkylammonium salts are preferred. Examples of the long-chain alkylammonium salt include dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide and the like.

  The amount of the structure-directing agent to be used is generally 0.05 to 1.0 mol, preferably 0.10 to 0.50 mol, per 1 mol of the silicon compound.

  The amount of water used in the preparation of mesoporous silica is usually 5 to 200 mol, preferably 20 to 100 mol, per 1 mol of the silicon compound. The mixing temperature is usually 20 to 200 ° C., preferably 20 to 150 ° C. The pressure at the time of mixing may be any of normal pressure, increased pressure, and reduced pressure, and is appropriately set. The mixing time is usually 0.1 to 400 hours, preferably 1 to 200 hours.

  Crystals can be recovered from the suspension containing the crystals obtained after mixing, for example, by filtering the suspension and drying the residue. In addition, you may perform a washing | cleaning process as needed before this drying. Such drying is usually performed in an air atmosphere, the drying temperature is about 40 to 120 ° C., and the drying time is about 2 to 24 hours. Drying is usually performed under normal pressure, but may be performed under reduced pressure. Further, it may be dried by spray drying, and the crystals may be recovered as a molded body.

  Removal of the structure-directing agent from the crystal may be performed by washing the crystal with an organic solvent such as toluene, methanol, ethanol, acetone, etc., or acidity such as hydrochloric acid (aqueous hydrogen chloride solution), sulfuric acid aqueous solution, nitric acid aqueous solution, etc. You may carry out by wash | cleaning with aqueous solution, and you may carry out by heat-processing at 200-800 degreeC. Any one of these may be employed, or two or more may be employed in combination. Among these, it is preferable to remove the structure-directing agent from the crystals by heat treatment at 200 to 800 ° C. The heat treatment may be performed in an oxygen-containing gas atmosphere or an inert gas atmosphere such as nitrogen. Further, the heat treatment may be performed in multiple stages in an atmosphere of an oxygen-containing gas or an inert gas.

The reaction of the lactone compound (I) with ammonia or the amine compound (II) in the presence of water and mesoporous silica may be performed in a batch system, a semi-batch system, or a continuous system. However, it is preferable to carry out by a continuous type from the point of productivity and operativity. 200-600 degreeC is preferable and, as for the reaction temperature in this reaction, 300-500 degreeC is more preferable. The reaction pressure is usually 0.1 to 1 MPa. When the reaction is carried out continuously, it can be suitably carried out in a fixed bed type or a fluidized bed type under gas phase conditions. The feed rate of the lactone compound (I) as a raw material is the feed rate per kg of catalyst (kg / kg). h), that is, as the space velocity WHSV ^{(h -1),} usually 1~50h ^-1, preferably 2~10h ^-1. When the reaction is carried out continuously, an inert gas such as nitrogen, argon or carbon dioxide may be supplied together with the raw material.

  Thus, the formula (III)

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるラクタム化合物〔ラクタム化合物（ＩＩＩ）〕及び／又は式（ＩＶ）

(Wherein R ¹ and R ² represent the same meaning as described above.)
A lactam compound [lactam compound (III)] and / or formula (IV)

（式中、Ｒ^１及びＲ^２は、前記と同じ意味を表す。）
で示されるアミド化合物〔アミド化合物（ＩＶ）〕を含む反応混合物を得ることができる。反応後の後処理操作については適宜選択されるが、例えば、適宜濾過やデカンテーション等により反応混合物からメソポーラスシリカを分離した後、抽出、蒸留、晶析等の操作を行うことにより、ラクタム化合物（ＩＩＩ）及び／又はアミド化合物（ＩＶ）を分離することができる。アミド化合物（ＩＶ）は、公知の方法、例えば、特開２００３−３２１４２７号公報に記載された方法等によって、分子内脱水縮合反応させることにより、ラクタム化合物（ＩＩＩ）に変換することができる。ゆえに、アミド化合物（ＩＶ）は、ラクタム化合物（ＩＩＩ）の製造における中間体として有用である。

(Wherein R ¹ and R ² represent the same meaning as described above.)
A reaction mixture containing the amide compound [amide compound (IV)] represented by formula (1) can be obtained. The post-treatment operation after the reaction is appropriately selected. For example, the mesoporous silica is appropriately separated from the reaction mixture by filtration, decantation, etc., and then subjected to operations such as extraction, distillation, crystallization, etc. III) and / or the amide compound (IV) can be separated. The amide compound (IV) can be converted to the lactam compound (III) by an intramolecular dehydration condensation reaction by a known method, for example, a method described in JP-A No. 2003-321427. Therefore, the amide compound (IV) is useful as an intermediate in the production of the lactam compound (III).

Examples of the present invention will be described below, but the present invention is not limited thereto. The space velocity WHSV (h ⁻¹ ) of the lactone compound (I) was calculated by dividing the supply rate (g / h) of the lactone compound (I) by the catalyst weight (g). The lactone compound (I), the lactam compound (III) and the amide compound (IV) are analyzed by gas chromatography. The conversion of the lactone compound (I), the selectivity of the lactam compound (III), and the amide compound (IV ), The number of moles of the supplied lactone compound (I) is a, the number of moles of the unreacted lactone compound (I) is b, the number of moles of the produced lactam compound (III) is c, and the produced amide compound is The number of moles of (IV) was calculated as d, respectively, using the following formula.

Conversion of lactone compound (I) (%) = [(ab) / a] × 100
-Selectivity (%) of lactam compound (III) = [c / (a−b)] × 100
-Selectivity (%) of amide compound (IV) = [d / (ab)] × 100

Example 1
(A) <Production of MCM-41 type mesoporous silica>
21.6 g (0.059 mol) of hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 215.4 g of ion-exchanged water were mixed and stirred vigorously. Under stirring, colloidal silica (Nissan Chemical Industry Co., Ltd. Snowtex 20, silica (SiO ₂ ) content 21 wt%, aluminum content 0.032 wt%) 127.6 g and 4 Then, 113.2 g of a 2 wt% aqueous sodium hydroxide solution was alternately added dropwise in small portions, and after the entire amount was added dropwise, the resulting mixture was stirred at 40 ° C. for 2 hours. The pH of the mixed solution after stirring was 11.8. This mixed solution was placed in a stainless steel autoclave and hydrothermally treated at 140 ° C. for 48 hours under stationary conditions. The obtained slurry was filtered, and the residue was washed with 2 L of ion exchange water and then dried at 80 ° C. overnight to obtain a dried product. 5 g of the obtained dried product was dispersed in 50 g of ion-exchanged water, and 7.3% by weight of hydrochloric acid was added little by little until the pH was stabilized at 6 to 7, and then allowed to stand at 80 ° C. for 20 hours. did. The slurry after standing was filtered, and the residue was washed with 500 mL of ion-exchanged water and then dried at 80 ° C. overnight to obtain white crystals. The obtained crystals were pulverized in a mortar, spread thinly on a magnetic dish, and heat-treated at 600 ° C. for 6 hours in an air atmosphere to obtain an MCM-41 type mesoporous silica catalyst (A). When the obtained catalyst (A) was analyzed by ICP emission analysis, the atomic ratio of silicon to aluminum (Si / Al) was 250.

(B) <ε-caprolactam [in the formula (III), R ¹ is a pentylene group, R ² is a hydrogen atom] and 6-hydroxyhexanamide [in the formula (IV), R ¹ is a pentylene group. A compound in which R ² is a hydrogen atom]
A catalyst layer is formed by filling 0.375 g of the catalyst (A) obtained in (a) above into a reaction tube made of quartz glass having an inner diameter of 12 mm, and at 350 ° C. under a flow of 4.2 L / h of nitrogen. Pre-heated for 2 hours. Subsequently, after the temperature of the catalyst layer was lowered to 300 ° C., ε-caprolactone [compound in which R ¹ is a pentylene group in the formula (I)] / water / ammonia [formula (2.43 L / h) Compound in which R ² is a hydrogen atom in II)] = 1.9 / 1 / 5.6 (molar ratio) of 1.17 L / h (ε-caprolactone WHSV = 3.6 h ⁻¹ ) The reaction was carried out by supplying the reaction tube at a speed. The reaction gas from 0 hour to 1 hour after the start of the reaction was collected and analyzed by gas chromatography. The conversion rate of ε-caprolactone was 17.7%, the selectivity of ε-caprolactam was 4.5%, and the selectivity of 6-hydroxyhexanamide was 74.7% (total selectivity 79.2%). ).

Example 2
<Production of ε-caprolactam and 6-hydroxyhexanamide>
A catalyst layer is formed by filling 0.375 g of the catalyst (A) obtained in Example 1 (a) into a quartz glass reaction tube having an inner diameter of 12 mm, and the temperature is set to 350 ° C. under a flow rate of 4.2 L / h. For 2 hours. Next, after the temperature of the catalyst layer was lowered to 300 ° C., a mixture of ε-caprolactone / water / ammonia = 1.9 / 1 / 9.3 (molar ratio) was added under a flow of 1.97 L / h of nitrogen. The reaction was carried out by supplying the reaction tube at a feed rate of 69 L / h (WHSV of ε-caprolactone = 3.6 h ⁻¹ ). The reaction gas from 0 hour to 1 hour after the start of the reaction was collected and analyzed by gas chromatography. The conversion of ε-caprolactone was 33.1%, the selectivity of ε-caprolactam was 3.3%, and the selectivity of 6-hydroxyhexanamide was 81.7% (total selectivity 85.0% ).

Comparative Example 1
The reaction was carried out in the same manner as in Example 1 (b) except that H-ZSM-5 [manufactured by PQ Corporation, atomic ratio of silicon to aluminum (Si / Al) = 140] was used instead of catalyst (A). went. The conversion rate of ε-caprolactone was 13.3%, the selectivity of ε-caprolactam was 16.5%, and the selectivity of 6-hydroxyhexanamide was 31.6% (total selectivity 48.1% ).

Example 3
<2-pyrrolidone [in the formula (III), R ¹ is a propylene group, R ² is a hydrogen atom] and 4-hydroxybutanamide [in the formula (IV), R ¹ is a propylene group, R Compound in which ² is a hydrogen atom]
A catalyst layer is formed by filling 0.375 g of the catalyst (A) obtained in Example 1 (a) into a quartz glass reaction tube having an inner diameter of 12 mm, and the temperature is set to 350 ° C. under a flow rate of 4.2 L / h. For 2 hours. Next, after the temperature of the catalyst layer was lowered to 300 ° C., γ-butyrolactone [compound in which R ¹ is a propylene group in formula (I)] / water / ammonia = 2. The mixture of 5/1 / 2.5 (molar ratio) was supplied to the reaction tube at a supply rate of 0.65 L / h (WHSV of γ-butyrolactone = 2.4 h ⁻¹ ) to carry out the reaction. The reaction gas from 0 hour to 1 hour after the start of the reaction was collected and analyzed by gas chromatography. The conversion of γ-butyrolactone was 48.1%, the selectivity for 2-pyrrolidone was 4.6%, and the selectivity for 4-hydroxybutanamide was 77.3% (total selectivity 81.9%). ).

Comparative Example 2
The reaction was performed in the same manner as in Example 3 except that H-ZSM-5 [manufactured by PQ Corporation, atomic ratio of silicon to aluminum (Si / Al) = 40] was used instead of the catalyst (A). The conversion of γ-butyrolactone was 26.7%, the selectivity for 2-pyrrolidone was 46.1%, and the selectivity for 4-hydroxybutanamide was 34.0% (total selectivity 80.1% ).

Claims (7)

Formula (I)

(In the formula, R ¹ represents an alkylene group having 3 to 7 carbon atoms.)
A lactone compound represented by formula (II)

(Wherein R ² represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a hydroxyalkyl group.)
The compound represented by formula (III) is reacted in the presence of water and mesoporous silica.

(Wherein R ¹ and R ² represent the same meaning as described above.)
A lactam compound represented by formula (IV)

(Wherein R ¹ and R ² represent the same meaning as described above.)
The manufacturing method of the amide compound shown by these.   The production method according to claim 1, wherein the mesoporous silica is MCM-41.   The manufacturing method according to claim 2, wherein the MCM-41 contains aluminum.   The production method according to any one of claims 1 to 3, wherein the amount of the compound represented by the formula (II) is 1 to 20 moles relative to 1 mole of the lactone compound represented by the formula (I). The production method according to claim 1, wherein R ² in formulas (II), (III), and (IV) is a hydrogen atom.   The production method according to claim 1, wherein the lactone compound represented by the formula (I) is γ-butyrolactone or ε-caprolactone.   The manufacturing method in any one of Claims 1-6 which perform the said reaction at 200-600 degreeC.