JP2006312606A - Mew azobenzene derivative compound, material for optical recording, information recording medium, method for improving photosensitivity, method for improving photoresponsiveness and method for controlling aggregation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a means for improving photosensitivity and photoresponsiveness of a donor-acceptor type azobenzene derivative. <P>SOLUTION: The compound containing azobenzene parts is represented by formula (II). The material for optical recording comprises the compound. The information recording medium has an optical recording layer containing the compound on a substrate. The method for improving photosensitivity or photoresponsiveness of an azobenzene derivative containing an electron-accepting group and an electron-donative group or the method for controlling aggregation of the azobenzene derivative comprises combining the azobenzene derivative with a molecule containing large steric hindrance either directly or through a connecting group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel compound useful as an optical recording material, and a method for improving photosensitivity and photoresponsiveness by suppressing aggregation of an azobenzene derivative.

  Optical recording materials are widely used for chemical sensors, display elements, liquid crystals, nonlinear materials, photorefractive materials, optical waveguides, and the like. Typical optical recording materials include dichromated gelatin, photopolymers, and thermoplastics.

  However, although dichromated gelatin is capable of high-resolution recording, it has low sensitivity to light and is weak to moisture. Photopolymers can be wet-processed with high sensitivity. However, it is necessary to prepare a plurality of materials such as monomers, polymerization initiators, and sensitizers at an appropriate mixing ratio, depending on the processing method after optical recording. It is difficult to handle easily because its characteristics are greatly different.

  On the other hand, thermoplastics are highly sensitive and rewritable materials, and have a high utility value as recording materials for optical information processing. However, for optical recording, it is necessary to always charge the recording layer by corona discharge, resulting in a complicated recording process and recording apparatus.

  In recent years, in order to improve the above problems, optical rewritable elements using photochromic materials have been developed. In particular, an azobenzene derivative is a photochromic material whose molecular structure reversibly changes from a trans form to a cis form upon light irradiation. Applications of liquid crystals, nonlinear materials, and photorefractive materials using this property to optical rewritable recording elements and optical switching elements have been studied (see Non-Patent Documents 1 to 5).

In general, photoisomerization of azobenzene from a trans form to a cis form is induced on the order of 10 ⁻¹² seconds. However, since the change from the cis form to the trans form is about 4 orders of magnitude slower than the change from the trans form to the cis form, it is important to promote the cis-trans response in order to achieve a fast response. . As a means for promoting the cis-trans response of azobenzene, it is conceivable to introduce an electron donating group (donor) and an electron accepting group (acceptor) into the azobenzene skeleton. However, the donor-acceptor type azobenzene derivative forms an aggregated structure accompanying molecular packing, resulting in limited photosensitivity and photoresponse.

On the other hand, it has been proposed to improve photosensitivity and photoresponsiveness by dispersing an azobenzene material in a polymer such as polymethyl methacrylate, polystyrene, and polyvinyl alcohol (see Non-Patent Documents 6 and 7). . However, when the azobenzene material is dispersed in the polymer, the aggregation structure can be suppressed, but the concentration of the material itself is lowered, so that it is difficult to obtain sufficient photosensitivity.
Ogura, K .; Hirabayashi, H .; Uejima, A .; Nakamura, K .; Jpn. J. et al. Appl. Phys. 1982, 21, 969. Eich, M.M. Wendorff, J .; H. Macromol. Chem. Rapid Commun. 1987, 8, 467. Gong, S.M. S. Christensen, D .; Zhang, J .; Wang, C .; H. J. et al. Phys. Chem. 1987, 91, 4504. Ikeda, T .; and Tsutsumi, O .; Science 1995, 268, 1873. Lagune Labartet, F.M. Freiberg, S .; Pellerin, C .; Pezolet, M .; Natsanson, A .; Rochon, P .; Macromolecules 2000, 33, 6815. Todorov, T .; Nikolova, L .; Tomova, N .; Appl. Opt. 1984, 23, 4309. Eich, M.M. Wendorff, J .; H. Reck, B .; Ringsdorf, H .; Macromol. Chem. Rapid Commun. 1987, 8, 59.

  An object of the present invention is to provide a means for improving the photosensitivity and photoresponsiveness of a donor-acceptor type azobenzene derivative.

［式中、
Ａ₁は、−Ｎ−、−Ｐ−、または−Ｂ−を示し、
Ｘ₁は、−ＮＨ₂、−Ｈ、−Ｃ_qＦ_2q+1、−ＳＣＨ₃、−Ｃ_qＨ_2q+1、−ＯＣ_qＨ_2q+1、−Ｆ、−Ｉ、−Ｃｌ、−Ｂｒ、−ＣＯＯＨ、−ＣＯＯＣＨ₃、−ＣＯＣＨ₃、−ＣＨＯ、−ＮＯ₂、または−ＣＮ（但し、ｑは１〜１０の範囲の整数である）を示し、
ａおよびｂは、それぞれ独立に０〜６の範囲の整数である］で表わされる化合物。
[２] 式（ＩＩ）：

［式中、
Ａ₂およびＡ₃は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

（但し、ｐは０〜１０の範囲の整数である）を示し、
Ｘ₂およびＸ₃は、それぞれ独立に、−ＮＨ₂、−Ｈ、−Ｃ_qＦ_2q+1、−ＳＣＨ₃、−Ｃ_qＨ_2q+1、−ＯＣ_qＨ_2q+1、−Ｆ、−Ｉ、−Ｃｌ、−Ｂｒ、−ＣＯＯＨ、−ＣＯＯＣＨ₃、−ＣＯＣＨ₃、−ＣＨＯ、−ＮＯ₂、または−ＣＮ（但し、ｑは１〜１０の範囲の整数である）を示し、
ｃおよびｄは、それぞれ独立に０〜６の範囲の整数である］で表わされる化合物。
[３] 式（ＩＩＩ）

［式中、
Ａ₅は、−Ｎ−、−Ｐ−、または−Ｂ−を示し、
Ａ₄およびＡ₆は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

（但し、ｐは０〜１０の範囲の整数である）を示し、
Ｘ₄、Ｘ₅およびＸ₆は、それぞれ独立に、−ＮＨ₂、−Ｈ、−Ｃ_qＦ_2q+1、−ＳＣＨ₃、−Ｃ_qＨ_2q+1、−ＯＣ_qＨ_2q+1、−Ｆ、−Ｉ、−Ｃｌ、−Ｂｒ、−ＣＯＯＨ、−ＣＯＯＣＨ₃、−ＣＯＣＨ₃、−ＣＨＯ、−ＮＯ₂、または−ＣＮ（但し、ｑは１〜１０の範囲の整数である）を示し、
ｅ、ｆ、ｇおよびｈは、それぞれ独立に０〜６の範囲の整数である］で表わされる化合物。
[４] 式（ＩＶ）

［式中、
Ａ₈およびＡ₉は、それぞれ独立に、−Ｎ−、−Ｐ−、または−Ｂ−を示し、
Ａ₇およびＡ₁₀は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

（但し、ｐは０〜１０の範囲の整数である）を示し、
Ｘ₇、Ｘ₈、Ｘ₉およびＸ₁₀は、それぞれ独立に、−ＮＨ₂、−Ｈ、−Ｃ_qＦ_2q+1、−ＳＣＨ₃、−Ｃ_qＨ_2q+1、−ＯＣ_qＨ_2q+1、−Ｆ、−Ｉ、−Ｃｌ、−Ｂｒ、−ＣＯＯＨ、−ＣＯＯＣＨ₃、−ＣＯＣＨ₃、−ＣＨＯ、−ＮＯ₂、または−ＣＮ（但し、ｑは１〜１０の範囲の整数である）を示し、
ｉ、ｊ、ｋ、ｌ、ｍおよびｎは、それぞれ独立に０〜６の範囲の整数である］で表わされる化合物。
[５] [１]〜[４]のいずれかに記載の化合物からなる光記録用材料。
[６] 基板上に光記録層を有する情報記録媒体であって、前記光記録層は、[１]〜[４]のいずれかに記載の化合物を含むことを特徴とする情報記録媒体。
[７] 電子受容基と電子供与基を有するアゾベンゼン誘導体を、直接または連結基を介して立体障害の大きな分子と結合させることにより、前記アゾベンゼン誘導体の光感度を向上させる方法。
[８] 電子受容基と電子供与基を有するアゾベンゼン誘導体を、直接または連結基を介して立体障害の大きな分子と結合させることにより、前記アゾベンゼン誘導体の光応答性を向上させる方法。
[９] 電子受容基と電子供与基を有するアゾベンゼン誘導体を、直接または連結基を介して立体障害の大きな分子と結合させることにより、前記アゾベンゼン誘導体の凝集を抑制する方法。
[１０] 前記立体障害の大きな分子が、ビナフチル骨格を含む、[７]〜[９]のいずれかに記載の方法。 Means for achieving the object is as follows.
[1] Formula (I):

[Where:
A ₁ represents -N-, -P-, or -B-,
X ₁ is —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , —F, —I, —Cl, —Br _{, -COOH, -COOCH 3, -COCH 3} , -CHO, -NO 2 , or -CN, (where, q is an integer in the range of 1 to 10) indicates,
a and b are each independently an integer in the range of 0 to 6.]
[2] Formula (II):

[Where:
A ₂ and A ₃ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₂ and X ₃ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , —F, — I, —Cl, —Br, —COOH, —COOCH ₃ , —COCH ₃ , —CHO, —NO ₂ , or —CN (where q is an integer in the range of 1 to 10);
c and d are each independently an integer in the range of 0 to 6.]
[3] Formula (III)

[Where:
A ₅ represents -N-, -P-, or -B-,
A ₄ and A ₆ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₄ , X ₅ and X ₆ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , — F, shown -I, -Cl, -Br, -COOH, -COOCH 3, -COCH 3, -CHO, a -NO ₂ or -CN, (where, q is an integer ranging from 1 to 10),
e, f, g and h are each independently an integer in the range of 0 to 6.]
[4] Formula (IV)

[Where:
A ₈ and A ₉ each independently represent —N—, —P—, or —B—;
A ₇ and A ₁₀ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₇ , X ₈ , X ₉ and X ₁₀ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , -F, -I, -Cl, -Br, -COOH, -COOCH ₃ , -COCH ₃ , -CHO, -NO ₂ , or -CN (where q is an integer in the range of 1 to 10) Indicate
i, j, k, l, m and n are each independently an integer in the range of 0 to 6.]
[5] An optical recording material comprising the compound according to any one of [1] to [4].
[6] An information recording medium having an optical recording layer on a substrate, wherein the optical recording layer contains the compound according to any one of [1] to [4].
[7] A method for improving the photosensitivity of the azobenzene derivative by bonding an azobenzene derivative having an electron-accepting group and an electron-donating group to a molecule having a large steric hindrance directly or via a linking group.
[8] A method for improving the photoresponsiveness of the azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group.
[9] A method for suppressing aggregation of the azobenzene derivative by bonding an azobenzene derivative having an electron-accepting group and an electron-donating group to a molecule having a large steric hindrance directly or via a linking group.
[10] The method according to any one of [7] to [9], wherein the molecule having a large steric hindrance includes a binaphthyl skeleton.

  According to the present invention, it is possible to provide a novel compound containing an azobenzene skeleton, which exhibits high sensitivity and high-speed response to light and is excellent in workability.

で表わされる化合物（以下、化合物Ｉという）；
式（ＩＩ）：

で表わされる化合物（以下、化合物ＩＩという）；
式（ＩＩＩ）

で表わされる化合物（以下、化合物ＩＩＩという）；
式（ＩＶ）

で表わされる化合物（以下、化合物ＩＶという）。
以下、化合物Ｉ、ＩＩ、ＩＩＩ、ＩＶをまとめて、本発明の化合物ともいう。 Hereinafter, the present invention will be described in more detail.

The compound of this invention consists of the following four aspects.
Formula (I):

A compound represented by formula (hereinafter referred to as compound I);
Formula (II):

A compound represented by formula (hereinafter referred to as compound II);
Formula (III)

A compound represented by formula (hereinafter referred to as compound III);
Formula (IV)

(Hereinafter referred to as Compound IV).
Hereinafter, the compounds I, II, III, and IV are collectively referred to as the compound of the present invention.

The donor-acceptor type azobenzene derivative having an electron accepting group and an electron donating group forms an aggregated structure accompanying molecular packing, resulting in limited photosensitivity and photoresponsiveness. On the other hand, in the compound of the present invention, the donor / acceptor type azobenzene derivative is bonded to binaphthyl. Binaphthyl has two naphthalene skeletons bonded between 1-1 'and has a twisted structure in the molecule. In the compound of the present invention, steric hindrance due to this twisted structure can suppress aggregation of azobenzene derivatives, and as a result, photosensitivity and photoresponsiveness can be improved.
Details of the compounds I, II, III and IV will be described below.

で表わされる。
式（Ｉ）中、Ａ₁は、−Ｎ−、−Ｐ−、または−Ｂ−を示す。また、式（Ｉ）中、Ｘ₁は、−ＮＨ₂、−Ｈ、−Ｃ_qＦ_2q+1、−ＳＣＨ₃、−Ｃ_qＨ_2q+1、−ＯＣ_qＨ_2q+1、−Ｆ、−Ｉ、−Ｃｌ、−Ｂｒ、−ＣＯＯＨ、−ＣＯＯＣＨ₃、−ＣＯＣＨ₃、−ＣＨＯ、−ＮＯ₂、または−ＣＮを示す。ここで、ｑは１〜１０、好ましくは１〜６の範囲の整数である。 Compound I
Compound I has the formula (I):

It is represented by
In formula (I), A ₁ represents —N—, —P—, or —B—. In the formula (I), X ₁ represents —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , —F, shown -I, -Cl, -Br, -COOH, -COOCH 3, -COCH 3, -CHO, a -NO ₂ or -CN,. Here, q is an integer in the range of 1 to 10, preferably 1 to 6.

In formula (I), A ₁ is an electron donating group (donor) and X ₁ is an electron accepting group (acceptor). In general, combining a weak electron donating donor with a weak electron accepting acceptor increases the stability of the cis isomer, resulting in a weak electron donating donor and a strong electron accepting donor or a donor with a strong electron donating property. And a weakly accepting acceptor tend to destabilize the cis form and accelerate isomerization from the cis form to the trans form (improves cis-trans responsiveness). In the present invention, the photosensitivity and photoresponsiveness of the resulting compound can be controlled by the combination of A ₁ and X ₁ .

In the formula (I), preferred combinations of the donor (A ₁ ) and the acceptor (X ₂ ) are as follows.
(1) The donor is —N— and the acceptor is NO ₂ ;
(2) Donor is —N— and acceptor is CN;
(3) donor-N-, -C is the acceptor _q F _{2q +} 1;
(4) The donor is -P- and the acceptor is NO ₂ ;
(5) Donor is -P- and acceptor is CN;
(6) donor -P-, acceptor -C _q F _{2q +} 1;
(7) Donor is -B- and acceptor is NO ₂ ;
(8) Donor is -B- and acceptor is CN;
(9) donor -B-, the acceptor -C _q F _{2q +} 1.

  In formula (I), a and b are each independently an integer of 0 to 6, preferably 0 to 2, more preferably 0 to 1. As a and b are smaller, a sterically hindered aggregation suppressing effect due to the twisted structure of the binaphthyl moiety can be obtained more effectively. In formula (I), a and b may be the same or different. From the viewpoint of ease of production, a and b are preferably the same, but from the viewpoint of suppressing aggregation, it may be preferable that a and b are different.

であってもよく、

であってもよい。 In Compound I, the twisted structure of the binaphthyl moiety is

May be,

It may be.

を、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、アゾベンゼン誘導体：

[式中、Ａ₁、Ｘ₁、ａおよびｂは前述と同義である。]
と反応させることにより、式（Ｉ）で表わされる化合物Ｉを得ることができる。光延反応の詳細については、例えば、Mitsunobu, O. Synthesis 1981, 1.を参照することができる。 Compound I can be synthesized by a known method. Examples of the method for synthesizing Compound I include the following methods using Mitsunobu reaction.
2,2′-dihydroxy-1,1′-binaphthyl:

In an appropriate solvent (eg tetrahydrofuran, ether) in the presence of triphenylphosphine and azodicarboxylic acid ester:

[Wherein, A ₁ , X ₁ , a and b are as defined above. ]
To give compound I represented by formula (I). For details of the Mitsunobu reaction, for example, Mitsunobu, O. Synthesis 1981, 1. can be referred to.

  2,2'-Dihydroxy-1,1'-binaphthyl and an azobenzene derivative used for the synthesis of Compound I can be synthesized by a known method, and are also commercially available. In addition, the target object which has a desired twist structure in a binaphthyl site | part can be obtained by selecting either R body and S body as raw material binaphthyl.

  The concentration and mixing ratio of 2,2'-dihydroxy-1,1'-binaphthyl and the azobenzene derivative in the reaction solution can be appropriately set. The mixing ratio (molar ratio) of 2,2'-dihydroxy-1,1'-binaphthyl and the azobenzene derivative can be, for example, about 1: 1. Moreover, reaction can be performed at 20 degreeC (room temperature)-50 degreeC, for example, and reaction time can be made into 12 hours-48 hours, for example. The target compound I can be purified by a known method such as silica gel column chromatography. The fact that Compound I was obtained can be confirmed by NMR, mass spectrometry, elemental analysis or the like.

（式中、ZはN、PまたはBを示す。） Specific examples of compound I include the following.

(In the formula, Z represents N, P or B.)

で表わされる。
式（ＩＩ）中、Ａ₂およびＡ₃は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

を示す。ここで、ｐは０〜１０、好ましくは０〜６の範囲の整数である。Ａ₂とＡ₃は同じであってもよく、異なっていてもよいが、製造の容易性等の点からは、同じであることが好ましい。 Compound II
Compound II has the formula (II):

It is represented by
In formula (II), A ₂ and A ₃ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH. _{2 -, - CH 2 S -} , - SCH 2 -, - N (C p H 2p + 1) -, or

Indicates. Here, p is an integer in the range of 0 to 10, preferably 0 to 6. A ₂ and A ₃ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In formula (II), X ₂ and X ₃ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , OC _q H _{2q + 1} , —F, —I, — shown _{Cl, -Br, -COOH, -COOCH 3} , -COCH 3, -CHO, a -NO ₂ or -CN,. Here, q is an integer in the range of 1 to 10, preferably 1 to 6. X ₂ and X ₃ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In formula (II), A ₂ and A ₃ are electron donating groups (donors), and X ₂ and X ₃ are electron accepting groups (acceptors). The influence of the strength of the donor and the acceptor on the stability of the cis isomer and the cis-trans responsiveness is as described above. In the present invention, it can be obtained by a combination of A ₂ , A ₃ and X ₂ , X _3. The photosensitivity and photoresponsiveness of the compound can be controlled. In formula (II), preferred combinations of donors (A ₂ , A ₃ ) and acceptors (X ₂ , X ₃ ) are as follows.

(1) The donor is —O— and the acceptor is —NO ₂ ;
(2) Donor is —O— and acceptor is —CN;
(3) Donor is —O—, acceptor is —C _q H _{2q + 1} ,
(4) Donor is —O—, acceptor is —C _q F _{2q + 1} ,
(5) donor _{-N (C p H 2p + 1} ) -, acceptor -NO _2;
(6) donor _{-N (C p H 2p + 1} ) -, acceptor -CN;
(7) donor _{-N (C p H 2p + 1} ) -, -C q H 2q + 1 is the acceptor,
(8) donor _{-N (C p H 2p + 1} ) -, acceptor -C _q F _{2q +} 1.

  In formula (II), c and d are each independently an integer in the range of 0-6, preferably 0-2, more preferably 0-1. As c and d are smaller, a sterically hindered aggregation suppressing effect due to the twisted structure of the binaphthyl moiety can be obtained more effectively. In formula (II), c and d may be the same or different. Although c and d are preferably the same from the viewpoint of ease of production, it may be preferable that c and d are different from the viewpoint of suppressing aggregation. In Compound II, as in Compound I, the twisted structure of the binaphthyl moiety can take two forms.

を、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、アゾベンゼン誘導体：

[式中、Ａ₂、Ｘ₂およびｃは、前述と同義である。]
と反応させることにより、式（ＩＩ）で表わされる化合物ＩＩを得ることができる。なお、Ａ₂とＡ₃、Ｘ₂とＸ₃がそれぞれ異なる化合物ＩＩを合成する場合には、対応する２種類のアゾベンゼン誘導体を使用すればよい。２，２’−ジヒドロキシ−１，１’−ビナフチルと原料アゾベンゼン誘導体は、公知の方法で合成することができ、また市販品としても入手可能である。なお、原料ビナフチルとしてＲ体、Ｓ体のいずれかを選択することにより、ビナフチル部位に所望のねじれ構造を有する目的物を得ることができる。 Compound II can be synthesized by a known method. For example, as a method for synthesizing Compound II in which A ₂ and A ₃ and X ₂ and X ₃ are the same, the following method using the Mitsunobu reaction described above can be exemplified.
2,2′-dihydroxy-1,1′-binaphthyl:

In an appropriate solvent (eg tetrahydrofuran, ether) in the presence of triphenylphosphine and azodicarboxylic acid ester:

[Wherein A ₂ , X ₂ and c are as defined above. ]
To give compound II represented by the formula (II). In addition, when synthesizing a compound II in which A ₂ and A ₃ and X ₂ and X ₃ are different from each other, two corresponding azobenzene derivatives may be used. 2,2′-dihydroxy-1,1′-binaphthyl and the raw material azobenzene derivative can be synthesized by a known method, and are also available as commercial products. In addition, the target object which has a desired twist structure in a binaphthyl site | part can be obtained by selecting either R body and S body as raw material binaphthyl.

The concentration and mixing ratio of 2,2′-dihydroxy-1,1′-binaphthyl and the azobenzene derivative in the reaction solution can be appropriately set. When synthesizing Compound II in which A ₂ and A ₃ and X ₂ and X ₃ are the same, the mixing ratio (molar ratio) of the raw material binaphthyl and the raw material azobenzene may be about 1: 2. When synthesizing compound II having different azobenzene moieties, two raw material azobenzene derivatives (azobenzene derivatives 1 and 2) are used, and first, 2,2′-dihydroxy-1,1 ′ is utilized using Mitsunobu reaction. -Reaction of binaphthyl and raw material azobenzene derivative 1 is carried out. Thereby, the intermediate body in which the azobenzene derivative was introduce | transduced into one OH group of raw material binaphthyl is obtained. Next, the intermediate can be reacted with the raw material azobenzene derivative 2 by using the above-mentioned Mitsunobu reaction, for example, at 1: 1 to obtain the target product.

  The reaction can be performed, for example, at 20 ° C. (room temperature) to 50 ° C., and the reaction time can be, for example, 12 hours to 48 hours. The target compound II can be purified by a known method such as silica gel column chromatography. The fact that Compound II was obtained can be confirmed by NMR, mass spectrometry, elemental analysis or the like.

Specific examples of compound II include the following.

によって表わされる。
式（ＩＩＩ）中、Ａ₅は、−Ｎ−、−Ｐ−または−Ｂ−を示す。また、式（ＩＩＩ）中、Ａ₄およびＡ₆は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

を示す。ここで、ｐは０〜１０、好ましくは０〜６の範囲の整数である。Ａ₄およびＡ₆は同じであってもよく、異なっていてもよいが、製造の容易性等の点からは、同じであることが好ましい。 Compound III
Compound III has the formula (III):

Is represented by
In formula (III), A ₅ represents —N—, —P— or —B—. In formula (III), A ₄ and A ₆ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, _{-OCH 2 -, - CH 2 S} -, - SCH 2 -, - N (C p H 2p + 1) -, or

Indicates. Here, p is an integer in the range of 0 to 10, preferably 0 to 6. A ₄ and A ₆ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In formula (III), X ₄ , X ₅ and X ₆ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _2q + 1, shown -F, -I, -Cl, -Br, -COOH, -COOCH 3, -COCH 3, -CHO, a -NO ₂ or -CN,. Here, q is an integer in the range of 1 to 10, preferably 1 to 6. X ₄ , X ₅ and X ₆ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In formula (III), A ₄ , A ₅ and A ₆ are electron donating groups (donors), and X ₄ , X ₅ and X ₆ are electron accepting groups (acceptors). The influence on the stability and cis-trans responsiveness of the cis isomer by the strength of the donor and acceptor is as described above. In the present invention, A ₄ , A ₅ , A ₆ and X ₄ , X ₅ , X ₆ In combination, the photosensitivity and photoresponsiveness of the resulting compound can be controlled. In formula (III), preferred combinations of donor 1 (A ₅ ), donor 2 (A ₄ , A ₆ ) and acceptor (X ₄ , X ₅ , X ₆ ) are as follows.

(1) Donor 1 is —N—, donor 2 is —O—, and acceptor is —NO ₂ ;
(2) Donor 1 is -P-, donor 2 is -O-, and acceptor is -NO ₂ ;
(3) Donor 1 is -B-, donor 2 is -O-, and acceptor is -NO ₂ ;
(4) Donor 1 is —N—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —NO ₂ ;
(5) Donor 1 is —P—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —NO ₂ ;
(6) Donor 1 is —B—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —NO ₂ ;
(7) Donor 1 is —N—, donor 2 is —O—, and acceptor is —CN;
(8) Donor 1 is —N—, donor 2 is —O—, and acceptor is —C _q H _{2q + 1} ;
(9) Donor 1 is —N—, donor 2 is —O—, and acceptor is —C _q F _{2q + 1} ;
(10) Donor 1 is -P-, donor 2 is -O-, and acceptor is -CN;
(11) Donor 1 is —P—, donor 2 is —O—, and acceptor is —C _q H _{2q + 1} ;
(12) Donor 1 is —P—, donor 2 is —O—, and acceptor is —C _q F _{2q + 1} ;
(13) Donor 1 is -B-, donor 2 is -O-, and acceptor is -CN;
(14) Donor 1 is —B—, donor 2 is —O—, and acceptor is —C _q H _{2q + 1} ;
(15) Donor 1 is -B-, donor 2 is -O-, and acceptor is -C _q F _{2q + 1} ;
(16) Donor 1 is —N—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —CN;
(17) Donor 1 is —N—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —C _q H _{2q + 1} ;
(18) Donor 1 is —N—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —C _q F _{2q + 1} ;
(19) Donor 1 -P-, donor 2 _{-N (C p 2 p + 1} ), acceptor -CN;
(20) Donor 1 -P-, donor 2 _{-N (C p 2 p + 1} ), acceptor -C _q H _{2q +} 1;
(21) Donor 1 -P-, donor 2 _{-N (C p 2 p + 1} ), -C is the acceptor _q F _{2q +} 1;
(22) Donor 1 is —B—, donor 2 is —N (C _p 2 _{p + 1} ), and the acceptor is —CN;
(23) Donor 1 -B-, donor 2 _{-N (C p 2 p + 1} ), -C is the acceptor _q H _{2q +} 1;
(24) Donor 1 -B-, donor 2 _{-N (C p 2 p + 1} ), -C is the acceptor _q F _{2q +} 1.

  In formula (I), e, f, g, and h are each independently an integer in the range of 0-6, preferably 0-2, more preferably 0-1. e, f, g and h may be the same or different. From the viewpoint of ease of production, e, f, g, and h are preferably the same, but from the viewpoint of suppressing aggregation, it may be preferable that e, f, g, and h are different.

であってもよく、

であってもよい。 In Compound III, the twisted structure of the binaphthyl moiety is

May be,

It may be.

を、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、アゾベンゼン誘導体３：

と反応させ、

[式中、Ａ₄、Ｘ₄およびｅは、前述と同義である。]
で表わされる中間体を得る。次いで、この中間体を、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、光延反応を利用してアゾベンゼン誘導体４：

[式中、Ａ₅、Ｘ₅、ｆおよびｇは、前述と同義である。]
と反応させることにより、目的物を得ることができる。 Compound III can be synthesized by a known method. For example, as a method for synthesizing compound III, the following method using the above-mentioned Mitsunobu reaction can be exemplified.
First, different types of raw material azobenzene derivatives (for example, two types; azobenzene derivatives 3 and 4) are prepared, and 2,2′-dihydroxy-1,1′-binaphthyl:

In an appropriate solvent (eg tetrahydrofuran, ether) in the presence of triphenylphosphine and azodicarboxylic acid ester:

React with

[Wherein, A ₄ , X ₄ and e are as defined above. ]
An intermediate represented by is obtained. This intermediate is then converted into an azobenzene derivative 4: using Mitsunobu reaction in the presence of triphenylphosphine and azodicarboxylic acid ester in a suitable solvent (eg, tetrahydrofuran, ether).

[Wherein, A ₅ , X ₅ , f and g are as defined above. ]
The desired product can be obtained by reacting with.

  The concentration and mixing ratio of 2,2'-dihydroxy-1,1'-binaphthyl and the azobenzene derivative in the reaction solution can be appropriately set. The mixing ratio (molar ratio) of 2,2′-dihydroxy-1,1′-binaphthyl and the azobenzene derivative 3 during the synthesis of the intermediate can be, for example, about 1: 1. The obtained intermediate and the azobenzene derivative The mixing ratio (molar ratio) with 4 can be, for example, about 2: 1. The reaction can be carried out, for example, at 20 ° C. (room temperature) to 50 ° C., and the reaction time can be 12 hours to 48 hours. The target compound, Compound III, can be purified by a known method such as silica gel column chromatography. The fact that Compound III was obtained can be confirmed by NMR, mass spectrometry, elemental analysis or the like.

Specific examples of compound III include the following.

で表わされる。
式（ＩＶ）中、Ａ₈およびＡ₉は、それぞれ独立に−Ｎ−、−Ｐ−、または−Ｂ−を示す。また、式（ＩＶ）中、Ａ₇およびＡ₁₀は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＯＯＣ−、−ＣＯＯ−、−ＳＯ₂−、−ＣＯＯＮＨ−、−ＣＨ₂Ｏ−、−ＯＣＨ₂−、−ＣＨ₂Ｓ−、−ＳＣＨ₂−、−Ｎ（Ｃ_pＨ_2p+1）−、または

を示す。ここで、ｐは０〜１０、好ましくは０〜６の範囲の整数である。Ａ₇、Ａ₈、Ａ₉およびＡ₁₀は同じであってもよく、異なっていてもよいが、製造の容易性等の点からは、同じであることが好ましい。 Compound IV
Compound IV has the formula (IV):

It is represented by
Wherein (IV), A ₈ and A ₉ are each independently -N -, - P-, or an -B-. In formula (IV), A ₇ and A ₁₀ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, _{-OCH 2 -, - CH 2 S} -, - SCH 2 -, - N (C p H 2p + 1) -, or

Indicates. Here, p is an integer in the range of 0 to 10, preferably 0 to 6. A ₇ , A ₈ , A ₉ and A ₁₀ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In the formula (IV), X ₇ , X ₈ , X ₉ and X ₁₀ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , -OC _q H _2q + 1, shown -F, -I, -Cl, -Br, -COOH, -COOCH 3, -COCH 3, -CHO, a -NO ₂ or -CN,. Here, q is an integer in the range of 1 to 10, preferably 1 to 6. X ₇ , X ₈ , X ₉ and X ₁₀ may be the same or different, but are preferably the same from the viewpoint of ease of production.

In formula (IV), A ₇ , A ₈ , A ₉ and A ₁₀ are electron donating groups (donors), and X ₇ , X ₈ , X ₉ and X ₁₀ are electron accepting groups (acceptors). The influence of the strength of the donor and the acceptor on the stability of the cis isomer and the cis-trans responsiveness is as described above. In the present invention, A ₇ , A ₈ , A ₉ and A ₁₀ and X ₇ , X ₈ , X ₉ and X ₁₀ can control the photosensitivity and photoresponsiveness of the resulting compound. In formula (III), a preferred combination of donor 1 (A ₈ , A ₉ ), donor 2 (A ₇ , A ₁₀ ) and acceptor (X ₇ , X ₈ , X ₉ and X ₁₀ ) has been previously described in formula (III ).

であってもよく、

であってもよい。 In Compound IV, the twisted structure of the binaphthyl moiety is

May be,

It may be.

  In formula (IV), i, j, k, l, m and n are each independently an integer in the range of 0-6, preferably 0-2, more preferably 0-1. i, j, k, l, m and n may be the same or different. From the viewpoint of ease of production, i, j, k, l, m, and n are preferably the same, but from the viewpoint of suppressing aggregation, i, j, k, l, m, and n are different. It may be preferable.

を、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、アゾベンゼン誘導体５：

と反応させ、

[式中、Ａ₈、Ｘ₈、ｊおよびｋは、前述と同義である。]
で表わされる中間体１を合成する。
また、別途、２，２’−ジヒドロキシ−１，１’−ビナフチルを、適当な溶媒（例えばテトラヒドロフラン、エーテル）中で、トリフェニルホスフィンおよびアゾジカルボン酸エステルの存在下、アゾベンゼン誘導体６：

と反応させ、

[式中、Ａ₇、Ｘ₇、およびｉは、前述と同義である。]
で表わされる中間体２を得る。次いで、中間体１と中間体２を、例えば光延反応を利用して反応させることにより、目的物を得ることができる。 Compound IV can be synthesized by a known method. For example, compound IV can be synthesized by the following method using the Mitsunobu reaction described above.
First, 2,2′-dihydroxy-1,1′-binaphthyl:

In an appropriate solvent (eg tetrahydrofuran, ether) in the presence of triphenylphosphine and azodicarboxylic acid ester:

React with

[Wherein, A ₈ , X ₈ , j and k are as defined above. ]
Intermediate 1 represented by
Separately, 2,2′-dihydroxy-1,1′-binaphthyl is azobenzene derivative 6 in the presence of triphenylphosphine and azodicarboxylic acid ester in a suitable solvent (for example, tetrahydrofuran, ether):

React with

[Wherein, A ₇ , X ₇ and i are as defined above. ]
Intermediate 2 represented by is obtained. Next, the target product can be obtained by reacting the intermediate 1 and the intermediate 2 using, for example, the Mitsunobu reaction.

  The concentration and mixing ratio of the raw material in the reaction solution can be set as appropriate. The mixing ratio (molar ratio) of 2,2′-dihydroxy-1,1′-binaphthyl and the azobenzene derivative 5 at the time of synthesizing the intermediate 1 can be, for example, about 1: 2. The mixing ratio (molar ratio) of 2,2′-dihydroxy-1,1′-binaphthyl and the azobenzene derivative 6 can be, for example, about 1: 1. Moreover, the mixing ratio of the intermediate body 1 and the intermediate body 2 can be about 1: 2, for example.

  The reaction can be performed, for example, at 20 ° C. (room temperature) to 50 ° C., and the reaction time can be, for example, 12 hours to 48 hours. The target compound IV can be purified by a known method such as silica gel column chromatography. The fact that Compound IV was obtained can be confirmed by NMR, mass spectrometry, elemental analysis or the like.

Specific examples of compound IV include the following.

[Optical recording materials]
The present invention further relates to an optical recording material comprising the aforementioned compound of the present invention.
Azobenzene has a cis isomer and a trans isomer, and a thermally stable one is a trans isomer. When the trans form is irradiated with light (for example, ultraviolet light), isomerization to the cis form occurs, and then it is left in the dark, or light with a wavelength longer than that used for trans-cis isomerization is irradiated. It is known that it again changes to a trans form. For example, when the compound of the present invention is irradiated with ultraviolet light, isomerization from a trans isomer to a cis isomer occurs at an azobenzene site. Furthermore, isomerization to the trans isomer occurs by leaving the cis isomer in a dark place or irradiating light having a longer wavelength than the light used for trans-cis isomerization. The compound of the present invention can be used as an optical rewritable optical recording material by utilizing this property. In particular, the compound of the present invention can exhibit high sensitivity and high-speed response (particularly cis-trans response) because aggregation is suppressed by steric hindrance at the binaphthyl site. Moreover, the compound of this invention also has the advantage that a process is easy so that it may mention later.

[Information recording medium]
The present invention also relates to an information recording medium having an optical recording layer on a substrate, wherein the optical recording layer contains the compound of the present invention.

  As the substrate, known substrates such as quartz, glass, polymethyl methacrylate, polystyrene, polyvinyl alcohol, polycarbonate, and polyimide can be used. The information recording medium of the present invention can be produced by a known method. For example, the information recording medium of the present invention can be easily prepared by applying a coating solution prepared by dissolving the compound of the present invention in a suitable solvent such as tetrahydrofuran, dichloromethane, chloroform, etc. onto a substrate and drying it. Can do. As a coating method, a known method can be used. Among these, when a spin coating method is used, a uniform thin film can be easily formed without dispersing the compound of the present invention in a polymer or the like. The optical recording layer thus formed contains the compound of the present invention, and preferably comprises the compound of the present invention, and can exhibit high sensitivity and high-speed response to light.

  In addition to the compound of the present invention, known additives can be added to the optical recording layer. It is also possible to provide a further layer such as a protective layer on the optical recording layer.

  By irradiating the information recording medium of the present invention with light, the azobenzene moiety in the compound contained in the optical recording layer can be changed from the trans isomer to the cis isomer, whereby information can be recorded. it can. Furthermore, this information recording medium may be left in a dark place or irradiated with light having a wavelength longer than that used for trans-cis isomerization to cause isomerization from the cis form to the trans form. it can. The magnetic recording medium of the present invention can easily record and rewrite information by causing isomerization of the azobenzene moiety as described above. As light used for optical recording, it is preferable to use light having a wavelength near the absorption peak of the compound contained in the optical recording layer. The wavelength of the light to irradiate can be 300-700 nm, for example.

[Photosensitivity improvement method, photoresponsiveness improvement method, aggregation suppression method]
The present invention further includes
A method for improving the photosensitivity of the azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group (hereinafter referred to as a photosensitivity improving method). ;
A method for improving the photoresponsiveness of the azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group (hereinafter referred to as a photoresponsiveness improving method) ;);
The azobenzene derivative having an electron-accepting group and an electron-donating group is bonded to a molecule having a large steric hindrance directly or via a linking group, thereby suppressing aggregation of the azobenzene derivative (hereinafter referred to as aggregation suppressing method).
About.

As described above, the donor-acceptor type azobenzene derivative having an electron-accepting group and an electron-donating group forms an aggregated structure accompanying molecular packing, resulting in limited photosensitivity and photoresponsiveness. Therefore, in the present invention, the donor-acceptor type azobenzene derivative is bonded to a molecule having a large steric hindrance directly or via a linking group. Thereby, aggregation of azobenzene derivatives can be suppressed, and as a result, photosensitivity and photoresponsiveness can be improved.
As described above, as a means for suppressing aggregation of the donor-acceptor type azobenzene derivative, it is conceivable to disperse the azobenzene derivative in a polymer. However, in a thin film formed by dispersing an azobenzene derivative in a polymer, the concentration of the azobenzene derivative inevitably decreases. On the other hand, according to the present invention, the aggregation of the donor-acceptor type azobenzene derivative can be suppressed without being dispersed in the polymer, so that a thin film containing the azobenzene derivative at a high concentration can be formed. The thin film thus obtained has a donor-acceptor type structure, so that the cis-trans isomerization rate is improved, and the azobenzene derivative is contained at a high concentration, so that the photosensitivity is high and it is extremely useful as an optical recording device.

  Examples of the donor-acceptor type azobenzene derivative include those having a structure contained in the compound of the present invention described above. Examples of the linking group include those contained in the aforementioned compound of the present invention.

  The molecule having a large steric hindrance preferably contains a binaphthyl skeleton. Thereby, as explained above, aggregation of azobenzene derivatives can be effectively suppressed by the steric hindrance of the binaphthyl twisted structure.

窒素雰囲気下、脱水テトラヒドロフラン（25 ml）中に(R)-2,2'-ジヒドロキシ-1,1'-ビナフチル（0.28 g, 1.0 mmol）、アルドリッチ社製ディスパーズレッド１（以下、「ＤＲ１」ともいう）（0.64 g, 2.0 mmol）、トリフェニルホスフィン（0.58 g, 2.2 mmol）を加えた後、アゾジカルボン酸ジエチルエステル（40％トルエン溶液）（1.6 ml, 3.5 mmol）を滴下した。その後、50℃で48時間 攪拌し、薄層クロマトグラフィーを用いて反応終了を確認した。溶媒を留去した後、シリカゲルカラムクロマトグラフィー（溶媒：トルエン，アセトン）によって化合物１を得た（0.38 g, 収率：43%）。 Hereinafter, the present invention will be described in more detail with reference to examples. However, this invention is not limited to the aspect shown in the Example.

[Example 1]
Synthesis of Compound II (1)

(R) -2,2'-dihydroxy-1,1'-binaphthyl (0.28 g, 1.0 mmol), Aldrich Disperse Red 1 (hereinafter "DR1") in dehydrated tetrahydrofuran (25 ml) under nitrogen atmosphere (Also called) (0.64 g, 2.0 mmol) and triphenylphosphine (0.58 g, 2.2 mmol) were added, and then azodicarboxylic acid diethyl ester (40% toluene solution) (1.6 ml, 3.5 mmol) was added dropwise. Thereafter, the mixture was stirred at 50 ° C. for 48 hours, and the completion of the reaction was confirmed using thin layer chromatography. After the solvent was distilled off, Compound 1 was obtained by silica gel column chromatography (solvent: toluene, acetone) (0.38 g, yield: 43%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.75 (t, 6H, CH _3- ), 2.58 (m, 4H, CH ₃ CH _2- ), 3.31 (t, 4H, -OCH ₂ CH ₂ N-), 4.05 (t, 4H, -OCH ₂ CH ₂ N-), 6.35 (d, 2H, aromatic rings), 7.13-7.37 (m, 8H, aromatic rings), 7.71 (d, 4H, aromatic rings ), 7.86 (d, 2H, aromatic rings), 7.89-7.93 (m, 6H, aromatic rings), 8.32 (d, 4H, aromatic rings). FAB-MS: m / z = 879.3 [M] ⁺ . Anal. Calc. For C ₅₂ H ₄₆ N ₈ O ₆ : C, 71.06; H, 5.27; N, 12.75. Found: C, 70.80; H, 5.19; N, 12.70.

窒素雰囲気下、脱水テトラヒドロフラン（15 ml）中に (R)-2,2'-ジヒドロキシ-1,1'-ビナフチル（0.28 g, 1.0 mmol）、ＤＲ1（0.32 g, 1.0 mmol）、トリフェニルホスフィン（0.29 g, 1.1 mmol）を加えた後、アゾジカルボン酸ジエチルエステル（40% トルエン溶液）（0.55 ml, 1.2 mmol）を滴下した。その後、50℃で12時間 攪拌し、薄層クロマトグラフィーを用いて反応終了を確認した。溶媒を留去した後、シリカゲルカラムクロマトグラフィー（溶媒：トルエン，アセトン）によって化合物 2 を得た（0.46 g, 収率：79%）。 [Example 2]
Synthesis of Compound III (1) Synthesis of Intermediate (Compound 2)

Under a nitrogen atmosphere, (R) -2,2'-dihydroxy-1,1'-binaphthyl (0.28 g, 1.0 mmol), DR1 (0.32 g, 1.0 mmol), triphenylphosphine (15 ml) in dehydrated tetrahydrofuran (15 ml) 0.29 g, 1.1 mmol) was added, and then azodicarboxylic acid diethyl ester (40% toluene solution) (0.55 ml, 1.2 mmol) was added dropwise. Thereafter, the mixture was stirred at 50 ° C. for 12 hours, and the completion of the reaction was confirmed using thin layer chromatography. After the solvent was distilled off, Compound 2 was obtained by silica gel column chromatography (solvent: toluene, acetone) (0.46 g, yield: 79%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.82 (t, 3H, CH ₃ CH ₂ N-), 2.65-2.83 (m, 2H, CH ₃ CH _2- ), 3.46 (t, 2H , -OCH ₂ CH ₂ N-), 4.14-4.27 (m, 2H, -OCH ₂ CH ₂ N-), 4.86 (s, 1H, -PhOH), 6.45 (d, 2H, aromatic rings), 7.01 (d , 1H, aromatic rings), 7.17-7.42 (m, 7H, aromatic rings), 7.74 (d, 2H, aromatic rings), 7.76-7.93 (m, 5H, aromatic rings), 8.03 (d, 1H, aromatic rings) , 8.32 (d, 2H, aromatic rings).

窒素雰囲気下，脱水テトラヒドロフラン（15 ml）中に化合物 2（0.295 g, 0.51 mmol）、アルドリッチ社製ディスパーズレッド１９（以下、「ＤＲ１９」ともいう）（0.085 g, 0.26 mmol）、トリフェニルホスフィン（0.199 g, 0.76 mmol）を加えた後、アゾジカルボン酸ジイソプロピルエステル（40%トルエン溶液）（0.42 ml, 0.8 mmol）を滴下した。その後、50 ℃で44時間攪拌し，薄層クロマトグラフィーを用いて反応終了を確認した。溶媒を留去した後，シリカゲルカラムクロマトグラフィー（溶媒：酢酸エチル，ヘキサン）によって化合物3を得た（0.12 g, 収率：32%）。 (2) Synthesis of Compound III (Compound 3)

Under a nitrogen atmosphere, Compound 2 (0.295 g, 0.51 mmol), Disperse Red 19 (hereinafter also referred to as “DR19”) (0.085 g, 0.26 mmol), triphenylphosphine (Aldrich) in dehydrated tetrahydrofuran (15 ml). 0.199 g, 0.76 mmol) was added, and then azodicarboxylic acid diisopropyl ester (40% toluene solution) (0.42 ml, 0.8 mmol) was added dropwise. Thereafter, the mixture was stirred at 50 ° C. for 44 hours, and the completion of the reaction was confirmed using thin layer chromatography. After the solvent was distilled off, compound 3 was obtained by silica gel column chromatography (solvent: ethyl acetate, hexane) (0.12 g, yield: 32%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 0.67 (t, 6H, CH ₃ CH ₂ N-), 2.30-2.35 (m, 4H, CH ₃ CH ₂ N-), 2.36-2.56 ( m, 4H, -OCH ₂ CH ₂ N- in DR19), 3.16-3.20 (m, 4H, -OCH ₂ CH ₂ N- in DR1), 3.54-3.58 (m, 4H, -OCH ₂ CH ₂ N- in DR19), 3.82-3.88 (m, 4H, -OCH ₂ CH ₂ N- in DR1), 5.86 (d, 2H, aromatic rings), 6.28 (d, 4H, aromatic rings), 7.00-7.17 (m, 12H, aromatic rings), 7.24-7.34 (d, 4H, aromatic rings), 7.55 (d, 2H, aromatic rings), 7.69-7.85 (d, 12H, aromatic rings), 7.92 (d, 6H, aromatic rings), 8.31- 8.34 (m, 6H, aromatic rings). FAB-MS: m / z = 1459.5 [M] ⁺ . Anal. Calc. For C ₈₈ H ₇₄ N ₁₂ O ₁₀ : C, 72.41; H, 5.11; N, 11.52. Found: C, 72.31; H, 5.12; N, 11.38.

アセトン（50 ml）中に (R)-2,2'-ジヒドロキシ-1,1'-ビナフチル（0.50 g, 1.74 mmol）、化合物4（1.40 g, 4.06 mmol）、炭酸カリウム（0.72 g, 5.22 mmol）、少量のヨウ化カリウムを加え、45時間還流した。反応終了を薄層クロマトグラフィーを用いて確認した。溶媒を留去した後、ジクロロメタンを用いて化合物を抽出した。抽出物を硫酸マグネシウムで乾燥し、溶媒を留去した。得られた固形物をメタノールで洗浄し、化合物5を得た（1.19 g, 収率：80%）。 [Example 3]
Synthesis of Compound II (2)

(R) -2,2'-dihydroxy-1,1'-binaphthyl (0.50 g, 1.74 mmol), compound 4 (1.40 g, 4.06 mmol), potassium carbonate (0.72 g, 5.22 mmol) in acetone (50 ml) ), A small amount of potassium iodide was added, and the mixture was refluxed for 45 hours. The completion of the reaction was confirmed using thin layer chromatography. After the solvent was distilled off, the compound was extracted with dichloromethane. The extract was dried over magnesium sulfate and the solvent was distilled off. The obtained solid was washed with methanol to obtain Compound 5 (1.19 g, yield: 80%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) 1.82-1.94 (m, 4H, binaphthyl-OCH ₂ CH ₂ CH ₂ O-Ph), 3.38-3.48 (m, 4H, binaphtyl-OCH ₂ CH ₂ CH ₂ O-Ph), 4.23 (m, 4H, binaphtyl-OCH ₂ CH ₂ CH ₂ O-Ph), 6.59 (d, 4H, aromatic rings), 7.14-7.19 (m, 4H, aromatic rings), 7.30 -7.34 (m, 2H, aromatic rings), 7.41 (d, 2H, aromatic rings), 7.84-7.88 (m, 4H, aromatic rings), 7.94-8.00 (m, 8H, aromatic rings), 8.36 (d, 4H Anal. Calc. for C ₅₀ H ₄₀ N ₆ O ₈ : C, 70.41; H, 4.73; N, 9.85. Found: C, 70.05; H, 4.92; N, 9.81.

Measurement of absorption spectrum The absorption spectrum in tetrahydrofuran of the compound 1 synthesized in Example 1, the compound 3 synthesized in Example 2 and DR1 was measured. The results are shown in FIG. The obtained spectra have maximum absorption wavelengths at 230 nm and 485 nm, respectively, and were found to be derived from binaphthyl sites, donor-acceptor type azobenzene sites, respectively. When the molar extinction coefficient per unit of azobenzene moiety (ε) was compared with DR1, it was found that ε of compounds 1 and 3 was proportional to the number of units in one molecule. In particular, ε at 485 nm of Compound 3 was approximately 100,000, which was found to be highly sensitive to light.

[Example 4]
Preparation of Thin Film Sample (Information Recording Medium) A chloroform solution (1% by mass) of Compound 1 synthesized in Example 1 was dropped on a quartz substrate and rotated at 2,500 rpm for 30 seconds to form a thin film. Thereafter, the solvent was removed at room temperature and under vacuum to obtain a measurement sample. FIG. 2 shows an absorption spectrum of Compound 1 in the thin film. The obtained spectrum had a spectrum shape almost similar to the spectrum in the solution shown in FIG. Thus, it can be seen that the compound of the present invention hardly shows a spectral shape change accompanying aggregation or the like even in a thin film.

  The compound of the present invention is extremely useful as an optical recording material because it is excellent in processability and exhibits high photosensitivity and photoresponsiveness.

The absorption spectrum in the solvent of the compound of this invention is shown. The absorption spectrum in the thin film of the compound of this invention is shown.

Claims (10)

Formula (I):

[Where:
A ₁ represents -N-, -P-, or -B-,
X ₁ is —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , —F, —I, —Cl, —Br _{, -COOH, -COOCH 3, -COCH 3} , -CHO, -NO 2 , or -CN, (where, q is an integer in the range of 1 to 10) indicates,
a and b are each independently an integer in the range of 0 to 6.] Formula (II):

[Where:
A ₂ and A ₃ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₂ and X ₃ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , —F, — I, —Cl, —Br, —COOH, —COOCH ₃ , —COCH ₃ , —CHO, —NO ₂ , or —CN (where q is an integer in the range of 1 to 10);
c and d are each independently an integer in the range of 0 to 6.] Formula (III)

[Where:
A ₅ represents -N-, -P-, or -B-,
A ₄ and A ₆ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₄ , X ₅ and X ₆ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , — F, shown -I, -Cl, -Br, -COOH, -COOCH 3, -COCH 3, -CHO, a -NO ₂ or -CN, (where, q is an integer ranging from 1 to 10),
e, f, g and h are each independently an integer in the range of 0 to 6.] Formula (IV)

[Where:
A ₈ and A ₉ each independently represent —N—, —P—, or —B—;
A ₇ and A ₁₀ are each independently —O—, —S—, —OOC—, —COO—, —SO ₂ —, —COONH—, —CH ₂ O—, —OCH ₂ —, —CH _{2. S -, - SCH 2 -,} - N (C p H 2p + 1) -, or

Where p is an integer in the range of 0-10,
X ₇ , X ₈ , X ₉ and X ₁₀ are each independently —NH ₂ , —H, —C _q F _{2q + 1} , —SCH ₃ , —C _q H _{2q + 1} , —OC _q H _{2q + 1} , -F, -I, -Cl, -Br, -COOH, -COOCH ₃ , -COCH ₃ , -CHO, -NO ₂ , or -CN (where q is an integer in the range of 1 to 10) Indicate
i, j, k, l, m and n are each independently an integer in the range of 0 to 6.] An optical recording material comprising the compound according to claim 1. An information recording medium having an optical recording layer on a substrate, wherein the optical recording layer contains the compound according to any one of claims 1 to 4. A method for improving the photosensitivity of the azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group. A method for improving the photoresponsiveness of an azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group. A method for suppressing aggregation of the azobenzene derivative by bonding an azobenzene derivative having an electron accepting group and an electron donating group to a molecule having a large steric hindrance directly or via a linking group. The method according to claim 7, wherein the highly sterically hindered molecule includes a binaphthyl skeleton.

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