JP4669704B2

JP4669704B2 - UV-decomposing compounds

Info

Publication number: JP4669704B2
Application number: JP2005026191A
Authority: JP
Inventors: 青木　　伸; 和紗桜間
Original assignee: Tokyo University of Science
Current assignee: Tokyo University of Science
Priority date: 2005-02-02
Filing date: 2005-02-02
Publication date: 2011-04-13
Anticipated expiration: 2025-02-02
Also published as: JP2006213615A

Description

本発明は、紫外線照射により、分解する新規化合物に関する。 The present invention relates to a novel compound that decomposes upon irradiation with ultraviolet rays.

紫外線を照射することにより、分解又は構造変化する化合物はいくつか知られており、これらは、パターニングすることで、文字や画像を形成することができる（例えば、特許文献１参照）等種々の用途が考えられる。
しかしながら、従来のこのような化合物は、必ずしも十分に満足なものではなかった。
特開２００４−９１３７５号公報 There are some known compounds that decompose or change their structure when irradiated with ultraviolet rays. These compounds can be used for various purposes such as patterning to form characters and images (see, for example, Patent Document 1). Can be considered.
However, such conventional compounds are not always satisfactory.
JP 2004-91375 A

従って、本発明の目的は、紫外線照射により、分解する新規な化合物を提供することである。 Accordingly, an object of the present invention is to provide a novel compound that decomposes upon irradiation with ultraviolet rays.

斯かる実情に鑑み、本発明者は鋭意研究を行った結果、下記式（Ｉ）で表される化合物を合成することに成功し、このものが紫外線により分解することを見出し本発明を完成した。
即ち、本発明は、次の化合物を提供するものである。 In view of such circumstances, the present inventors have conducted extensive research, and as a result, succeeded in synthesizing a compound represented by the following formula (I), and found that this was decomposed by ultraviolet rays, thereby completing the present invention. .
That is, the present invention provides the following compounds.

＜１＞下記式（ＩＩ）で表される化合物。 < 1 > A compound represented by the following formula (II).

［式（ＩＩ）中、Ｒ¹は、置換基を有していてもよいアリール、アルキル又はヘテロ環基を示し、Ｒは、水素原子、ハロゲン原子若しくはスルホニルアミド基、又は置換基を有していてもよいアミノ、アルキル若しくはアリール基を示し、Ｒ^４は、置換基を有していてもよいアミノ若しくはアミノスルホニル基を示す。Ｒ ^５、Ｒ^６、Ｒ^７及びＲ^８は、水素原子、ハロゲン原子、水酸基、スルホニルアミド基、ニトロ基又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示す。］ [In the formula (II), R ¹ represents an aryl, alkyl or heterocyclic group which may have a substituent, and R has a hydrogen atom, a halogen atom or a sulfonylamide group, or a substituent. R ⁴ represents an optionally substituted amino, alkyl or aryl group, and R ⁴ represents an optionally substituted amino or aminosulfonyl group. R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonylamide group, a nitro group or an amino, aminosulfonyl, alkyl or aryl group which may have a substituent. ]

＜２＞式（ＩＩ）中、Ｒが、アルキル基又は、次の基(a)若しくは (b)である＜１＞記載の化合物。 During <2> formula (II), R is an alkyl group or a following group (a) or (b) <1> Symbol mounting compound.

［式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²及びＲ¹³は、水素原子、低級アルキル基、アリール基又はヘテロ環基を示し、ｍ〜ｑはそれぞれ独立に１、２又は３を示し、ｒは０、１又は２を示す。］ [Wherein, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent a hydrogen atom, a lower alkyl group, an aryl group or a heterocyclic group, and m to q each independently represent 1, 2 or 3. , R represents 0, 1 or 2. ]

＜３＞式中Ｒ¹が、フェニル基であることを特徴とする＜１＞又は＜２＞記載の化合物。 < 3 > The compound according to <1 > or <2 >, wherein R ¹ is a phenyl group.

＜４＞式中Ｒ⁴がジメチルアミノスルホニル基である＜１＞〜＜３＞の何れか１項記載の化合物。 < 4 > The compound according to any one of <1> to < 3 >, wherein R ⁴ is a dimethylaminosulfonyl group.

＜５＞＜１＞〜＜４＞の何れか１項記載の化合物に紫外線を照射して、前記式（II）におけるＲ ^１ −ＳＯ _２Ｏ−基を、ＨＯ−基に変換させることを特徴とする該化合物の分解方法。 <5> <1> - by irradiating ultraviolet rays to a compound according to any one of <4>, the ^R 1 _-SO 2 O-group in the formula (II), the Rukoto is converted into HO- group A method for decomposing the compound.

本発明によれば、紫外線により分解する新規な化合物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the novel compound decomposed | disassembled by an ultraviolet-ray can be provided.

本発明の化合物は、下記式（Ｉ）で表されるものである。 The compound of the present invention is represented by the following formula (I).

［式（Ｉ）中、Ｒ¹は、置換基を有していてもよいアリール、アルキル又はヘテロ環基を示し、Ｒは、水素原子、ハロゲン原子若しくはスルホニルアミド基、又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示し、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、及びＲ⁶は、水素原子、ハロゲン原子、水酸基、スルホニルアミド基、ニトロ基、又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示すが、Ｒ²とＲ³〜Ｒ⁶の何れか１つとが結合して環を形成してもよい。］ [In the formula (I), R ¹ represents an aryl, alkyl or heterocyclic group which may have a substituent, and R has a hydrogen atom, a halogen atom or a sulfonylamide group, or a substituent. Represents an amino, aminosulfonyl, alkyl or aryl group, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonylamide group, a nitro group, or a substituent. Represents an amino, aminosulfonyl, alkyl or aryl group optionally having R 1, R ² may be bonded to any one of R ^{3 to} R ⁶ to form a ring. ]

式中Ｒ¹−ＳＯ₂−は、紫外線により脱離する基である。ここで、Ｒ¹はアリール基、アルキル基又はヘテロ環基を示し、具体的には、フェニル基、ナフチル基、メチル基、エチル基、ピリジル基等が挙げられる。アリール基、アルキル基又はヘテロ環基は、さらに置喚基を有していても良く、このような置換基としては、ハロゲン原子、水酸基、スルホニルアミド基、アミノ基、ニトロ基、アルキルアミノ基、アルキル基、（置換）アリール基等が挙げられる。このうち、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられる。アルキル基としては、総炭素数１〜３０のアルキル基が好ましく、総炭素数１〜２０のアルキル基がさらに好ましい。また、このアルキル基は置換基を有していてもよい。具体例としては、メチル基、エチル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３，５，５−トリメチルヘキシル基、ドデシル基、オクタデシル基、ベンジル基、ピリジルメチル基、ピリミジニルメチル基等が挙げられ、メチル基、エチル基、ブチル基、ヘキシル基、ベンジル、ピリジルメチル基が特に好ましい。 In the formula, R ¹ —SO ₂ — is a group capable of leaving by ultraviolet rays. Here, R ¹ represents an aryl group, an alkyl group, or a heterocyclic group, and specific examples include a phenyl group, a naphthyl group, a methyl group, an ethyl group, and a pyridyl group. The aryl group, alkyl group or heterocyclic group may further have an anchoring group, and examples of such a substituent include a halogen atom, a hydroxyl group, a sulfonylamide group, an amino group, a nitro group, an alkylamino group, Examples thereof include an alkyl group and a (substituted) aryl group. Among these, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable. Moreover, this alkyl group may have a substituent. Specific examples include methyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, octadecyl, benzyl, pyridylmethyl, pyrimidinylmethyl. A methyl group, an ethyl group, a butyl group, a hexyl group, a benzyl, and a pyridylmethyl group are particularly preferable.

式（Ｉ）中、Ｒは、水素原子、ハロゲン原子若しくはスルホニルアミド基、又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示す。このうち、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられる。アミノ基は更に置換基を有していてもよく、この様な置換基としては、アルキル基、アリール基、ヘテロ環基等が挙げられ、更に、２つの置換基が連結して環を形成してもよい。アミノ基に置換するアルキル基としては、総炭素数１〜３０のアルキル基が好ましく、総炭素数１〜２０のアルキル基がさらに好ましい。また、このアルキル基は置換基を有していてもよい。具体例としては、メチル基、エチル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３，５，５−トリメチルヘキシル基、ドデシル基、オクタデシル基、ベンジル基、ピリジルメチル基、ピリミジニルメチル基等が挙げられ、メチル基、エチル基、ブチル基、ヘキシル基、ベンジル、ピリジルメチル基が特に好ましい。
アミノ基に置換するアリール基、ヘテロ環基としては、フェニル基、ナフチル基、ピリジル基等が挙げられる。このアリール基、ヘテロ環基は、置喚基を有していても良く、このような置換基としては、ハロゲン原子、水酸基、スルホニルアミド基、アミノ基、アルキルアミノ基、ニトロ基、アルキル基、（置換）アリール基等が挙げられる。
アミノ基の２つの置換基が連結して形成される環としては、例えば上記式(a)で表される基が好ましい。上記式(a)中、Ｒ⁹、Ｒ¹⁰及びＲ¹¹は、水素原子、低級アルキル基、アリール基又はヘテロ環基を示すが、水素原子が好ましい。 In formula (I), R represents a hydrogen atom, a halogen atom or a sulfonylamide group, or an amino, aminosulfonyl, alkyl or aryl group which may have a substituent. Among these, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The amino group may further have a substituent, and examples of such a substituent include an alkyl group, an aryl group, a heterocyclic group, and the like, and further, two substituents are connected to form a ring. May be. The alkyl group substituted on the amino group is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Moreover, this alkyl group may have a substituent. Specific examples include methyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, octadecyl, benzyl, pyridylmethyl, pyrimidinylmethyl. A methyl group, an ethyl group, a butyl group, a hexyl group, a benzyl, and a pyridylmethyl group are particularly preferable.
Examples of the aryl group and heterocyclic group substituted on the amino group include a phenyl group, a naphthyl group, and a pyridyl group. This aryl group and heterocyclic group may have a locating group, and examples of such a substituent include a halogen atom, a hydroxyl group, a sulfonylamide group, an amino group, an alkylamino group, a nitro group, an alkyl group, (Substituted) aryl groups and the like can be mentioned.
As a ring formed by connecting two substituents of an amino group, for example, a group represented by the above formula (a) is preferable. In the above formula (a), R ⁹ , R ¹⁰ and R ¹¹ represent a hydrogen atom, a lower alkyl group, an aryl group or a heterocyclic group, and preferably a hydrogen atom.

Ｒで示されるアルキル基としては、総炭素数１〜３０のアルキル基が好ましく、総炭素数１〜２０のアルキル基がさらに好ましい。また、このアルキル基は置換基を有していてもよい。具体例としては、メチル基、エチル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３，５，５−トリメチルヘキシル基、ドデシル基、オクタデシル基、ベンジル基、アミノメチル、ピリジルメチル基、ピリミジニルメチル基等が挙げられ、エチル基、ブチル基、ヘキシル基、ベンジル、ピリジルメチル基が特に好ましい。また、上記式(b)で表される基も好ましい。 The alkyl group represented by R is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Moreover, this alkyl group may have a substituent. Specific examples include methyl group, ethyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, 3,5,5-trimethylhexyl group, dodecyl group, octadecyl group, benzyl group, aminomethyl, pyridylmethyl group. And pyrimidinylmethyl group and the like, and ethyl group, butyl group, hexyl group, benzyl and pyridylmethyl group are particularly preferable. A group represented by the above formula (b) is also preferable.

Ｒで示されるアリール基及びヘテロ環基としては、フェニル基、ナフチル基、ピリジル基等が挙げられる。このアリール基は、置喚基を有していても良く、このような置換基としては、ハロゲン原子、水酸基、スルホニルアミド基、アミノ、アルキルアミノ、アルキル、（置換）アリール基等が挙げられる。 Examples of the aryl group and heterocyclic group represented by R include a phenyl group, a naphthyl group, and a pyridyl group. The aryl group may have an anchoring group, and examples of such a substituent include a halogen atom, a hydroxyl group, a sulfonylamide group, amino, alkylamino, alkyl, and a (substituted) aryl group.

式（Ｉ）中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、水素原子、ハロゲン原子、水酸基、スルホニルアミド基、又は置換基を有していてもよいアミノ、アルキル若しくはアリール基を示す。 In the formula (I), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonylamide group, or an optionally substituted amino, alkyl or aryl group Indicates.

このうち、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられる。アミノ基及びアミノスルホニル基は更に置換基を有していてもよく、この様な置換基としては、アルキル基、アリール基等が挙げられ、更に、２つの置換基が連結して環を形成してもよい。アミノ基に置換するアルキル基としては、総炭素数１〜３０のアルキル基が好ましく、総炭素数１〜２０のアルキル基がさらに好ましい。また、このアルキル基は置換基を有していてもよい。具体例としては、メチル基、エチル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３，５，５−トリメチルヘキシル基、ドデシル基、オクタデシル基、ベンジル基、ピリジルメチル基、ピリミジニルメチル基等が挙げられ、エチル基、ブチル基、ヘキシル基、ベンジル、ピリジルメチル基が特に好ましい。
アミノ基に置換するアリール基としては、フェニル基、ナフチル基等が挙げられる。このアリール基は、置喚基を有していても良く、このような置換基としては、ハロゲン原子、水酸基、スルホニルアミド基、アミノ基、ニトロ基、アルキルアミノ基、アルキル基、（置換）アリール基等が挙げられる。 Among these, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The amino group and aminosulfonyl group may further have a substituent. Examples of such a substituent include an alkyl group and an aryl group, and two substituents are linked to form a ring. May be. The alkyl group substituted on the amino group is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Moreover, this alkyl group may have a substituent. Specific examples include methyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, octadecyl, benzyl, pyridylmethyl, pyrimidinylmethyl. Group, etc., and an ethyl group, a butyl group, a hexyl group, a benzyl, and a pyridylmethyl group are particularly preferable.
Examples of the aryl group substituted on the amino group include a phenyl group and a naphthyl group. This aryl group may have a placement group, and examples of such a substituent include a halogen atom, a hydroxyl group, a sulfonylamide group, an amino group, a nitro group, an alkylamino group, an alkyl group, and a (substituted) aryl. Groups and the like.

Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶で示されるアルキル基としては、総炭素数１〜３０のアルキル基が好ましく、総炭素数１〜２０のアルキル基がさらに好ましい。また、このアルキル基は置換基を有していてもよい。具体例としては、メチル基、エチル基、ブチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、３，５，５−トリメチルヘキシル基、ドデシル基、オクタデシル基、ベンジル基、ピリジルメチル基、ピリミジニルメチル基等が挙げられ、エチル基、ブチル基、ヘキシル基、ベンジル、ピリジルメチル基が特に好ましい。 The alkyl group represented by R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. Moreover, this alkyl group may have a substituent. Specific examples include methyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, octadecyl, benzyl, pyridylmethyl, pyrimidinylmethyl. Group, etc., and an ethyl group, a butyl group, a hexyl group, a benzyl, and a pyridylmethyl group are particularly preferable.

Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶で示されるアリール基としては、フェニル基、ナフチル基等が挙げられる。このアリール基は、置喚基を有していても良く、このような置換基としては、ハロゲン原子、水酸基、スルホニルアミド基、アミノ、アルキルアミノ、アルキル、（置換）アリール基等が挙げられる。 Examples of the aryl group represented by R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a phenyl group and a naphthyl group. The aryl group may have an anchoring group, and examples of such a substituent include a halogen atom, a hydroxyl group, a sulfonylamide group, amino, alkylamino, alkyl, and a (substituted) aryl group.

また、Ｒ²とＲ³〜Ｒ⁶の何れか１つの基とは結合して環を形成してもよい。このような環を形成したものの例としては、上記式（ＩＩ）で表される化合物が挙げられる。式（ＩＩ）中、形成された環は、更に、置換基Ｒ⁷、Ｒ⁸を有していてもよい。Ｒ⁷、Ｒ⁸で示される置換基としては、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶で例示したものと同じものが挙げられ、好ましい基も同様である。
以下に、本発明化合物の具体例を示すが本発明は、これらに限定されるものではない。 R ² and any one of R ^{3 to} R ⁶ may be bonded to form a ring. An example of such a ring formed is a compound represented by the above formula (II). In formula (II), the formed ring may further have substituents R ⁷ and R ⁸ . Examples of the substituent represented by R ⁷ and R ⁸ include the same groups as those exemplified for R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and preferred groups are also the same.
Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

本発明化合物は、例えば次の式に従って合成することができる。 The compound of the present invention can be synthesized, for example, according to the following formula.

［式中、Ｒ¹は、置換基を有していてもよいアリール、アルキル又はヘテロ環基を示し、Ｒは、水素原子、ハロゲン原子若しくはスルホニルアミド基、又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示し、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、及びＲ⁶は、水素原子、ハロゲン原子、水酸基、スルホニルアミド基、ニトロ基、又は置換基を有していてもよいアミノ、アミノスルホニル、アルキル若しくはアリール基を示すが、Ｒ²とＲ³〜Ｒ⁶の何れか１つとが結合して環を形成してもよい。
halはハロゲン原子を示す。］
即ち、原料化合物（１１）の水酸基にＲ¹−ＳＯ₂−のハロゲン化物を反応させることにより本発明化合物（Ｉ）を得ることができる。原料化合物（１１）は、文献（G.K.Walkup, B.Imperiali, J.Org.Chem.63,6727-6731, 1998）を参照することにより得ることができる。また、一般式（１）中のＲで示される基の導入は、常法により行うことができる。 [Wherein, R ¹ represents an aryl, alkyl or heterocyclic group which may have a substituent, and R may have a hydrogen atom, a halogen atom or a sulfonylamide group, or a substituent. Represents an amino, aminosulfonyl, alkyl or aryl group, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ have a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonylamide group, a nitro group, or a substituent. An amino, aminosulfonyl, alkyl, or aryl group that may be present is shown, and R ² and any one of R ^{3 to} R ⁶ may combine to form a ring.
hal represents a halogen atom. ]
That is, the compound (I) of the present invention can be obtained by reacting the halide of R ¹ —SO ₂ — with the hydroxyl group of the starting compound (11). The starting compound (11) can be obtained by referring to literature (GK Walkup, B. Imperiali, J. Org. Chem. 63, 6727-6731, 1998). In addition, the introduction of the group represented by R in the general formula (1) can be performed by a conventional method.

本発明化合物は、紫外線を照射すると次のように基Ｒ¹−ＳＯ₂−が外れる。 When the compound of the present invention is irradiated with ultraviolet rays, the group R ¹ —SO ₂ — is removed as follows.

［式中、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、前記と同じものを示す。］
従って、この反応を利用する種々の用途が考えられる。例えば次の化合物に紫外線を照射すると発色するので、感光性の材料としての用途が考えられる。 [Wherein, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as described above. ]
Therefore, various uses utilizing this reaction are conceivable. For example, since the following compound is colored when irradiated with ultraviolet rays, it can be used as a photosensitive material.

以下に本発明の実施例について説明するが、これに限定されるものではない。また実施例中の％は、特に断らない限り、重量（質量）基準である。
［実施例１］
化合物（Ｉ）の合成 Examples of the present invention will be described below, but the present invention is not limited thereto. Further,% in the examples is based on weight (mass) unless otherwise specified.
[Example 1]
Synthesis of compound (I)

・8-ベンゼンスルホニルオキシ-2-メチルキノリン-5-(N,N-ジメチル)スルホンアミド (15)の合成
11(1.7 g, 6.4 mmol) をジクロロメタン13mlに溶かし０℃まで氷冷後、トリエチルアミン (780 mg, 7.7 mmol, 1.2 eq)を加え、ベンゼンスルホニルクロライド (1.3g, 7.1 mmol, 1.1 eq) を1時間かけて滴下した。さらに室温で1.5時間撹拌し、水 5mlを加えて0.5時間撹拌後、炭酸カリウム水溶液とジクロロメタンで抽出した。ジクロロメタン層を炭酸カリウムで脱水し、シリカゲルクロマトグラフィー（展開溶媒 AcOEt / n-ヘキサン=1 : 4）で精製して15を無色透明のアモルファスとして得た。(2.5 g, 6.1 mmol, 96 %) ・ Synthesis of 8-benzenesulfonyloxy-2-methylquinoline-5- (N, N-dimethyl) sulfonamide (15)
11 (1.7 g, 6.4 mmol) was dissolved in 13 ml of dichloromethane and cooled to 0 ° C with ice. Triethylamine (780 mg, 7.7 mmol, 1.2 eq) was added and benzenesulfonyl chloride (1.3 g, 7.1 mmol, 1.1 eq) was added for 1 hour. It was dripped over. The mixture was further stirred at room temperature for 1.5 hours, added with 5 ml of water, stirred for 0.5 hour, and extracted with an aqueous potassium carbonate solution and dichloromethane. The dichloromethane layer was dehydrated with potassium carbonate and purified by silica gel chromatography (developing solvent AcOEt / n-hexane = 1: 4) to obtain 15 as a colorless transparent amorphous. (2.5 g, 6.1 mmol, 96%)

IR (neat; NaCl plate) 3092, 3066, 2962, 2923, 1598, 1497, 1450, 1375, 1343, 1 188, 1151, 1060, 955, 797, 726 cm^-1
¹H NMR (CDCl₃) δ = 8.93 (1H, J = 8.7 Hz, d), 8.10 (1H, J = 8.3 Hz, d), 8.0 1 (2H, J = 8.3 Hz, d), 7.73 (1H, J = 8.3 Hz, d), 7.62 (1H, J = 7.6, 1.4 Hz, dd), 7.48 (2H, J = 8.0, 1.6 Hz, dd), 7.35 (1H, J = 8.9 Hz, d), 2.81 (6H, s), 2.55 (3H, s)
¹³C NMR (CDCl₃) δ = 160.1, 148.1, 140.7, 135.4, 133.9, 132.9, 131.3, 128.4, 128.3, 128.2, 124.2, 123.8, 120.936.98, 24.59 IR (neat; NaCl plate) 3092, 3066, 2962, 2923, 1598, 1497, 1450, 1375, 1343, 1 188, 1151, 1060, 955, 797, 726 cm ^-1
¹ H NMR (CDCl ₃ ) δ = 8.93 (1H, J = 8.7 Hz, d), 8.10 (1H, J = 8.3 Hz, d), 8.0 1 (2H, J = 8.3 Hz, d), 7.73 (1H, J = 8.3 Hz, d), 7.62 (1H, J = 7.6, 1.4 Hz, dd), 7.48 (2H, J = 8.0, 1.6 Hz, dd), 7.35 (1H, J = 8.9 Hz, d), 2.81 ( 6H, s), 2.55 (3H, s)
¹³ C NMR (CDCl ₃ ) δ = 160.1, 148.1, 140.7, 135.4, 133.9, 132.9, 131.3, 128.4, 128.3, 128.2, 124.2, 123.8, 120.936.98, 24.59

・8-ベンゼンスルホニルオキシ-5-(N,N-ジメチル)スルホンアミド-2-ブロモメチルキノリン (16) の合成
15 (1.5 g, 3.7 mmol)を蒸留四塩化炭素190mlに溶かした。その後N-ブロモスクシンイミド(NBS) (380 mg, 2.6 mmol, 0.6 eq)と2,2'-アゾビス-2-メチルプロピオニトリル(AIBN)(触媒量) を少量ずつ加えながら8時間還流した。室温まで放冷した後、溶媒を減圧留去し、残渣をジクロロメタンに溶かして炭酸ナトリウム/ チオ硫酸ナトリウム= 1 : 1飽和水溶液で洗浄した。水層をジクロロメタンで抽出し、ジクロロメタン層を合わせて無水硫酸ナトリウムで脱水した。溶媒を減圧留去し、シリカゲルクロマトグラフィー（展開溶媒 AcOEt / n-hexane=1:5）で精製し、無色透明のアモルファスとして16を得た。（250 mg, 0.52 mmol, 14 %）原料回収は860 mg (2.1 mmol, 56 %) だった。・ Synthesis of 8-benzenesulfonyloxy-5- (N, N-dimethyl) sulfonamido-2-bromomethylquinoline (16)
15 (1.5 g, 3.7 mmol) distilled carbon tetrachloride Dissolved in 190 ml. Thereafter, N-bromosuccinimide (NBS) (380 mg, 2.6 mmol, 0.6 eq) and 2,2′-azobis-2-methylpropionitrile (AIBN) (catalytic amount) were added in small portions and refluxed for 8 hours. After allowing to cool to room temperature, the solvent was distilled off under reduced pressure, and the residue was dissolved in dichloromethane and sodium carbonate. / sodium thiosulfate = 1: Washed with a saturated aqueous solution. The aqueous layer was extracted with dichloromethane, and the dichloromethane layers were combined and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent AcOEt / n-hexane = 1: 5) to obtain 16 as a colorless transparent amorphous. (250 mg, 0.52 mmol, 14%) The raw material recovery was 860 mg (2.1 mmol, 56%).

IR (KBr pellet) 3092, 2921, 1706, 1596, 1498, 1460, 1375, 1343, 1189, 11 47, 1054, 957, 799, 619 cm^-1
¹H NMR (CDCl₃) δ = 9.05 (1H, J = 9.0 Hz, d), 8.18 (1H, J = 8.3 Hz, d), 8.0 0 (2H, J = 8.5 Hz, d), 7.80 (1H, J = 8.3 Hz, d), 7.67 (1H, J = 8.9 Hz, d), 7.65 (1H, J = 7.4), 7.52 (2H, J = 7.8 Hz, t), 4.4 2 (2H, s), 2.83 (6H, s)
¹³C NMR (CDCl₃) δ = 158.1, 149.0, 140.9, 135.9, 134.9, 134.4, 132.0, 130.2, 129.0, 125.4, 123.4, 121.9, 37.42, 33.08 IR (KBr pellet) 3092, 2921, 1706, 1596, 1498, 1460, 1375, 1343, 1189, 11 47, 1054, 957, 799, 619 cm ^-1
¹ H NMR (CDCl ₃ ) δ = 9.05 (1H, J = 9.0 Hz, d), 8.18 (1H, J = 8.3 Hz, d), 8.0 0 (2H, J = 8.5 Hz, d), 7.80 (1H, J = 8.3 Hz, d), 7.67 (1H, J = 8.9 Hz, d), 7.65 (1H, J = 7.4), 7.52 (2H, J = 7.8 Hz, t), 4.4 2 (2H, s), 2.83 (6H, s)
¹³ C NMR (CDCl ₃ ) δ = 158.1, 149.0, 140.9, 135.9, 134.9, 134.4, 132.0, 130.2, 129.0, 125.4, 123.4, 121.9, 37.42, 33.08

・1-(8-ベンゼンスルホニルオキシ-5-(N,N-ジメチル)スルホンアミド-キノリニルメチル)-4,7,10-トリス(tert-ブトキシカルボニル)-1,4,7,10-テトラアザシクロドデカン (18) の合成
17 (585 mg, 1.24 mmol) をアセトニトリル50mlに溶かした後、16 (658 mg, 1.35 mmol, 1.1 eq)と炭酸ナトリウム(225 mg, 2.12 mmol, 1.7 eq)を加え、６０℃で15 時間撹拌した。室温まで放冷し不要物をろ去した後、溶媒を減圧留去し、シリカゲルクラマトグラフィー（展開溶媒 MeOH / CH₂Cl₂=1 : 80）で精製し薄黄色のアモルファスとして18を得た。(1.0 g, 1.14 mmol, 92 %) 1- (8-Benzenesulfonyloxy-5- (N, N-dimethyl) sulfonamido-quinolinylmethyl) -4,7,10-tris (tert-butoxycarbonyl) -1,4,7,10-tetraaza Synthesis of cyclododecane (18)
After dissolving 17 (585 mg, 1.24 mmol) in 50 ml of acetonitrile, 16 (658 mg, 1.35 mmol, 1.1 eq) and sodium carbonate (225 mg, 2.12 mmol, 1.7 eq) was added, and the mixture was stirred at 60 ° C. for 15 hours. After allowing to cool to room temperature and filtering off unnecessary materials, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent MeOH / CH ₂ Cl ₂ = 1: 80) to obtain 18 as a pale yellow amorphous. (1.0 g, 1.14 mmol, 92%)

IR (KBr pellet) 2975, 2931, 1685, 1462, 1415, 1365, 1250, 1154, 1059, 976, 95 6, 808, 727, 599 cm^-1
¹H NMR (CDCl₃) δ = 8.96 (1H, J = 8.9 Hz, d), 8.11 (1H, J = 8.0 Hz, d), 8.0 0 (2H, J = 7.1, 1.2 Hz, dd), 7.65 (1H, J = 4.4, t), 7.61(2H, J = 8.3, d), 7.53 (2H, J = 8.0 Hz, t), 3.96 (2H, s), 3.56-2.78 (16H, br), 2.83 (6H, s), 1.54-1.42 (36 H, br)
¹³C NMR (CDCl₃) δ = 149.1, 141.3, 136.3, 134.3, 133.5, 131.7, 129.5, 129.1, 128.5, 128.3, 125.4, 124.3, 120.4, 81.30, 79.50, 57.05, 55. 14, 54.21, 49.89, 47.78, 37.38, 36.62, 28.69, 28.46 IR (KBr pellet) 2975, 2931, 1685, 1462, 1415, 1365, 1250, 1154, 1059, 976, 95 6, 808, 727, 599 cm ^-1
¹ H NMR (CDCl ₃ ) δ = 8.96 (1H, J = 8.9 Hz, d), 8.11 (1H, J = 8.0 Hz, d), 8.0 0 (2H, J = 7.1, 1.2 Hz, dd), 7.65 ( 1H, J = 4.4, t), 7.61 (2H, J = 8.3, d), 7.53 (2H, J = 8.0 Hz, t), 3.96 (2H, s), 3.56-2.78 (16H, br), 2.83 ( 6H, s), 1.54-1.42 (36 H, br)
¹³ C NMR (CDCl ₃ ) δ = 149.1, 141.3, 136.3, 134.3, 133.5, 131.7, 129.5, 129.1, 128.5, 128.3, 125.4, 124.3, 120.4, 81.30, 79.50, 57.05, 55. 14, 54.21, 49.89, 47.78 , 37.38, 36.62, 28.69, 28.46

・1-(8-ヒドロキシ-5-(N,N-ジメチル)スルホンアミド-キノリニルメチル)-4,7,10 -トリス(tert-ブトキシカルボニル)-1,4,7,10-テトラアザシクロドデカン(19) の合成
18 (1.0 g, 1.1 mmol) をメタノール 40 mlに溶かし、28% アンモニア水溶液35 mlを加えて5日間還流した。溶媒を除去し、シリカゲルクロマトグラフィー（展開溶媒 MeOH / CH₂Cl₂=1 : 100）で精製し、19を薄黄色のアモルファスで得た。（820 mg, 1.1 mmol, 97 %） 1- (8-hydroxy-5- (N, N-dimethyl) sulfonamido-quinolinylmethyl) -4,7,10-tris (tert-butoxycarbonyl) -1,4,7,10-tetraazacyclododecane ( 19) Synthesis
18 (1.0 g, 1.1 mmol) was dissolved in 40 ml of methanol, 35 ml of 28% aqueous ammonia solution was added, and the mixture was refluxed for 5 days. The solvent was removed and the residue was purified by silica gel chromatography (developing solvent MeOH / CH ₂ Cl ₂ = 1: 100) to obtain 19 as a pale yellow amorphous. (820 mg, 1.1 mmol, 97%)

IR (KBr pellet) 2974, 1689, 1564, 1502, 1462, 1415, 1365, 1320, 1251,0 1154, 959, 858, 773, 716, 548 cm^-1
¹H NMR (CD₃OD) δ = 9.01 (1H, J = 9.0 Hz, d), 8.10 (1H, J = 8.5 Hz, d), 7.7 5 (1H, J = 8.5 Hz, d), 7.20 (1H, J = 8.3 Hz, d), 4.12 (2H, s ), 3.31-3.64 (10H, br), 3.30 (5H, s), 2.68-2.77 (10H, br), 0 .91-1.49 (30H, br)
¹³C NMR (CD₃OD) δ = 159.6, 159.2, 157.9, 157.5, 157.4, 140.9, 139.2, 135.4, 134.0, 126.2, 125.8, 123.0, 120.7, 115.4, 110.2, 97.3, 95.6 , 95.5, 81.3, 81.2, 59.1, 57.7, 57.5, 57.4, 56.1, 56.0, 37.8 , 29.1, 28.9 IR (KBr pellet) 2974, 1689, 1564, 1502, 1462, 1415, 1365, 1320, 1251,0 1154, 959, 858, 773, 716, 548 cm ^-1
¹ H NMR (CD ₃ OD) δ = 9.01 (1H, J = 9.0 Hz, d), 8.10 (1H, J = 8.5 Hz, d), 7.7 5 (1H, J = 8.5 Hz, d), 7.20 (1H , J = 8.3 Hz, d), 4.12 (2H, s), 3.31-3.64 (10H, br), 3.30 (5H, s), 2.68-2.77 (10H, br), 0.99-1.49 (30H, br )
¹³ C NMR (CD ₃ OD) δ = 159.6, 159.2, 157.9, 157.5, 157.4, 140.9, 139.2, 135.4, 134.0, 126.2, 125.8, 123.0, 120.7, 115.4, 110.2, 97.3, 95.6, 95.5, 81.3, 81.2, 59.1, 57.7, 57.5, 57.4, 56.1, 56.0, 37.8, 29.1, 28.9

・1-(8-ベンゼンスルホニルオキシ-5-(N,N-ジメチル)スルホンアミド-キノリルメチル)-1,4,7,10-テトラアザシクロドデカン (22) の合成
19 (30 mg, 0.11 mmol)をジクロロメタン10 mlに溶かし、ジクロロメタン1mlで薄めたトリフルオロ酢酸(TFA)(150 mg, 1.39 mmol, 40 eq) を加えた。室温で17時間撹拌後、溶媒を減圧留去し、トルエンでTFAを共沸させた。残渣を少量のエタノールに溶かし、ジエチルエーテルで再沈殿すると白色粉体として22を得た。 (26 mg, 87 %)
融点 159-160 ℃
¹H NMR (D₂O) δ = 9.11 (1H, J = 8.8 Hz, d), 8.15 (1H, J = 8.0 Hz, d), 7.87 (2H, J = 8.4 Hz, d), 7.81 (1H, J = 7.6 Hz, t), 7.78 (1H, J = 8.8 Hz, d), 7.63 (2H, J = 8.4 Hz, t), 7.43 (1H, J = 8.4 Hz, d), 4.1 8 (2H, s), 3.30-3.07 (16H, br), 2.82 (6H, s)
¹³C NMR １７３．０，１７２．６，１６９．９，１５８．０，１５１．５，
１４５．７，１４５．０，１４２．８，１４０．８，１４０．３，
１３９．５，１３８．４，１３５．４，１３１．１，１２８．１，
１２４．２，６８．０，５８．７，５４．１，５１．９，５１．５，
４６．７
元素分析 C₃₂ F₉H₄₁N₆O₁₂S₂
理論値 C : 41.03 %, H : 4.41 %, N : 8.97 %
測定値 C : 40.92 %, H : 4.58 %, N : 9.40 % Synthesis of 1- (8-benzenesulfonyloxy-5- (N, N-dimethyl) sulfonamido-quinolylmethyl) -1,4,7,10-tetraazacyclododecane (22)
19 (30 mg, 0.11 mmol) was dissolved in 10 ml of dichloromethane, and dichloromethane 1 Trifluoroacetic acid (TFA) (150 mg, 1.39 mmol, 40 eq) diluted in ml was added. After stirring at room temperature for 17 hours, the solvent was distilled off under reduced pressure, and TFA was azeotroped with toluene. The residue was dissolved in a small amount of ethanol and reprecipitated with diethyl ether to obtain 22 as a white powder. (26 mg, 87%)
Melting point 159-160 ℃
¹ H NMR (D ₂ O) δ = 9.11 (1H, J = 8.8 Hz, d), 8.15 (1H, J = 8.0 Hz, d), 7.87 (2H, J = 8.4 Hz, d), 7.81 (1H, J = 7.6 Hz, t), 7.78 (1H, J = 8.8 Hz, d), 7.63 (2H, J = 8.4 Hz, t), 7.43 (1H, J = 8.4 Hz, d), 4.1 8 (2H, s ), 3.30-3.07 (16H, br), 2.82 (6H, s)
¹³ C NMR 173.0, 172.6, 169.9, 158.0, 151.5,
145.7, 145.0, 142.8, 140.8, 140.3,
139.5, 138.4, 135.4, 131.1, 128.1,
124.2, 68.0, 58.7, 54.1, 51.9, 51.5,
46.7
Elemental analysis C ₃₂ F ₉ H ₄₁ N ₆ O ₁₂ S ₂
Theoretical value C: 41.03%, H: 4.41%, N: 8.97%
Measured value C: 40.92%, H: 4.58%, N: 9.40%

・1-(8-(4-フルオロベンゼンスルホニルオキシ)-5-(N,N-ジメチル)スルホンアミド -キノリルメチル)- 4,7,10-tris(tert_ブトキシカルボニル)-1,4,7,10-テトラアザシクロドデカン (20) の合成
19 (30 mg, 0.041 mmol) をジクロロメタン10 mlに溶かし０℃まで氷冷後、トリエチルアミン (5 mg, 0.049 mmol)を加え、4-フルオロベンゼンスルホニルクロライド (9.6 mg, 0.049 mmol) を滴下した。さらに室温で30 時間撹拌し、水 1 mlを加えて0.5時間撹拌後、炭酸カリウム水溶液とジクロロメタンで抽出した。ジクロロメタン層を炭酸カリウムで脱水し溶媒を減圧留去した後、シリカゲルクロマトグラフィー（展開溶媒 MeOH / CH₂Cl₂=1 : 200）で精製して20を薄黄色透明のアモルファスとして得た。(40 mg, 0.045 mmol, > 99 %)
¹H NMR (CDCl₃) δ = 8.96 (1H, J = 11 Hz, d), 8.13 (1H, J = 11 Hz, d), 8.04 (2H, J = 9.3, 5.4, dd), 7.64 (2H, J = 11, d), 7.26 (1H, d), 7. 21 (1H, J = 11 Hz, d), 3.98 (2H, s), 3.47-2.80 (16H, br), 2.82 (6H, s), 1.58-1.26 (36H, br) 1- (8- (4-Fluorobenzenesulfonyloxy) -5- (N, N-dimethyl) sulfonamido-quinolylmethyl) -4,7,10-tris (tert_butoxycarbonyl) -1,4,7, Synthesis of 10-tetraazacyclododecane (20)
19 (30 mg, 0.041 mmol) was dissolved in dichloromethane (10 ml) and cooled to 0 ° C with ice. Triethylamine (5 mg, 0.049 mmol) was added, and 4-fluorobenzenesulfonyl chloride (9.6 mg, 0.049 mmol) was added dropwise. The mixture was further stirred at room temperature for 30 hours, added with 1 ml of water, stirred for 0.5 hour, and extracted with an aqueous potassium carbonate solution and dichloromethane. The dichloromethane layer was dehydrated with potassium carbonate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent MeOH / CH ₂ Cl ₂ = 1: 200) to obtain 20 as a light yellow transparent amorphous. (40 mg, 0.045 mmol,> 99%)
¹ H NMR (CDCl ₃ ) δ = 8.96 (1H, J = 11 Hz, d), 8.13 (1H, J = 11 Hz, d), 8.04 (2H, J = 9.3, 5.4, dd), 7.64 (2H, J = 11, d), 7.26 (1H, d), 7.21 (1H, J = 11 Hz, d), 3.98 (2H, s), 3.47-2.80 (16H, br), 2.82 (6H, s) , 1.58-1.26 (36H, br)

・1-(8-(2,3,4,5,6-ペンタフルオロベンゼンスルホニルオキシ)-5-(N,N-ジメチル) スルホンアミド-キノリルメチル)- 4,7,10-tris(tert_ブトキシカルボニル)-1,4,7, 10-テトラアザシクロドデカン (21) の合成
19 (35 mg, 0.048 mmol) をジクロロメタン10 mlに溶かし０℃まで氷冷後、トリエチルアミン (10 mg, 0.10 mmol)を加え、2,3,4,5,6-ペンタフルオロベンゼンスルホニルクロライド (16 mg, 0.060 mmol) を滴下した。さらに室温で4日間撹拌し、水 1 mlを加えて0.5時間撹拌後、炭酸カリウム水溶液とジクロロメタンで抽出した。ジクロロメタン層を炭酸カリウムで脱水し溶媒を減圧留去した後、シリカゲルクロマトグラフィー（展開溶媒 MeOH / CH₂Cl₂=1 : 200）で精製して21を無色透明のアモルファスとして得た。(38 mg, 0.039 mmol, 82 %)
¹H NMR (CDCl₃) δ = 8.98 (1H, J = 12 Hz, d), 8.18 (1H, J = 11 Hz, d), 7.76 (1H, J = 12, d), 7.70 (1H, J = 12, d), 3.82-2.66 (18H, br), 2. 82 (6H, s), 1.66-1.25 (36H, br)
¹³C NMR (CDCl₃) δ = 159.0, 156.0, 155.6, 148.4, 147.0, 143.7, 140.6, 133.8, 133.0, 129.3, 125.6, 124.3, 121.4, 79.74, 58.55, 54.79, 51. 11, 49.98, 47.37, 37.38, 28.64, 28.36 1- (8- (2,3,4,5,6-pentafluorobenzenesulfonyloxy) -5- (N, N-dimethyl) sulfonamido-quinolylmethyl) -4,7,10-tris (tert_butoxy Synthesis of (carbonyl) -1,4,7,10-tetraazacyclododecane (21)
19 (35 mg, 0.048 mmol) was dissolved in 10 ml of dichloromethane and cooled to 0 ° C with ice. Triethylamine (10 mg, 0.10 mmol) was added and 2,3,4,5,6-pentafluorobenzenesulfonyl chloride (16 mg , 0.060 mmol) was added dropwise. The mixture was further stirred at room temperature for 4 days, 1 ml of water was added, and the mixture was stirred for 0.5 hour, followed by extraction with an aqueous potassium carbonate solution and dichloromethane. The dichloromethane layer was dehydrated with potassium carbonate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent MeOH / CH ₂ Cl ₂ = 1: 200) to obtain 21 as a colorless transparent amorphous. (38 mg, 0.039 mmol, 82%)
¹ H NMR (CDCl ₃ ) δ = 8.98 (1H, J = 12 Hz, d), 8.18 (1H, J = 11 Hz, d), 7.76 (1H, J = 12, d), 7.70 (1H, J = 12, d), 3.82-2.66 (18H, br), 2. 82 (6H, s), 1.66-1.25 (36H, br)
¹³ C NMR (CDCl ₃ ) δ = 159.0, 156.0, 155.6, 148.4, 147.0, 143.7, 140.6, 133.8, 133.0, 129.3, 125.6, 124.3, 121.4, 79.74, 58.55, 54.79, 51. 11, 49.98, 47.37, 37.38 , 28.64, 28.36

・1-(8-(4-フルオロベンゼンスルホニルオキシ)-5-(N,N-ジメチル)スルホンアミド -キノリルメチル)-1,4,7,10-テトラアザシクロドデカン (23) の合成
20 (36 mg, 0.040 mmol)をジクロロメタン3 mlに溶かし、ジクロロメタン3mlで薄めたトリフルオロ酢酸(TFA)(150 mg, 1.3 mmol) を加えた。室温で4日間撹拌後、溶媒を減圧留去し、トルエンでTFAを共沸させた。残渣を少量のエタノールに溶かし、ジエチルエーテルで再沈殿すると白色粉体として23を得た。 (15 mg, 45 %)
融点 164-166 ℃
¹H NMR (D₂O) δ = 9.12 (1H, J = 12 Hz, d), 8.15 (1H, J = 11 Hz, d), 7.93 (2 H, J = 9.6, 6.8 Hz, dd), 7.79 (1H, J = 12 Hz, d), 7.40 (1H, J = 12 Hz, d), 7.37 (2H, J = 12 Hz, t), 4.18 (2H, s), 3.36-3.06 (16H , br), 2.82 (6H, s)
元素分析 C₃₀ F₇H₃₉N₆O₁₀S₂
理論値 C : 42.86 %, H : 4.68 %, N : 10.00 %, S : 7.63
測定値 C : 42.88 %, H : 4.67 %, N : 9.90 %, S : 7.79 Synthesis of 1- (8- (4-fluorobenzenesulfonyloxy) -5- (N, N-dimethyl) sulfonamido-quinolylmethyl) -1,4,7,10-tetraazacyclododecane (23)
Dissolve 20 (36 mg, 0.040 mmol) in 3 ml of dichloromethane. Trifluoroacetic acid (TFA) (150 mg, 1.3 mmol) diluted with ml was added. After stirring at room temperature for 4 days, the solvent was distilled off under reduced pressure, and TFA was azeotroped with toluene. The residue was dissolved in a small amount of ethanol and reprecipitated with diethyl ether to obtain 23 as a white powder. (15 mg, 45%)
Melting point 164-166 ℃
¹ H NMR (D ₂ O) δ = 9.12 (1H, J = 12 Hz, d), 8.15 (1H, J = 11 Hz, d), 7.93 (2 H, J = 9.6, 6.8 Hz, dd), 7.79 (1H, J = 12 Hz, d), 7.40 (1H, J = 12 Hz, d), 7.37 (2H, J = 12 Hz, t), 4.18 (2H, s), 3.36-3.06 (16H, br) , 2.82 (6H, s)
Elemental analysis C ₃₀ F ₇ H ₃₉ N ₆ O ₁₀ S ₂
Theoretical value C: 42.86%, H: 4.68%, N: 10.00%, S: 7.63
Measured value C: 42.88%, H: 4.67%, N: 9.90%, S: 7.79

・1-(8-(2,3,4,5,6-ペンタフルオロベンゼンスルホニルオキシ)-5-(N,N-ジメチル) スルホンアミド-キノリルメチル)-1,4,7,10- テトラアザシクロドデカン (24) の合成
21 (20 mg, 0.02 mmol)をジクロロメタン3 mlに溶かし、ジクロロメタン1 mlで薄めたトリフルオロ酢酸(TFA)(150 mg, 1.3 mmol) を加えた。室温で4日時間撹拌後、溶媒を減圧留去し、トルエンでTFAを共沸させた。残渣を少量のエタノールに溶かし、ジエチルエーテルで再沈殿すると白色粉体として24を得た。 (11 mg, 53 %)
融点 180-184 ℃
¹H NMR (D₂O) δ = 9.15 (1H, J = 12 Hz, d), 8.26 (1H, J = 11 Hz, d), 7.83 (1 H, J = 12 Hz, d), 7.79 (1H, J = 11 Hz, d), 4.21 (2H, s), 3.29-3. 06 (16H, br), 2.84 (6H, s)
元素分析 C₃₂ F₁₁H₃₉N₆O₁₀ S₂
理論値 C : 40.85 %, H : 4.18 %, N : 8.93 %
測定値 C : 40.52 %, H : 4.52 %, N : 8.96 % 1- (8- (2,3,4,5,6-pentafluorobenzenesulfonyloxy) -5- (N, N-dimethyl) sulfonamido-quinolylmethyl) -1,4,7,10-tetraazacyclo Synthesis of dodecane (24)
21 (20 mg, 0.02 mmol) was dissolved in 3 ml of dichloromethane, and trifluoroacetic acid (TFA) (150 mg, 1.3 mmol) diluted with 1 ml of dichloromethane was added. After stirring for 4 hours at room temperature, the solvent was distilled off under reduced pressure, and TFA was azeotroped with toluene. The residue was dissolved in a small amount of ethanol and reprecipitated with diethyl ether to obtain 24 as a white powder. (11 mg, 53%)
Melting point 180-184 ℃
¹ H NMR (D ₂ O) δ = 9.15 (1H, J = 12 Hz, d), 8.26 (1H, J = 11 Hz, d), 7.83 (1 H, J = 12 Hz, d), 7.79 (1H , J = 11 Hz, d), 4.21 (2H, s), 3.29-3. 06 (16H, br), 2.84 (6H, s)
Elemental analysis C ₃₂ F ₁₁ H ₃₉ N ₆ O ₁₀ S ₂
Theoretical value C: 40.85%, H: 4.18%, N: 8.93%
Measured value C: 40.52%, H: 4.52%, N: 8.96%

８−ベンゼンスルホニルオキシ−２−（ビス（２−ピリジルメチル）アミノ）メチル−５−ジメチルアミノスルホニルキノリン（２６）．
８−ベンゼンスルホニルオキシ−２−ブロモメチル−５−ジメチルアミノスルホニルキノリン（０．２３ｇ，０．４６ｍｍｏｌ）、ジピコリルアミン（８４ｍｇ，０．４２ｍｍｏｌ）、Ｎａ₂ＣＯ₃（８１ｍｇ，０．７６ｍｍｏｌ）をアセニトリル（３ｍＬ）中で３時間加熱還流した。反応液中の不溶物をろ去し、反応液を減圧蒸留した後、粗生成物をシリカゲルカラムクロマトグファフィー（溶出溶媒：ＣＨ₂Ｃｌ₂／ＭｅＯＨ＝４０：１）で精製し目的化合物２６をオレンジ色の油状物質として得た（１６０ｍｇ，５７％）。
¹ＨＮＭＲ（３００ＭＨｚ，ＴＭＳ／ＣＤＣｌ₃）δ：２．８３（ｓ，６Ｈ），３．８０（ｓ，２Ｈ），３．８４（ｓ，４Ｈ），７．１８（ｄｄｄ，２Ｈ，Ｊ＝１．０，６．０，１２Ｈｚ），７．４０−７．４５（ｍ，２Ｈ），７．５１−７．６０（ｍ，２Ｈ），７．６８（ｄｄｄ，２Ｈ，Ｊ＝１．８，７．５，８．１Ｈｚ），７．７２（ｄ，１Ｈ，Ｊ＝８．２Ｈｚ），７．８７（ｄ，１Ｈ，Ｊ＝８．７Ｈｚ），７．９５−８．１４（ｍ，２Ｈ），８．１２（ｄ，１Ｈ，Ｊ＝８．２Ｈｚ），８．５７（ｄｄｄ，２Ｈ，Ｊ＝１．０，２．７，３．０Ｈｚ），８．９８（ｄ，１Ｈ，Ｊ＝８．７Ｈｚ）． 8-Benzenesulfonyloxy-2- (bis (2-pyridylmethyl) amino) methyl-5-dimethylaminosulfonylquinoline (26).
8-Benzenesulfonyloxy-2-bromomethyl-5-dimethylaminosulfonylquinoline (0.23 g, 0.46 mmol), dipicolylamine (84 mg, 0.42 mmol), Na ₂ CO ₃ (81 mg, 0.76 mmol) was added to acenitrile. (3 mL) was heated to reflux for 3 hours. Insoluble matter in the reaction solution was removed by filtration, the reaction solution was distilled under reduced pressure, and the crude product was purified by silica gel column chromatography (elution solvent: CH ₂ Cl ₂ / MeOH = 40: 1) to obtain the target compound 26. Obtained as an orange oil (160 mg, 57%).
¹ H NMR (300 MHz, TMS / CDCl ₃ ) δ: 2.83 (s, 6H), 3.80 (s, 2H), 3.84 (s, 4H), 7.18 (ddd, 2H, J = 1.0, 6.0, 12 Hz), 7.40-7.45 (m, 2H), 7.51-7.60 (m, 2H), 7.68 (ddd, 2H, J = 1.8) 7.5, 8.1 Hz), 7.72 (d, 1H, J = 8.2 Hz), 7.87 (d, 1H, J = 8.7 Hz), 7.95-8.14 (m, 2H), 8.12 (d, 1H, J = 8.2 Hz), 8.57 (ddd, 2H, J = 1.0, 2.7, 3.0 Hz), 8.98 (d, 1H, J = 8.7 Hz).

２−（ビス（２−ピリジルメチル）アミノ）メチル−５−ジメチルアミノスルホニル−８−ヒドロキシキノリン４ＨＣｌ塩（２７・４ＨＣｌ）．
８−ベンゼンスルホニルオキシ−２−（ビス（２−ピリジルメチル）アミノ）メチル−５−ジメチルアミノスルホニルキノリン（０．１０ｇ，０．１７ｍｍｏｌ）のメタノール溶液（３ｍＬ）に１ＮＮａＯＨ（１ｍＬ）を加えて一晩加熱還流した。反応液を減圧留去し、ＣＨ₂Ｃｌ₂と飽和Ｎａ₂ＣＯ₃を加えて分液した。水層をＣＨ₂Ｃｌ₂で再抽出し、あつめた有機層をＫ₂ＣＯ₃で乾燥、ろ過、減圧留去して粗生成物をシリカゲルカラムクロマトグラフィー（溶出溶媒：ＣＨ₂Ｃｌ₂・ＭｅＯＨ＝４０：１）で精製し、目的化合物をオレンジ色の油状物質として得た（５９ｍｇ）。得られた油状物質をエタノール（５ｍＬ）に溶解し、エーテルを徐々に加えると、目的とする２７を淡黄色粉末の４ＨＣｌ塩（２７・４ＨＣｌ）として得た（５５ｍｇ，収率５４％）。
¹ＨＮＭＲ（３００ＭＨｚ，ＴＭＳ／ＣＤＣｌ₃）δ：２．７５（ｓ，６Ｈ），４．２７（ｓ，２Ｈ），４．５６（ｓ，４Ｈ），７．２９（ｄ，１Ｈ，Ｊ＝８．４Ｈｚ），７．５５（ｄ，１Ｈ，Ｊ＝９．０Ｈｚ），７．７３−７．７８（ｍ，２Ｈ），７．９４−７．９７（ｍ，２Ｈ），８．１１（ｄ，１Ｈ，Ｊ＝８．４Ｈｚ），８．３１−８．３７（ｍ，２Ｈ），８．６２−８．６４（ｍ，２Ｈ），８．７６（ｄ，１Ｈ，Ｊ＝９．０Ｈｚ）．
¹³ＣＮＭＲ（７５ＭＨｚ，ＴＭＳ／ＣＤＣｌ₃）δ：３６．０８，５６．９３，５９．９８，１０９．９３，１１９．８，１２３．３７，１２４．００，１２５．１５，１２６．４１，１３２．７９，１３４．２４，１４０．５１，１４５．９７，１５２．２２，１５６．０３．
元素分析Ｃ₂₄Ｈ₂₉Ｎ₅Ｏ₃ＳＣｌ₄：
理論値Ｃ：４７．３０％、Ｈ：４．８０％、Ｎ：１１．４９％．
測定値Ｃ：４７．１９％、Ｈ：５．０７％、Ｎ：１１．３２％ 2- (Bis (2-pyridylmethyl) amino) methyl-5-dimethylaminosulfonyl-8-hydroxyquinoline 4HCl salt (27.4 HCl).
To a methanol solution (3 mL) of 8-benzenesulfonyloxy-2- (bis (2-pyridylmethyl) amino) methyl-5-dimethylaminosulfonylquinoline (0.10 g, 0.17 mmol) was added 1N NaOH (1 mL). Heated to reflux overnight. The reaction solution was distilled off under reduced pressure, and CH ₂ Cl ₂ and saturated Na ₂ CO ₃ were added for liquid separation. The aqueous layer was re-extracted with CH ₂ Cl ₂ , and the combined organic layer was dried over K ₂ CO ₃ , filtered and evaporated under reduced pressure, and the crude product was subjected to silica gel column chromatography (elution solvent: CH ₂ Cl ₂ · MeOH = 40: 1) to give the target compound as an orange oil (59 mg). The obtained oily substance was dissolved in ethanol (5 mL), and ether was gradually added to obtain the target 27 as a 4HCl salt (27.4HCl) as a pale yellow powder (55 mg, yield 54%).
¹ H NMR (300 MHz, TMS / CDCl ₃ ) δ: 2.75 (s, 6H), 4.27 (s, 2H), 4.56 (s, 4H), 7.29 (d, 1H, J = 8.4 Hz), 7.55 (d, 1H, J = 9.0 Hz), 7.73-7.78 (m, 2H), 7.94-7.97 (m, 2H), 8.11 ( d, 1H, J = 8.4 Hz), 8.31-8.37 (m, 2H), 8.62-8.64 (m, 2H), 8.76 (d, 1H, J = 9.0 Hz) ).
¹³ C NMR (75 MHz, TMS / CDCl ₃ ) δ: 36.08, 56.93, 59.98, 109.93, 119.8, 123.37, 124.00, 125.15, 126.41, 132 79, 134.24, 140.51, 145.97, 152.22, 156.03.
Elemental analysis _{_{_{_{C 24 H 29 N 5 O 3}}}} SCl 4:
Theoretical value C: 47.30%, H: 4.80%, N: 11.49%.
Measurement value C: 47.19%, H: 5.07%, N: 11.32%

応用例
上記で得られた化合物２２に328 nmのUVを３時間照射しUV測定を行ったところ、化合物２５と同様のUVスペクトルがえられた。
従って、化合物２２は、紫外線照射により、フェニルスルホニル基が脱離することが判る。
また、上記の如く、化合物２６をＺｎ²⁺存在下光照射するとアンケージ（uncage）が進行して蛍光が増大した。 Application Example When the compound 22 obtained above was irradiated with UV at 328 nm for 3 hours and subjected to UV measurement, a UV spectrum similar to that of the compound 25 was obtained.
Therefore, it can be seen that the phenylsulfonyl group is eliminated from the compound 22 when irradiated with ultraviolet rays.
Further, as described above, when compound 26 was irradiated with light in the presence of Zn ²⁺ , uncage progressed and fluorescence increased.

本発明化合物は、紫外線により一部の基が離脱するので、この性質を利用して感光性材料等の分野での応用が期待できる。 Since a part of the group of the compound of the present invention is released by ultraviolet rays, application in the field of photosensitive materials can be expected by utilizing this property.

Claims

A compound represented by the following formula (II).

[In Formula (II), R ¹ represents an aryl, alkyl or heterocyclic group which may have a substituent, and R has a hydrogen atom, a halogen atom or a sulfonylamide group, or a substituent. R ⁴ represents an optionally substituted amino, alkyl or aryl group, and R ⁴ represents an optionally substituted amino or aminosulfonyl group. R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonylamide group, a nitro group or an amino, aminosulfonyl, alkyl or aryl group which may have a substituent. ]

In formula (II), R is an alkyl group or the following groups (a) or (b) a is claim 1 Symbol placement compound.

[Wherein, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent a hydrogen atom, a lower alkyl group, an aryl group or a heterocyclic group, and m to q each independently represent 1, 2 or 3. , R represents 0, 1 or 2. ]

The compound according to claim 1 or 2 , wherein R ¹ is a phenyl group.

The compound according to any one of claims 1 to 3 , wherein R ⁴ is a dimethylaminosulfonyl group.

By irradiating ultraviolet rays to the compound of any one of claims 1-4, the R ¹ -SO 2 _O-group in the formula (II), said compound characterized Rukoto is converted into HO- group Disassembly method.