JP2006290771A - Anthracene-based organic zeolite analog, production method, and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic zeolite stable to air and humidity, facilitating the treatment and having excellent adsorptivity. <P>SOLUTION: The anthracene-based organic zeolite has a porous organic crystal structure obtained by dissolving, for example, 9,10-bis[3,5-bis(4-hydroxybiphenyl)-1-phenyl]anthracene in ethyl acetate, and adding chloroform to the resultant solution. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an anthracene-based organic zeolite analogue having a porous organic crystal structure, a production method thereof, its use, and production intermediates thereof.

9,10-bis (3,5-dihydroxy-1-phenyl) anthracene (hereinafter abbreviated as BHPA) has been reported to form a hydrogen bond network and exhibit a porous behavior (non- (See Patent Documents 1 and 2). This porous organic crystal has the ability to adsorb water, methanol, acetone, and other polar solvents (guest molecules) in a solid state.
However, in BHPA, in the state where the guest molecule is removed from the crystal (initial state), the cavity due to the hydrogen bond network is crushed. For this reason, the specific surface area in an initial state is as very small as about 7 m < ² > / g. In addition, guest molecules having a weak interaction force such as methane gas and nitrogen gas are hardly adsorbed (the stabilization energy necessary for expanding the cavity cannot be obtained).

An amorphous polymer obtained by networking BHPA with a metal alkoxide is also known (see Non-Patent Document 3). This polymer is porous and has a cavity that cannot be crushed because it is a metal complex, and has been shown to work as a solid Lewis acid.
However, this metal alkoxide type porous material is unstable to air and moisture and is not easy to handle.
In addition, other examples of organic crystals having cavities that do not collapse are mostly organometallic complexes, which have the disadvantage of using heavy metals that are environmentally harmful such as copper, cobalt, cadmium and manganese ( Regarding organic zeolite analogues composed of organometallic complexes: see Non-Patent Documents 4 and 5).

  On the other hand, there is a construction example of an organic zeolite analog consisting of a porous organic crystal of a pure organic compound that does not contain metal atoms etc., and has a hydrogen bonding network that has a strong hydrogen bonding force and does not collapse the cavity even when guest molecules are removed. One case has been reported (see Patent Document 1). This analog is a 9,10-bis (3,5-dicarboxy-1-phenyl) anthracene (hereinafter abbreviated as BCAPA) compound, which has been confirmed to adsorb methane and low molecular organic solvents. ing. However, the adsorption performance is not always sufficient, and in order to make it more practical, it is essential to improve the adsorption performance.

JP 2004-256487 A “J. Am. Chem. Soc.” (USA), 1995, Vol. 117, No. 32, p. 8341-8352 “J. Am. Chem. Soc.” (USA), 1998, 120, 35, p. 8933-8940 “J. Am. Chem. Soc.” (USA), 1998, 120, 33, p. 8539-8540 “Angew. Chem. Int. Ed.” (Germany), 2000, Vol. 39, No. 12, p. 2082-2084 “Chemistry of Materials (Chem. Mater.)” (USA), 2000, Vol. 12, No. 5, p. 1288-1299

  The present invention has been made in view of such circumstances, and is expected to be used as a gas occlusion body, a low concentration organic molecule adsorbent, a fluorescent adsorbent, a metal scavenger, a reaction catalyst, and the like. An object of the present invention is to provide an anthracene-based organic zeolite analog that is stable in air and moisture, is easy to handle, and has excellent adsorption performance, a method for producing the same, and a use thereof.

  As a result of intensive investigations to achieve the above object, the present inventors have found that 9,10-bis [3,5-bis (4-hydroxybiphenyl) -1-phenyl] anthracene compound, 9,10-bis A compound having an anthracene structure, such as [3,5-bis (4-carboxyphenyl) -1-phenyl] anthracene compound, is stable and easy to handle, and has excellent adsorption performance. The present invention was completed by finding that the compound is suitable as a body.

（式中、Ｒ¹及びＲ²は、それぞれ独立して水素原子、ハロゲン原子、シアノ基、炭素数１〜１０のアルキル基、ヒドロキシ基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアルコキシカルボニル基、カルボキシル基、ニトロ基又はアミノ基を表す。ｐ、ｑ及びｎは、それぞれ独立して１〜４の整数を表す。破線は、分子間水素結合を表す。）
（２）式［２］で表される多孔質有機結晶構造を有するアントラセン系有機ゼオライト類縁体。

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及び「波線」は上記と同じ意味を表す。）
（３）式［３］で表される多孔質有機結晶構造を有するアントラセン系有機ゼオライト類縁体。

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及び「波線」は上記と同じ意味を表す。）
（４）式［４］で表される多孔質有機結晶構造を有するアントラセン系有機ゼオライト類縁体。

（式中、Ｒ¹、Ｒ²、ｐ、ｑ、ｎ及び「波線」は上記と同じ意味を表す。）
（５）式［５］で表される多孔質有機結晶構造を有するアントラセン系有機ゼオライト類縁体。

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及び「波線」は上記と同じ意味を表す。）
（６）式［６］で表されるアントラセン系化合物。

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及びｎは上記と同じ意味を表す。Ｒ³は、それぞれ独立してトリフルオロメチルスルホニルオキシ基、炭素数１〜１０のアルコキシ基、ヒドロキシ基、シアノ基又はカルボキシル基を表す。）
（７）式［７］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−メトキシフェニル）−１−フェニル］アントラセン化合物を脱アルキル分解することを特徴とする、式［８］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−ヒドロキシフェニル）−１−フェニル］アントラセン化合物の製造法。
（８）式［９］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは上記と同じ意味を表す。）
で表される９，１０−ビス（３，５−ジヒドロキシ−１−フェニル）アントラセン化合物と、トリフルオロメタンスルホン酸無水物とを塩基の存在下に反応させて、式［１０］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表し、Ｔｆはトリフルオロメチルスルホニル基を表す。）
で表される９，１０−ビス［３，５−ビス（トリフルオロメチルスルホニルオキシ）−１−フェニル］アントラセン化合物とし、この化合物を、パラジウム触媒の存在下、式［１１］

で表される４−メトキシボロン酸と反応させて、式［７］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−メトキシフェニル）−１−フェニル］アントラセン化合物として、さらにこれを脱アルキル分解することを特徴とする、式［８］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−ヒドロキシフェニル）−１−フェニル］アントラセン化合物の製造法。
（９）式［１２］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−メトキシビフェニル）−１−フェニル］アントラセン化合物を脱アルキル分解することを特徴とする、式［１３］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−ヒドロキシビフェニル）−１−フェニル］アントラセン化合物の製造法。
（１０）式［８］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス（３，５−ビス（４−ヒドロキシフェニル）−１−フェニル）アントラセン化合物と、トリフルオロメタンスルホン酸無水物とを塩基の存在下に反応させて、式［１４］

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及びＴｆは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−トリフルオロメチルスルホニルオキシフェニル）−１−フェニル］アントラセン化合物とし、これを、パラジウム触媒の存在下、式［１１］

で表される４−メトキシボロン酸と反応させて、式［１２］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−メトキシビフェニル）−１−フェニル］アントラセン化合物とし、さらにこれを脱アルキル分解することを特徴とする、式［１３］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−ヒドロキシビフェニル）−１−フェニル］アントラセン化合物の製造法。
（１１）式［１５］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−シアノフェニル）−１−フェニル］アントラセン化合物を加水分解することを特徴とする式［１６］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−カルボキシフェニル）−１−フェニル］アントラセン化合物の製造法。
（１２）式［１４］

（式中、Ｒ¹、Ｒ²、ｐ、ｑ及びＴｆは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−トリフルオロメチルスルホニルオキシフェニル）−１−フェニル］アントラセン化合物と、式［１７］

（式中、Ｍは、水素原子、アルカリ金属又はアルカリ土金属を表す。）
で表されるシアノ化合物を、パラジウム触媒の存在下反応させて、式［１５］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−シアノフェニル）−１−フェニル］アントラセン化合物を得た後、これを加水分解することを特徴とする式［１６］

（式中、Ｒ¹、Ｒ²、ｐ及びｑは、上記と同じ意味を表す。）
で表される９，１０−ビス［３，５−ビス（４−カルボキシフェニル）−１−フェニル］アントラセン化合物の製造法。
（１３）［１］〜［５］のいずれかのアントラセン系有機ゼオライト類縁体からなる吸蔵体。
（１４）有機分子の吸蔵用である（１３）の吸蔵体。 That is, the present invention provides the following (1) to (14).
(1) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [1].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p, q and n each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.)
(2) An anthracene-based organic zeolite analog having a porous organic crystal structure represented by the formula [2].

(In the formula, R ¹ , R ² , p, q and “wavy line” have the same meaning as described above.)
(3) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [3].

(In the formula, R ¹ , R ² , p, q and “wavy line” have the same meaning as described above.)
(4) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [4].

(In the formula, R ¹ , R ² , p, q, n and “wavy line” have the same meaning as described above.)
(5) An anthracene-based organic zeolite analog having a porous organic crystal structure represented by the formula [5].

(In the formula, R ¹ , R ² , p, q and “wavy line” have the same meaning as described above.)
(6) An anthracene compound represented by the formula [6].

(Wherein R ¹ , R ² , p, q and n represent the same meaning as described above. R ³ each independently represents a trifluoromethylsulfonyloxy group, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, Represents a cyano group or a carboxyl group.)
(7) Formula [7]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
A dealkylolysis of a 9,10-bis [3,5-bis (4-methoxyphenyl) -1-phenyl] anthracene compound represented by formula [8]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxyphenyl) -1-phenyl] anthracene compound represented by these.
(8) Formula [9]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
Is reacted with a trifluoromethanesulfonic anhydride in the presence of a base to give a compound of the formula [10]

(Wherein R ¹ , R ² , p and q represent the same meaning as described above, and Tf represents a trifluoromethylsulfonyl group.)
9,10-bis [3,5-bis (trifluoromethylsulfonyloxy) -1-phenyl] anthracene compound represented by the formula [11] in the presence of a palladium catalyst.

Is reacted with 4-methoxyboronic acid represented by the formula [7]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The compound represented by the formula [8] is characterized by further dealkylating the 9,10-bis [3,5-bis (4-methoxyphenyl) -1-phenyl] anthracene compound represented by the formula:

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxyphenyl) -1-phenyl] anthracene compound represented by these.
(9) Formula [12]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
A dealkylolysis of a 9,10-bis [3,5-bis (4-methoxybiphenyl) -1-phenyl] anthracene compound represented by formula [13]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxybiphenyl) -1-phenyl] anthracene compound represented by these.
(10) Formula [8]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
9,10-bis (3,5-bis (4-hydroxyphenyl) -1-phenyl) anthracene compound and trifluoromethanesulfonic anhydride are reacted in the presence of a base to give a compound of the formula [14 ]

(In the formula, R ¹ , R ² , p, q and Tf represent the same meaning as described above.)
9,10-bis [3,5-bis (4-trifluoromethylsulfonyloxyphenyl) -1-phenyl] anthracene compound represented by the formula [11] in the presence of a palladium catalyst.

Is reacted with 4-methoxyboronic acid represented by the formula [12]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
Wherein the 9,10-bis [3,5-bis (4-methoxybiphenyl) -1-phenyl] anthracene compound represented by the formula [13] is further subjected to dealkylolysis.

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxybiphenyl) -1-phenyl] anthracene compound represented by these.
(11) Formula [15]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
And a 9,10-bis [3,5-bis (4-cyanophenyl) -1-phenyl] anthracene compound represented by the formula: [16]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
A method for producing a 9,10-bis [3,5-bis (4-carboxyphenyl) -1-phenyl] anthracene compound represented by the formula:
(12) Formula [14]

(In the formula, R ¹ , R ² , p, q and Tf represent the same meaning as described above.)
And a 9,10-bis [3,5-bis (4-trifluoromethylsulfonyloxyphenyl) -1-phenyl] anthracene compound represented by the formula: [17]

(In the formula, M represents a hydrogen atom, an alkali metal or an alkaline earth metal.)
Is reacted in the presence of a palladium catalyst to give a compound of the formula [15]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
Formula 9, wherein the 9,10-bis [3,5-bis (4-cyanophenyl) -1-phenyl] anthracene compound represented by formula (1) is obtained and then hydrolyzed.

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-carboxyphenyl) -1-phenyl] anthracene compound represented by these.
(13) An occlusion body comprising an anthracene-based organic zeolite analogue according to any one of [1] to [5].
(14) The occlusion body of (13) for occlusion of organic molecules.

The anthracene-based organic zeolite analog of the present invention has a hydrogen bonding network that has a strong hydrogen bonding force and does not collapse the cavity even when guest molecules are removed. Moreover, since this zeolite analog is a pure organic compound which does not contain heavy metals, it also has the characteristics that it is stable to air and moisture and easy to handle. Therefore, this organic zeolite analog is a promising compound expected to be used as a gas occlusion body, a low concentration organic molecule adsorbent, a fluorescent adsorbent, a metal scavenger, a reaction catalyst, and the like.
Organic zeolite analogs comprising the compounds represented by the following formulas (BBHPA and BCPA) in which R ¹ and R ² are both hydrogen atoms in the formulas [8], [13] and [16] which are representative examples of the present invention Is an adsorbent excellent in the adsorptivity of various organic gases, so that it can be effectively used as a precision gas separation agent. It is also advantageous from the viewpoint of disposal.

Hereinafter, the present invention will be described in more detail.
The anthracene-based organic zeolite analog according to the present invention is represented by the above formulas [1] to [5]. Moreover, the anthracene compound used as the raw material and an intermediate body is represented by the said Formula [6]. Representative anthracene compounds for constructing these anthracene-based organic zeolite analogs are represented by the above formulas [8], [13] and [16].
First, specific examples of R ¹ and R ² in the above formulas will be described below.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, s- Butyl, n-pentyl, n-hexyl, 2-ethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl -1-methylpropyl, 1-ethyl-2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpe Chill, 3-methylpentyl and 4-methylpentyl, and the like.

  The alkoxy group having 1 to 10 carbon atoms may be linear, branched or cyclic. For example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t- Butoxy, n-pentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1,2-trimethylpropoxy, 1,2 , 2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1 , 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethyl Butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy and 4-methyl-pentyloxy, and the like.

The alkoxycarbonyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl , S-butoxycarbonyl, t-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethyl Propoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl, 1-ethyl-1-methylpropoxycarbonyl, 1-ethyl-2-methylpropoxycarbonyl, 1- Tylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxy Carbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-methylpentyloxycarbonyl, 2-methylpentyloxycarbonyl, 3-methylpentyloxycarbonyl and 4-methyl Examples include pentyloxycarbonyl.
In the above, “n” means normal, “i” means iso, “s” means secondary, and “t” means tertiary.

Next, a method for producing BBHPA and BCPA in which R ¹ and R ² are both hydrogen atoms in formulas [8], [13] and [16], which are representative examples of the present invention, will be described below. These compounds can be synthesized by the routes shown in the following scheme 1-1 and scheme 1-2, respectively.

  That is, first, BHPA and trifluoromethanesulfonic anhydride are reacted in the presence of a base to form BTPA, and then reacted with 4-methoxyphenylboronic acid in the presence of a palladium catalyst to form BBMA. This BBMA is dealkylated with boron tribromide to give BBHA, which is again reacted with trifluoromethanesulfonic anhydride in the presence of a base to give BBTA. Further, in the presence of a palladium catalyst, BBTA and 4-methoxyphenylboronic acid are reacted to form BBMPA, which is dealkylated with boron tribromide to obtain the target BBHPA.

(1) Manufacturing method of BBHPA First, it demonstrates from the 1st process of manufacturing BTPA.
The raw material BHPA can be synthesized by the following scheme 2-1 and scheme 2-2.

（式中、Ｘは、ハロゲン原子を表す。）

(In the formula, X represents a halogen atom.)

  That is, by preparing a Grignard reagent from a 1-halogeno-3,5-dimethoxybenzene compound and magnesium and reacting this reagent with a 9,10-dihalogenoanthracene compound in the presence of a nickel complex catalyst, 9,10-bis (3,5-dimethoxy-1-phenyl) anthracene (hereinafter abbreviated as BDMPA) is obtained. Next, the target BHPA is obtained by reacting this BDMPA with boron tribromide [Reference: “Supramol. Chem.”, 1995, Vol. 4, p. 229-241].

  As the other raw material, trifluoromethanesulfonic anhydride, a commercially available product can be used as it is. The amount used is not particularly limited, but is preferably 4.0 to 12.0 molar equivalents relative to 1.0 mole of BHPA. The reaction proceeds smoothly due to the presence of the base. Examples of the base include chain alkylamine compounds represented by trimethylamine, triethylamine and tripropylamine, aromatic amine compounds represented by pyridine, aniline, N-methylaniline and 2,6-lutidine, 5-diazabicyclo [4.3.0] no-5-ene (DBN), 1,4-diazabicyclo [2.2.2] octane (DBO) and 1,8-diazabicyclo [5.4.0] undece Examples thereof include cyclic alkylamine compounds typified by 7-ene (DBU) and the like, metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate. Particularly preferred among these bases are pyridine and 2,6-lutidine. The amount used is not particularly limited, but is preferably 4.0 to 12.0 molar equivalents relative to 1.0 mole of BHPA.

  In this reaction, it is preferable to use a solvent. The types include halogenated hydrocarbon compounds such as methylene chloride, chloroform, 1,2-dichloroethane, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP). Examples thereof include aliphatic amide compounds such as 1,3-dimethyl-2-imidazolidinone (DMI). Of these, halogenated hydrocarbon compounds are particularly preferred. The amount used is not particularly limited as long as the reaction proceeds smoothly, but is preferably 1 to 200 times by mass, and more preferably 5 to 150 times by mass, relative to BHPA.

The reaction temperature is preferably in the range of −50 to 150 ° C., particularly preferably in the range of −10 to 100 ° C.
The reaction time is usually about 1 to 30 hours. The follow-up of the reaction can be confirmed by the presence or absence of raw materials by thin layer chromatography.
Since the reaction proceeds almost quantitatively, when the halogenated hydrocarbon compound is a solvent after completion of the reaction, the target BTPA is obtained by washing with water and then concentrating.

Next, the second step of obtaining BBMA from BTPA by reacting with 4-methoxyphenylboronic acid in the presence of a palladium catalyst will be described.
As 4-methoxyphenylboronic acid, a commercially available product can be used as it is.
Examples of the catalyst include palladium black, which is zero-valent palladium, palladium supported on activated carbon, silica, etc., and various palladium complexes represented by tetrakis (triphenylphosphine) palladium, and further, palladium chloride, which is divalent palladium. In the case of palladium acetate, triphenylphosphine is preferably allowed to coexist as a ligand.
The amount used is not particularly limited, but is preferably 1 to 50 mol%, particularly 5 to 30 mol%, based on BTPA, in terms of reaction yield.

Moreover, it is preferable to make a base exist in the case of the said reaction. The types include alkali metal and alkaline earth metal salts typified by sodium carbonate, potassium carbonate and calcium carbonate, and organic bases typified by pyridine and triethylamine.
In addition, it is also preferable that additives such as lithium chloride, lithium bromide and lithium iodide coexist. The addition amount is not particularly limited, but is preferably 1 to 20 molar equivalents, particularly 5 to 15 molar equivalents with respect to BTPA in terms of reaction yield.
Further, in this reaction, it is preferable to use a solvent. Examples of the type include lower alcohols typified by methanol and ethanol, aromatic hydrocarbons typified by benzene, toluene, xylene and the like. , 4-dioxane, tetrahydrofuran, 1,2-dimethoxyethane and the like, and cyclic and chain ethers. These can be used alone or in combination. The amount used is not particularly limited as long as the reaction proceeds smoothly, but is preferably 5 to 1000 times by mass, particularly 10 to 100 times by mass with respect to the solubility of the reaction reagent with respect to BTPA. .

The reaction temperature is preferably in the range of 20 to 200 ° C, particularly preferably in the range of 50 to 150 ° C.
The reaction time is usually about 1 to 30 hours. The follow-up of the reaction can be confirmed by the presence or absence of raw materials by thin layer chromatography.
Since the reaction proceeds almost quantitatively, after completion of the reaction, after removing the residual solid base by filtration, the filtrate is concentrated, the residue is dispersed in ethanol, and the resulting precipitate is dried to obtain BBMA. can get.

Next, the third step of obtaining BBHA from BBMA by dealkylation with boron tribromide will be described.
Commercially available boron tribromide can be used as it is. Moreover, the usage-amount is although it does not specifically limit, 2-20 molar equivalent is preferable with respect to BBMA, Furthermore, 4-10 molar equivalent is preferable.
Also in this reaction, it is preferable to use a solvent, and examples of the type include halogenated hydrocarbons represented by methylene chloride, 1,2-dichloroethane and the like. The amount used is not particularly limited as long as the reaction proceeds smoothly, but it is preferably 5 to 100 times by mass, particularly 10 to 50 times by mass with respect to the BBMA in terms of solubility of the reaction reagent. .
The reaction temperature is preferably in the range of -20 to 200 ° C, particularly preferably in the range of -10 to 100 ° C.
The reaction time is usually about 1 to 30 hours. The follow-up of the reaction can be confirmed by the presence or absence of raw materials by thin layer chromatography.

The fourth step of obtaining BBTA from BBHA may be performed in the same manner as the first step.
The fifth step of obtaining BBMPA from BBTA may be performed in the same manner as the second step.
The sixth step of obtaining BBHPA from BBMPA may be performed in the same manner as the third step.

(2) BCPA Production Method First, the first step of obtaining BBCA by cyanating BBTA will be described.
As the cyano compound as the cyanation reagent, for example, hydrogen cyanide, alkali metal cyanide, alkaline earth metal cyanide, metal cyanide and the like can be used. Specific examples include sodium cyanide, potassium cyanide, magnesium cyanide, calcium cyanide and copper cyanide. In particular, safe and economical sodium cyanide and potassium cyanide are preferable, and the amount used is not particularly limited, but is preferably 4.0 to 20.0 molar equivalents relative to the raw material BBTA.

  In this reaction, it is effective to make a catalyst exist, and as its kind, palladium complex represented by tris (dibenzylideneacetone) -chloroform-dipalladium complex, bis (diphenylphosphino) ferrocene (dppf) and the like are used. It is done. Although the usage-amount of a palladium complex is not specifically limited, 1.0-20.0 mol% is preferable with respect to BBTA of a raw material. Moreover, although the usage-amount of dppf is not specifically limited, 0.5-10.0 mol% is preferable with respect to BBTA of a raw material.

Moreover, it is preferable to use a solvent, and the types thereof include aliphatic nitrile compounds such as acetonitrile and propionitrile, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone ( Examples thereof include aliphatic amide compounds such as NMP) and 1,3-dimethyl-2-imidazolidinone (DMI). Of these, acetonitrile is particularly preferred. The amount used is preferably 1 to 50 times by mass, particularly 5 to 20 times by mass, relative to BBTA, in terms of the reaction yield.
The reaction temperature is preferably in the range of 0 to 200 ° C, particularly preferably in the range of 20 to 150 ° C.
The reaction time is usually about 1 to 30 hours. The tracking of the reaction can be confirmed by the presence or absence of the raw material by thin layer chromatography.
The target BBCA is isolated by purifying the reaction product by post-treatment alumina column chromatography or the like.

Next, the second step of obtaining BCPA from BBCA will be described.
Conversion from a cyano compound to a carboxylic acid compound includes two methods, a hydrolysis method using a base and a hydrolysis method using an acid, and any of these methods can be applied in this step. Among them, the hydrolysis method using a base is preferable from the viewpoint of increasing the yield of the target product. Therefore, the base hydrolysis method will be described below.
As the kind of base, an alkali metal hydroxide or an alkali earth metal hydroxide is economical and preferable. Specifically, sodium hydroxide, potassium hydroxide, etc. are mentioned as an example. The amount used is not particularly limited, but is preferably 10 to 1500 moles per BBCA in terms of reaction yield.
As the solvent, water and a mixed solvent of aliphatic lower alcohols such as methanol and ethanol are preferable. The amount of use thereof is not particularly limited, but is preferably 5 to 50 times by mass with respect to BBCA from the viewpoint that the reaction proceeds smoothly.

The reaction temperature is preferably in the range of 20 to 200 ° C, particularly preferably in the range of 50 to 150 ° C.
The reaction time is usually about 1 to 200 hours. The follow-up of the reaction can be confirmed by the presence or absence of raw materials by thin layer chromatography.
After completion of the reaction, the alcohol used as a solvent is distilled off, and acid such as hydrochloric acid or sulfuric acid is added to make it acidic, whereby the desired BCPA is obtained as crystals. The crystal is washed with water and dried to obtain a purified pure target product.
In addition, each reaction demonstrated above may be performed under a normal pressure or under pressure, and can also be performed by a batch method or a continuous method.

Next, a method for synthesizing an organic zeolite analog from an organic zeolite compound such as BBHA, BBHPA and BCPA obtained by the above method will be described.
An organic zeolite analog can be obtained by dissolving the above organic zeolite compound in ethyl acetate, filtering the precipitate obtained by adding chloroform, and drying under reduced pressure. Alternatively, an organic zeolite analog can be obtained by drying the organic zeolite compound under reduced pressure.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
The analytical methods used in the examples are as follows.
[1] ¹ H-NMR
Equipment used: Solid-state NMR (Bruker DPX-300) manufactured by Nippon Bruker Co., Ltd.
[2] Infrared spectroscopy (IR)
Equipment used: Perkin Elmer Japan, FT-IR Spector SPECTRUM 2000
Measurement conditions: KBr tablet method, measurement range 4000-400 cm ⁻¹ .
[3] Thermogravimetric analysis (TG)
Equipment used: Actuated differential thermobalance TG-8120 manufactured by Rigaku Corporation.
[4] Structural analysis of organic zeolite analogues (measurement of PXRD pattern)
Equipment used: Rigaku RAD-PC X-ray diffractometer or RAD-C X-ray diffractometer.
[5] Vapor adsorption characteristic measurement Adsorption isotherms of various adsorbates were measured with a constant volume vapor adsorption measuring apparatus.
Vapor adsorption conditions: Measured with BELSORP18 SP-V (Nippon Bell).
Equipment specifications: sample chamber volume 15 mL, measurement temperature 25 ° C. ± 0.1 ° C., sample amount 300 mg, pretreatment temperature 100 ° C., pretreatment vacuum degree 0.001 torr or less, pretreatment time 18 hours, gas chamber capacity 176.36 mL, Dead volume measuring gas He.

[Reference Example 1] Synthesis of BDMPA

(1) Grignard reaction Under nitrogen, 10 ml of tetrahydrofuran (THF) was added to magnesium (2.11 g, 0.087 mol), and magnesium was activated with a small amount of dibromoethane. From a dropping funnel, 1-chloro-3,5-dimethoxybenzene (10 g, 0.058 mol) in THF (20 mL) was slowly added. When about 7 mL was dropped, the dropping was stopped and the reaction vessel was heated to reflux once. After confirming that the solution was slightly green, all the rest was dropped, and then heated under reflux for about 24 hours to prepare a Grignard reagent.
(2) Cross-coupling reaction Under nitrogen, 9,10-dibromoanthracene (5.83 g, 0.015 mol) and [NiCl ₂ (dppp)] (0.19 g, 1 mol%) were mixed with benzene and THF (benzene). (40 mL). The Grignard reagent prepared earlier was transferred to the dropping funnel and slowly dropped. After completion of dropping, the mixture was stirred at room temperature for 12 hours or more. After completion of the reaction, the reaction solution was concentrated and extracted with chloroform (or methylene chloride). The mixture was treated with dilute hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over sodium sulfate. The solvent was distilled off to obtain a crude product. This was washed with methanol and then dried to obtain 4.73 g (yield 61.5%) of a highly pure target BDMPA.

[Reference Example 2] Synthesis of BHPA

  Under dry air (the reaction does not proceed under nitrogen), 9,10-bis (3,5-dimethoxy-1-phenyl) anthracene [BDMPA] (7.52 g, 0.0167 mol) was dissolved in 120 mL of methylene chloride, Cooled in an ice bath. A methylene chloride solution (about 120 mL) of boron tribromide (23.4 g, 0.0934 mol) was slowly added dropwise from a dropping funnel under light shielding, and stirring was continued for about 12 hours. After completion of the reaction, water was slowly added to the reaction solution under water cooling (same volume as methylene chloride). Most of the methylene chloride was distilled off with an evaporator, and this was extracted with ethyl acetate. After treating with saturated sodium bicarbonate water, water, and saturated saline, and drying over sodium sulfate, the solvent was distilled off to obtain a crude product. This was applied to a silica gel flash column (eluent: ethyl acetate) to remove the origin component. The fraction containing the desired product was concentrated and treated with a small amount of activated carbon (the yellow color of the liquid was considerably lost). Finally, the target product is dissolved in a minimum amount of ethyl acetate, and the crystals obtained by standing in a hexane (or benzene) atmosphere are dried by heating to obtain a pure BHPA yield of 6.02 g (yield 91.3). %)was gotten.

[Reference Example 3] Synthesis of BTPA

Under a nitrogen atmosphere, 2,6-lutidine (46 mL, 0.0191 mol) and 800 mL of methylene chloride were added to BHPA (7.73 g, 0.00195 mol). While cooling on an ice bath, trifluoromethanesulfonic anhydride (35 mL, 0.191 mol) was slowly added and stirred as it was for about 6 hours. After completion of the reaction, the reaction solution was extracted with chloroform, treated with water, an aqueous copper sulfate solution, water and saturated brine in that order, and dried over sodium sulfate. After distilling off the solvent, the resulting crude product was washed with ethanol to obtain the desired pure BTPA yield of 16.08 g (yield 88.9%). The chemical structure of BTPA was confirmed from the following analysis results.
¹ H-NMR (300 MHz, CDCl ₃ / DMSO-d ₆ ): δ [ppm] = 7.15 (t, 2H), 6.92 (d, 4H), 6.87-6.79 (m, 8H).
Elemental analysis: measured value; C, 39.19; H, 1.60%. Theoretical value; as C ₃₀ H ₁₄ F ₁₂ O ₁₂ S ₄ : C, 39.05, H, 1.53.

[Example 1] Synthesis of BBMA

  Triflate BTPA 9.00 g (9.75 mmol), 4-methoxyphenylboronic acid 6.54 g (43.1 mmol), lithium chloride 4.93 g (116.2 mmol), tetrakis (triphenylphosphine) palladium 2.16 g (1. 86 mmol) was dissolved in about 100 mL of ethanol, about 180 mL of toluene, and about 540 mL of 1,4-dioxane. When it was difficult to dissolve, heat was applied in an oil bath at 60 to 90 ° C. A sodium carbonate aqueous solution was added, and the mixture was stirred at 90 ° C. for about 12 hours. After completion of the reaction, filtration was performed to remove sodium carbonate, and the filtrate was concentrated. This operation was repeated several times. The mixture was filtered with ethanol, and the crude product on the filter paper was dissolved in chloroform and concentrated. Disperse with ethanol and concentrate. This operation was repeated several times. Finally, 7.06 g (yield 95.89%) of the target product BBMA was obtained by filtering with ethanol.

[Example 2] Synthesis of BBHA

  In an ice bath, 13.68 g (0.0181 mol) of BBMA obtained in Example 1 was dissolved in about 400 mL of methylene chloride. A solution prepared by dissolving 25 g (0.0998 mol) of boron tribromide in about 300 mL of methylene chloride was slowly added dropwise under light shielding and stirred for about 12 hours. After completion of the reaction, about 700 mL of water having the same volume as methylene chloride was slowly added under ice cooling, and then sodium bicarbonate was added until the reaction solution became neutral. Only methylene chloride was distilled off and extracted with ethyl acetate. The mixture was treated twice with water, further treated with saturated brine, dried over sodium sulfate, and the solvent was distilled off. This was applied to a silica gel flash column to remove the origin component. This was concentrated, dissolved in a minimum amount of ethyl acetate, and concentrated by adding chloroform. Thereafter, precipitation with chloroform and filtration yielded a target BBHA yield of 12.16 g (yield 96.05%).

[Example 3] Synthesis of BBTA

  In an ice bath, 8.74 g (0.0125 mol) of BBHA obtained in Example 2 was dissolved in about 500 mL of methylene chloride. 2,6-Lutidine 28.5 mL (0.118 mol) and trifluoromethanesulfonic anhydride 21 mL (0.115 mol) were added and stirred for about 6 hours. After completion of the reaction, the mixture was extracted with chloroform. Then, after processing in order of water, saturated copper sulfate aqueous solution, water, and a saturated salt solution, it was made to dry on sodium sulfate, and the solvent was distilled off. The obtained crude product was filtered and washed with ethanol to obtain 12.04 g (yield 78.38%) of the target BBTA.

Example 4 Synthesis of BBMPA

  BBTA 7.76 g (6.32 mmol) obtained in Example 3, 4.28 g (28.2 mmol) of 4-methoxyphenylboronic acid, 3.21 g (75.7 mmol) of lithium chloride, tetrakis (triphenylphosphine) palladium 1. 45 g (1.25 mmol) was dissolved in about 60 mL of ethanol, about 140 mL of toluene, and about 380 mL of 1,4-dioxane. When it was difficult to dissolve, heat was applied in an oil bath at 60 to 90 ° C. A sodium carbonate aqueous solution was added, and the mixture was stirred at 90 ° C. for about 12 hours. After completion of the reaction, filtration was performed to remove sodium carbonate, and the filtrate was concentrated. This operation was repeated several times. The mixture was filtered with ethanol, and the crude product on the filter paper was dissolved in chloroform and concentrated. Disperse with ethanol and concentrate. This operation was repeated several times. Finally, filtration with ethanol yielded 4.41 g (yield 65.87%) of the target product BBMPA.

[Example 5] Synthesis of BBHPA

In an ice bath, 4.79 g (4.52 mmol) of BBMPA obtained in Example 4 was dissolved in about 250 mL of methylene chloride. A solution prepared by dissolving 25 g (99.8 mmol) of boron tribromide in about 150 mL of methylene chloride was slowly added dropwise under light shielding and stirred for about 12 hours. After completion of the reaction, about 400 mL of water having the same volume as methylene chloride was slowly added under ice cooling, and then sodium bicarbonate was added until the reaction solution became neutral. Only methylene chloride was distilled off and extracted with ethyl acetate. The mixture was treated twice with water, further treated with saturated brine, dried over sodium sulfate, and the solvent was distilled off. This was applied to a silica gel flash column to remove the origin component. This was concentrated, dissolved in a minimum amount of ethyl acetate, and concentrated by adding chloroform. Thereafter, precipitation with chloroform and filtration yielded a target BBHPA yield of 2.876 g (yield 63.43%). From IR, a peak corresponding to the structure was obtained. This IR chart is shown in FIG.
IR (KBr) [cm ^-1 ] = 3530 1655 1591 1499 1260 1171 820 769 667.
^A consistent result was obtained from the proton number of ¹ H-NMR. This NMR chart is shown in FIG.
¹ H-NMR (300 MHz DMSO) δ [ppm] = 9.60 (s, 4H) 8.25 (s, 2H) 7.94-7.96 (d, 8H) 7.81-7.85 (m, 4H) 7.78 (d, 4H) 7.70 (d , 8H) 7.55 (d, 8H) 7.43-7.50 (m, 4H) 6.88 (d, 8H).

[Example 6] Synthesis of BBTA

The reaction was performed under nitrogen. BBTA 5.00 g (4.1 mmol) obtained in Example 3, tris (dibenzylideneacetone) -chloroform-dipalladium complex 0.508 g (0.46 mmol), bis (diphenylphosphino) ferrocene 1.10 g (2.0 mmol) ) And 3.40 g (52 mmol) of potassium cyanide, about 50 ml of acetonitrile was added. This suspension was stirred at 60 ° C. for about 120 hours. The reaction mixture was concentrated and chloroform was added. Insoluble inorganic substances were filtered off, and all the solvent of the mother liquor was distilled off to obtain a solid. This solid was dispersed in para-xylene and collected on a funnel. The filter receiver was replaced with a new one, and the solid on the funnel was dissolved again with chloroform. By this operation, impurities that did not dissolve in chloroform were removed. The chloroform solution accumulated in the receiver was concentrated and applied to an alumina flash column (neutral, eluent chloroform) to remove the origin component. The eluate was concentrated and then treated with a small amount of activated carbon. Activated carbon was filtered off, and chloroform of the filtrate was completely distilled off with an evaporator. The obtained solid was dispersed in acetonitrile, and this was collected by filtration to obtain 2.25 g (yield: 75.2%) of the target BBCA. The compound was identified by ¹ H-NMR.
¹ H-NMR (DMSO-d ₆ / CDCl ₃ ) δ [ppm] = 7.31-7.347 (q, 4H, anthracene-H) 7.68-7.74 (m, 16H, anthracene-H, aromatic-H) 7.83-7.86 ( d, 8H, aromatic-H) 8.01 (s, 2H, aromatic-H).

Example 7 Synthesis of BCPA

To 0.1102 g (0.136 mmol) of tetraphenylcyano compound, 19.3 mL of a 10 mol / L aqueous sodium hydroxide solution and 19.3 mL of ethanol were added. The mixture was heated to reflux for about 123 hours. Ethanol in the reaction solution was distilled off with an evaporator. When 20 mL of concentrated hydrochloric acid was added to this under ice cooling, the target product was precipitated. Using a centrifuge, washing was repeated with water until the washing liquid containing the target product became neutral. The target product BCPA yield 0.13 g (yield 100%) was obtained by drying at 100 ° C. under reduced pressure. The compound was identified by ¹ H-NMR and IR. ^A consistent result was obtained from the proton number of ¹ H-NMR. From IR, a peak which is a C═O stretching vibration band of an aromatic carboxylic acid body was obtained at 1700-1680 cm ⁻¹ . The NMR chart is shown in FIG. 3, and the IR chart is shown in FIG.
¹ H-NMR (DMSO-d ₆ ) δ [ppm] = 7.51 (q, 4H, anthracene-H), 7.76 (q, 4H, anthracene-H), 7.89 (s, 4H, aromatic-H), 8.06 ( m, 16H, aromatic-H), 8.34 (s, 2H, aromatic-H).
IR (KBr) 1691.3cm ^-1 .

[Example 8] Solubility of BBHPA About the solubility of BBHPA, about 2 mg of a sample was weighed into a 1.8 mL sample tube with a spatula, and the solvent was dropped dropwise using a Pasteur. Then, the amount of solvent required for dissolution was calculated backward to calculate the solubility. Table 1 shows the solubility and solubility of BBHPA in each solvent.

Example 9 Synthesis of BBHPA Organic Zeolite Analogue BBHPA was dissolved in ethyl acetate, chloroform was added, and the resulting precipitate was filtered and dried under reduced pressure at 60 ° C. to obtain a powdery BBHPA organic zeolite analog. This powder was measured by ¹ H-NMR, and it was confirmed that there was no solvent peak.
The powder X-ray diffraction pattern (PXRD pattern) was analyzed for the crystallinity of the BBHPA organic zeolite analog. The obtained powder was finely crushed in a mortar and placed on a glass sample plate for measurement. PXRD data for the BBHPA organic zeolite analog is shown in FIG. This measurement data revealed that the BBHPA organic zeolite analogue was crystalline.
Measuring equipment: Rigaku RAD-PC X-ray diffractometer (measured to 30 KV, 20 mA, Cu-Kα radiation, X-ray wavelength 1.5418 nm, 2θ = 50 deg)

[Example 10] Molecular adsorption capacity of BBHPA organic zeolite analogues A vapor adsorption apparatus Belsorb 18SP-V manufactured by Nippon Bell Co., Ltd. was used to measure the adsorption isotherm of molecules. The following features were revealed.
(1) Adsorption of N ₂ molecule at 77K FIG. 6 shows an adsorption isotherm of N ₂ molecule. From this adsorption isotherm, a phase straight line was created according to the Langmuir equation, and a straight line with good regularity was obtained between the relative pressures of 0 to 0.4.
The saturated adsorption amount determined from the slope of this straight line was 10.56 mL / g, and it was revealed that the specific surface area using nitrogen was about 50 m ² / g.
This result was found to be about 10 times higher than the specific surface area of the BBHA organic zeolite analogue (about 5 m ² / g).

(2) Vapor adsorption of acetone at 298 K FIG. 7 shows an adsorption isotherm of acetone, which is a polar solvent. The adsorption isotherm is shown in comparison with the results for BBHA organic zeolite analogues.
Compared to BBHA organic zeolite analogues, BBHPA organic zeolite analogues have sharper adsorption in the low pressure region. Moreover, although both hosts are two-stage adsorption isotherms, the first stage of the BBHA organic zeolite analog is around 0.5 relative pressure, whereas the BBHPA organic zeolite analog has a relative pressure of 0. A value as low as 1 was shown. This supported the above-mentioned consideration of expansion of the specific surface area.

(3) Vapor adsorption of ethyl acetate at 298 K FIG. 8 shows an adsorption isotherm of ethyl acetate, which is a polar solvent having a carbonyl group having a slightly higher molecular weight than acetone. The BBHPA organic zeolite analog was confirmed to be adsorbed in the low pressure region as in the case of acetone. In addition, at the time of desorption, the BBHA organic zeolite analog was hardly desorbed, whereas the BBHPA organic zeolite analog was much easier to desorb.
(4) Vapor adsorption of benzene at 298 K FIG. 9 shows an adsorption isotherm of benzene as a nonpolar solvent. Adsorption in the low pressure region can be confirmed in the same manner as described above, and the BBHA organic zeolite analogue adsorbed about 2 molecules of benzene when compared with the saturated adsorption amount, whereas the BBHPA organic zeolite analogue contained about 4 molecules. The adsorption amount was about twice. Thus, an increase in the amount of adsorption of a non-polar solvent such as benzene is a feature that has not been observed so far, and it can be said that the performance as an adsorbent is improved.

(5) Vapor adsorption of n-hexane at 298K FIG. 10 shows an adsorption isotherm of n-hexane, which is a nonpolar solvent. While benzene is adsorbed by π / π interaction, n-hexane is a straight-chain hydrocarbon that does not interact, so the number of adsorbed molecules is low, but it is related to BBHPA organic zeolite. In the body, the amount of adsorption is higher than that of the BBHA organic zeolite analog.
(6) H ₂ O vapor adsorption at 298 K FIG. 11 shows an adsorption isotherm of H ₂ O. The BBHPA organic zeolite analog showed adsorption of about 4 molecules of H ₂ O. This is considered to indicate that the functional group of the host is a hydroxyl group and is adsorbed by the interaction.

[Example 11] Solubility of BCPA The solubility of BCPA was calculated in the same manner as in Example 8. Table 2 shows the solubility and solubility of BCPA in each solvent.

[Example 12] Heat resistance of BCPA In order to investigate the decomposition temperature of BCPA, TG measurement was performed. Thermogravimetric analysis (TG) was carried out under the following experimental conditions using BCPA synthesized in the above-mentioned examples after confirming by ¹ H-NMR and then completely distilling off the solvent by drying under reduced pressure at 200 ° C. .

<Experimental condition 1>
1 Measurement item Thermogravimetric decrease 2 Measurement temperature 25 ° C-500 ° C-25 ° C
3 Atmosphere 4 Measurement sample 3.891 mg
5 Reference sample Al ₂ CO ₃
6 Heating rate 5.0K / min
7 Sample Pan Pt

<Experimental condition 2>
1 Measurement item Thermogravimetric reduction 2 Measurement temperature 25 ° C to 200 ° C to 25 ° C to 200 ° C to 25 ° C to 450 ° C to 25 ° C
3 Atmosphere 4 Measurement sample 2.627mg
5 Reference sample Al ₂ CO ₃
6 Temperature rising speed 10.0K / min
7 Sample Pan Pt

The measurement result of the experimental condition 1 is shown in FIG. 12, and the measurement result of the experimental condition 2 is shown in FIG.
From the graph, the decomposition point at which BCPA weight loss was observed was measured at 384 ° C. Since it was 395 degreeC in the conventional BCAPA, it was confirmed that it has the heat resistance which is hardly inferior. Moreover, if the decomposition temperature is not exceeded, heat resistance will not be lowered even if heat is repeatedly applied. From this, it can be said that when the organic solvent is used as a guest, it has sufficient heat resistance to withstand the repeated use of the guest by heating.

[Example 13] Synthesis of BCPA organic zeolite analog BCPA was dissolved in ethyl acetate, chloroform was added, and the resulting precipitate was filtered and dried under reduced pressure at 200 ° C to obtain a powdery BCPA organic zeolite analog. This powder was measured by ¹ H-NMR, and it was confirmed that there was no solvent peak.
PXRD measurements were performed to investigate the crystallinity of BCPA organic zeolite analogs. The powder X-ray diffractometer (PXRD) is an X-ray diffractometer RAD-C manufactured by Rigaku Corporation. The tube voltage is 30 kV, the tube current is 20 mA, the filter is Ni, the thickness is 0.021 mm, and BCPA organic is used under the following experimental conditions. The crystallinity of the zeolite analogue was measured.

Experimental conditions Scanning axis: 2θ / θ
Measuring method: Continuous divergence slit: 1 deg
Scattering slit: 1 deg
Integration count: Once Calculation unit: cps
Receiving slit: 0.3mm
Starting angle: 2,000
End angle: 60.000
Sampling: 0.020
Scan speed: 2,000

  PXRD data of only the BCPA organic zeolite analog (host) obtained under this experimental condition is shown in FIG. Further, FIG. 15 shows PXRD data in which cyclohexanone was dropped onto a host obtained under the same conditions. Further, FIG. 16 shows PXRD obtained by drying the sample to which cyclohexanone was dropped by heating at 200 ° C. under reduced pressure.

From the data of the host only in FIG. 14, peaks can be confirmed at 5.96 (°), 12.00 (°), and 24.06 (°), indicating that the powder of the BCPA organic zeolite analog is crystalline. It became clear.
From the data obtained by adding cyclohexanone as a guest to the host in FIG. 15, 14.34 (°), 16.44 (°), 17.02 (°), 17.86 (°), 19.52 (°), 22 The peaks shifted to .92 (°) and 24.66 (°), and it was revealed that adsorption occurred due to the structural change. Moreover, since the powder pattern in which about 13.4 molecules of guest molecules were confirmed immediately after dropping and the powder pattern in which the number of molecules became 2.88 molecules after 86 hours did not change, the guest molecules were adsorbed to form a stable shape. You can see that

Furthermore, the state of the apohost obtained by completely distilling off the solvent by heating and drying at 200 ° C. under reduced pressure in the host containing guest shows the powder pattern of FIG. Once the structural change is caused by guest adsorption, it does not completely return to the original state even if the guest is removed. Therefore, the characteristic peak at 5.96 (°) was reduced because the regularity of the structure was reduced. However, it can be said that the basic powder pattern is essentially the same because it is almost the same as the fresh state of the host alone. When the guest was dropped again into this apohost state, it shifted to a peak as shown in FIG. 14 due to the structural change, and thus it became clear that it has a feature that can be repeatedly used as a host.
It was confirmed that when the solution was dissolved again in sodium hydroxide and ethanol by applying heat at 85 ° C. and concentrated hydrochloric acid was added for precipitation, it returned closer to fresh.

[Example 14] Molecular adsorption ability of BCPA organic zeolite analog A vapor adsorption apparatus Belsorb 18SP-V manufactured by Nippon Bell Co., Ltd. was used to measure the adsorption isotherm of molecules. As a comparative control, the molecular adsorption ability of BCAPA described in Patent Document 1 was also measured. As a result, the following features became clear.

(1) Adsorption of N ₂ molecule at 77K FIG. 17 shows an adsorption isotherm of N ₂ molecule. The BCPA organic zeolite analog showed only about 1/3 of the adsorption of the BCAPA organic zeolite analog, although the side chain was extended.
From the adsorption isotherm of this BCPA organic zeolite analog, a phase line was created according to the Langmuir equation, and a straight line with good regularity was obtained in the first half of the adsorption curve. The saturated adsorption amount obtained from the slope of this straight line was 29.96 mL / g, and it was revealed that the specific surface area using nitrogen was about 130 m ² / g.
Since the specific surface area of the BCAPA organic zeolite analog was 480 m ² / g, it decreased to about ¼, and the calculation result confirmed the result of vapor adsorption of nitrogen. However, since this specific surface area is much higher than other organic substances, it can be said to be porous, and it can be said that pores are maintained even in a guest-free state.

(2) Vapor adsorption of acetone at 298 K FIG. 18 shows an adsorption isotherm of acetone, which is a polar solvent.
(3) Vapor adsorption of ethyl acetate at 298 K FIG. 19 shows an adsorption isotherm of ethyl acetate, which is a polar solvent.
(4) Vapor adsorption of benzene at 298 K FIG. 20 shows an adsorption isotherm of benzene, which is a nonpolar solvent.
(5) Vapor adsorption of n-hexane at 298 K FIG. 21 shows an adsorption isotherm of n-hexane, which is a nonpolar solvent.
(6) H ₂ O vapor adsorption at 298 K FIG. 22 shows an adsorption isotherm of H ₂ O.

  From the above results, for benzene and hexane, which are non-polar solvents, the BCPA organic zeolite analog showed the same amount of adsorption as the BCAPA organic zeolite analog. In addition, with polar solvents such as acetone and ethyl acetate, the measurement result was about twice as much as the BCAPA organic zeolite analog. Although the specific surface area in the initial state is low, the reason why the adsorption amount is improved is that the organic crystals are adsorbed by changing the structure. That is, in the adsorption of organic molecules of BCPA organic zeolite, the guest molecules act as driving-faces to cause structural changes, and when saturated by the guest in the first stage, the structural changes attempt to become stable, resulting in Leads to more adsorption.

Further, in the BCPA organic zeolite analogue, adsorption from a low pressure region was observed, which is a characteristic not seen in the BCAPPA organic zeolite analogue. From this, it can be seen that the threshold value is low because a larger hole than the tetracarboxylic acid body is maintained in a guest-free state.
The fact that vacancies can be maintained has the advantage that extra energy is not required to adsorb the guest and it does not take time. On the other hand, once adsorbed, the host is easy to desorb. The guest is difficult to desorb due to adsorption while the structure changes. Thus, it was revealed that BCPA organic zeolite analogues have unprecedented adsorption characteristics.
The BCPA organic zeolite analog showed a large amount of adsorption of about 5 molecules in water adsorption. When the host was synthesized, the yield was 118.9%, but this data proved that water was adsorbed.

It is a figure which shows IR data of BBHPA. It is a figure which shows the < ¹ > H-NMR data of BBHPA. It is a figure which shows IR data of BCPA. It is a figure which shows the < ¹ > H-NMR data of BCPA. It is a figure which shows the PXRD data of a BBHPA organic zeolite analog. BBHPA is a diagram showing the adsorption isotherm of N ₂ molecules at 77K organic zeolite analogues. It is a figure which shows the adsorption isotherm of acetone in 298K of a BBHPA organic zeolite analog. It is a figure which shows the adsorption isotherm of ethyl acetate in 298K of a BBHPA organic zeolite analog. It is a figure which shows the adsorption isotherm of benzene in 298K of a BBHPA organic zeolite analog. It is a figure which shows the adsorption isotherm of n-hexane in 298K of a BBHPA organic zeolite analog. BBHPA is a diagram showing adsorption isotherm of H ₂ O at 298K organic zeolite analogues. It is a figure which shows the thermogravimetric analysis data by the experimental condition 1 of BCPA. It is a figure which shows the thermogravimetric analysis data by the experimental condition 2 of BCPA. It is a figure which shows the PXRD data of a BCPA organic zeolite analog. It is a figure which shows the PXRD data of the sample which dripped cyclohexanone to the BCPA organic zeolite analog. It is a figure which shows the PXRD data of the sample which dipped cyclohexanone to the BCPA organic zeolite analog, and was dried under reduced pressure heating at 200 degreeC. BCPA is a diagram showing the adsorption isotherm of N ₂ molecules at 77K organic zeolite analogues. It is a figure which shows the adsorption isotherm of acetone in 298K of a BCPA organic zeolite analog. It is a figure which shows the adsorption isotherm of ethyl acetate in 298K of BCPA organic zeolite analog. It is a figure which shows the adsorption isotherm of benzene in 298K of a BCPA organic zeolite analog. It is a figure which shows the adsorption isotherm of n-hexane in 298K of a BCPA organic zeolite analog. FIG. 3 shows an adsorption isotherm of H ₂ O at 298 K of a BCPA organic zeolite analogue.

Claims (14)

An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [1].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p, q and n each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [2].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p and q each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [3].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p and q each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [4].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p, q and n each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.) An anthracene-based organic zeolite analogue having a porous organic crystal structure represented by the formula [5].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. The alkoxycarbonyl group, carboxyl group, nitro group or amino group of p and q each independently represents an integer of 1 to 4. The broken line represents an intermolecular hydrogen bond.) An anthracene compound represented by the formula [6].

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Each represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and R ³ each independently represents a trifluoromethylsulfonyloxy group, an alkoxy group having 1 to 10 carbon atoms, a hydroxy group, a cyano group or a carboxyl group. P, q and n each independently represent an integer of 1 to 4) Formula [7]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and p and q each independently represents an integer of 1 to 4.)
A dealkylolysis of a 9,10-bis [3,5-bis (4-methoxyphenyl) -1-phenyl] anthracene compound represented by formula [8]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxyphenyl) -1-phenyl] anthracene compound represented by these. Formula [9]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and p and q each independently represents an integer of 1 to 4.)
Is reacted with a trifluoromethanesulfonic anhydride in the presence of a base to give a compound of the formula [10]

(Wherein R ¹ , R ² , p and q represent the same meaning as described above, and Tf represents a trifluoromethylsulfonyl group.)
9,10-bis [3,5-bis (trifluoromethylsulfonyloxy) -1-phenyl] anthracene compound represented by the formula [11] in the presence of a palladium catalyst.

Is reacted with 4-methoxyboronic acid represented by the formula [7]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The compound represented by the formula [8] is characterized by further dealkylating the 9,10-bis [3,5-bis (4-methoxyphenyl) -1-phenyl] anthracene compound represented by the formula:

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxyphenyl) -1-phenyl] anthracene compound represented by these. Formula [12]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and p and q each independently represents an integer of 1 to 4.)
A dealkylolysis of a 9,10-bis [3,5-bis (4-methoxybiphenyl) -1-phenyl] anthracene compound represented by formula [13]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxybiphenyl) -1-phenyl] anthracene compound represented by these. Formula [8]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and p and q each independently represents an integer of 1 to 4.)
9,10-bis (3,5-bis (4-hydroxyphenyl) -1-phenyl) anthracene compound and trifluoromethanesulfonic anhydride are reacted in the presence of a base to give a compound of the formula [14 ]

(Wherein R ¹ , R ² , p and q represent the same meaning as described above, and Tf represents a trifluoromethylsulfonyl group.)
9,10-bis [3,5-bis (4-trifluoromethylsulfonyloxyphenyl) -1-phenyl] anthracene compound represented by the formula [11] in the presence of a palladium catalyst.

Is reacted with 4-methoxyboronic acid represented by the formula [12]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
And a 9,10-bis [3,5-bis (4-methoxybiphenyl) -1-phenyl] anthracene compound represented by the formula [13]:

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-hydroxybiphenyl) -1-phenyl] anthracene compound represented by these. Formula [15]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, and p and q each independently represents an integer of 1 to 4.)
And a 9,10-bis [3,5-bis (4-cyanophenyl) -1-phenyl] anthracene compound represented by the formula: [16]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-carboxyphenyl) -1-phenyl] anthracene compound represented by these. Formula [14]

(In formula, R < ¹ > and R < ² > are respectively independently a hydrogen atom, a halogen atom, a cyano group, a C1-C10 alkyl group, a hydroxyl group, a C1-C10 alkoxy group, and C1-C10. Represents an alkoxycarbonyl group, a carboxyl group, a nitro group or an amino group, wherein p and q each independently represent an integer of 1 to 4, and Tf represents a trifluoromethylsulfonyl group.)
A 9,10-bis [3,5-bis (4-trifluoromethylsulfonyloxyphenyl) -1-phenyl] anthracene compound represented by the formula: [17]

(In the formula, M represents a hydrogen atom, an alkali metal or an alkaline earth metal.)
Is reacted in the presence of a palladium catalyst to give a compound of the formula [15]

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
Formula [16], wherein the 9,10-bis [3,5-bis (4-cyanophenyl) -1-phenyl] anthracene compound represented by formula (1) is obtained and then hydrolyzed.

(In the formula, R ¹ , R ² , p and q have the same meaning as described above.)
The manufacturing method of the 9,10-bis [3,5-bis (4-carboxyphenyl) -1-phenyl] anthracene compound represented by these.   The occlusion body which consists of an anthracene-type organic zeolite analog of any one of Claims 1-5. The occlusion body according to claim 13 for occlusion of organic molecules.

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