JP2893182B1 - 2,7-diaza-1,2,3,6,7,8-hexahydropyrene compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound, 2,7-diaza-1,2,2
A 3,6,7,8-hexahydropyrene compound is provided. SOLUTION: 2,7-diaza-1,2,3,6,7,
8-hexahydropyrene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, 2,7-diaza-1,2,3,6,7,8-hexahydropyrene compound and a method for producing this compound.

[0002]

2. Description of the Related Art Conventionally, naphthalene has a peri position (1,8).
Position) with a 2-azatrimethylene group (—CH ₂ —NH—C
A 2-azaperinaphtan compound in which H _2- is cyclized is known. However, 2,7-diaza-1,2,3,6 of a bispericyclic system in which a 2-azatrimethylene group is cyclized at the other peri-position (positions 4 and 5) of the naphthalene ring.
The 7,8-hexahydropyrene compound is an unknown compound up to the present due to difficulties in synthetic chemistry, though various uses due to the presence of a hetero atom in the skeleton are expected.

[0003]

Accordingly, the present invention provides
A novel compound, 2,7-diaza-1,2,3,6
An object of the present invention is to provide a 7,8-hexahydropyrene compound and a method for producing these compounds.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the reaction of a bisperi-substituted naphthalene compound. As a result, 1,4,5,8-tetrakis (halogenomethyl) naphthalene and By reacting with amines, 2,7-diaza-1,2,2,
The inventors have found that a 3,6,7,8-hexahydropyrene skeleton can be synthesized, and based on this finding, have accomplished the present invention. That is, the present invention provides: (1) 2,7-diaza-1, represented by the following formula (I):
2,3,6,7,8-hexahydropyrene.

Formula (I)

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(2) A 2,7-diaza-1,2,3,6,7,8-hexahydropyrene compound represented by the following formula (II):

Formula (II)

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(Wherein R represents (a) a benzyl group, (b) a sulfonyl group, (c) an acyl group, or (d) a carboalkoxy group.) (3) Formula (I) described in (1). 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the following formula (III): Manufacturing method.

Formula (III)

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(4) 1,4 represented by the following formula (IV)
5,8-Tetrakis (halogenomethyl) naphthalene is treated with benzylamine.
2,7-dibenzyl-2,7-diaza-1, represented by
A method for producing 2,3,6,7,8-hexahydropyrene.

Formula (IV)

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Formula (IIa)

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(X represents a halogen atom.) (5) 1,4,5,8-tetrakis (halogenomethyl) naphthalene represented by the following formula (IV) is treated with paratoluenesulfonamide. 2,7-diparatoluenesulfonyl-2,7- represented by the following formula (IIb):
A method for producing diaza-1,2,3,6,7,8-hexahydropyrene.

Formula (IV)

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Formula (IIb)

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(Wherein X represents a halogen atom) (6) 2,7-diaza-1,2,3,6,7,8-hexahydro represented by formula (I) described in (1). 2,7-diparatoluenesulfonyl-2,7-diaza-1,2,3,6,7,8- represented by the following formula (IIb), wherein pyrene is treated with paratoluenesulfonyl chloride. A method for producing hexahydropyrene.

Formula (IIb)

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(7) The method is characterized in that 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the formula (I) described in (1) is treated with benzoyl chloride. 2,7-dibenzoyl- represented by the following formula (IIc):
A method for producing 2,7-diaza-1,2,3,6,7,8-hexahydropyrene.

Formula (IIc)

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(8) 2,7-dibenzyl-2,7-diaza-1,2,3,6,7,8- represented by the following formula (IIa)
2,7-dicarbethoxy-2,7-diaza-1,2,3,6,7,8- represented by the following formula (IId), wherein hexahydropyrene is treated with ethyl formate. A method for producing hexahydropyrene.

Formula (IIa)

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Formula (IId)

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(9) 2,7-Diparatoluenesulfonyl-2,7-diaza-1,2,2,2 represented by the following formula (IIb)
3,6,7,8-Hexahydropyrene is treated with hydrobromic acid, and 2,7-diaza-1,2,3 represented by the formula (I) described in (1). A method for producing 6,7,8-hexahydropyrene.

Formula (IIb)

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(10) 2, represented by the following formula (IId):
7-dicarbethoxy-2,7-diaza-1,2,3
6,7,8-Hexahydropyrene is treated with an alkali aqueous solution, and the 2,7-diaza-1,2,3,6,7,2 represented by the formula (I) according to the above (1) is characterized in that: A method for producing 8-hexahydropyrene.

Formula (IId)

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Is provided.

[0028]

DETAILED DESCRIPTION OF THE INVENTION First, the 2,7-diaza-1,2,3,6,7,8-hexahydropyrene compound of the general formula (II) of the present invention will be described. Examples of the sulfonyl group for R include, for example, a methanesulfonyl group, an ethanesulfonyl group, a propanesulfonyl group, a butanesulfonyl group and the like, preferably an alkylsulfonyl group having 1 to 4 carbon atoms, a paratoluenesulfonyl group, a parabromobenzenesulfonyl group And an arylsulfonyl group having preferably 6 to 10 carbon atoms such as paranitrobenzenesulfonyl group. The acyl group of R is preferably an aliphatic acyl group having 1 to 10 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, a decanoyl group, a benzoyl group, or a naphthoyl group, and preferably has 7 to 7 carbon atoms. 1
And 1 aromatic acyl group. Examples of the carboalkoxy group for R include those preferably having 2 to 5 carbon atoms, such as carbomethoxy, carboethoxy and carbobutoxy.

Next, the method for producing the compound according to the present invention will be specifically described. In the present invention, 2,7-dibenzyl-2,7-diaza-1,2,3,6,7,8-hexahydro represented by the formula (IIa), wherein R in the general formula (II) is a benzyl group. Pyrene is prepared as 1,4,5,8 represented by the formula (IV).
-Can be produced by reacting benzylamine with tetrakis (halogenomethyl) naphthalene. These 2,7
-Dibenzyl-2,7-diaza-1,2,3,6,7,
In the production of 8-hexahydropyrene, first, the raw material 1,4,5,8-tetrakis (halogenomethyl) naphthalene (IV) is mixed with an organic solvent such as acetonitrile and the same solvent containing a base such as benzylamine and potassium carbonate. And heat-treat this mixture. Thus occurs ring closure reaction with the peri-position of the halogenomethyl group (-CH ₂ X) and benzylamine molecule of the compound (IV), bis naphthalene containing a nitrogen atom in the ring -
2,7-Dibenzyl-2,7-diaza-1,2,3,6,7,8-hexahydropyrene of the per-6-cyclic system (II
a) is generated. This reaction is usually performed at the boiling temperature of the solvent, and the reaction time of 1-2 days is sufficient. It is preferable to constantly stir the reaction solution effectively to increase the reaction yield. The reaction molar ratio of the compound represented by the formula (IV) to benzylamine can be determined stoichiometrically, but is usually 1: 2 to 1: 4, preferably 1: 2.
5 to 1: 3. In this reaction, the reaction solution changes from an initial white suspension to a pale yellow suspension as the reaction proceeds. After completion of the reaction, the reaction mixture is treated with water, and the resulting precipitate is collected by filtration and collected to give 2,7-dibenzyl-2,7-diaza-1,2,3 represented by the formula (IIa).
6,7,8-Hexahydropyrene can be obtained.

In the present invention, R in the general formula (II)
Is a carboethoxy group, 2,7 represented by the formula (IId)
-Dicarbethoxy-2,7-diaza-1,2,3
6,7,8-Hexahydropyrene can be produced by treating a compound of formula (IIa) with ethyl chloride formate. The 2,7-dicarbethoxy-2,7-diaza-1,2,3,6,7,8-hexahydropyrene (II
In the production of d), the compound of the formula (IIa) as a raw material is first heat-treated with ethyl chloride formate in an organic solvent such as tetrahydrofuran. As a result, an exchange reaction occurs between the molecule (IIa) and the ethyl formate molecule, and the two benzyl groups of (IIa) are converted to the carboxy group (—CO 2
2,7-dicarbethoxy substituted with OC ₂ H ₅ )
2,7-diaza-1,2,3,6,7,8-hexahydropyrene (IId) is produced.

This reaction is usually carried out at the boiling temperature of the solvent, and a reaction time of 1.5 to 3 hours is sufficient. The reaction molar ratio of the compound represented by the formula (IIa) to ethyl formate can be determined stoichiometrically, but is usually 1: 2 to 1: 5, preferably 1: 3 to 1: 4. It is. When the reaction is performed in this manner, the reaction solution changes from an initial white suspension to a light brown solution as the reaction proceeds. After the completion of the reaction, the residue obtained by removing the solvent under reduced pressure is subjected to silica gel chromatography and recrystallization to carry out a separation and purification operation, whereby the compound represented by the formula (IId) 2 is obtained.
7-dicarbethoxy-2,7-diaza-1,2,3
6,7,8-Hexahydropyrene can be obtained.

In the present invention, 2,7- represented by the formula (IIb) wherein R is a paratoluenesulfonyl group in the general formula (II)
Diparatoluenesulfonyl-2,7-diaza-1,2,2
3,6,7,8-Hexahydropyrene can be obtained from 1,4,5,8-tetrakis (halogenomethyl) represented by the formula (IV)
It can be produced by treating naphthalene with paratoluenesulfonamide. The 2,7-diparatoluenesulfonyl-2,7-diaza-1,2,3,6
In the production of 7,8-hexahydropyrene (IIb), first, the raw material 1,4,5,8-tetrakis (halogenomethyl) naphthalene (IV) is used together with paratoluenesulfonamide and an organic solvent containing a base such as potassium carbonate. This mixture is heated in a solvent such as DMF. Thus, the halogenomethyl group at the peri-position of (IV) (—CH ₂
X) and a paratoluenesulfonamide (H ₂ N-Ts) molecule undergo a ring-closing reaction, and 2,7-diparatoluene of a bis-per-6-cyclic system of naphthalene containing a nitrogen atom in the ring Sulfonyl-2,7-diaza-1,2,3,6
7,8-Hexahydropyrene (IIb) is produced.

This reaction is usually carried out at the boiling temperature of the solvent, and a reaction time of 13 to 18 hours is sufficient. The reaction molar ratio of the compound represented by the formula (IV) and paratoluenesulfonamide can be determined stoichiometrically, but is usually 1: 2 to 1: 4, preferably 1: 2.
１ ： 1: 2.5. When the reaction is performed in this manner, the reaction solution changes from an initial white suspension to a yellow suspension as the reaction proceeds. After completion of the reaction, the reaction mixture is treated with water, and the resulting precipitate is collected by filtration and recrystallized.
2,7-Diparatoluenesulfonyl-2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the formula (IIb) can be obtained.

The 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the formula (I) of the present invention is
2,7-dicarboethoxy-2,7 represented by the formula (IId)
-Produced by treating diaza-1,2,3,6,7,8-hexahydropyrene with alkali. In the production of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene (I), the starting material 2,7-dicarboethoxy-2,7-diaza-1,2,3 , 6,7,8
Heat treatment of hexahydropyrene (IId) with an aqueous alkali solution such as sodium hydroxide or potassium hydroxide; As a result, hydrolysis and decarboxylation of two carboethoxy groups in the raw material molecules occur due to the action of the alkali,
2,7-diaza-1,2,3,6,7,8-hexahydropyrene (I) having two secondary amino groups (-NH-)
Is generated.

This reaction is usually carried out at the boiling temperature of the solvent, and the reaction time of 18 to 25 hours is sufficient. When the reaction is performed in this manner, the reaction solution changes from an initial white suspension to a yellow solution and further to a brown solution as the reaction proceeds. After the completion of the reaction, the solid precipitated by treatment with ice water was collected by filtration, and the obtained crude product was recrystallized and purified to obtain 2,7-diaza-formula represented by the formula (I).
1,2,3,6,7,8-hexahydropyrene can be obtained. 2,7-diacyl-2,7-diaza-1,2,2, wherein R is an acyl group in the general formula (II) of the present invention.
3,6,7,8-Hexahydropyrene acts on 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the formula (I) with a predetermined acylating agent. It can be manufactured by doing. The amount of the acylating agent used is
It is preferably 3 to 10 mol, more preferably 5 to 7 mol, per 1 mol of the compound of the formula (I). Examples of the acylating agent include acyl halides such as benzoyl chloride, acetyl chloride, naphthoyl chloride, furoyl chloride, and toluoyl chloride, and acid anhydrides such as benzoic anhydride, acetic anhydride, and phthalic anhydride.

This reaction is preferably carried out in an organic solvent such as pyridine, and the reaction temperature varies depending on the type of the acylating agent. Is in the range of 0 ° C. to room temperature. When the reaction is performed in this manner, the reaction solution changes from initially colorless to light brown as the reaction proceeds. After the completion of the reaction, this solution is treated with water and subjected to an extraction operation to obtain a compound (I) in which the hydrogen atoms of two amino groups (—NH—) are substituted with an acyl group (for example, a compound in which the acyl group is a benzoyl group). In this case, -NH- is a benzoylamino group (-N (COC ₆
H ₅₎ -) was converted to 2,7-dibenzoyl -2,
7-diaza-1,2,3,6,7,8-hexahydropyrene (IIc)) is obtained.

According to the present invention, 2,2 represented by the formula (IIb)
7-diparatoluenesulfonyl-2,7-diaza-1,
2,3,6,7,8-Hexahydropyrene is prepared by treating 1,4,5,8-tetrakis (halogenomethyl) naphthalene of formula (IV) with p-toluenesulfonamide as described above. Alternatively, 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the formula (I) can be produced by treating with paratoluenesulfonyl chloride.

This reaction is preferably carried out in an organic solvent such as pyridine, and the reaction temperature ranges from room temperature to 60 ° C. immediately after the addition of the sulfonylating agent, and the subsequent standing temperature ranges from 0 ° C. to room temperature. 2,7-diaza represented by the formula (I)
The reaction molar ratio of 1,2,3,6,7,8-hexahydropyrene and paratoluenesulfonyl chloride can be determined stoichiometrically, but is usually 1: 2 to 1:10, preferably 1: 1: 4 to 1: 6. When the reaction is performed in this manner, the reaction solution changes from an initial white suspension to a light brown suspension as the reaction proceeds. After the reaction was completed, the reaction solution was treated with water, and the precipitated solid was collected, recrystallized, and purified.
Two amino groups of (I) (-NH-) hydrogen atom para-toluenesulfonyl group _{(-SO 2 C 6 H 4 -pCH} 3)
Substituted with 2,7-diparatoluenesulfonyl-
2,7-diaza-1,2,3,6,7,8-hexahydropyrene (IIb) is obtained. (IIb) obtained in this way
Was consistent with (IIb) described above, which was synthesized by treating the compound of formula (IV) with p-toluenesulfonamide.

According to the present invention, 2,
As described above, 7-diaza-1,2,3,6,7,8-hexahydropyrene can be used for the 2,7 represented by the formula (IId).
-Dicarbethoxy-2,7-diaza-1,2,3
It can be produced by treating 6,7,8-hexahydropyrene with an alkali, or by treating a compound of formula (IIb) with hydrobromic acid. In the production of the compound of the formula (I) of the present invention, the starting 2,7-diparatoluenesulfonyl-2,7
Heat treatment of diaza-1,2,3,6,7,8-hexahydropyrene (IIb) with hydrobromic acid; As a result, a hydrolysis reaction occurs due to the action of the acid, and 2
2,7-diaza-1,2,2 having two secondary amino groups (—NH—) by leaving two paratoluenesulfonyl groups
3,6,7,8-Hexahydropyrene (I) is produced.

This reaction is usually carried out at the boiling temperature of the solvent, and the reaction time of 18 to 25 hours is sufficient. The amount of the acid used is usually 5 to 1 mol of the compound of the formula (IIb).
Although it is 10 to 10 mol, the acid itself can be used as a solvent. Determined by When the reaction is performed in this manner, the reaction solution turns dark red. This is treated with ice water,
An extraction operation is performed according to a conventional method, and the obtained crude product is recrystallized and purified to obtain a compound of the formula (I). The data of the compound of formula (I) thus obtained, such as physical properties and analytical values, completely coincided with the data of the compound of formula (I) synthesized by treating the compound of formula (IId) with alkali. In the present invention, the 2,7- compound represented by the formula (III)
Diazapyrene is a 2,7-diaza- compound represented by the formula (I).
It is produced by treating 1,2,3,6,7,8-hexahydropyrene with manganese dioxide.

In the production of 2,7-diazapyrene (III) of the present invention, the compound of the formula (I) as a raw material is heated in an inert solvent such as benzene together with an oxidizing agent such as manganese dioxide. Then, a dehydrogenation reaction occurs due to the oxidizing action of manganese dioxide, and 2,7-diazapyrene (III) in which the compound of the formula (I) as a raw material is hexadehydrogenated is generated.
The amount of the oxidizing agent to be used is preferably 5 to 20 mol, more preferably 8 to 12 mol, per 1 mol of the compound of the formula (I). The reaction is usually carried out at the boiling temperature of the solvent, and a reaction time of 12 to 18 hours is sufficient. The reaction is carried out in this manner, and after completion of the reaction, the reaction solution is filtered to remove the catalyst, and the crude product obtained by removing the solvent is purified.
2,7-diazapyrene represented by the formula (III) can be obtained.

[0042]

Next, the present invention will be described in more detail with reference to examples. Example 1 A mixture of 90 ml of acetonitrile containing 2.75 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (IV), 1.2 ml of benzylamine and 3.56 g of potassium carbonate was refluxed for 2 days. After the reaction, a white solid precipitated by treatment with ice water was collected, and 2.12 g (yield 99%) of 2,7 was obtained.
-Dibenzyl-2,7-diaza-1,2,3,6,7,
8-Hexahydropyrene (IIa) was obtained. Mp. 213 ° C. (decomposition) Mass spectrometry (m / z); 390 (M ⁺ ) IR (Nujol); 3056, 3030, 1597,
1500,1455,1318,1095,985,8
25,740,695 (cm ^-1 )

Example 2 A solution of 1.00 g of ethyl formate in tetrahydrofuran 5
ml of 2,7-dibenzyl-2,7-diaza-1,
2,3,6,7,8-hexahydropyrene (IIa) 0.3
The solution was added to 5 ml of a tetrahydrofuran solution containing 98 g, and the mixture was stirred at 55 ° C. for 2 hours. After the reaction, the solvent was removed under reduced pressure, and the obtained solid was purified by chromatography on silica gel and then recrystallized from a mixture of benzene and hexane to give 0.31 g of colorless microcrystals (yield 86
%) Of 2,7-dicarbethoxy-2,7-diaza-
1,2,3,6,7,8-Hexahydropyrene (IId) was obtained. Mp. 186-189 ° C. Rf (silica gel / dichloromethane); 0.13 elemental analysis; measured value; C, 67.50, H, 6.53 calculated value; C, 67.78, H, 6.26 (C ₂₀ H ₂₂ O ₄ N ₂₎ mass spectrometry (m / z); 354 ( M +) IR (Nujol); 3026,2986,1695,1603,1521,1 263,1235,1109,1040,893,830,760cm -1 1 H-NMR (deuterated chloroform); δ 1.27 (t, J = 7.2 Hz, 6H, CH ₃ ), 4.17 (q, J = 7.2 Hz, 4H, Ethyl-CH ₂ ), 4.89 (s, 8H, ArCH ₂ N) ), 7.23 (s, 4H, ArH)

Example 3 DM containing 0.497 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (IV), 0.342 g of paratoluenesulfonamide and 1.38 g of anhydrous potassium carbonate
12 ml of the F solution was refluxed for 15 hours. The solid obtained by treating the reaction solution with ice water was crystallized from chloroform,
As colorless microcrystals, 0.210 g (yield 41%) of 2,
7-diparatoluenesulfonyl-2,7-diaza-1,
2,3,6,7,8-Hexahydropyrene (IIb) was obtained. Mp. 300-302 ° C (decomposition) Rf (silica gel / dichloromethane); 0.32 elemental analysis; measured value: C 64.50, H 4.91 Calculated value: C 64.86, H 5.05 (C ₂₈ H ₂₆ O ₄ S ₂ N ₂₎ mass spectrometry (m / z); 518 ( M +) IR (Nujol); 3026,1600,1338,1160,954,81 3,770,663,570,544cm -1 1 H-NMR (Deuterated chloroform); δ 2.32 (s, 6H, CH ₃ ), 4.54 (s, 8H, ArCH ₂ N), 7.10 (ABd, J = 8.3 Hz, 4H, p-CH ₃ C ₆ H ₄ -H _{3 ′) , 5 '), 7.12 (s} , 4H, naphthalene H), 7.57 (ABd, J = 8.3Hz, 4H, p-CH 3 C 6 H 4 -H 2', 6 ')

Example 4 2,7-Dicarboethoxy-2,7-diaza-1,2,2
3,6,7,8-Hexahydropyrene (IId) 1.78
g, sodium hydroxide 3.3 g, dioxane 50 ml,
And a mixture of 70 ml of water was heated to reflux for 22 hours. After the reaction, the resulting brown solution was treated with ice water, and the precipitated solid was collected and stirred with 200 ml of dilute hydrochloric acid at 0 ° C. for 1 hour. After removing insoluble substances by filtration and further removing dichloromethane-soluble substances, the aqueous solution was made alkaline and subjected to an extraction treatment according to a conventional method. The crude product thus obtained is crystallized from dichloromethane to yield colorless fine crystals,
0.742 g (yield 71%) of 2,7-diaza-1,
2,3,6,7,8-Hexahydropyrene (I) was obtained. Mp. 214 ° C (decomposition) Rf (silica gel / dichloromethane-methanol, 1:
1); 0.17 elemental analysis; measured value; C 79.70, H 6.59 calculated value; C 79.96, H 6.71 (C ₁₄ H ₁₄ N ₂ ) mass spectrometry (m / z); 210 (M ⁺ ) IR (Nujol); 3180, 3060, 1598,
1309,910,825cm ^{-1 1} H-NMR (heavy chloroform); δ 4.28 (s, 10H , ArCH 2
NH), 7.11 (s, 4H, ArH)

Example 5 2,7-Diparatoluenesulfonyl-2,7-diaza-
1,2,3,6,7,8-hexahydropyrene (IIb)
A mixture of 0.130 g, 0.140 g of phenol, 3 ml of propionic acid and 20 ml of hydrobromic acid was heated under reflux for 20 hours. After cooling to room temperature, the diethyl ether-soluble substance was removed, and the aqueous solution was made alkaline and extracted with dichloromethane. The crude product thus obtained was crystallized from dichloromethane to give 0.014 g (27% yield) of 2,7.
-Diaza-1,2,3,6,7,8-hexahydropyrene (I) was obtained. Mp. 206 ° C (decomposition). The 2,7-diaza-1,2,3,6,7,8 obtained in this example
-Physical property values, analytical values and spectral data of hexahydropyrene (I) were consistent with the data of (I) obtained in Example 4.

Example 6 A solution of 0.040 g of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene (I) in 2 ml of a pyridine was prepared.
2 ml of a pyridine solution containing 0.600 g of benzoyl chloride
Was added. The mixture was reacted at 60 ° C. for 20 minutes and then at room temperature for 3 days, then treated with ice water and extracted with dichloromethane. The residue obtained by removing the solvent under reduced pressure was crystallized using a mixed solvent of hexane-chloroform,
As colorless microcrystals, 0.051 g (66% yield) of 2,
7-dibenzoyl-2,7-diaza-1,2,3,6
7,8-Hexahydropyrene (IIc) was obtained. Mp. 277 ° C (decomposition) Rf (silica gel / benzene-methanol); 0.32 elemental analysis; measured value: C 80.50, H 5.45 Calculated value: C 80.36, H 5.30 (C ₂₈ H ₂₂ O ₂ N ₂₎ mass spectrometry (m / z); 418 ( M +) IR (Nujol); 3050,1630,1600,1580,1412,1 268,1145,1010,830,800,730,700,650cm -1 ¹ H-NMR (deuterated chloroform); δ 5.04 (s, 8H, ArCH ₂ N), 7.23 (s, 4H, naphthalene H) 7.43 (s, 10H, phenyl H)

Example 7 To a 2 ml pyridine solution of 0.044 g of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene (I)
3 ml of a pyridine solution containing 0.360 g of paratoluenesulfonyl chloride was added. Mix the mixture at 60 ° C for 30 minutes,
Then, after reacting at room temperature for 4 days, the mixture was treated with ice water. The precipitated solid was collected by filtration, crystallized from chloroform, and 0.93 g (86% yield) of 2,7-diparatoluenesulfonyl-2,7-diaza-1,2,3,6,7,
8-Hexahydropyrene (IIb) was obtained. Mp. 300 ~
301 ° C. The physical properties, analytical values, and spectral data of 2,7-diparatoluenesulfonyl-1,2,3,6,7,8-hexahydropyrene (IIb) obtained in this example are shown in Example 3. This was consistent with the obtained data of (IIb).

Example 8 0.240 g of 2,7-diaza-1,2,3,6,7,8-hexahydropyrene (I), manganese dioxide 1.10
g and 80 ml of benzene were heated under reflux for 15 hours. After the reaction, manganese dioxide was removed from the reaction solution by filtration, and the solvent was removed under reduced pressure to obtain a brown residue. The crude product thus obtained was purified by chromatography on silica gel and then recrystallized from a mixed solvent of chloroform-methanol to obtain green microcrystals.
0.070 g (yield 49%) of 2,7-diazapyrene (III) was obtained. Mp. 275-277 ° C Rf (silica gel / chloroform-methanol); 0.40 elemental analysis; measured value: C 82.45, H 4.20 Calculated value: C 82.33, H 3.95 (C ₁₄ H ₈ N ₂₎ ) mass spectrometry (m / z); 204 ( M +) IR (Nujol); 3040,3010,1574,1392,1035,8 92,717cm -1 1 H-NMR ( heavy chloroform); δ 8.15 (s, 4H _{, ArH 4,5,9,10) 9.49 (s,} 4H, ArH 1,3,6,8)

[0050]

According to the present invention, as a novel compound,
2,7-diaza-1,2,3,6,7,8-hexahydropyrene and its 2,7-disubstituted derivatives are obtained. Such a compound has a unique reactivity derived from a nitrogen atom and has a unique molecular environment in which two hetero atoms are located in a bisperi position. In addition, it is useful as a heavy metal scavenger and a raw material for producing a surfactant.

Claims (10)

(57) [Claims] 1. A 2,7-diaza-1,2,3,6,7,8-hexahydropyrene represented by the following formula (I). Formula (I) 2. A 2,7-diaza-1,2,3,6,7,8-hexahydropyrene compound represented by the following formula (II). Formula (II) (Wherein R is (a) a benzyl group, (b) a sulfonyl group,
(C) an acyl group or (d) a carboalkoxy group. ) 3. The compound represented by the formula (I) according to claim 1,
7-diaza-1,2,3,6,7,8-hexahydropyrene is treated with an oxidizing agent;
A method for producing 2,7-diazapyrene represented by the formula: Formula (III) 4. The 1,4,5,8 represented by the following formula (IV)
2,7-dibenzyl-2,7-diaza-1,2,2, represented by the following formula (IIa), wherein tetrakis (halogenomethyl) naphthalene is treated with benzylamine.
A method for producing 3,6,7,8-hexahydropyrene. Formula (IV) Formula (IIa) (In the formula, X represents a halogen atom.) 5. The method according to claim 1, wherein
2,7-Diparatoluenesulfonyl-2,7-diaza-1,2,3 represented by the following formula (IIb), wherein 8-tetrakis (halogenomethyl) naphthalene is treated with paratoluenesulfonamide. , 6,7,8-Hexahydropyrene production method. Formula (IV) Formula (IIb) (In the formula, X represents a halogen atom.) 6. The compound represented by the formula (I) according to claim 1,
2,7-Diparatoluenesulfonyl- represented by the following formula (IIb), wherein 7-diaza-1,2,3,6,7,8-hexahydropyrene is treated with paratoluenesulfonyl chloride. 2,7-diaza-1,2,3,6
A method for producing 7,8-hexahydropyrene. Formula (IIb) 7. The compound represented by the formula (I) according to claim 1,
2,7-dibenzoyl-2,7-diaza represented by the following formula (IIc), wherein 7-diaza-1,2,3,6,7,8-hexahydropyrene is treated with benzoyl chloride. A method for producing 1,2,3,6,7,8-hexahydropyrene. Formula (IIc) 8. A 2,7-dibenzyl-2,7-diaza-1,2,3,6,7,8-compound represented by the following formula (IIa):
2,7-dicarbethoxy-2,7-diaza-1,2,3,6,7,8- represented by the following formula (IId), wherein hexahydropyrene is treated with ethyl formate. A method for producing hexahydropyrene. Formula (IIa) Formula (IId) 9. A 2,7-diparatoluenesulfonyl-2,7-diaza-1,2,2, represented by the following formula (IIb):
3. The 2,7-diaza-1,2,3,6 represented by the formula (I) according to claim 1, wherein 3,6,7,8-hexahydropyrene is treated with hydrobromic acid. , 7,8-Hexahydropyrene production method. Formula (IIb) 10. A 2,7-dicarbethoxy-2,7-diaza-1,2,3,6,7, represented by the following formula (IId):
The compound represented by the formula (I) according to claim 1, wherein 8-hexahydropyrene is treated with an aqueous alkali solution.
A method for producing 7-diaza-1,2,3,6,7,8-hexahydropyrene. Formula (IId)