JP5569879B2 - Fluorescent compound and method for producing the same - Google Patents

Description

  The present invention relates to a novel fluorescent compound and a method for producing the same.

  Fluorescent compounds are used in a wide range of fields such as electroluminescence (EL) materials and paints, but they can be detected easily and with high sensitivity, so in recent years detection and analysis of trace substances, and tracking of reaction processes For example, it is increasingly used in the entire analysis field. In such an analysis field, a fluorescent organic compound is often used because of the necessity of binding to a target compound, and a new fluorescent compound with higher sensitivity is required.

On the other hand, as conventional fluorescent organic compounds, there are many compounds having a polycyclic structure having an aromatic ring or an aromatic heterocyclic ring as a basic skeleton. And many raw material compounds used when synthesizing such a fluorescent compound have low reactivity, and it is necessary to use dangerous compounds in combination as raw materials or to adopt severe reaction conditions. Therefore, the actual situation is that there are problems such as requiring special equipment and complicated processes.
For example, it is known that anthracene, which is a typical fluorescent polycyclic aromatic compound, can be separated from coal tar. Chemical synthesis methods include a method of reducing anthraquinone, tetrabromoethane and benzene. Alternatively, a method of condensing benzyl chlorides by Friedel-Crafts reaction is known (see Non-Patent Document 1).

  On the other hand, in order to obtain a fluorescent compound having a higher function or a new function, various attempts have been made to modify the structure of the fluorescent compound itself. As such a fluorescent compound, for example, a compound in which an organic group is introduced into a pyrene derivative (see Patent Document 1) and a compound in which an organic group is introduced into perylene (see Patent Document 2) are disclosed.

JP 2006-117593 A JP-A-5-156244

Iwanami Dictionary of Physical and Chemical Sciences, 5th edition, p60 (Iwanami Shoten)

However, for fluorescent polycyclic aromatic compounds such as anthracene, a simple and efficient production method that replaces the conventional production method, including the method described in Non-Patent Document 1, is still known. It is not done.
Moreover, in the fluorescent compounds as described in Patent Documents 1 and 2, a simple and efficient production method of the raw fluorescent compound itself is not known.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the novel fluorescent compound which can be manufactured simply and efficiently, and its manufacturing method.

To solve the above problem,
The present invention provides a fluorescent compound represented by the following general formula (1).

(Wherein R ¹¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ¹² is a hydrogen atom or a linear or branched chain having 1 to 3 carbon atoms ; It is an alkyl group; R ¹³ represents a hydrogen atom, a linear or branched alkyl group or phenyl group having 1 to 3 carbon atoms; R ¹⁴ is a straight-chain hydrogen atom or having 1 to 10 carbon atoms a Jo or branched alkyl group, the alkyl group may be one carbon atom is substituted with a carbonyl group, in which case the carbonyl group in the carbonyl group, in R ^14, wherein carbonyl than the oxygen atom which is bonded to the group located at the terminal side; R ¹⁵ is a hydrogen atom or a carbon number be 1 to 3 linear or branched alkyl group; R ¹⁶ is a carbon number 1 to 3 linear Is an branched alkyl group; ^{R 17} and ^{R 18} are hydrogen atoms; R ¹³ and ^{R 14} form a ring bonded to each other also rather good; ^however, the ^{R 12} and ^{R 13} When one is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms. Excluding cases where

  The present invention also provides a fluorescent compound represented by the following general formula (2).

(Wherein R ²¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²⁰ , R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ each independently represent a hydrogen atom. Or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ²² , R ²³ , R ²⁶ and R ²⁷ are each independently a linear or branched chain group having 1 to 3 carbon atoms. The alkyl group of

  Moreover, this invention has the process of carrying out the electrolytic reaction of the compound represented by the following general formula (1a), and the compound represented by the following general formula (1b), The following general formula (1) The manufacturing method of the fluorescent compound represented by these is provided.

(Wherein R ¹¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ¹² is a hydrogen atom or a linear or branched chain having 1 to 3 carbon atoms ; It is an alkyl group; R ¹³ represents a hydrogen atom, a linear or branched alkyl group or phenyl group having 1 to 3 carbon atoms; R ¹⁴ is a straight-chain hydrogen atom or having 1 to 10 carbon atoms a Jo or branched alkyl group, the alkyl group may be one carbon atom is substituted with a carbonyl group, in which case the carbonyl group in the carbonyl group, in R ^14, wherein carbonyl than the oxygen atom which is bonded to the group located at the terminal side; R ¹⁵ is a hydrogen atom or a carbon number be 1 to 3 linear or branched alkyl group; R ¹⁶ is a carbon number 1 to 3 linear Is an branched alkyl group; ^{R 17} and ^{R 18} are hydrogen atoms; R ¹³ and ^{R 14} form a ring bonded to each other also rather good; ^however, the ^{R 12} and ^{R 13} When one is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms. Excluding cases where

  Moreover, this invention is the process of carrying out the electrolytic reaction of the compound represented by the following general formula (2a), the compound represented by the following general formula (2b), and the compound represented by the following general formula (2c). A method for producing a fluorescent compound represented by the following general formula (2A), (2B) or (2C) is provided.

(In the formula, R ²¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²⁰ , R ²⁴ ′, R ²⁵ ′, R ²⁸ ′ and R ²⁹ ′ are each Independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²² ′, R ²³ ′, R ²⁶ ′ and R ²⁷ ′ each independently has 1 to 3 carbon atoms. A linear or branched alkyl group .)

  ADVANTAGE OF THE INVENTION According to this invention, the novel fluorescent compound which can be manufactured simply and efficiently can be provided.

  The present invention will be described in detail below. In the present specification, the “group” includes not only a group of atoms but also a single atom, and may be ionic. Further, when the fluorescent compound of the present invention has chirality, all stereoisomers (enantiomers and diastereomers) are included in the present invention.

<Fluorescent compound>
(Fluorescent compound (1))
The fluorescent compound of the present invention (fluorescent compound (1)) is represented by the following general formula (1).

(In the formula, R ¹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and when it is a group other than a hydrogen atom, it is one other than the carbon atom bonded to the adjacent carbonyl group. The above carbon atom may be substituted with a hetero atom-containing group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group, other than a hydrogen atom bonded to a carbon atom bonded to an adjacent carbonyl group. One or more hydrogen atoms may be substituted with a hetero atom-containing group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group; R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group or an aryl group, wherein one or more hydrogen atoms are replaced by a group containing a hetero atom, an alkyl group, an alkenyl group or an alkynyl group It may also be one or more groups containing carbon atoms is a heteroatom, an alkylene group may be substituted with an alkenylene group or an alkynylene ^{group; R 14, R 15, R} 16, R 17 and ^{R 18} are Each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and one or more hydrogen atoms may be substituted with a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group Preferably, one or more carbon atoms may be substituted with a group containing a hetero atom, an alkylene group, an alkenylene group, an alkynylene group or an arylene group; any of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is mutually May be bonded to each other to form a ring, or any of R ¹¹ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring. However, when one of R ¹² and R ¹³ is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms.)

In the formula, R ¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

The alkyl group for R ¹¹ may be linear, branched or cyclic, but is preferably linear or branched.
The linear and branched alkyl groups preferably have 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and 1 to 3 carbon atoms. Is most preferred. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert- Examples include a pentyl group, n-hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
The cyclic alkyl group may be either a monocyclic structure or a polycyclic structure, but is preferably a monocyclic structure. The cyclic alkyl group preferably has 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and particularly preferably 5 to 15 carbon atoms.
Examples of the cyclic alkyl group having a monocyclic structure include monovalent groups in which one hydrogen atom is removed from a monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane.
Examples of the cyclic alkyl group having a polycyclic structure include monovalent groups in which one hydrogen atom is removed from a polycycloalkane such as norbornane, isobornane, dicyclopentane, adamantane, tricyclodecane, and tetracyclododecane.

Examples of the alkenyl group for R ¹¹ include a group in which one single bond (C—C) between carbon atoms in the alkyl group is substituted with a double bond (C═C).
The position of the double bond is not particularly limited, but it is preferably as far as possible from the carbon atom bonded to the adjacent carbonyl group (carbonyl group bonded to the benzene ring).

Examples of the alkynyl group in R ¹¹ include a group in which one single bond (C—C) between carbon atoms in the alkyl group is substituted with a triple bond (C≡C).
The position of the triple bond is the same as that of the double bond of the alkenyl group.

The aryl group in R ¹¹ may be either a monocyclic structure or a polycyclic structure, and preferred examples include phenyl group, 1-naphthyl group, 2-naphthyl group, azulenyl group, anthryl group, phenanthrenyl group, fluorenyl group and the like. Are more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and particularly preferably a phenyl group.

The alkyl group, alkenyl group, alkynyl group or aryl group in R ¹¹ is one or more other than the hydrogen atom bonded to the carbon atom bonded to the adjacent carbonyl group (carbonyl group bonded to the benzene ring). These hydrogen atoms may be substituted with a substituent. Examples of the substituent include a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

The group containing a hetero atom replacing the hydrogen atom of R ¹¹ is a group composed of a hetero atom or a plurality of atoms containing a hetero atom.
Preferable examples of the hetero atom replacing the hydrogen atom of R ¹¹ include a halogen atom, an oxygen atom (═O), a sulfur atom (═S) and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the group composed of a plurality of atoms including the heteroatom that replaces the hydrogen atom of R ¹¹ include a hydroxyl group (—OH), a thiol group (—SH), and a carboxy group (—C (═O) —OH). A group represented by the formula “—C (═S) —OH”, a group represented by the formula “—C (═S) —SH”, and a group represented by the formula “—C (═O) —SH”. Groups, amino groups (—NH ₂ ), amide groups (—C (═O) —NH ₂ ), thioamide groups (—C (═S) —NH ₂ ), cyano groups (—C≡N) and the like. .

The alkyl group, alkenyl group, alkynyl group, and aryl group that replace the hydrogen atom of R ¹¹ are the same as the alkyl group, alkenyl group, alkynyl group, and aryl group in R ¹¹ .

The number of the substituents for substituting the hydrogen atom of R ¹¹ is not particularly limited, can be appropriately selected according to the purpose, and all hydrogen atoms that can be substituted with the substituents may be substituted with the substituents.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose.
The is not particularly limited also the position of the substituent group, farther from the carbon atom bonded to the carbonyl group adjacent to the R ¹¹ (carbonyl group R ¹¹ is bonded) preferred.

In the alkyl group, alkenyl group, alkynyl group or aryl group in R ¹¹ , one or more carbon atoms other than the carbon atom bonded to the adjacent carbonyl group (carbonyl group bonded to the benzene ring) are substituted. It may be replaced with. Examples of the substituent include a group containing a hetero atom, an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.

The group containing a hetero atom replacing the carbon atom of R ¹¹ is a group composed of a hetero atom or a plurality of atoms containing a hetero atom.
Examples of the hetero atom for substituting the carbon atom of R ¹¹ include an oxygen atom (—O—), a sulfur atom (—S—), a nitrogen atom (—N═), and a phosphorus atom (—P =, ═P≡). Can be illustrated.
Examples of preferable R ¹¹ when the carbon atom is substituted with an oxygen atom include an alkoxyalkyl group.
Preferred R ¹¹ when the carbon atom is substituted with a sulfur atom includes a thioalkoxyalkyl group.
Examples of preferable R ¹¹ when the carbon atom is substituted with a nitrogen atom include a dialkylaminoalkyl group.

Examples of the group composed of a plurality of atoms including the heteroatom that replaces the carbon atom of R ¹¹ include a carbonyl group (—C (═O) —), a carbonyloxy group (—C (═O) —O—). ), A group containing a carbonyl group such as an oxycarbonyl group (—O—C (═O) —); a group in which one or more oxygen atoms of the group containing the carbonyl group are substituted with a sulfur atom; A group represented by the formula “—NH—C (═S) —”; a group represented by the formula “P (—O—) ₃ ”; A group represented by “O═P (—OH) (— O—) ₂ ” and the like can be exemplified.

The alkylene group, alkenylene group, alkynylene group or arylene group that substitutes for the carbon atom of R ^{11 is} a divalent group in which one hydrogen atom is removed from the alkyl group, alkenyl group, alkynyl group, or aryl group in R ¹¹ . Examples are groups.

The number of the substituents for substituting the carbon atom of R ¹¹ is not particularly limited, can be appropriately selected according to the purpose, and all the carbon atoms that can be substituted with the substituents may be substituted with the substituents.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose. For example, two or more adjacent carbon atoms may be all substituted with the substituent.
The is not particularly limited also the position of the substituent group, farther from the carbon atom bonded to the carbonyl group adjacent to the R ¹¹ (carbonyl group R ¹¹ is bonded) preferred.

In the fluorescent compound (1), for example, one or more of the hydrogen atoms in R ¹¹ are substituted with an alkenyl group and / or an alkynyl group, or one or more of the carbon atoms are substituted with an alkenylene group and / or alkynylene. By substituting with a group, R ¹¹ can be a group having a plurality of double bonds and / or triple bonds. In this case, the total number of double bonds and the total number of triple bonds in R ¹¹ are each preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2.

R ¹¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom or an alkyl group having no substituent, and the hydrogen atom or carbon number is 1 to 1. Particularly preferred are 5 straight-chain or branched alkyl groups.

In the formula, R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
However, the case where one of R ¹² and R ¹³ is a hydrogen atom and the other is a group other than an aryl group is excluded. That is, the compound (1) includes those in which both of R ¹² and R ¹³ are hydrogen atoms, and those in which one of R ¹² and R ¹³ is a hydrogen atom and the other is an alkyl group, an alkenyl group, or an alkynyl group. Absent. When one of R ¹² and R ¹³ is a hydrogen atom, the other is an aryl group. In addition, when one of R ¹² and R ¹³ is an alkyl group, an alkenyl group or an alkynyl group, the other is an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

The alkyl group, alkenyl group, alkynyl group or aryl group in R ¹² and R ¹³ is the same as the alkyl group, alkenyl group, alkynyl group or aryl group in R ¹¹ .

In the alkyl group, alkenyl group, alkynyl group or aryl group in R ¹² and R ¹³ , one or more hydrogen atoms may be substituted with a substituent. Examples of the substituent include a group containing a hetero atom, an alkyl group, an alkenyl group, and an alkynyl group, and those having a high electron donating property are preferable.

The group containing a hetero atom that replaces the hydrogen atom of R ¹² and R ¹³ is the same as the group that replaces the hydrogen atom of R ¹¹ , and preferably a hydroxyl group (—OH) or a thiol group (—SH). And an amino group (—NH ₂ ), an amide group (—C (═O) —NH ₂ ), a thioamide group (—C (═S) —NH ₂ ) and the like.

The alkyl group, alkenyl group and alkynyl group for substituting the hydrogen atoms of R ¹² and R ¹³ are the same as the alkyl group, alkenyl group and alkynyl group in R ¹¹ .

The number of the substituents for substituting the hydrogen atoms of R ¹² and R ¹³ is not particularly limited, can be appropriately selected according to the purpose, and all the hydrogen atoms that can be substituted with the substituents are substituted with the substituents. Also good.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose.
The position of the substituent is not particularly limited. However, it is preferable that the distance from the carbon atom to which R ¹² and R ¹³ are bonded (the carbon atom constituting the dihydrofuran ring).

In the alkyl group, alkenyl group, alkynyl group or aryl group in R ¹² and R ¹³ , one or more carbon atoms may be substituted with a substituent. Examples of the substituent include a hetero atom-containing group, an alkylene group, an alkenylene group, and an alkynylene group.

The group containing the hetero atom which substitutes the carbon atom of R ¹² and R ¹³ is the same as the group which substitutes the carbon atom of R ¹¹ . Specifically, it is as follows.
Of the groups containing a heteroatom, examples of the heteroatom include the same heteroatoms that substitute for the carbon atom of R ¹¹ .
Examples of the group composed of a plurality of atoms including a hetero atom include a group represented by the formula “—NH—C (═O) —” and a formula “—NH—C (═S) —”. Examples include groups.
Examples of the alkylene group, alkenylene group and alkynylene group substituting the carbon atoms of R ¹² and R ¹³ are the same as the alkylene group, alkenylene group and alkynylene group substituting the carbon atom of R ¹¹ .

The number of the substituents for substituting the carbon atoms of R ¹² and R ¹³ is not particularly limited, can be appropriately selected according to the purpose, and all the carbon atoms that can be substituted with the substituents are substituted with the substituents. Also good.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose. For example, two or more adjacent carbon atoms may be all substituted with the substituent.
The position of the substituent is not particularly limited. However, it is preferable that the distance from the carbon atom to which R ¹² and R ¹³ are bonded (the carbon atom constituting the dihydrofuran ring).

When R ¹² is a group having a plurality of double bonds and / or triple bonds, the total number of double bonds and the total number of triple bonds in R ¹² are the same as in R ¹¹ .
R ¹³ is, in a case where a group having a plurality of double bonds and / or triple bonds, the total number of the double bond in R ^13, same is true for the total number of triple bonds.

In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ (hereinafter sometimes abbreviated as R ^{14 to} R ¹⁸ ) are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. It is.
However, in the present invention, the case where R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms is excluded. That is, the compound having such a combination of R ^{11 to} R ¹⁸ is not included in the fluorescent compound (1).

The alkyl group, alkenyl group, alkynyl group or aryl group in R ^{14 to} R ¹⁸ is the same as the alkyl group, alkenyl group, alkynyl group or aryl group in R ¹¹ .

In the alkyl group, alkenyl group, alkynyl group or aryl group in R ^{14 to} R ¹⁸ , one or more hydrogen atoms may be substituted with a substituent. Examples of the substituent include a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
The group, heteroalkyl group, alkenyl group, alkynyl group or aryl group containing a heteroatom that replaces the hydrogen atom of R ^{14 to} R ¹⁸ is the same as the one that replaces the hydrogen atom of R ¹¹ .

The number of the substituents for substituting the hydrogen atoms of R ^{14 to} R ¹⁸ is not particularly limited and can be appropriately selected depending on the purpose, and all the hydrogen atoms that can be substituted with the substituents are substituted with the substituents. Also good.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose.
The position of the substituent is not particularly limited. However, in the case of R ¹⁴ and R ^15, the distance from the carbon atom to which they are bonded (the carbon atom constituting the dihydrofuran ring) is more preferable.

In the alkyl group, alkenyl group, alkynyl group or aryl group in R ^{14 to} R ¹⁸ , one or more carbon atoms may be substituted with a substituent. Examples of the substituent include a group containing a hetero atom, an alkylene group, an alkenylene group, an alkynylene group, or an arylene group.
The group, the alkylene group, the alkenylene group, the alkynylene group, or the arylene group containing the hetero atom that substitutes for the carbon atoms of R ^{14 to} R ¹⁸ are the same as those that substitute the carbon atom of R ¹¹ .

The number of the substituents for substituting the carbon atoms of R ^{14 to} R ¹⁸ is not particularly limited and can be appropriately selected depending on the purpose, and all the carbon atoms that can be substituted with the substituents are substituted with the substituents. Also good.
The substituent may be one kind or two or more kinds. In the case of two or more types, these combinations and ratios can be appropriately selected according to the purpose. For example, two or more adjacent carbon atoms may be all substituted with the substituent.
The position of the substituent is not particularly limited. However, in the case of R ¹⁴ and R ^15, the distance from the carbon atom to which they are bonded (the carbon atom constituting the dihydrofuran ring) is more preferable.

One or more of R ¹⁴ to R ¹⁸ is is a group having a plurality of double bonds and / or triple bonds, the total number of the double bond in any one of R ¹⁴ to R ^18, a triple bond the total number is the same as in the case of ^{R 11,} respectively.

Any of R ^{12 to} R ¹⁵ may be bonded to each other to form a ring. Here, "form a ring", or twofold either R ¹² to R ¹⁵ forms a mutual coupling between the atoms contained in the group, R ¹² forming the bond and any two or more to R ^15, together with the carbon atoms constituting the dihydrofuran ring to which they are attached, refers to forming a ring. At this time, the atom forming the bond is not necessarily the terminal of these groups (the terminal opposite to the dihydrofuran ring side), and is one for each of R ^{12 to} R ^15. Not necessarily.
The ring at this time may be either a monocyclic structure or a polycyclic structure, but is preferably a monocyclic structure.

Any of R ¹¹ and R ^{16 to} R ¹⁸ may be bonded to each other to form a ring. Here, “form a ring” means the same as when R ^{12 to} R ¹⁵ form a ring, and any two or more of R ¹¹ , R ^{16 to} R ¹⁸ are attached to the group. A ring is formed together with any two or more of R ¹¹ , R ^{16 to} R ¹⁸ forming a bond between the contained atoms, and the skeleton of the benzene derivative to which these are bonded. Refers to forming. At this time, the atom forming the bond is not necessarily the terminal of these groups (the terminal opposite to the side of the benzene ring), one for each of R ¹¹ , R ^{16 to} R ^18. Not necessarily.

R ¹² and R ¹³ are preferably a hydrogen atom or an optionally substituted alkyl group or aryl group, more preferably a hydrogen atom or an alkyl group or aryl group not having a substituent. A hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group is particularly preferable.
The combination of R ¹² and R ¹³ is preferably an alkyl group which may have a substituent, or an aryl group and a hydrogen atom which may have a substituent, and has a substituent. It is more preferable that they are not alkyl groups, or an aryl group and a hydrogen atom which do not have a substituent, and a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group and hydrogen. Particularly preferred is an atom.

R ¹⁴ and R ¹⁵ are preferably a hydrogen atom or an alkyl group which may have a substituent, and may be a straight chain having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent or A branched alkyl group is more preferable.
The combination of R ¹⁴ and R ¹⁵ is preferably an alkyl group which may have a substituent, an alkyl group which may have a substituent and a hydrogen atom, or a hydrogen atom, A linear or branched alkyl group having 1 to 10 carbon atoms which may have a group, a linear or branched chain group having 1 to 10 carbon atoms which may have a substituent It is more preferable that they are an alkyl group and a hydrogen atom, or hydrogen atoms.

R ¹⁶ is preferably an alkyl group, alkenyl group, alkynyl group or aryl group which may have a substituent, more preferably an alkyl group which may have a substituent. It is particularly preferable that the alkyl group does not have an alkyl group, and most preferable is a linear or branched alkyl group having 1 to 5 carbon atoms.

R ¹⁷ and R ¹⁸ are preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom.

The fluorescent compound (1) is preferably a dihydrobenzofuran skeleton that can stably maintain a conjugated system that delocalizes electrons between a benzene ring and a carbonyl group bonded to the benzene ring. . In order to maintain such a conjugated system stably, for example, when R ¹¹ has a substituent, the position of the carbon atom or hydrogen atom substituted with the substituent is adjacent to R ¹¹ . It is better to keep away from the carbon atom bonded to the carbonyl group (carbonyl group bonded to the benzene ring).

  Preferred examples of the fluorescent compound (1) include compounds represented by the following formulas (1) -1 to (1) -15, but are not limited thereto.

(Fluorescent compound (2))
The fluorescent compound of the present invention (fluorescent compound (2)) is represented by the following general formula (2). That is, it differs from the fluorescent compound (1) in that it has two dihydrofuran rings instead of one.

(In the formula, R ²¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and when it is a group other than a hydrogen atom, it is one other than the carbon atom bonded to the adjacent carbonyl group. The above carbon atom may be substituted with a hetero atom-containing group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group, other than a hydrogen atom bonded to a carbon atom bonded to an adjacent carbonyl group. One or more hydrogen atoms may be substituted with a hetero atom-containing group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group; R ²⁰ , R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ are each independently A hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, wherein one or more hydrogen atoms contain a hetero atom, an alkyl group, an alkenyl group, Group, an alkynyl group or may be substituted with an aryl group, may be substituted with one or more groups containing carbon atoms is a heteroatom, an alkylene group, an alkenylene group, an alkynylene group or an arylene group; R ²² , R ²³ , R ²⁶ and R ²⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and one or more hydrogen atoms containing a hetero atom, an alkyl group, an alkenyl group or an alkynyl group May be substituted with one or more groups, and one or more carbon atoms may be substituted with a group containing a heteroatom, an alkylene group, an alkenylene group or an alkynylene group; R ²² , R ²³ , R ²⁴ and R ²⁵ either may form a ring bonded to one ^another, one of R ^26, R ^{27, R 28} and ^{R 29} are bonded to each other May form a may be R ²⁰ and R ²¹ are not combined to form a ring with each other; however, a one is a hydrogen atom R ²² and R ²³ other is a group other than an aryl group And the case where one of R ²⁶ and R ²⁷ is a hydrogen atom and the other is a group other than an aryl group.)

In the formula, R ²¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and is the same as R ¹¹ in the fluorescent compound (1).
The alkyl group, alkenyl group, alkynyl group or aryl group in R ²¹ is one or more other than the hydrogen atom bonded to the carbon atom bonded to the adjacent carbonyl group (carbonyl group bonded to the benzene ring). In which one or more carbon atoms other than the carbon atom bonded to the adjacent carbonyl group are heterogeneous may be substituted with a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. It may be substituted with an atom-containing group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group. The substituent in which the hydrogen atom at this time is substituted is the same as the substituent in which the hydrogen atom in R ¹¹ is substituted. Further, the substituent group in which carbon atoms are also substituted, the carbon atoms in R ¹¹ is the same as the substituent to be replaced. The number and position of the substituents hydrogen or carbon atom is substituted is the same as the case of the substituent in R ^11.

R ²¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom or an alkyl group having no substituent, and the hydrogen atom or carbon number is 1 to 1. Particularly preferred are 5 straight-chain or branched alkyl groups.

In the formula, R ²⁰ , R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and R ^{14 to} R in the fluorescent compound (1) ¹⁸ is the same.
The alkyl group, alkenyl group, alkynyl group or aryl group in R ²⁰ , R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ is a group in which one or more hydrogen atoms contain a hetero atom, an alkyl group, an alkenyl group, an alkynyl group or It may be substituted with an aryl group, and one or more carbon atoms may be substituted with a group containing a hetero atom, an alkylene group, an alkenylene group, an alkynylene group or an arylene group. The said substituent by which the hydrogen atom at this time is substituted is the same as the substituent by which the hydrogen atom in R < ¹⁴ > -R < ¹⁸ > is substituted. Further, the substituent group in which carbon atoms are also substituted, the carbon atoms in R ¹⁴ to R ¹⁸ is the same as the substituent to be replaced. The number and position of the substituents hydrogen or carbon atom is substituted is the same as the case of the substituent in R ¹⁴ to R ^18.

In the formula, R ²² , R ²³ , R ²⁶ and R ²⁷ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and are the same as R ¹² and R ¹³ in the fluorescent compound (1). It is.
In the alkyl group, alkenyl group, alkynyl group or aryl group in R ²² , R ²³ , R ²⁶ and R ²⁷ , one or more hydrogen atoms are substituted with a group containing a hetero atom, an alkyl group, an alkenyl group or an alkynyl group. One or more carbon atoms may be substituted with a group containing a hetero atom, an alkylene group, an alkenylene group or an alkynylene group. The said substituent by which the hydrogen atom at this time is substituted is the same as the substituent by which the hydrogen atom in R < ¹² > and R < ¹³ > is substituted. Moreover, the said substituent by which a carbon atom is substituted is the same as the substituent by which the carbon atom in R < ¹² > and R < ¹³ > is substituted. The number and position of the substituents hydrogen or carbon atom is substituted is the same as the case of substituents on R ¹² and R ^13.

However, in the present invention, the case where one of R ²² and R ²³ is a hydrogen atom and the other is a group other than an aryl group is excluded. That is, those in which both R ²² and R ²³ are hydrogen atoms, those in which one of R ²² and R ²³ is a hydrogen atom and the other is an alkyl group, an alkenyl group, or an alkynyl group are included in the fluorescent compound (2). Not included. In the fluorescent compound (2), when one of R ²² and R ²³ is a hydrogen atom, the other is an aryl group. When one of R ²² and R ²³ is an alkyl group, an alkenyl group or an alkynyl group, the other is an alkyl group, an alkenyl group, an alkynyl group or an aryl group.
Similarly, in the present invention, the case where one of R ²⁶ and R ²⁷ is a hydrogen atom and the other is a group other than an aryl group is excluded. Here, the combination of R ²⁶ and R ^{27 is the same as} the combination of R ²² and R ²³ .

Any of R ^{22 to} R ²⁵ may be bonded to each other to form a ring. Here, “form a ring” means the same thing as the case where R ^{12 to} R ^{15 of the} fluorescent compound (1) form a ring.
The ring at this time may be either a monocyclic structure or a polycyclic structure, but is preferably a monocyclic structure.
Similarly, any of R ^{26 to} R ²⁹ may be bonded to each other to form a ring, and the ring at this time may be either a monocyclic structure or a polycyclic structure. A ring structure is preferred.
R ²⁰ and R ²¹ may be bonded to each other to form a ring. Here, “form a ring” means the same as in the case where R ^{12 to} R ^{15 of the} fluorescent compound (1) form a ring, and R ²⁰ and R ²¹ have It means that a bond is formed between the contained atoms and a ring is formed with R ²⁰ and R ²¹ and the skeleton of the benzene derivative to which these are bonded.

R ²⁰ is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Particularly preferred is a hydrogen atom.

R ²² , R ²³ , R ²⁶ and R ²⁷ are preferably a hydrogen atom or an alkyl group or aryl group which may have a substituent, and may be an alkyl group which may have a substituent. Are more preferable, an alkyl group having no substituent is particularly preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is most preferable.
The combination of R ²² and R ²³ , and R ²⁶ and R ²⁷ is an alkyl group that may have a substituent, or an aryl group and a hydrogen atom that may have a substituent. Preferably, the alkyl groups having no substituent are more preferable, and linear or branched alkyl groups having 1 to 5 carbon atoms are particularly preferable.

R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ are preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or an alkyl group which has no substituent. A hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms is particularly preferable.
The combination of R ²⁴ and R ²⁵ and R ²⁸ and R ²⁹ may be an alkyl group which may have a substituent, or an alkyl group and a hydrogen atom which may have a substituent. Preferably, it is more preferably an alkyl group having no substituent or an alkyl group having no substituent and a hydrogen atom, and a linear or branched alkyl group having 1 to 5 carbon atoms. And particularly preferably a hydrogen atom.

As the fluorescent compound (2), as in the fluorescent compound (1), in the dihydrobenzofuran skeleton, a conjugation that delocalizes electrons between a benzene ring and a carbonyl group bonded to the benzene ring. Those capable of stably maintaining the system are preferred. In order to stably maintain such a conjugated system, for example, when R ²¹ has a substituent, the position of the carbon atom or hydrogen atom substituted with the substituent is adjacent to R ²¹ . It is better to keep away from the carbon atom bonded to the carbonyl group (carbonyl group bonded to the benzene ring).

  Preferred examples of the fluorescent compound (2) include compounds represented by the following formulas (2) -1 to (2) -14, but are not limited thereto.

  Fluorescent compounds (1) and (2) are novel compounds, and the fluorescence yield is preferably 0.1 or more, more preferably 0.15 or more. Here, the fluorescence yield is determined by, for example, the method described in Examples described later. Since the fluorescence yield is high in this way, the fluorescent compounds (1) and (2) are used as labeling reagents for target compounds in analysis fields such as detection and analysis of trace substances and tracking of reaction processes. Useful.

<Method for producing fluorescent compound (1)>
The method for producing the fluorescent compound (1) of the present invention is represented by a compound represented by the following general formula (1a) (hereinafter sometimes abbreviated as compound (1a)) and the following general formula (1b). And a compound (hereinafter sometimes abbreviated as compound (1b)).

(In the formula, R ¹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and when it is a group other than a hydrogen atom, it is one other than the carbon atom bonded to the adjacent carbonyl group. The above carbon atom may be substituted with a hetero atom-containing group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group, other than a hydrogen atom bonded to a carbon atom bonded to an adjacent carbonyl group. One or more hydrogen atoms may be substituted with a hetero atom-containing group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group; R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group or an aryl group, wherein one or more hydrogen atoms are replaced by a group containing a hetero atom, an alkyl group, an alkenyl group or an alkynyl group It may also be one or more groups containing carbon atoms is a heteroatom, an alkylene group may be substituted with an alkenylene group or an alkynylene ^{group; R 14, R 15, R} 16, R 17 and ^{R 18} are Each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and one or more hydrogen atoms may be substituted with a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group Preferably, one or more carbon atoms may be substituted with a group containing a hetero atom, an alkylene group, an alkenylene group, an alkynylene group or an arylene group; any of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is mutually May be bonded to each other to form a ring, or any of R ¹¹ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring. However, when one of R ¹² and R ¹³ is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms.)

In the formula, R ^{11 to} R ¹⁸ are the same as described above.

The electrolytic reaction may be performed according to a normal electrolysis method.
In this electrolytic reaction, the compound (1a) is oxidized on the anode to generate a cation species of a ketone body, and one molecule of this ketone body, which is an active species, undergoes a [3 + 2] cycloaddition reaction with one molecule of the compound (1b). Thus, the fluorescent compound (1) is considered to be generated. That is, the compound (1a) is activated by electrolysis.

In the compound (1a), when R ¹⁶ is a hydrogen atom, one molecule of the compound (1a) and two molecules of the compound (1b) may react to produce a fluorescent compound having two dihydrofuran rings. The fluorescent compound (1) having only one dihydrofuran ring can be preferentially produced by adjusting the amount of the compound (1b) used relative to the compound (1a) so as not to be excessively large. However, the amount of compound (1b) used at this time is preferably adjusted as appropriate in consideration of the reactivity of the raw materials. In the compound (1a), when R ¹⁶ is a group other than a hydrogen atom, the compound (1b) has only one dihydrofuran ring even if the amount of the compound (1b) used relative to the compound (1a) is excessive. The fluorescent compound (1) can be selectively produced.

The amount of compound (1b) used relative to 1 mol of compound (1a) during the reaction is preferably 1 to 15 mol, preferably 2 to 12 mol, regardless of whether R ¹⁶ is a hydrogen atom or not. Is more preferable. Furthermore, when R ¹⁶ is a hydrogen atom, the upper limit of the amount of compound (1b) used may be 20 mol.

  The reaction solvent is not particularly limited as long as it does not react with the raw material and can be used in the electrolytic reaction. For example, when using a raw material with high solubility in water, it is preferable to use water, and when using a raw material with low solubility in water, nitromethane, nitroethane, nitropropane, trichloromethane (chloroform) It is preferable to use organic solvents such as 2-methyl-2-propanol (tert-butanol), trifluoroethanol, propionitrile, dimethylacetamide, and ethylene glycol dimethyl ether. Moreover, the mixed solvent which used 2 or more types of solvents together may be sufficient. What is necessary is just to adjust suitably the combination and ratio of each solvent in the case of using together 2 or more types of solvents according to the objective.

  Further, at the time of reaction, the reaction may be carried out in a two-layer system using a solvent that is separated without being mixed with the reaction solvent. Here, the solvent used in combination is one in which the solubility of the fluorescent compound (1) produced by the reaction is high. By carrying out the reaction in a two-layer system, the raw materials dissolved in the reaction solvent react to produce a fluorescent compound (1), and this fluorescent compound (1) is not the reaction solvent but is used in combination. By setting so as to dissolve in the solvent, the fluorescent compound (1) is separated from impurities, the deterioration of the fluorescent compound (1) due to oxidation, etc., or the corrosion of the electrode is suppressed. be able to. As the reaction solvent, when a highly polar solvent such as nitromethane exemplified above is used, it is preferable to use a low polarity organic solvent in combination. Here, examples of the low-polar organic solvent include hydrocarbon-based organic solvents such as hexane. The said solvent to be used together may be used individually by 1 type, may be used as 2 or more types of mixed solvents, and what is necessary is just to adjust suitably the combination and ratio of each solvent in a mixed solvent.

  The amount of the reaction solvent used may be appropriately adjusted according to the type of raw material used, but is preferably 5 to 100 L per 1 mol of the total number of moles of the compounds (1a) and (1b), and 10 to 70 L. It is more preferable that

The temperature of the reaction solution during the electrolytic reaction is preferably 10 to 40 ° C, and more preferably 15 to 30 ° C.
The material of the electrode used in the electrolytic reaction may be a known material, and a combination of materials used as an anode and a cathode may be appropriately selected in consideration of conditions such as reaction solvent species and potential. Specific examples of preferable electrode materials include carbon, platinum, iron, stainless steel, aluminum, nickel, gold, tungsten, ITO (indium tin oxide), and the like.
The electrolysis conditions may be appropriately adjusted so that the yield of the target product is improved according to the type of raw material used. Preferable conditions include, for example, conditions in which a current of about 1.5 to 6 F / mol is applied to the reference electrode at a voltage of about 0.5 to 3 V, but is not limited thereto.
What is necessary is just to adjust reaction time suitably according to electrolysis conditions.

  After completion of the reaction, if necessary, any known post-treatment operation such as extraction, washing, pH adjustment, filtration, concentration, drying, etc. is performed on the obtained reaction solution alone or in combination as appropriate, The target fluorescent compound (1) may be taken out by any of the operations such as crystallization, concentration and reprecipitation. Further, the extracted fluorescent compound (1) may be further purified by performing any known purification operation such as crystallization or column chromatography once or a plurality of times.

Conventional fluorescent compounds are produced by reacting in a normal liquid phase reaction, but due to the low reactivity of raw materials, complicated processes and processes with dangerous reaction conditions are required, and the yield is low. It was inferior to safety and economy.
On the other hand, the fluorescent compound (1) of the present invention can be produced in a high yield by a simple and safe process by performing an electrolytic reaction, even if a raw material having low reactivity in a normal liquid phase reaction is used. Because it can be manufactured, it is excellent in safety and economy. Moreover, the fluorescent compound (1) can be produced from the compounds (1a) and (1b) having no fluorescence.

<Method for producing fluorescent compound (2)>
The method for producing the fluorescent compound (2A), (2B) or (2C) of the present invention (hereinafter sometimes collectively referred to as fluorescent compound (2)) is represented by the following general formula (2a). Compound (hereinafter sometimes abbreviated as compound (2a)), a compound represented by the following general formula (2b) (hereinafter sometimes abbreviated as compound (2b)), and the following general formula ( And 2c) (hereinafter, may be abbreviated as compound (2c)).

(In the formula, R ²¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and when it is a group other than a hydrogen atom, it is one other than the carbon atom bonded to the adjacent carbonyl group. The above carbon atom may be substituted with a hetero atom-containing group, an alkylene group, an alkenylene group, an alkynylene group or an arylene group, other than a hydrogen atom bonded to a carbon atom bonded to an adjacent carbonyl group. One or more hydrogen atoms may be substituted with a group containing a hetero atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group; R ²⁰ , R ²⁴ ′, R ²⁵ ′, R ²⁸ ′ and R ²⁹ ′ Are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, wherein one or more hydrogen atoms contain a hetero atom, an alkyl group, an Kenyir group, an alkynyl group or may be substituted with an aryl group, may be substituted with one or more groups containing carbon atoms is a heteroatom, an alkylene group, an alkenylene group, an alkynylene group or an arylene group; R ²² ', R ²³ ', R ²⁶ 'and R ²⁷ ' are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, a group in which one or more hydrogen atoms contain a hetero atom, an alkyl group, May be substituted with an alkenyl group or an alkynyl group, and one or more carbon atoms may be substituted with a group containing a hetero atom, an alkylene group, an alkenylene group or an alkynylene group; R ²² ′, R ²³ ′, one of R ²⁴ 'and ^{R 25'} is may form a ring bonded to each ^{other, R 26 ', R 27'} , one of ^{R 28} 'and ^{R 29'} It may be mutually bonded to form a ring, which may be the R ²⁰ and R ²¹ are bonded to each other to form a ring; provided that one of R ^{22 'and} R ^23' are hydrogen atoms (The case where the other is a group other than an aryl group and the case where one of R ²⁶ ′ and R ²⁷ ′ is a hydrogen atom and the other is a group other than an aryl group is excluded.)

In the formula, R ²⁰ and R ²¹ are the same as described above.
R ²² ′, R ²³ ′, R ²⁶ ′ and R ²⁷ ′ are the same as R ²² , R ²³ , R ²⁶ and R ^{27 in the} fluorescent compound (2).
R ²⁴ ′, R ²⁵ ′, R ²⁸ ′ and R ²⁹ ′ are the same as R ²⁴ , R ²⁵ , R ²⁸ and R ^{29 in the} fluorescent compound (2).

The electrolytic reaction may be performed according to a normal electrolysis method.
In this electrolytic reaction, the compound (2a) is oxidized on the anode to generate a cation species of a ketone body, and one molecule of this ketone body which is an active species is a total of two molecules of the compound (2b) and / or (2c). It is considered that the fluorescent compound (2A), (2B) or (2C) is produced by [3 + 2] cycloaddition reaction for each molecule. That is, the compound (2a) is activated by electrolysis. The compound (2a) differs from the compound (1a) in that there are always two reaction sites during the cycloaddition reaction.

Compounds (2b) and (2c) may be the same as or different from each other.
When the compounds (2b) and (2c) are the same, the combination of raw materials to be reacted is one, the compounds (2A) to (2C) are the same, and in the generated fluorescent compound (2), The groups bonded to the carbon atoms constituting the dihydrofuran ring are the same in the two dihydrofuran rings, and are apparently symmetrical.

On the other hand, when the compounds (2b) and (2c) are different, there are three combinations of raw materials to be reacted, and the compounds (2A) to (2C) are different.
In this case, the compound (2A) is produced by reacting one molecule of the compound (2a) with one molecule of the compound (2b) and one molecule of the compound (2c). In the compound (2A), for example, when the compounds (2b) and (2c) have substantially the same reactivity, the molar number of one of the compounds (2b) and (2c) with respect to the compound (2a) In this case, the ratio (molar ratio) of compound (2b): compound (2c) is preferably 6: 4 to 4: 6, and preferably 5: 5. Is more preferable. On the other hand, when the compounds (2b) and (2c) have different reactivities, the compound (2A) has priority over the above case by, for example, relatively increasing the number of moles having a lower reactivity. It may be adjusted so that it is generated.

On the other hand, since compound (2B) is produced by reacting one molecule of compound (2a) with two molecules of compound (2b), for example, compounds (2b) and (2c) have substantially the same reactivity. When the amount of the compound (2b) is included, the amount of the compound (2b) can be suppressed by preventing the number of moles of the compound (2b) from being excessively larger than the number of moles of the compound (2c). On the other hand, when the compound (2b) is more reactive than the compound (2c), the number of moles of the compound (2b) is further reduced as compared with the above case so that the formation of the compound (2B) is suppressed. Adjust to.
In addition, since compound (2C) is formed by reacting one molecule of compound (2a) with two molecules of compound (2c), for example, when compounds (2b) and (2c) have approximately the same reactivity The amount of the compound (2c) can be suppressed by preventing the number of moles of the compound (2c) from being excessively larger than the number of moles of the compound (2b). On the other hand, when the compound (2c) is more reactive than the compound (2b), the number of moles of the compound (2c) is further reduced as compared with the above case so that the formation of the compound (2C) is suppressed. Adjust to.

  As described above, when the same compounds (2b) and (2c) are used, or different compounds are used, compound (2A) can be prepared by appropriately adjusting the number of moles in consideration of their reactivity. ) To (2C), the desired one can be preferentially produced.

  The total amount of the compounds (2b) and (2c) used per 1 mol of the compound (2a) during the reaction is preferably 2 to 25 mol, more preferably 4 to 20 mol.

  The type and amount of the reaction solvent, the temperature of the reaction solution during the electrolytic reaction, the electrode combination, the electrolysis conditions, the reaction time, and the like may be the same as in the method for producing the fluorescent compound (1).

  After completion of the reaction, as in the case of the fluorescent compound (1), a post-treatment operation is performed on the reaction solution obtained as necessary, and the target fluorescent compound (2) is taken out and further required. You may refine | purify according to.

  Like the fluorescent compound (1), the fluorescent compound (2) of the present invention undergoes an electrolytic reaction, so that it is simple and safe even when a raw material having low reactivity in a normal liquid phase reaction is used. Since it can be produced in a high yield by the process, it is excellent in safety and economy. Moreover, the fluorescent compound (2) can be produced from the compounds (2a), (2b) and (2c) which do not have fluorescence.

  As described above, the fluorescent compound (1) of the present invention can be produced by electrolytic reaction of the compound (1a) which is a phenol derivative and the compound (1b) which is an alkene derivative. The fluorescent compound (2) of the present invention can be produced by subjecting the compound (2a) which is a phenol derivative and the compounds (2b) and (2c) which are alkene derivatives to electrolytic reaction. And these phenol derivatives and alkene derivatives which are raw materials are compounds which do not have fluorescence, and using these raw materials, fluorescent compound (1) or (2) which is excellent in fluorescence can be simply and It can be produced in a high yield by a safe process. The fluorescent compounds (1) and (2) are extremely important due to their own fluorescence, but as described above, they can be easily and safely produced from a compound having no fluorescence in a high yield. Is also extremely important. This is because such features can be used for various purposes.

  For example, the compounds (1b), (2b) and (2c) are all stable compounds and can be stored for a long time even at room temperature. Therefore, when a composition containing an appropriate amount of these alkene derivatives is prepared and an attempt is made to form characters, patterns or images using the compositions, the characters, patterns or images resulting from the alkene derivatives are apparently used. It can be made unrecognizable. However, the fluorescent compound (1) or (1) or (2) is brought into contact with a cation species of a ketone body obtained by subjecting the compound (1a) or (2a), which is a phenol derivative, to electrolysis. 2) can be generated, and characters, patterns, or images that have not been recognized before can be clearly recognized by fluorescence. This is possible because the reaction between the phenol derivative and the alkene derivative proceeds efficiently in one step without accompanying dangerous conditions. Thus, a system including the composition containing the alkene derivative, the phenol derivative, and means for electrolyzing the phenol derivative is suitable for application to a security system, for example.

  In addition, the amount of the fluorescent compounds (1) and (2) increases in proportion to the amount of energization in the electrolytic reaction, and the fluorescence intensity increases in proportion to the amount of energization. It can also be used for conversion.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples. In the following examples, the unit “M” represents “mol / L”. The yield of the fluorescent compound (1) or (2) is a value calculated by ¹ H-NMR based on the compound (1a) or (2a).

<Oxidation potential measuring device, electrolytic reaction device>
In the following examples, after measuring the oxidation potential of the compound (1a) or (2a), an electrolytic reaction was performed to produce a fluorescent compound (1) or (2). The apparatus used for the measurement of the oxidation potential of the compounds (1a) and (2a) and the apparatus used for the electrolytic reaction are shown below.

(Oxidation potential measuring device)
Cyclic voltammetry HSV-100 (trade name, manufactured by Hokuto Denko)
Anode: Glassy carbon (outer diameter 6.0 mm, inner diameter 3.0 mm)
Cathode: platinum rod (diameter 2.0mm)
Reference electrode: Silver / silver chloride (electrolytic reactor)
Electrolytic device HABF-501A or HABF501 (trade name, manufactured by Hokuto Denko)
Anode: Carbon felt, 20mm x 40mm
Cathode: platinum plate, 20 mm x 20 mm
Reference electrode: Silver / silver chloride

<Analyzer>
The produced fluorescent compound (1) or (2) was measured for spectral data by nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and mass spectrometry (MS), and the structure was identified. The analyzers used in each method are shown below.

(Nuclear magnetic resonance system)
JEOL ALPHA-600 (600MHz, 150MHz) (manufactured by JEOL Ltd.)
JEOL AL-400 (400MHz, 100MHz) (manufactured by JEOL Ltd.)
Internal standard ¹ H-NMR: TMS (Δ = 0.00), ¹³ C-NMR: CDCl ₃ (δ = 77.03)
(Infrared spectrophotometer)
JASCO FT / IR-4100 (manufactured by JASCO Corporation)
Sample preparation method Oily substance: rock salt plate method, crystal: KBr method (mass spectrometer)
JMS-K9 (manufactured by JEOL Ltd.)

<Calculation of fluorescence yield>
Using the produced fluorescent compound (1) or (2), the fluorescence spectrum was measured by the method shown below, and the fluorescence yield was calculated from the area value and the like using the following formula (I). At the same time, the wavelength at which the absorbance was maximum (λ _abs.max ) and the wavelength at which the fluorescence spectrum intensity was maximum (λ _fl.max ) were determined. More specifically, it is as follows.

(Measurement of fluorescence spectrum and absorbance)
The fluorescence spectrum was measured by a relative evaluation method using a 1.0 N aqueous quinine sulfate solution as a standard sample.
That is, an evaluation sample in which the produced fluorescent compound (1) or (2) is dissolved in chloroform at a predetermined concentration is prepared, and the concentration at the excitation wavelength of the evaluation sample and the standard sample is 0.05 Abs or less. And using a spectrophotometer (U-3500, manufactured by Hitachi). At this time, λ _{abs. max} was determined.
Subsequently, the fluorescence spectrum of these samples was measured using a fluorometer (FP-6600, manufactured by JASCO Corporation), and the area value was determined. For the evaluation sample, at the same time, using the fluorometer, the λ _fl. Each _max was determined.

(Calculation of fluorescence yield)
Subsequently, the fluorescence yield of the fluorescent compound (1) or (2) was calculated using the following formula (I).
_{Φ x = Φ r · (FA} x / FA r) · (A r / A x) · (n x 2 / n r 2) ···· (I)
(Where Φ _x is the fluorescence yield of the evaluation sample; Φ _r is the fluorescence yield of the standard sample; FA _x is the area value of the fluorescence spectrum of the evaluation sample; FA _r is the fluorescence spectrum of the standard sample) It is the area value; a _x is the absorbance at the excited wavelength of the evaluation sample; a _r is an absorbance at the excitation wavelength of the standard sample; n _x is a refractive index of chloroform; n _r is the refractive water Rate.)

<Manufacture of fluorescent compounds>
[Example 1]
(Production of fluorescent compound (1) -1)
Lithium perchlorate (0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxybenzaldehyde (0.1 mmol) and 2-methyl-2-butene (1.0 mmol) were added, carbon felt as the anode, and platinum plate as the cathode. And constant potential electrolysis (1.3 V with respect to the reference electrode) at room temperature. After electrification at 3.0 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying over magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 30: 1 (volume ratio)) to obtain fluorescent compound (1) -1 (yield 52 %).

The spectrum data of the obtained fluorescent compound (1) -1 are shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 10.20 (1H, s), 7.02 (1H, d, J = 2.2 Hz), 6.93 (1H, m), 3.79 (3H, s), 3.14 (1H, q, J = 7.3 Hz), 1.52 (3H, s), 1.32 (3H, s), 1.24 (3H, d, J = 7.3 Hz)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 188.40, 156.35, 153.94, 137.21, 119.89, 118.63, 105.94, 92.23, 55.96, 45.02, 27.93, 22.03, 14.49
IR νmax (cm ^-1 ): 2961, 2923, 2850, 1684, 1460, 1394, 1267, 1034
MS (relative intensity%): 220 (M ⁺ , 100), 205 (15), 177 (34), 159 (59), 121 (27), 105 (13), 91 (49), 77 (55)
λ _abs.max (nm): 367
λ _fl.max (nm): 454
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -1 was 0.26.

[Example 2]
(Production of fluorescent compound (2) -1)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2,5-dihydroxybenzaldehyde (13.8 mg, 0.1 mmol) and 2-methyl-2-butene (106 μL, 1.0 mmol) were added, and carbon felt and cathode were added to the anode. Using a platinum plate, constant potential electrolysis (1.2 V with respect to the reference electrode) was performed at room temperature. After electrification with 4.4 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying with magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 15: 1 (volume ratio)) to obtain fluorescent compound (2) -1 (yield 71). %).

The spectrum data of the obtained fluorescent compound (2) -1 are shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 10.27 (1H, s), 6.74 (1H, s), 6.73 (1H, s), 3.44 (1H, q, J = 7.3 Hz), 3.11 (1H, q, J = 7.3 Hz), 3.08 (1H, q, J = 7.3 Hz), 1.51 (3H, s), 1.49 (3H, s), 1.44 (3H, s), 1.33 (3H, s), 1.30 ( 3H, s), 1.29 (3H, s), 1.21 (3H, d, J = 7.3 Hz), 1.11 (3H, d, J = 7.3 Hz)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 189.08, 156.35, 151.80, 134.30, 134.26, 131.13, 116.20, 116.13, 113.01, 112.87, 91.78, 91.52, 89.13, 45.49, 45.46, 45.24, 45.21, 28.28, 28.20 , 28.13, 28.02, 22.48, 22.45, 22.11, 22.03, 15.97, 15.80, 14.79, 14.46
IR νmax (cm ^-1 ): 2972, 2927, 2867, 2850, 2756, 1684, 1444, 1394, 1300, 1061
MS (relative intensity%): 274 (M ⁺ , 75), 259 (100), 217 (27), 105 (8), 91 (23), 77 (31)
λ _abs.max (nm): 395
λ _fl.max (nm): 495
Moreover, the fluorescence yield of the obtained fluorescent compound (2) -1 was 0.65.

[Example 3]
(Production of fluorescent compound (1) -2)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxyacetophenone (16.6 mg, 0.1 mmol) and styrene (34.4 μL, 0.3 mmol) were added, carbon felt as the anode, and platinum as the cathode. Using the plate, constant potential electrolysis (1.1 V with respect to the reference electrode) was performed at room temperature. After energization at 2.5 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying over magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1 (volume ratio)) to obtain fluorescent compound (1) -2 (yield 100). %).

The spectrum data of the obtained fluorescent compound (1) -2 are shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 7.39 (4H, d, J = 3.7 Hz), 7.34 (1H, m), 7.23 (1H, d, J = 2.9 Hz), 6.97 (1H, m) , 5.87 (1H, dd, J = 8.8 Hz, J = 8.8 Hz), 3.80 (3H, s), 3.64 (1H, dd, J = 16.1 Hz, J = 8.8 Hz), 3.19 (1H, dd, J = 16.1 Hz, J = 8.1 Hz), 2.66 (3H, s)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 196.64, 154.68, 154.00, 141.42, 130.27, 128.71, 128.16, 125.47, 119.82, 118.53, 109.34, 84.97, 55.96, 37.86, 31.25
IR νmax (cm ^-1 ): 3066, 3033, 3000, 2939, 2839, 2833, 1672, 1461, 1189, 1038
MS (relative intensity%): 268 (M ⁺ , 59), 253 (22), 165 (27), 152 (21), 105 (14), 91 (22), 77 (36), 43 (100)
λ _abs.max (nm): 350
λ _fl.max (nm): 430
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -2 was 0.19.

[Example 4]
(Production of fluorescent compound (1) -3)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxyacetophenone (16.6 mg, 0.1 mmol) and an appropriate amount of isobutene were added, a carbon felt was used for the anode, and a platinum plate was used for the cathode, Then, constant potential electrolysis (1.1 V with respect to the reference electrode) was performed. After energization at 2.5 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying with magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1 (volume ratio)) to obtain fluorescent compound (1) -3 (yield 84). %).

The spectrum data of the obtained fluorescent compound (1) -3 are shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 7.17 (1H, d, J = 2.9 Hz), 6.93 (1H, m), 3.78 (3H, s), 3.00 (2H, s), 2.61 (3H, s), 1.51 (6H, s)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 197.05, 154.37, 153.42, 131.15, 119.88, 118.97, 108.94, 88.09, 55.96, 42.32, 31.22, 28.19
IR νmax (cm ^-1 ): 2972, 2933, 2844, 1672, 1467, 1372, 1145, 1044
MS (relative intensity%): 220 (M ⁺ , 60), 205 (42), 177 (7), 163 (23), 105 (6), 91 (19), 77 (16), 43 (100)
λ _abs.max (nm): 351
λ _fl.max (nm): 432
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -3 was 0.25.

[Example 5]
(Production of fluorescent compound (1) -4)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxyacetophenone (16.6 mg, 0.1 mmol) and 2,3-dimethyl-2-butene (119 μL, 1 mmol) were added, and carbon felt was added to the anode. Then, constant potential electrolysis (1.1 V with respect to the reference electrode) was performed at room temperature using a platinum plate as the cathode. After energization at 2.5 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying over magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1 (volume ratio)) to obtain fluorescent compound (1) -4 (yield 92 %).

The spectrum data of the obtained fluorescent compound (1) -4 are shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 7.15 (1H, d, J = 2.9 Hz), 6.84 (1H, d, J = 2.9 Hz), 3.79 (3H, s), 2.62 (3H, s) , 1.35 (6H, s), 1.19 (6H, s)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 197.03, 153.80, 152.82, 142.15, 120.26, 116.85, 108.21, 93.06, 55.90, 45.73, 31.23, 23.90, 23.00
IR νmax (cm ^-1 ): 2972, 2939, 2872, 2839, 1678, 1461, 1372, 1211, 1111
MS (relative intensity%): 248 (M ⁺ , 71), 233 (82), 191 (14), 91 (15), 77 (15), 65 (8), 43 (100)
λ _abs.max (nm): 348
λ _fl.max (nm): 433
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -4 was 0.31.

[Example 6]
(Production of fluorescent compound (1) -5)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxyacetophenone (16.6 mg, 0.1 mmol) and 1-methylcyclohexane (71.2 μL, 0.6 mmol) were added, and carbon felt was added to the anode. Using a platinum plate as the cathode, constant potential electrolysis (1.1 V with respect to the reference electrode) was performed at room temperature. After electrification at 3.0 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Next, after drying over magnesium sulfate, the mixture was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1 (volume ratio)) to obtain fluorescent compound (1) -5 (yield 80). %).

The spectrum data of the obtained fluorescent compound (1) -5 are shown below. As is apparent from the following spectral data, the fluorescent compound (1) -5 was a mixture of diastereomers.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 7.15 (1H, d, J = 2.9 Hz), 6.87 (1H, m), 3.79 (3H, s), 3.08 (1H, t, J = 5.1 Hz) , 2.62 (3H, s), 1.91 (1H, m), 1.73 (2H, m), 1.59 (2H, m), 1.33 (2H, m), 1.54 (3H, s)
δ 7.11 (1H, d, J = 2.9 Hz), 6.84 (1H, m), 3.79 (3H, s), 2.95 (1H, m), 2.64 (3H, s), 2.16 (2H, m), 2.00 ( 1H, td, J = 12.5 Hz, J = 4.4 Hz), 1.80 (2H, m), 1.50 to 1.43 (3H, m), 1.14 (3H, s)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 197.10, 154.21, 153.65, 136.47, 120.57, 117.47, 108.25, 90.05, 55.91, 46.37, 34.12, 31.26, 25.84, 25.46, 20.88, 17.53
δ 197.17, 154.67, 153.75, 135.68, 120.77, 116.65, 107.28, 92.01, 55.87, 51.44, 36.71, 31.30, 23.49, 23.02, 21.74, 17.53
IR νmax (cm ^-1 ): 2933, 2861, 1672, 1461, 1378, 1261, 1195, 1038
MS (relative intensity%): 260 (M ⁺ , 54), 245 (9), 217 (18), 192 (60), 91 (15), 77 (20), 43 (100)
λ _abs.max (nm): 350
λ _fl.max (nm): 432
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -5 was 0.22.

[Example 7]
(Production of fluorescent compound (1) -6)
Lithium perchlorate (6.3834 g, 0.06 mol) was dissolved in nitromethane (20 mL) to prepare a 3M lithium perchlorate / nitromethane solution. Acetic acid (1 mL) was added thereto, 2-hydroxy-5-methoxyacetophenone (16.6 mg, 0.1 mmol) and citronellyl acetate (59.5 mg, 0.3 mmol) were added, carbon felt at the anode, and carbon felt at the cathode. Using a platinum plate, constant potential electrolysis (1.1 V with respect to the reference electrode) was performed at room temperature. After energization at 2.5 F / mol, the product was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Subsequently, after drying with magnesium sulfate, it was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1 (volume ratio)) to obtain fluorescent compound (1) -6 (yield 86). %).

The spectral data of the obtained fluorescent compound (1) -6 is shown below.
¹ H-NMR (CDCl ₃ ; 600 MHz): δ 7.17 (1H, d, J = 2.2 Hz), 6.93 (1H, m), 4.12 (2H, m), 3.79 (3H, s), 2.93 (1H, q, J = 8.1 Hz), 2.60 (3H, s), 2.05 (3H, s), 2.04 (3H, s), 1.73 to 1.57 (4H, m), 1.51 (3H, s), 1.50 (3H, s ), 1.37 (3H, s), 1.36 (3H, s), 1.27 (1H, m), 0.96 (3H, d, J = 6.6 Hz), 0.95 (3H, d, J = 6.6 Hz)
¹³ C-NMR (CDCl ₃ ; 150 MHz): δ 197.02, 171.14, 171.10, 153.69, 153.66, 153.38, 153.35, 136.02, 136.01, 119.99, 118.90, 118.75, 108.55, 108.51, 90.96, 90.92, 62.73, 60.35, 55.93 , 50.52, 50.49, 35.41, 35.35, 34.93, 34.82, 31.24, 30.25, 28.84, 28.77, 27.49, 27.42, 22.12, 22.07, 21.01, 20.98, 19.34, 19.31, 14.16
IR νmax (cm ^-1 ): 2961, 2933, 2867, 1739, 1672, 1461, 1372, 1239, 1044
λ _abs.max (nm): 350
λ _fl.max (nm): 432
Moreover, the fluorescence yield of the obtained fluorescent compound (1) -6 was 0.26.

  The obtained fluorescent compounds (1) -1 to (1) -6, (2) -1 all had an excellent fluorescent yield equal to or higher than that of conventional fluorescent compounds.

  The present invention can be used in analysis fields such as detection and analysis of trace substances, tracking of reaction processes, and various security fields.

Claims (4)

A fluorescent compound represented by the following general formula (1).

(Wherein R ¹¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ¹² is a hydrogen atom or a linear or branched chain having 1 to 3 carbon atoms ; It is an alkyl group; R ¹³ represents a hydrogen atom, a linear or branched alkyl group or phenyl group having 1 to 3 carbon atoms; R ¹⁴ is a straight-chain hydrogen atom or having 1 to 10 carbon atoms a Jo or branched alkyl group, the alkyl group may be one carbon atom is substituted with a carbonyl group, in which case the carbonyl group in the carbonyl group, in R ^14, wherein carbonyl than the oxygen atom which is bonded to the group located at the terminal side; R ¹⁵ is a hydrogen atom or a carbon number be 1 to 3 linear or branched alkyl group; R ¹⁶ is a carbon number 1 to 3 linear Is an branched alkyl group; ^{R 17} and ^{R 18} are hydrogen atoms; R ¹³ and ^{R 14} form a ring bonded to each other also rather good; ^however, the ^{R 12} and ^{R 13} When one is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms. Excluding cases where A fluorescent compound represented by the following general formula (2).

(Wherein R ²¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²⁰ , R ²⁴ , R ²⁵ , R ²⁸ and R ²⁹ each independently represent a hydrogen atom. Or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ²² , R ²³ , R ²⁶ and R ²⁷ are each independently a linear or branched chain group having 1 to 3 carbon atoms. The alkyl group of Fluorescence represented by the following general formula (1), characterized by having a step of subjecting a compound represented by the following general formula (1a) and a compound represented by the following general formula (1b) to an electrolytic reaction Compound production method.

(Wherein R ¹¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms ; R ¹² is a hydrogen atom or a linear or branched chain having 1 to 3 carbon atoms ; It is an alkyl group; R ¹³ represents a hydrogen atom, a linear or branched alkyl group or phenyl group having 1 to 3 carbon atoms; R ¹⁴ is a straight-chain hydrogen atom or having 1 to 10 carbon atoms a Jo or branched alkyl group, the alkyl group may be one carbon atom is substituted with a carbonyl group, in which case the carbonyl group in the carbonyl group, in R ^14, wherein carbonyl than the oxygen atom which is bonded to the group located at the terminal side; R ¹⁵ is a hydrogen atom or a carbon number be 1 to 3 linear or branched alkyl group; R ¹⁶ is a carbon number 1 to 3 linear Is an branched alkyl group; ^{R 17} and ^{R 18} are hydrogen atoms; R ¹³ and ^{R 14} form a ring bonded to each other also rather good; ^however, the ^{R 12} and ^{R 13} When one is a hydrogen atom and the other is a group other than an aryl group, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁶ are methyl groups, and R ¹⁵ , R ¹⁷ and R ¹⁸ are hydrogen atoms. Excluding cases where It has the process of carrying out the electrolytic reaction of the compound represented by the following general formula (2a), the compound represented by the following general formula (2b), and the compound represented by the following general formula (2c), The manufacturing method of the fluorescent compound represented by the following general formula (2A), (2B) or (2C).

(In the formula, R ²¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²⁰ , R ²⁴ ′, R ²⁵ ′, R ²⁸ ′ and R ²⁹ ′ are each Independently a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms; R ²² ′, R ²³ ′, R ²⁶ ′ and R ²⁷ ′ each independently has 1 to 3 carbon atoms. A linear or branched alkyl group .)