JP7436985B2 - Organosilane compounds and mesoporous organosilica - Google Patents

Description

The present invention relates to an organic silane compound and a mesoporous organic silica, and more particularly to an organic silane compound having a phenanthroline ring and a mesoporous organic silica.

Conventionally, it has been studied to improve the properties of mesoporous silica by introducing organic groups having various functional groups into mesoporous silica in which mesopores are regularly arranged. For example, Japanese Patent Application Laid-open No. 2009-49346 (Patent Document 1) discloses an energy conversion material comprising a porous body having an electron donor in its skeleton and an electron acceptor arranged in the pores of this porous body. is described, and as the porous body having an electron donor in the skeleton, a porous silica body having an organic group functioning as an electron donor such as Cu(2,9-diphenyl-1,10-phenanthroline) ²⁺ is used. Are listed.

Inorganica Chimica Acta, 2000, Vol. 297, pp. 156-161 (Non-patent Document 1) and Microporous and Mesoporous Materials, 2008, Vol. 116, pp. 28-35 (Non-patent Document 2), An organic silane compound in which a degradable silyl group and a phenanthroline ring are bonded via a urea bond has been described, and ACS Appl. Mater. Interface, 2017, Vol. 9, pp. 3774-3784 (Non-Patent Document 3) describes an organic silane compound in which a hydrolyzable silyl group and a phenanthroline ring are bonded via an amide bond.

Furthermore, J. Phys. Chem. B 2005, Vol. 109, pp. 15278-15287 (Non-Patent Document 4) describes a mesoporous organic silica having a phenanthroline ring synthesized using the organic silane compound described in Non-Patent Document 1 and a tetraalkoxysilane. J. Phys. Chem. C 2009, Vol. 113, pp. 2603-2610 (Non-patent Document 5) describes a mesoporous organic material having a phenanthroline ring synthesized using the organic silane compound described in Non-patent Document 2 and an ethane-crosslinked organic silane compound. Silica is listed.

JP2009-49346A

Kloster et al., Inorganica Chimica Acta, 2000, Vol. 297, pp. 156-161. Guo et al., Microporous and Mesoporous Materials, 2008, Vol. 116, pp. 28-35. Yuan et al., ACS Appl. Mater. Interface, 2017, Volume 9, pp. 3774-3784 Peng et al., J. Phys. Chem. B 2005, Volume 109, Pages 15278-15287 Guo et al., J. Phys. Chem. C 2009, Volume 113, Pages 2603-2610

However, in the mesoporous organic silicas described in Non-Patent Documents 4 and 5, the bond stability under hydrolysis conditions and heating conditions is not necessarily sufficient, and the present inventors have found that there is a problem that the phenanthroline ring is missing. found out.

The present invention has been made in view of the problems of the prior art described above, and provides a mesoporous organic silica having excellent bond stability without loss of phenanthroline rings under hydrolysis conditions or heating conditions, and The object of the present invention is to provide an organic silane compound having a phenanthroline ring from which this mesoporous organic silica can be obtained.

As a result of extensive research to achieve the above object, the present inventors have discovered that the phenanthroline ring can be produced by using an organic silane compound prepared by bonding a phenanthroline ring and a hydrolyzable silyl group via an alkylene group. The present inventors have discovered that mesoporous organic silica having excellent bonding stability can be obtained without any loss of bonding properties, and have completed the present invention.

That is, the organosilane compound of the present invention has the following formula (1):

[In the above formula (1), at least two groups among R ¹ to R ⁸ (preferably at least two groups among R ² , R ³ , R ⁶ and R ⁷ ) are represented by the following formula (2) :

(In the above formula (2), Y represents an alkylene group having 1 to 6 carbon atoms, R ^a represents an alkyl group having 1 to 6 carbon atoms, R ^b represents a substituted or unsubstituted allyl group, and m is 1 or 2, n is an integer from 0 to 3)
The remaining groups among R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, or a benzoyl group. , an amino group, an amide group, an imido group, a nitro group, and a cyano group]
It is characterized by being expressed as

The mesoporous organic silica of the present invention is a polymer of an organic silane compound represented by the above formula (1), and in the above formula (1), R ¹ ～R ⁸ at least one group of (preferably R ² ,R ³ ,R ⁶ ,R ⁷ at least two groups) are groups represented by the above formula (2), and R ¹ ～R ⁸ The remaining groups are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imido group, a nitro group, and A monovalent or divalent organic group selected from the group consisting of cyano groups, in the formula (2), Y represents an alkylene group having 1 to 6 carbon atoms, and R ^a represents an alkyl group having 1 to 6 carbon atoms, and R ^b represents a substituted or unsubstituted allyl group, m is 1 or 2, and n is an integer of 0 to 3.

The mesoporous organic silica of the present invention has the following formula (3):

[In the above formula (3), at least one group among R ¹ to R ⁸ is the following formula (4):

(In the above formula (4), Y represents an alkylene group having 1 to 6 carbon atoms, R ^b represents a substituted or unsubstituted allyl group, R ^c represents a hydrogen atom or a silyl group, and k represents 1 or 2 , i is an integer from 1 to 3, j is an integer from 0 to 2, 1≦i+j≦3, and there are multiple combinations of i and j expressed by the above formula (4). Each group is independent, and * is the bonding site with the adjacent structure)
The remaining groups among R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, or a benzoyl group. , an amino group, an amide group, an imido group, a nitro group, and a cyano group]
It is characterized by being expressed as

In the mesoporous organic silica of the present invention, it is preferable that at least two groups among R ² , R ³ , R ⁶ , and R ⁷ in the formula (3) are groups represented by the formula (4). .

It should be noted that it is not necessarily clear why by using the organosilane compound of the present invention, a mesoporous organosilica having excellent bond stability can be obtained without losing the phenanthroline ring under hydrolysis conditions or heating conditions. However, the present inventors speculate as follows. That is, in the organic silane compound of the present invention, the phenanthroline ring and the hydrolyzable silyl group are bonded via an alkylene group, and this bond is maintained even in the mesoporous organic silica that is the polymer thereof. The alkylene group has excellent hydrolysis resistance and heat decomposition resistance, and in the mesoporous organic silica of the present invention, the phenanthroline ring and the hydrolyzable silyl group are bonded via such an alkylene group. It is presumed that excellent bond stability can be obtained without loss of the phenanthroline ring under hydrolysis conditions or heating conditions.

On the other hand, in the mesoporous organic silicas described in Non-Patent Documents 4 and 5, a phenanthroline ring and a hydrolyzable silyl group are bonded via a urea bond or an amide bond. Since the urea bonds and the amide bonds are easily hydrolyzed and thermally decomposed, in the mesoporous organic silicas described in Non-Patent Documents 4 and 5, the urea bonds and the amide bonds are easily degraded under hydrolysis conditions or heating conditions. It is presumed that the phenanthroline ring is lost due to cleavage due to hydrolysis or thermal decomposition.

According to the present invention, it is possible to obtain mesoporous organic silica having excellent bond stability without loss of phenanthroline rings under hydrolysis conditions or heating conditions.

1 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B1. It is a graph showing the nitrogen adsorption/desorption isotherm of the mesoporous organic silica having a phenanthroline ring obtained in Example B1. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B2. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B2. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B3. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B3. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B4. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B4. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B5. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B5. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B6. It is a graph showing the nitrogen adsorption/desorption isotherm of the mesoporous organic silica having a phenanthroline ring obtained in Example B6. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B7. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B7. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B8. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B8. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B9. 2 is a graph showing nitrogen adsorption/desorption isotherms of mesoporous organic silica having a phenanthroline ring obtained in Example B9. It is a graph showing the X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Example B10. It is a graph showing the nitrogen adsorption/desorption isotherm of mesoporous organic silica having a phenanthroline ring obtained in Example B10. It is a graph showing the X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B1. It is a graph showing the nitrogen adsorption/desorption isotherm of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B1. 2 is a graph showing an X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B2. It is a graph showing the nitrogen adsorption/desorption isotherm of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B2. It is a graph showing the X-ray diffraction pattern of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B3. It is a graph showing a nitrogen adsorption/desorption isotherm of mesoporous organic silica having a phenanthroline ring obtained in Comparative Example B3. 2 is a graph showing the retention rate of phenanthroline rings in a hydrolysis resistance test of mesoporous organic silicas having phenanthroline rings obtained in Examples B5 to B6 and Comparative Examples B2 to B3. It is a graph showing the retention rate of phenanthroline rings in a heat resistance test of mesoporous organic silicas having phenanthroline rings obtained in Examples B4 and B6 and Comparative Examples B1 and B3.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments.

<Organosilane compound>
First, the organic silane compound of the present invention will be explained. The organic silane compound of the present invention has the following formula (1):

At least one group of R ¹ to R ⁸ in the formula (1) is represented by the following formula (2):

It is a group represented by

In the organosilane compound of the present invention, the group represented by formula (2) is a group that serves as a crosslinking point, and in the group that has a crosslinking point (crosslinking group) formed by the reaction of this group that serves as a crosslinking point. Since the phenanthroline rings are three-dimensionally crosslinked by the siloxane bonds (Si--O bonds), it is possible to obtain mesoporous organic silica that exhibits high durability against mechanical and chemical effects. In addition, from the viewpoint of effectively improving the coordination power of the obtained mesoporous organic silica with respect to metal ions, among R ¹ to R ⁸ in the formula (1) (more preferably R ² , R ³ , R ⁶ , R ⁷ ) is preferably a group represented by the formula (2) above. In this case, the plurality of groups represented by the formula (2) may be the same or different.

Y in the formula (2) represents an alkylene group having 1 to 6 carbon atoms. Alkylene groups having such a number of carbon atoms have excellent hydrolysis resistance and heat decomposition resistance, and by using such an organic silane compound, the phenanthroline ring will not be lost under hydrolysis conditions or heating conditions. , mesoporous organic silica having a periodic mesoporous structure and excellent bond stability can be obtained. On the other hand, when the number of carbon atoms in the alkylene group exceeds the above upper limit, it becomes difficult to synthesize mesoporous organic silica having a periodic mesoporous structure. On the other hand, when Y in the above formula (2) is a single bond, the Si-C bond between the phenanthroline ring and the hydrolyzable silyl group may cause an ipso-substitution reaction with H ⁺ or demand reaction by OH ^-. Because it is susceptible to nuclear attack, the Si--C bonds are broken under hydrolysis or heating conditions, and the phenanthroline ring is missing in the resulting mesoporous organic silica. Furthermore, the Si--C bonds have low bond stability and are easily broken even during the preparation of mesoporous organic silica. Furthermore, when Y in the formula (2) is a urea bond (aminocarbamoyl group) or an amide bond (carbamoyl group), the urea bond or The amide bond is cleaved and the phenanthroline ring is missing.

Further, the alkylene group may be a linear saturated hydrocarbon group or a branched saturated hydrocarbon group. When the alkylene group is a branched saturated hydrocarbon group, the number of carbon atoms in the alkylene group is the number of carbon atoms in the main chain. Therefore, a branched alkylene group has a structure in which carbon atoms other than the terminals of an alkylene group having 2 to 6 carbon atoms are substituted with a hydrocarbon group. Moreover, other substituents other than the hydrocarbon group may be bonded to such an alkylene group.

R ^a in the formula (2) represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms). Furthermore, R ^b in the formula (2) represents a substituted or unsubstituted allyl group. Examples of the substituents in the substituted allyl group include hydrocarbon groups.

m in the formula (2) is 1 or 2. When m is 2, the plurality of hydrolyzable silyl groups may be the same or different. Further, n in the above formula (2) is an integer of 0 to 3. When n is 0 to 1, a plurality of R ^b 's may be the same or different. Furthermore, when n is 2 to 3, a plurality of R ^a 's may be the same or different. Furthermore, n is preferably 1 to 3, more preferably 2 to 3, from the viewpoint that the condensation reaction of the organosilane compound progresses easily and the structure after condensation is stabilized.

The remaining groups of R ¹ to R ⁸ in the formula (1) are each independently a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 12 carbon atoms). 12), a monovalent group selected from the group consisting of an alkoxy group (preferably having 1 to 12 carbon atoms), a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imido group, a nitro group, and a cyano group Or it is a divalent organic group.

Examples of the alkyl group include a methyl group, ethyl group, propyl group, butyl group, etc., and examples of the aryl group include a monocyclic aromatic ring such as a phenyl group, and an aromatic condensed ring such as a naphthyl group and a fluorenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

Among these monovalent or divalent organic groups, hydrogen atoms, methyl groups, ethyl groups, and methoxy groups are preferred from the viewpoint of obtaining mesoporous organic silica that exhibits high durability against mechanical and chemical actions. , phenyl group, and phenoxy group are preferable, and hydrogen atom is more preferable.

Such an organic silane compound of the present invention includes, for example, a phenanthroline compound in which a halogen atom is bonded to a carbon at a desired position of the phenanthroline ring, and a halogen compound of an alkylmagnesium having 1 to 6 carbon atoms having a hydrolyzable silyl group. It can be produced by reacting with a chemical compound. In this reaction, the alkyl group having 1 to 6 carbon atoms having a hydrolyzable silyl group is substituted with a halogen atom bonded to a carbon at a desired position of the phenanthroline ring, thereby forming a desired position of the phenanthroline ring. An organic silane compound (organosilane compound represented by the above formula (1)) in which the alkyl group having the hydrolyzable silyl group is bonded to the carbon is produced.

Such a reaction is usually carried out in an organic solvent in the presence of a catalyst. Examples of the organic solvent include tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, diethylene glycol dimethyl ether (also known as diglyme), 1,4-dioxane, and toluene. Further, as the catalyst, [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride, [1,4- Bis(diphenylphosphino)butane]nickel(II) dichloride, bis(triphenylphosphine)nickel(II) dichloride, and the like. The reaction temperature is preferably -78 to 200°C.

Furthermore, the organic silane compound of the present invention can be prepared by, for example, treating a phenanthroline compound having a methyl group bonded to a carbon at a desired position of the phenanthroline ring with a base, and furthermore having a hydrolyzable silyl group having 1 to 5 carbon atoms. It is also possible to produce it by reacting an alkyl halide. In this reaction, the alkyl group having 1 to 5 carbon atoms having a hydrolyzable silyl group is bonded to a methyl group bonded to a carbon at a desired position of the phenanthroline ring, thereby forming a hydrolyzable silyl group with the phenanthroline ring. An organic silane compound (organosilane compound represented by the above formula (1)) in which a silyl group is bonded to an alkylene group having 2 to 6 carbon atoms is produced.

Such a reaction is usually carried out in an organic solvent in the presence of a base. Examples of the organic solvent include tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, diethylene glycol dimethyl ether (also known as diglyme), and 1,4-dioxane. Further, examples of the base include lithium diisopropylamide, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium tetramethylpiperidide, and the like. The reaction temperature is preferably -78 to 100°C.

<Mesoporous organic silica>
Next, the mesoporous organic silica of the present invention will be explained. The mesoporous organic silica of the present invention has the following formula (3):

At least one group of R ¹ to R ⁸ in the formula (3) is represented by the following formula (4):

It is a group represented by Examples of such mesoporous organic silica include a polymer of the organic silane compound of the present invention represented by the above formula (1).

In the mesoporous organic silica of the present invention, the group represented by the formula (4) is a group having a crosslinking point (crosslinking group), and the phenanthroline ring is tertiary formed by the siloxane bond (Si-O bond) in this crosslinking group. Because it is inherently crosslinked, the mesoporous organic silica of the present invention exhibits high durability against mechanical and chemical actions. In addition, from the viewpoint of effectively improving the coordination force for metal ions, among R ¹ to R ⁸ (more preferably among R ² , R ³ , R ⁶ , and R ⁷ ) in the formula (3), It is preferable that two or more of the groups are groups represented by the above formula (4). In this case, the plurality of groups represented by the formula (4) may be the same or different.

In the mesoporous organic silica of the present invention, even if the structure containing the phenanthroline ring represented by the formula (3) is contained in the skeleton of the mesoporous organic silica, ) may be combined with

Y in the formula (4) represents an alkylene group having 1 to 6 carbon atoms. An alkylene group having such a number of carbon atoms has excellent hydrolysis resistance and thermal decomposition resistance, and mesoporous organic silica having an alkylene group having a carbon number within the above range is capable of absorbing phenanthroline under hydrolytic conditions or heating conditions. It has a periodic mesoporous structure with no missing rings, and has excellent bonding stability. On the other hand, if the number of carbon atoms in the alkylene group exceeds the above upper limit, it is difficult to form a periodic mesoporous structure. On the other hand, when Y in the above formula (4) is a single bond, the Si-C bond between the phenanthroline ring and the hydrolyzable silyl group may cause an ipso-substitution reaction with H ⁺ or demand reaction by OH ^-. Because it is susceptible to nuclear attack, the Si--C bond is broken under hydrolysis or heating conditions, resulting in the loss of the phenanthroline ring. Furthermore, the Si--C bonds have low bond stability and are easily broken even during the preparation of mesoporous organic silica. Furthermore, when Y in the formula (4) is a urea bond (aminocarbamoyl group) or an amide bond (carbamoyl group), the urea bond or amide bond is cleaved under hydrolysis conditions or heating conditions, and phenanthroline The ring is missing.

Further, the alkylene group may be a linear saturated hydrocarbon group or a branched saturated hydrocarbon group. When the alkylene group is a branched saturated hydrocarbon group, the number of carbon atoms in the alkylene group is the number of carbon atoms in the main chain. Therefore, a branched alkylene group has a structure in which carbon atoms other than the terminals of an alkylene group having 2 to 6 carbon atoms are substituted with a hydrocarbon group. Moreover, other substituents other than the hydrocarbon group may be bonded to such an alkylene group.

R ^b in the formula (4) represents a substituted or unsubstituted allyl group. Examples of the substituents in the substituted allyl group include hydrocarbon groups. R ^c in the above formula (4) represents a hydrogen atom or a silyl group, and ^the silyl group includes an alkylsilyl group such as a trimethylsilyl group. preferable.

* in the formula (4) is a bonding site with an adjacent structure. The adjacent structure includes a repeating unit consisting of the structure represented by the formula (3) in mesoporous organic silica, a structure represented by the formula (5) described below, and a structure represented by the formula (6) described below. etc. In addition, when a structure containing a phenanthroline ring represented by the above formula (3) is bonded to the pore inner surface (pore wall) of ordinary mesoporous silica, the surface structure of the mesoporous silica can be mentioned, Preferably, the bonding site is bonded to a silicon atom on the surface of the mesoporous silica.

k in the formula (4) is 1 or 2. When k is 2, the plurality of silyl groups may be the same or different. Further, in the above formula (4), i is an integer of 1 to 3 (preferably an integer of 2 to 3), j is an integer of 0 to 2 (preferably an integer of 0 to 1), and 1≦i+j ≦3 (preferably 2≦i+j≦3). Note that the combinations of i and j are each independent among the plurality of groups represented by the formula (4), and in all the groups represented by the formula (4) in the mesoporous organic silica of the present invention. It doesn't have to be the same.

The remaining groups of R ¹ to R ⁸ in the formula (3) are each independently a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 12 carbon atoms). 12), a monovalent group selected from the group consisting of an alkoxy group (preferably having 1 to 12 carbon atoms), a phenoxy group, a hydroxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imido group, a nitro group, and a cyano group Or it is a divalent organic group.

Examples of the alkyl group include a methyl group, ethyl group, propyl group, butyl group, etc., and examples of the aryl group include a monocyclic aromatic ring such as a phenyl group, and an aromatic condensed ring such as a naphthyl group and a fluorenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

Among these monovalent or divalent organic groups, from the viewpoint of improving the mechanical strength and chemical stability of mesoporous organic silica, hydrogen atoms, methyl groups, ethyl groups, methoxy groups, phenyl groups, and phenoxy groups are preferred. is preferable, and a hydrogen atom is more preferable.

In the mesoporous organic silica having the structure represented by the above formula (3), there is no particular restriction on the proportion of the structure represented by the above formula (3) as long as it is 1 mol% or more, but metal ions may be immobilized. When applied to a solid catalyst, it is preferably 1 to 90 mol%, more preferably 2 to 80 mol%, from the viewpoint of stabilizing the periodic mesoporous structure and ensuring an appropriate amount of metal ions to be immobilized. ~50 mol% is particularly preferred.

When the proportion of the structure represented by the above formula (3) is less than 100 mol%, the structure other than the structure represented by the above formula (3) (hereinafter referred to as "other structure") is the following formula (5). and (6):

Structures represented by these structures are preferred, and either one or both of these structures may be included.

In the formula (5), R ⁹ is a divalent to tetravalent organic group, such as an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), or an arylene group (preferably having 6 carbon atoms). ~12) etc. In the above formulas (5) and (6), R ^d each independently represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) or a substituted or unsubstituted allyl group, and the allyl group is a methyl group, etc. may have a substituent. Furthermore, in the formulas (5) and (6), ^Re each independently represents a hydrogen atom or a silyl group, examples of the silyl group include alkylsilyl groups such as trimethylsilyl, and ^Re represents a steric A hydrogen atom is preferred from the viewpoint of suppressing damage.

Moreover, * in the above formulas (5) and (6) is a bonding site with an adjacent structure. The adjacent structure includes a repeating unit consisting of a structure represented by the formula (3) in mesoporous organic silica, a structure represented by the formula (5), a structure represented by the formula (6), and a mesoporous organic silica. Examples include the surface structure of silica (preferably silicon atoms on the surface of mesoporous silica).

r in the formula (5) is each independently 1 or 2, and p in the formulas (5) and (6) is each independently an integer of 1 to 3 (preferably an integer of 2 to 3). , q in the above formulas (5) and (6) is each independently an integer of 0 to 2 (preferably an integer of 0 to 1), and 1≦p+q≦3 (preferably 2≦p+q≦3). . Note that the combinations of p and q are each independent in the structure represented by the formula (5) or (6), which exists in plurality, and all of the combinations of the formula (5) or ( It is not necessary that the structures represented by 6) are the same.

In the mesoporous organic silica having the structure represented by the above formula (3), the proportion of such other structures is 99 mol% or less with respect to the total amount with the structure represented by the above formula (3). There is no particular restriction if there is, but from the viewpoint of stabilizing the periodic mesoporous structure and ensuring an appropriate amount of metal ions to be immobilized when metal ions are immobilized and applied to a solid catalyst, 99~ It is preferably 10 mol%, more preferably 98 to 20 mol%, and particularly preferably 95 to 50 mol%.

The mesoporous organic silica of the present invention has a structure having mesopores (mesopore structure). The pore diameter (central pore diameter) in such a mesopore structure is preferably 1 to 50 nm, more preferably 1.5 to 30 nm. If the central pore diameter is less than the above lower limit, the effect on substance diffusion is large, so coordination of metal ions is difficult to occur, and even if metal ions are immobilized and applied to a solid catalyst, catalytic reactions are difficult to occur. On the other hand, if the upper limit is exceeded, a periodic mesoporous structure tends to be difficult to form.

Further, the total pore volume in the mesopore structure is preferably 0.1 to 2 cm ³ /g, more preferably 0.2 to 1 cm ³ /g. If the total pore volume is less than the lower limit, even if metal ions are immobilized and applied to a solid catalyst, the amount of immobilized metal ions will be limited, so catalytic reactions will tend to be difficult to occur.

Further, in the mesoporous organic silica of the present invention, the specific surface area is preferably 100 to 1500 cm ² /g, more preferably 250 to 1000 cm ² /g. When the specific surface area is less than the lower limit, even if metal ions are immobilized and applied to a solid catalyst, the amount of immobilized metal ions is limited, so that catalytic reactions tend to be difficult to occur.

The central pore diameter can be determined by the DFT (Density-Functional-Theory) method based on the nitrogen adsorption/desorption isotherm, and the total pore capacity can be determined by t-plot based on the nitrogen adsorption/desorption isotherm. The specific surface area can be determined by the BET (Brunauer-Emmett-Teller) method based on the nitrogen adsorption/desorption isotherm.

Further, it is preferable that the X-ray diffraction pattern of the mesoporous organic silica of the present invention has one or more diffraction peaks at a diffraction angle corresponding to a d value of 1.5 to 30 nm. An X-ray diffraction peak means that a periodic structure with a d value corresponding to the peak angle exists in the sample. Therefore, the presence of one or more diffraction peaks at a diffraction angle corresponding to a d value of 1.5 to 30 nm means that the pores are regularly arranged at an interval of 1.5 to 30 nm. This means that it has a pore structure. Mesoporous organic silica with such a regular mesopore structure has a large specific surface area and pore capacity, so it is advantageous for adsorbing metal ions, and it also immobilizes metal ions to form a solid catalyst. It is advantageous for catalytic reactions within pores when applied to

Further, in the mesoporous organic silica of the present invention, the content of phenanthroline rings is preferably 0.1 to 3.0 mmol/g, more preferably 0.15 to 1 mmol/g per unit mass of the mesoporous organic silica. When the content of the phenanthroline ring is less than the above lower limit, coordination of metal ions tends to be difficult to occur.

Such a mesoporous organic silica of the present invention can be produced by hydrolyzing and polycondensing an organic silane compound represented by the above formula (1) in the presence of a surfactant by a known method and containing the surfactant. It can be produced by forming an organic silica mesostructure and removing the surfactant from this organic silica mesostructure by a known method. In this reaction, the hydrolyzable silyl group of the organosilane compound represented by formula (1) is hydrolyzed to produce a silanol group (Si-OH), and the subsequent polycondensation reaction produces a siloxane bond (Si-OH). By forming O--Si), mesoporous organic silica (mesoporous organic silica represented by the above formula (3)) in which a phenanthroline ring is bonded to mesoporous organic silica via an alkylene group is generated.

Further, the mesoporous organic silica of the present invention can also be produced by, for example, hydrolyzing and condensing the organic silane compound represented by the formula (1) and mesoporous silica using a known method. In this reaction, the hydrolyzable silyl group of the organosilane compound represented by the above formula (1) is hydrolyzed to generate a silanol group (Si-OH), and this silanol group forms a silanol group (Si-OH) on the surface of the mesoporous silica. By reacting with Si—OH), mesoporous organic silica (mesoporous organic silica represented by the above formula (3)) in which a phenanthroline ring is bonded to mesoporous silica via an alkylene group is produced.

Furthermore, when producing the mesoporous organic silica of the present invention, the proportion of the organic silane compound represented by the formula (1) is not particularly limited as long as it is 1 mol% or more based on 100 mol% of all organic silane compounds. However, when metal ions are immobilized on the obtained mesoporous organic silica and applied to a solid catalyst, from the viewpoint of stabilizing the periodic mesoporous structure and securing an appropriate amount of metal ions immobilized, 90 mol% is preferable, 2 to 80 mol% is more preferable, and 5 to 50 mol% is particularly preferable.

When the proportion of the organosilane compound represented by the above formula (1) is less than 100 mol%, an organosilane compound other than the organosilane compound represented by the above formula (1) (hereinafter referred to as "other organosilane compound") As, the following formulas (7) and (8):

The organic silane compounds represented by these are preferred, and either one or both of these organic silane compounds may be included.

In the formula (7), R ⁹ is a divalent to tetravalent organic group, such as an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), or an arylene group (preferably having 6 carbon atoms). ~12) etc. In the formulas (7) and (8), R ^d each independently represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) or a substituted or unsubstituted allyl group, and the allyl group is a methyl group, etc. may have a substituent. Further, in the formulas (7) and (8), R ^f each independently represents an alkyl group.

In the formula (7), r is each independently 1 or 2, and when r is 2, the plurality of hydrolyzable silyl groups may be the same or different. Further, s in the above formulas (7) and (8) is each independently an integer of 0 to 3. When n is 0 to 1, a plurality of R ^d's may be the same or different. Furthermore, when n is 2 to 3, a plurality of R ^fs may be the same or different. Furthermore, n is preferably 1 to 3, more preferably 2 to 3, from the viewpoint that the condensation reaction of the organosilane compound progresses easily and the structure after condensation is stabilized.

When producing the mesoporous organic silica of the present invention, the proportion of such other organic silane compounds is not particularly limited as long as it is 99 mol% or less with respect to 100 mol% of all organic silane compounds, but the mesoporous organic silica obtained When metal ions are immobilized on organic silica and applied to a solid catalyst, 99 to 10 mol% is preferable from the viewpoint of stabilizing the periodic mesoporous structure and ensuring an appropriate amount of immobilized metal ions. More preferably 98 to 20 mol%, particularly preferably 95 to 50 mol%.

There is no particular restriction on the method of hydrolysis/(poly)condensation when producing the mesoporous organic silica of the present invention, and for example, the method described in JP-A No. 2014-193457 and JP-A No. 2017-029926 is adopted. can do. Furthermore, examples of the surfactant used in producing the mesoporous organic silica of the present invention include the surfactants described in JP-A No. 2014-193457 and JP-A No. 2017-029926. By using such a surfactant, mesoporous organic silica having regular mesopores can be obtained. Furthermore, as a method for removing such a surfactant from the organic silica mesostructure, for example, the methods described in JP-A No. 2014-193457 and JP-A No. 2017-029926 can be adopted.

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The 3,8-dibromo-1,10-phenanthroline used in the Examples and Comparative Examples was manufactured by Tetrahedron Lett. , 2004, 45, 2801-2803, and (triisopropoxysilyl)methylmagnesium chloride was synthesized with reference to J. Organomet. Chem. , 1993, 451, C1-C3, and 3-iodopropyltriisopropoxysilane was synthesized with reference to J. Mater. Chem. , 2005, 15, 803-809, and 3-iodopropyltriallylsilane was synthesized with reference to Org. Biomol. Chem. , 2006, 4, 211-223. Other synthetic reagents and solvents were purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Co., Ltd., Fujifilm Wako Pure Chemical Industries, Ltd., and Kanto Kagaku Co., Ltd., and were used as they were.

(Example A1)
<Synthesis of 3,8-bis((triisopropoxysilyl)methyl)-1,10-phenanthroline>
Outside the glove box, 3,8-dibromo-1,10-phenanthroline (Br-Phen-Br, 1.49 g, 4.4 mmol) was placed in a 125 ml acid-resistant and pressure-resistant reaction vessel (manufactured by Parr) equipped with a stirrer. Weighed. This reaction container was placed in a glove box, and [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride (NiCl ₂ (dppp), 138 mg, 0.255 mmol) and ultra-dehydrated tetrahydrofuran (THF, 50 ml) were added. Added in order. Next, while stirring, (triisopropoxysilyl)methylmagnesium chloride (12.5 mmol) in tetrahydrofuran (THF, 18 ml) was added dropwise using a syringe over 3 minutes. Next, the reaction container was sealed and stirred at room temperature for 1 hour, and then stirred for 17 hours while heating at 140°C using an oil bath, and the following reaction formula (S1):

The reaction represented by was performed. Thereafter, the reaction vessel was allowed to cool to room temperature, then transferred to a 1 L separatory funnel, and quenched by adding distilled water (100 ml). Extraction was performed three times using chloroform (150 ml), and the organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After filtering the dried organic layer, the solvent was distilled off under reduced pressure. The resulting residue was dissolved in hexane (330 ml) and stirred for 15 minutes. The supernatant was filtered through Celite, and the residue was dissolved in hexane (330 ml) and filtered through Celite. This operation was repeated three times. The obtained hexane solution was concentrated using an evaporator to obtain a crude product. The obtained crude product was subjected to medium pressure preparative liquid chromatography (manufactured by Yamazen Co., Ltd., silica gel column, column size: 3 L, developing solvent: hexane/ethyl acetate = 7/3 → 6/4, flow rate: 60 ml/min). Purification was performed to obtain a pale yellow powder (yield: 1.11 g, yield: 41%).

This pale yellow powder was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 3,8-bis((triisopropoxysilyl)methyl)-1,10-phenanthroline (SiOPr-Me-Phen-Me-SiOPr). ). The results are shown below.
¹ H-NMR (600 MHz, CDCl ₃ ): δ9.01 (s, 2H), 8.00 (s, 2H), 7.65 (s, 2H), 4.21 (sept, J=6.0Hz, 6H), 2.35 (s, 4H), 1.15 (d, J=6.0Hz, 36H).
^13C -NMR (125MHz, _CDCl3 ): δ151.7, 143.7, 134.7, 133.2, 127.8, 126.0, 65.6, 25.5, 19.4.

(Example A2)
<Synthesis of 4,7-bis(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline>
Under an argon atmosphere, 4,7-dimethyl-1,10-phenanthroline (Me-Phen-Me, 1.00 g, 4.80 mmol) was weighed into a two-neck flask equipped with a stirrer, and dehydrated tetrahydrofuran (THF, 100 ml) was weighed. ) was added. After cooling the reaction vessel to 0° C., lithium diisopropylamide (LDA, 10.0 ml, 10.0 mmol, 1.0 M in hexane/tetrahydrofuran solution) was added and the reaction mixture was stirred at 0° C. for 2 hours. After cooling the reaction mixture to -78°C, 3-iodopropyltriisopropoxysilane (3.67 g, 9.80 mmol) was added dropwise at 0°C, and the mixture was stirred at 0°C for 1 hour. LDA (2.00 ml, 2.00 mmol, 1.0 M in hexane/tetrahydrofuran solution) was added and stirred at room temperature for 2 hours, followed by the following reaction formula (S2):

The reaction represented by was performed. After diluting the obtained reaction product with diethyl ether (20 ml), a saturated aqueous sodium chloride solution was added, and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over anhydrous sodium sulfate, then filtered and concentrated. The obtained crude product was purified by alumina column chromatography (developing solvent: hexane/chloroform/ethanol = 10/10/1) to obtain a brown transparent liquid (yield: 2.50 g, yield: 74%). .

This brown transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 4,7-bis(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline (SiOPr-Bu-Phen-Bu -SiOPr). The results are shown below.
^1H -NMR (400MHz, _CDCl3 ): δ9.04 (d, J = 4.8Hz, 2H), 8.04 (s, 2H), 7.44 (d, J = 4.4Hz, 2H), 4.20 (sept, J=5.2Hz, 6H), 3.34 (t, J=7.6Hz, 4H), 1.88-1.80 (m, 4H), 1.64-1.55 (m, 4H), 1.18 (d, J=6.8Hz, 36H), 0.70-0.66 (m, 4H).
^13C -NMR (100MHz, _CDCl3 ): δ149.8, 148.5, 146.7, 127.0, 122.8, 121.8, 64.9, 33.8, 32.2, 25.5 , 23.2, 11.9.

(Example A3)
<Synthesis of 4-(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline>
Under an argon atmosphere, 4-methyl-1,10-phenanthroline (Phen-Me, 1.00 g, 5.15 mmol) was weighed into a two-necked flask equipped with a stirrer, and dehydrated tetrahydrofuran (THF, 200 ml) was added. . After cooling the reaction vessel to 0°C, lithium diisopropylamide (LDA, 5.15ml, 5.15mmol, 1.0M in hexane/tetrahydrofuran solution) was added and the reaction mixture was stirred at 0°C for 2 hours. To this reaction mixture, 3-iodopropyltriisopropoxysilane (3.85 g, 5.15 mmol) was added dropwise at 0°C and stirred at room temperature for 20 hours, followed by the following reaction formula (S3):

The reaction represented by was performed. After diluting the obtained reaction product with diethyl ether (20 ml), distilled water was added and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate, then filtered and concentrated. The obtained crude product was purified by alumina column chromatography (developing solvent: hexane/chloroform/ethanol = 10/10/1) to obtain an orange transparent liquid (yield: 1.54 g, yield: 68%). .

This orange transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 4-(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline (Phen-Bu-SiOPr). confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ9.18 (dd, J = 4.0 Hz, 1.6 Hz, 1H), 9.05 (d, J = 4.4 Hz, 1H), 8.24 (dd , J=8.0Hz, 1.6Hz, 1H), 8.05 (d, J=9.2Hz, 1H), 7.79 (d, J=9.2Hz, 1H), 7.61 (dd, J = 8.4Hz, 4.8Hz, 1H), 7.46 (d, J = 4.4Hz, 1H), 4.20 (sept, J = 6.0Hz, 3H), 3.14 (t, J =8.0Hz, 2H), 1.88-1.80 (m, 2H), 1.63-1.56 (m, 2H), 1.18 (d, J = 6.8Hz, 18H), 0 .70-0.66 (m, 2H).
^13C -NMR (100MHz, _CDCl3 ): δ150.2, 149.9, 148.8, 146.7, 146.3, 135.7, 128.1, 127.6, 125.9, 123.1 , 122.9, 122.4, 64.9, 33.7, 32.3, 25.6, 23.2, 11.9.

(Example A4)
<Synthesis of 3,4,8-trimethyl-7-(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline>
Under an argon atmosphere, 3,4,7,8-tetramethyl-1,10-phenanthroline (Me2-Phen-Me2, 500 mg, 2.11 mmol) was weighed into a two-necked flask equipped with a stirrer, and dehydrated tetrahydrofuran ( THF, 60 ml) was added. After cooling the reaction vessel to 0°C, lithium diisopropylamide (LDA, 4.22ml, 4.22mmol, 1.0 M in hexane/tetrahydrofuran solution) was added and the reaction mixture was stirred at 0°C for 3 hours. To this reaction mixture, 3-iodopropyltriisopropoxysilane (790 mg, 2.11 mmol) was added dropwise at 0°C and stirred for 1 hour at 0°C, followed by the following reaction formula (S4):

The reaction represented by was performed. After diluting the obtained reaction product with diethyl ether (20 ml), distilled water was added and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate, then filtered and concentrated. The obtained crude product was purified by alumina column chromatography (developing solvent: hexane/chloroform/ethanol = 10/10/1) to obtain a pale yellow solid (yield: 770.4 mg, yield: 75%). .

This pale yellow solid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was identified as 3,4,8-trimethyl-7-(4-(triisopropoxysilyl)butyl)-1,10-phenanthroline (Me2-Phen (-Me)-Bu-SiOPr). The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ8.92-8.90 (m, 2H), 8.02-7.89 (m, 2H), 4.21 (sept, J=6.0Hz, 3H ), 3.10 (t, J=7.6Hz, 2H), 2.68 (s, 3H), 2.53 (s, 6H), 1.74-1.60 (m, 2H), 1. 19 (d, J=5.6Hz, 18H), 0.71-0.67 (m, 2H).
^13C -NMR (100MHz, _CDCl3 ): δ151.9, 151.5, 145.8, 145.4, 145.1, 141.1, 130.3, 129.7, 126.6, 126.1 , 122.0, 121.9, 64.9, 33.3, 28.3, 25.6, 23.8, 17.5, 16.9, 14.4, 12.0.

(Example A5)
<Synthesis of 4,7-bis(4-(trialylsilyl)butyl)-1,10-phenanthroline>
Under an argon atmosphere, 4,7-dimethyl-1,10-phenanthroline (Me-Phen-Me, 500 mg, 2.40 mmol) was weighed into a 200 ml two-necked flask equipped with a stirrer, and dehydrated tetrahydrofuran (THF, 60 ml) was added. added. After cooling the reaction vessel to 0° C., lithium diisopropylamide (LDA, 5.0 ml, 5.0 mmol, 1.0 M in hexane/tetrahydrofuran solution) was added and the reaction mixture was stirred at 0° C. for 2 hours. After cooling the reaction mixture to -20°C, 3-iodopropyltriallylsilane (1.54 g, 4.80 mmol) was added dropwise and stirred at -20°C for 20 hours, followed by the following reaction formula (S5):

The reaction represented by was performed. After diluting the obtained reaction product with diethyl ether (20 ml), distilled water was added and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate, then filtered and concentrated. The obtained crude product was purified by alumina column chromatography (developing solvent: hexane/chloroform/ethanol = 10/10/1) to obtain a brown solid (yield: 1.43 g, yield: 100%).

This brown solid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 4,7-bis(4-(triallysilyl)butyl)-1,10-phenanthroline (Si(allyl)-Bu-Phen- It was confirmed that the material was Bu-Si(allyl). The results are shown below.
^1H -NMR (400MHz, _CDCl3 ): δ9.05 (d, J = 4.8Hz, 2H), 8.04 (s, 2H), 7.43 (d, J = 4.4Hz, 2H), 5.83-5.72 (m, 6H), 4.92-4.73 (m, 12H), 3.14 (t, J=8.0Hz, 4H), 1.86-1.79 (m , 4H), 1.60 (d, J=8.4Hz, 12H), 1.55-1.45 (m, 4H), 0.72-0.67 (m, 4H).
^13C -NMR (100MHz, _CDCl3 ): δ149.9, 148.3, 146.8, 134.2, 127.0, 122.9, 121.8, 113.7, 34.2, 32.1 , 23.6, 19.6, 11.5.

(Example A6)
<Synthesis of 4-(4-(trialylsilyl)butyl)-1,10-phenanthroline>
Under an argon atmosphere, 4-methyl-1,10-phenanthroline (Phen-Me, 1.0 g, 5.15 mmol) was weighed into a 200 ml two-necked flask equipped with a stirrer, and dehydrated tetrahydrofuran (THF, 60 ml) was added. Ta. After cooling the reaction vessel to 0° C., lithium diisopropylamide (LDA, 6.0 ml, 6.0 mmol, 1.0 M in hexane/tetrahydrofuran solution) was added and the reaction mixture was stirred at 0° C. for 2 hours. After cooling the reaction mixture to -20°C, 3-iodopropyltriallylsilane (1.65g, 5.15mmol) was added dropwise and stirred at -20°C for 3 hours, and the resulting reaction mixture was added with LDA (0.5g, 5.15mmol). 3ml, 0.3mmol, 1.0M in hexane/tetrahydrofuran solution) was added and stirred at -20°C for 1 hour, followed by the following reaction formula (S6):

The reaction represented by was performed. After diluting the obtained reaction product with diethyl ether (20 ml), distilled water was added and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over anhydrous magnesium sulfate, then filtered and concentrated. The obtained crude product was purified by alumina column chromatography (developing solvent: hexane/chloroform/ethanol = 10/10/1) to obtain a brown solid (yield: 1.91 g, yield: 96%).

This brown solid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and was found to be 4-(4-(triallysilyl)butyl)-1,10-phenanthroline (Phen-Bu-Si(allyl)). It was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ9.18 (dd, J = 4.8 Hz, 2.0 Hz, 1H), 9.07 (d, J = 4.8 Hz, 1H), 8.24 (dd , J=8.0Hz, 1.6Hz, 1H), 8.04 (d, J=9.2Hz, 1H), 7.81 (d, J=9.2Hz, 1H), 7.62 (dd, J = 8.0Hz, 4.0Hz, 1H), 7.45 (d, J = 4.4Hz, 1H), 5.83-5.72 (m, 3H), 4.92-4.84 (m , 6H), 3.14 (t, J = 8.0Hz, 2H), 1.86-1.79 (m, 2H), 1.60 (d, J = 8.0Hz, 6H), 1.55 -1.45 (m, 2H), 0.72-0.67 (m, 2H).
^13C -NMR (100MHz, _CDCl3 ): δ150.3, 149.9, 148.5, 146.7, 146.3, 135.7, 134.2, 128.1, 127.5, 125.9 , 123.0, 122.9, 122.3, 113.7, 34.2, 32.2, 23.6, 19.6, 11.5.

(Comparative example A1)
<Synthesis of 5-[bis[3-(triethoxysilyl)propylcarbamoyl]amino]-1,10-phenanthroline>
In an argon atmosphere, 5-amino-1,10-phenanthroline (Phen-Am, 1.50 g, 7.68 mmol) was weighed into a two-necked flask equipped with a stirrer, and dissolved in dehydrated chloroform (THF, 150 ml). Ta. Thereafter, 3-(triethoxysilyl)propyl isocyanate (12.75 g, 51.5 mmol) was added, and the reaction solution was concentrated under reduced pressure until it became about 10 ml. The obtained concentrate was stirred at 80° C. for 24 hours, and the following reaction formula (S7):

The reaction represented by was performed. The obtained reaction solution was cooled to room temperature and then concentrated under reduced pressure, and hexane (300 ml) was added to the obtained crude product. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain a cream-colored powder (yield: 3.32 g, yield: 63%).

This cream-colored powder was identified by ¹ H-NMR measurement and was found to be 5-[bis[3-(triethoxysilyl)propylcarbamoyl]amino]-1,10-phenanthroline (Phen-Am-bis(Calb-Pr-SiOEt). )). The results are shown below.
^1H -NMR (400MHz, _CDCl3 ): δ9.13 (dd, J=4.4Hz, 2.0Hz, 1H), 9.10 (dd, J=4.4Hz, 2.0Hz, 1H), 8 .49 (dd, J=8.0Hz, 1.6Hz, 1H), 8.06-8.03 (m, 2H), 7.80 (dd, J=8.0Hz, 4.4Hz, 1H), 7.74 (dd, J=8.4Hz, 4.4Hz, 1H), 3.69 (q, J=7.2Hz, 12H), 3.09-2.97 (m, 4H), 1.47 -1.39 (m, 4H), 1.12 (t, J=7.2Hz, 18H), 0.47-0.43 (m, 4H).

(Example B1)
A nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 333 mg, 0.47 mmol) and sodium chloride (1.00 g) were placed in a 110 ml vial equipped with a stirrer. , 17.1 mmol) was weighed out, and distilled water (17.3 ml) and concentrated hydrochloric acid (1.15 ml) were added. The resulting reaction mixture was stirred at 60° C. for 2 hours to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the SiOPr-Me-Phen-Me-SiOPr (148 mg, 0.24 mmol) obtained in Example A1 and 1,2-bis(triethoxysilyl) were added. A solution of ethane (469 mg, 1.32 mmol) in ethanol (0.33 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, then allowed to stand for 24 hours while heating at 80°C, and the following reaction formula (P1) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a methylene group. This organic silica mesostructure was suspended overnight in a mixed solution of ethanol (100 ml) and 2 mol/L hydrochloric acid (3.0 ml) to remove the template surfactant, and the cream-colored phenanthroline ring was formed through only methylene groups. A bonded mesoporous organic silica powder (Phen-Me-Et-PMO-1a) was obtained (yield: 300 mg).

The X-ray diffraction pattern of this Phen-Me-Et-PMO-1a was analyzed using a powder X-ray diffractometer (“RINT-TTR” manufactured by Rigaku Co., Ltd.) using Cu-Kα as the X-ray source and a current value of 300 mA. When measured under the condition of a voltage value of 50 mV, a diffraction peak due to a regular mesostructure was observed at 2θ=1.24° (d=7.12 nm), as shown in FIG. 1A. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Me-Et-PMO-1a was measured using a specific surface area/pore distribution measuring device ("Nova3000e" manufactured by Quantachrome), it was found that As shown in (black circles indicate adsorption and white circles indicate desorption), it was type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Me-Et-PMO-1a had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Me-Et-PMO-1a was calculated by the BET (Brunauer-Emmett-Teller) method (P/P ₀ = 0.1 The central pore diameter d was calculated using the _DFT (Density-Functional-Theory) method to be 4.7 nm, and the total pore volume was 600 m ² /g. V _P was calculated by the t-plot method (calculated within the range of P/P ₀ =0.6 to 0.8) and was found to be 0.50 cm ³ /g. In addition, the amount of nitrogen contained in the Phen-Me-Et-PMO-1a was measured by CHN elemental analysis (requested from A Rabbit Science Co., Ltd.), and from the obtained nitrogen amount, the amount of nitrogen contained in the Phen-Me-Et-PMO-1a was measured. The amount of phenanthroline ring immobilized in -1a was determined to be 0.87 mmol/g.

(Example B2)
In a 110 ml vial equipped with a stirring bar, a nonionic surfactant (“P123” manufactured by Aldrich, HO(CH ₂ CH ₂ O) ₂₀ (CH ₂ CH(CH ₃ )O) ₇₀ (CH ₂ CH ₂ O) was added. ) ₂₀ H), 811 mg, 0.14 mmol) and potassium chloride (5.17 g, 69.3 mmol) were weighed, and distilled water (28.5 ml) and concentrated hydrochloric acid (4.05 ml) were added. The resulting reaction mixture was ice-cooled to completely dissolve the nonionic surfactant. The temperature of the obtained nonionic surfactant aqueous solution was raised to 45° C., and while stirring, the SiOPr-Me-Phen-Me-SiOPr (384 mg, 0.623 mmol) obtained in Example A1 and 1,2 -Bis(triethoxysilyl)ethane (1.25 g, 3.52 mmol) in ethanol solution (1 ml) was added. The resulting reaction mixture was stirred at 45°C for 24 hours, then allowed to stand for 24 hours while heating at 90°C, and the following reaction formula (P2) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (P123) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a methylene group. This organic silica mesostructure was suspended overnight in a mixed solution of ethanol (150 ml) and 2 mol/L hydrochloric acid (4.24 ml) to remove the template surfactant, and the cream-colored phenanthroline ring was formed through only methylene groups. A bonded mesoporous organic silica powder (Phen-Me-Et-PMO-1b) was obtained (yield: 732 mg).

The X-ray diffraction pattern of this Phen-Me-Et-PMO-1b was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Me-Et-PMO-1b was measured in the same manner as in Example B1, the results were as shown in FIG. 2B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Me-Et-PMO-1b had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Me-Et-PMO-1b was calculated in the same manner as in Example B1, and was found to be 648 m ² /g, with the center The pore diameter _dDFT was calculated to be 8.1 nm, and the total pore volume _VP was calculated to be 0.50 cm ³ /g. Furthermore, the amount of phenanthroline ring immobilized in the Phen-Me-Et-PMO-1a was determined in the same manner as in Example B1, and was found to be 0.71 mmol/g.

(Example B3)
A nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 750 mg, 1.06 mmol) and sodium chloride (3.00 g) were placed in a 110 ml vial equipped with a stirrer. , 51.3 mmol), and added distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml). The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the SiOPr-Bu-Phen-Bu-SiOPr (331 mg, 0.473 mmol) obtained in Example A2 and 1,2-bis(triethoxysilyl) were added. A solution of ethane (1.51 g, 4.26 mmol) in ethanol (1 ml) was added. The resulting reaction mixture was stirred at 60° C. for 24 hours, and then left to stand for 24 hours while heating at 80° C. to form the following reaction formula (P3):

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended in a mixed solution of ethanol (100 ml) and 2 mol/L hydrochloric acid (3.0 ml) overnight to remove the template surfactant, and the white phenanthroline ring was suspended only through the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-1a) was obtained (yield: 801 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-1a was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-1a was measured in the same manner as in Example B1, the results were as shown in FIG. 3B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Bu-Et-PMO-1a had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-1a was calculated in the same manner as in Example ^B1 . The pore diameter _dDFT was calculated to be 4.6 nm, and the total pore volume _VP was calculated to be 0.62 cm ³ /g. Furthermore, the amount of phenanthroline ring immobilized in the Phen-Bu-Et-PMO-1a was determined in the same manner as in Example B1, and was found to be 0.45 mmol/g.

(Example B4)
In a 110 ml vial equipped with a stirring bar, a nonionic surfactant (“P123” manufactured by Aldrich, HO(CH ₂ CH ₂ O) ₂₀ (CH ₂ CH(CH ₃ )O) ₇₀ (CH ₂ CH ₂ O) was added. ) ₂₀ H), 811 mg, 0.14 mmol) and potassium chloride (5.17 g, 69.3 mmol) were weighed, and distilled water (28.5 ml) and concentrated hydrochloric acid (4.05 ml) were added. The resulting reaction mixture was ice-cooled to completely dissolve the nonionic surfactant. The temperature of the obtained nonionic surfactant aqueous solution was raised to 45° C., and while stirring, the SiOPr-Bu-Phen-Bu-SiOPr (404 mg, 0.577 mmol) obtained in Example A2 and 1,2 -Bis(triethoxysilyl)ethane (1.16 g, 3.27 mmol) in ethanol solution (1 ml) was added. The obtained reaction mixture was stirred at 45° C. for 24 hours, and then left to stand for 24 hours while heating at 90° C. to form the following reaction formula (P4):

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (P123) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended in a mixed solution of ethanol (150 ml) and 2 mol/L hydrochloric acid (4.24 ml) overnight to remove the template surfactant, and the cream-colored phenanthroline ring was formed through only the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-1b) was obtained (yield: 712 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-1b was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-1b was measured in the same manner as in Example B1, and as shown in FIG. 4B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Bu-Et-PMO-1b had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-1b was calculated in the same manner as in Example ^B1 . The pore diameter _dDFT was calculated to be 7.0 nm, and the total pore volume _VP was calculated to be 0.48 cm ³ /g. Further, the amount of immobilized phenanthroline ring in the Phen-Bu-Et-PMO-1b was determined in the same manner as in Example B1, and was found to be 0.78 mmol/g.

(Example B5)
A nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 375 mg, 0.527 mmol) and sodium chloride (2.25 g) were placed in a 110 ml vial equipped with a stirring bar. , 38.5 mmol) was weighed out, and distilled water (39 ml) and concentrated hydrochloric acid (2.50 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the SiOPr-Bu-Phen-Bu-SiOPr obtained in Example A2 (273 mg, 0.389 mmol) and tetraethoxysilane (2.18 ml, 13. 00 mmol) in ethanol (0.75 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, then allowed to stand for 24 hours while heating at 90°C, and the following reaction formula (P5) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended in a mixed solution of ethanol (150 ml) and 2 mol/L hydrochloric acid (4.24 ml) overnight to remove the template surfactant, and the white phenanthroline ring was suspended only through the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-PMO) was obtained (yield: 772 mg).

When the X-ray diffraction pattern of this Phen-Bu-PMO was measured in the same manner as in Example B1, it showed a regular mesostructure at 2θ = 1.56° (d = 5.66 nm), as shown in Figure 5A. The resulting diffraction peaks were observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-PMO was measured in the same manner as in Example B1, it was found that the type IV there were. Therefore, it was confirmed from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm that the Phen-Bu-PMO had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-PMO was calculated in the same manner as in Example B1, and it was found to be 750 m ² /g, and the central pore diameter d _{The DFT} was calculated to be 4.4 nm, and the total pore volume _VP was calculated to be 0.59 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Bu-PMO was determined in the same manner as in Example B1, and was found to be 0.45 mmol/g.

(Example B6)
Mesoporous silica FSM-16 (manufactured by Taiyo Kagaku Co., Ltd., 2.50 g) was weighed into a 200 ml three-neck flask equipped with a reflux tube, a septum, and a stirrer, and toluene (75 ml) was added. While stirring the resulting reaction mixture, a toluene solution (30 ml) of the SiOPr-Bu-Phen-Bu-SiOPr (1.26 g, 1.79 mmol) obtained in Example A2 and trifluoroacetic acid (0.45 ml) were added. ) was added. The obtained reaction mixture was stirred under reflux for 20 hours, and the following reaction formula (P6):

The reaction represented by was performed. The generated precipitate was filtered out by pressure filtration. In order to remove the unreacted SiOPr-Bu-Phen-Bu-SiOPr, the resulting residue was subjected to Soxhlet extraction using toluene and methanol, and dried under vacuum, so that the pale orange phenanthroline ring was separated only through the butylene group. A bonded mesoporous silica powder (Phen-Bu-FMS16) was obtained (yield: 3.46 g).

When the X-ray diffraction pattern of this Phen-Bu-FMS16 was measured in the same manner as in Example B1, it showed a regular mesostructure at 2θ = 1.88° (d = 4.70 nm), as shown in Figure 6A. The resulting diffraction peaks were observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-FMS16 was measured in the same manner as in Example B1, it was found that the nitrogen adsorption/desorption isotherm of the Phen-Bu-FMS16 was type IV as shown in FIG. there were. Therefore, it was confirmed from the X-ray diffraction pattern and the nitrogen adsorption/desorption isotherm that the Phen-Bu-FMS16 had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-FMS16 was calculated in the same manner as in Example B1, and it was found to be 633 m ² /g, and the central pore diameter d _DFT was calculated to be 4.1 nm, and total pore volume _VP was calculated to be 0.50 cm ³ /g. Furthermore, the amount of phenanthroline ring immobilized in the Phen-Bu-FMS16 was determined in the same manner as in Example B1, and was found to be 0.43 mmol/g.

(Example B7)
In a 110 ml vial equipped with a stirrer, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.00 g, 1.41 mmol) and sodium chloride (3 .00 g, 51.3 mmol) was weighed out, and distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the Phen-Bu-SiOPr (212 mg, 0.482 mmol) obtained in Example A3 and 1,2-bis(triethoxysilyl)ethane (1. A solution of 54 g, 4.34 mmol) in ethanol (1 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, then allowed to stand for 24 hours while heating at 80°C, and the following reaction formula (P7) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended overnight in a mixed solution of ethanol (200 ml) and 2 mol/L hydrochloric acid (5.6 ml) to remove the template surfactant, and the cream-colored phenanthroline ring was formed through only the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-2) was obtained (yield: 751 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-2 was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-2 was measured in the same manner as in Example B1, the results were as shown in FIG. 7B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Bu-Et-PMO-2 had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-2 was calculated in the same manner as in Example B1, and was found to be 708 m ² /g, with the center The pore diameter _dDFT was calculated to be 4.4 nm, and the total pore volume V _P was calculated to be 0.58 cm ³ /g. Furthermore, the amount of phenanthroline ring immobilized in the Phen-Bu-Et-PMO-2 was determined in the same manner as in Example B1, and was found to be 0.51 mmol/g.

(Example B8)
In a 110 ml vial equipped with a stirrer, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.00 g, 1.41 mmol) and sodium chloride (3 .00 g, 51.3 mmol) was weighed out, and distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the Me2-Phen(-Me)-Bu-SiOPr (233 mg, 0.482 mmol) obtained in Example A4 and 1,2-bis(triethoxy A solution of silyl)ethane (1.54 g, 4.34 mmol) in ethanol (1 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, and then allowed to stand for 24 hours while heating at 80°C, resulting in the following reaction formula (P8):

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended overnight in a mixed solution of ethanol (200 ml) and 2 mol/L hydrochloric acid (5.6 ml) to remove the template surfactant, and the cream-colored phenanthroline ring was formed through only the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-3) was obtained (yield: 813 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-3 was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-3 was measured in the same manner as in Example B1, the results were as shown in FIG. 8B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Bu-Et-PMO-3 had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-3 was calculated in the same manner as in Example ^B1 . The pore diameter _dDFT was calculated to be 4.6 nm, and the total pore volume _VP was calculated to be 0.63 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Bu-Et-PMO-3 was determined in the same manner as in Example B1, and was found to be 0.45 mmol/g.

(Example B9)
In a 110 ml vial equipped with a stirrer, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.00 g, 1.41 mmol) and sodium chloride (3 .00 g, 51.3 mmol) was weighed out, and distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the Si(allyl)-Bu-Phen-Bu-Si(allyl) (286 mg, 0.482 mmol) obtained in Example A5 and 1,2- A solution of bis(triethoxysilyl)ethane (1.54 g, 4.34 mmol) in ethanol (1 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, then allowed to stand for 24 hours while heating at 80°C, and the following reaction formula (P9) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended in a mixed solution of ethanol (200 ml) and 2 mol/L hydrochloric acid (5.6 ml) overnight to remove the template surfactant, and the white phenanthroline ring was formed through only the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-4) was obtained (yield: 786 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-4 was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-4 was measured in the same manner as in Example B1, the results were as shown in FIG. 9B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Bu-Et-PMO-4 had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-4 was calculated in the same manner as in Example B1, and was found to be 891 m ² /g, with the center The pore diameter _dDFT was calculated to be 4.4 nm, and the total pore volume _VP was calculated to be 0.68 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Bu-Et-PMO-4 was determined in the same manner as in Example B1, and was found to be 0.41 mmol/g.

(Example B10)
In a 110 ml vial equipped with a stirrer, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.00 g, 1.41 mmol) and sodium chloride (3 .00 g, 51.3 mmol) was weighed out, and distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the Phen-Bu-Si(allyl) (183 mg, 0.482 mmol) obtained in Example A6 and 1,2-bis(triethoxysilyl)ethane were added. (1.54 g, 4.34 mmol) in ethanol solution (1 ml) was added. The resulting reaction mixture was stirred at 60°C for 24 hours, then allowed to stand for 24 hours while heating at 80°C, and the following reaction formula (P10) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij76) and in which a phenanthroline ring was bonded to mesoporous organic silica only through a butylene group. This organic silica mesostructure was suspended in a mixed solution of ethanol (200 ml) and 2 mol/L hydrochloric acid (5.6 ml) overnight to remove the template surfactant, and the white phenanthroline ring was formed through only the butylene group. A bonded mesoporous organic silica powder (Phen-Bu-Et-PMO-5) was obtained (yield: 731 mg).

The X-ray diffraction pattern of this Phen-Bu-Et-PMO-5 was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, when the nitrogen adsorption/desorption isotherm of the Phen-Bu-Et-PMO-5 was measured in the same manner as in Example B1, the results were as shown in FIG. 10B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, it was confirmed from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm that the Phen-Bu-Et-PMO-5 had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Bu-Et-PMO-5 was calculated in the same manner as in Example B1, and was found to be 810 m ² /g, with the center The pore diameter _dDFT was calculated to be 4.3 nm, and the total pore volume _VP was calculated to be 0.64 cm ³ /g. Furthermore, the amount of phenanthroline ring immobilized in the Phen-Bu-Et-PMO-5 was determined in the same manner as in Example B1, and was found to be 0.58 mmol/g.

(Comparative example B1)
In a 110 ml vial equipped with a stirrer, a nonionic surfactant (“Brij76” manufactured by Aldrich, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH, 1.00 g, 1.41 mmol) and sodium chloride (3 .00 g, 51.3 mmol) was weighed out, and distilled water (52 ml) and concentrated hydrochloric acid (3.46 ml) were added. The resulting reaction mixture was stirred at 60° C. for 1 hour to completely dissolve the nonionic surfactant. While stirring the obtained nonionic surfactant aqueous solution, the Phen-Am-bis(Calb-Pr-SiOEt) (167 mg, 0.242 mmol) obtained in Comparative Example A1 and 1,2-bis(trifluoride) were added. An ethanol solution (1 ml) of ethoxysilyl)ethane (1.62 g, 4.58 mmol) was added. The resulting reaction mixture was stirred at 60° C. for 24 hours, then allowed to stand for 24 hours while heating at 80° C. to form the following reaction formula (P11):

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (Brij 76), in which a phenanthroline ring was bonded to mesoporous organic silica via an aminocarbamoyl group and a propylene group. Ta. This organic silica mesostructure was suspended in a mixed solution of ethanol (203 ml) and 2 mol/L hydrochloric acid (5.75 ml) overnight to remove the template surfactant, and the cream-colored phenanthroline ring was combined with the aminocarbamoyl group and propylene group. A mesoporous organic silica powder (Phen-Am-Calb-Pr-Et-PMO) bonded through groups was obtained (yield: 685 mg).

The X-ray diffraction pattern of this Phen-Am-Calb-Pr-Et-PMO was measured in the same manner as in Example B1, and as shown in Figure 11A, 2θ = 1.40° (d = 6.30 nm). Diffraction peaks due to regular mesostructure were observed. In addition, the nitrogen adsorption/desorption isotherm of the Phen-Am-Calb-Pr-Et-PMO was measured in the same manner as in Example B1, and the results are shown in FIG. 11B (in the figure, black circles indicate adsorption and white circles indicate desorption). As such, it was type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Am-Calb-Pr-Et-PMO had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Am-Calb-Pr-Et-PMO was calculated to be 956 m ² /g in the same manner as in Example B1. The central pore diameter _dDFT was calculated to be 4.6 nm, and the total pore volume _VP was calculated to be 0.82 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Am-Calb-Pr-Et-PMO was determined in the same manner as in Example B1, and was found to be 0.28 mmol/g.

(Comparative example B2)
A cationic surfactant, hexadecyltrimethylammonium bromide (CTAB, [CH ₃ (CH ₂ ) ₁₅ N(CH ₃ ) ₃ ]Br, 946 mg, 2.60 mmol) was weighed into a 110 ml vial equipped with a stirrer. Then, distilled water (22.4 ml) and concentrated aqueous ammonia (10.3 ml) were added. The resulting reaction mixture was stirred at 50° C. for 1 hour to completely dissolve the cationic surfactant, and then cooled to room temperature. While stirring the obtained nonionic surfactant aqueous solution, the Phen-Am-bis(Calb-Pr-SiOEt) (514 mg, 0.745 mmol) obtained in Comparative Example A1 and tetraethoxysilane (4.17 ml) were added. , 18.6 mmol) in ethanol (1 ml) was added. The resulting reaction mixture was stirred at room temperature for 24 hours, then allowed to stand for 24 hours while heating at 90°C, and the following reaction formula (P12) was obtained:

The reaction represented by was performed. The generated precipitate was filtered using a pressure filtration device to obtain an organic silica mesostructure containing a template surfactant (CTAB), in which a phenanthroline ring was bonded to mesoporous organic silica via an aminocarbamoyl group and a propylene group. Ta. This organic silica mesostructure was suspended overnight in a mixed solution of ethanol (366 ml) and 2 mol/L hydrochloric acid (10.4 ml) to remove the template surfactant, and the pale yellow phenanthroline ring was combined with an aminocarbamoyl group and a propylene group. A mesoporous organic silica powder (Phen-Am-Calb-Pr-PMO) bonded through groups was obtained (yield: 1.23 g).

The X-ray diffraction pattern of this Phen-Am-Calb-Pr-PMO was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, the nitrogen adsorption/desorption isotherm of the Phen-Am-Calb-Pr-PMO was measured in the same manner as in Example B1, and as shown in FIG. 12B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, it was confirmed from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm that the Phen-Am-Calb-Pr-PMO had regular and uniform mesopores. Furthermore, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Am-Calb-Pr-PMO was calculated in the same manner as in Example ^B1 . The pore diameter _dDFT was calculated to be 3.7 nm, and the total pore volume _VP was calculated to be 0.61 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Am-Calb-Pr-PMO was determined in the same manner as in Example B1, and was found to be 0.42 mmol/g.

(Comparative example B3)
Mesoporous silica FSM-16 (manufactured by Taiyo Kagaku Co., Ltd., 1.50 g) was weighed into a 200 ml three-necked flask equipped with a reflux tube, a septum, and a stirrer, and toluene (75 ml) was added. While stirring the resulting reaction mixture, a toluene solution (15 ml) of the Phen-Am-bis(Calb-Pr-SiOEt) (517 mg, 0.750 mmol) obtained in Comparative Example A1 was added. The obtained reaction mixture was stirred at 120°C for 24 hours, and the following reaction formula (P13):

The reaction represented by was performed. The generated precipitate was filtered out by pressure filtration. In order to remove the unreacted Phen-Am-bis (Calb-Pr-SiOEt), the resulting residue was subjected to Soxhlet extraction using toluene and methanol, and dried under vacuum, and the cream-colored phenanthroline ring was converted into an aminocarbamoyl ring. A mesoporous silica powder (Phen-Am-Calb-Pr-FMS16) in which groups were bonded through propylene groups was obtained (yield: 1.77 g).

The X-ray diffraction pattern of this Phen-Am-Calb-Pr-FMS16 was measured in the same manner as in Example B1, and as shown in FIG. A diffraction peak due to the mesostructure was observed. In addition, the nitrogen adsorption/desorption isotherm of the Phen-Am-Calb-Pr-FMS16 was measured in the same manner as in Example B1, and as shown in FIG. 13B (in the figure, black circles indicate adsorption and white circles indicate desorption). , type IV. Therefore, from the X-ray diffraction pattern and nitrogen adsorption/desorption isotherm, it was confirmed that the Phen-Am-Calb-Pr-FMS16 had regular and uniform mesopores. Further, based on the obtained nitrogen adsorption/desorption isotherm, the specific surface area S _BET of the Phen-Am-Calb-Pr-FMS16 was calculated in the same manner as in Example B1, and was found to be 650 m ² /g, with the center The pore diameter _dDFT was calculated to be 4.1 nm, and the total pore volume _VP was calculated to be 0.52 cm ³ /g. Further, the amount of phenanthroline ring immobilized in the Phen-Am-Calb-Pr-FMS16 was determined in the same manner as in Example B1, and was found to be 0.36 mmol/g.

<Hydrolysis resistance test>
The Phen-Bu-PMO obtained in Example B5, the Phen-Am-Calb-Pr-PMO obtained in Comparative Example B2, the Phen-Bu-FMS16 obtained in Example B6, or Comparative Example B3. 100 mg of the Phen-Am-Calb-Pr-FMS16 obtained above was weighed into 110 ml vials, and 6 mol/L hydrochloric acid (10 ml) was added. After the vial tube was sealed, the reaction mixture was allowed to stand for 3 days while being heated at 100° C., and the mesoporous organic silica was subjected to a hydrolysis treatment. Thereafter, the mixture was cooled to room temperature, the mesoporous organic silica was filtered out by vacuum filtration, the residue was washed with ethanol (50 ml), and then dried at 50° C. under vacuum.

The nitrogen content of mesoporous organic silica before and after hydrolysis treatment was measured by CHN elemental analysis (requested from A Rabbit Science Co., Ltd.), and the amount of immobilized phenanthroline rings before and after hydrolysis treatment was determined from the nitrogen amount obtained. , the retention rate of the phenanthroline ring after the hydrolysis treatment was calculated. The results are shown in FIG. The retention rate of the phenanthroline ring after the hydrolysis treatment in the mesoporous organic silicas obtained in Comparative Examples B2 and B3 is determined by the following reaction formula (I):

The calculation was made assuming that the process progresses as follows.

As shown in FIG. 14, in the mesoporous organic silicas (Examples B5 and B6) in which phenanthroline rings are bonded only through alkylene groups, the retention rate of phenanthroline rings after hydrolysis treatment is 100% or more. It was confirmed that most of the phenanthroline rings remained even under hydrolysis conditions. The reason why the retention rate of phenanthroline rings after hydrolysis treatment was 100% or more in the mesoporous organic silicas obtained in Examples B5 and B6 is that uncondensed alkoxy groups and silanol moieties were removed under acidic heating conditions. This is thought to be because the amount of nitrogen per unit mass in the mesoporous organic silica increased due to dehydration condensation.

On the other hand, mesoporous organic silicas in which the phenanthroline ring is bonded via an aminocarbamoyl group (urea bond) and an alkylene group (Comparative Examples B2 and B3) are similar to the mesoporous organic silicas obtained in Examples B5 and B6. Although the amount of nitrogen per unit mass is thought to increase due to dehydration condensation of uncondensed alkoxy groups and silanol moieties under acidic heating conditions, the retention rate of phenanthroline rings after hydrolysis treatment decreased significantly. It was found that the phenanthroline ring was lost from mesoporous organosilica under hydrolysis conditions.

In addition, the filtrate after hydrolyzing the mesoporous organic silica obtained in Examples B5 and B6 was clear and colorless, but the mesoporous organic silica obtained in Comparative Examples B2 and B3 was not subjected to the hydrolyzing treatment. The filtrate after application had a yellow color. This yellow color is thought to be due to 5-amino-1,10-phenanthroline missing from the mesoporous organic silica.

From the above results, the mesoporous organic silica in which the phenanthroline ring is bonded only through an alkylene group is superior to the mesoporous organic silica in which the phenanthroline ring is bonded through an aminocarbamoyl group (urea bond) and an alkylene group. It was found that it has excellent hydrolysis resistance and has excellent properties as a catalyst carrier.

<Heat resistance test>
The Phen-Bu-Et-PMO-1b obtained in Example B4, the Phen-Am-Calb-Pr-Et-PMO obtained in Comparative Example B1, and the Phen-Bu- obtained in Example B6. 75 mg of each of FMS16 or the Phen-Am-Calb-Pr-FMS16 obtained in Comparative Example B3 was weighed into a crucible, and the temperature was raised to 350 ° C. in 2 hours under a nitrogen stream (1 L / min), and then It was baked at 350°C for 4 hours. Thereafter, it was cooled to room temperature, the residue was washed with chloroform (50 ml) and ethanol (50 ml), and then dried at 50° C. under vacuum.

The nitrogen content of mesoporous organic silica before and after heat treatment was measured by CHN elemental analysis (requested from A Rabbit Science Co., Ltd.), and from the obtained nitrogen content, the amount of immobilized phenanthroline rings before and after hydrolysis treatment was determined. The retention rate of the phenanthroline ring after the hydrolysis treatment was calculated. The results are shown in FIG. The retention rate of the phenanthroline ring after the hydrolysis treatment in the mesoporous organic silicas obtained in Comparative Examples B1 and B3 is determined by the following reaction formula (II):

The calculation was made assuming that the process progresses as follows.

As shown in FIG. 15, in the mesoporous organic silicas (Examples B4 and B6) in which phenanthroline rings are bonded only through alkylene groups, the retention rate of phenanthroline rings after heat treatment is 100% or more, It was confirmed that most of the phenanthroline rings remained even under high temperature heating conditions. The reason why the retention rate of phenanthroline rings after heat treatment was 100% or more in the mesoporous organic silicas obtained in Examples B4 and B6 is that uncondensed alkoxy groups and silanol moieties under high temperature heating conditions This is thought to be because the amount of nitrogen per unit mass in the mesoporous organic silica increased due to dehydration condensation.

On the other hand, in mesoporous organic silicas (Comparative Examples B1 and B3) in which the phenanthroline ring is bonded via an aminocarbamoyl group (urea bond) and an alkylene group, the mesoporous organic silicas obtained with mesoporous organic silicas 4 and 6 are Similarly, although uncondensed alkoxy groups and silanol moieties are thought to dehydrate and condense under high-temperature heating conditions, increasing the amount of nitrogen per unit mass, the retention rate of phenanthroline rings after heat treatment is large. It was found that the phenanthroline ring was lost from the mesoporous organic silica under heating conditions at high temperatures.

From the above results, the mesoporous organic silica in which the phenanthroline ring is bonded only through an alkylene group is superior to the mesoporous organic silica in which the phenanthroline ring is bonded through an aminocarbamoyl group (urea bond) and an alkylene group. It was found that it has excellent thermal decomposition resistance and has excellent properties as a catalyst carrier.

As explained above, according to the present invention, it is possible to obtain mesoporous organic silica having excellent bond stability without the loss of phenanthroline rings under hydrolysis conditions or heating conditions. Therefore, since the mesoporous organic silica of the present invention has excellent hydrolysis resistance and thermal decomposition resistance, it is useful as a support for various catalysts in organic synthesis reactions using organic solvents or water as a solvent.

Claims (6)

The following formula (1):
[In the above formula (1), at least two groups of R ¹ to R ⁸ are represented by the following formula (2):
(In the above formula (2), Y represents an alkylene group having 1 to 6 carbon atoms, R ^a represents an alkyl group having 1 to 6 carbon atoms, R ^b represents a substituted or unsubstituted allyl group, and m is 1 or 2, n is an integer from 0 to 3)
The remaining groups among R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, or a benzoyl group. , an amino group, an amide group, an imido group, a nitro group, and a cyano group]
An organic silane compound characterized by the following: The organic compound according to claim 1, wherein at least two groups among R ² , R ³ , R ⁶ , and R ⁷ in the formula (1) are groups represented by the formula (2). Silane compound. The following formula (1):
[In the above formula (1), at least one group among R ¹ to R ⁸ is the following formula (2):
(In the above formula (2), Y represents an alkylene group having 1 to 6 carbon atoms, R ^a represents an alkyl group having 1 to 6 carbon atoms, R ^b represents a substituted or unsubstituted allyl group, and m is 1 or 2, n is an integer from 0 to 3)
The remaining groups among R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, or a benzoyl group. , an amino group, an amide group, an imido group, a nitro group, and a cyano group]
A mesoporous organic silica characterized by being a polymer of an organic silane compound represented by : R in the above formula (1) ² ,R ³ ,R ⁶ ,R ⁷ The mesoporous organic silica according to claim 3, wherein at least two of the groups are groups represented by the formula (2). The following formula (3):
[In the above formula (3), at least one group among R ¹ to R ⁸ is the following formula (4):
(In the above formula (4), Y represents an alkylene group having 1 to 6 carbon atoms, R ^b represents a substituted or unsubstituted allyl group, R ^c represents a hydrogen atom or a silyl group, and k represents 1 or 2 , i is an integer from 1 to 3, j is an integer from 0 to 2, 1≦i+j≦3, and there are multiple combinations of i and j expressed by the above formula (4). Each group is independent, and * is the bonding site with the adjacent structure)
The remaining groups among R ¹ to R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a hydroxy group, an acetyl group, or a benzoyl group. , an amino group, an amide group, an imido group, a nitro group, and a cyano group]
A mesoporous organic silica characterized by the following: The mesoporous according to claim 5 , wherein at least two groups of R ² , R ³ , R ⁶ , and R ⁷ in the formula (3) are groups represented by the formula (4). Organic silica.