JP5090107B2 - Method for producing tetrakis (allyloxyphenyl) hydrocarbon compound - Google Patents

Description

  The present invention relates to a method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound, and more particularly to a method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound in a high yield.

  Conventionally, thermosetting resins have been widely used as materials for electrical and electronic parts and structural materials. It is well known that a compound having two or more polymerizable unsaturated bonds is used as a curing agent or a crosslinking agent for curing or crosslinking in such a thermosetting resin. By the way.

  As one of such curing agents and crosslinking agents, for example, 2,2-bis (p-allyloxyphenyl) propane having two allyloxyphenyl groups which are polymerizable functional groups in the molecule is used. As can be mentioned, 2,2-bis (p-allyloxyphenyl) propane is easily produced by allyl etherification of the phenolic OH group of bisphenol A. Specifically, it is produced by reacting bisphenol A with an allyl halide such as allyl chloride in the presence of a basic catalyst such as sodium hydroxide.

  However, in order to obtain a curing agent and a cross-linking agent that give a cured product having high heat resistance, the present inventor used an allyl etherified product of a tetrakisphenol compound having four polymerizable functional groups in the molecule in the same manner as described above. As a result, it became clear that there were major problems in practical use. That is, when a tetrakisphenol compound and allyl chloride were reacted in the presence of a known basic catalyst such as sodium hydroxide, the reaction between the tetrakisphenol compound and allyl chloride hardly progressed. The yield of the allyl etherified tetrakisphenol compound is less than 20%, and it has become clear that improvement of the yield is indispensable for industrial production.

  By the way, in Patent Document 1 and Patent Document 2, 1- (4-allyloxyphenyl) -1,2,2- in which one of four phenolic OH groups of a tetrakisphenol-based compound is allyl etherified. Tris (4-hydroxyphenyl) ethane is disclosed. However, such a compound has only one group having a polymerizable unsaturated bond in the molecule, and is merely a compound different from the desired allyl etherified product of four phenolic OH groups. Is. Patent Document 3 discloses 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane and the like in which four phenolic OH groups of a tetrakisphenol compound are allyl etherified. There, however, nothing is made clear about the method for increasing the yield.

JP-A-7-330652 JP-A-8-208549 Japanese Patent Laid-Open No. 11-43448

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is a tetrakis (allyloxyphenyl) hydrocarbon compound capable of remarkably increasing the yield. It is in providing the manufacturing method of.

  And as a result of the present inventor's earnest examination about the manufacturing method of a tetrakis (allyloxyphenyl) hydrocarbon compound, a yield can be remarkably improved especially by using allyl bromide among allyl halides. As a result, the present invention has been completed.

［式中、Ｒ ¹ 〜Ｒ⁴ は、それぞれ、炭素数１〜４の直鎖状又は分岐鎖を有するアルキル基であり、それらは同一環内又は異なる環内で互いに同一であってもよいし、異なっていてもよく、また、ａ，ｂ，ｃ及びｄは、それぞれ、０又は１〜４の整数である。]

［式中、Ｒ ¹ 〜Ｒ⁴ 、並びにａ，ｂ，ｃ及びｄは、前記一般式（Ｉ）と同じ。]
That is, the present invention relates to a method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound represented by the following general formula (I), wherein the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the following general formula (II) And a method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound, characterized in that is reacted with allyl bromide in the presence of a basic catalyst.

[ Wherein, R ^{1 to} R ⁴ are each an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, and they may be the same in the same ring or in different rings. May be different, and a, b, c and d are each 0 or an integer of 1-4. ]

[ Wherein, R ^{1 to} R ⁴ and a, b, c and d are the same as those in the general formula (I). ]

  Thus, in the method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound according to the present invention, 4 in the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) in the presence of a basic catalyst. Among allyl halides, allyl bromide is used as an allyl substrate (allyl compound) that reacts with two phenolic OH groups to produce allyl ether, and is represented by the general formula (II). The reactivity with the tetrakis (hydroxyphenyl) hydrocarbon compound is remarkably improved. As a result, the yield of the tetrakis (allyloxyphenyl) hydrocarbon compound represented by the general formula (I) as described above is remarkably increased. It is supposed to be.

  By the way, the tetrakis (allyloxyphenyl) hydrocarbon compound produced by the present invention is a compound having a structure represented by the general formula (I), and allyloxy which is a polymerizable functional group in one molecule. It is a tetrakisphenol derivative having four phenyl groups.

In general formula (I), R ^{1 to} R ⁴ are each independently an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group. R ^{1 to} R ⁴ may be the same or different in the same benzene ring or in different benzene rings. Further, a, b, c and d are each 0 or an integer of 1 to 4.

Here, examples of the tetrakis (allyloxyphenyl) represented by the general formula (I) include 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane, 1,1,2,2- Tetrakis (4-allyloxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-allyloxy-2,5-dimethylphenyl) ethane, 1,1,2,2-tetrakis (4-allyloxy- 3,5-dimethylphenyl) ethane, may be mentioned 1,1,2,2-tetrakis (4-allyloxy -5-tert-butyl-2-methylphenyl) ethanone down like.

In the present invention, the tetrakis (allyloxyphenyl) hydrocarbon compound as described above converts the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) into an odor in the presence of a basic catalyst. It is produced by reacting with allyl bromide. Incidentally, during such the general formula (II), R ¹ ~R ⁴ and a, b, c and d, the R ¹ to R ⁴ and a general formula (I), b, are the same as c and d, In order to avoid duplication, the description thereof will be omitted.

  That is, according to the production method according to the present invention, an allyl halide is used as an allyl substrate which is reacted with a phenolic OH group in a tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) to generate an allyl ether. Among them, in particular, since allyl bromide is used, the reactivity with the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) is remarkably improved. The tetrakis (allyloxyphenyl) hydrocarbon compound represented by (I) can be produced with a very high yield in a short reaction time.

  Here, the amount of allyl bromide used is such that all phenolic OH groups in the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) are reacted. Is usually 4.0 mol or more, preferably 4.0 to 20.0 mol, more preferably 6.0 to 10.0 mol, with respect to 1 mol of the tetrakis (hydroxyphenyl) hydrocarbon compound represented by It is desirable to be set to.

  In addition, allyl bromide and the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) can be reacted in the presence of a basic catalyst. Alkali metal hydroxides such as sodium, potassium hydroxide and lithium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal phosphates such as sodium phosphate; sodium methoxide, sodium ethoxide and sodium butoxide Alkali metal alcoholates such as trimethylamine, triethylamine, diisopropylethylamine, pyridine, tertiary, such as 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane Amines, etc., one of which is simply In, or two or more are combined with. Among these, when an alkali metal hydroxide, an alkali metal carbonate, or potassium carbonate is used, the final product of the present invention can be obtained in a higher yield.

  Here, as the usage-amount of this basic catalyst, a general usage-amount is employ | adopted, with respect to 1 equivalent of phenolic OH groups of the tetrakis (hydroxyphenyl) hydrocarbon compound shown by General formula (II), Usually, it is used so that it becomes 1 equivalent or more, preferably 1.5 equivalent to 4 equivalent.

  In addition, the solvent used in the reaction of the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) and allyl bromide is not particularly limited, and a solvent similar to the conventional solvent is appropriately used. It will be selected and used. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol and butanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, dimethyl Examples include formamide, N-methylpyrrolidone, and mixtures thereof. Among these, the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) as a raw material is dissolved, while the tetrakis (allyloxyphenyl) hydrocarbon represented by the general formula (I) as a product is dissolved. If a solvent that does not dissolve the compound is used, the product can be easily isolated and purified, and the yield can be further increased. For example, when 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane is produced, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane is dissolved and 1,1,2, , 2-tetrakis (4-allyloxyphenyl) ethane that does not dissolve can be suitably employed.

  Furthermore, the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the general formula (II) is reacted with allyl bromide to produce a tetrakis (allyloxyphenyl) hydrocarbon compound represented by the general formula (I). In this case, it is desirable to react in an inert gas atmosphere such as nitrogen. Moreover, reaction temperature is 10-120 degreeC normally, Preferably it sets in the range of 20-110 degreeC suitably. If the reaction temperature is less than 10 ° C., the reaction takes a long time. Conversely, if it exceeds 120 ° C., a side reaction occurs. Moreover, although reaction time changes according to reaction temperature and mixing | blending conditions, generally it is desirable to set it as about 1 to 24 hours.

  Thus, in the presence of a basic catalyst, the tetrakis (hydroxyphenyl) hydrocarbon compound represented by the above general formula (II) and allyl bromide are reacted in a predetermined solvent by heating for a predetermined time. Thus, the tetrakis (allyloxyphenyl) hydrocarbon compound represented by the general formula (I) is produced. And a product will be isolated and refine | purified after completion | finish of reaction. The isolation / purification method is not particularly limited, and a conventionally known method can be adopted.For example, an organic solvent such as ethyl acetate is added to the product after completion of the reaction including a catalyst and the like. Water is added, and the organic phase is separated by liquid separation treatment. Further, water is added to the organic phase, and the organic phase is washed several times with water, and then concentrated under reduced pressure to distill off the organic solvent. If necessary, a method of washing with an appropriate solvent can be suitably employed.

  The tetrakis (allyloxyphenyl) hydrocarbon compound represented by the general formula (I) produced as described above has four allyloxyphenyl groups which are polymerizable functional groups in one molecule. For example, it is advantageously used as a curing agent or a crosslinking agent for a thermosetting resin because it has a property of giving a cured product having high heat resistance.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements and the like can be added.

Example 1
In a reaction vessel equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introducing tube, 21.2 g (53.2 mmol) of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, potassium carbonate 29. 8 g (215.6 mmol) and 100 g of methanol were charged, and mixed with stirring while blowing nitrogen. Next, 38.6 g (318.9 mmol) of allyl bromide was added thereto, the temperature was raised to 65 ° C., and the mixture was reacted at that temperature for 2 hours. Then, it cooled to room temperature and obtained white solid by filtration. The obtained solid was dissolved in ethyl acetate, water was added to the organic phase, and the mixture was stirred, washed and separated to remove the aqueous phase containing potassium carbonate and the like. Further, the operation of adding water to the organic phase and washing it was repeated several times until the pH of the aqueous phase became neutral, and then the washed organic phase was concentrated under reduced pressure until crystal precipitation was observed. Next, a large amount of methanol was added, followed by cooling and crystallization, followed by filtration and drying to obtain 25.4 g (45.5 mmol) of product. The yield was determined by dividing the number of moles of the obtained product by the number of moles of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (53.2 mmol) used as a raw material. As shown in Table 1, the yield was 85.5%.

  In addition, when the obtained product was analyzed on the purity analysis conditions and melting | fusing point analysis conditions shown below, purity was 97.4% and melting | fusing point was 128 degreeC. Moreover, when the obtained product was investigated by the nuclear magnetic resonance method (NMR method), as shown by the NMR spectrum (1H-NMR, solvent: deuterated chloroform) of FIG. 1, 1,1,2,2 -It was confirmed that it was tetrakis (4-allyloxyphenyl) ethane.

<Purity analysis>
Purity analysis was performed by JASCO High Performance Liquid Chromatography LC-2000Plus (column: Shiseido SUPERIOREX ODS, carrier: 0.1% phosphoric acid aqueous solution / acetonitrile = 50 / 50-0 / 100 gradient, 1 ml / min, detector: UV detector (254 nm).
<Melting point analysis>
The melting point was analyzed using a Rigaku thermal analyzer DSC 8320 type (heating rate: 5 ° C./min, N ₂ flow rate: 60 ml / min).

Example 2
In Example 1 above, the white product was obtained in the same manner as in Example 1 except that potassium carbonate was changed to 17.2 g (431.2 mmol) of sodium hydroxide and the reaction time was extended to 5 hours. As a result, 19.9 g (35.6 mmol) of 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane was obtained. Then, the purity of the obtained product was analyzed in the same manner as in Example 1, and it was 97.1%. The yield was 67.0% as shown in Table 1 below.

Example 3
In Example 1 above, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was replaced with 24.2 g (53.2 mmol) of 1,1,2,2-tetrakis (4-hydroxy-3-methylphenyl) ethane. Except that the reaction time was extended to 5 hours, and the same operation as in Example 1 was performed to obtain 1,1,2,2-tetrakis (4-allyloxy-3-methyl), which is a white product. 23.1 g (37.6 mmol) of phenyl) ethane were obtained. And it was 94.1% when the purity of the obtained product was analyzed like Example 1. FIG. The yield was 70.6% as shown in Table 1 below.

Comparative Example 1
In Example 1 above, allyl bromide was changed to 24.4 g (318.9 mmol) of allyl chloride, and the reaction time was extended to 24 hours. Thus, 10.1, g (18.1 mmol) of 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane was obtained. And when it analyzed like Example 1 and the purity of the obtained product was 97.0%. The yield was 34.0% as shown in Table 1 below.

Comparative Example 2
In Example 1 above, allyl bromide was changed to 24.4 g (318.9 mmol) of allyl chloride, and potassium carbonate was changed to 17.2 g (431.2 mmol) of sodium hydroxide, and the reaction time was changed to 24 hours. The same operation as in Example 1 was performed except that the product was extended to 5.4 g (9.7 mmol) of 1,1,2,2-tetrakis (4-allyloxyphenyl) ethane as a white product. It was. Then, the purity of the obtained product was analyzed in the same manner as in Example 1, and it was 96.6%. The yield was 18.2% as shown in Table 1 below.

Comparative Example 3
In Example 1, allyl bromide was changed to 24.4 g (318.9 mmol) of allyl chloride, and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was changed to 1,1,2,2 -Tetrakis (4-hydroxy-3-methylphenyl) ethane was changed to 24.2 g (53.2 mmol), and the reaction time was extended to 24 hours. 14.8 g (12.8 mmol) of 1,2,2-tetrakis (4-allyloxy-3-methylphenyl) ethane was obtained. And when it analyzed like Example 1 and the purity of the obtained product was 93.5%. The yield was 24.0% as shown in Table 1 below.

  As is apparent from the results in Table 1, when allyl bromide is used as the allyl substrate to be reacted with the phenolic OH group, the yield is high even when the reaction time is short. Recognize. In particular, when allyl bromide is used as the allyl substrate and potassium carbonate is used as the basic catalyst, a yield of 85.5% is achieved in 2 hours, and the yield is significantly improved. It is recognized that

2 is an NMR spectrum of the product obtained in Example 1.

Claims (1)

A method for producing a tetrakis (allyloxyphenyl) hydrocarbon compound represented by the following general formula (I),
Production of tetrakis (allyloxyphenyl) hydrocarbon compound characterized by reacting tetrakis (hydroxyphenyl) hydrocarbon compound represented by the following general formula (II) with allyl bromide in the presence of a basic catalyst Method.

[ Wherein, R ^{1 to} R ⁴ are each an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, and they may be the same in the same ring or in different rings. May be different, and a, b, c and d are each 0 or an integer of 1-4. ]

[ Wherein, R ^{1 to} R ⁴ and a, b, c and d are the same as those in the general formula (I). ]

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