JP2016199471A - Method of producing bicyclic amine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a bicyclic amine compound having a long catalytic activity life.SOLUTION: There is provided a method for producing a bicyclic amine compound represented by formula (2) using an inorganic oxide represented by formula (1) as a catalyst. AMNPO(1) [A is a metal; M is an alkali metal; N is an alkaline earth metal; P is phosphorus; O is oxygen; subscripts a to e are molar numbers of each element; b/a=0.001 to 0.3; c/a=0.001 to 0.1; d/a=0.001 to 0.3; e is a value determined by the bonding state of each atom] [Rto Reach independently represents H, an alkyl group having 1-4 carbon atoms, a hydroxymethyl group or an alkoxy group having 1-4 carbon atoms; X represents a carbon atom or a nitrogen atom; and Y represents H, an alkyl group having 1-4 carbon atoms, a hydroxyl group or a hydroxyalkyl group having 1-4 carbon atoms.]SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a bicyclic amine compound.

  Bicyclic amine compounds are known as compounds useful for, for example, pharmaceutical and agrochemical intermediates, organic synthesis catalysts, chemical adsorbents, antibacterial agents, and the like (see, for example, Patent Document 1).

  As a method for producing a bicyclic amine compound, the applicant of the present invention has the following formula:

[Wherein, R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms. X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms. ]
Intramolecular dehydration in the gas phase in the presence of a solid catalyst

[Wherein, R _{1 to} R ₈ , X and Y are as defined above. ]
In the method for producing a compound represented by the following formula:
A _a M _b P _c O _d
[In the formula, A represents one or more elements selected from the group consisting of Si, Al, Mg, Ti and Zr, M represents an alkali metal, P represents phosphorus, and O represents oxygen. . Subscripts a to d represent the number of moles of each element, b / a = 0.001 to 0.3 (molar ratio), c / a = 0.001 to 0.3 (molar ratio), and d is It represents a value that can be arbitrarily taken depending on the bonding state of each atom. However, when A represents two or more elements, the subscript a represents the number of moles of the element having the largest number of moles. ]
A patent application has already been filed for a method for producing a bicyclic amine compound using an inorganic oxide represented by (see Patent Document 2).

  Patent Document 2 discloses a production method by gas phase reaction, and describes that by-product tar content can be reduced by using a specific solid catalyst. However, there has been no problem to be solved in industrially continuous production because no study has been made on suppression of deterioration of the catalyst and long-term operation evaluation has only been conducted for about one week.

JP 2010-037325 A JP 2012-149048 A

  An object of the present invention is to provide a production method that has a sufficient catalytic activity, suppresses deterioration of the catalyst as much as possible, maintains the catalytic activity for a long time, and efficiently obtains a bicyclic amine compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that the condensation of the phosphoric acid component, which is one of the causes of catalyst deterioration, can be suppressed by the addition of alkaline earth metal elements, and the above problems are solved. A means for solving the problem has been found and the present invention has been completed. That is, this invention is a manufacturing method of the bicyclic amine compound as shown below.

  [1] The following formula (1)

[Wherein, R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms. X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms. ]
From the compound represented by formula (2)

[Wherein, R _{1 to} R ₈ , X and Y are as defined above. ]
In the method for producing a compound represented by the following formula (3)
A _{a Mb} N _c P _d O _e (3)
[In the formula, A represents a metal, M represents an alkali metal, N represents an alkaline earth metal, P represents phosphorus, and O represents oxygen. Subscripts a to e represent the number of moles of each element, and b / a = 0.001 to 0.3 (molar ratio), c / a = 0.001 to 0.1 (molar ratio), d / a = 0. 0.001 to 0.3 (molar ratio), and e represents a value that can be arbitrarily taken depending on the bonding state of each atom. ]
The manufacturing method of the bicyclic amine compound characterized by using the inorganic oxide shown by these as a catalyst.

  [2] The method for producing a bicyclic amine compound according to the above [1], wherein in the formulas (1) and (2), Y is a hydrogen atom or a hydroxymethyl group.

  [3] The method for producing a bicyclic amine compound according to the above [1] or [2], wherein in the formulas (1) and (2), X is a nitrogen atom.

[4] In the formulas (1) and (2), R _{1 to} R ₈ each independently represent a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a hydroxymethyl group (provided that R _{1 to} R ₈ Are not all the same substituents.) The method for producing a bicyclic amine compound according to any one of [1] to [3] above.

  [5] The method for producing a bicyclic amine compound according to any one of the above [1] to [4], wherein in the formula (3), A is Al or Si.

  [6] In the formula (3), M is at least one selected from the group consisting of Na, K, Rb, and Cs. A method for producing an amine compound.

  [7] In the formula (3), N is at least one selected from the group consisting of Mg, Ca, Sr and Ba, and the bicyclic structure according to any one of the above [1] to [6] A method for producing an amine compound.

  Hereinafter, the present invention will be described in detail.

  The present invention provides a bicyclic amine represented by the above formula (2) by intramolecular dehydration of a hydroxyl group-containing cyclic amine compound represented by the above formula (1) in the gas phase in the presence of an inorganic oxide catalyst. It is characterized by obtaining a compound.

  In the present invention, in the above formula (1), X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms.

In the present invention, the substituents R _{1 to} R ₈ in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy having 1 to 4 carbon atoms. Represents a group.

  In the present invention, among the compounds represented by the above formula (1), specific examples of the compound in which X is a carbon atom include the following compounds (exemplified compound numbers 1 to 6). The invention is not limited to these examples.

  Specific examples of the compound in which X is a carbon atom among the bicyclic amine compounds represented by the above formula (2) include the following compounds (exemplified compound numbers 7 to 10). However, the present invention is not limited to these.

  Next, the intramolecular dehydration reaction of the hydroxyl group-containing cyclic amine compound of the present invention using an inorganic oxide catalyst will be described.

  In the present invention, the inorganic oxide catalyst is not particularly limited, but is more preferably a solid catalyst in which an acid component, a base component, or both are supported on a carrier.

  As the solid catalyst carrier, for example, an inorganic oxide is used. The inorganic oxide is not particularly limited, and examples thereof include silicon oxide, aluminum oxide, aluminosilicate, zeolite, magnesium oxide, titanium oxide, and zirconium oxide.

  It is preferable to use an inorganic acid as the acid component. Although it does not specifically limit as an inorganic acid, For example, phosphoric acid, phosphonic acid, phosphinic acid, phosphine oxide, various phosphates, sulfonic acid, etc. are mentioned as a suitable thing.

  As the base component, an alkali metal element and an alkaline earth metal element are preferably contained. Although it does not specifically limit as an alkali metal element, For example, Li, Na, K, Rb, Cs etc. are mentioned. Although it does not specifically limit as an alkaline-earth metal element, For example, Mg, Ca, Sr, Ba etc. are mentioned.

  The raw material for such a base component is not particularly limited, and examples thereof include oxides, hydroxides, halides, carbonates, nitrates, and sulfates thereof. In the present invention, the method for preparing the solid catalyst is not particularly limited, but, for example, a generally performed preparation method can be used. Specifically, the above-described solid catalyst raw material (for example, catalyst carrier, acid component raw material, base component raw material, etc.) is dissolved or suspended in water, and after steps such as stirring, heating, concentration, and drying, Examples thereof include a method of forming a solid catalyst through further firing.

  Although it does not specifically limit as a calcination temperature of a solid catalyst, Usually, it is the range of 300-1100 degreeC, Preferably it is the range of 400-700 degreeC. By setting it as the range of 400-700 degreeC, physical properties, such as acid-base intensity | strength of a solid catalyst, and a specific surface area, can be improved, and catalyst activity and a selectivity can be improved more.

  Moreover, although baking of a solid catalyst is not specifically limited, What is necessary is just to perform in air or nitrogen atmosphere.

  There is no particular limitation on the method of adding the alkaline earth metal element to the solid catalyst, even if the alkaline earth metal and the support are mixed and fired at the same time, or the support is fired to obtain an aqueous solution of the alkaline earth metal element salt. It may be kneaded and supported.

  In the present invention, the intramolecular dehydration reaction is mainly performed in the gas phase, but is preferably performed in a fixed bed flow system.

  According to the present invention, by including an alkaline earth metal in the catalyst component, it is possible to prolong the life of the catalyst as compared with the conventional one and to produce the bicyclic amine compound industrially continuously and stably. is there.

It is a figure which shows the change of the yield by reaction time in an Example and a comparative example. It is a figure which shows the chart of P-NMR of the solid catalyst obtained by the reference example.

  The present invention will be described in more detail based on the following reference examples and examples, but the present invention should not be construed as being limited thereto.

Reference Example 1 (Preparation of catalyst A)
60.0 g of commercially available aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd.) and 0.70 g of calcium nitrate as a catalyst carrier were mixed with 100 ml of water and evaporated to dryness using an evaporator. Baked for hours. This was mixed with 19.1 g of cesium carbonate and 4.75 g of an aqueous phosphoric acid solution, and after adding 100 ml of water, it was evaporated to dryness using an evaporator. This solid was dried in a muffle furnace at 200 ° C. for 4 hours in an air atmosphere, crushed to 3.5 mesh, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Ca, a = 1, b = 0) 1. c = 0.0025, d = 0.07, hereinafter referred to as Catalyst A).

Reference Example 2 (Preparation of catalyst B)
In Reference Example 1, except that 1.39 g of calcium nitrate was used, a catalyst was prepared according to the method described in Reference Example 1, and a gas phase reaction catalyst (A = Al, M = Cs, N = Ca, a = 1, b = 0.1, c = 0.005, d = 0.07, hereinafter referred to as catalyst B). The catalyst was measured by P-NMR.

Reference Example 3 (Preparation of catalyst C)
In Reference Example 1, except that 2.80 g of calcium nitrate was used, a catalyst was prepared according to the method described in Reference Example 1, and a gas phase reaction catalyst (A = Al, M = Cs, N = Ca, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as Catalyst C).

Reference Example 4 (Preparation of catalyst D)
In Reference Example 1, a catalyst was prepared according to the method described in Reference Example 1 except that 0.77 g of barium nitrate was used instead of calcium nitrate, and a gas phase reaction catalyst (A = Al, M = Cs, N = Ba, a = 1, b = 0.1, c = 0.0025, d = 0.07, hereinafter referred to as Catalyst D).

Reference Example 5 (Preparation of catalyst E)
In Reference Example 1, except that 1.54 g of barium nitrate was used instead of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Ba, a = 1, b = 0.1, c = 0.005, d = 0.07, hereinafter referred to as catalyst E). The catalyst was measured by P-NMR.

Reference Example 6 (Preparation of catalyst F)
In Reference Example 1, a catalyst was prepared according to the method described in Reference Example 1 except that 3.09 g of barium nitrate was used instead of calcium nitrate, and a gas phase reaction catalyst (A = Al, M = Cs, N = Ba, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as catalyst F).

Reference Example 7 (Preparation of catalyst G)
In Reference Example 1, except that 1.24 g of strontium nitrate was used instead of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Sr, a = 1, b = 0.1, c = 0.005, d = 0.07, hereinafter referred to as catalyst G).

Reference Example 8 (Preparation of catalyst H)
30.0 g of commercially available aluminum oxide (Sumitomo Chemical Co., Ltd.), 9.5 g of cesium carbonate, and 2.38 g of an aqueous phosphoric acid solution were mixed as a catalyst carrier, 100 ml of water was added, and the mixture was evaporated to dryness using an evaporator. This solid was dried in an air atmosphere at 200 ° C. for 4 hours in a muffle furnace, crushed to 3.5 mesh, and a gas phase reaction catalyst (A = Al, M = Cs, a = 1, b = 0.1, d = 0.07, hereinafter referred to as Catalyst H). The catalyst was measured by P-NMR.

Reference Example 9 (Preparation of catalyst I)
In Reference Example 1, except that 42.1 g of calcium nitrate was used, a catalyst was prepared according to the method described in Reference Example 1, and a gas phase reaction catalyst (A = Al, M = Cs, N = Ca, a = 1, b = 0.1, c = 0.15, d = 0.07, hereinafter referred to as Catalyst I).

Reference Example 10 (Preparation of catalyst J)
In Reference Example 1, except that 4.76 g of iron nitrate nonahydrate was used instead of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Fe, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as catalyst J).

Reference Example 11 (Preparation of catalyst K)
In Reference Example 1, except that 1.07 g of vanadium oxide was used in place of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a gas phase reaction catalyst (A = Al, M = Cs, N = V, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as catalyst K).

Reference Example 12 (Preparation of catalyst L)
In Reference Example 1, except that 4.71 g of chromium nitrate nonahydrate was used instead of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Cr, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as catalyst L).

Reference Example 13 (Preparation of catalyst M)
In Reference Example 1, except that 3.38 g of manganese nitrate hexahydrate was used instead of calcium nitrate, a catalyst was prepared according to the method described in Reference Example 1, and a catalyst for gas phase reaction (A = Al, M = Cs, N = Mn, a = 1, b = 0.1, c = 0.01, d = 0.07, hereinafter referred to as catalyst M).

Example 1 (Synthesis of Exemplified Compound 10 Using Catalyst A)
Exemplified Compound 6 [N- (2,3-dihydroxypropyl) piperazine] was dissolved in water to prepare a 11.25 wt% aqueous solution raw material. A quartz reaction tube having a diameter of 15 mm was packed with ceramic Raschig rings (diameter 3 mm × length 3 mm × thickness 1 mm) so that the catalyst A was 20 ml and the upper and lower portions thereof had a length of 23 cm. The temperature of the catalyst layer was kept at 380 ° C., and the raw material body containing the prepared exemplary compound 6 was dropped from above at a rate of 0.3 g / min for 24 hours. The obtained reaction gas mixture was cooled with a condenser, and the reactant was analyzed by gas chromatography. As a result, the conversion of Exemplified Compound 6 was 97%, and the selectivity to Exemplified Compound 10 was 54%, for a total yield. Was 52%. The reaction results are shown in Table 1.

Example 2 (Synthesis of Exemplified Compound 10 Using Catalyst B)
In Example 1, the method described in Example 1 was followed except that Catalyst B prepared in Reference Example 2 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 97%, the selectivity to Exemplified Compound 10 was 56%, and the total yield was 54%. The reaction results are shown in Table 1.

Example 3 (Synthesis of Exemplified Compound 10 Using Catalyst C)
In Example 1, the method described in Example 1 was followed except that Catalyst C prepared in Reference Example 3 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 99%, the selectivity to Exemplified Compound 10 was 39%, and the total yield was 39%. The reaction results are shown in Table 1.

Example 4 (Synthesis of Exemplified Compound 10 Using Catalyst D)
In Example 1, the method described in Example 1 was followed except that Catalyst D prepared in Reference Example 4 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 95%, the selectivity to Exemplified Compound 10 was 53%, and the total yield was 51%. The reaction results are shown in Table 1.

Example 5 (Synthesis of Exemplified Compound 10 Using Catalyst E)
In Example 1, the method described in Example 1 was followed except that Catalyst E prepared in Reference Example 5 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 95%, the selectivity to Exemplified Compound 10 was 55%, and the total yield was 52%. The reaction results are shown in Table 1.

Example 6 (Synthesis of Exemplified Compound 10 Using Catalyst F)
In Example 1, the method described in Example 1 was followed except that Catalyst F prepared in Reference Example 6 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 98%, the selectivity to Exemplified Compound 10 was 41%, and the total yield was 40%. The reaction results are shown in Table 1.

Example 7 (Synthesis of Exemplified Compound 10 Using Catalyst G)
In Example 1, the method described in Example 1 was followed except that the catalyst G prepared in Reference Example 7 was used instead of the catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 99%, the selectivity to Exemplified Compound 10 was 54%, and the total yield was 53%. The reaction results are shown in Table 1.

Example 8 (Synthesis of Exemplified Compound 7 Using Catalyst B)
In Example 1, the method described in Example 1 was followed except that Catalyst B prepared in Reference Example 2 was used instead of Catalyst A, and Example Compound 3 was used instead of Example Compound 6. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 3 was 99%, the selectivity to Exemplified Compound 7 was 38%, and the total yield was 38%. The reaction results are shown in Table 1.

Example 9 (Synthesis of Exemplified Compound 8 Using Catalyst B)
In Example 1, the method described in Example 1 was followed except that the catalyst B prepared in Reference Example 2 was used instead of the catalyst A, and the exemplified compound 4 was used instead of the exemplified compound 6. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 4 was 99%, the selectivity to Exemplified Compound 8 was 45%, and the total yield was 45%. The reaction results are shown in Table 1.

Example 10 (Synthesis of Exemplified Compound 10 Using Catalyst B)
In Example 1, the catalyst B prepared in Reference Example 2 was used instead of the catalyst A, the reaction was continued for 360 hours, and the reaction temperature was increased from the initial 380 ° C. to 406 ° C. in order to maintain a high conversion rate. The method described in Example 1 was followed except that. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 95%, the selectivity to Exemplified Compound 10 was 50%, and the total yield was 48%. The reaction results are shown in Table 1.

Example 11 (Synthesis of Exemplified Compound 10 Using Catalyst E)
In Example 1, the catalyst E prepared in Reference Example 5 was used instead of the catalyst A, the reaction was continued for 360 hours, and the reaction temperature was increased from the initial 380 ° C. to 406 ° C. in order to maintain a high conversion rate. The method described in Example 1 was followed except that. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 95%, the selectivity to Exemplified Compound 10 was 53%, and the total yield was 50%. The reaction results are shown in Table 1.

Comparative Example 1 (Synthesis of Exemplary Compound 10 Using Catalyst H)
In Example 1, the method described in Example 1 was followed except that catalyst H prepared in Reference Example 8 was used instead of catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 97%, the selectivity to Exemplified Compound 10 was 56%, and the total yield was 54%. The reaction results are shown in Table 2.

Comparative Example 2 (Synthesis of Exemplified Compound 10 Using Catalyst H)
In Example 1, the catalyst H prepared in Reference Example 8 was used instead of the catalyst A, the reaction was continued for 360 hours, and the reaction temperature was increased from the initial 380 ° C. to 424 ° C. in order to maintain a high conversion rate. The method described in Example 1 was followed except that. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 94%, the selectivity to Exemplified Compound 10 was 44%, and the total yield was 41%. The reaction results are shown in Table 2.

Comparative Example 3 (Synthesis of Exemplified Compound 10 Using Catalyst I)
In Example 1, the method described in Example 1 was followed except that Catalyst I prepared in Reference Example 9 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 97%, the selectivity to Exemplified Compound 10 was 27%, and the total yield was 26%. The reaction results are shown in Table 2.

Comparative Example 4 (Synthesis of Exemplified Compound 10 Using Catalyst J)
In Example 1, the method described in Example 1 was followed except that Catalyst J prepared in Reference Example 10 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 95%, the selectivity to Exemplified Compound 10 was 46%, and the total yield was 44%. The reaction results are shown in Table 2.

Comparative Example 5 (Synthesis of Exemplified Compound 10 Using Catalyst K)
In Example 1, the method described in Example 1 was followed except that Catalyst K prepared in Reference Example 11 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 71%, the selectivity to Exemplified Compound 10 was 33%, and the total yield was 23%. The reaction results are shown in Table 2.

Comparative Example 6 (Synthesis of Exemplified Compound 10 Using Catalyst L)
In Example 1, the method described in Example 1 was followed except that Catalyst L prepared in Reference Example 12 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 76%, the selectivity to Exemplified Compound 10 was 44%, and the total yield was 33%. The reaction results are shown in Table 2.

Comparative Example 7 (Synthesis of Exemplified Compound 10 Using Catalyst M)
In Example 1, the method described in Example 1 was followed except that Catalyst M prepared in Reference Example 13 was used instead of Catalyst A. As a result of analyzing the reaction solution by gas chromatography, the conversion of Exemplified Compound 6 was 71%, the selectivity to Exemplified Compound 10 was 47%, and the total yield was 33%. The reaction results are shown in Table 2.

  From the results of Tables 1 and 2, by adding an alkaline earth metal element, the condensation of phosphoric acid, which is a catalyst component, can be suppressed, the catalyst durability is improved compared to conventional catalysts, and the reaction is continued for a long time. The catalyst performance was maintained even when performed.

  The present invention has a possibility of being used as a method for producing a bicyclic amine compound known as a useful compound for, for example, a pharmaceutical / agrochemical intermediate, a catalyst for organic synthesis, a chemical adsorbent, an antibacterial agent, and the like.

Claims (7)

Following formula (1)

[Wherein, R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms. X represents a carbon atom or a nitrogen atom, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a hydroxyalkyl group having 1 to 4 carbon atoms. ]
From the compound represented by formula (2)

[Wherein, R _{1 to} R ₈ , X and Y are as defined above. ]
In the method for producing a compound represented by the following formula (3)
A _{a Mb} N _c P _d O _e (3)
[In the formula, A represents a metal, M represents an alkali metal, N represents an alkaline earth metal, P represents phosphorus, and O represents oxygen. Subscripts a to e represent the number of moles of each element, and b / a = 0.001 to 0.3 (molar ratio), c / a = 0.001 to 0.1 (molar ratio), d / a = 0. 0.001 to 0.3 (molar ratio), and e represents a value that can be arbitrarily taken depending on the bonding state of each atom. ]
The manufacturing method of the bicyclic amine compound characterized by using the inorganic oxide shown by these as a catalyst. In formula (1) and (2), Y is a hydrogen atom or a hydroxymethyl group, The manufacturing method of the bicyclic amine compound of Claim 1 characterized by the above-mentioned. In formula (1) and (2), X is a nitrogen atom, The manufacturing method of the bicyclic amine compound of Claim 1 or Claim 2 characterized by the above-mentioned. In formulas (1) and (2), R _{1 to} R ₈ each independently represent a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a hydroxymethyl group (provided that R _{1 to} R ₈ are all the same) The method for producing a bicyclic amine compound according to any one of claims 1 to 3, wherein the bicyclic amine compound does not become a substituent. In formula (3), A is Al or Si, The manufacturing method of the bicyclic amine compound in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The bicyclic amine compound according to any one of claims 1 to 5, wherein in the formula (3), M is at least one selected from the group consisting of Na, K, Rb and Cs. Method. The formula (3), wherein N is at least one selected from the group consisting of Mg, Ca, Sr and Ba, The bicyclic amine compound according to any one of claims 1 to 6, Method.

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