JPH1149724A - Alicyclic dicarboxylic acid diallyl derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative, useful for the production of a polyester having improved chemical resistance. SOLUTION: This method for producing a derivative of a tricyclo [5.2.1.0<2> ,<6> ]decane-8,9-dicarboxylic acid diallyl derivative of formula I [(n) is 0-3], e.g. tricyclo[5.2.1.0<2> ,<6> ]decane-8,9-dicarboxylic acid diallyoxyethyl, is obtained by reacting (A) tricyclo[5.2.1.0<2> ,<6> ]decane-8,9-dicarboxylic acid of formula II with (B) an allyl alcohol derivative of formula III in the presence of (C) 0.1-100 wt.% inorganic mineral acid (sulfuric acid, etc.), heteropolyacid (H3 PW12 O40 , etc.), organic acid (p-toluene sulfonic acid, etc.), cation exchanging resin (amberlite IR120, etc.), or H-type zeolite (H-ZSM-5, etc.), as a catalyst at 50-200 deg.C for 1-50 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to [1]

[0002]

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[0003] The present invention relates to a diallyl derivative of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylate represented by the formula (n represents 0 to 3) and a method for producing the same.

[0004]

2. Description of the Related Art Heretofore, equation [5]

[0005]

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[0006] The tricyclo [5.2.1.0
^2,6 ] de-3-cene-8,9-dicarboxylate diallyl (abbreviated as TDEA) is known (Japanese Patent Publication No. Hei 5-
17228). However, polyesters using TDEA have a problem of unstable chemical resistance due to the presence of a double bond in the cyclopentene ring.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a raw material monomer from which a polyester having improved chemical resistance can be obtained.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention relates to formula [1]

[0009]

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Wherein n represents 0 to 3; and a diallyl derivative of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid. Equation [2]

[0011]

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The tricyclo [5.2.1.0 represented by the following formula:
^2,6 ] decane-8,9-dicarboxylic acid and formula [3]

[0013]

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Wherein an allyl alcohol derivative represented by the formula (n represents 0 to 3) is reacted with an inorganic mineral acid, heteropoly acid, organic acid, cation exchange resin or H-type zeolite as a catalyst. [5.2.1.0 ^2,6 ] decane-8,9- represented by the above formula [1]
The present invention relates to a method for producing a dicarboxylic acid.

Further, the equation [4]

[0016]

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(Wherein, R represents an alkyl group having 1 to 10 carbon atoms).
^{A 2,6} ] decane-8,9-dicarboxylic acid ester derivative and an allyl alcohol derivative represented by the above formula [3] are combined with an inorganic mineral acid, heteropoly acid, organic acid, cation exchange resin, H-type zeolite or II type. A tricyclo [5.2.1.0 ^2,6 ] decane represented by the formula [1], wherein the reaction is carried out using a fatty acid salt of an aromatic compound as a catalyst.
The present invention relates to a method for producing 8,9-dicarboxylic acid.

Hereinafter, the present invention will be described in detail.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a diallyl tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylate derivative represented by the above formula [1] according to the present invention comprises the following reaction: Represented by the scheme.

[0020]

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(Wherein n represents 0 to 3) Tricyclo [5.2.1.0 ^2,6 ] decane as a starting material
8,9-Dicarboxylic acid (hereinafter abbreviated as DH-TCDC) is tricyclo [5.2.1.0 ^2,6 ] de-3-.
It is obtained by reducing sen-8,9-dicarboxylic acid (hereinafter abbreviated as TCD). In addition, this TC
D is tricyclo [5.2.D. Obtained from, for example, dicyclopentadiene, carbon monoxide and alkyl alcohols.
1.0 ^2,6 ] de-3-cene-8,9-dicarboxylic acid.

The allyl alcohol derivative, which is another starting material, has the formula [3]

[0023]

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(Where n represents 0 to 3).
Specific examples include allyl alcohol, ethylene glycol allyl ether, diethylene glycol allyl ether, and triethylene glycol allyl ether. As these raw materials, commercially available products can be used as they are. The use amount is economically 2 to 20 equivalents, more preferably 2 to 8 equivalents to DH-TCDC.

This reaction requires a catalyst. As the catalyst, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used.
Sulfuric acid is preferred. Organic acids such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and trifluoroacetic acid can also be used.
Toluenesulfonic acid is preferred. Furthermore, examples of the catalyst include tungstic acid, molybdic acid, and heteropoly acids thereof. Specific examples of the heteropolyacid include H ₃ P
_{W 12 O 40, H 3 PW} 12 O 40 · 6H 2 O, H 4 SiW
₁₂ O ₄₀ , H ₄ TiW ₁₂ O ₄₀ , H ₅ CoW ₁₂ O ₄₀ , H ₅ Fe
_{W 1 2 O 40, H 6} P 2 W 18 O 62, H 7 PW 11 O 33, H 4 TiM
_{o 12 O 40, H 3 PMo} 12 O 40, H 7 PMo 11 O 39, H 6 P 2
Mo ₁₈ O ₆₂ , H ₄ PMoW ₁₁ O ₄₀ , H ₄ PVMo ₁₁ O ₄₀ ,
H ₄ SiMo ₁₂ O ₄₀ , H ₅ PV ₂ Mo ₁₀ O ₄₀ , H ₃ PMo ₆
Typical examples include W ₆ O ₄₀ and H _0.5 Cs _2.5 PW ₁₂ O ₄₀ . Further, a catalyst in which these are supported on carbon or silica may be used. Among these _{heteropolyacids, H 3 PW 12 O 40,} H 3 PW 12 O 40 · 6H 2 O, H 3 P
Mo ₁₂ O _{40 and the} like are particularly preferred.

Further, cation exchange resins such as Amberlyst IR120, H-type zeolites such as H-ZSM-5, and the like can also be used. The amount of these catalysts used is
0.1 to 100% by weight based on DH-TCDC can be used, and 1 to 20% by weight is economically preferable. In this reaction, a large excess amount of the allyl alcohol derivative can be used, but a solvent can be used by reducing the amount of the allyl alcohol derivative to near the theoretical amount. Examples of the type of the solvent include 1,2-dichloroethane (EDC) and 1,1,1-
Examples include halogenated hydrocarbons such as trichloroethane, aromatic hydrocarbons such as toluene and xylene, and ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether.

The amount of the solvent used is 1 to DH-TCDC.
It is 20 times by weight, more preferably 1 to 6 times by weight. The reaction temperature is 50-200 ° C, more preferably 70-15 ° C.
0 ° C. The reaction can be carried out under normal pressure or under pressure. The reaction time can be 1 to 50 hours, and usually 2 to 12 hours is practical. The reaction can be batch or continuous. The reaction can be tracked by sampling the reaction solution and analyzing it by gas chromatography. After the reaction, when the solvent is used, the target substance can be purified by distillation and / or column chromatography after distilling off the solvent.

Further, as an alternative to the method for producing the compound of the present invention, a transesterification method represented by the following reaction scheme can be carried out.

[0029]

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(R represents an alkyl group having 1 to 10 carbon atoms.) That is, dialkyl tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylate (hereinafter referred to as DH- T
Abbreviated as CDE. ) Is tricyclo [5.2.1.0
^2,6 ] de-3-cene-8,9-dicarboxylate. The alkyl group of DH-TCDE has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.

By reacting the DH-TCDE with the above-mentioned allyl alcohol derivative in the presence of a catalyst, transesterification occurs, and the desired allyl ester derivative is obtained. Examples of the catalyst include mineral acids, heteropoly acids, organic acids, cation exchange resins and H-type zeolites, as well as 3
ZnO-2B ₂ O _3, cadmium acetate, fatty acid salts of Periodic Table Group II compounds such as zinc acetate and calcium acetate and the like can be used.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 A 100 ml four-necked flask was charged with tricyclo [5.2.1.0.
^2,6 ] decane-8,9-dicarboxylic acid (DH-TCDC
13.5 g (60 mmol), 54.3 g of 1,2-dichloroethane and 2.0 g of 97% sulfuric acid were charged, and 14.0 g of allyl alcohol (240 mm
ol) was added dropwise. Subsequently, the mixture was heated and stirred under reflux for 7 hours. After cooling, it was washed with water, washed with a 5% aqueous sodium hydroxide solution, washed with water, concentrated and distilled.

Boiling point: 133-134 ° C./0.3 mmHg
13.0 g of a fraction (40 Pa) was obtained. The analysis results of this oily substance were as follows. Yield 71% MASS (FAB +, e / m (%)): 305 (M +
1, 15), 247 (100), 133 (17), 67
(20). ¹ H-NMR (CDCl ₃ , δ ppm): 1.54 (s,
4H), 1.56 (s, 2H), 1.69 to 1.71.
(M, 1H), 2.22 (d, J = 10.1 Hz, 1
H), 2.45 (s, 2H), 2.48 (s, 2H),
2.96 (s, 2H), 4.44 to 4.56 (m, 4
H), 5.21 (d, J = 10.3 Hz, 2H), 5.
30 (d, J = 17.2 Hz, 2H), 5.84-5.
94 (m, 2H). From the above results, this oily substance was found to be tricyclo [5.2.
1.0 ^2,6 ] decane-8,9-dicarboxylate (abbreviated as TCAE).

Examples 2-8 1.12 g of DH-TCDC (5
mmol), 1.74 g of allyl alcohol (30 mmol
l) and the solvents and catalysts shown in Table 1 were charged and reacted at a predetermined temperature. After completion of the reaction, the reaction solution was analyzed by gas chromatography. The results are shown in Table 1.

[0035]

[Table 1]

Example 9 Tricyclo [5.2.1.0 was placed in a 100 ml four-necked flask.
^2,6 ] decane-8,9-dicarboxylic acid (DH-TCD
C) 2.24 g (10 mmol), 10 g of toluene and 0.45 g of 97% sulfuric acid were charged, and 4.08 g (40 mmol) of allylethoxyethanol was added dropwise with stirring.
Subsequently, the mixture was heated and stirred at reflux (110 ° C.) for 4 hours.
After cooling, wash with water and 5% aqueous sodium hydroxide,
After washing with water, it was concentrated.

The obtained oily substance was purified by column chromatography to give an oily substance having a purity of 98.2% as 3.02.
g were obtained. The analysis results of this oily substance were as follows. MASS (FD +, e / m (%)): 393 (M + 1,
72), 335 (47), 291 (100), 146
(27), 84 (42). ¹ H-NMR (CDCl ₃ , δ ppm): 1.52-1.
56 (m, 6H), 1.67 to 1.73 (m, 1H),
2.18 (d, J = 10.3 Hz, 1H), 2.44
(S, 2H), 2.48 (s, 2H), 2.96 (s, 2H)
2H), 3.61 (t, J = 4.9 Hz, 4H), 4.
00 to 4.02 (m, 4H), 4.08 to 4.13
(M, 2H), 4.19-4.24 (m, 2H), 5.
19 (d, J = 14.3 Hz, 2H), 5.28 (d,
J = 17.2 Hz, 2H), 5.85 to 5.95 (m,
2H). ¹³ H-NMR (CDCl ₃ , δ ppm): 26.6, 2
8.8, 40.5, 44.2, 44.9, 45.3, 6
3.6,67.9,72.0,76.9,77.2,7
7.5, 117.2, 134.5, 173.6 Based on the above results, the oily substance was found to be tricyclo [5.2.
1.0 ^2,6 ] decane-8,9-diallyloxyethyl dicarboxylate (abbreviated as TCAEE). Example 10 The reaction was carried out at 82 ° C. for 9 hours in the same manner as in Example 9 except that the solvent was changed to EDC. This EDC solution was analyzed by gas chromatography to find that TCAEE was 88.8%,
Unreacted DH-TCDC was 5.1%. Example 11 The same procedure as in Example 9 was carried out except that the catalyst was changed to 0.45 g of p-toluenesulfonic acid monohydrate.
The reaction was performed for 4 hours. This EDC solution was analyzed by gas chromatography to find that TCAEE 92.3% and unreacted DH
-TCDC 5.8%. Example 12 4.48 g of DH-TCDC in a 100 ml four-necked flask
(20 mmol), 50 g of toluene, 8.0 g (80 mmol) of allylethoxyethanol and 1.1 g of p-toluenesulfonic acid monohydrate were charged and heated with stirring. The mixture was stirred at 95 ° C. for 24 hours to complete the reaction. Then, after washing with water and a 5% aqueous sodium hydroxide solution, and further washing with water, the toluene phase was concentrated to obtain a crude oily substance 7.2.
g was obtained. The oily crude was distilled under reduced pressure to obtain a fraction bp of 180 to 182 ° C / 0.2 mmHg (26.7P
6.1 g of TCAEE of a) was obtained.

[0038]

The polyester obtained from the alicyclic monomer is known to have excellent physical and chemical properties such as transparency, heat resistance, chemical resistance and dimensional stability. Polyesters to which a saturated alicyclic dicarboxylic acid diallyl derivative is added have excellent properties in which these properties are further improved, and are useful as various optical and structural materials such as optical discs, optical card substrates, and liquid crystal display element substrates. Material.

[Brief description of the drawings]

FIG. 1 ¹ H-NMR of TCAE obtained in Example 1
By chart.

FIG. 2 ¹ H-NM of TCAEE obtained in Example 9
Chart by R.

FIG. 3 ¹³ H-NM of TCAEE obtained in Example 9
Chart by R.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 67/03 C07C 67/03 67/08 67/08 // C07B 61/00 300 C07B 61/00 300

Claims (3)

[Claims] [Claim 1] Formula [1] (In the formula, n represents 0 to 3.) A diallyl derivative of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylate represented by the following formula: 2. Formula [2] Tricyclo [5.2.1.0 ^2,6 ] decane represented by
8,9-dicarboxylic acid and a compound of the formula [3] (Wherein n represents 0 to 3), wherein an allyl alcohol derivative represented by the following formula is reacted with an inorganic mineral acid, a heteropoly acid, an organic acid, a cation exchange resin or an H-type zeolite as a catalyst. 1] (In the formula, n represents 0 to 3.) A method for producing a diallyl derivative of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid represented by the following formula: 3. Formula [4] (Wherein, R represents an alkyl group having 1 to 10 carbon atoms.) Tricyclo [5.2.1.0 ^2,6 ] decane-
An 8,9-dicarboxylic acid ester derivative and a compound of the formula [3] (Wherein n represents 0 to 3) with an allyl alcohol derivative represented by the following formula: using an inorganic mineral acid, a heteropoly acid, an organic acid, a cation exchange resin, an H-type zeolite or a fatty acid salt of a Group II compound as a catalyst. Formula [1] characterized by the following: (In the formula, n represents 0 to 3.) A method for producing a diallyl derivative of tricyclo [5.2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid represented by the following formula: