JPH02225476A - Novel methine compound and methine dye - Google Patents

Abstract

NEW MATERIAL:A methine compound expressed by formula I (CYA is atomic group having a cyanin chromogenic structure; L is bivalent linking group consisting of atom or atomic group containing at least one of C, N, S and O; Het is a group having 5- to 7-membered heterocyclic ring containing at least one N atom; l1 is 1 or 2; l2 is 0 or 1; l3 is 1, 2 or 3). EXAMPLE:A compound expressed by formula II. USE:Effectively used as a sensitizing coloring matter and dye for photographic sensitive materials (silver halide photographic and electrophotographic materials), useful as a sensitizing coloring matter and dye for other organic photosensitive materials and further coloring matter for laser recording materials, dye for filters, coloring matter for medicines and agricultural chemicals, dye for dying pulp, cell, etc. PREPARATION:A sensitizing coloring matter part is linked to a nitrogen- containing heterocyclic part utilizing reaction for forming bonds including various reactions for forming amide bond and ester bonds to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel methine compound useful as a coloring agent and a methine dye (pigment) using the same.

(Prior Art) Various cyanine dyes have been known in the past. The chromogen structure of cyanine dyes consists of two so-called basic nuclei and a conjugated double bond chain connecting them. However, cyanine dyes that have a nitrogen-containing heterocyclic group as a substituent linked to this cyanine chromogen structure, especially a nitrogen-containing heterocyclic group that can chemically or physically adsorb heavy metals such as silver ions, are not known. It wasn't.

(Problem 1a to be solved by the present invention) The present invention provides a novel compound and cyanine dye (pigment) having a nitrogen-containing heterocyclic group capable of chemically or physically adsorbing a heavy metal or a heavy metal ion as a substituent. That's true.

(Means for Solving the Problems) The present invention is a novel methine compound and methine dye represented by the following general formula (1).

General formula (1) % formula % In the formula, CYA represents an atomic group having a cyanine chromogen structure, and L is an atom or atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom. Het represents a group having a 5- to 7-membered heterocyclic ring containing at least one nitrogen atom, ll is 1 or 2, 1 is O or 1, 1 is a divalent linking group consisting of is 1,2. Or represents 3.

Note that the heterocycle represented by Het may contain a heteroatom other than a nitrogen atom.

In general formula (1), the group represented by CYA is usually a conjugated double ring so that a nitrogen-containing heterocyclic nucleus called a basic nucleus and another nitrogen-containing heterocyclic nucleus can be conjugated with each other. A group having a cyanine dye structure formed by being connected through a bond.

Examples of cyanine dyes include T and H.

James Q ” Theory of Photo
graphic Process1977 MaC@
Chapter 8, D, M published by 1llan.

5tur++er” The Chemistry
of fleterocyclic Compou
r+ds ed, A, Weissberger
and E, C.

Taylor, 1977 John Wil
It is described in Chapter 8 of EY and 5ons (New York). Examples of preferable basic nuclei used in these cyanine dyes include oxazoline,
Oxazole, benzoxazole, naphthothiazole, thiazoline, thiazole, benzothiazole, naphthothiazole, dihydronaphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, 3H-indole, benzindole, imidacilline, imidazole, benzimidazole, naphthimidazole , pyridine, quinoline, imidazo(4,5-b
) quinoxaline, loridine, tellurazole, penzotelllazole, naphthotellazole, and the like.

L is a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom,
Represents a divalent linking group consisting of an atom or atomic group containing at least one species.

Preferably, an alkylene group (e.g., methylene group, ethylene group, propylene group, butylene group, pentylene group, etc.), an arylene group (e.g., phenylene group, naphthylene group, etc.), an alkenylene group (e.g., ethylene group, propenylene group, etc.) , sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N-(R
1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), a heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2,4- Diyl group, pyrimidine-2,4-diyl group, quinoxaline2.
represents a divalent linking group having 20 or less carbon atoms, which is formed by combining one or more 3-diyl groups, etc.).

2, is 1 or 2, ! , is O or 1, ! , is 1, 2. or 3 represents.

Represents an integer.

Preferably 11 is 1, i8 is 0 or 1,! .

represents 1 or 2.

Hat is a saturated or unsaturated 5- to 7-membered heteroatom that contains at least one nitrogen atom and may also contain other heteroatoms (e.g., oxygen atom, sulfur atom, selenium atom, tellurium atom). Represents a compound moiety containing a ring.

Preferably, it has a structure represented by general formulas (n) to (VT).

Substituents on the substituents listed in the section for explanation of each substituent include alkyl groups, alkenyl groups, aryl groups, hydroxy groups, carboxyl groups, sulfo groups, nitro groups, cyano groups,
Examples include a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acylamino group, a sulfonamino group, a carbamoyl group, and a sulfamoyl group.

General formula (n) ■In the formula, V+, V! , Vs, Va are hydrogen atoms, substituted or unsubstituted alkyl groups (for example, methyl, ethyl,
Propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, sulfopropyl, diethylaminoethyl, cyanopropyl, adamantyl, P-chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetyl aminoethyl, etc.),
Unsubstituted or substituted alkenyl groups (e.g. allyl, styryl, etc.), unsubstituted or substituted alkenyl groups (e.g. phenyl, naphthyl, p-carboxyphenyl, 3.5-
Dicarboxyphenyl, m-sulfophenyl, P-acetamidophenyl, 3-caprylamidophenyl, p-
Sulfamoylphenyl, m-hydroxyphenyl, p
-nitrophenyl, 3.5-dichlorophenyl, p-phenyl, 0-phenyl, p-cyanophenyl, p-N'
methylureidophenyl, m-fluorophenyl, p-
tolyl, m-)lyl, etc.), optionally substituted heterocyclic residues (e.g. pyridyl, 5-methyl-2-pyridyl, thienyl, etc.), halogen atoms (e.g. chlorine, bromine, fluorine), mercapto groups, cyano groups , carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, amino group, nitro group, optionally substituted alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy, etc.), substituted aryloxy groups (e.g., phenoxy, p-methylphenoxy, p-chlorophenoxy, etc.), acyl groups (e.g., acetyl, benzoyl, etc.), acylamino groups (e.g., acetyl, benzoyl, etc.), which may be
(e.g., acetylamino, caproylamino, etc.), sulfonyl groups (e.g., methanesulfonyl, benzenesulfonyl, etc.), sulfonylamino groups (e.g., methanesulfonylamino, benzenesulfonylamino, etc.), substituted amino groups (e.g., diethylamino, hydroxyamino, etc.) , represents an alkyl or arylthio group (e.g., methylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), an alkoxycarbonyl group (e.g., methoxycarbonyl, etc.), an aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.), and these substituents include , furthermore, by a divalent linking group or a single bond, Ha
t may be substituted.

Mata, v+, ■t, 'I/1. At least one of V4 may be a divalent linking group or a single bond.

General formula (Ill) In the formula, Xl represents an oxygen atom, a sulfur atom, or NR'',
(R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted ring group, or a substituted or unsubstituted heterocyclic group) 5. (16) and Vma have the same meanings as V' to (4) in the general formula (U), respectively, and also represent the divalent linking group or single bond described above.

Furthermore, (5) and (4) may be combined to form a benzo or naphtho condensed ring.

On these benzo and naphtho condensed rings and Rt (excluding the case of hydrogen atoms), substituents and/or linking groups shown in v1 to 4 in the above general formula (II) (or a single bond) can be added. may be replaced.

General Formula (IV) Further, VIO and Vlff are a connecting group or a single bond, and in the formula, X4 represents an oxygen atom, a sulfur atom, or N''-R'.

R3 represents the same meaning as R1 shown in the above general formula (III).

In addition, ■a and ■drops are ■1 to ■1 in the general formula (II) above.
■In addition to representing the same meaning as 4, each represents the divalent linking group or single bond mentioned above.

General formula (V’) You can.

General formula (Vl) IS where Vl4. Vl5 represents the same meaning as (1) to (4) shown in the general formula (II).

Also, ■14. Vl! 1 may be a linking group or a single bond.

Next, a preferred structure of the compound represented by the general formula (1) is shown in the general formula (■).

In the formula, X5 R4.8% Also, ■1.

Vl in represents a nitrogen atom or C-R'.

is R2 in the general formula (III), y++, y+
t and (2)+i each represent the same meaning as in the above general formulas (If) to v4.

In the formula,
>c (CH3)□, represents -CH-CH-.

Gl, Gl, and R@ may be the same or different, and each represents an alkyl group, an aryl group, an alkenyl group, or a heterocyclic group, which may be unsubstituted or substituted, and may be a divalent group. It may be a linking group or a single bond.

Preferably, the alkyl group and alkenyl group have 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. group, octyl group, dodecyl group, octadecyl group, allyl group, 2-butenyl group], substituted alkyl group having 1 to 1 carbon atoms, more preferably 1 to 10 carbon atoms, substituted alkenyl group [e.g. benzyl group, phenethyl group, p-sulfo-2-phenethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-methoxyethyl Ll (2-methoxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2(3-sulfopropoxy)ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfatopropyl group, 2-(pyrrolidine-2- on-1-yl)ethyl group,
Tetrafurfuryl group, 3-acetoxypropyl group, ethoxycarbonylethyl group, 3-cyanopropyl group, 2-
Methanesulfonylaminoethyl group, 2-carbamoylethyl group, 22.3.3-tetrafluoropropyl group, 2
-ethylthioethyl group, 2-chloro-2-butenyl group], substituted and unsubstituted aryl groups, and substituted and unsubstituted heterocyclic groups having 18 or less carbon atoms, more preferably 10 or less carbon atoms. Substituted aryl groups [e.g. phenyl group, naphthyl group, tolyl group, anisyl group, 4-chlorophenyl group, sulfophenyl group, carboxyphenyl group, ethoxycarbonylphenyl group, 3-hydroxyphenyl group, 3-chloro-p-tolyl group etc., substituted and unsubstituted heterocyclic groups [e.g. pyridyl group, 3chloro-2-pyridyl group, 6-chloro-4-methoxy-1,3
, 5-) riazin-2-yl group, etc.].

G3 represents a hydrogen atom, a fluorine atom, and n! is 1 or more, an optionally substituted lower alkyl group having 8 or less carbon atoms and an alkylene bridge with G1, and 5 which may contain an oxygen atom, a sulfur atom and/or a nitrogen atom in the ring constituent atoms. It represents the ability to form a ring member or a six-membered ring, and may also be a divalent linking group or a single bond.

G4.6% is a hydrogen atom, a fluorine atom, an optionally substituted lower alkyl group with 8 or less carbon atoms, an optionally substituted lower alkoxy group with 8 or less carbon atoms, an optionally substituted lower alkyl group with 8 or less carbon atoms, and an optionally substituted lower alkyl group with 8 or less carbon atoms. In addition to representing the following aryl group, when nt is 2 or more, G3 and the nearest GS and/or different G4 and G4 and/or GS and GS are connected to the ring constituent atoms such as oxygen atom, sulfur atom and/or Alternatively, it represents the ability to form a 5- or 6-membered ring that may contain a nitrogen atom. It may also be a linking group or a single bond.

nj and n3 may each be the same or different and represent 0 or ].

nt is 0. 1. 2. represents 3 or 4, preferably 0. 1. 2. Or 3.

Yl represents a cationic group, Wl represents an anionic group,
kl and ni! is 0 or l, depending on the presence or absence of ionic groups.

Examples of cationic groups include alkali metal cations (
Examples include Na', Φ, etc.) quaternary ammonium salts (eg, triethylammonium, pyridinium, etc.).

In addition, examples of anionic groups include halogen anions (
(e.g. chloride, iosito), sulfonates (e.g. methanesulfonate, P-)luenesulfonate, etc.),
These include sulfates (such as methyl sulfate), borates (such as tetrafluoroborate), phosphates (such as hexafluorophosphate), and the like.

L Het, lr, lr, 1s are expressed by the general formula (1
) Nori, l1et, ll, is, l,
expresses the same meaning as

B', B", B', B', E', E', E"E4 is a hydrogen atom, a halogen atom (e.g. chlorine atom, fluorine atom, bromine atom, etc.), hydroxy group, cyano group, trifluoromethyl group, nitro group, methylenedioxy group, carboxyl group, sulfo group, substituted or unsubstituted alkyl group with 10 or less carbon atoms, substituted or unsubstituted aryl group with 10 or less carbon atoms, substituted or unsubstituted aryl group with 10 or less carbon atoms. Substituted alkoxy group, alkylthio group having 8 or less carbon atoms, arylthio group having 8 or less carbon atoms, acylamino group having 8 or less carbon atoms, alkoxycarbonyl group having 8 or less carbon atoms, acyl group having 10 or less carbon atoms,
It also represents a divalent linking group or a single bond.

In the present invention, the compound represented by -a formula (■) is B'
B", Bri, B', E', E", EtsuE', G', G"
, G', G' and Ro, and ■1 to yi of the compound represented by the general formula (11) to general formula (Vl)
It is a compound in which at least one of s, R1, and Rs is chemically bonded via a divalent linking group or a single bond.

The bonding position is preferably Gl, G'', R'', B', B'', B'' or the 84th position as a substituent on the methine dye side.

-a A more preferable structure of the methine dye represented by formula (■) is shown by the following general formula (■).

General formula (■) (Y") k+ + (u"'), x-th in the z formula,
X1g may be the same or different, and may be a sulfur atom, an oxygen atom, a selenium atom, >NR", 'C(
CHs)i or / -CH-CH-.

Gl, G", and R" have the same meanings as G'IQt in general formula (■), but at least one of G" and G" is a substituent (D-1) C, 11° GI3 is the general formula (■) 03 and G", and GIS is the general formula (
■) G4. Represents the same meaning as GS.

[3+1. B11. B13. BI3. El
l, Elffi, E13E14 is B in the general formula (■)
', B'', BsEl, Bg, E3, E
Each represents the same meaning as a.

However, G13. G”, G”, B”, B”, B”B”, E
Items E Il, Ell, and B14 do not contain divalent linking groups or single bonds.

nIl, 011. nIl, kll, kll,
Yll, WII are nl, nl, of general formula (■)
They have the same meaning as nl, kl, kffYl, and Wl, respectively.

L, , and Het are respectively represented by the general formula (■).

It has the same meaning as Het.

Il, □ is Ol or l Z+S is 1.2. Or represents 3.

Specific examples of the methine compound and methine dye of the present invention are shown below.

(D-4) (D-7) (D-8) R (D-9) C■.

(D (D 1.1) (D (D r]1+ (D-1,7) (D-18) to 7, (D (D (D-21) (D-25) (D ■ (D D-27) (D (D (D (D 36)) (D (D VN (D-33) (D-34) (D-39) Shifi3 (D-43) In organic chemistry, various well-known bond-forming reactions such as amide bond-forming reactions and ester bond-forming reactions are used to combine a sensitizing dye moiety and a nitrogen-containing heterocyclic moiety represented by Hat. A method of linking a nitrogen-containing heterocyclic moiety represented by Het to a raw material and an intermediate for the synthesis of a sensitizing dye, and then carrying out a dyeing reaction; conversely, a method of synthesizing a nitrogen-containing heterocyclic moiety represented by Het Any method may be used, such as a method in which a nitrogen-containing heterocyclic moiety represented by Het is synthesized after linking raw materials and intermediates to a sensitizing dye moiety, and the synthesis can be selected as appropriate.Synthetic reactions for these linkages For example, Nippon Kagaku Yoshin, New Experimental Chemistry Course 14, Synthesis and Reactions of Organic Compounds, Volumes IV, Maruzen, Tokyo (1977), Yoshibe Ogata, Organic Reactive Oils, Maruzen, Tokyo (1962). ), L, F, Fieser an
dM, Fieser, AdvancedOrg
anic Chemistry+ Maruzen, Tokyo (19
(1962), the bottom line on many organic synthesis reactions can be used as a reference.

(Effects of the Invention) The novel methine compounds and methine dyes of the present invention are effective as sensitizing dyes and dyes for photographic materials (silver halide photography, electrophotography), and are also effective as sensitizing dyes for other organic photographic materials. Effective as pigments and dyes. In addition, it is effective as a dye for laser recording materials, a dye for filters, a dye for pharmaceuticals and agricultural chemicals, and a dye for staining bulbs, cells, etc.

Example 1 (Synthesis of dye D-7) 3-(5-aminopentyl)-3'-ethyl 9-methylthiacarbocyanine promide hydropromide 190■
, triethylamine 0.15 ad! acetonitrile 6
0- and stirred at room temperature. After 10 minutes, 160 μl of 5-phenoxycarbonylbenzotriazole was added, and the reaction mixture was reacted at room temperature for 3 hours and then at 60°C for 8 hours. The reaction mixture was subjected to silica gel column chromatography (eluent: methanol/chloroform-1/3 vol/ νof)
Next, 191 g of the target dye was obtained by purification.

Dark reddish-purple crystal (melting point 155-161'C) Methanol λmax Co 5 4 4 nm FAB-MS (posi) m/e -581 (M
Br)" Example 2 (Synthesis of dye D-10) 3-(5-aminopentyl)-31-ethyl 9-methylthiacarbocyanine promide hydropromide 200■
, triethylamine 0.1.5d to acetonitrile 10
The mixture was added to a mixed solvent of 0d and chloroform 50+d, and stirred at room temperature. After 10 minutes, 1 g of 200 Il of 6-(4-chlorophenoxycarbonylmethyl)-1,3,3a,7-chitrazaindene was added, and the mixture was heated at room temperature for 1 hour, then at 60°C.
The reaction mixture reacted for 10 hours was purified by silica gel column chromatography (eluent: methanol/chloroform-1/3 vol/vol.) to obtain 153 g of the target dye.

Dark red-purple crystal (melting point 148-155'c) Methanol λ max: 546 nm FAB-MS (posi) a/s = 6 1
2 (M-Br)' Example 3 (Synthesis of dye D-18) 3-(5-aminopentyl)-3',9-di-engineered thiacarbocyanine promide hydropromide 200 mg,
0.10m of triethylamine, 50d of acetonitrile and 50ai of chloroform! was added to a mixed solvent of and stirred at room temperature. After 10 minutes, 160 ml of i(3-phenoxycarbonylaminophenyl)-5-mercaptotetrazole was added and reacted at 60'C for 8 hours. After cooling to room temperature, the formed crystals were collected and washed with methanol to obtain 50 ml of the desired dye.

Dark red-purple crystal (melting point 160-175°C) Methanol λmax 2544 nm FAB-MS (post) ale = 669
(M-Br)' Example 4 (Synthesis of dye D-38) 3-(5-aminopentyl)-31-ethyl 9-methylthiacarbocyanine promide hydropromide 200■
, 0.15 ml of triethylamine was added to 50 ml of methanol, and the mixture was stirred at room temperature.

5 back 4-chloro6-methyl-1.3.3a.

100 μl of 7-chitrazaindene was added and reacted at room temperature for 2 hours, and further reacted at 60° C. for 4 hours.

The reaction mixture was subjected to silica gel column chromatography (eluent: methanol/chloroform-1/3 vol/vo
1) to obtain 80 ml of the target dye.

Dark red-purple crystals (melting point 133-140'c) methanol λ max 544 nm FAB-MS (post) ale = 5 6
8 (M-Br)” Example 5 (Synthesis of dye D-41) 3-(3-(vinylcarbonylamino)propyl)-
150 ml of 31-ethyl-9-methylthiacarbocyanine bromide and 150 ml of 5-amino-IH-indazole were added to 100 d of methanol and reacted for 2 hours at room temperature and then for 6 hours under refluxing methanol. - The reaction mixture was purified by silica gel column chromatography (eluent: methanol/chloroform-3/7 sol/vol) to obtain the target dye 25.

Dark red crystalline methanol λ max 545 nm FAB-MS (post) ale = 595
(M-Br)" Example 6 (Synthesis of dye D-12) 1(3-(vinylcarbonylamino)propyl]-3'
-Ethylthiamonomethine cyanine bromide 12ON and 5
-Aminoimidazole! Starting from 00■, the same operation as in Example 5 was carried out to obtain 271 mg of the desired dye.

Yellow crystal, λP'a-~424nmFAB-MS
(post) ale-555(M-Br)" Example 7 (Synthesis of dye D-43) 3-(3-(4,6-dichloro-13,5triazin)-1-ylamino)propyl)-3' Ethyl-9-phenylthiacarbocyanine bromide 150■,5-(2
-aminoethylamino)benzotriazole 80 mg,
Triethylamine 0゜1yd acetonitrile 20af
and chloroform 20d for 6 hours at room temperature.
The reaction was further carried out at 40°C for 4 hours.

The reaction mixture was subjected to silica gel column chromatography (eluent: methanol/chloroform = 3/7 vol/v
After purification using at), salt exchange was performed using sodium perchlorate to obtain the desired dye 45.

Dark red crystalline methanol λmax 559 nm Example a Staining of TP paper A M1500 methanol solution of the compound D-7 of the present invention was dropped onto Toyo Rogi (N11131) and then air-dried.
The filter paper was well stained reddish-purple.

Example 9 Compounds of the present invention D-10, D-12, D-15, D-18, D-3 in place of D-7 by the same method as in Example 1
8, D-41, and D-43 were used.

All dyed paper well.

Example 10 A colorless cotton cloth was soaked in an M1500 methanol solution of the compound D-10 of the present invention for 20 minutes, and then taken out and air-dried. The cotton cloth was well dyed reddish-purple.

Claims (1)

[Claims] (1) A methine compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, CYA represents an atomic group having a cyanine chromogen structure, and L represents at least one of carbon atom, nitrogen atom, sulfur atom, and oxygen atom. Represents a divalent linking group consisting of an atom or atomic group containing a species, Het represents a group having a 5- to 7-membered heterocycle containing at least one nitrogen atom, l_1
, is 1 or 2, l_2 is 0 or 1, l_3 is 1, 2
, or 3. (2) A methine dye represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, CYA represents an atomic group having a cyanine chromogen structure, and L represents at least one of carbon atom, nitrogen atom, sulfur atom, and oxygen atom. Represents a divalent linking group consisting of an atom or atomic group containing a species, Het represents a group having a 5- to 7-membered heterocycle containing at least one nitrogen atom, l_1
is 1 or 2, l_2 is 0 or 1, l_3 is 1, 2,
Or represents 3. ]