JP4788858B2 - Isophthalic acid compound and process for producing the same - Google Patents

Description

【０００７】
（式中、Ｒ⁵、Ｒ⁶及びＲ⁷はそれぞれ独立に水素原子または式［２］
【０００８】
【化１２】

【０００９】
（式中、Ｒ¹は水素原子または炭素数１〜４のアルキル基を表し、Ｒ²及びＲ³ は、水素原子または炭素数１〜１０のアルキル基を表す。）
で表される（置換）アクリロイル基を表し、少なくとも一つ以上は（置換）アクリロイル基を示す。）
で表されるイソフタル酸化合物及びその製造法に関する。
【００１０】
又、本発明は、式［３］
【００１１】
【化１３】

【００１２】
で表されるビス（２−ヒドロキシエチル）５−ヒドロキシイソフタレート（ＢＨ５ＨＩ）と式［４］
【００１３】
【化１４】

【００１４】
（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、前記と同じ意味を表す。）
で表される（置換）アクリル酸化合物とを、酸触媒下反応させるか、また、
前記式［３］で表されるＢＨ５ＨＩと式［５］
【００１５】
【化１５】

【００１６】
（式中、Ｒ¹、Ｒ²及びＲ³は、前記と同じ意味を表し、Ｘは、ハロゲン原子を表す。）
で表されるアクリル酸ハライド化合物を塩基、金属及び金属化合物の存在下で反応させて、前記式［１］で表されるイソフタル酸化合物の製造法に関する。以下、本発明を詳細に説明する。
【００１７】
【発明の実施の形態】
本発明の前記式［１］で表されるイソフタル酸化合物の製造法は、下記の二つの反応スキームで表される。
【００１８】
【化１６】

【００１９】
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＸは、前記と同じ意味を表す。）
先ず（１）から説明する。原料の式［３］で表されるＢＨ５ＨＩは、特願２０００−２０６４９９号に記載の様に、５−ヒドロキシイソフタル酸化合物とエチレングリコールを原料として、酸、金属又は金属化合物を触媒として効率良く製造することができる。
【００２０】
一方、一般式［４］で表されるアクリル酸化合物は、Ｒ¹が水素または炭素数１〜４のアルキル基を表し、好ましくは水素原子または炭素数１〜２である。また、Ｒ²、Ｒ³及びＲ⁴は炭素数１〜１０であり、好ましくは水素原子または炭素数１〜５である。
【００２１】
具体的には、アクリル酸、メタアクリル酸、チグリル酸、３，３−ジメチルアクリル酸、２−メチル−２−ペンテン酸、２−エチル−２−ヘキセン酸及び２−オクテン酸等、及びそれらの炭素数１〜１０のアルキルエステル化合物、具体的には、アクリル酸メチル、アクリル酸エチル、メタアクリル酸メチル、メタアクリル酸エチル、チグリル酸メチル、チグリル酸エチル、３，３−ジメチルアクリル酸メチル、３，３−ジメチルアクリル酸エチル、２−メチル−２−ペンテン酸メチル、２−メチル−２−ペンテン酸エチル、２−エチル−２−ヘキセン酸メチル、２−エチル−２−ヘキセン酸エチル、２−オクテン酸メチル及び２−オクテン酸エチル等が挙げられる。
【００２２】
本反応は、酸触媒が必要であり、酸触媒としては、硫酸、塩酸及び硝酸等の鉱酸が使用でき、特には、硫酸が好ましい。また、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸及びトリフルオロ酢酸等の有機酸も使用でき、特にはベンゼンスルホン酸、ｐ−トルエンスルホン酸が好ましい。アクリル酸化合物の使用量は、理論量から大過剰量を用いることができる。
【００２３】
更に、酸触媒としてタングステン酸、モリブデン酸或いはこれらのヘテロポリ酸が挙げられる。ヘテロポリ酸の具体例としては、Ｈ₃ＰＷ₁₂Ｏ₄₀、Ｈ₄ＳｉＷ₁₂Ｏ₄₀、Ｈ₄ＴｉＷ₁₂Ｏ₄₀、Ｈ₅ＣｏＷ₁₂Ｏ₄₀、Ｈ₅ＦｅＷ₁₂Ｏ₄₀、Ｈ₆Ｐ₂Ｗ₁₈Ｏ₆₂、Ｈ₇ＰＷ₁₁Ｏ₃₃、 Ｈ₄ＴｉＭｏ₁₂Ｏ₄₀、Ｈ₃ＰＭｏ₁₂Ｏ₄₀、Ｈ₇ＰＭｏ₁₁Ｏ₃₉、Ｈ₆Ｐ₂Ｍｏ₁₈Ｏ₆₂、Ｈ₄ＰＭｏＷ₁₁Ｏ₄₀、Ｈ₄ＰＶＭｏ₁₁Ｏ₄₀、Ｈ₄ＳｉＭｏ₁₂Ｏ₄₀、Ｈ₅ＰＶ₂Ｍｏ₁₀Ｏ₄₀、Ｈ₃ＰＭｏ₆Ｗ₆Ｏ₄₀、Ｈ_0.5Ｃｓ_2.5ＰＷ₁₂Ｏ₄₀及びそれらの水和物等が代表的なものとして挙げられる。また、これらを炭素やシリカに担持させた触媒等が挙げられる。これらのヘテロポリ酸の中では、Ｈ₃ＰＷ₁₃Ｏ₄₀、Ｈ₃ＰＭｏ₁₂Ｏ₄₀及びそれらの水和物等が特に好ましい。
【００２４】
また更に、アンバーリストＩＲ１２０等の陽イオン交換樹脂、Ｈ−ＺＳＭ−５等のＨ型ゼオライト等も使用することができる。
【００２５】
特に、エステル交換法の場合の触媒としては、前述の鉱酸類、ヘテロポリ酸類、有機酸、陽イオン交換樹脂及びＨ型ゼオライトの他に、３ＺｎＯ−２Ｂ₂Ｏ₃ 、酢酸カドミウム、酢酸亜鉛及び酢酸カルシウムに代表される周期律表第II族化合物の脂肪酸塩等が使用できる。これらの触媒の使用量は、ＢＨ５ＨＩに対し０．１〜１００重量％が使用でき、経済的には、１〜２０重量％が好ましい。
【００２６】
本反応は、アクリル酸化合物を大過剰用いることもできるが、溶媒を用いて行うこともでき、通常は、溶媒を使用することが好ましい。溶媒の種類としては、１，２−ジクロロエタン（ＥＤＣ）や１，１，１−トリクロロエタン等のハロゲン化炭化水素類、ベンゼン、トルエンやキシレン等の芳香族炭化水素類、１，２−ジメトキシエタンやジエチレングリコールジメチルエーテル等のエーテル類等が挙げられる。
【００２７】
溶媒の使用量は、ＢＨ５ＨＩに対し１〜２０重量倍、より好ましくは１〜６重量倍である。反応温度は、５０〜２００℃、より好ましくは７０〜１５０℃である。反応は常圧でも加圧でも行うことができる。反応時間は、１〜５０時間で行うことができ、通常２〜１２時間で行うのが実用的である。
【００２８】
次に、反応スキーム（２）の製造法について述べる。一般式［５］で表されるアクリル酸ハライド化合物は、そのＲ¹、Ｒ²及びＲ³は前記と同じであり、具体的には、アクリル酸、メタアクリル酸、チグリル酸、３，３−ジメチルアクリル酸、２−メチル−２−ペンテン酸、２−エチル−２−ヘキセン酸及び２−オクテン酸等のハライドである。ハロゲンの種類としては、沸素、塩素、臭素及び沃素であり、経済的には塩素である。特には、アクリル酸クロライドやメタアクリル酸クロライドが使用される。その使用量は、ＢＨ５ＨＩの理論量に対し１〜２モル倍、より好ましくは１〜１．５モル倍である。
【００２９】
本反応は、塩基が必要であり、その例としては、アルカリ金属やアルカリ土金属の炭酸塩や水酸化物等の無機塩基、脂肪族や芳香族の有機塩基及びアルカリ金属やアルカリ土金属の脂肪酸塩等が使用できる。その具体例としては、炭酸ナトリウム、炭酸カリウム、炭酸マグネシウム、炭酸カルシウム、炭酸水素ナトリウム、炭酸水素カリウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、トリメチルアミン、トリエチルアミン、トリプロピルアミン、ピリジン、ピコリン、アニリン、酢酸ナトリウム及び蓚酸ナトリウム等が一例として挙げられる。特には、炭酸ナトリウムやトリエチルアミンが好ましい。その使用量は、ＢＨ５ＨＩの理論量に対し１〜２モル倍、より好ましくは１〜１．５モル倍であり、アクリル酸ハライド化合物と等量が好ましい。又、金属又は金属水素化錯体を用いることもできる。
【００３０】
金属としては、周期律表第１族のアルカリ金属及び第２族のアルカリ土金属が適応でき、具体的には、リチウム、ナトリウム、カリウム、マグネシウム及びカルシウム等である。更に金属化合物としては、水素化リチウム、水素化ナトリウム、水素化カリウム、水素化アルミニウムリチウム、水素化アルミニウムナトリウム、水素化アルミニウムカリウム、水素化ホウ素リチウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム等の金属水素化錯体、水酸化ナトリウム、水酸化カリウム等の金属水酸化物、炭酸ナトリウム、炭酸カリウム等の金属炭酸塩等が挙げられる。特には、ナトリウムや水素化ナトリウムが好ましい。その使用量は前記と同様である。
【００３１】
本反応は、溶媒を使用することが好ましい。溶媒の種類としては、テトラヒドロフラン（ＴＨＦ）、ジオキサン、１，２−ジメトキシエタンやジエチレングリコールジメチルエーテル等のエーテル等が挙げられる。溶媒の使用量は、ＢＨ５ＨＩに対し１〜２０重量倍、より好ましくは１〜６重量倍である。反応温度は、−２０〜１００℃、特には０〜５０℃が好ましい。
【００３２】
反応後は、水を添加し、残余酸クロライドを加水分解してから、溶媒を留去し、難水溶性溶媒（エーテル系やエステル系）で抽出した後、蒸留又はカラムクロマトグラフィーで精製し、目的物を得ることができる。以上の本発明の反応及び精製は、回分式でも連続式でも可能である。以下に、本反応によって得られる生成物を挙げる。
【００３３】
【化１７】

【００３４】
（式中、Ｒ¹、Ｒ²及びＲ³は、前記と同じ意味を表す。）
【００３５】
【実施例】
以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１
【００３６】
【化１８】

【００３７】
１００ｍｌ四口反応フラスコにＢＨ５ＨＩ１．３５ｇ（５ｍｍｏｌ）とＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）１７ｇを仕込み、５℃に冷却した。この撹拌下に、水素化ナトリウム（純度６０％）０．７２ｇ（１８ｍｍｏｌ）を添加し１．５時間攪拌した。更に、５℃でメタアクリロイルクロライド３．１４ｇ（３０ｍｍｏｌ）を滴下した。５℃で１時間撹拌を続けた後、更に２５℃で６時間反応させた。反応液に氷を添加してから濃縮しＤＭＡｃを留去した。残渣に酢酸エチル／水を加えて抽出し、濾過により不溶固形物を除去後、濾液の有機層を濃縮乾燥すると油状物３．４４ｇが得られた。この油状物をｎ−ヘプタン／酢酸エチル＝１９／１〜３／１でシリカゲルカラムクロマトグラフィーにより精製すると、１，３−ビス（２−メタアクリロイルオキシエトキシカルボニル）−５−メタアクリロイルオキシベンゼン（ＢＭＭＢと略記する。）０．５９ｇ（収率２４．９％）が得られた。
【００３８】
MASS(FAB⁺,m/e(%))：475([M+H]⁺,15),431(25),389(63),345(94),124(100),113(100).
¹H-NMR(CDCl₃,δppm)：1.82(s,６H),1.95(s,3H),4.38 (dd,J₁=3.21Hz,J₂=4.74Hz,4H), 4.49 (dd,J₁=3.21Hz,J₂=4.74Hz,4H),5.48(t,J=1.53Hz,2H),5.71(d,J=1.53Hz,1H), 6.03(s,2H),6.28(s,1H),7.89(dd,J₁=1.53Hz,J₂=3.36Hz,2H), 8.45(t,J=1.52Hz,1H)．
¹³C-NMR(CDCl₃,δppm)：17.78(2),17.81,61.98(2),62.93(2),125.96(2),127.16(2),127.68,127.93,131.39(2),134.84,135.45(2),150.66,164.24,164.99,166.87．[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an isophthalic acid compound having a (substituted) acryloyl group and a method for producing the same. The compound of the present invention relates to radical polymerization and ultraviolet curable monomers in the field of materials such as EL (electroluminescence) protective film resins, dental adhesives and special paints.
[0002]
[Prior art]
In JP-A-5-214045, there are descriptions of acryloyl compounds of existing aromatic carboxylic acids such as benzoic acid, phthalic acid, trimellitic acid and pyromellitic acid, but sufficient results have not yet been obtained.
[0003]
[Problems to be solved by the invention]
An object is to provide a monomer having 1 to 3 (substituted) acryloyl groups as a raw material for an acrylic polymer.
[0004]
[Means for Solving the Problems]
In order to solve the above problems, the present inventor has conducted earnest research. By using bis (2-hydroxyethyl) 5-hydroxyisophthalate (abbreviated as BH5HI) described in Japanese Patent Application No. 2000-206499 filed earlier by the present inventors, a novel acryloyl compound is obtained. The present invention has been completed.
[0005]
That is, the compound of the present invention has the formula [1]
[0006]
Embedded image

[0007]
Wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or the formula [2]
[0008]
Embedded image

[0009]
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Represents a (substituted) acryloyl group, and at least one represents a (substituted) acryloyl group. )
The isophthalic acid compound represented by these, and its manufacturing method.
[0010]
The present invention also provides the formula [3]
[0011]
Embedded image

[0012]
And bis (2-hydroxyethyl) 5-hydroxyisophthalate (BH5HI) represented by the formula [4]
[0013]
Embedded image

[0014]
(Wherein R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
Or a (substituted) acrylic acid compound represented by
BH5HI represented by the formula [3] and the formula [5]
[0015]
Embedded image

[0016]
(In the formula, R ¹ , R ² and R ³ represent the same meaning as described above, and X represents a halogen atom.)
The present invention relates to a method for producing an isophthalic acid compound represented by the above formula [1] by reacting an acrylic acid halide compound represented by formula (1) in the presence of a base, a metal and a metal compound. Hereinafter, the present invention will be described in detail.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The production method of the isophthalic acid compound represented by the formula [1] of the present invention is represented by the following two reaction schemes.
[0018]
Embedded image

[0019]
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X represent the same meaning as described above.)
First, (1) will be described. As described in Japanese Patent Application No. 2000-206499, BH5HI represented by the formula [3] of the raw material is efficiently produced using a 5-hydroxyisophthalic acid compound and ethylene glycol as raw materials and an acid, metal or metal compound as a catalyst. can do.
[0020]
On the other hand, in the acrylic acid compound represented by the general formula [4], R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or 1 to 2 carbon atoms. R ² , R ³ and R ⁴ have 1 to 10 carbon atoms, preferably a hydrogen atom or 1 to 5 carbon atoms.
[0021]
Specifically, acrylic acid, methacrylic acid, tiglylic acid, 3,3-dimethylacrylic acid, 2-methyl-2-pentenoic acid, 2-ethyl-2-hexenoic acid, 2-octenoic acid, and the like, and their C1-C10 alkyl ester compounds, specifically, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl tiglate, ethyl tiglate, methyl 3,3-dimethylacrylate, Ethyl 3,3-dimethylacrylate, methyl 2-methyl-2-pentenoate, ethyl 2-methyl-2-pentenoate, methyl 2-ethyl-2-hexenoate, ethyl 2-ethyl-2-hexenoate, 2 -Methyl octenoate, ethyl 2-octenoate, etc. are mentioned.
[0022]
This reaction requires an acid catalyst. As the acid catalyst, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used, and sulfuric acid is particularly preferable. Further, organic acids such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and trifluoroacetic acid can be used, and benzenesulfonic acid and p-toluenesulfonic acid are particularly preferable. The use amount of the acrylic acid compound can be a large excess from the theoretical amount.
[0023]
Further, examples of the acid catalyst include tungstic acid, molybdic acid, and heteropolyacids thereof. Specific examples of the heteropolyacid include H ₃ PW ₁₂ O ₄₀ , H ₄ SiW ₁₂ O ₄₀ , H ₄ TiW ₁₂ O ₄₀ , H ₅ CoW ₁₂ O ₄₀ , H ₅ FeW ₁₂ O ₄₀ , and H ₆ P ₂ W ₁₈ O. _{62, H 7 PW 11 O 33} , H 4 TiMo 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 Typical examples include O ₄₀ , H ₄ SiMo ₁₂ O ₄₀ , H ₅ PV ₂ Mo ₁₀ O ₄₀ , H ₃ PMo ₆ W ₆ O ₄₀ , H _0.5 Cs _2.5 PW ₁₂ O ₄₀ and their hydrates. It is done. Moreover, the catalyst etc. which carry | supported these on carbon and a silica are mentioned. Among these heteropolyacids, H ₃ PW ₁₃ O ₄₀ , H ₃ PMo ₁₂ O ₄₀ and their hydrates are particularly preferable.
[0024]
Furthermore, cation exchange resins such as Amberlyst IR120, H-type zeolite such as H-ZSM-5, and the like can also be used.
[0025]
In particular, as a catalyst in the transesterification method, in addition to the aforementioned mineral acids, heteropoly acids, organic acids, cation exchange resins and H-type zeolite, 3ZnO-2B ₂ O ₃ , cadmium acetate, zinc acetate and calcium acetate A fatty acid salt of a Group II compound of the periodic table represented by These catalysts can be used in an amount of 0.1 to 100% by weight, preferably 1 to 20% by weight, based on BH5HI.
[0026]
Although this reaction can use an acrylic acid compound in large excess, it can also be performed using a solvent and it is preferable to use a solvent normally. Examples of the solvent include halogenated hydrocarbons such as 1,2-dichloroethane (EDC) and 1,1,1-trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, 1,2-dimethoxyethane, And ethers such as diethylene glycol dimethyl ether.
[0027]
The usage-amount of a solvent is 1-20 weight times with respect to BH5HI, More preferably, it is 1-6 weight times. The reaction temperature is 50 to 200 ° C, more preferably 70 to 150 ° C. The reaction can be carried out at normal pressure or at elevated pressure. The reaction time can be 1 to 50 hours, and it is practically 2 to 12 hours.
[0028]
Next, the manufacturing method of reaction scheme (2) is described. In the acrylic acid halide compound represented by the general formula [5], R ¹ , R ² and R ³ are the same as described above. Specifically, acrylic acid, methacrylic acid, tiglylic acid, 3,3- Halides such as dimethylacrylic acid, 2-methyl-2-pentenoic acid, 2-ethyl-2-hexenoic acid and 2-octenoic acid. Halogen is fluorine, chlorine, bromine and iodine, and economically it is chlorine. In particular, acrylic acid chloride and methacrylic acid chloride are used. The amount used is 1 to 2 mol times, more preferably 1 to 1.5 mol times the theoretical amount of BH5HI.
[0029]
This reaction requires a base, examples of which include inorganic bases such as alkali metals and alkaline earth metal carbonates and hydroxides, aliphatic and aromatic organic bases, and fatty acids of alkali metals and alkaline earth metals. Salt and the like can be used. Specific examples thereof include sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, trimethylamine, triethylamine, tripropylamine, Examples include pyridine, picoline, aniline, sodium acetate and sodium oxalate. In particular, sodium carbonate and triethylamine are preferable. The amount used is 1-2 mol times, more preferably 1-1.5 mol times the theoretical amount of BH5HI, and is preferably the same amount as the acrylic acid halide compound. A metal or a metal hydride complex can also be used.
[0030]
As the metal, alkali metals belonging to Group 1 of the Periodic Table and alkaline earth metals belonging to Group 2 can be used, and specifically, lithium, sodium, potassium, magnesium, calcium, and the like. In addition, examples of metal compounds include metals such as lithium hydride, sodium hydride, potassium hydride, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, lithium borohydride, sodium borohydride, and potassium borohydride. Examples thereof include hydrogenated complexes, metal hydroxides such as sodium hydroxide and potassium hydroxide, and metal carbonates such as sodium carbonate and potassium carbonate. In particular, sodium and sodium hydride are preferable. The amount used is the same as described above.
[0031]
This reaction preferably uses a solvent. Examples of the solvent include tetrahydrofuran (THF), dioxane, ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether. The usage-amount of a solvent is 1-20 weight times with respect to BH5HI, More preferably, it is 1-6 weight times. The reaction temperature is preferably -20 to 100 ° C, particularly 0 to 50 ° C.
[0032]
After the reaction, water is added to hydrolyze the residual acid chloride, and then the solvent is distilled off, extracted with a hardly water-soluble solvent (ether type or ester type), and then purified by distillation or column chromatography. The object can be obtained. The above reaction and purification of the present invention can be performed batchwise or continuously. The products obtained by this reaction are listed below.
[0033]
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[0034]
(Wherein R ¹ , R ² and R ³ represent the same meaning as described above.)
[0035]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
[0036]
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[0037]
A 100 ml four-neck reaction flask was charged with 1.35 g (5 mmol) of BH5HI and 17 g of N, N-dimethylacetamide (DMAc) and cooled to 5 ° C. Under this stirring, 0.72 g (18 mmol) of sodium hydride (purity 60%) was added and stirred for 1.5 hours. Further, 3.14 g (30 mmol) of methacryloyl chloride was added dropwise at 5 ° C. Stirring was continued at 5 ° C. for 1 hour, and further reacted at 25 ° C. for 6 hours. Ice was added to the reaction solution, followed by concentration to distill off DMAc. The residue was extracted with ethyl acetate / water, insoluble solids were removed by filtration, and the organic layer of the filtrate was concentrated to dryness to give 3.44 g of an oil. This oily substance was purified by silica gel column chromatography with n-heptane / ethyl acetate = 19/1 to 3/1 to obtain 1,3-bis (2-methacryloyloxyethoxycarbonyl) -5-methacryloyloxybenzene (BMMB). 0.59 g (yield 24.9%) was obtained.
[0038]
MASS (FAB ⁺ , m / e (%)): 475 ([M + H] ⁺ , 15), 431 (25), 389 (63), 345 (94), 124 (100), 113 (100).
¹ H-NMR (CDCl ₃ , δ ppm): 1.82 (s, 6H), 1.95 (s, 3H), 4.38 (dd, J ₁ = 3.21 Hz, J ₂ = 4.74 Hz, 4H), 4.49 (dd, J ₁ = 3.21Hz, J ₂ = 4.74Hz, 4H), 5.48 (t, J = 1.53Hz, 2H), 5.71 (d, J = 1.53Hz, 1H), 6.03 (s, 2H), 6.28 (s, 1H) , 7.89 (dd, J ₁ = 1.53Hz, J ₂ = 3.36Hz, 2H), 8.45 (t, J = 1.52Hz, 1H).
¹³ C-NMR (CDCl ₃ , δ ppm): 17.78 (2), 17.81, 61.98 (2), 62.93 (2), 125.96 (2), 127.16 (2), 127.68, 127.93, 131.39 (2), 134.84, 135.45 (2), 150.66,164.24,164.99,166.87.

Claims (5)

Formula [1]

Wherein R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or a formula [2]

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Represents a (substituted) acryloyl group, and at least one represents a (substituted) acryloyl group. )
An isophthalic acid compound represented by Formula [3]

And bis (2-hydroxyethyl) 5-hydroxyisophthalate represented by the formula [4]

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
And a (substituted) acrylic acid compound represented by the formula [1]

Wherein R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or a formula [2]

(Wherein R ¹ , R ² and R ³ represent the same meaning as described above.)
Represents a (substituted) acryloyl group, and at least one represents a (substituted) acryloyl group. )
The manufacturing method of the isophthalic acid compound represented by these. The process for producing an isophthalic acid compound according to claim 2, wherein the acid catalyst is p-toluenesulfonic acid, benzenesulfonic acid or sulfuric acid. Formula [3]

And bis (2-hydroxyethyl) 5-hydroxyisophthalate represented by the formula [5]

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a halogen atom. )
Wherein the acrylate halide compound represented by the formula is reacted in the presence of a base, a metal and a metal compound [1]

Wherein R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or a formula [2]

(Wherein R ¹ , R ² and R ³ represent the same meaning as described above.)
Represents a (substituted) acryloyl group, and at least one represents a (substituted) acryloyl group. )
The manufacturing method of the isophthalic acid compound represented by these. The process for producing an isophthalic acid compound according to claim 4, wherein the base is an alkylamine and the metal compound is a metal hydride complex or a metal carbonate.