JP2010111661A - Method for producing aromatic sulfonyl chloride and aromatic sulfonic acid compound, and aromatic sulfonic acid compound, and production intermediate therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aromatic sulfonyl chloride from a thiocarbamate compound without using chlorine gas requiring caution in handling. <P>SOLUTION: The method for producing the aromatic sulfonyl chloride represented by formula (2) includes reacting the thiocarbamate compound represented by formula (1) with N-chlorosuccinimide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an aromatic sulfonyl chloride and an aromatic sulfonic acid compound, and an aromatic sulfonic acid compound and a production intermediate thereof.

  Aromatic sulfonyl chloride is useful, for example, as a raw material for synthesis of a sulfonylurea compound having herbicidal activity (see, for example, Patent Document 1).

  As a method for producing the aromatic sulfonyl chloride, for example, Patent Document 1 discloses a method for producing 2-phenylbenzenesulfonyl chloride by reacting 2-phenylphenyldimethylthiocarbamate with chlorine gas.

JP 60-84260 A

  However, the method disclosed in Patent Document 1 has a problem that chlorine gas requiring attention in handling is essential.

  Under such circumstances, there has been a demand for a method for producing an aromatic sulfonyl chloride from a thiocarbamate compound without using a chlorine gas which requires careful handling.

  As a result of intensive studies on a production method capable of overcoming the above-mentioned problems, the present inventor has found a method for producing an aromatic sulfonyl chloride from a thiocarbamate compound without using chlorine gas which requires careful handling. The inventors have found a method for producing an aromatic sulfonic acid compound from an aromatic sulfonyl chloride, and have reached the present invention.

That is, the present invention provides the inventions described in the following [1] to [13].
[1] Formula (1)

（式中、Ａｒは下記群Ｐ１から選ばれる１以上の置換基を有していてもよい芳香族基を表わし、
Ｒ¹およびＲ^２は、それぞれ独立に炭素数１〜１２のアルキル基を表わすか、または
Ｒ¹とＲ^２とが一緒になって炭素数３〜７のポリメチレン基を表す。
ｎは１〜４の整数を表わす。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。）
で示されるチオカーバメート化合物とＮ−クロロスクシンイミドとを、第１級または第２級アルコールの存在下に反応させる工程を含む式（２）

(In the formula, Ar represents an aromatic group which may have one or more substituents selected from the following group P1,
R ¹ and R ² each independently represents an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms.
n represents an integer of 1 to 4.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
Wherein the thiocarbamate compound represented by the formula (2) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

（式中、Ａｒおよびｎは、それぞれ上記で定義された通り。）
で示される芳香族スルホニルクロリドの製造方法。
〔２〕第１級または第２級アルコールがメタノール、エタノールおよび２−プロパノールからなる群から選ばれる〔１〕に記載される製造方法。
〔３〕反応させる工程で得られた反応混合物をカラムクロマトグラフィーにより精製する工程を含む〔１〕または〔２〕に記載される製造方法。
〔４〕式（１）および式（２）における芳香族基が１，１’−ビナフチル基である〔１〕〜〔３〕のいずれかに記載される製造方法。
〔５〕式（１）で示されるチオカーバメート化合物が式（３）

(Wherein Ar and n are as defined above.)
The manufacturing method of aromatic sulfonyl chloride shown by these.
[2] The production method according to [1], wherein the primary or secondary alcohol is selected from the group consisting of methanol, ethanol and 2-propanol.
[3] The production method according to [1] or [2], including a step of purifying the reaction mixture obtained in the step of reacting by column chromatography.
[4] The production method according to any one of [1] to [3], wherein the aromatic group in Formula (1) and Formula (2) is a 1,1′-binaphthyl group.
[5] The thiocarbamate compound represented by the formula (1) is represented by the formula (3)

（式中、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜１２のアルキル基を表わすか、またはＲ^１とＲ^２とが一緒になって炭素数３〜７のポリメチレン基を表し、
Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。）
で示される化合物であり、式（２）で示される芳香族スルホニルクロリドが式（４）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
Wherein the aromatic sulfonyl chloride represented by the formula (2) is represented by the formula (4)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ上記で定義した通り。）
で示される化合物である〔１〕〜〔３〕のいずれかに記載される製造方法。
〔６〕式（３）および式（４）におけるＲ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８がいずれも水素原子である〔５〕に記載される製造方法。
〔７〕式（３）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
The production method according to any one of [1] to [3], which is a compound represented by the formula:
[6] The production method according to [5], wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} formula (3) and formula (4) are all hydrogen atoms.
[7] Formula (3)

（式中、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜１２のアルキル基を表わすか、またはＲ^１とＲ^２とが一緒になって炭素数３〜７のポリメチレン基を表し、
Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。）
で示されるチオカーバメート化合物とＮ−クロロスクシンイミドとを、第１級または第２級アルコールの存在下に反応させ式（４）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
A thiocarbamate compound represented by the formula (4) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ上記で定義した通り。）
で示される芳香族スルホニルクロリドを得る工程と、
得られた芳香族スルホニルクロリドを加水分解する工程と
を含む式（５）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
Obtaining an aromatic sulfonyl chloride represented by:
And hydrolyzing the resulting aromatic sulfonyl chloride (5)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ上記で定義した通り。）
で示される芳香族ジスルホン酸の製造方法。
〔８〕加水分解により得られる反応混合物を、下記工程（ａ）〜（ｃ）に付す〔７〕に記載される製造方法。
（ａ）反応混合物へ揮発性溶媒に溶解した塩化水素を加えて中和し、濃縮する工程。
（ｂ）目的物を溶解溶媒に溶解し不溶の無機塩を濾過により除去する工程。
（ｃ）上記（ｂ）の工程における濾液を濃縮する工程。
〔９〕式（３）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
The manufacturing method of aromatic disulfonic acid shown by these.
[8] The production method according to [7], wherein the reaction mixture obtained by hydrolysis is subjected to the following steps (a) to (c).
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture for neutralization and concentration.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b).
[9] Formula (3)

（式中、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜１２のアルキル基を表わすか、またはＲ^１とＲ^２とが一緒になって炭素数３〜７のポリメチレン基を表し、
Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。）
で示されるチオカーバメート化合物とＮ−クロロスクシンイミドとを、第１級または第２級アルコールの存在下に反応させ式（４）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
A thiocarbamate compound represented by the formula (4) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ上記で定義した通り。）
で示される芳香族スルホニルクロリドを得る工程と、
得られた芳香族スルホニルクロリドと式（６）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
Obtaining an aromatic sulfonyl chloride represented by:
The resulting aromatic sulfonyl chloride and formula (6)

（式中、Ｒ^９は水素原子、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数１〜１２のアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数３〜１２のシクロアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルケニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルキニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数６〜１８のアリール基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数７〜１８のアラルキル基または炭素数２〜１２のアシル基を表し、
ｍは１以上の整数を表す。
群Ｐ２：ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、炭素数７〜１２のアリールオキシカルボニル基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数２〜１２のアシルアミノ基、メルカプト基、炭素数１〜１２のアルキルチオ基、炭素数２〜１２のアシルチオ基。）
で示されるアミノ化合物とを反応させる工程を含む式（７）

(In the formula, R ⁹ has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. From an alkynyl group having 2 to 12 carbon atoms which may have a substituent of the above, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and from the following group P2 Represents an aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have one or more selected substituents;
m represents an integer of 1 or more.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
A step of reacting with an amino compound represented by formula (7):

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびｍは、それぞれ上記で定義した通り。）
で示されるジスルホニルイミド化合物の製造方法。
〔１０〕式（７）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and m are as defined above.)
The manufacturing method of the disulfonyl imide compound shown by these.
[10] Formula (7)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表し、
Ｒ^９は水素原子、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数１〜１２のアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数３〜１２のシクロアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルケニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルキニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数６〜１８のアリール基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数７〜１８のアラルキル基または炭素数２〜１２のアシル基を表し、
ｍは１以上の整数を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。
群Ｐ２：ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、炭素数７〜１２のアリールオキシカルボニル基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数２〜１２のアシルアミノ基、メルカプト基、炭素数１〜１２のアルキルチオ基、炭素数２〜１２のアシルチオ基。）
で示されるジスルホニルイミド化合物。
〔１１〕〔９〕で得られるジスルホニルイミド化合物を加水分解する工程を含む式（８）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ⁹ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
The disulfonyl imide compound shown by these.
[11] Formula (8) including the step of hydrolyzing the disulfonylimide compound obtained in [9]

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表し、
Ｒ^１０は水素原子、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数１〜１２のアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数３〜１２のシクロアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルケニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルキニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数６〜１８のアリール基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数７〜１８のアラルキル基または炭素数２〜１２のアシル基を表し、
ｍは１以上の整数を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。
群Ｐ２：ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、炭素数７〜１２のアリールオキシカルボニル基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数２〜１２のアシルアミノ基、メルカプト基、炭素数１〜１２のアルキルチオ基、炭素数２〜１２のアシルチオ基。）
で示される芳香族モノスルホン酸の製造方法。
〔１２〕加水分解により得られる反応混合物を、下記工程（ａ）〜（ｃ）に付す〔１１〕に記載される製造方法。
（ａ）反応混合物へ揮発性溶媒に溶解した塩化水素を加えて中和し、濃縮する工程。
（ｂ）目的物を溶解溶媒に溶解し不溶の無機塩を濾過により除去する工程。
（ｃ）上記（ｂ）の工程における濾液を濃縮する工程。
〔１３〕式（８）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
The manufacturing method of aromatic monosulfonic acid shown by these.
[12] The production method according to [11], wherein the reaction mixture obtained by hydrolysis is subjected to the following steps (a) to (c).
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture for neutralization and concentration.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b).
[13] Formula (8)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または下記群Ｐ１から選ばれる置換基を表し、
Ｒ^１０は水素原子、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数１〜１２のアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数３〜１２のシクロアルキル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルケニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数２〜１２のアルキニル基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数６〜１８のアリール基、下記群Ｐ２から選ばれる１以上の置換基を有していてもよい炭素数７〜１８のアラルキル基または炭素数２〜１２のアシル基を表し、
ｍは１以上の整数を表す。
群Ｐ１：炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素数１〜１２のアルコキシ基、炭素数３〜１２のシクロアルキルオキシ基、炭素数６〜１８のアリール基、炭素数６〜１８のアリールオキシ基、炭素数７〜１８のアラルキル基、炭素数７〜１８のアリールアルコキシ基、炭素数２〜１２のアシル基、炭素数２〜１２のアシルオキシ基、ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、ハロゲノ基、二トロ基、シアノ基。
群Ｐ２：ヒドロキシカルボニル基、炭素数２〜１２のアルコキシカルボニル基、炭素数７〜１２のアリールオキシカルボニル基、アミノ基、炭素数１〜１２のアルキルアミノ基、炭素数２〜１２のアシルアミノ基、メルカプト基、炭素数１〜１２のアルキルチオ基、炭素数２〜１２のアシルチオ基。）
で示される芳香族モノスルホン酸。

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
Aromatic monosulfonic acid represented by

  According to the present invention, an aromatic sulfonyl chloride can be produced from a thiocarbamate compound without using a chlorine gas that requires careful handling. Moreover, an aromatic sulfonic acid compound can be produced from the obtained aromatic sulfonyl chloride.

  In the formula (1), examples of the aromatic group represented by Ar include a phenyl group, a naphthyl group, and a 1,1′-binaphthyl group, and the aromatic group includes an alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyloxy group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, carbon An aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, It may have one or more substituents selected from the group P1 consisting of a halogeno group, a ditro group and a cyano group.

In the group P1, as the alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group , Nonyl group, decyl group, undecyl group, dodecyl group,
Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyl Examples include oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group,
Examples of the cycloalkyloxy group having 3 to 12 carbon atoms include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.

Examples of the aryloxy group having 6 to 18 carbon atoms include phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, and naphthyloxy group.
Examples of the aralkyl group having 7 to 18 carbon atoms include a benzyl group and a diphenylmethyl group,
Examples of the arylalkoxy group having 7 to 18 carbon atoms include a benzyloxy group, a 2-phenylethoxy group, and a 1-phenylethoxy group.
Examples of the acyl group having 2 to 12 carbon atoms include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group,
Examples of the acyloxy group having 2 to 12 carbon atoms include acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, and octanoyloxy group.
Examples of the alkoxycarbonyl group having 2 to 12 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a tert-butoxycarbonyl group.
Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  Examples of Ar include a phenyl group, 2-methylphenyl group, 2-phenylphenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-methylphenyl group, 2-isopropylphenyl group, and 2-tert-butylphenyl group. 2,6-dimethylphenyl group, 2-tert-butyl-6-methylphenyl group, 1-naphthyl group, 2-naphthyl group, 3-nitrophenyl group, 3-cyanophenyl group, 2-acetyloxyphenyl group, 2-acetylphenyl group, 2-benzylphenyl group, 1,1′-biphenyl group, 4,4′-dichloro-1,1′-biphenyl group, 4,4′-dibromo-1,1′-biphenyl group, 1,1′-binaphthyl group, 4,4′-dichloro-1,1′-binaphthyl group, 2,2′-dichloro-1,1′-binaphthyl group, 6,6′-di Loro-1,1′-binaphthyl group, 4,4′-dibromo-1,1′-binaphthyl group, 3,3′-dibromo-1,1′-binaphthyl group, 3,3′-dibromo-1,1 A '-binaphthyl group is exemplified, and a phenyl group or a 1,1'-binaphthyl group is preferable.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and the like.
Examples of the polymethylene group having 3 to 7 carbon atoms represented by R ¹ and R ² together include a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.
R ¹ and R ² are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

  Examples of the thiocarbamate compound represented by the formula (1) (hereinafter, abbreviated as compound (1)) include S-phenyl-N, N-dimethylthiocarbamate, S-phenyl-N, N-diethylthiocarbamate, S- (2-methylphenyl) -N, N-dimethylthiocarbamate, S- (2-phenylphenyl) -N, N-dimethylthiocarbamate, S- (4-methylphenyl) -N, N-dimethylthiocarbamate , S- (2-chlorophenyl) -N, N-dimethylthiocarbamate, S- (3-methylphenyl) -N, N-dimethylthiocarbamate, S- (2-isopropylphenyl) -N, N-dimethylthiocarbamate , S- (2-tert-butylphenyl) -N, N-dimethylthiocarbamate, S- (2,6-dimethylpheny ) -N, N-dimethylthiocarbamate, S- (2-tert-butyl-6-methylphenyl) -N, N-dimethylthiocarbamate, S- (1-naphthyl) -N, N-dimethylthiocarbamate, S -(3-nitrophenyl) -N, N-dimethylthiocarbamate, S- (3-cyanophenyl) -N, N-dimethylthiocarbamate, S- (2-acetyloxyphenyl) -N, N-dimethylthiocarbamate , S- (2-acetylphenyl) -N, N-dimethylthiocarbamate, S- (2-benzylphenyl) -N, N-dimethylthiocarbamate, 1,1′-binaphthalene-2,2′-diyl S, S-bis (N, N-dimethylthiocarbamate), 1,5-naphthalenediyl S, S-bis (N, N-dimethylthiocarbamate) 1,2,4-naphthalenetriyl S, S, S-tris (N, N-dimethylthiocarbamate), 1,1′-binaphthalene-2,2 ′, 3,3′-tetrayl S, S, S, S-tetrakis (N, N-dimethylthiocarbamate).

  Such a compound (1) can be produced according to the method described in, for example, JP-A-60-84260 or Synlett 1996, 1054. For example, the formula (9)

（式中、Ａｒおよびｎは、それぞれ上記で定義した通り。）
で示される化合物（以下、化合物（９）と略記する。）と式（１０）

(In the formula, Ar and n are as defined above.)
(Hereinafter abbreviated as compound (9)) and formula (10)

（式中、Ｒ¹およびＲ^２はそれぞれ上記で定義した通り。Ｘはクロロ基等のハロゲノ基を表わす。）
で示される化合物とを反応させて得られる式（１１）

(In the formula, R ¹ and R ² are each as defined above. X represents a halogeno group such as a chloro group.)
Formula (11) obtained by reacting with a compound represented by formula (11)

（式中、Ａｒ、Ｒ¹およびｎは、それぞれ上記と定義した通り。）
で示される化合物を熱転移せしめることにより製造することができる。

(Wherein Ar, R ¹ and n are as defined above.)
It can manufacture by carrying out the heat transition of the compound shown by these.

  As N-chlorosuccinimide, a commercially available product can be used, or it can be produced and used by any known method. When n in the formula (1) is 1, the amount of N-chlorosuccinimide used is preferably 1 to 5 moles relative to the compound (1), and more preferably 2 to 4 moles in terms of improving the yield. 2.5 to 3.5 mole times is more preferable. When n in the formula (1) is 2 to 4, the amount of N-chlorosuccinimide used is preferably an amount obtained by multiplying the amount of N-chlorosuccinimide used when n is 1 by n.

  The reaction between compound (1) and N-chlorosuccinimide is carried out in the presence of a primary or secondary alcohol. Examples of the primary alcohol include primary alcohols having 1 to 12 carbon atoms such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and 1-octanol. Examples of the secondary alcohol include secondary alcohols having 3 to 12 carbon atoms such as 2-propanol, 2-butanol, 2-pentanol, and 2-hexanol. Preferably, it is a C1-C4 primary alcohol or a C3-C4 secondary alcohol, More preferably, it is methanol, ethanol, or 2-propanol, More preferably, it is methanol. When n in the formula (1) is 1, the usage amount of the primary or secondary alcohol is preferably 1 mol times or more with respect to the compound (1), and the upper limit is not limited. For example, a large excess amount can be used also as a solvent. When n in Formula (1) is 2 to 4, the amount of primary or secondary alcohol used is the amount obtained by multiplying the amount of primary or secondary alcohol used when n is 1 by n. Can be used.

  The reaction of the compound (1) and N-chlorosuccinimide is carried out by mixing the compound (1), N-chlorohalosuccinimide and a primary or secondary alcohol. The mixing can also be performed in the presence of a solvent. Examples of the solvent include ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as chloroform, nitrile solvents such as acetonitrile, and ester solvents such as ethyl acetate alone or mixed solvents, Preferably it is an ether solvent, More preferably, it is tetrahydrofuran. The amount of such solvent used is not particularly limited.

  The reaction temperature is preferably −50 to 100 ° C., more preferably 0 to 50 ° C. The reaction time varies depending on the type of compound (1) to be used and the reaction temperature, but is preferably 48 hours or less and more preferably 30 minutes to 30 hours in terms of improving the yield. The progress of the reaction can be confirmed by analytical means such as thin layer chromatography and high performance liquid chromatography.

  After completion of the reaction, for example, the reaction mixture is concentrated, whereby the aromatic sulfonyl chloride represented by the formula (2) (hereinafter referred to as compound (2)) can be taken out. In addition, after the reaction mixture is directly or after being concentrated, the compound (2) can be taken out by adding water and, if necessary, adding an insoluble organic solvent to water and performing extraction, and concentrating the resulting organic layer. it can. Further, after the reaction mixture is directly or after being concentrated, it can be purified by column chromatography to remove by-product highly polar impurities and to extract the compound (2) with higher purity. A method of purifying the reaction mixture as it is or after concentrating, followed by column chromatography is preferable in terms of obtaining a highly pure compound (2). As stationary phases used for column chromatography, normal phase silica gel, silica, celite, alumina, hydroxyapatite, cellulose, agarose, glass, activated clay, calcium hydroxide, diatomaceous earth, glass, florisil, molecular sieves, anion exchange resin, Examples include bentonite, ceramic, shirasu, white clay, cationic ion exchange resin, and activated carbon. In addition, it is also possible to use a reverse-phase linear alkyl group, an aromatic functional group, a hydrophilic functional group, or a polar inclusion type functional group chemically bonded to a silica gel. Two or more stationary phases may be mixed. As a stationary phase, a normal phase silica gel is preferable at the point which removes the high polar impurity contained in the obtained reaction mixture, and a commercially available thing can be used as a normal phase silica gel. The amount of stationary phase used is not particularly limited. As an elution solvent for column chromatography, aromatic solvents such as benzene, toluene, ethylbenzene, anisole, o-xylene, m-xylene, p-xylene, and industrial xylene are preferable. Such an aromatic solvent may be mixed with a solvent such as an ether solvent such as tetrahydrofuran, a halogenated hydrocarbon solvent such as chloroform, a nitrile solvent such as acetonitrile, or an ester solvent such as ethyl acetate in order to adjust the elution strength. However, when recovering the solvent, the aromatic solvent alone is preferred. As the aromatic solvent, toluene is preferable in terms of low toxicity and low boiling point. The extracted compound (2) can be purified by a purification means such as recrystallization, column chromatography, or distillation.

  Examples of the compound (2) thus obtained include benzenesulfonic acid chloride, 2-methylbenzenesulfonic acid chloride, 2-phenylbenzenesulfonic acid chloride, 4-methylbenzenesulfonic acid chloride, 2-chlorobenzenesulfonic acid chloride, 2-isopropyl. Benzenesulfonic acid chloride, 2-tert-butylbenzenesulfonic acid chloride, 2,6-dimethylbenzenesulfonic acid chloride, 2-tert-butyl-6-methylbenzenesulfonic acid chloride, naphthalene-1-sulfonic acid chloride, naphthalene-2 -Sulfonic acid chloride, 3-nitrobenzenesulfonic acid chloride, 3-cyanobenzenesulfonic acid chloride, 2-acetyloxybenzenesulfonic acid chloride, 2-acetylbenzenesulfonic acid chloride, 2-benzi Benzenesulfonic acid chloride, 1,1′-biphenyl-2,2′-disulfonic acid dichloride, 4,4′-dichloro-1,1′-biphenyl-2,2′-disulfonic acid dichloride, 4,4′-dibromo -1,1'-biphenyl-2,2'-disulfonic acid dichloride, 1,1'-binaphthalene-2,2'-disulfonic acid dichloride, 1,5-naphthalenedisulfonic acid dichloride, 4,4'-dichloro-1 , 1′-Binaphthalene-2,2′-disulfonic acid dichloride, 4,4′-dibromo-1,1′-binaphthalene-2,2′-disulfonic acid dichloride, 3,3′-dichloro-1,1′- Binaphthalene-2,2′-disulfonic acid dichloride, 3,3′-dibromo-1,1′-binaphthalene-2,2′-disulfonic acid dichloride, 6,6′-dichloro -1,1'-binaphthalene-2,2'-disulfonic acid dichloride, 6,6'-dibromo-1,1'-binaphthalene-2,2'-disulfonic acid dichloride, 1,2,4-naphthalene trisulfonic acid Examples include trichloride and 1,1′-binaphthalene-2,2 ′, 3,3′-tetrasulfonic acid tetrachloride.

  By using a compound represented by formula (3) as compound (1) (hereinafter abbreviated as compound (3)), a compound represented by formula (4) as compound (2) (hereinafter compound (4)). Can be abbreviated.).

In the formula (3), the polymethylene group of ^{R 1} and ^{R 2} an alkyl group having 1 to 12 carbon atoms represented, and ^{R 1} and ^{R 2} carbon atoms and represented together 3-7, formula ( Examples thereof include the same groups as the alkyl group having 1 to 12 carbon atoms represented by R ¹ and R ² in 1) and the polymethylene group having 3 to 7 carbon atoms represented by R ¹ and R ^{2 taken} together. R ¹ and R ² are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

In the formulas (3) and (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the group P1. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably all hydrogen atoms.

  Compound (3) and compound (4) are compounds having axial asymmetry, and optically active compound (3) and optically active compound (4) are preferred in that they are used as intermediates for the production of asymmetric catalysts. The optically active compound (3) is produced by using, for example, a commercially available optically active 1,1′-binaphthalene-2,2′-diol as the compound (9) in the production method of the compound (1) described above. it can. The optically active compound (4) can be produced by reacting the optically active compound (3) with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

  By hydrolyzing the compound (4), the compound (4) is led to an aromatic disulfonic acid represented by the formula (5) (hereinafter abbreviated as compound (5)). For the hydrolysis, an alkali is preferably used. Examples of the alkali include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium methoxide, potassium methoxide and sodium ethoxide. An alkali metal alkoxide is mentioned. The amount of alkali used is preferably 2 moles or more, more preferably 10 moles to 30 moles, relative to compound (4).

  The hydrolysis is preferably performed in the presence of a solvent. As the solvent, alcohol solvents such as methanol, ethanol and propanol are preferable. Alcohol solvents include nitrile solvents such as acetonitrile, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as diethyl ether, tetrahydrafuran, 1,4-dioxane and anisole, and halogenated solvents such as chloroform, dichloromethane and tetrachloroethane. It can also be used as a mixture with a hydrocarbon solvent, water or the like.

  The reaction temperature for the hydrolysis is preferably in the range of −10 ° C. to the boiling point of the solvent used, and more preferably 0 ° C. to 40 ° C. The reaction time varies depending on the type of solvent and alkali and the reaction temperature, but is preferably 3 minutes to 15 hours. The progress of the reaction can be confirmed by analytical means such as thin layer chromatography and high performance liquid chromatography. After completion of the reaction, the compound (5) can be obtained by subjecting it to post-treatments such as extraction, recrystallization, and various chromatography.

Compound (5) can also be isolated by performing the following steps (a) to (c). By this isolation method, the compound (5) with high purity can be taken out by a simple operation.
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture obtained by hydrolysis to neutralize and concentrating.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b).
When isolating the compound (5) by performing the above steps (a) to (c), when obtaining the compound (4), the reaction mixture containing the compound (4) is directly or after being concentrated, It is preferable to purify by column chromatography.

  Examples of hydrogen chloride dissolved in the volatile solvent include a hydrogen chloride-dioxane solution, a hydrogen chloride-ethyl acetate solution, a hydrogen chloride-methanol solution, and the like, and commercially available products are preferably used.

  Examples of the solvent used for dissolving the target product include alcohol solvents such as methanol, ethanol and propanol, nitrile solvents such as acetonitrile, aromatic hydrocarbon solvents such as toluene and xylene, diethyl ether, tetrahydrafuran, 1, Examples include ether solvents such as 4-dioxane and anisole, and halogenated hydrocarbon solvents such as chloroform and tetrachloroethane, and preferably tetrahydrofuran and acetonitrile. Two or more solvents may be mixed and used. A dissolving solvent that does not dissolve the inorganic salt to be removed in the step (b) is preferred.

  Specific examples of the compound (5) thus obtained include 1,1′-binaphthalene-2,2′-disulfonic acid and 3,3′-dimethyl 1,1′-binaphthalene-2,2′-. Disulfonic acid, 3,3′-di-tert-butyl-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3′-diphenyl-1,1′-binaphthalene-2,2′-disulfonic acid 3,3′-di- (2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonic acid, 3,3′-dibromo-1,1′-binaphthalene-2,2′-disulfone Acid, 3,3′-difluoro-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3′-dimethoxy-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3 ′ -Diphenylmethoxy-1,1'-binaphthalene 2,2′-disulfonic acid, 3,3′-diphenoxy-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3′-di- (2-methylphenoxy) -1,1′-binaphthalene -2,2'-disulfonic acid,

6,6′-dimethyl-1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-di-tert-butyl-1,1′-binaphthalene-2,2′-disulfonic acid, 6, 6′-diphenyl-1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-di- (2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonic acid, 6 , 6′-Dibromo-1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-difluoro-1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-dimethoxy- 1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-diphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonic acid, 6,6′-diphenoxy-1,1′- Binaphthalene-2,2′-disulfonic acid, 6, '- di - (2-methylphenoxy) -1,1'-binaphthalene-2,2'-disulfonic acid,

3,3 ′, 6,6′-tetramethyl-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3 ′, 6,6′-tetra-tert-butyl-1,1′-binaphthalene -2,2'-disulfonic acid, 3,3 ', 6,6'-tetraphenyl-1,1'-binaphthalene-2,2'-disulfonic acid, 3,3', 6,6'-tetra- ( 2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonic acid, 3,3 ′, 6,6′-tetrabromo-1,1′-binaphthalene-2,2′-disulfonic acid, 3, 3 ', 6,6'-tetrafluoro-1,1'-binaphthalene-2,2'-disulfonic acid, 3,3', 6,6'-tetramethoxy-1,1'-binaphthalene-2,2 ' -Disulfonic acid, 3,3 ', 6,6'-tetraphenylmethoxy-1,1'-bina Talen-2,2′-disulfonic acid, 3,3 ′, 6,6′-tetraphenoxy-1,1′-binaphthalene-2,2′-disulfonic acid, 3,3 ′, 6,6′-tetra- (2-Methylphenoxy) -1,1′-binaphthalene-2,2′-disulfonic acid.

  Next, a disulfonylimide compound represented by the formula (7) (hereinafter abbreviated as compound (7)) and a production method thereof will be described. The compound (4) is led to the compound (7) by reacting with the amino compound represented by the formula (6) (hereinafter abbreviated as the compound (6)).

In the formula (6), examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the alkenyl group having 2 to 12 carbon atoms include an ethenyl group and an allyl group,
Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group and a propargyl group,
Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.
Examples of the aralkyl group having 7 to 18 carbon atoms include a benzyl group and a diphenylmethyl group,
These are hydroxycarbonyl group, C2-C12 alkoxycarbonyl group, C7-C12 aryloxycarbonyl group, amino group, C1-C12 alkylamino group, C2-C12 acylamino group, mercapto It may have one or more substituents selected from the group P2 consisting of a group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms.
Examples of the acyl group having 2 to 12 carbon atoms represented by R ⁹ include an acetyl group, a propionyl group, and a pivaloyl group.

In group P2, examples of the alkoxycarbonyl group having 2 to 12 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and a tert-butoxycarbonyl group.
Examples of the aryloxycarbonyl group having 7 to 12 carbon atoms include a phenoxycarbonyl group, a 2-methylphenoxycarbonyl group, and a 4-methylphenoxycarbonyl group.
Examples of the alkylamino group having 1 to 12 carbon atoms include a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group.
Examples of the acylamino group having 2 to 12 carbon atoms include an acetylamino group, a propionylamino group, and a pivaloylamino group.
Examples of the alkylthio group having 1 to 12 carbon atoms include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.
Examples of the acylthio group having 2 to 12 carbon atoms include an acetylthio group, a propionylthio group, and a pivaloylthio group.

R ⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from group P2, and may have one substituent selected from group P2. A C 1-4 alkyl group is more preferred.

  m is an integer greater than or equal to 1, Preferably it is 1-10, More preferably, it is 1-5.

  Examples of the compound (6) include 2-hydroxyethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-n-butoxyethylamine, 2-tert-butoxyethylamine, 2- (phenylmethoxy) ethylamine, 2-vinyloxyethylamine, 2- (1-methylvinyloxy) ethylamine, 2- (1-propenyloxy) ethylamine, 2-allyloxyethylamine, 2-ethynyloxyethylamine, 2-phenyloxyethylamine, 2- (2-hydroxy Carbonylethoxy) ethylamine, 2- (hydroxycarbonylmethoxy) ethylamine, 2- (2-hydroxyethoxy) ethylamine, 2- (2-methoxyethoxy) ethylamine, 2- (2-ethoxyethoxy) ethyl Amine, 2- (2-propoxyethoxy) ethylamine, 2- (2-n-butoxyethoxy) ethylamine, 2- (2-tert-butoxyethoxy) ethylamine, 2- (2- (phenylmethoxy) ethoxy) ethylamine, 2 -(2-vinyloxyethoxy) ethylamine, 2- (2- (1-methylvinyloxy) ethoxy) ethylamine, 2- (2- (1-propenyloxy) ethoxy) ethylamine, 2- (2-allyloxyethoxy) ethylamine 2- (2-ethynyloxyethoxy) ethylamine, 2- (2-phenyloxyethoxy) ethylamine, 2- (2- (2-hydroxycarbonylethoxy) ethoxy) ethylamine, 2- (2- (2-tert-butoxy) Carbonylethoxy) ethoxy) ethylamine, 2- (2- ( Mud alkoxycarbonyl) ethoxy) ethylamine, 2- (2- (tert- butoxycarbonyl) ethoxy) ethylamine,

2- (2- (2-hydroxyethoxy) ethoxy) ethylamine, 2- (2- (2-methoxyethoxy) ethoxy) ethylamine, 2- (2- (2-ethoxyethoxy) ethoxy) ethylamine, 2- (2- (2-propoxyethoxy) ethoxy) ethylamine, 2- (2- (2-butoxyethoxy) ethoxy) ethylamine, 2- (2- (2-tert-butoxyethoxy) ethoxy) ethylamine, 2- (2- (2 -(Phenylmethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2-vinyloxyethoxy) ethoxy) ethylamine, 2- (2- (2- (1-methylvinyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (1-propenyloxy) ethoxy) ethoxy) ethylamine, 2- (2- (2-allyloxy) Toxi) ethoxy) ethylamine, 2- (2- (2-ethynyloxyethoxy) ethoxy) ethylamine, 2- (2- (2-phenyloxyethoxy) ethoxy) ethylamine, 2- (2- (2- (2-hydroxy Carbonylethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2-hydroxycarbonylethoxy)) Ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ) Ethoxy) ethylamine, 2- (2- (2- (tert-but) Xoxycarbonylmethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ethoxy) ethoxy) ethylamine, 2- (2- (2- (2- (tert-butoxycarbonyl) Methoxy) ethoxy) ethoxy) ethoxy) ethylamine.

  As compound (6), a commercially available product can be used, or a compound produced by any known method can be used. The amount of compound (6) to be used is preferably 1 mol times or more, more preferably 1 to 20 mol times relative to compound (4).

  The reaction between the compound (4) and the compound (6) is preferably performed in the presence of a solvent. Examples of such a solvent include aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, acetonitrile, hexamethylphosphoric triamide, n-hexane, cyclohexane, n-pentane, toluene, Examples include hydrocarbon solvents such as xylene, ether solvents such as diethyl ether, tetrahydrafuran, 1,4-dioxane, anisole, and halogenated hydrocarbon solvents such as chloroform and tetrachloroethane. It can also be used. As the solvent, an ether solvent is preferably used. The amount of solvent used is not particularly limited.

  In addition, by making a base exist in reaction of a compound (4) and a compound (6), reaction can be accelerated | stimulated and hydrogen chloride produced | generated with progress of reaction can also be capture | acquired. Examples of the base used include organic bases such as triethylamine, diisopropylethylamine, N-methylimidazole, pyridine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, sodium carbonate, potassium carbonate, cesium carbonate And inorganic bases such as The base is preferably 2 mol times or more, more preferably 2 to 5 mol times based on the compound (4).

  The reaction temperature ranges from −10 ° C. to the boiling point of the solvent used, but is preferably 0 ° C. to 40 ° C. The reaction time varies depending on the type of solvent and the reaction temperature, but is preferably 3 minutes to 15 hours. The progress of the reaction can be confirmed by analytical means such as thin layer chromatography and high performance liquid chromatography. The compound (7) can be taken out by subjecting the mixture obtained after completion of the reaction to post-treatments such as extraction, recrystallization, and various chromatography. The extracted compound (7) can be purified by a purification means such as recrystallization or column chromatography.

  As the compound (7) thus obtained, for example, N- (2-hydroxyethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2-hydroxyethyl) -3,3′- Dimethyl-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2-hydroxyethyl) -3,3'-di-tert-butyl-1,1'-binaphthalene-2,2'- Disulfonylimide, N- (2-hydroxyethyl) -3,3′-diphenyl-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2-hydroxyethyl) -3,3′- Di- (2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2-hydroxyethyl) -3,3′-dibromo-1,1′-binaphthalene-2, 2'-disul Nilimide, N- (2-hydroxyethyl) -3,3′-difluoro-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2-hydroxyethyl) -3,3′-dimethoxy- 1,1′-binaphthalene-2,2′-disulfonylimide, N- (2-hydroxyethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N -(2-hydroxyethyl) -3,3'-diphenoxy-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2-hydroxyethyl) -3,3'-di- (2- Methylphenoxy) -1,1′-binaphthalene-2,2′-disulfonylimide,

N- (2- (2-hydroxyethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-dimethyl -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-di-tert-butyl-1,1'-binaphthalene-2 , 2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2 -Hydroxyethoxy) ethyl) -3,3'-di- (2-methylphenyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-dibromo- , 1′-Binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-difluoro-1,1′-binaphthalene-2,2′-disulfonyl Imido, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-dimethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) Ethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-diphenoxy-1, 1′-Binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-di- (2-methylphenoxy) -1,1′-binaphthalene-2 , '- disulfonylimide,

N- (2- (2-methoxyethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-dimethyl -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3'-di-tert-butyl-1,1'-binaphthalene-2 , 2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-diphenyl-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-di- (2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) Ethyl) -3,3'-dibromo- , 1′-Binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-difluoro-1,1′-binaphthalene-2,2′-disulfonyl Imido, N- (2- (2-methoxyethoxy) ethyl) -3,3′-dimethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) Ethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-diphenoxy-1, 1′-Binaphthalene-2,2′-disulfonylimide, N- (2- (2-methoxyethoxy) ethyl) -3,3′-di- (2-methylphenoxy) -1,1′-binaphthalene-2 , 2'-Gis Honiruimido,

N- (2- (2-vinyloxyethoxy) ethyl) -1,1′-vinaphthalene-2,2′-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3 ′ -Dimethyl-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3'-di-tert-butyl-1,1'- Binaphthalene-2,2′-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-diphenyl-1,1′-binaphthalene-2,2′-disulfonylimide, N -(2- (2-vinyloxyethoxy) ethyl) -3,3'-di- (2-methylphenyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- ( 2-vinyloxyethoxy) ethyl) -3,3 ' Dibromo-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-difluoro-1,1′-binaphthalene-2,2 '-Disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3'-dimethoxy-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- ( 2-vinyloxyethoxy) ethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3, 3'-diphenoxy-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-vinyloxyethoxy) ethyl) -3,3'-di- (2-methylphenoxy)- 1,1'-Binaf Ren-2,2'-di-imide,

N- (2- (2-hydroxyethoxy) ethyl) -6,6′-dimethyl-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-di-tert-butyl-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-diphenyl-1 , 1'-Binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-di- (2-methylphenyl) -1,1'-binaphthalene- 2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6′-dibromo-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2 -(2-hydroxyethoxy Ethyl) -6,6'-difluoro-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-dimethoxy-1,1 '-Binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-diphenylmethoxy-1,1'-binaphthalene-2,2'-disulfonylimide N- (2- (2-hydroxyethoxy) ethyl) -6,6′-diphenoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl ) -6,6′-di- (2-methylphenoxy) -1,1′-binaphthalene-2,2′-disulfonylimide,

N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetramethyl-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2 -Hydroxyethoxy) ethyl) -3,3 ', 6,6'-tetra-tert-butyl-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) Ethyl) -3,3 ', 6,6'-tetraphenyl-1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3' , 6,6′-tetra- (2-methylphenyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetrabromo-1,1′-binaphtha -2,2'-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ', 6,6'-tetrafluoro-1,1'-binaphthalene-2,2'- Disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetramethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- ( 2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetraphenylmethoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxy Ethoxy) ethyl) -3,3 ′, 6,6′-tetraphenoxy-1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-hydroxyethoxy) ethyl) -3, 3 ′, 6,6′-tetra- ( - methylphenoxy) -1,1'-binaphthalene-2,2'-di-imide,

N- (2- (2-hydroxycarbonylethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2-tert-butoxycarbonylethoxy) ethyl) -1, 1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2- (2-hydroxycarbonylethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2- (2- (2- ( 2-hydroxycarbonylethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2- (2- (2-tert) Butoxycarbonylethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2- (2- (2- (2-hydroxycarbonylethoxy) ethoxy)) Ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) Ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide,

N- (2- (hydroxycarbonylmethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (tert-butoxycarbonylmethoxy) ethyl) -1,1′-binaphthalene -2,2'-disulfonylimide, N- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- ( 2- (tert-Butoxycarbonylmethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide, N- (2- (2- (2- (2-hydroxycarbonylmethoxy) ethoxy) ethoxy) Ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2- (2- (tert-butoxycarbonylmeth) Cis) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ethoxy) ethoxy) Ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide, N- (2- (2- (2- (2- (tert-butoxycarbonylmethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1) , 1'-binaphthalene-2,2'-disulfonylimide.

  Next, an aromatic monosulfonic acid represented by formula (8) (hereinafter abbreviated as compound (8)) and a production method thereof will be described. By contacting the compound (7) with an alkali, the disulfonylimide contained in the compound (7) is hydrolyzed, and the compound (7) is led to the compound (8).

  Examples of the alkali used for the hydrolysis include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium methoxide, potassium methoxide and sodium ethoxide. The amount of alkali used is preferably 2 moles or more, more preferably 10 moles to 30 moles, relative to compound (7).

  Hydrolysis is preferably performed in the presence of a solvent. As the solvent, alcohol solvents such as methanol, ethanol and propanol are preferable. Alcohol solvents are nitrile solvents such as acetonitrile, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as diethyl ether, tetrahydrafuran, 1,4-dioxane and anisole, and halogenated solvents such as chloroform, dichloromethane and tetrachloroethane. You may mix and use with a hydrocarbon solvent.

  The reaction temperature ranges from −10 ° C. to the boiling point of the solvent used, but preferably 0 ° C. to 40 ° C. The reaction time varies depending on the type of alkali and solvent and the reaction temperature, but is preferably 3 minutes to 15 hours. The degree of progress of the reaction can be confirmed by an analytical means such as thin layer chromatography or high performance liquid chromatography. The compound (8) can be taken out by subjecting the mixture obtained after completion of the reaction to post-treatment such as extraction, recrystallization, and various chromatography.

Compound (8) can also be isolated by performing the following steps (a) to (c). By this isolation method, the compound (8) with high purity can be taken out by a simple operation.
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture obtained by hydrolysis, neutralizing, and concentrating.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b).
When isolating the compound (8) by performing the above steps (a) to (c), when obtaining the compound (4), the reaction mixture containing the compound (4) is directly or after being concentrated, It is preferable to purify by column chromatography.

  Examples of hydrogen chloride dissolved in the volatile solvent include a hydrogen chloride-dioxane solution, a hydrogen chloride-ethyl acetate solution, a hydrogen chloride-methanol solution, and the like, and commercially available products are preferably used.

  Examples of the solvent used for dissolving the target product include alcohol solvents such as methanol, ethanol and propanol, nitrile solvents such as acetonitrile, aromatic hydrocarbon solvents such as toluene and xylene, diethyl ether, tetrahydrafuran, 1, Examples include ether solvents such as 4-dioxane and anisole, and halogenated hydrocarbon solvents such as chloroform and tetrachloroethane, and preferably tetrahydrofuran and acetonitrile. Two or more solvents may be mixed and used. A dissolving solvent in which the inorganic salt removed in the step (b) is not dissolved is preferable.

  As the compound (8) thus obtained, for example, N- (2-hydroxyethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2-hydroxyethyl) -3,3 '-Dimethyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2-hydroxyethyl) -3,3'-di-tert-butyl-1,1'-binaphthalene-2 -Aminosulfonyl-2'-sulfonic acid, N- (2-hydroxyethyl) -3,3'-diphenyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2-hydroxy Ethyl) -3,3'-di- (2-methylphenyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2-hydroxyethyl) -3,3'- Bromo-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2-hydroxyethyl) -3,3′-difluoro-1,1′-binaphthalene-2-aminosulfonyl-2 ′ -Sulfonic acid, N- (2-hydroxyethyl) -3,3'-dimethoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2-hydroxyethyl) -3,3 '-Diphenylmethoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2-hydroxyethyl) -3,3'-diphenoxy-1,1'-binaphthalene-2-aminosulfonyl -2'-sulfonic acid, N- (2-hydroxyethyl) -3,3'-di- (2-methylphenoxy) -1,1'-binaphthalene-2-aminosulfonyl-2 - sulfonic acid,

N- (2- (2-hydroxyethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′ -Dimethyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-di-tert-butyl-1,1 ' -Binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-diphenyl-1,1'-binaphthalene-2-aminosulfonyl-2'- Sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-di- (2-methylphenyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N − 2- (2-hydroxyethoxy) ethyl) -3,3′-dibromo-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl)- 3,3′-Difluoro-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3′-dimethoxy-1,1 ′ -Binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-diphenylmethoxy-1,1'-binaphthalene-2-aminosulfonyl-2 ' -Sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3'-diphenoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N (2- (2-hydroxyethoxy) ethyl) -3,3'-di - (2-methylphenoxy) -1,1'-binaphthalene -2 aminosulfonyl-2'-sulfonic acid,

N- (2- (2-methoxyethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3 ′ -Dimethyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3'-di-tert-butyl-1,1 ' -Binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3'-diphenyl-1,1'-binaphthalene-2-aminosulfonyl-2'- Sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3′-di- (2-methylphenyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N -(2- (2 Methoxyethoxy) ethyl) -3,3′-dibromo-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3′- Difluoro-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3′-dimethoxy-1,1′-binaphthalene-2- Aminosulfonyl-2′-sulfonic acid, N- (2- (2-methoxyethoxy) ethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N -(2- (2-methoxyethoxy) ethyl) -3,3'-diphenoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-methoxy) Ethoxy) ethyl) -3,3'-di - (2-methylphenoxy) -1,1'-binaphthalene -2 aminosulfonyl-2'-sulfonic acid,

N- (2- (2-vinyloxyethoxy) ethyl) -1,1′-vinaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3, 3′-dimethyl-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-di-tert-butyl-1 , 1′-Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-diphenyl-1,1′-binaphthalene-2-aminosulfonyl -2'-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3'-di- (2-methylphenyl) -1,1'-binaphthalene-2-aminosulfonyl-2 ' -Sulfonic acid, N- 2- (2-vinyloxyethoxy) ethyl) -3,3′-dibromo-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl ) -3,3′-difluoro-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-dimethoxy-1 , 1′-Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-diphenylmethoxy-1,1′-binaphthalene-2-amino Sulfonyl-2′-sulfonic acid, N- (2- (2-vinyloxyethoxy) ethyl) -3,3′-diphenoxy-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N (2- (2-vinyloxy ethoxy) ethyl) -3,3'-di - (2-methylphenoxy) -1,1'-binaphthalene -2 aminosulfonyl-2'-sulfonic acid,

N- (2- (2-hydroxyethoxy) ethyl) -6,6'-dimethyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) Ethyl) -6,6'-di-tert-butyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6 ' -Diphenyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-di2 (2-methylphenyl) -1 , 1′-Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6′-dibromo-1,1′-binaphthalene-2-aminosulfonyl- 2 -Sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-difluoro-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2 -Hydroxyethoxy) ethyl) -6,6'-dimethoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6 ' -Diphenylmethoxy-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-diphenoxy-1,1'-binaphthalene- 2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -6,6'-di- (2-methylphenoxy) -1,1'-binaphthalene-2 Aminosulfonyl 2'acid,

N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetramethyl-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetra-tert-butyl-1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2 -Hydroxyethoxy) ethyl) -3,3 ', 6,6'-tetraphenyl-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl ) -3,3 ′, 6,6′-tetra- (2-methylphenyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) Ethyl) -3,3 ', 6 6'-tetrabromo-1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ', 6,6'-tetrafluoro- 1,1′-Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetramethoxy-1,1′- Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetraphenylmethoxy-1,1′-binaphthalene-2- Aminosulfonyl-2′-sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetraphenoxy-1,1′-binaphthalene-2-aminosulfonyl-2 ′ Sulfonic acid, N- (2- (2-hydroxyethoxy) ethyl) -3,3 ′, 6,6′-tetra- (2-methylphenoxy) -1,1′-binaphthalene-2-aminosulfonyl-2 ′ -Sulfonic acid,

N- (2- (2-hydroxycarbonylethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2-tert-butoxycarbonylethoxy) ethyl)- 1,1′-Binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2- (2-hydroxycarbonylethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl- 2′-sulfonic acid, N- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2 -(2- (2- (2-hydroxycarbonylethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2 ' Sulfonic acid, N- (2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2- (2- (2- (2-hydroxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2 -(2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid,

N- (2- (hydroxycarbonylmethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (tert-butoxycarbonylmethoxy) ethyl) -1,1 ′ -Binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2- (tert-butoxycarbonylmethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2- (2- (2- (2- ( Hydroxycarbonylmethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- ( -(2- (2- (tert-butoxycarbonylmethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene-2-aminosulfonyl-2'-sulfonic acid, N- (2- (2- (2- (2- (2- (hydroxycarbonylmethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid, N- (2- (2- (2- (2- (2- ( tert-butoxycarbonylmethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
0.30 g (1.66 mmol) of S-phenyldimethylthiocarbamate was dissolved in a mixed solution of 5 mL of methanol / tetrahydrofuran (weight ratio 1/1), and 0.66 g (4.98 mmol) of N-chlorosuccinimide was added thereto at room temperature. Added in. The mixture was reacted at room temperature for 1 hour and then concentrated under reduced pressure. The obtained concentrated residue was purified by column chromatography (stationary phase: normal phase silica gel 10 g, eluent: toluene) to obtain 0.25 g of benzenesulfonic acid chloride. Yield 86%.
The quality before and after column chromatography purification was confirmed under the following thin layer chromatography analysis conditions. Compared with the concentrated residue before the purification treatment, the benzenesulfonic acid chloride after the purification treatment had high purity because high polar impurities were removed. In addition, before and after column chromatography purification, no high-polarity impurities, i.e., low-polar impurities, were observed on the thin-layer chromatography, as compared with benzenesulfonic acid chloride. From this result, it is understood that high-purity benzenesulfonic acid chloride can be obtained by purification using a short column that can remove high-polarity impurities, for example, packed with normal phase silica gel as a stationary phase.

<Thin layer chromatography analysis conditions>
Stationary phase: Normal phase silica gel Developing solvent: Hexane / ethyl acetate = 3/1
Detection wavelength: UV 254nm
Rf value: benzenesulfonic acid chloride 0.63
S-phenyldimethylthiocarbamate 0.21
<Mass spectrum>
EI-MS (m / z, %) 176 (M +, 28), 141 (6), 77 (100), 51 (23) [M + calculated for C 6 H 5 ClO 2 S: 175.97].

[Examples 2 to 4]
The same procedure as in Example 1 was performed except that the reaction shown in Table 1 was used for 24 hours.
As a result of analyzing the obtained concentrated residue before column chromatography purification under the same thin layer chromatography analysis conditions as in Example 1, it was confirmed that benzenesulfonic acid chloride was produced in any of Examples 2-4. did it. On the thin-layer chromatography, the presence of impurities having higher mobility than that of benzenesulfonic acid chloride, that is, low-polar impurities, was not observed. Moreover, the purity of benzenesulfonic acid chloride was Example 2, Example 3, and Example 4 from the highest one on the thin layer chromatography.

[Example 5]
(S) -1,1′-Binaphthalene-2,2′-dithiolbis (dimethylcarbamate) (0.85 g, 0.0018 mol) synthesized according to the method described in Synlett 1996, 1054 was mixed with methanol and tetrahydrofuran. It melt | dissolved in the solvent (weight ratio 1/1, 10 mL), and N-chlorosuccinimide (1.47 g, 0.011 mol) was added there at room temperature. After stirring the mixture at room temperature for 30 minutes, the raw material (S) -1,1′-binaphthalene-2,2′-dithiolbis (dimethylcarbamate) has disappeared under the following thin-layer chromatography analysis conditions. It was confirmed. Saturated aqueous sodium hydrogen carbonate (10 mL) was added to the resulting reaction mixture, and the mixture was stirred for 5 minutes. Then, ethyl acetate (50 mL) was added for extraction treatment, and the organic layer obtained by liquid separation was added to saturated aqueous sodium bicarbonate (20 mL). And washed 3 times. The organic layer is dried over sodium sulfate and concentrated under reduced pressure. The concentrated residue is obtained by column chromatography (stationary phase: normal phase silica gel 30 g, eluent: hexane / ethyl acetate = 5/1 → 4/1 → 2/1). → 1/1), and further, the concentrate containing the target product is purified by column chromatography (stationary phase: normal phase silica gel) using toluene as an eluent, and (S) -1,1′- 0.60 g of binaphthalene-2,2′-disulfonic acid dichloride was obtained. Yield 72%.

<Thin layer chromatography analysis conditions>
Stationary phase: Normal phase silica gel Developing solvent: Hexane / ethyl acetate = 3/1
Detection wavelength: UV 254nm
Rf value: (S) -1,1′-binaphthalene-2,2′-disulfonic acid dichloride
0.55
(S) -1,1′-Binaphthalene-2,2′-dithiolbis
(Dimethyl carbamate) 0.12
<Mass spectrum>
FD-MS (m / z) 450 [M + calculated for C 20 H 12 Cl 2 O 4 S 2: 449.96].

[Example 6]
(S) -1,1′-Binaphthalene-2,2′-dithiolbis (dimethylcarbamate) (5.0 g, 0.0109 mol) was dissolved in a mixed solvent of methanol and tetrahydrofuran (weight ratio 1/1, 100 mL). N-chlorosuccinimide (8.07 g, 0.0651 mol) was added thereto at room temperature. After stirring the mixture at room temperature for 30 minutes, the raw material (S) -1,1′-binaphthalene-2,2′-dithiolbis (dimethylcarbamate) has disappeared under the following thin-layer chromatography analysis conditions. It was confirmed. Saturated aqueous sodium hydrogen carbonate (50 mL) was added to the resulting reaction mixture, and the mixture was stirred for 5 minutes. Then, ethyl acetate (200 mL) was added for extraction treatment, and the organic layer obtained by liquid separation was saturated aqueous sodium bicarbonate (200 mL). And washed 3 times. The organic layer is dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue is purified by column chromatography (stationary phase: normal phase silica gel 100 g, eluent: toluene), and concentrated under reduced pressure to obtain hexane. To obtain 2.50 g of a white solid of (S) -1,1′-binaphthalene-2,2′-disulfonic acid dichloride. Yield 51%.

[Example 7]
(S) -1,1′-Binaphthalene-2,2′-disulfonic acid dichloride (0.10 g, 0.22 mmol) obtained in Example 5 was dissolved in 10 mL of methanol, and sodium hydroxide (0. 20 g, 5 mmol) was added at room temperature and the resulting mixture was stirred at room temperature for 5 hours. A hydrogen chloride-dioxane solution (4 mol / L, 1.5 mL, 6 mmol) was added to the reaction mixture, and then the solvent and excess hydrogen chloride were removed by concentrating the mixture under reduced pressure. 30 mL of tetrahydrofuran was added to the concentrated residue, insoluble sodium chloride was removed by filtration, and the filtrate was concentrated to obtain 95 mg of (S) -1,1′-binaphthalene-2,2′-disulfonic acid. Yield> 99%.

<Thin layer chromatography analysis>
Stationary phase: Normal phase silica gel Developing solvent: Chloroform / methanol = 3/1
Detection wavelength: UV 254nm
Rf value: 0.09
<Mass spectrum>
ESI (-) - MS (m / z) 413 [[M-1] - calculated for C 20 H 13 O 6 S 2: 413.02].

[Example 8]

実施例５で得られた（Ｓ）−１，１’−ビナフタレン−２，２’−ジスルホン酸ジクロリド（０．１０ｇ、０．２２ｍｍｏｌ）をテトラヒドロフラン１０ｍＬに溶解し、そこへ２−（２−ヒドロキシエトキシ）エチルアミン）（０．１ｍＬ、５ｍｍｏｌ）を室温で加え、得られた混合物を室温で１時間攪拌した。反応混合物を濃縮した後、濃縮残渣をショートカラム（固定相：順相シリカゲル、溶出液：メタノール）で精製し、目的物を有する画分の濃縮残渣をさらにショートカラム（固定相：順相シリカゲル、溶出液：メタノールヘキサン／酢酸エチル＝１／２）に供し、（Ｓ）−Ｎ−（２−（２−ヒドロキシエトキシ）エチル）−１，１’−ビナフタレン−２，２’−ジスルホニルイミド０．１１ｇ得た。収率９８％。

(S) -1,1′-Binaphthalene-2,2′-disulfonic acid dichloride (0.10 g, 0.22 mmol) obtained in Example 5 was dissolved in 10 mL of tetrahydrofuran, and 2- (2-hydroxy) was added thereto. Ethoxy) ethylamine) (0.1 mL, 5 mmol) was added at room temperature and the resulting mixture was stirred at room temperature for 1 hour. After the reaction mixture is concentrated, the concentrated residue is purified with a short column (stationary phase: normal phase silica gel, eluent: methanol), and the concentrated residue of the fraction having the target compound is further purified with a short column (stationary phase: normal phase silica gel, Eluent: methanol hexane / ethyl acetate = 1/2) and (S) —N- (2- (2-hydroxyethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide 0 .11 g was obtained. Yield 98%.

<Thin layer chromatography analysis>
Stationary phase: Normal phase silica gel Developing solvent: Hexane / ethyl acetate = 3/1
Detection wavelength: UV 254nm
Rf value: 0.11
<NMR spectrum>
¹ H-NMR (CDCl ₃ , 270 MHz) 2.38 (brs, 1H), 3.49-3.82 (m, 6H), 4.01-4.19 (m, 2H), 7.37 ( d, J = 7.9 Hz, 2H), 7.42 (dd, J = 1.2 Hz, 6.6 Hz, 2H), 7.68 (dd, J = 1.5 Hz, 6.6 Hz, 2H), 8 .07 (d, J = 8.2H, 2H), 8.20 (d, H = 8.7 Hz, 2H), 8.24 (d, J = 8.9 Hz, 2H).

[Example 9]

実施例８で得られた（Ｓ）−Ｎ−（２−（２−ヒドロキシエトキシ）エチル）−１，１’−ビナフタレン−２，２’−ジスルホニルイミド（０．１１ｇ、０．２２ｍｍｏｌ）をメタノール１０ｍＬに溶解し、そこへ水酸化ナトリウム（０．２０ｇ、５ｍｍｏｌ）を室温で加え、得られた混合物を室温で５時間攪拌した。反応混合物に塩化水素−ジオキサン溶液（４ｍｏｌ／Ｌ、１．５ｍＬ、６ｍｍｏｌ）を加えた後、混合物を減圧濃縮して溶媒と過剰の塩化水素を除去した。濃縮残渣に３０ｍＬのテトラヒドロフランを加え、不溶の塩化ナトリウムを濾過により除去した後、濾液を濃縮することにより（Ｓ）−Ｎ−（２−（２−ヒドロキシエトキシ）エチル）−１，１’−ビナフタレン−２−アミノスルホニル−２’−スルホン酸０．１１ｇを得た。収率＞９９％。

(S) -N- (2- (2-hydroxyethoxy) ethyl) -1,1'-binaphthalene-2,2'-disulfonylimide (0.11 g, 0.22 mmol) obtained in Example 8 was used. Dissolved in 10 mL of methanol, sodium hydroxide (0.20 g, 5 mmol) was added thereto at room temperature, and the resulting mixture was stirred at room temperature for 5 hours. After adding a hydrogen chloride-dioxane solution (4 mol / L, 1.5 mL, 6 mmol) to the reaction mixture, the mixture was concentrated under reduced pressure to remove the solvent and excess hydrogen chloride. 30 mL of tetrahydrofuran was added to the concentrated residue, insoluble sodium chloride was removed by filtration, and the filtrate was concentrated to give (S) -N- (2- (2-hydroxyethoxy) ethyl) -1,1′-binaphthalene. 0.11 g of 2-aminosulfonyl-2′-sulfonic acid was obtained. Yield> 99%.

<Thin layer chromatography analysis>
Stationary phase: Normal phase silica gel Developing solvent: Chloroform / methanol = 3/1
Detection wavelength: UV 254nm
Rf value: 0.50
<Mass spectrum>
^{ESI (+) - MS (m} / z) 502 [MH + calculated for C 24 H 24 NO 7 S 2: 502.10].

[Example 10]

実施例６で得られた（Ｓ）−１，１’−ビナフタレン−２，２’−ジスルホン酸ジクロリド（０．３０ｇ、０．６７ｍｍｏｌ）をテトラヒドロフラン５ｍＬに溶解し、そこへ２−（２−（２−（２−（２−ｔｅｒｔ−ブトキシカルボニルエトキシ）エトキシ）エトキシ）エトキシ）エチルアミン（０．３２ｇ、１ｍｍｏｌ）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパン（０．１３ｇ、１ｍｏｌ）を室温で加え、得られた混合物を室温で１時間攪拌した。反応混合物に１ｍｏｌ／Ｌ硫酸水素カリウム水溶液と酢酸エチルとを加えて混合し、分液して得られた有機層を濃縮した。濃縮残渣をカラムクロマトグラフィー（固定相：順相シリカゲル３０ｇ、溶出液：ヘキサン／酢酸エチル＝２：１→１：１）で精製し、（Ｓ）−Ｎ−（２−（２−（２−（２−（２−ｔｅｒｔ−ブトキシカルボニルエトキシ）エトキシ）エトキシ）エトキシ）エチル）−１，１’−ビナフタレン−２，２’−ジスルホニルイミド０．３０ｇ得た。収率６５％。

(S) -1,1′-Binaphthalene-2,2′-disulfonic acid dichloride (0.30 g, 0.67 mmol) obtained in Example 6 was dissolved in 5 mL of tetrahydrofuran, and 2- (2- (2- ( 2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethylamine (0.32 g, 1 mmol), N, N, N ′, N′-tetramethyl-1,3-diaminopropane (0 .13 g, 1 mol) was added at room temperature and the resulting mixture was stirred at room temperature for 1 hour. A 1 mol / L potassium hydrogen sulfate aqueous solution and ethyl acetate were added to the reaction mixture and mixed, and the organic layer obtained by liquid separation was concentrated. The concentrated residue was purified by column chromatography (stationary phase: normal phase silica gel 30 g, eluent: hexane / ethyl acetate = 2: 1 → 1: 1), and (S) -N- (2- (2- (2- (2- 0.30 g of (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2,2′-disulfonylimide was obtained. Yield 65%.

<Thin layer chromatography analysis>
Stationary phase: Normal phase silica gel Developing solvent: Hexane / ethyl acetate = 2/1
Detection wavelength: UV 254nm
Rf value: 0.27
<NMR spectrum>
¹ H-NMR (CDCl ₃ , 270 MHz) 1.44 (s, 9H), 2.50 (t, J = 6.6 Hz, 2H), 3.61-4.12 (m, 18H), 7.33 −7.45 (m, 4H), 7.68 (dd, J = 1.3 Hz, 6.6 Hz, 2H), 8.06 (d, J = 7.9H, 2H), 8.19 (d, H = 8.7 Hz, 2H), 8.23 (d, J = 8.9 Hz, 2H).

[Example 11]

実施例１０で得られた（Ｓ）−Ｎ−（２−（２−（２−（２−（２−ｔｅｒｔ−ブトキシカルボニルエトキシ）エトキシ）エトキシ）エトキシ）エチル）−１，１’−ビナフタレン−２，２’−ジスルホニルイミド（０．３０ｇ、０．４３ｍｍｏｌ）をテトラヒドロフラン５ｍＬに溶解し、そこへナトリウムメトキシド（０．３５ｇ、６．４３ｍｍｏｌ）を室温で加え、得られた混合物を室温で１時間攪拌した。反応混合物に塩化水素−ジオキサン溶液（４ｍｏｌ／Ｌ、２．４ｍＬ、９．６５ｍｍｏｌ）を加えた後、混合物を減圧濃縮して溶媒と過剰の塩化水素を除去した。濃縮残渣に３０ｍＬのテトラヒドロフランを加え、不溶の塩化ナトリウムを濾過により除去した後、濾液を濃縮することにより（Ｓ）−Ｎ−（２−（２−（２−（２−（２−ｔｅｒｔ−ブトキシカルボニルエトキシ）エトキシ）エトキシ）エトキシ）エチル）−１，１’−ビナフタレン−２−アミノスルホニル−２’−スルホン酸０．２０ｇを得た。収率７１％。

(S) -N- (2- (2- (2- (2- (2-tert-butoxycarbonylethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1'-binaphthalene- obtained in Example 10 2,2′-Disulfonylimide (0.30 g, 0.43 mmol) was dissolved in 5 mL of tetrahydrofuran, sodium methoxide (0.35 g, 6.43 mmol) was added thereto at room temperature, and the resulting mixture was added at room temperature. Stir for 1 hour. A hydrogen chloride-dioxane solution (4 mol / L, 2.4 mL, 9.65 mmol) was added to the reaction mixture, and the mixture was concentrated under reduced pressure to remove the solvent and excess hydrogen chloride. 30 mL of tetrahydrofuran was added to the concentrated residue, insoluble sodium chloride was removed by filtration, and the filtrate was concentrated to give (S) -N- (2- (2- (2- (2- (2-tert-butoxy). 0.20 g of carbonylethoxy) ethoxy) ethoxy) ethoxy) ethyl) -1,1′-binaphthalene-2-aminosulfonyl-2′-sulfonic acid was obtained. Yield 71%.

<Thin layer chromatography analysis>
Stationary phase: Normal phase silica gel Developing solvent: Chloroform / methanol = 5/1
Detection wavelength: UV 254nm
Rf value: 0.42
<Mass spectrum>
ESI (-) - MS (m / z) 660 [[M-H] - calculated for C 31 H 34 NO 11 S 2: 660.16].

  Aromatic sulfonyl chloride is useful, for example, as a raw material for synthesis of a sulfonylurea compound having herbicidal activity (see, for example, Patent Document 1). The present invention can be used as a method for producing such a compound. An aromatic sulfonic acid compound produced from an aromatic sulfonyl chloride can be used as, for example, a catalyst for asymmetric reaction (see, for example, Journal of the American Chemical Society 2008, 130, 16858-16860), and poly. By modifying with (oxyethylene), for example, application to an electrolyte membrane or the like is also expected (see, for example, Langmuir 2000, 16, 9662-9665).

Claims (13)

Formula (1)

(In the formula, Ar represents an aromatic group which may have one or more substituents selected from the following group P1,
R ¹ and R ² each independently represents an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms.
n represents an integer of 1 to 4.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
Wherein the thiocarbamate compound represented by the formula (2) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

(Wherein Ar and n are as defined above.)
The manufacturing method of aromatic sulfonyl chloride shown by these. The production method according to claim 1, wherein the primary or secondary alcohol is selected from the group consisting of methanol, ethanol and 2-propanol. The production method according to claim 1 or 2, comprising a step of purifying the reaction mixture obtained in the step of reacting by column chromatography. The production method according to any one of claims 1 to 3, wherein the aromatic group in the formulas (1) and (2) is a 1,1'-binaphthyl group. The thiocarbamate compound represented by the formula (1) is represented by the formula (3)

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
Wherein the aromatic sulfonyl chloride represented by the formula (2) is represented by the formula (4)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
The production method according to any one of claims 1 to 3, wherein the compound is represented by the formula: The production method according to claim 5, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} Formula (3) and Formula (4) are all hydrogen atoms. Formula (3)

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
A thiocarbamate compound represented by the formula (4) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
Obtaining an aromatic sulfonyl chloride represented by:
And hydrolyzing the resulting aromatic sulfonyl chloride (5)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
The manufacturing method of aromatic disulfonic acid shown by these. The manufacturing method described in Claim 7 which attaches | subjects the reaction mixture obtained by a hydrolysis to the following process (a)-(c).
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture for neutralization and concentration.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b). Formula (3)

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, or R ¹ and R ² together represent a polymethylene group having 3 to 7 carbon atoms;
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a substituent selected from the following group P1.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group. )
A thiocarbamate compound represented by the formula (4) is reacted with N-chlorosuccinimide in the presence of a primary or secondary alcohol.

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.)
Obtaining an aromatic sulfonyl chloride represented by:
The resulting aromatic sulfonyl chloride and formula (6)

(In the formula, R ⁹ has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. From an alkynyl group having 2 to 12 carbon atoms which may have a substituent of the above, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and from the following group P2 Represents an aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have one or more selected substituents;
m represents an integer of 1 or more.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
A step of reacting with an amino compound represented by formula (7):

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and m are as defined above.)
The manufacturing method of the disulfonyl imide compound shown by these. Formula (7)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ⁹ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
The disulfonyl imide compound shown by these. Formula (8) including the process of hydrolyzing the disulfonyl imide compound obtained by Claim 9.

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
The manufacturing method of aromatic monosulfonic acid shown by these. The manufacturing method described in Claim 11 which attaches | subjects the reaction mixture obtained by a hydrolysis to the following process (a)-(c).
(A) A step of adding hydrogen chloride dissolved in a volatile solvent to the reaction mixture for neutralization and concentration.
(B) A step of dissolving the target product in a dissolving solvent and removing insoluble inorganic salts by filtration.
(C) A step of concentrating the filtrate in the step (b). Formula (8)

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a substituent selected from the following group P1;
R ¹⁰ may have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. A C3-C12 cycloalkyl group, a C2-C12 alkenyl group which may have one or more substituents selected from the following group P2, and one or more substituents selected from the following group P2. An optionally substituted alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have one or more substituents selected from the following group P2, and one or more selected from the following group P2. An aralkyl group having 7 to 18 carbon atoms or an acyl group having 2 to 12 carbon atoms, which may have a substituent of
m represents an integer of 1 or more.
Group P1: C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C3-C12 cycloalkyloxy group, C6-C18 aryl group An aryloxy group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, and hydroxycarbonyl Group, C2-C12 alkoxycarbonyl group, halogeno group, ditro group, cyano group.
Group P2: a hydroxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 12 carbon atoms, an amino group, an alkylamino group having 1 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, A mercapto group, an alkylthio group having 1 to 12 carbon atoms, and an acylthio group having 2 to 12 carbon atoms. )
Aromatic monosulfonic acid represented by