JP3012933B1 - Dithianaphthalenophane compound and method for producing the same - Google Patents

Abstract

The present invention relates to a novel compound, 2,15-dithia [4.
4] (1,8) naphthalenophane, a derivative thereof, and a method for producing these compounds. SOLUTION: 2,15-dithia [4.4] (1,8)
Naphthalenophane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound, 2,15-dithia [4.4] (1,8) naphthalenophane compound and a method for producing the same.

[0002]

2. Description of the Related Art The peri-position (1,8-position) of naphthalene is 2-
Thiatrimethylene group (-CH₂SCH ₂Replaced with-)
2,13-dithia [3.3] (1,8) naphthalenopha
Are known in the art. However, 2-thiatrime
2-thiatetramethyi having a methylene chain one longer than the tylene group
Len group (-CH₂SCH₂CH₂-) Is naphthalene pen
2,15-dithia [4.4] (1,8) crosslinked at the l-position
Naphthalenophane has a wide range of applications, as described below.
Despite promising applications, synthetic chemistry
Due to the difficulty, it is a compound that has not been published in the literature to date.

[0003]

Accordingly, the present invention provides
A novel compound, 2,15-dithia [4.4] (1,
8) An object of the present invention is to provide a naphthalenophane compound and a method for producing the compound.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the bimolecular pericyclization reaction of 1,8-disubstituted naphthalene compounds and found that bismercaptan (bismercaptide) 2,15-dithia [4.4] by using a substitution reaction with
The present inventors have found that a (1,8) naphthalenophane skeleton can be synthesized, and have made the present invention based on this finding. That is, the present invention provides (1) 2,15 represented by the following formula (I):
-Dithia [4.4] (1,8) naphthalenophane, formula (I)

[0005]

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(2) 2,15- represented by the following formula (II)
Dithia [4.4] (1,8) naphthalenophane compound,
Formula (II)

[0007]

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(3) 1,8- represented by the following formula (III)
Formula (I) according to (1), wherein bis (2-substituted ethyl) naphthalene is reacted with 1,8-bis (mercaptomethyl) naphthalene represented by the following formula (IV):
A method for producing 2,15-dithia [4.4] (1,8) naphthalenophane represented by the formula (III)

[0009]

Embedded image (In the formula, X is a halogen atom or a sulfonyloxy group.)

Formula (IV)

[0011]

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And (4) treating the 2,15-dithia [4.4] (1,8) naphthalenophane represented by the formula (I) described in (1) with an oxidizing agent. 2,15-dithia [4.4] represented by the formula (II) described in the item (2)
It is intended to provide a method for producing a (1,8) naphthalenophane compound.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the compound represented by the formula (I) is a compound represented by the formula (III):
Substituted ethyl) naphthalene and 1,8-
It can be produced by reacting bis (mercaptomethyl) naphthalene in the presence of an alkali or base catalyst. In the formula (III), X represents Br, I, Cl
And a sulfonyloxy group such as MsO and TsO. Further, the compound represented by the formula (II)
It can be produced by treating a compound of the formula (I) with an oxidizing agent.

According to the production method (I) of the present invention, first, an organic solution in which the original family (III) and (IV) are dissolved in an organic solvent, and an alcohol solution containing a catalyst alkali or base are prepared. The reaction is carried out by mixing these two solutions. Examples of the organic solvent include hydrocarbon solvents such as hexane and heptane; aromatic solvents such as benzene and toluene; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; halogen solvents such as chloroform and carbon tetrachloride; and acetonitrile. Aprotic polar solvents can be used. As the alkali of the catalyst, a monovalent metal hydroxide such as sodium hydroxide or potassium hydroxide, a divalent alkaline earth metal hydroxide such as barium hydroxide or magnesium hydroxide can be used,
Usually, these are used by dissolving them in an alcoholic solvent such as methanol or ethanol. The base refers to an alkoxide of a metal atom such as sodium methoxide and sodium ethoxide. In this case, when an alkali is used as a catalyst, it is preferable that these alcohol solvents contain a few percent of water.

The reaction is carried out by mixing the organic solution prepared by dissolving (III) and (IV) of the family and an alcohol solution containing an alkali or a base as a catalyst. In this case, the former may be added to the latter or vice versa. However, it is preferable to add the solution slowly and dropwise at a rate of 1 ml every 4 to 5 minutes. In order to increase the reaction yield, the reaction is constantly and efficiently stirred, and after the addition of the reaction component solution, the reaction solution is further stirred for 2 to 3 hours to terminate the reaction. The reaction molar ratio between the compound represented by the formula (III) and the compound represented by the formula (IV) can be stoichiometrically determined, and is usually 1: 1 to 1: 1.3. Preferably it is 1: 1.05-1: 1.1. The amount of the alkali or base used in the catalyst can be determined as appropriate, but usually,
The equivalent ratio is 1.3 to 1.7 with respect to 1,8-bis (2-substituted ethyl) naphthalene 1 of the formula (III). The reaction temperature is preferably 0 to 50 ° C, more preferably 1 to 50 ° C.
0-30 ° C.

When the reaction is carried out as described above, the mercaptide of 1,8-bis (mercaptomethyl) naphthalene (IV) and 1,8-bis (2-substituted ethyl) naphthalene (III And the condensation reaction proceeds to produce a cloudy solution. After the reaction is completed, the solvent is removed, and the residue is treated with water to obtain a crude product. The crude product is purified by recrystallization, and is obtained by condensing and cyclizing one molecule of the parent family (III) and one molecule (IV). 2, represented by (I)
15-Dithia [4.4] (1,8) naphthalenophane can be obtained. Further, an inert group which does not affect the dehydrohalogenation reaction may be introduced on each naphthalene ring of the compound represented by the general formula (III) or (IV) used in the reaction of the present invention. Good. Examples of such a substituent include an alkyl group, an aryl group, an alkenyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a nitro group, an alkylthio group, an ester group, a carboxyl group, a sulfonyl group, and a halogen atom. .

Next, the obtained 2,15-dithia [4.
4] (1,8) Naphthalenophane (I) is reacted with an oxidizing agent to carry out an oxidation reaction to give 2,15-dithia [4.4].
2,15-dithia [4.4] (1,8) naphthalenophane 2,2,15,15-tetraoxide compound represented by the formula (II), which is a derivative of (1,8) naphthalenophane, can get. As the oxidizing agent, hydrogen peroxide, manganese dioxide, chromic anhydride and the like are used. This oxidation reaction is carried out in a solvent such as acetic acid, acetone or carbon tetrachloride, and the reaction temperature varies depending on the type of the oxidizing agent, but is generally in the range of 70 to 100 ° C. When the reaction is carried out in this manner, the reaction solution changes from an initially colorless color to a pale yellow suspension as the reaction proceeds. If this solution is treated with water after the completion of the reaction, 2,15-dithia [4.4] (1,8) naphthalenophane (I) is obtained by oxidizing two sulfur atoms to sulfone. [4.4] (1,8) Naphthalenophane compound (II) is obtained.

The 2,15-dithia obtained by the present invention [4.
4] (1,8) naphthalenophane (I) and its derivative 2,15-dithia [4.4] (1,8) naphthalenophane-2,2,15,15-tetraoxide (I
I) is a novel compound.

[0019]

Next, the present invention will be described in more detail with reference to examples. Example 1 1,8-bis (2-bromoethyl) naphthalene 2.28
9 g and 1,473 g of 1,8-bis (mercaptomethyl) naphthalene in 300 ml of a benzene solution were dissolved in 95% ethanol 75 containing 1.147 g of potassium hydroxide.
0 ml of the stirring solution was added dropwise at room temperature over 24 hours.
After the reaction mixture was further stirred at room temperature for 2.5 hours, the solvent was removed from the resulting suspension under reduced pressure. Water to residue 500
The precipitate was filtered, collected, and dried. The thus obtained crude product was purified by recrystallization from a mixed solvent of ethanol and dichloromethane, and as colorless microcrystals, 1.856 g (yield 70%) of the compound represented by the formula (I) 2, 15-Dithia [4.4] (1,8) naphthalenophane was obtained. Mp. 273.5 ° C (decomposition). R
_{f (SiO 2 / CH 2 Cl} 2); 0.62. M ⁺ (m /
z); 400.

Comparative Example 1 3.08 g of 1,8-bis (mercaptomethyl) naphthalene was added to a stirred solution of 50 ml of DME containing 0.81 g of sodium hydride, and 10 minutes later, 1,8-bis (2-bromoethyl) was added. ) 50 ml of a DME solution in which 2.40 g of naphthalene was dissolved was added over 1 hour. After the reaction solution was further stirred at 50 ° C. for 2 hours, the solvent was removed from the resulting suspension under reduced pressure, and the residue was treated in a usual manner. The product thus obtained was a brown tar-like substance produced by a multimolecular reaction. Example 2 To 16 ml of an acetic acid suspension containing 0.212 g of 2,15-dithia [4.4] (1,8) naphthalenophane (I), 3
6 ml of a 5% hydrogen peroxide solution was added, and the mixture was heated and stirred so as not to boil to cause a reaction. Sixteen hours later, the resulting pale yellow suspension was treated with ice water, and the resulting precipitate was filtered, collected, and dried to give 0.153 g of pale yellow powdery microcrystals.
(Yield 63%) of 2,15-dithia [4.4] (1,8) naphthalenophane derivative represented by the formula (II)
5-dithia [4.4] (1,8) naphthalenophane
2,2,15,15-Tetraoxide was obtained. M
p. 360 ° C (decomposition). M ^<+> (m / z); 464.

[0021]

As described above, according to the present invention, 2,15-dithia [4.4] (1,8) is a novel compound.
Naphthalenophane and its derivative 2,15-dithia [4.4] (1,8) naphthalenophane-2,2,
15,15-Tetraoxide is obtained. Since such compounds have a peculiar reactivity derived from a pericyclic system and a sulfur atom, they can be used as a source for the production of novel polymers such as polyethers and polyesters. It can also be used as a raw material for manufacturing heavy metal scavengers and surfactants. Further, since such a compound has a unique macrocyclic structure, it is expected to be applied to the development of a novel chiral host compound useful as a molecular recognition agent for biological substances such as metal ions and amino acids. The compounds of the present invention also have the advantage that they can be easily produced from the conventionally known substance 1,8-bis (mercaptomethyl) naphthalene.

Claims (4)

(57) [Claims] 1. A 2,15-dithia [4.4] (1,8) naphthalenophane represented by the following formula (I). Formula (I) 2. A 2,15-dithia [4.4] (1,8) naphthalenophane compound represented by the following formula (II). Formula (II) 3. A method comprising reacting 1,8-bis (2-substituted ethyl) naphthalene represented by the following formula (III) with 1,8-bis (mercaptomethyl) naphthalene represented by the following formula (IV): The method for producing 2,15-dithia [4.4] (1,8) naphthalenophane represented by the formula (I) according to claim 1, characterized in that: Formula (III) (In the formula, X is a halogen atom or a sulfonyloxy group.) Formula (IV) 4. The compound represented by the formula (I) according to claim 1,
The 2,15-dithia [4.4] represented by the formula (II) according to claim 2, wherein 15-dithia [4.4] (1,8) naphthalenophane is treated with an oxidizing agent. (1,
8) A method for producing a naphthalenophane compound.