JP2009084220A - New polymerizable compound - Google Patents
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- JP2009084220A JP2009084220A JP2007256381A JP2007256381A JP2009084220A JP 2009084220 A JP2009084220 A JP 2009084220A JP 2007256381 A JP2007256381 A JP 2007256381A JP 2007256381 A JP2007256381 A JP 2007256381A JP 2009084220 A JP2009084220 A JP 2009084220A
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- 0 C*(C*)C(C1)Sc(c(*)c(C)c(*)c2*)c2C1=O Chemical compound C*(C*)C(C1)Sc(c(*)c(C)c(*)c2*)c2C1=O 0.000 description 1
- WMWUWXCHAXLQQT-UHFFFAOYSA-N C=CCOC(C(CC(c1c2)=O)Sc1ccc2Cl)=O Chemical compound C=CCOC(C(CC(c1c2)=O)Sc1ccc2Cl)=O WMWUWXCHAXLQQT-UHFFFAOYSA-N 0.000 description 1
- MHGIWGIQIPLCSZ-UHFFFAOYSA-O [OH2+]C(C(C1)Sc(ccc(Cl)c2)c2C1=O)=O Chemical compound [OH2+]C(C(C1)Sc(ccc(Cl)c2)c2C1=O)=O MHGIWGIQIPLCSZ-UHFFFAOYSA-O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
Abstract
Description
本発明は、分子内にヘテロ環構造と重合性基とを有する新規化合物に関し、詳細には、増感色素として有用な新規重合性化合物に関する。 The present invention relates to a novel compound having a heterocyclic structure and a polymerizable group in the molecule, and particularly relates to a novel polymerizable compound useful as a sensitizing dye.
重合能を有する化合物は各種硬化性組成物に有用であり、特に、紫外線などの活性放射線の照射により硬化可能な組成物としては、放射線照射により高感度で硬化し、優れた硬化膜を形成することが求められ、なかでも、有色の硬化膜を形成しうる着色硬化性組成物が、例えば、インク組成物などに活用されている。
紫外線光による硬化型インクジェット方式は、比較的低臭気であり、速乾性、インク吸収性の無い被記録媒体への記録ができる点で、近年注目されつつある。
このような光重合硬化型のインク組成物に用いられる光重合開始剤としては、ベンジル、ベンゾイン、ベンゾインエチルエーテル、ミヒラーケトン、アントラキノン、アクリジン、フェナジン、ベンゾフェノン、2−エチルアントラキノン等が一般的である(例えば、特許文献1参照)。しかしながら、これらの一般的な光重合開始剤を用いた場合、光重合性組成物の硬化感度が十分とはいえず画像形成における像露光に長時間を要し、細密な画像を形成しようとする場合は、画像形成工程中にわずかな振動があると良好な画質の画像が形成されないという問題がある。さらに、露光の光源のエネルギー放射量の総量が増大するために、それに伴う多大な発熱の放射を考慮する必要があった。
A compound having a polymerizing ability is useful for various curable compositions. In particular, as a composition that can be cured by irradiation with active radiation such as ultraviolet rays, it is cured with high sensitivity by irradiation to form an excellent cured film. In particular, a colored curable composition capable of forming a colored cured film is used in, for example, an ink composition.
The curable inkjet method using ultraviolet light has been attracting attention in recent years because it has a relatively low odor and can record on a recording medium having no quick drying and no ink absorption.
As the photopolymerization initiator used in such a photopolymerization-curable ink composition, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like are common ( For example, see Patent Document 1). However, when these general photopolymerization initiators are used, the curing sensitivity of the photopolymerizable composition is not sufficient, and it takes a long time for image exposure in image formation and attempts to form a fine image. In such a case, there is a problem that an image with good image quality cannot be formed if there is slight vibration during the image forming process. Furthermore, since the total amount of energy radiation of the light source for exposure increases, it is necessary to consider the radiation of a large amount of heat accompanying it.
従来、放射線硬化型の重合性化合物における放射線に対する感度を高める方法として、光重合開始剤と共に増感色素を用いることが提案され、種々の重合開始系を使用することが開示されている。例えば増感色素として、チオキサントン系化合物を使用することが提案されている(例えば、特許文献1、特許文献2参照)。しかし、チオキサントン系化合物をはじめとする増感色素は、重合性組成物の硬化後にも、硬化膜中に他の化合物と結合することなくモノマーとして残存するため、硬化膜と接触している他の物質に移動する、低分子量成分であるために硬化膜中で可塑剤と同様の挙動を示し、膜強度を低下させる、或いは、硬化膜表面のべとつきを引き起こし表面硬化感度の低下させる、といった問題を生じやすい傾向にある。
このため、増感色素としての機能に優れ、硬化性組成物に用いた場合も、硬化膜の耐ブロッキング性に優れた増感剤が求められていた。
For this reason, the sensitizer which was excellent in the function as a sensitizing dye and was excellent in the blocking resistance of a cured film also when used for the curable composition was calculated | required.
本発明の目的は、増感色素として有用な、新規重合性化合物を提供することにある。 An object of the present invention is to provide a novel polymerizable compound useful as a sensitizing dye.
本発明者らは上記課題を解決するため、鋭意検討を重ねた結果、重合性基を置換基として有する増感色素として、分子内にヘテロ環構造を有する特定の化合物を見出し、本発明を完成した。
即ち、本発明は以下に示すとおりである。
<1> 下記一般式(I)で表される化合物。
As a result of intensive studies to solve the above problems, the present inventors have found a specific compound having a heterocyclic structure in the molecule as a sensitizing dye having a polymerizable group as a substituent, and completed the present invention. did.
That is, the present invention is as follows.
<1> A compound represented by the following general formula (I).
一般式(I)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。X1は以下に示す群より選択される一価の置換基を表す。nは0または1を表す。 In general formula (I), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. X 1 represents a monovalent substituent selected from the group shown below. n represents 0 or 1.
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上から構成される二価の連結基を表す。
<2> 下記一般式(II)で表される化合物。
L represents a divalent linking group composed of one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
<2> A compound represented by the following general formula (II).
一般式(II)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。X2は以下に示す群より選択される一価の置換基を表す。nは0または1を表す。 In general formula (II), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. X 2 represents a monovalent substituent selected from the group shown below. n represents 0 or 1.
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。
<3> 下記一般式(III)で表される化合物。
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
<3> A compound represented by the following general formula (III).
一般式(III)中、R1、R2、R3、R4は、それぞれ独立に水素原子、アルキル基、又は、ハロゲン原子を表す。但し、R1、R2、R3、R4のいずれか一つは−X3である。
R5、R6は、それぞれ独立に水素原子、又は、メチル基を表す。
ここで、X3は以下に示す群より選択される一価の置換基を表す。
In general formula (III), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or a halogen atom. However, any one of R 1, R 2, R 3 , R 4 is -X 3.
R 5 and R 6 each independently represents a hydrogen atom or a methyl group.
Here, X 3 represents a monovalent substituent selected from the following group.
nは0もしくは1を表す。
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。
なお、前記各式中、「*」は複素環への連結部位を表す。
n represents 0 or 1.
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
In each of the above formulas, “*” represents a site connected to a heterocyclic ring.
前記一般式(I)から一般式(III)で表される重合性化合物は、いずれも新規化合物であり、ヘテロ環構造に起因して、増感色素として有用であり、例えば、重合開始剤、及びエチレン性不飽和結合を有する重合性化合物とともに硬化性組成物に使用することで、その効果が著しい。以下、本発明の新規重合性化合物を、「特定重合性化合物」と称する。 The polymerizable compounds represented by the general formulas (I) to (III) are all novel compounds, and are useful as sensitizing dyes due to the heterocyclic structure. For example, a polymerization initiator, And the effect is remarkable by using it for a curable composition with the polymeric compound which has an ethylenically unsaturated bond. Hereinafter, the novel polymerizable compound of the present invention is referred to as “specific polymerizable compound”.
本発明によれば、増感色素として有用な、新規重合性化合物を提供することができる。 According to the present invention, a novel polymerizable compound useful as a sensitizing dye can be provided.
以下、本発明を詳細に説明する。
<1> 下記一般式(I)で表される化合物。
Hereinafter, the present invention will be described in detail.
<1> A compound represented by the following general formula (I).
一般式(I)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。X1で表される一価の置換基の導入位置としてはR2が好ましく、置換基としてはアルキル基、ハロゲン原子が好ましい。さらに好ましい置換基としてはメチル基、もしくはクロロ基が挙げられる。
nは0または1を表し、0がより好ましい。
X1は以下に示す群より選択される一価の置換基を表す。
In general formula (I), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. As the introduction position of the monovalent substituent represented by X 1 , R 2 is preferable, and as the substituent, an alkyl group and a halogen atom are preferable. More preferred substituents include a methyl group or a chloro group.
n represents 0 or 1, and 0 is more preferable.
X 1 represents a monovalent substituent selected from the group shown below.
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上から構成される二価の連結基を表す。
好ましい連結基Lとしては、以下に示す構造が挙げられる。なお、連結基が非対称の場合、向きはどちらでもよい。
L represents a divalent linking group composed of one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
Preferred examples of the linking group L include the structures shown below. When the linking group is asymmetric, the direction may be either.
Lとしては、さらに好ましくは以下に示す構造が挙げられる。 As L, the structure shown below is more preferable.
以下に、一般式(I)で表される化合物の具体例〔例示化合物(I−1)〜(I−36)〕を、その骨格と置換基とを記載することで例示する。 Hereinafter, specific examples of the compound represented by the general formula (I) [Exemplary compounds (I-1) to (I-36)] are exemplified by describing the skeleton and substituents thereof.
<2> 下記一般式(II)で表される化合物。 <2> A compound represented by the following general formula (II).
一般式(II)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。置換基の導入位置としてはR2が好ましく、置換基としてはアルキル基、ハロゲン原子が好ましい。さらに好ましい置換基としてはメチル基、もしくはクロロ基が挙げられる。
nは0または1を表し、0がより好ましい。
X2は以下に示す群より選択される一価の置換基を表す。
In general formula (II), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. As the introduction position of the substituent, R 2 is preferable, and as the substituent, an alkyl group and a halogen atom are preferable. More preferred substituents include a methyl group or a chloro group.
n represents 0 or 1, and 0 is more preferable.
X 2 represents a monovalent substituent selected from the group shown below.
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。
好ましい連結基Lとしては、以下に示す構造が挙げられる。なお、連結基が非対称の場合、向きはどちらでもよい。
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
Preferred examples of the linking group L include the structures shown below. When the linking group is asymmetric, the direction may be either.
Lとしては、さらに好ましくは以下に示す構造が挙げられる。 As L, the structure shown below is more preferable.
またX1としては以下の構造が最も好ましい。 X 1 is most preferably the following structure.
以下に、一般式(II)で表される化合物の具体例〔例示化合物(II−1)〜(II−10)〕をその骨格と置換基とを記載することで例示する。 Below, the specific example [Exemplary compound (II-1)-(II-10)] of a compound represented by general formula (II) is illustrated by describing the frame | skeleton and a substituent.
<3> 下記一般式(III)で表される化合物。 <3> A compound represented by the following general formula (III).
一般式(III)中、R1、R2、R3、R4は、それぞれ独立に水素原子、アルキル基、又は、ハロゲン原子を表す。
R5、R6は、それぞれ独立に水素原子、又は、メチル基を表す。
但し、R1、R2、R3、R4のいずれか一つは−X3であり、R2が−X3であることが好ましい。
ここで、X3は以下に示す群より選択される一価の置換基を表す。
In general formula (III), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or a halogen atom.
R 5 and R 6 each independently represents a hydrogen atom or a methyl group.
However, any one of R 1 , R 2 , R 3 and R 4 is —X 3 , and R 2 is preferably —X 3 .
Here, X 3 represents a monovalent substituent selected from the following group.
nは0もしくは1を表す。
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。
好ましい連結基Lとしては、以下に示す構造が挙げられる。なお、連結基が非対称の場合、向きはどちらでもよい。
n represents 0 or 1.
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
Preferred examples of the linking group L include the structures shown below. When the linking group is asymmetric, the direction may be either.
Lとしては、さらに好ましくは以下に示す構造が挙げられる。 As L, the structure shown below is more preferable.
またX3としては以下の構造が最も好ましい。 X 3 is most preferably the following structure.
以下に、一般式(III)で表される化合物の具体例〔例示化合物(III−1)〜(III−36)〕を、その骨格と置換基とを記載することで例示する。 Below, the specific example [Exemplary compound (III-1)-(III-36)] of a compound represented by general formula (III) is illustrated by describing the frame | skeleton and a substituent.
これらの特定重合性化合物は、ヘテロ環構造部分が増感色素としての機能を有するため、硬化性組成物に添加する増感色素として有用である。特に、増感色素として重合開始剤の活性光線照射による分解を促進させる効果があるのみならず、分子内にラジカルによって反応する重合性基を有することから、エネルギー付与により形成された硬化膜中に固定化され、低分子量成分特有のブリードが抑制される。
本発明の特定重合性化合物は、増感色素、特に、表面のべたつきが問題になる紫外線硬化型のインク組成物に用いる増感色素として有用である。
These specific polymerizable compounds are useful as sensitizing dyes to be added to the curable composition because the heterocyclic structure portion functions as a sensitizing dye. In particular, it not only has the effect of accelerating the decomposition of the polymerization initiator by actinic ray irradiation as a sensitizing dye, but also has a polymerizable group that reacts with radicals in the molecule, so in a cured film formed by applying energy. Immobilized and bleed specific to low molecular weight components is suppressed.
The specific polymerizable compound of the present invention is useful as a sensitizing dye, in particular, a sensitizing dye used for an ultraviolet curable ink composition in which surface stickiness is a problem.
以下に本発明の特定重合性化合物の合成例及び同定データを示す。
(実施例1)
一般式(III)で表される特定重合性化合物の合成方法について代表的な具体例を以下に示す。
〔例示化合物(III−3)の合成〕
下記構造の化合物A2.08gを2−ブタノン10mlに溶かし、トリエチルアミン1.11gを加えた。更に、冷却バスを用いて0℃まで降温し、アククリル酸クロリド1.00gをゆっくり加えた。その後、室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水を加え酢酸エチルで抽出した。抽出液を飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。濃縮した濾液をシリカゲルカラム(展開溶液:ヘキサン/酢酸エチル)を用いて精製した。すると目的化合物(III−3)を収量1.8gで得た。
Synthesis examples and identification data of the specific polymerizable compound of the present invention are shown below.
Example 1
Typical specific examples of the synthesis method of the specific polymerizable compound represented by the general formula (III) are shown below.
[Synthesis of Exemplified Compound (III-3)]
2.08 g of compound A having the following structure was dissolved in 10 ml of 2-butanone, and 1.11 g of triethylamine was added. Further, the temperature was lowered to 0 ° C. using a cooling bath, and 1.00 g of acrylic acid chloride was slowly added. Then, it heated up to room temperature and stirred for 3 hours. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The concentrated filtrate was purified using a silica gel column (developing solution: hexane / ethyl acetate). Then, the target compound (III-3) was obtained with a yield of 1.8 g.
NMR (300 MHz, CDCl3, σ(ppm)): 8.06 (1H, d, J=2.4Hz), 7.35 (1H, dd, J=2.4Hz, 8.4Hz), 7.17 (1H, d, J=8.4Hz), 6.52 (1H, dd, J=1.5Hz, 17.1Hz), 6.12 (1H, dd, J=10.5Hz, 17.1Hz), 5.96 (1H, dd, J=1.5Hz, 10.5Hz), 2.87 (2H, s), 1.46 (6H, s)
なお、化合物AはBioorganic&Medicinal Chemistry (1999),7(7),1321−1338.記載の方法で合成できる。
合成スキームは以下に示すとおりである。
NMR (300 MHz, CDCl3, σ (ppm)): 8.06 (1H, d, J = 2.4 Hz), 7.35 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7.17 (1H, d, J = 8.4 Hz), 6.52 (1H, dd, J = 1.5 Hz, 17.1 Hz), 6.12 (1H, dd, J = 10.5 Hz, 17.1 Hz), 5.96 (1H, dd, J = 1.5 Hz, 10.5 Hz), 2.87 (2H, s), 1.46 (6H, s)
In addition, Compound A is Bioorganic & Medicinal Chemistry (1999), 7 (7), 1321-1338. It can be synthesized by the method described.
The synthesis scheme is as shown below.
(実施例2)
一般式(I)で表される特定重合性化合物の合成方法について代表的な具体例を以下に示す。
〔例示化合物(I−4)の合成〕
下記構造の化合物B 2.42gとDMAP(ジメチルアミノピリジン)0.10gをTHF20mlに溶かし、化合物C 2.32gを加えた。更に、冷却バスを用いて0℃まで降温し、DCC(ジシクロヘキシルカルボジイミド)をゆっくり加えた。その後、室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水を加え酢酸エチルで抽出した。抽出液を希塩酸、飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。濃縮した濾液をシリカゲルカラム(展開溶液:ヘキサン/酢酸エチル)を用いて精製した。すると目的化合物(I−4)を収量2.8gで得た。
NMR(300MHz,CDCl3,σ(ppm)):8.08(1H,d,J=2.4Hz),7.36(1H,dd,J=2.4Hz,8.4Hz),7.18(1H,d,J=8.4Hz),6.40(1H,dd,J=1.5Hz,17.1Hz),6.07(1H,dd,J=10.5Hz,17.1Hz),5.87(1H,dd,J=1.5Hz,10.5Hz),4.34(4H,m),4.13(1H,m)3.18(2H,m)
なお、化合物Bは、特開平2−255677号公報記載の方法で合成できる。
合成スキームは以下に示すとおりである。
(Example 2)
Typical specific examples of the synthesis method of the specific polymerizable compound represented by the general formula (I) are shown below.
[Synthesis of Exemplified Compound (I-4)]
2.42 g of compound B having the following structure and 0.10 g of DMAP (dimethylaminopyridine) were dissolved in 20 ml of THF, and 2.32 g of compound C was added. Further, the temperature was lowered to 0 ° C. using a cooling bath, and DCC (dicyclohexylcarbodiimide) was slowly added. Then, it heated up to room temperature and stirred for 3 hours. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The concentrated filtrate was purified using a silica gel column (developing solution: hexane / ethyl acetate). Then, the target compound (I-4) was obtained with a yield of 2.8 g.
NMR (300 MHz, CDCl 3, σ (ppm)): 8.08 (1H, d, J = 2.4 Hz), 7.36 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7.18 ( 1H, d, J = 8.4 Hz), 6.40 (1H, dd, J = 1.5 Hz, 17.1 Hz), 6.07 (1H, dd, J = 10.5 Hz, 17.1 Hz), 5 .87 (1H, dd, J = 1.5 Hz, 10.5 Hz), 4.34 (4H, m), 4.13 (1H, m) 3.18 (2H, m)
Compound B can be synthesized by the method described in JP-A-2-255777.
The synthesis scheme is as shown below.
(実施例3)
〔例示化合物(I−19)の合成〕
下記構造の化合物B 2.42gとK2CO32.0gをDMF100mlに溶かし、冷却バスを用いて0℃まで降温した。アリールブロマイド2.0gをゆっくり滴下し、その後室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水にあけ、生成した固体をろ過した。この固体を酢酸エチル、ヘキサンで再結晶し、目的化合物(I−19)を収量2.2gで得た。
NMR(300MHz,CDCl3,σ(ppm)):8.09(1H,d,J=2.1Hz),7.37(1H,dd,J=2.1Hz,8.4Hz),7.20(1H,d,J=8.4Hz),5.82(1H,m),5.26(2H,m),4.62(2H,d,J=5.7Hz),4.14(1H,t,J=5.4Hz),3.19(1H,d,J=5.4Hz)
合成スキームは以下に示すとおりである。
(Example 3)
[Synthesis of Exemplified Compound (I-19)]
Compound B (2.42 g) and K 2 CO 3 ( 2.0 g) having the following structure were dissolved in 100 ml of DMF, and the temperature was lowered to 0 ° C. using a cooling bath. 2.0 g of aryl bromide was slowly added dropwise, and then the temperature was raised to room temperature and stirred for 3 hours. After completion of the reaction, the reaction solution was poured into water and the produced solid was filtered. This solid was recrystallized from ethyl acetate and hexane to obtain the target compound (I-19) in a yield of 2.2 g.
NMR (300 MHz, CDCl3, σ (ppm)): 8.09 (1H, d, J = 2.1 Hz), 7.37 (1H, dd, J = 2.1 Hz, 8.4 Hz), 7.20 ( 1H, d, J = 8.4 Hz), 5.82 (1H, m), 5.26 (2H, m), 4.62 (2H, d, J = 5.7 Hz), 4.14 (1H, t, J = 5.4 Hz), 3.19 (1H, d, J = 5.4 Hz)
The synthesis scheme is as shown below.
(実施例4)
〔例示化合物(I−24)の合成〕
下記構造の化合物B 24.3gとK2CO327.6gとよう化カリウム8.3gをDMF100mlに溶かし、冷却バスを用いて0℃まで降温したp−クロロビニルスチレン14.4gをゆっくり滴下し、その後室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水にあけ、酢酸エチルで抽出した。抽出液を希塩酸、飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。析出した固体を酢酸エチル、ヘキサンで再結晶し、目的化合物(I−24)を収量12.0gで得た。
NMR(300MHz,CDCl3,σ(ppm)):8.05(1H,d,J=2.4Hz),7.34(3H,m),7.17(3H,m),6.70(1H,dd,J=10.8Hz,17.4Hz),5.76(1H,dd,J=0.6Hz,17.4Hz),5.28(1H,dd,J=0.6Hz,10.8Hz),5.12(2H,m),4.12(1H,m)3.18(2H,m)
合成スキームは以下に示すとおりである。
Example 4
[Synthesis of Exemplified Compound (I-24)]
Compound B (24.3 g), K 2 CO 3 ( 27.6 g) and potassium iodide (8.3 g) were dissolved in DMF (100 ml), and p-chlorovinylstyrene (14.4 g) was slowly dropped to 0 ° C. using a cooling bath. Then, the temperature was raised to room temperature and stirred for 3 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The precipitated solid was recrystallized from ethyl acetate and hexane to obtain the target compound (I-24) in a yield of 12.0 g.
NMR (300 MHz, CDCl3, σ (ppm)): 8.05 (1H, d, J = 2.4 Hz), 7.34 (3H, m), 7.17 (3H, m), 6.70 (1H) , Dd, J = 10.8 Hz, 17.4 Hz), 5.76 (1H, dd, J = 0.6 Hz, 17.4 Hz), 5.28 (1H, dd, J = 0.6 Hz, 10.8 Hz) ), 5.12 (2H, m), 4.12 (1H, m) 3.18 (2H, m)
The synthesis scheme is as shown below.
(実施例5)
一般式(II)で表される特定重合性化合物の合成方法について代表的な具体例を以下に示す。
〔例示化合物(II−4)の合成〕
下記式で示す化合物B24.2gとDMAP(ジメチルアミノピリジン)1.0gをEtOH200mlに溶かした。更に、冷却バスを用いて0℃まで降温し、DCC(ジシクロヘキシルカルボジイミド)22.7gをゆっくり加えた。その後、室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水を加え酢酸エチルで抽出した。抽出液を希塩酸、飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。濃縮した濾液をシリカゲルカラム(展開溶液:ヘキサン/酢酸エチル)を用いて精製した。すると化合物Dを収量20.5gで得た。
化合物D:NMR(300MHz,CDCl3,σ(ppm)):8.08(1H,d,J=2.4Hz),7.36(1H,dd,J=2.4Hz,8.4Hz),7.19(1H,d,J=8.4Hz),4.18(2H,m),4.11(1H,t,J=5.4Hz)3.17(2H,d,J=5.4Hz),3.17(3H,t,J=7.2Hz)
合成スキームは以下に示すとおりである。
(Example 5)
Typical specific examples of the method for synthesizing the specific polymerizable compound represented by the general formula (II) are shown below.
[Synthesis of Exemplary Compound (II-4)]
24.2 g of compound B represented by the following formula and 1.0 g of DMAP (dimethylaminopyridine) were dissolved in 200 ml of EtOH. Further, the temperature was lowered to 0 ° C. using a cooling bath, and 22.7 g of DCC (dicyclohexylcarbodiimide) was slowly added. Then, it heated up to room temperature and stirred for 3 hours. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The extract was washed with dilute hydrochloric acid and saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The concentrated filtrate was purified using a silica gel column (developing solution: hexane / ethyl acetate). Compound D was obtained in a yield of 20.5 g.
Compound D: NMR (300 MHz, CDCl3, σ (ppm)): 8.08 (1H, d, J = 2.4 Hz), 7.36 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7 .19 (1H, d, J = 8.4 Hz), 4.18 (2H, m), 4.11 (1H, t, J = 5.4 Hz) 3.17 (2H, d, J = 5.4 Hz) ), 3.17 (3H, t, J = 7.2 Hz)
The synthesis scheme is as shown below.
化合物D 17.2gとエチレングリコール14.3mlを1.28gのp−トルエンスルホン酸1水塩触媒と共に250mlのトルエンで共沸蒸留した。24時間後、冷却した溶液を0.50Mの水酸化ナトリウム100mlで二度洗浄し、水100mlで二度洗浄した。有機相を無水硫酸マグネシウムで乾燥し、すべての溶剤をロータリーエバポレーターで除去したところ淡黄色の液体を得た。フラスコにLiAlH4 1.40gとTHF60mlを入れ、化合物Bをゆっくり滴下した。その後3時間攪拌後TLCで化合物Bの消費を確認してから、冷却バスを用いて0℃まで降温し、水をゆっくり滴下した。反応液をろ過後、ろ液に1N塩酸を15ml加え、24h攪拌した。その後、反応液に水を加え酢酸エチルで抽出した。抽出液を、飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。濃縮した濾液をシリカゲルカラム(展開溶液:ヘキサン/酢酸エチル)を用いて精製した。すると目的化合物Eを収量12.5gで得た。
化合物E:NMR(300MHz,CDCl3,σ(ppm)):8.03(1H,d,J=2.4Hz),7.36(1H,dd,J=2.4Hz,8.4Hz),7.23(1H,d,J=8.4Hz),3.83(2H,dd,J=2.4Hz,6.3Hz),3.65(1H,m),3.12(1H,dd,J=4.2Hz,16.8Hz),2.99(1H,dd,J=8.1Hz,16.8Hz)
合成スキームは以下に示すとおりである。
17.2 g of compound D and 14.3 ml of ethylene glycol were azeotropically distilled with 250 ml of toluene together with 1.28 g of p-toluenesulfonic acid monohydrate catalyst. After 24 hours, the cooled solution was washed twice with 100 ml of 0.50 M sodium hydroxide and twice with 100 ml of water. The organic phase was dried over anhydrous magnesium sulfate, and all solvents were removed with a rotary evaporator to obtain a pale yellow liquid. LiAlH 4 1.40 g and THF 60 ml were placed in the flask, and Compound B was slowly added dropwise. Then, after stirring for 3 hours, consumption of Compound B was confirmed by TLC, and then the temperature was lowered to 0 ° C. using a cooling bath, and water was slowly added dropwise. After filtration of the reaction solution, 15 ml of 1N hydrochloric acid was added to the filtrate and stirred for 24 hours. Then, water was added to the reaction solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The concentrated filtrate was purified using a silica gel column (developing solution: hexane / ethyl acetate). Then, the target compound E was obtained with a yield of 12.5 g.
Compound E: NMR (300 MHz, CDCl 3, σ (ppm)): 8.03 (1H, d, J = 2.4 Hz), 7.36 (1 H, dd, J = 2.4 Hz, 8.4 Hz), 7 .23 (1H, d, J = 8.4 Hz), 3.83 (2H, dd, J = 2.4 Hz, 6.3 Hz), 3.65 (1H, m), 3.12 (1H, dd, J = 4.2 Hz, 16.8 Hz), 2.99 (1H, dd, J = 8.1 Hz, 16.8 Hz)
The synthesis scheme is as shown below.
化合物E 12.0gを2−ブタノン50mlに溶かし、トリエチルアミン5.85gを加えた。更に、冷却バスを用いて0℃まで降温し、アククリル酸クロリド5.22gをゆっくり加えた。その後、室温まで昇温させ、3時間攪拌した。反応終了後、反応液に水を加え酢酸エチルで抽出した。抽出液を飽和食塩水で洗浄、硫酸マグネシウムで乾燥後濾過、濾液をエバポレーターで濃縮した。濃縮した濾液をシリカゲルカラム(展開溶液:ヘキサン/酢酸エチル)を用いて精製した。すると目的化合物(II−4)を収量8.5gで得た。
NMR(300MHz,CDCl3,σ(ppm)):8.06(1H,d,J=2.4Hz),7.37(1H,dd,J=2.4Hz,8.4Hz),7.22(1H,d,J=8.4Hz),6.40(1H,dd,J=1.5Hz,17.1Hz),6.08(1H,dd,J=10.5Hz,17.1Hz),5.87(1H,dd,J=1.5Hz,10.5Hz),4.38(2H,m),3.81(1H,m),3.12(1H,dd,J=3.9Hz,16.5Hz),2.97(1H,dd,J=8.4Hz,16.5Hz)
合成スキームは以下に示すとおりである。
Compound E (12.0 g) was dissolved in 2-butanone (50 ml), and triethylamine (5.85 g) was added. Furthermore, the temperature was lowered to 0 ° C. using a cooling bath, and 5.22 g of acrylic acid chloride was slowly added. Then, it heated up to room temperature and stirred for 3 hours. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated with an evaporator. The concentrated filtrate was purified using a silica gel column (developing solution: hexane / ethyl acetate). Then, the target compound (II-4) was obtained with a yield of 8.5 g.
NMR (300 MHz, CDCl3, [sigma] (ppm)): 8.06 (1H, d, J = 2.4 Hz), 7.37 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7.22 ( 1H, d, J = 8.4 Hz), 6.40 (1H, dd, J = 1.5 Hz, 17.1 Hz), 6.08 (1H, dd, J = 10.5 Hz, 17.1 Hz), 5 .87 (1H, dd, J = 1.5 Hz, 10.5 Hz), 4.38 (2H, m), 3.81 (1H, m), 3.12 (1H, dd, J = 3.9 Hz, 16.5 Hz), 2.97 (1H, dd, J = 8.4 Hz, 16.5 Hz)
The synthesis scheme is as shown below.
Claims (3)
一般式(I)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。X1は以下に示す群より選択される一価の置換基を表す。nは0または1を表す。
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上から構成される二価の連結基を表す。 The compound represented by the following general formula (I).
In general formula (I), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. X 1 represents a monovalent substituent selected from the group shown below. n represents 0 or 1.
L represents a divalent linking group composed of one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
一般式(II)中、R1、R2、R3、R4はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、又は、ハロゲン原子を表す。X2は以下に示す群より選択される一価の置換基を表す。nは0または1を表す。
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。 The compound represented by the following general formula (II).
In general formula (II), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. X 2 represents a monovalent substituent selected from the group shown below. n represents 0 or 1.
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
一般式(III)中、R1、R2、R3、R4は、それぞれ独立に水素原子、アルキル基、又は、ハロゲン原子を表す。但し、R1、R2、R3、R4のいずれか一つは−X3である。
R5、R6は、それぞれ独立に水素原子、又は、メチル基を表す。
ここで、X3は以下に示す群より選択される一価の置換基を表す。
nは0もしくは1を表す。
Lは、アルキレン基、アルキレンオキシ基、及び、エステル基からなる群より選択される一種又は二種以上が結合してなる二価の連結基を表す。 A compound represented by the following general formula (III).
In general formula (III), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or a halogen atom. However, any one of R 1, R 2, R 3 , R 4 is -X 3.
R 5 and R 6 each independently represents a hydrogen atom or a methyl group.
Here, X 3 represents a monovalent substituent selected from the following group.
n represents 0 or 1.
L represents a divalent linking group formed by bonding one or more selected from the group consisting of an alkylene group, an alkyleneoxy group, and an ester group.
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