JPH11279119A - 1,8-bis(substituted ethyl)naphthalene compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound substituted with a group having an active group, e.g. alkoxycarbonyl group at the peri-position of naphthalene and useful as e.g. a raw material for synthesizing new type polymers crosslinked at peri- positions, heavy metal scavenger. SOLUTION: This new compound is expressed by formula I [R<1> is H or the like; R<2> is an alkyl or the like; (n) is 2 or 3], e.g. 1,8-bis(2',2'- diethoxycarbonylethyl)naphthalene. The compound of formula I is obtained by reacting (A) 1,8-bis(substituted ethyl)naphthalene of formula II [e.g. 1,8-bis(bromomethyl)naphthalene] with (B) a compound of the formula, HC(COOR<2> )3 (e.g. trlethoxycarbonylmethane) in the presence of (C) (i) a basic catalyst, e.g. sodium ethoxide or (ii) a phase-transfer catalyst, e.g. tetrabutylammonium chloride, preferably, in a solvent, e.g. ethanol, preferably, at 70-90 deg.C, normally for 5-20 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 1,8-bis (substituted ethyl) naphthalene compound and a method for producing the same.

[0002]

2. Description of the Related Art Compounds having an active group at the peri-position of naphthalene are expected as new materials that can be used in various applications, such as new polymers crosslinked at the peri-position. Further, depending on the characteristics of the active group, utilization as a raw material of a heavy metal scavenger is expected. As one of such compounds, naphthalene in which the peri position is substituted with a group having an alkoxycarbonyl group is considered, but this is a compound that is difficult to synthesize and has not been described in any literature.

[0003]

Accordingly, the present invention provides
An object of the present invention is to provide a novel compound in which the peri position of naphthalene is substituted with a group having an active group such as an alkoxycarbonyl group, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, by using trialkoxycarbonylmethane as the alkyl acceptor, the peralkylation of the naphthalene at the peri-position proceeds and the efficiency is improved. It has been found that 1,8-bis (alkoxycarbonylethyl) naphthalene compound is often formed, and the present invention has been accomplished based on this finding. That is, the present invention relates to (1) Formula (I)

[0005]

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Wherein R ¹ is a hydrogen atom or an alkyl group;
Cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an alkylthio group, an arylthio group, a sulfinyl group, a sulfonyl group, a nitro group, an ester group or carboxyl group, R ² is an alkyl Group, cycloalkyl group, aryl group, aralkyl group or heterocyclic group. n represents 2 or 3. 1,8-bis (substituted ethyl) represented by)
Naphthalene compounds, and (2) Formula (II)

[0007]

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Wherein R ¹ has the same meaning as defined in formula (I), and R ³ represents an electron withdrawing group.
An 8-bis (substituted methyl) naphthalene and a compound represented by the formula (III) HC (COOR ² ) ₃ (wherein R ² has the same meaning as defined in the formula (I)) are used as a base catalyst or an interphase. An object of the present invention is to provide a method for producing a 1,8-bis (substituted ethyl) naphthalene compound represented by the formula (I) described in (1), wherein the reaction is carried out in the presence of a transfer catalyst.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention has the above formula (I)
Is represented by In the formula, R ¹ represents a hydrogen atom or an alkyl group (saturated or unsaturated, linear or branched; preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 5 to 6 carbon atoms), aryl Group (preferably having 6 carbon atoms)
-10), an aralkyl group (preferably having 7 to 9 carbon atoms),
Heterocyclic group (preferably a 5- to 6-membered ring, preferably oxygen, nitrogen, sulfur as a hetero atom), alkoxy group (preferably having 1 to 4 carbon atoms), aryloxy group (preferably having 6 to 10 carbon atoms), amino group An alkylthio group (preferably having 1 to 4 carbon atoms) and an arylthio group (preferably having 6 carbon atoms)
To 10), a sulfinyl group (e.g., preferably an alkylsulfinyl group having 1 to 4 carbon atoms, preferably 6 carbon atoms)
An arylsulfonyl group having 10 to 10 carbon atoms, a sulfonyl group (e.g., preferably an alkylsulfonyl group preferably having 1 to 4 carbon atoms, preferably an arylsulfonyl group having 6 to 10 carbon atoms), a nitro group, an ester group (e.g., preferably An alkoxycarbonyl group having 1 to 4 carbon atoms) or a carboxyl group.

In the formula (I), R ² is an alkyl group (preferably having 1 to 6 carbon atoms, which may be saturated or unsaturated, linear or branched. For example, primary alkyl groups such as methyl, ethyl and the like) , A secondary alkyl group such as isopropyl and isobutyl, a tertiary alkyl group such as t-butyl and t-pentyl), a cycloalkyl group (preferably having 5 to 5 carbon atoms).
6), an aryl group (preferably having 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 9 carbon atoms) or a heterocyclic group (preferably a 5- to 6-membered ring, preferably oxygen, nitrogen, and sulfur as hetero atoms) It is. These may be substituted with a halogen atom or the like. n is 2 or 3;
When n is 2, the compound of the formula (I) is 1,8-bis (2 ′,
2′-disubstituted ethyl) naphthalene, when n is 3, 1
8-bis (2 ′, 2 ′, 2′-trisubstituted ethyl) naphthalene.

The compound of the formula (I) of the present invention has the above-mentioned formula (I)
It is obtained by reacting 1,8-bis (substituted methyl) naphthalene represented by I) with a compound represented by formula (III) in the presence of a base catalyst or a phase transfer catalyst. In formula (II), R ¹ has the same meaning as in formula (I), and R ³ represents an electron withdrawing group. Examples of R ³ include a halogen atom (eg, chlorine, bromine or iodine atom), a sulfonyloxy group (eg, an alkylsulfonyloxy group such as a mesyloxy group, and an arylsulfonyloxy group such as a tosyloxy group). In formula (III), R ² has the same meaning as in formula (I).

In the present invention, when the compound represented by the formula (II) is reacted with the compound represented by the formula (III) in the presence of a base catalyst, a compound of the formula (I) wherein n is 2 is obtained. . Examples of the base catalyst that can be used in the present invention include potassium t-butoxide and sodium t-butoxide.
Alkoxides such as pentoxide, sodium ethoxide, sodium methoxide and sodium isopropoxide; metal hydrides such as sodium hydride and potassium hydride; and metal amides such as sodium amide. The amount of the base catalyst used is usually the formula (II)
2 to 3 mol, preferably 2.2 mol, per 1 mol of compound
~ 2.3 mol. This base catalyst is reacted with the compound of the formula (II) and the compound of the formula (III) by heating and stirring. At this time, the compound of the formula (III) is used in an amount of usually 2 to 2.5 mol, preferably 2.1 to 1 mol of the compound of the formula (II).
To 2.2 mol. The reaction temperature is preferably between 50 and 12
0 ° C, more preferably 70 to 90 ° C. The reaction time is not particularly limited, but is usually 5 to 20 hours.

This reaction is preferably carried out in a solvent,
For example, alcohols (methanol, ethanol, 2-propanol, t-butanol, t-pentanol, etc.), ethers (dimethoxyethane, dioxane, etc.), aromatic solvents (benzene, etc.), halogen solvents (dichloromethane, etc.), An aprotic polar solvent (acetonitrile, dimethylformamide, dimethylsulfoxide, etc.) or a mixed solvent thereof can be used. After the reaction, the resulting crude product is subjected to an extraction treatment according to a conventional method and recrystallized to obtain a target 1,8-bis (2 ′, 2′-disubstituted ethyl) naphthalene compound.

Further, the compound represented by the formula (II) and the compound represented by the formula (I
When the compound represented by the formula (II) is reacted in the presence of a phase transfer catalyst, a compound of the formula (I) wherein n is 3 is obtained. As the phase transfer catalyst that can be used in the present invention, a tetraalkylammonium salt (for example, tetrabutylammonium chloride, tetrabutylammonium bromide) is preferable. The amount of the phase transfer catalyst to be used is generally 0.5 to 1.3 mol, preferably 0.7 to 1.0 mol, per 1 mol of the compound of the formula (II). The phase transfer catalyst is reacted with the compound of the formula (II) and the compound of the formula (III) by stirring. At this time, the compound of the formula (III) is usually used in an amount of 2 to 3 moles per mole of the compound of the formula (II),
Preferably, it is 2.3 to 2.5 mol. The reaction temperature is preferably 10 to 60C, more preferably 20 to 40C. The reaction time is not particularly limited, but is usually 10 to 25 hours.

This reaction is preferably carried out in a solvent,
For example, it is preferable to add an alkaline aqueous solution together with an aromatic solvent (such as benzene) or a halogen-based solvent (such as chloroform or dichloromethane). The alkaline aqueous solution preferably has a pH of 10 to 12, and the amount used is preferably 0.2 to 0.3 with respect to the solvent 1 in a volume ratio. After the reaction, the resulting crude product is subjected to extraction treatment according to a conventional method and purified by chromatography or the like to obtain the desired 1,8-bis (2 ′, 2 ′, 2′-trisubstituted ethyl) naphthalene compound Is obtained.

Among the compounds represented by formula (I) of the present invention, those in which R ² has polymerizability (for example, R ² is vinyl, methacryl, 2-chloroallyl, 4-vinylphenyl, 4-vinyl) The compound having a benzyl group or the like) can be homopolymerized or copolymerized by a commonly used method such as radical polymerization or ionic polymerization, and can be a polymer crosslinked at the peri position. Further, the ester group of the compound represented by the formula (I) is reacted with an amine (eg, a diamine) to form a polyamide, the polyester is reacted with an alcohol (eg, a diol), or the polyester represented by the formula (I). It is also possible to obtain a polyether or a polyester by converting the ester group of the compound to be converted to a hydroxyl group or the like.

[0017]

Next, the present invention will be described in more detail with reference to examples. Example 1 To 15 ml of an ethanol solution of 1.00 g of triethoxycarbonylmethane and 0.31 g of sodium ethoxide,
0.63 g of 1,8-bis (bromomethyl) naphthalene was added, and the mixture was heated under reflux for 6 hours. After the reaction, the crude crystals obtained by extraction in a conventional manner were recrystallized from hexane to give 0.565 g (yield 60%) of pure 1,8-bis (2′2′-) as colorless microcrystals. Diethoxycarbonylethyl) naphthalene was obtained. Melting point: 92.5-94 ° C Elemental analysis: C 66.32, H 6.91 Calculated: C 66.08, H 6.83 (C ₂₆ H ₃₂ O ₈ ) Rf (silica gel / dichloromethane): 0 .35 M ⁺ (m / z): 472 νC = O: 1740 cm ⁻¹ δ ¹ H (deuterated chloroform): 1.10 (t, J = 7.5)
Hz, 12H), 3.70 (m, 6H), 4.12
(Q, J = 6.5 Hz, 8H), 7.25-7.85
(M, 6H)

Example 2 1.995 g of triethoxycarbonylmethane, 1,8-
A 25% aqueous sodium hydroxide solution 1 was added to 40 ml of a dichloromethane solution of 1.125 g of bis (bromomethyl) naphthalene and 0.80 g of tetrabutylammonium chloride.
0 ml was added. After stirring at room temperature for 18 hours, the crude product obtained by extraction treatment in a conventional manner was purified by silica gel chromatography, and 1.566 g (yield: 71%) was obtained.
, Pure 1,8-bis (2 ', 2', 2'-triethoxycarbonylethyl) naphthalene (colorless paste) was obtained. Elemental analysis Measured value: C 62.01, H 6.84 Calculated value: C 62.32, H 6.54 (C ₃₂ H
₄₀ O ₁₂ ) Rf (silica gel / dichloromethane): 0.40 M ⁺ (m / z): 616 νC = O: 1740 cm ⁻¹ δ ¹ H (deuterated chloroform): 1.03 (t, J = 7.5)
Hz, 18H), 4.01 (q, J = 7.5 Hz, 12
H), 4.32 (s, 4H), 7.16-7.75.
(M, 6H)

[0019]

The novel 1,8-bis (substituted ethyl) naphthalene compound of the present invention has a unique property because it has an active group at the peri-position of naphthalene, and is used as a raw material for a new polymer crosslinked at the peri-position. It can also be used as a raw material for heavy metal scavengers. The method for producing the compound of the present invention is simple, can be mass-produced, and can be suitably carried out industrially.

Claims (2)

[Claims] 1. A compound of the formula (I) (Wherein R ¹ is a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an alkylthio group,
Arylthio group, a sulfinyl group, a sulfonyl group, a nitro group, an ester group or carboxyl group, R ²
Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group. n represents 2 or 3. )
1,8-bis (substituted ethyl) naphthalene compound represented by the formula: 2. A compound of the formula (II) (Wherein R ¹ has the same meaning as defined in formula (I), and R ³
Represents an electron withdrawing group. 1,8-bis (substituted methyl) naphthalene represented by the formula (III) HC (COOR ² ) ₃ (wherein R ² has the same meaning as defined in the formula (I)) Is reacted in the presence of a base catalyst or a phase transfer catalyst, the method for producing a 1,8-bis (substituted ethyl) naphthalene compound represented by the formula (I) according to claim 1.