JP2003261785A - Method for producing methine dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic method for producing a methine dye suitable for a dye-forming reaction so as to afford an asymmetric dye. <P>SOLUTION: The method for producing the methine dye represented by general formula (I) (wherein, L<SB>1</SB>to L<SB>7</SB>denote each a methine group; p<SB>1</SB>and p<SB>2</SB>denote each 0 or 1; n<SB>1</SB>denotes 0, 1, 2, 3 or 4; Z<SB>1</SB>and Z<SB>2</SB>denote each an atomic group required to form a nitrogen-containing heterocyclic ring; R<SB>1</SB>and R<SB>2</SB>denote each an alkyl group; M<SB>1</SB>denotes a counterion for equilibrating the charge; and m<SB>1</SB>denotes a number of ≥0 required to neutralize the charge of the molecule) is carried out as follows. A compound represented by general formula (II) [or general formula (III)] (wherein, L<SB>8</SB>to L<SB>11</SB>denote each the same meaning as L<SB>1</SB>to L<SB>7</SB>; p<SB>3</SB>and p<SB>4</SB>denote each the same meaning as p<SB>1</SB>and p<SB>2</SB>; Z<SB>3</SB>and Z<SB>4</SB>denote each the same meaning as Z<SB>1</SB>and Z<SB>2</SB>; R<SB>3</SB>and R<SB>4</SB>denote each the same meaning as R<SB>1</SB>and R<SB>2</SB>; Q<SB>1</SB>and Q<SB>2</SB>denote each a group required to form a methine chain by nucleophilic attack of methylene base; M<SB>2</SB>and M<SB>3</SB>denote each the same meaning as M<SB>1</SB>; and m<SB>2</SB>and m<SB>3</SB>denote each the same meaning as m<SB>1</SB>) is reacted with a compound represented by general formula (IV) [or general formula (V)] (wherein, L<SB>12</SB>to L<SB>15</SB>denote each the same meaning as L<SB>1</SB>to L<SB>7</SB>; p<SB>5</SB>and p<SB>6</SB>denote each the same meaning as p<SB>1</SB>and p<SB>2</SB>; Z<SB>5</SB>and Z<SB>6</SB>denote each the same meaning as Z<SB>1</SB>and Z<SB>2</SB>; R<SB>5</SB>and R<SB>6</SB>denote each the same meaning as R<SB>1</SB>and R<SB>2</SB>; M<SB>4</SB>and M<SB>5</SB>denote each the same meaning as M<SB>1</SB>; m<SB>4</SB>and m<SB>5</SB>denote each the same meaning as m<SB>1</SB>; L<SB>1a</SB>denotes an active methyl group; and L<SB>1b</SB>denotes a methine group) in the presence of an organophosphorus compound to afford the methine dye. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Method for producing methine dyes used as materials for medicine, diagnosis, etc.
About. [0002] 2. Description of the Related Art Methine dyes represented by cyanine dyes
Many synthetic methods have been reported, for example, T. H. James
ed., The Theory of Photographic Process 3rd ed., M
acmillan, N. Y., 1966 and F. M. Hamer, The Chemistry
of Heterocyclic Compounds, Vol. 18, The Cyanine Dy
es and Related Compounds, A. Weissberger, ed., Int
erscience, N. Y., 1964 and G. E. Ficken, The Chemistr
y of Synthetic Dyes, Vol. 4, K. Venkataraman, ed.,
 Academic Press, N. Y., 1971. Only
However, when synthesizing asymmetric dyes, symmetric dyes are easily produced as a by-product.
Effective method with detailed explanation of conditions, pigment ratio, etc.
Little is known. (Japanese Patent Laid-Open No. 9-203993,
(JP-A-8-269909, JP-A-6-138574) [0003] Accordingly, it is an object of the present invention.
Efficiently synthesize the desired dye, especially
To obtain asymmetric dyes
Providing conditions for the dyeing reaction. [0004] [Means for Solving the Problems] As a result of various studies,
The present inventors perform the reaction in the presence of an organophosphorus compound.
It was found that the purpose was achieved. That is, the present invention
Was achieved by the following (1) to (4). (1) reacting in the presence of an organophosphorus compound;
Method for producing methine dye characterized by obtaining methine dye
Law, (2) Organophosphorus compound is trivalent organophosphorus
The methine dye according to (1), which is a compound
Production method, (3) The methine dye is represented by the general formula (I)
(1) or (2), characterized in that
A method for producing the methine dye described in the above, [0008] [Chemical 6] Where L₁, L₂, L_Three, L_Four, L_Five, L₆,
And L₇Each represents a methine group. These are replacing
Even if nearby methine groups are bonded to form a ring
Good. p₁And p₂Each represents 0 or 1. n₁Is 0,
1, 2, 3 or 4 is represented. Z₁And Z₂Each contains nitrogen
This represents a group of atoms necessary for forming a heterocycle. However, this
They may be condensed. Also nearby methine groups and nitrogen
It may be bonded to the above substituent to form a ring. Snow
L₁~ L₇Are respectively L₁~ L₇, Z₁, R₁, Z₂Also
Is R₂And may be bonded to each other to form a ring. (Example
For example, n₁Different when L is 2 or more_FourTies together
Together, they can form a 5- or 6-membered ring. ) R₁And R₂Each
Each represents an alkyl group. M₁Is the counter ion for charge balancing
Represents m₁Is 0 or more necessary to neutralize the charge of the molecule
Represents the number of ) (4) a compound represented by the general formula (II):
Or represented by the general formula (III) which is the resonance structure of (II)
At least one compound selected from the following compounds:
A compound represented by the general formula (IV) or (IV)
Selected from the compound represented by the general formula (V) which is a resonance structure
Characterized by reacting at least one compound
The production of the methine dye according to (1), (2) or (3)
Manufacturing method. [0011] [Chemical 7] (Wherein L₈, And L₉Each represents a methine group
The These may be substituted. p _ThreeRepresents 0 or 1
The Z_ThreeIs the group of atoms required to form a nitrogen-containing heterocycle
Represents. However, this may be condensed. Also nearby
Even if it is combined with a methine group or a nitrogen substituent to form a ring
Good. Q₁By a methylene-based nucleophilic attack
Represents a group necessary to form a chain. This is a nitrogen replacement
It may be bonded to a group to form a ring. R_ThreeIs alkyl
Represents a group. M₂Represents a counter ion for charge balancing and m₂
Indicates a number greater than or equal to zero required to neutralize the charge of the molecule
The ) In relation to the formula (I), L₈, And L₉Is
L₁, And L₂Or L₆, And L₇And p_ThreeIs
p₁Or p₂Is the same as Z_ThreeIs Z₁Or Z₂Is the same as
R_ThreeIs R₁Or R₂Is the same. [0013] [Chemical 8] (Wherein L_Ten, L₁₁, P_Four, Z_Four, Q₂,
R_Four, M_ThreeAnd m_ThreeIs L in formula (II)₈, L₉,
p_Three, Z_Three, Q₁, R_Three, M₂And m₂It is synonymous with. ) In relation to the formula (I), L_Ten, And L₁₁Is L
₁, And L₂Or L₆, And L₇And p_FourIs p₁
Or p₂Is the same as Z_FourIs Z₁Or Z₂Is the same as
R_FourIs R₁Or R₂Is the same. [0015] [Chemical 9](Wherein L₁₂, And L₁₃Each has a methine group
Represent. These may be substituted. L_1aIs active methyl
Represents a group. p_FiveRepresents 0 or 1. Z_FiveIs a nitrogen-containing heterocycle
It represents an atomic group necessary for forming. However, this is a condensed ring
You may do it. Also with nearby methine groups and nitrogen substituents
It may combine to form a ring. R_FiveIs an alkyl group
Represent. M_FourRepresents a counter ion for charge balancing and m_FourIs minutes
This represents a number of 0 or more necessary to neutralize the charge of the child. ) In relation to the formula (I), L₁₂, And L₁₃Is L
₁, And L₂Or L₆, And L₇And p_FiveIs p₁
Or p₂Is the same as Z_FiveIs Z₁Or Z₂Is the same as
R_FiveIs R₁Or R₂Is the same. [0017] Embedded image (Wherein L_1bIs a methine group, L_1aOr
This is a deprotonated structure. L₁₄, L₁₅, P₆,
Z₆, R₆, M_FiveAnd m_FiveIs L in formula (IV)₁₂,
L₁₃, P_Five, Z_Five, R_Five, M_FourAnd m_FourIt is synonymous with. ) In relation to the formula (I), L₁₄, And L₁₅Is L
₁, And L₂Or L₆, And L₇And p₆Is p₁
Or p₂Is the same as Z₆Is Z₁Or Z₂Is the same as
R₆Is R₁Or R₂Is the same. Furthermore, the formulas (I) and (I
In relation to I) and (IV), L₈, And L₉But
L₁, And L₂And p_ThreeIs p₁Is the same as Z
_ThreeIs Z₁And R_ThreeIs R₁Is the same as
L₁₂, And L₁₃Is L₆, And L₇And p_FiveIs p₂
Is the same as Z_FiveIs Z₂And R_FiveIs R₂Same as
It is. [0019] BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in further detail below.
The General formula (I), (II), (III), (IV),
And L in (V)₁, L₂, L_Three, L_Four, L_Five, L₆,
L₇, L₈, L ₉, L_Ten, L₁₁, L₁₂, L₁₃, L₁₄,as well as
L₁₅Are each a methine group or a substituted methine group {eg substituted
Or an unsubstituted alkyl group (eg methyl group, ethyl
Group, 2-carboxyethyl group), substituted or unsubstituted
An aryl group (eg, phenyl group, o-carboxyphene)
Nyl group), halogen atom, alkoxy group (for example, meth)
Xy group, ethoxy group), amino group (for example, N, N-di)
Phenylamino group, N-methyl-N-phenylamino
Group, N-methylpiperazino group), etc.
Etc., and may form a ring with other methine groups
Well, or you can form a ring with an auxiliary color group. L in the general formula (IV)_1aIs active methyl
Represents a group. That is, it is deprotonated by a base and nucleophilic.
A group capable of expressing (ie, can be methylene-based)
Group), specifically, a methyl group or an electron-withdrawing group
Is a substituted methyl group. Substituent of substituted methyl group
For example, N-position substituent R of nitrogen-containing heterocycle_FiveAnd 5,
Examples include those that form 6- to 7-membered rings, specifically
(As a group linking methyl group and N-position substituent) ethylene
Group, propylene group, butylene group, ethylenedioxy group, etc.
It is. An unsubstituted methyl group is preferable. General formula
L in (V) _1bAre these L_1aDeprotonated
Further, it is an optionally substituted methine group. General formulas (I), (II), (III),
P in (IV) and (V)₁, P₂, P_Three, P_Four,
p_FiveAnd p₆Each represents 0 or 1. Preferably p₁
= P₂= P_Three= P_Four= P_Five= P₆= 0. Formula (I)
N₁Represents 0, 1, 2, 3 or 4. Preferably 0 or
Is 1. General formulas (I), (II), (III),
M in (IV) and (V)₁, M₂, M_Three, M_Four,
And M_FiveEach represents a charge neutralizing ion. Some compounds are positive
Ion, anion, or net ionic charge
It depends on the substituent. Typical sun
On is ammonium ion, alkali metal ion, and
Alkaline earth metal ions, while anions are inorganic ions.
Either ON or organic ions may be used. Yoio
Examples of sodium ions and potassium ions
, Triethylammonium ion, pyridinium ion
Anions include, for example, halogen anions
Substituted aryl sulfonate ions (eg p-tolue
Sulfonate ions), alkyl sulfate ions (for example,
Methyl sulfate ion), sulfate ion, perchlorate ion,
Examples include trifluoroborate ion and acetate ion.
The m₁, M₂, M_Three, M_FourAnd m_FiveEach neutralize charge
Represents the number required to General formulas (I), (II), (III),
Z in (IV) and (V)₁, Z₂, Z_Three, Z_Four,
Z_FiveAnd Z₆Are each a nitrogen-containing heterocycle, preferably
5- and 6-membered nitrogen-containing heterocycles, which are further condensed
May be. The condensed ring may be an aromatic ring or a non-aromatic ring.
Any aromatic ring may be used. Preferably it is an aromatic ring, for example
Hydrocarbon aromatic rings such as benzene ring and naphthalene ring
And heteroaromatic rings such as pyrazine ring and thiophene ring
Can be mentioned. Nitrogen-containing heterocycles include thiazoline nuclei and thia
Zole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, oxazoline nucleus, oxazole nucleus, benzoxa
Sol nucleus, naphthoxazole nucleus, selenazoline nucleus,
Renazol nucleus, benzoselenazole nucleus, naphthoselenazo
-Nuclear 3,3-dialkylindolenine nucleus (e.g.
3,3, -dimethylindolenine), imidazoline nucleus,
Imidazole nucleus, Benzimidazole nucleus, Naphthimida
Zole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quino
Phosphorus nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-i
Soquinoline nucleus, imidazo [4,5-b] quinoxaline
Nucleus, oxadiazol nucleus, thiadiazole nucleus, tetrazo
Nuclei and pyrimidine nuclei. Like
Benzothiazole nucleus, naphthothiazole nucleus,
Nzooxazole nucleus or naphthoxazole nucleus
The These may have a substituent and are preferably substituted.
Groups include phenyl groups, halogen atoms, and alkoxy groups.
Or an alkyl group. Of alkoxy and alkyl groups
The number of carbon atoms is 1 to 20, preferably 1 to 10, more preferably
Preferably it is 1-5. General formulas (I), (II), (III),
R in (IV) and (V)₁, R₂, R_Three, R_Four,
R_FiveAnd R₆Are each an alkyl group having 1 to 20 carbon atoms.
For example, methyl group, ethyl group, n-propyl group, n
-Butyl group, n-pentyl group, n-hexyl group, n-he
Ptyl group, n-nonyl group, i-propyl group, i-butyl
Group, i-pentyl group, t-butyl group and the like. these
May be substituted. As a preferred substituent group,
Sulfo group, carboxy group, alkoxy group, alkenyl
Group, an amide group. When the substituent is a sulfo group,
These counter cations include alkali metals, quaternary ammonia.
For example, sodium, potassium,
Pyridinium, 1-ethylpyridinium, triethyla
Such as ammonium. R₁, R₂, R_Three, R_Four, R_Five, And
And R₆Preferably, methyl group, ethyl group, propylene
Group, sulfoethyl group, sulfopropyl group, sulfobuty
Group, carboxyethyl group, or methoxyethyl group
is there. Q in the general formula (II)₁Is methylenebe
Necessary for generating methine chains by nucleophilic attack
Represents a radical. Q₁Can form any methine chain.
The compound represented by the general formula (II)
The product should also be expressed as a compound represented by the general formula (VI)
Can do. [0027] Embedded image (In the formula, A represents a substituent having a leaving ability.
However, any substituent having a known leaving ability is preferred.
Used. n₂Is 0, 1, 2, 3 or 4
The Preferably 0 or 1. L₁₆, And L₁₇Is it
L in general formula (I)_Three, And L_FourIt is synonymous with. L₈,
L₉, P_Three, Z_Three, R_Three , M₂And m₂Is the general formula
L of (II)₈, L₉, P_Three, Z_Three, R_Three, M₂And m₂When
It is synonymous. ) A is, for example, T. H. James ed., The Theor
y of Photographic Process 3rd ed., Macmillan, N.
Y., 1966, having the elimination ability described on pages 205 to 211
Substituents. Preferably, an alkoxy group, a
Alkylthio, chloro, anilino, or dialkyl
It is a ruamino group. Particularly preferred is an alkoxy group
The Q in the general formula (III)₂Is methylene
Necessary to generate methine chains by base nucleophilic attack
Represents an important group. Q₂To form any methine chain
For example, the terminal is alkylcarbonyl
Group, arylcarbonyl group, formyl group, nitroso group, etc.
I can give it. Preferably an alkylcarbonyl group, a
A reelcarbonyl group and a formyl group. The compounds represented by the general formula (I) are so-called
Symmetric dye (ie R₁= R₂, L₁ = L₆, L₂= L₇, L_Three
= L_Five, Z₁= Z₂And p₁= P₂But if not)
Nominal dye (ie, R₁≠ R₂, L₁≠ L₆, L₂≠ L₇, L_Three≠
L_Five, Z₁ ≠ Z₂And p₁≠ p ₂At least the pair
If there is one or more). Preferably an asymmetric dye
is there. As an example of a methine dye synthesis scheme,
The following is shown. [0033] Embedded imageIn the presence of an organophosphorus compound and a base, in general
Formula (II-1) (wherein Z ″ represents a substituent on the benzene ring)
Represent. When s is 2, Z ″ bonds to each other to form a benzene ring, etc.
May be formed. p and s each represent an integer, preferably
Or p is 1 to 5 and s is 1 to 3, more preferably p.
Represents 2 to 4, and s represents 1 or 2. ) And general formula (IV-
1) (wherein Z ′ represents a substituent on the benzene ring, r is
2), Z ″ bonds to form a benzene ring or the like.
Also good. q and r each represents an integer, preferably q is 1
-5, r represents 1-3, more preferably q is 2-4,
r represents 1 or 2; ) To give a general formula
(I-1) (wherein Z ′, Z ″, p, q, r, and s are
It is synonymous with the above. M represents counter ion for charge balance
The ) Asymmetric methine dyes represented by
Can be obtained. Methylene base used in the process according to the invention
Examples of bases for generating hydrogen include organic bases (for example,
Liethylamine, 1,8-diazabicyclo [5.4.
0. ] Undece-7-ene, pyridine, etc.) or al
Use kill metal compounds or alkaline earth metal compounds
Rukoto can. Preferably sodium t-butoxy
And sodium hydride. The equivalent of the base is the general formula (IV) or
For the compound represented by formula (V), preferably 0.1
Equivalent to 10 equivalents, more preferably 0.5 equivalents to 5 equivalents
Amount. Particularly preferably 1.0 equivalent to 2.5 equivalents
is there. Regarding the reaction temperature in the process according to the invention,
It can be used in the temperature range from the freezing point to the boiling point of the solvent.
Come, but preferably from -80 ℃ to 100 ℃
Or -40 ° C to 80 ° C. Particularly preferably -20
From 40 ° C to 40 ° C. Regarding the reaction time in the process according to the invention,
The reaction is complete in 30 minutes to 20 hours. Preferably
Is from 1 hour to 10 hours, more preferably from 1 hour
5 hours. In the process according to the invention, in particular with regard to the solvent.
There is no limit. For example, toluene, xylene,
Hydrocarbon solvents such as men, methyl alcohol, ethyl
Alcohol-based solvents such as alcohol and isopropanol
Medium, tetrahydrofuran, 1,3-dioxolane, t-
Ethers such as butyl methyl ether and dimethoxyethane
Nitrous solvents such as acetonitrile and benzonitrile
Such as ril-based solvents, chlorobenzene and o-dichlorobenzene.
Any halogenated solvent, N-methylpyrrolidinone, dimethyl
Formamide, dimethylacetamide and dimethylsulfate
A polar solvent such as oxide is preferred. Above all, Arco
Solvent, ether solvent, nitrile solvent, and electrode
Further preferred is a solvent. The amount of the solvent used is the general formula (II) or one
For 1 mmol of the compound represented by the general formula (III),
0.5 to 30 ml, preferably 1 to 20 ml
1, more preferably 1 ml to 10 ml. The organophosphorus compound used in the present invention is a trivalent compound.
It is an organophosphorus compound. Trivalent organophosphorus compounds have the general formula
(VII). [0042] Embedded image Where Y₁, Y₂And Y_ThreeIs an alkyl group
(Preferably having 1 to 30 carbon atoms such as methyl, ethyl,
Isopropyl, t-butyl, cyclohexyl), aryl
Group (preferably having 6 to 30 carbon atoms such as phenyl,
Ril, naphthyl, anthryl, phenanthryl), hete
A roaryl group (preferably having 1 to 20 carbon atoms, such as 2-
Thienyl, 2-furyl, 2-pyrrolyl, 2-pyridy
), An alkoxy group (preferably having 1 to 30 carbon atoms, eg
Methoxy, ethoxy, isopropoxy, t-butoxy
Si, n-octyloxy) and aryloxy groups (preferably
Preferably it has 6 to 30 carbon atoms, such as phenoxy, toluluo
Xyl, naphthyloxy, anthryloxy, phenanthate
Riloxy). Preferably aryl group, aryl
It is an oxy group. Y₁, Y₂And Y_ThreeAre all the same but different
It may be. These groups are further substituted (for example,
Alkyl group, aryl group, alkoxy group, halogen source
Child, nitro group, cyano group). Of the above organophosphorus compounds,
Nylphosphine (VII-1) and triphenylphospha
Ito (VII-2) is easy to obtain and handle
Therefore, it is particularly preferable. The amount of the organic phosphorus compound used is the general formula (II)
Alternatively, for the compound represented by the general formula (III),
Preferably from 0.1 equivalents to 10 equivalents, more preferably
0.5 to 5 equivalents. In the following, general formula (I), general formula (II),
Structures of compounds represented by general formula (IV) and general formula (VII)
However, the present invention is not limited by these.
Is not something Compound of the general formula (I)
Example [0047] [Table 1] Specific examples of compounds represented by formula (II) [0049] [Table 2]Specific examples of compounds represented by formula (IV) [0051] [Table 3] Specific examples of compounds represented by formula (VII)
Example [0053] [Table 4]In the table, Ph is phenyl, o-Tol is o-
Tolyl, p-Tol is p-tolyl, Cy is cyclohexyl
Represents EXAMPLES The present invention will be described in detail below based on examples.
However, the present invention is not limited in any way by these examples.
It is not something. [0055] Embedded image Example 1: Starting material N-sulfopropyl-2- (β-ethoxy
Ii) -Vinyl-3-ethyl-naphtho (1,2-d) Oki
Preparation of Sazole (II-1) First, N-sulfobutyl-2-methyl-5-alkyl described below.
Same as the preparation method of lorobenzothiazole (IV-1)
N-sulfopropyl-2-methyl-naphth obtained as above
(1,2-d) oxazole 91.61 g, trieth
126.90 g of xylethylmethane and m-cresol
After adding 450ml, heat stirring at 120 ° C for 25 minutes
do. When water-cooled to 80 ° C., ethyl acetate 45
Add 0 ml and cool on ice for 1 hour. The crystals obtained are filtered off
And then wash with 450 ml of ethyl acetate and 450 ml of acetone.
Purify. The crude crystals were mixed with 200 ml of methanol and 2-pro
When recrystallized in a mixed solvent of Panol 1.6 l, purity 66
%, Yield 85% N-sulfopropyl-2- (β-eth
Xy) -vinyl-3-ethyl-naphtho (1,2-d)
150.4 g of xazole (II-1) was obtained. Starting material N-sulfobutyl-2-me
Preparation of til-5-chlorobenzothiazole (IV-1) First, 2-methyl-5-chlorobenzothiazol 1
Charged 8.96 g and butane sultone 20.60 g
Then add 5 ml of anisole and heat stir at 170 ° C for 6 hours.
Stir. When allowed to cool to 100 ° C., 2-prop
Add 50 ml of diol and heat to reflux for 30 minutes. So
After cooling to 40 ° C. and adding 50 ml of acetone,
The crystals were separated by filtration to give N-sulfobutyl in a yield of 94%.
-2-methyl-5-chlorobenzothiazole (IV-
1) 30.80 g was obtained. Synthesis of methine dye (I-1) First, 10 ml of 1,3-dioxolane with N-sulfo
Butyl-2-methyl-5-chlorobenzothiazole (I
V-1) 1.63 g and N-sulfopropyl-2- (β-
Ethoxy) -vinyl-3-ethyl-naphtho (1,2-
d) 1.14 g of oxazole (II-1) was added.
After cooling to 0 ° C., triphenyl phosphite (VI
I-2) 0.60 g was added. The reaction mixture is left for 20 minutes
After stirring at 0 ° C. for a while, sodium t-butoxide 0.8
5 g was added. After stirring for 2 hours at 0 ° C., acetonitrile
20 ml of water was added to disperse the crystals. Filter this mixture
As a result, 2.84 g of crude crystals were obtained. Asymmetry in crystals
Methine dye (I-1) has a yield of 48% of the theoretical value (HPL
C conversion), and the dye selectivity was 99%. Thiazo
Almost symmetric and oxazole symmetric dyes are formed
I did not. The obtained (I-1) is λmax = 537.0.
nm. Example 2: Initially 10 ml of 1,3-di
N-sulfobutyl-2-methyl-5-chloro to oxolane
1.63 g of lobenzothiazole (IV-1) and N-sulfur
Hopropyl-2- (β-ethoxy) -vinyl-3-ethyl
Ru-naphtho (1,2-d) oxazole (II-1)
1.14 g was added. After cooling to 0 ° C,
0.50 g of nylphosphine (VII-1) was added. This
After stirring the reaction mixture for 20 minutes at 0 ° C., sodium
0.85 g of t-butoxide was added. Stir at 0 ° C for 2 hours
And then add 20 ml of acetonitrile to disperse the crystals.
Let Filtration of this mixture gave 2.74 g of crude crystals.
It was. The asymmetric methine dye (I-1) in the crystal is
The yield is 44% (HPLC conversion), and the dye selectivity is 9
It was 9%. Thiazole symmetrical dye and oxazole pair
Little nominal pigment was produced. Comparative Example 1: Initially 10 ml of 1,3-di
N-sulfobutyl-2-methyl-5-chloro to oxolane
1.63 g of lobenzothiazole (IV-1) and N-sulfur
Hopropyl-2- (β-ethoxy) -vinyl-3-ethyl
Ru-naphtho (1,2-d) oxazole (II-1)
1.14 g was added. After cooling to 0 ° C,
0.85 g of tert-butoxide was added. 2 hours stirring at 0 ℃
After stirring, add 20 ml of acetonitrile to disperse the crystals
I let you. Filtration of this mixture gave 2.75 g of crude crystals.
It was. The asymmetric methine dye (I-1) in the crystal is the theoretical value.
Yield of 21% (in terms of HPLC), and the dye selectivity is
99%. Thiazole symmetrical dyes and oxazoles
Little symmetrical dye was produced. Example 3: Initially 4.0 ml of 1,3-
Dioxolane with 0.85 g of sodium t-butoxide
After charging and cooling to 0 ° C., N-sulfobutyl-2-
Methyl-5-chlorobenzothiazole (IV-1) 2.
24 g, triphenyl phosphite (VII-2) 0.
Add 89 g and 4.0 ml 1,3-dioxolane
It was. The reaction mixture was stirred for 20 minutes at 0 ° C. and then N-
Sulfopropyl-2- (β-ethoxy) -vinyl-3-
Ethyl-naphtho (1,2-d) oxazole (II-
1) 1.14 g was added. After stirring at 0 ° C for 2 hours,
20 ml of cetonitrile was added to disperse the crystals. this
The mixture was filtered to obtain 3.40 g of crude crystals. crystal
The asymmetric methine dye (I-1) contained 67% of the theoretical value.
Rate (HPLC conversion), and the dye selectivity was 99%.
It was. Thiazole symmetric dyes and oxazole symmetric dyes are mostly
It did not generate almost. Comparative Example 2: First, 4.0 ml of 1,3-
Dioxolane with 0.85 g of sodium t-butoxide
After charging and cooling to 0 ° C., N-sulfobutyl-2-
Methyl-5-chlorobenzothiazole (IV-1)
Add 63 g and 4.0 ml 1,3-dioxolane
It was. The reaction mixture was stirred for 20 minutes at 0 ° C. and then N-
Sulfopropyl-2- (β-ethoxy) -vinyl-3-
Ethyl-naphtho (1,2-d) oxazole (II-
1) 1.14 g was added. After stirring at 0 ° C for 1 hour,
N-sulfopropyl-2- (β-ethoxy) -vinyl
-3-ethyl-naphtho (1,2-d) oxazole (I
V-1) 1.14 g was added. Stir at 0 ° C for 1.5 hours
Then, add 20 ml of acetonitrile to disperse the crystals.
It was. Filtration of this mixture gave 3.76 g of crude crystals.
It was. The asymmetric methine dye (I-1) in the crystal has a theoretical value of 5
The yield is 3% (in terms of HPLC) and the dye selectivity is 99.
%Met. Thiazole symmetric dyes and oxazole symmetries
Little pigment was produced. Comparative Example 3: First 4.0 ml of dimethyl
1,8-Diazabicyclo [5.4.
0. ] 1.35g of undec-7-ene was charged, N-s
Rufobutyl-2-methyl-5-chlorobenzothiazole
(IV-1) 1.63 g and 4.0 ml of dimethylsulfur
Added hydroxide. The reaction mixture is stirred for 20 minutes at room temperature.
After stirring, N-sulfopropyl-2- (β-ethoxy)
-Vinyl-3-ethyl-naphtho (1,2-d) oxazo
1.14 g of (II-1) was added. 1 hour stirring at room temperature
After stirring, N-sulfopropyl-2- (β-ethoxy was further added.
Ii) -Vinyl-3-ethyl-naphtho (1,2-d) Oki
1.14 g of Sazol (IV-1) was added. 1 hour at room temperature
After half agitation, 0.77 g of sodium iodide and aceto
20 ml of nitrile was added to disperse the crystals. This mixture
The product was filtered to obtain 3.64 g of crude crystals. In crystals
The asymmetric methine dye (I-1) has a yield of 20% of the theoretical value.
(HPLC conversion) and the dye selectivity was 89%.
It was. The formation of a symmetric dye was confirmed. [0064] According to the method of the present invention, it is represented by the formula (I).
Simple and inexpensive methine dyes, even if they are asymmetric dyes
In addition, it is possible to synthesize with high yield and purity.
It was.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuyoshi Yamakawa             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 4H056 CA01 CC02 CC08 CE03 CE06                       DD01 DD19 DD23 DD30

Claims (1)

[Claims] In the presence of an organophosphorus compound, the following general formula (I)
Selected from compounds represented by I) and general formula (III)
At least one compound having the following general formula (IV)
And at least selected from compounds represented by formula (V)
And reacting one compound with the following general formula (I)
Methine dye characterized by obtaining methine dye represented
Manufacturing method. [Chemical 1] (Where L₁, L₂, L_Three, L_Four, L_Five, L₆, And L₇Each
Represents a methine group. These may be substituted.
p₁And p₂Each represents 0 or 1. n₁Is 0, 1,
2, 3 or 4 is represented. Z₁And Z₂Are each nitrogen-containing complex
Represents a group of atoms necessary to form a ring, which is a condensed ring
You may do it. R₁And R₂Each represents an alkyl group
The L₁~ L₇, Z₁, R₁, Z₂And R₂Are two each
May be bonded to each other to form a ring. M₁Is the charge
Represents the counterion for equilibrium, m₁Neutralizes molecular charge
It represents a number greater than or equal to 0 required to do. ) [Chemical 2] (Where L₈, And L₉Each represents a methine group. They are
May be substituted. p _ThreeRepresents 0 or 1. Z_ThreeIs nitrogenous
Represents a group of atoms necessary to form a prime heterocycle,
It may be condensed. Q₁Is a methylene-based nucleophilic attack
Represents a group necessary for generating a methine chain. R
_ThreeRepresents an alkyl group. L₈, L₉, Z_Three, Q₁And
And R_ThreeEach of which is bonded to each other to form a ring
May be. M₂Represents the counter ion for charge balance,
m₂Indicates a number greater than or equal to zero required to neutralize the charge of the molecule
The ) [Chemical Formula 3] (Where L_Ten, L₁₁, P_Four, Z_Four, Q₂, R_Four, M_Three,as well as
m_ThreeIs L in formula (II)₈, L₉, P_Three, Z_Three, Q₁,
R_Three, M₂And m₂It is synonymous with. ) [Formula 4] (Where L₁₂, And L₁₃Each represents a methine group. these
May be substituted. L_1aRepresents an active methyl group. p
_FiveRepresents 0 or 1. Z_FiveTo form a nitrogen-containing heterocycle
Represents a necessary atomic group, and this may be condensed. R
_FiveRepresents an alkyl group. L₁₂, L₁₃, Z_Five, L_1aOh
And R_FiveEach of which is bonded to each other to form a ring
It may be. M_FourRepresents the counter ion for charge balancing
M_Four Is a number greater than or equal to zero required to neutralize the charge of the molecule
Represents. ) [Chemical formula 5] (Where L_1bIs a methine group, L₁₄, L₁₅, P₆,
Z₆, R₆, M_FiveAnd m_FiveIs L in formula (IV)₁₂,
L₁₃, P_Five, Z_Five, R_Five, M_FourAnd m_FourIt is synonymous with. )